Patent Application
20240176242
The present invention relates to a pattern forming method, a method for producing an electronic device, an actinic ray-sensitive or radiation-sensitive resin composition, and a resist film.
Since the advent of a resist for KrF excimer laser (248 nm), a pattern forming method utilizing chemical amplification has been used in order to compensate for a decrease in sensitivity due to light absorption. For example, in a positive chemical amplification method, first, a photoacid generator included in regions to be exposed is decomposed by light irradiation to generate acid. Subsequently, in a process of baking after exposure (PEB: Post Exposure Bake) or the like, for example, an alkali-insoluble group of a resin included in an actinic ray-sensitive or radiation-sensitive resin composition is changed, by the catalytic action of the generated acid, to an alkali-soluble group to change the solubility in a developer. Development is then performed using, for example, a basic aqueous solution. Thus, exposed regions are removed to obtain a desired pattern.
In order to miniaturize semiconductor elements, the wavelengths of exposure light sources have been shortened and the numerical apertures (NAs) of projection lenses have been increased, and currently, exposure apparatuses using ArF excimer laser having a wavelength of 193 nm as light sources have been developed. Furthermore, in recent years, pattern forming methods using extreme ultraviolet rays (EUV light: Extreme Ultraviolet) and an electron beam (EB: Electron Beam) as light sources are also being studied.
Under such circumstances, pattern forming methods using actinic ray-sensitive or radiation-sensitive resin compositions having various configurations have been proposed.
For example, JP2019-211531A discloses a positive resist composition for EUV lithography including a polymer that undergoes an increase in solubility in a developer caused by scission of the main chain due to irradiation with EUV light, and a pattern forming method using the positive resist composition.
In general, a resist film formed from a resist composition is controlled such that the time from the end of exposure treatment to the start of development treatment (hereinafter, also referred to as a “waiting time before development”) is constant for the purpose of suppressing a variation in sensitivity. However, the waiting time before development may vary because of, for example, a failure of a developing apparatus or the like, and in such a case, there is a problem in that the sensitivity of the resist film varies, and consequently, the line width of a pattern to be obtained varies from a desired value. Therefore, from the viewpoint of performance stability, there has been a demand for a pattern forming method in which even if the waiting time before development varies, the variation in the line width of a pattern to be formed is small.
The inventors of the present invention have studied the resist film formed from the resist composition described in JP2019-211531A and have found that, when the waiting time before development varies, the line width of a pattern to be formed varies significantly, and there is room for further improvement in this respect.
In view of the above, an object of the present invention is to provide a pattern forming method in which even if the time from the end of exposure treatment to the start of development treatment (waiting time before development) varies, a variation in the line width of a pattern to be formed is small.
Another object of the present invention is to provide a method for producing an electronic device, the method relating to the pattern forming method.
Furthermore, another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition and a resist film that are suitable for the pattern formation.
The inventors of the present invention have found that the following configurations enable achievement of the above-described objects.
[1] A pattern forming method having a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive resin composition;
[2] The pattern forming method according to [1], wherein the group that decreases polarity is a group that decreases polarity due to action of acid and is a functional group represented by Formula (KD1) described later, a monovalent functional group formed by removing one hydrogen atom that one or more of Rd5 to Rd10 in a compound represented by Formula (KD2) described later have, or a monovalent functional group formed by removing one hydrogen atom that a ring member atom has in any of a ring formed by bonding Rd6 and Rd7together and a ring formed by bonding Rd8 and Rd9 together in the compound represented by Formula (KD2) described later.
[3] The pattern forming method according to [1], wherein the group that decreases polarity is an acid-decomposable group having a structure in which a polar group is protected with a protective group that leaves due to action of acid, and
[4] The pattern forming method according to any one of [1] to [3], wherein the polar group is one or more functional groups selected from the group consisting of an alcoholic hydroxy group, a phenolic hydroxy group, and a carboxyl group.
[5] The pattern forming method according to [4], wherein the compound that reacts with the polar group is a compound selected from the group consisting of a tertiary alcohol, a tertiary ether, an epoxide, a vinyl ether, an olefin, a benzyl ether, benzyl alcohol, and a carboxylic acid.
[6] The pattern forming method according to any one of [1] to [5], wherein the resin X1 and the resin X2 further have an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating, and the composition further includes an onium salt compound.
[7] The pattern forming method according to [6], wherein the interactive group is one or more functional groups selected from the group consisting of a phenolic hydroxy group, a carboxyl group, a sulfonic group, an amide group, and a sulfonamide group.
[8] The pattern forming method according to any one of [1] to [7], wherein the resin X1 and the resin X2 further have an onium salt group that is decomposed due to action of exposure.
[9] The pattern forming method according to [8], wherein the onium salt group is an onium salt group that is decomposed due to action of exposure, the onium salt group being selected from the group consisting of a group represented by Formula (O1) described later and a group represented by Formula (O2) described later.
[10] The pattern forming method according to any one of [1] to [9], wherein the resin X1 and the resin X2 are resins that undergo a decrease in molecular weight due to action of exposure, acid, base, or heating.
[11] The pattern forming method according to [10], wherein the resin X1 and the resin X2 are resins that undergo a decrease in molecular weight caused by scission of a main chain due to action of exposure, acid, base, or heating.
[12] The pattern forming method according to [10] or [11], wherein the resin X1 and the resin X2 include a repeating unit represented by Formula (XP) described later and a repeating unit represented by Formula (XQ) described later.
[13] The pattern forming method according to any one of [1] to [12], wherein the resin X1 and the resin X2 further have a reactive group A, and the composition further includes a crosslinking agent having a reactive group B that reacts with the reactive group A, or
[14] The pattern forming method according to [1], wherein the composition satisfies the requirement A1 or the requirement A2 and further includes a resin Y1.
[15] The pattern forming method according to [14], wherein the resin Y1 has an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating, and the composition further includes an onium salt compound.
[16] The pattern forming method according to [15], wherein the interactive group is one or more functional groups selected from the group consisting of a phenolic hydroxy group, a carboxyl group, a sulfonic group, an amide group, and a sulfonamide group.
[17] The pattern forming method according to any one of [14] to [16], wherein the resin Y1 further has an onium salt group that is decomposed due to action of exposure.
[18] The pattern forming method according to [17], wherein the onium salt group is an onium salt group that is decomposed due to action of exposure, the onium salt group being selected from the group consisting of a group represented by Formula (O1) described later and a group represented by Formula (O2) described later.
[19] The pattern forming method according to any one of [14] to [18], wherein the resin Y1 is a resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating.
[20] The pattern forming method according to [19], wherein the resin Y1 is a resin that undergoes a decrease in molecular weight caused by scission of a main chain due to action of exposure, acid, base, or heating.
[21] The pattern forming method according to [19] or [20], wherein the resin Y1 includes a repeating unit represented by Formula (XP) described later and a repeating unit represented by Formula (XQ) described later.
[22] The pattern forming method according to any one of [14] to [21], wherein the resin Y1 further has a reactive group A, and the composition further includes a crosslinking agent having a reactive group B that reacts with the reactive group A, or the resin Y1 further has the reactive group A and the reactive group B, and a bond formed by the reactive group A and the reactive group B is broken by action of exposure, acid, base, or heating.
[23] An actinic ray-sensitive or radiation-sensitive resin composition satisfying any one of requirements A11 to A14 below.
[24] An actinic ray-sensitive or radiation-sensitive resin composition satisfying any one of requirements A21 to A23 below.
[25] An actinic ray-sensitive or radiation-sensitive resin composition satisfying a requirement A1 or a requirement A2 below and including a resin Y31 that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating.
[26] An actinic ray-sensitive or radiation-sensitive resin composition satisfying any one of requirements A41 to A45 below.
[27] The actinic ray-sensitive or radiation-sensitive resin composition according to [23], wherein the interactive group is one or more functional groups selected from the group consisting of a phenolic hydroxy group, a carboxyl group, a sulfonic group, an amide group, and a sulfonamide group.
[28] The actinic ray-sensitive or radiation-sensitive resin composition according to [24], wherein the onium salt group is an onium salt group that is decomposed due to action of exposure, the onium salt group being selected from the group consisting of a group represented by Formula (O1) described later and a group represented by Formula (O2) described later.
[29] The actinic ray-sensitive or radiation-sensitive resin composition according to [25], wherein the resin Y31 includes a repeating unit represented by Formula (XP) described later and a repeating unit represented by Formula (XQ) described later.
[30] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [23] to [29], wherein the group that decreases polarity is a group that decreases polarity due to action of acid and is a functional group represented by Formula (KD1) described later, a monovalent functional group formed by removing one hydrogen atom that one or more of Rd5to Rd10 in a compound represented by Formula (KD2) described later have, or a monovalent functional group formed by removing one hydrogen atom that a ring member atom has in any of a ring formed by bonding Rd6 and Rd7 together and a ring formed by bonding Rd8 and Rd9together in the compound represented by Formula (KD2) described later.
[31] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [23] to [29], wherein the group that decreases polarity is an acid-decomposable group having a structure in which a polar group is protected with a protective group that leaves due to action of acid, and
[32] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [23] to [29], wherein the polar group is one or more functional groups selected from the group consisting of an alcoholic hydroxy group, a phenolic hydroxy group, and a carboxyl group.
[33] The actinic ray-sensitive or radiation-sensitive resin composition according to [32], wherein the compound that reacts with the polar group is a compound selected from the group consisting of a tertiary alcohol, a tertiary ether, an epoxide, a vinyl ether, an olefin, a benzyl ether, benzyl alcohol, and a carboxylic acid.
[34] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [23] to [33].
[35] A method for producing an electronic device, the method including the pattern forming method according to any one of [1] to [22].
The present invention can provide a pattern forming method in which even if the time from the end of exposure treatment to the start of development treatment (waiting time before development) varies, a variation in the line width of a pattern to be formed is small.
The present invention can also provide a method for producing an electronic device, the method relating to the pattern forming method.
Furthermore, the present invention can also provide an actinic ray-sensitive or radiation-sensitive resin composition and a resist film that are suitable for the pattern formation.
The present invention will be described in detail below.
The constituent features described below may be described based on representative exemplary embodiments of the present invention; however the present invention is not limited to such exemplary embodiments.
With respect to expressions of groups (atomic groups) in the present specification, an expression without the term of substituted or unsubstituted encompasses groups having no substituent and also groups having a substituent without departing from the spirit and scope of the present invention. For example, “alkyl group” encompasses not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, “organic group” refers to a group including at least one carbon atom.
The substituent is preferably a monovalent substituent unless otherwise specified.
In the present specification, “actinic ray” or “radiation” means, for example, an emission-line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, or an electron beam (EB: Electron Beam). In the present specification, “light” means an actinic ray or a radiation.
In the present specification, “exposure” includes, unless otherwise specified, not only exposure with, for example, an emission-line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, or EUV light but also patterning with an electron beam or a corpuscular beam such as an ion beam.
In the present specification, a range of numerical values expressed with “to” mean a range that includes a numerical value before “to” as a lower limit value and a numerical value after “to” as an upper limit value.
The bonding direction of a divalent group expressed in the present specification is not limited unless otherwise specified. For example, in a compound represented by a formula “X—Y—Z” where Y is —COO—, Y may be —CO—O— or —O—CO—. Furthermore, the compound may be “X—CO—O—Z” or “X—O—CO—Z”.
In the present specification, (meth) acrylate represents acrylate and methacrylate, and (meth) acryl represents acryl and methacryl.
In the present specification, a weight-average molecular weight (Mw), a number-average molecular weight (Mn), and a dispersity (also referred to as a “molecular weight distribution”) (Mw/Mn) of a resin are defined as polystyrene equivalent values determined, using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC, manufactured by Tosoh Corporation), by GPC measurement (solvent: tetrahydrofuran, amount of flow (amount of sample injected): 10 μL, column: TSK gel Multipore HXL-M, manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL/min, detector: differential refractive index detector (Refractive Index Detector)).
In the present specification, the acid dissociation constant (pKa) represents pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 on the basis of the Hammett's substituent constants and the database of values in publicly known documents. A11 the values of pKa described in the present specification are values determined by calculation using this software package.
Software package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs)
Alternatively, pKa can also be determined by a molecular orbital calculation method. A specific method thereof may be a method of achieving the determination by calculating H+ dissociation free energy in an aqueous solution on the basis of a thermodynamic cycle. With regard to the method of calculating H+ dissociation free energy, the calculation can be performed by, for example, DFT (density functional theory); however, various other methods have been reported in documents etc., and the method is not limited to this. Note that there are a plurality of pieces of software capable of performing DFT; for example, Gaussian 16 may be used.
As described above, pKa in the present specification refers to a value determined by calculation using the software package 1 on the basis of the Hammett's substituent constants and the database of values in publicly known documents; however, when pKa cannot be calculated by this method, a value determined using Gaussian 16 on the basis of DFT (density functional theory) is employed.
In addition, as described above, pKa in the present specification refers to “pKa in an aqueous solution”; however, when pKa in an aqueous solution cannot be calculated, “pKa in a dimethyl sulfoxide (DMSO) solution” is employed.
In the present specification, examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the present specification, “solid content” means a component forming a resist film and does not include solvents. Even when a component has the form of liquid, the component is regarded as a solid content as long as it is a component forming the resist film.
A values of log P (octanol/water partition coefficient) given in the present specification is a value calculated using ChemBioDraw Ultra (Version16.0.14) unless otherwise specified.
A pattern forming method according to the present invention has a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as a “resist composition” or a “composition”);
According to the pattern forming method of the present invention having the above configuration, even if the time from the end of exposure treatment to the start of development treatment (waiting time before development) varies, a variation in the line width of a pattern to be formed is small.
This is not clear in detail, but the inventors of the present invention presume as follows.
Conventionally, it is known that the dissolution contrast of pattern formation can be reversed by changing a developer from an aqueous alkali solution to an organic solvent. For example, it is known that when a resin that has a protective group and undergoes an increase in polarity due to deprotection during exposure treatment and optional post-exposure heating is used, a positive pattern is obtained by alkali development and a negative pattern is obtained by organic solvent development.
On the other hand, recently, the inventors have found that when a resist film using a resin that has a protective group that undergoes a decrease in polarity during exposure treatment and optional post-exposure heating is subjected to organic solvent development treatment after the exposure treatment and optional post-exposure heating, not only can a positive image be formed, but also a change in sensitivity when the waiting time before development varies can be specifically suppressed. This effect was not exhibited by a publicly known method in which a positive image can be formed by the conventional organic solvent development.
Here, the resin X1 can undergo a decrease in polarity due to action of exposure, acid, base, or heating. The resin X2 is used in combination with a compound that reacts with the polar group in the resin X2 due to action of exposure, acid, base, or heating (capping agent) and can thereby undergo a decrease in polarity when subjected to action of exposure, acid, base, or heating. Note that, in pattern formation, exposure treatment and optional post-exposure heat treatment are usually performed, and the condition (exposure, acid, base, or heating) that acts on the resin X1 and the resin X2 is a factor that can occur in the resist film during the exposure treatment and the post-exposure heat treatment. Presumably, in the resin X1 and the resin X2, the polarity is decreased by the exposure treatment and the optional post-exposure heat treatment, and due to this, the intermolecular forces of the respective components in the resist film before development are reduced, so that the resist film is rapidly subjected to structural relaxation to be in a stable state. It is considered that, as a result, a change in sensitivity is less likely to occur when the waiting time before development varies.
In addition, in pattern formation of the present invention, whereas the polarity of exposed regions of the resin X1 and the resin X2 decreases, a decrease in the polarity is suppressed in unexposed regions. That is, the dissolution contrast between exposed regions and unexposed regions enables the formation of a pattern.
Furthermore, surprisingly, it has been confirmed that when a resist film including the resin X1 or resin X2, which is a resin having a protective group that undergoes a decrease in polarity during exposure treatment and optional post-exposure heating, is treated with an alkali developer to form a negative-type pattern, a change in sensitivity when the waiting time before development varies cannot be suppressed.
In the following description, the feature that even if the time from the end of exposure treatment to the start of development treatment (waiting time before development) varies, a variation in the line width of a pattern formed is smaller is also referred to as “a better effect of the present invention is provided”.
First, a resist composition used in the pattern forming method according to the present invention will be described below.
The resist composition is typically preferably a positive resist composition and is a resist composition for organic solvent development.
The resist composition is typically a chemically amplified resist composition.
The resist composition satisfies a requirement A1 or a requirement A2 below.
Hereinafter, the resin X1 included in the resist composition will be described.
The resin X1 may be any resin having a polarity-decreasing group.
An example of preferred embodiments of the resin X1 will be described below.
An embodiment (Embodiment 1) of the resin X1 is, for example, an embodiment in which the resin has a polarity-decreasing group and has an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating (interactive group).
An embodiment (Embodiment 2) of the resin X1 is, for example, an embodiment in which the resin has a polarity-decreasing group and has an onium salt group that is decomposed due to action of exposure.
An embodiment (Embodiment 3) of the resin X1 is, for example, an embodiment in which the resin has a polarity-decreasing group and undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating. One form of Embodiment 3 may be an embodiment in which the decrease in molecular weight is caused by the decomposition of the main chain due to action of exposure.
An embodiment (Embodiment 4) of the resin X1 is, for example, an embodiment in which the resin has a polarity-decreasing group and has a reactive group A.
An embodiment (Embodiment 5) of the resin X1 is, for example, an embodiment in which the resin has a polarity-decreasing group and has a reactive group A and a reactive group B that reacts with the reactive group A.
An embodiment (Embodiment 6) of the resin X1 is, for example, an embodiment in which the resin has a polarity-decreasing group and has a polar group.
An embodiment (Embodiment 7) of the resin X1 is, for example, an embodiment to which at least two or more of Embodiments 1 to 6 above correspond. Such an embodiment may be, for example, an embodiment in which the resin has a polarity-decreasing group, an onium salt group that is decomposed due to action of exposure, and an interactive group. Alternatively, such an embodiment may be, for example, an embodiment in which the resin has a polarity-decreasing group, an onium salt group that is decomposed due to action of exposure, and an interactive group and undergoes a decrease in molecular weight due to action of exposure, acid, or base.
The resin X1 may be any resin having a polarity-decreasing group, but preferably includes a repeating unit having a polarity-decreasing group from the viewpoint of providing a better effect of the present invention.
In Embodiments 1 to 6, the polarity-decreasing group refers to a group that decreases polarity due to action of exposure, acid, base, or heating.
In Embodiment 1, the interactive group refers to an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating. In the case of Embodiment 1, the composition further includes an onium salt compound that can generate a bond due to an interaction with the interactive group in the resin X1.
In the resist film including the resin X1 of Embodiment 1, the interaction between the onium salt compound and the interactive group in the resin is released by action of exposure, acid, base, or heating. Consequently, the intermolecular forces of the respective components in the resist film before development are thereby further reduced, the resist film tends to take a more stable state upon structural relaxation, and a change in sensitivity when the waiting time before development varies is less likely to occur.
In addition, in the resist film including the resin X1 of Embodiment 1, the interaction between the onium salt compound and the interactive group in the resin is released by action of exposure, acid, base, or heating, and an exposed region is thereby more easily dissolved in organic solvent-based developers, and, as a result, the resolution of a pattern to be formed is also further improved.
The resin X1 of Embodiment 1 preferably includes a repeating unit having an interactive group from the viewpoint of providing a better effect of the present invention.
In the resist film including the resin X1 of Embodiment 2, the onium salt is decomposed due to exposure, and the intermolecular forces of the respective components in the resist film before development are thereby further reduced, the resist film tends to take a more stable state upon structural relaxation, and a change in sensitivity when the waiting time before development varies is less likely to occur.
In addition, in the resist film including the resin X1 of Embodiment 2, the onium salt is decomposed due to exposure, and an exposed region is thereby more easily dissolved in organic solvent-based developers, and, as a result, the resolution of a pattern to be formed is also further improved.
The resin X1 of Embodiment 2 preferably includes a repeating unit having an onium salt group from the viewpoint of providing a better effect of the present invention.
In the resist film including the resin X1 of Embodiment 3, the molecular weight of the resin X1 is decreased by action of exposure, acid, base, or heating, and the intermolecular forces of the respective components in the resist film before development are thereby further reduced, the resist film tends to take a more stable state upon structural relaxation, and a change in sensitivity when the waiting time before development varies is less likely to occur.
In addition, in the resist film including the resin X1 of Embodiment 3, the molecular weight of the resin X1 is decreased by action of exposure, acid, base, or heating, and an exposed region is thereby more easily dissolved in organic solvent-based developers, and, as a result, the resolution of a pattern to be formed is also further improved.
In Embodiments 4 and 5, the reactive group A means a group that is bonded to a crosslinking agent including a reactive group B that reacts (undergoes a crosslinking reaction) with the reactive group A or a reactive group B in the resin X1 to form a bond in the resist film. The bond between the reactive group A and the reactive group B is broken by action of exposure, acid, base, or heating. In Embodiment 5, since the resin X1 has the reactive group B in its molecule, the composition may not include a crosslinking agent including the reactive group B.
In each of the resist films including the resins X1 of Embodiments 4 and 5, a bond is formed by the reactive group A and the reactive group B before exposure, but the bond formed by the reactive group A and the reactive group B is broken by action of exposure, acid, base, or heating, and the intermolecular forces of the respective components in the resist film before development are thereby further reduced, the resist film tends to take a more stable state upon structural relaxation, and a change in sensitivity when the waiting time before development varies is less likely to occur.
In addition, in each of the resist films including the resins X1 of Embodiments 4 and 5, the bond formed by the reactive group A and the reactive group B is broken by action of exposure, acid, base, or heating, and an exposed region is thereby more easily dissolved in organic solvent-based developers, and, as a result, the resolution of a pattern to be formed is also further improved.
The resins X1 of Embodiments 4 and 5 preferably include a repeating unit having a reactive group A from the viewpoint of providing a better effect of the present invention.
The resin X1 of Embodiment 5 preferably includes a repeating unit having a reactive group A and a repeating unit having a reactive group B from the viewpoint of providing a better effect of the present invention.
When the resist composition includes the resin X1 of Embodiment 4 or 5, the resist composition also preferably further includes a photoacid generator.
The types of the reactive group A and the reactive group B will be described in detail later, but both groups are also preferably groups whose reaction proceeds under heating.
The bond formed by the reaction between the reactive group A and the reactive group B may be a covalent bond or a non-covalent bond. The non-covalent bond may be, for example, an ionic bond (for example, an ionic bond formed between a carboxylic group and an amino group).
When the composition includes the resin X1 of Embodiment 6, the composition further includes a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent).
Note that the resin X1 may have, before the action of exposure, acid, base, or heating, both the polarity-decreasing group and a group after the decrease in polarity, the group being generated from the polarity-decreasing group by action of exposure, acid, base, or heating.
First, the polarity-decreasing group, and the interactive group, the onium salt group, the reactive group A, the reactive group B, and the polar group that may be included in the resin X1 will be described below.
The polarity-decreasing group refers to a group that decreases polarity due to action of exposure, acid, base, or heating, as described above.
Whether or not a group corresponds to the polarity-decreasing group can be determined by determining log P (octanol/water partition coefficient) based on the chemical structures before and after being subjected to the action of exposure, acid, base, or heating, and determining whether or not there is an increase in log P after being subjected to the action of exposure, acid, base, or heating.
Herein, log P is an index indicating properties of hydrophilicity and hydrophobicity of a chemical structure and may be referred to as a hydrophilicity-hydrophobicity parameter. The log P can be calculated using, for example, ChemBioDraw Ultra (Version16.0.14).
A mechanism in which the polarity-decreasing group decreases polarity due to action of exposure, acid, base, or heating is not particularly limited. Examples of the mechanism of a decrease in polarity include the following.
The mechanisms will be described below.
Mechanism in Which Polarity Is Decreased by Elimination Reaction Due to Action of Acid, Represented by Formula (K1), and Mechanism in Which Polarity Is Decreased by Elimination Reaction Caused by Cyclization Reaction Due to Action of Acid, Represented by Formula (K2)
In the mechanism represented by Formula (K1) above, Rk1 and Rk2 represent an organic group including a hydrogen atom. Specifically, Rk1 and Rk2 are each preferably an organic group including a hydrogen atom that is added to Rk3 due to action of acid to cause it to leave as Rk3H. Rk1 and Rk2 are preferably each independently an alkyl group (which may be linear, branched, or cyclic) or an aryl group, and at least one of Rk1 or Rk2 is more preferably an alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6. The aryl group is preferably a phenyl group.
Rk1 and Rk2 may be bonded together to form an alicyclic ring. The number of ring member atoms of the alicyclic ring is not particularly limited, but is, for example, 5 to 7.
Rk3 is preferably a group that can leave as Rk3H upon addition of a hydrogen atom due to action of acid, and specifically, more preferably a group that can leave as Rk3H upon addition of a hydrogen atom that leaves from Rk1 and Rk2 due to action of acid. Rk3 is preferably, for example, a hydroxy group (—OH), an alkoxy group (—ORS), an ester group (—OCORS), or a carbonate group (—OCOORS). RS above represents an organic group and is preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6.
In a resin having the polarity-decreasing group, one of Rk1 and Rk2 may be bonded to another atom in the resin to form a ring structure.
Note that, in one form of the polarity-decreasing group in the mechanism represented by Formula (K1) above, the polarity-decreasing group may correspond to a reactive group A or a reactive group B described later.
In the mechanism represented by Formula (K2) above, Rk4 represents —ORT, —NRTRU, or —SRT. RT represents a hydrogen atom or an organic group that leaves due to action of acid. RU represents a hydrogen atom or an organic group.
In Formula (K2), Q represents —O—, —NRU—, or —S— remaining from the Rk4 group after a cyclization reaction.
Rk3 is not particularly limited as long as it is a group that can leave as Rk5H upon addition of a hydrogen atom. Examples thereof include a hydroxy group (—OH), an alkoxy group (—ORV), a substituted or unsubstituted amino group (—NH2, —NHRW, or —NRWRX (where RW and RX represent an organic group, provided that, in the case of NRWRX, either one of RW and RX represents an organic group that can leave in the cyclization reaction).
When Rk4 is, for example, —OH and is a phenolic hydroxy group, it also corresponds to an interactive group or a polar group. When Rk4 is, for example, —OH and is an alcoholic hydroxy group, it also corresponds to a polar group. When Rk3 is, for example, —OH, —NH2, —NHRW, or —NRWRX, the group represented by —CO—Rk5 clearly shown in (K2) also correspond to an interactive group (in the cases of a carboxyl group and an amide group) or a polar group (in the case of a carboxyl group).
The organic group that leaves due to action of acid and represented by RT above is preferably an alkyl group (which may be linear, branched or cyclic) or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6. The aryl group is preferably a phenyl group. The alkyl group and the aryl group may further have a substituent.
The organic group represented by RU above is not particularly limited, but is preferably an alkyl group (which may be linear, branched, or cyclic) or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6. The aryl group is preferably a phenyl group. The alkyl group and the aryl group may further have a substituent.
RV above represents an organic group that can leave in the cyclization reaction and is more preferably an alkyl group (which may be linear, branched, or cyclic) or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6. The aryl group is preferably a phenyl group. The alkyl group and the aryl group may further have a substituent.
The organic groups represented by RW and RX are not particularly limited, but are each preferably an alkyl group (which may be linear, branched, or cyclic) or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6. The aryl group is preferably a phenyl group. The alkyl group and the aryl group may further have a substituent. The alkyl groups and the aryl group also correspond to the organic groups that can leave in the cyclization reaction.
A specific example of the polarity-decreasing group that decreases polarity due to the mechanism represented by Formula (K1) above is a functional group represented by Formula (KD1) below.
Specific examples of the polarity-decreasing group that decreases polarity due to the mechanism represented by Formula (K2) above include a monovalent functional group formed by removing one hydrogen atom that one or more of Rd5 to Rd10 in a compound represented by Formula (KD2) below have, and a monovalent functional group formed by removing one hydrogen atom that a ring member atom has in any of a ring formed by bonding Rd6 and Rd7together and a ring formed by bonding Rd8 and Rd9 together in the compound represented by Formula (KD2) below.
In Formula (KD1) above, Rd1, Rd2, and Rd3 have the same definitions and preferred embodiments as in Rk1, Rk2, and Rk3, respectively, in Formula (K1) above. In Formula (KD1), * represents a bonding site.
In Formula (KD2) above, Rd4 and Rd11 have the same definitions and preferred embodiments as in Rk4 and Rk5, respectively, in Formula (K2) above.
Rd5 to Rd10 each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited and may be, for example, a halogen atom, an alkyl group (which may be linear, branched, or cyclic), or an alkoxy group (which may be linear, branched, or cyclic). The number of carbon atoms of the alkyl group and the alkyl group moiety in the alkoxy group is, for example, preferably 1 to 10, more preferably 1 to 6. The alkyl group and the alkoxy group may further have a substituent.
In addition, Rd6 and Rd7 or Rd8 and Rd9 may be bonded together to form a ring. The ring formed by bonding Rd6 and Rd7 together and the ring formed by bonding Rd8 and Rd9 together are not particularly limited, and may be an alicyclic ring or an aromatic ring, but is preferably an aromatic ring. The aromatic ring is preferably, for example, a benzene ring. When Rd6 and Rd7 are bonded together to form an aromatic ring (for example, a benzene ring), Rd5 and Rd8 each serve as a direct bond. When Rd8 and Rd9 are bonded together to form an aromatic ring (for example, a benzene ring), Rd7 and Rd10 each serve as a direct bond.
However, in the compound represented by Formula (KD2) above, at least one of Rd5 to Rd10 represents a hydrogen atom, or Rd6 and Rd7 are bonded together to form a ring or Rd8 and Rd9 are bonded together to form a ring, and an atom that constitutes the ring has one or more hydrogen atoms.
It is also preferable that the polarity-decreasing group that decreases polarity due to the mechanism represented by Formula (K2) above be a group represented by Formula (KD2-1) below.
In Formula (KD2-1), Rd4 and Rd9 to Rd11 have the same definitions and preferred embodiments as in Rd4 and Rd9 to Rd11, respectively, in Formula (KD2).
Rs represents a substituent. The substituent is not particularly limited and may be, for example, a halogen atom, an alkyl group, or an alkoxy group. The number of carbon atoms of the alkyl group and the alkyl group moiety in the alkoxy group is, for example, preferably 1 to 10, more preferably 1 to 6.
The polarity-decreasing group may be, for example, an acid-decomposable group provided by protecting a polar group with a protective group that leaves due to action of acid, in which the polar group generated after acid decomposition is more hydrophobic than the acid-decomposable group before acid decomposition.
Examples of the acid-decomposable group include groups having the following configurations.
Acid-Decomposable Group
The acid-decomposable group refers to a group that is decomposed due to action of acid to generate a polar group and typically has a structure in which the polar group is protected with a leaving group that leaves due to action of acid.
The polar group is preferably an alkali soluble group, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxy group, fluorinated alcohol groups, a sulfonic group, a phosphate group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, and an alcoholic hydroxy group.
Of these, the polar group is preferably a carboxyl group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic group.
Examples of the leaving group that leaves due to action of acid include groups represented by Formulae (Y1) to (Y4).
—C(Rx1)(Rx2)(Rx3) Formula (Y1)
—C(═O)OC(Rx1)(Rx2)(Rx3) Formula (Y2)
—C(R36)(R37)(OR38) Formula (Y3)
—C(Rn)(H)(Ar) Formula (Y4)
In Formula (Y1) and Formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). Note that, when all of Rx1 to Rx3 are alkyl groups (linear or branched), at least two of Rx1 to Rx3 are preferably methyl groups.
In particular, Rx1 to Rx3 preferably each independently represent a linear or branched alkyl group, and Rx1 to Rx3 more preferably each independently represent a linear alkyl group.
Two of Rx1 to Rx3 may be bonded together to form a monocycle or a polycycle.
The alkyl group in Rx1 to Rx3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, or a t-butyl group.
The cycloalkyl group in Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
The aryl group in Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, for example, a phenyl group, a naphthyl group, or an anthryl group.
The alkenyl group in Rx1 to Rx3 is preferably a vinyl group.
The ring formed by bonding two of Rx1 to Rx3 together is preferably a cycloalkyl group. The cycloalkyl group formed by bonding two of Rx1 to Rx3 together is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, more preferably a monocyclic cycloalkyl group having 5 or 6 carbon atoms.
In the cycloalkyl group formed by bonding two of Rx1 to Rx3 together, for example, one of methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom, such as a carbonyl group, or a vinylidene group. In the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups.
The group represented by Formula (Y1) or Formula (Y2) preferably has an embodiment in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded together to form the above-described cycloalkyl group.
When the resist composition is, for example, a resist composition for EUV exposure, the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group represented by Rx1 to Rx3 and the ring formed by bonding two of Rx1 to Rx3 together also preferably further have, as a substituent, a fluorine atom or an iodine atom.
In Formula (Y3), R36 to R38 each independently represent a hydrogen atom or a monovalent organic group. R37 and R38 may be bonded together to form a ring. The monovalent organic group may be, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R36 is also preferably a hydrogen atom.
Note that the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may include a heteroatom such as an oxygen atom and/or a group having a heteroatom, such as a carbonyl group. For example, in the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group, for example, one or more methylene groups may be replaced by a heteroatom such as an oxygen atom and/or a group having a heteroatom, such as a carbonyl group. An example of such a group is an alkylcarbonyl group.
When the resist composition is, for example, a resist composition for EUV exposure, the monovalent organic group represented by R36 to R38 and the ring formed by bonding R37 and R38 together also preferably further have, as a substituent, a fluorine atom or an iodine atom.
Formula (Y3) is preferably a group represented by Formula (Y3-1) below.
Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (for example, a group formed by provided an alkyl group and an aryl group).
M represents a single bond or a divalent linking group.
Q represents an alkyl group that may include a heteroatom, a cycloalkyl group that may include a heteroatom, an aryl group that may include a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (for example, a group provided by combining an alkyl group and a cycloalkyl group).
In the alkyl group and the cycloalkyl group, for example, one of methylene groups may be replaced by a heteroatom such as an oxygen atom or a group having a heteroatom, such as a carbonyl group.
Note that one of L1 and L2 is preferably a hydrogen atom and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group provided by combining an alkylene group and an aryl group.
At least two of Q, M, and L1 may be bonded together to form a ring (preferably a five-membered or six-membered ring).
From the viewpoint of miniaturization of patterns, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. The secondary alkyl group may be, for example, an isopropyl group, a cyclohexyl group, or a norbornyl group, and the tertiary alkyl group may be, for example, a tert-butyl group or an adamantane group. In these embodiments, since Tg (glass transition temperature) and activation energy of the resin into which the acid-decomposable group is introduced are increased, film hardness is ensured, and fogging can be suppressed.
When the resist composition is, for example, a resist composition for EUV exposure, the alkyl group, the cycloalkyl group, the aryl group, and the combination thereof, the groups being represented by L1 and L2, also preferably further have, as a substituent, a fluorine atom or an iodine atom. It is also preferable that the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group include, in addition to a fluorine atom and an iodine atom, a heteroatom such as an oxygen atom (specifically, in the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group, for example, one of methylene groups be replaced by a heteroatom such as an oxygen atom or a group having a heteroatom, such as a carbonyl group).
It is also preferable that when the resist composition is, for example, a resist composition for EUV exposure, in the alkyl group that may include a heteroatom, the cycloalkyl group that may include a heteroatom, the aryl group that may include a heteroatom, the amino group, the ammonium group, the mercapto group, the cyano group, the aldehyde group, and the combination thereof, the groups being represented by Q, the heteroatom be a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.
In Formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded together to form a non-aromatic ring. Ar is more preferably an aryl group.
When the resist composition is, for example, a resist composition for EUV exposure, the aromatic ring group represented by Ar, and the alkyl group, the cycloalkyl group, and the aryl group represented by Rn also preferably have, as a substituent, a fluorine atom and an iodine atom.
From the viewpoint of further improving acid decomposability, in the leaving group protecting the polar group, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof), a ring member atom adjacent to a ring member atom directly bonded to the polar group (or a residue thereof) in the non-aromatic ring also preferably does not have, as a substituent, a halogen atom such as a fluorine atom.
Alternatively, the leaving group that leaves due to action of acid may be a 2-cyclopentenyl group having a substituent (e.g., an alkyl group), such as 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (e.g., an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.
The acid-decomposable group serving as the polarity-decreasing group corresponds to a group in which a polar group generated after acid decomposition is more hydrophobic than the acid-decomposable group before acid decomposition.
Whether or not the polar group generated after acid decomposition is more hydrophobic than the acid-decomposable group before acid decomposition is determined by determining log P (octanol/water partition coefficient) based on each of the chemical structures of the acid-decomposable group and the polar group, and determining on the basis of the obtained values. The log P can be calculated using, for example, ChemBioDraw Ultra (Version16.0.14).
Accordingly, the acid-decomposable group serving as the polarity-decreasing group corresponds to an acid-decomposable group having a structure in which a polar group is protected with a protective group that leaves due to action of acid, where the log P of the acid-decomposable group is smaller than the log P of the polar group after the protective group leaves.
The difference between the log P of the acid-decomposable group and the log P of the polar group is not particularly limited, but is, for example, preferably 0.3 or more, more preferably 0.6 or more.
The interactive group will be described below.
The interactive group is a group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating.
The interactive group is preferably a group capable of forming an association structure due to an interaction with the onium salt compound, more preferably a group having a proton donor property or a proton acceptor property. The group having a proton donor property corresponds to a group having a free hydrogen atom, and the group having a proton acceptor property may be, for example, a group having a lone pair, such as a nitrogen atom or an oxygen atom. The interactive group is particularly preferably a phenolic hydroxy group, a carboxyl group, a sulfonic group, an amide group, or a sulfonamide group from the viewpoint of better interaction with the onium salt compound.
The phenolic hydroxy group means a hydroxy group bonded, as a substituent, to a ring member atom of an aromatic ring.
The aromatic ring is not limited to a benzene ring, and may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic ring may be monocyclic or polycyclic.
The amide group is not particularly limited, but may be, for example, —C(═O)—NHRB(where RB represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or —NH—C(═O)—RBx (where RBX represents an alkyl group having 1 to 5 carbon atoms).
The amino group is not particularly limited, but may be, for example, —NHRC (where RC represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
Note that when the composition includes an onium salt compound and a capping agent, for example, a carboxyl group in the resin corresponds to both an interactive group and a polar group. When the composition includes an onium salt compound and a crosslinking agent including a reactive group B, for example, a carboxyl group in the resin corresponds to both an interactive group and a reactive group A.
An onium salt group that is decomposed due to action of exposure will be described below.
The onium salt group is a group having an onium salt structure (a group having a moiety having an ion pair of a cation and an anion) and is preferably a group having a moiety represented by “Xn−nM+” (where n represents, for example, an integer of 1 to 3 and preferably represents 1 or 2). M+ represents a moiety including a positively charged atom or atomic group, and Xn− represents a moiety including a negatively charged atom or atomic group. The anion in the onium salt group is preferably a non-nucleophilic anion (an anion having a very low ability to cause a nucleophilic reaction).
In particular, the onium salt group is more preferably a group selected from the group consisting of a group represented by Formula (O1) below and a group represented by Formula (O2) below.
*—XAn−nMA+ Formula (O1)
*—MB+XB− Formula (O2)
In Formula (O1), XAn− represents a monovalent anionic group having a charge number of n. MA+ represents an organic cation. n represents 1 or 2. * represents a bonding site.
In Formula (O2), MB+ represents a monovalent organic cationic group. XB− represents an organic anion. * represents a bonding site.
The organic anions represented by XAn− and XB− are each preferably a non-nucleophilic anion (an anion having a very low ability to cause a nucleophilic reaction).
The group represented by Formula (O1) and the group represented by Formula (O2) will be described in detail below.
In Formula (O1), XAn− represents a monovalent anionic group having a charge number of n (where n is 1 or 2).
The monovalent anionic group having a charge number of n (where n is 1 or 2) and represented by XAn− is not particularly limited, but is preferably, for example, a group selected from the group consisting of groups represented by Formulae (B-1) to (B-15) below. The groups represented by Formulae (B-1) to (B-14) below correspond to monovalent anionic groups having a charge number of 1, and the group represented by Formula (B-15) below corresponds to a monovalent anionic group having a charge number of 2.
In Formulae (B-1) to (B-14), * represents a bonding site.
In Formulae (B-1) to (B-5) and Formula (B-12), each RX1 independently represents a monovalent organic group.
In Formula (B-7) and Formula (B-11), RX2's each independently represent a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group. Two RX2's in Formula (B-7) may be the same or different.
In Formula (B-8), RXF1's represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of two RXF1's represents a fluorine atom or a peffluoroalkyl group. Two RXF1's in Formula (B-8) may be the same or different.
In Formula (B-9), RX3 represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer of 0 to 4. When n1 represents an integer of 2 to 4, a plurality of RX3's may be the same or different.
In Formula (B-10), RXF2 represents a fluorine atom or a perfluoroalkyl group.
The partner bonded to the bonding site represented by * in Formula (B-14) is preferably a phenylene group that may have a substituent. Examples of the substituent that the phenylene group may have include halogen atoms.
In Formulae (B-1) to (B-5) and Formula (B-12), each RX1 independently represents a monovalent organic group.
RX1 is preferably an alkyl group (which may be linear or branched and preferably has 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic and preferably has 3 to 20 carbon atoms), or an aryl group (which may be monocyclic or polycyclic and preferably has 6 to 20 carbon atoms). The above group represented by RX1 may have a substituent.
In RX1 in Formula (B-5), the atom directly bonded to N— is also preferably neither a carbon atom in —CO— nor a sulfur atom in —SO2—.
The cycloalkyl group in RX1 may be monocyclic or polycyclic.
Examples of the cycloalkyl group in RX1 include a norbornyl group and an adamantyl group.
The substituent that the cycloalkyl group in RX1 may have is not particularly limited, but is preferably an alkyl group (which may be linear or branched and preferably has 1 to 5 carbon atoms). One or more of carbon atoms which are ring member atoms of the cycloalkyl group in RX1 may be replaced by carbonyl carbon atoms. The number of carbon atoms of the alkyl group in RX1 is preferably 1 to 10, more preferably 1 to 5.
The substituent that the alkyl group in RX1 may have is not particularly limited, but is preferably, for example, a cycloalkyl group, a fluorine atom, or a cyano group.
Examples of the cycloalkyl group serving as the substituent are also the same as the cycloalkyl groups described in the case where RX1 is a cycloalkyl group.
When the alkyl group in RX1 has a fluorine atom serving as the substituent, the alkyl group may be a perfluoroalkyl group.
In addition, one or more —CH2— of the alkyl group in RX1 may be substituted with carbonyl groups.
The aryl group in RX1 is preferably a benzene ring group.
The substituent that the aryl group in RX1 may have is not particularly limited, but is preferably an alkyl group, a fluorine atom, or a cyano group. Examples of the alkyl group serving as the substituent are also the same as the alkyl groups described in the case where RX1 is an alkyl group.
In Formulae (B-7) and (B-11), each RX2 independently represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group. Two RX2's in Formula (B-7) may be the same or different.
The substituent that is other than a fluorine atom and a perfluoroalkyl group and represented by RX2 is preferably an alkyl group other than a perfluoroalkyl group, or a cycloalkyl group.
Examples of the alkyl group include alkyl groups excluding perfluoroalkyl groups from the alkyl groups described in the case where RX1 is an alkyl group. The alkyl group preferably does not have a fluorine atom.
Examples of the cycloalkyl group include the cycloalkyl groups described in the case where RX1 is a cycloalkyl group. The cycloalkyl group preferably does not have a fluorine atom.
In Formula (B-8), RXF1's represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the plurality of RXF1's represents a fluorine atom or a perfluoroalkyl group. Two RXF1's in Formula (B-8) may be the same or different. The number of carbon atoms of the perfluoroalkyl group represented by RXF1 is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 6.
In Formula (B-9), RX3 represents a hydrogen atom, a halogen atom, or a monovalent organic group. Examples of the halogen atom serving as RX3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In particular, a fluorine atom is preferred.
The monovalent organic group serving as RX3 is the same as the monovalent organic group described as RX1.
In Formula (B-10), RXF2 represents a fluorine atom or a peffluoroalkyl group.
The number of carbon atoms of the perfluoroalkyl group represented by RXF2 is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 6.
*—BM1—LM—BM2 Formula (B-15)
In Formula (B-15), BM1 represents a divalent anionic group represented by any one of Formulae (BB-1) to (BB-4) below. LM represents a single bond or a divalent linking group. BM2 represents a group selected from the group consisting of Formula (B-1) to Formula (B-14) described above.
Examples of the divalent linking group represented by LM include, but are not particularly limited to, —CO—, —NR—, —O—, —S—, —SO—, —SO2—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic heterocyclic group (preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic hydrocarbon ring group (preferably a six- to ten-membered ring, more preferably a six-membered ring), and a divalent linking group provided by combining a plurality of these. R above is, for example, a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. The substituent is, for example, a halogen atom (preferably a fluorine atom).
The divalent linking group represented by LM is particularly preferably an alkylene group. The alkylene group is preferably substituted with a fluorine atom and may be a perfluoro group.
The organic cation represented by MA+ in Formula (O1) is preferably an organic cation represented by Formula (ZaI) (cation (ZaI)) or an organic cation represented by Formula (ZaII) (cation (ZaII)).
In Formula (ZaI) above,
R201, R202, and R203 each independently represent an organic group.
The number of carbon atoms of the organic group serving as R201, R202, or R203 is usually 1 to 30, preferably 1 to 20. Furthermore, two of R201 to R203 may be bonded together to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R201 to R203 together include alkylene groups (such as a butylene group and a pentylene group) and —CH2—CH2—O—CH2—CH2—.
In Formula (ZaI), preferred embodiments of the organic cation include, as described later, cation (ZaI-1), cation (ZaI-2), an organic cation represented by Formula (ZaI-3b) (cation (ZaI-3b)), and an organic cation represented by Formula (ZaI-4b) (cation (ZaI-4b)).
First, cation (ZaI-1) will be described.
Cation (ZaI-1) is an arylsulfonium cation represented by Formula (ZaI) above where at least one of R201 to R203 is an aryl group.
In the arylsulfonium cation, all of R201 to R203 may be aryl groups, or some of R201 to R203 may be an aryl group and the remainder may be an alkyl group or a cycloalkyl group. Alternatively, one of R201 to R203 may be an aryl group and the other two of R201 to R203 may be bonded together to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R201 to R203 include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and/or a carbonyl group (such as a butylene group, a pentylene group, and —CH2—CH2—O—CH2—CH2—).
Examples of the arylsulfonium cation include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
The aryl group included in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having, for example, an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or the cycloalkyl group that the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, more preferably, for example, a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.
Substituents that the aryl group, the alkyl group, and the cycloalkyl group in R201 to R203 may have are preferably each independently an alkyl group (having, for example, 1 to 15 carbon atoms), a cycloalkyl group (having, for example, 3 to 15 carbon atoms), an aryl group (having, for example, 6 to 14 carbon atoms), an alkoxy group (having, for example, 1 to 15 carbon atoms), a cycloalkylalkoxy group (having, for example, 1 to 15 carbon atoms), a halogen atom (for example, fluorine or iodine), a hydroxy group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group.
The substituents each may further have a substituent, if possible. For example, the alkyl group also preferably has a halogen atom as a substituent to serve as an alkyl halide group such as a trifluoromethyl group.
In addition, it is also preferable that any combination of the above substituents form an acid-decomposable group. Examples of the acid-decomposable group include the same acid-decomposable groups as those described as examples of the polarity-decreasing group.
Next, cation (ZaI-2) will be described.
Cation (ZaI-2) is a cation represented by Formula (ZaI) where R201 to R203 each independently represent an organic group having no aromatic ring. Here, the aromatic ring also encompasses aromatic rings including heteroatoms.
In R201 to R203, the organic group having no aromatic ring generally has 1 to 30 carbon atoms and preferably has 1 to 20 carbon atoms.
R201 to R203 are preferably each independently an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, still more preferably a linear or branched 2-oxoalkyl group.
The alkyl group and the cycloalkyl group in R201 to R203 may be, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (such as a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
R201 to R203 may be further substituted with a halogen atom, an alkoxy group (having, for example, 1 to 5 carbon atoms), a hydroxy group, a cyano group, or a nitro group.
In addition, it is also preferable that substituents in R201 to R203 each independently form an acid-decomposable group as a result of any combination of the substituents.
Next, cation (ZaI-3b) will be described.
Cation (ZaI-3b) is a cation represented by Formula (ZaI-3b) below.
In Formula (ZaI-3b),
R1c to R5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxy group, a nitro group, an alkylthio group, or an arylthio group.
R6c and R7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
Rx and Ry each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
In addition, it is also preferable that substituents in R1c to R7c and Rx and Ry each independently form an acid-decomposable group as a result of any combination of the substituents.
Any two or more of R1c to R5c, R5c and R6c, R6c and R7c, R5c and Rx, and Rx and Ry may be individually bonded together to form rings, and these rings may each independently include an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
The rings each may be an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by a combination of two or more of these rings. The ring may be a three- to ten-membered ring, and is preferably a four- to eight-membered ring, more preferably a five- or six-membered ring.
Examples of the groups formed by bonding together any two or more of R1c to R5c, R6c and R7c, and Rx and Ry include alkylene groups such as a butylene group and a pentylene group. A methylene group in such an alkylene group may be substituted with a heteroatom such as an oxygen atom.
The groups formed by bonding together R5c and R6c, and R5c and Rx are each preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
R1c to R5c, R6c, R7c, Rx, Ry, and the rings formed by individually bonding together any two or more of R1c to R5c, R5c and R6c, R6c and R7c, R5c and Rx, and Rx and Ry may have a substituent.
Next, cation (ZaI-4b) will be described.
Cation (ZaI-4b) is a cation represented by Formula (ZaI-4b) below.
In Formula (ZaI-4b),
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
R13 represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxy group, an alkyl group, an alkyl halide group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group including a cycloalkyl group as a part thereof). These groups may have a substituent.
R14 represents a hydroxy group, a halogen atom (for example, a fluorine atom or an iodine atom), an alkyl group, an alkyl halide group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group including a cycloalkyl group as a part thereof). These groups may have a substituent. When a plurality of R14's are present, the plurality of R14's each independently represent the above-mentioned group, for example, a hydroxy group.
R15's each independently represent an alkyl group, a cycloalkyl group, or a naphthyl group. Two R15's may be bonded together to form a ring. When two R15's are bonded together to form a ring, the ring skeleton may include a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R15's are preferably alkylene groups and bonded together to form a ring structure. Note that the alkyl group, the cycloalkyl group, the naphthyl group, and the ring formed by bonding two R15's together may have a substituent.
In Formula (ZaI-4b), the alkyl groups in R13, R14, and R15's are preferably linear or branched. The number of carbon atoms of such an alkyl group is preferably 1 to 10. The alkyl group is more preferably, for example, a methyl group, an ethyl group, a n-butyl group, or a t-butyl group.
In addition, it is also preferable that substituents in R13 to R15's and Rx and Ry each independently form an acid-decomposable group as a result of any combination of the substituents.
Next, Formula (ZaII) will be described.
In Formula (ZaII), R204 and R205 each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group in R204 and R205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group in R204 and R205 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and the cycloalkyl group in R204 and R205 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
The aryl group, the alkyl group, and the cycloalkyl group in R204 and R205 may each independently have a substituent. Examples of the substituent that the aryl group, the alkyl group, and the cycloalkyl group in R204 and R205 may have include alkyl groups (having, for example, 1 to 15 carbon atoms), cycloalkyl groups (having, for example, 3 to 15 carbon atoms), aryl groups (having, for example, 6 to 15 carbon atoms), alkoxy groups (having, for example, 1 to 15 carbon atoms), halogen atoms, a hydroxy group, and a phenylthio group. In addition, it is also preferable that substituents in R204 and R205 each independently form an acid-decomposable group as a result of any combination of the substituents.
The monovalent organic cationic group represented by MB+ in Formula (O2) is particularly preferably an organic cationic group represented by Formula (ZBI) below or an organic cationic group represented by Formula (ZBII) below.
In Formula (ZBI) above, R301 and R302 each independently represent an organic group. The number of carbon atoms of the organic group serving as R301 or R302 is usually 1 to 30, preferably 1 to 20. R303 represents a divalent linking group.
Two of R301 to R303 may be bonded together to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by bonding two of R301 to R303 together include alkylene groups (such as a butylene group and a pentylene group) and —CH2—CH2—O—CH2—CH2—.
The organic group serving as R301 and R302 is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, or an aryl group.
The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having, for example, an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
The alkyl group or the cycloalkyl group is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Substituents that the aryl group, the alkyl group, and the cycloalkyl group in R301 and R302 may have may each independently be an alkyl group (having, for example, 1 to 15 carbon atoms), a cycloalkyl group (having, for example, 3 to 15 carbon atoms), an aryl group (having, for example, 6 to 14 carbon atoms), an alkoxy group (having, for example, 1 to 15 carbon atoms), a cycloalkylalkoxy group (having, for example, 1 to 15 carbon atoms), a halogen atom, a hydroxy group, or a phenylthio group.
The divalent linking group serving as R303 is not particularly limited, but preferably represents an alkylene group, a cycloalkylene group, an aromatic group, or a group provided by combining two or more of these groups.
The alkylene group may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms. The aromatic ring constituting the aromatic group is not particularly limited, but may be, for example, an aromatic ring having 6 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. A benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.
The alkylene group, the cycloalkylene group, and the aromatic group may further have a substituent.
In Formula (ZBII) above, R304 represents an aryl group, an alkyl group, or a cycloalkyl group. R305 represents a divalent linking group.
The aryl group in R304 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group in R304 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and the cycloalkyl group in R304 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (such as a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
The aryl group, the alkyl group, and the cycloalkyl group in R304 may each independently have a substituent. Examples of the substituent that the aryl group, the alkyl group, and the cycloalkyl group in R304 may have include alkyl groups (having, for example, 1 to 15 carbon atoms), cycloalkyl groups (having, for example, 3 to 15 carbon atoms), aryl group (having, for example, 6 to 15 carbon atoms), alkoxy groups (having, for example, 1 to 15 carbons), halogen atoms, a hydroxy group, and a phenylthio group.
The divalent linking group as R315 is not particularly limited, but preferably represents an alkylene group, a cycloalkylene group, an aromatic group, or a group formed by combining two or more thereof.
The alkylene group may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms. The aromatic ring constituting the aromatic group is not particularly limited, but may be, for example, an aromatic ring having 6 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. The aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
The alkylene group, the cycloalkylene group, and the aromatic group may further have a substituent.
The organic anion represented by XB− in Formula (O2) is preferably a non-nucleophilic anion (an anion having a very low ability to cause a nucleophilic reaction).
Examples of the non-nucleophilic anion include sulfonate anions (such as aliphatic sulfonate anions, aromatic sulfonate anions, and a camphorsulfonate anion), carboxylate anions (such as aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylate anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
The aliphatic moieties in the aliphatic sulfonate anions and the aliphatic carboxylate anions may each be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms.
The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom, and may be a perfluoroalkyl group).
The aryl groups in the aromatic sulfonate anions and the aromatic carboxylate anions are each preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
The above-mentioned alkyl group, cycloalkyl group, and aryl group may have a substituent. Specific examples of the substituent include, but are not particularly limited to, a nitro group, halogen atoms such as a fluorine atom and a chlorine atom, a carboxy group, a hydroxy group, an amino group, a cyano group, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).
The aralkyl groups in the aralkyl carboxylate anions are each preferably an aralkyl group having 7 to 14 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
An example of the sulfonylimide anions is a saccharin anion.
The alkyl groups in the bis(alkylsulfonyl)imide anions and the tris(alkylsulfonyl)methide anions are preferably alkyl groups having 1 to 5 carbon atoms. A substituent of such an alkyl group may be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, or a cycloalkylaryloxysulfonyl group, and is preferably a fluorine atom or an alkyl group substituted with a fluorine atom.
The alkyl groups in such a bis(alkylsulfonyl)imide anion may be bonded together to form a ring structure. This increases the acid strength.
The non-nucleophilic anion is preferably an aliphatic sulfonate anion in which at least the α position of sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl groups are substituted with fluorine atoms, or a tris(alkylsulfonyl)methide anion in which the alkyl groups are substituted with fluorine atoms.
The organic anion represented by XB− in Formula (O2) is also preferably, for example, an organic anion represented by Formula (DA) below.
A
31
θ-La1-Ra1 (DA)
In Formula (DA), A31− represents an anionic group. Ra1 represents a hydrogen atom or a monovalent organic group. La1 represents a single bond or a divalent linking group.
A31− represents an anionic group. The anionic group represented by A31− is not particularly limited, but is preferably, for example, a group selected from the group consisting of groups represented by Formulae (B-1) to (B-14) above.
The monovalent organic group in Ra1 is not particularly limited, but generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Ra1 is preferably an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms.
The cycloalkyl group may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, still more preferably a cycloalkyl group having 3 to 10 carbon atoms.
The aryl group may be monocyclic or polycyclic, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably an aryl group having 6 to 10 carbon atoms.
The cycloalkyl group may include a heteroatom as a ring member atom.
The heteroatom is not particularly limited, and may be, for example, a nitrogen atom or an oxygen atom.
The cycloalkyl group may include a carbonyl bond (>C═O) as a ring member atom. The alkyl group, the cycloalkyl group, and the aryl group may further have a substituent.
The divalent linking group serving as La1 is not particularly limited, but represents an alkylene group, a cycloalkylene group, an aromatic group, —O—, —CO—, —COO—, or a group provided by combining two or more of these groups.
The alkylene group may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms. The aromatic ring constituting the aromatic group is not particularly limited, but may be, for example, an aromatic ring having 6 to 20 carbon atoms, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring. The aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
The alkylene group, the cycloalkylene group, and the aromatic group may further have a substituent, and the substituent is preferably a halogen atom.
A31− and Ra1 may be bonded together to form a ring.
The polar group is not particularly limited, but is preferably, for example, an alcoholic hydroxy group, a phenolic hydroxy group, or a carboxyl group from the viewpoint of better reactivity with a capping agent described later.
The phenolic hydroxy group means a hydroxy group bonded, as a substituent, to a ring member atom of an aromatic ring.
The aromatic ring is not limited to a benzene ring, and may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic ring may be monocyclic or polycyclic.
The alcoholic hydroxy group is distinguished from the phenolic hydroxy group and means, in the present specification, a hydroxy group bonded, as a substituent, to an aliphatic hydrocarbon group.
Reactive Group A and Reactive Group B That Reacts with Reactive Group A
The combination of the reactive group A and the reactive group B that reacts with the reactive group A is not particularly limited, and a combination of publicly known functional groups can be used. In particular, a combination in which one of the reactive group A and the reactive group B is a vinyl ether group (CH2=CH—O—) and the other is a carboxylic group (carboxyl group), a sulfonic group, or a group represented by General formula (A) is preferred from the viewpoint of excellent reactivity and decrosslinkability between the reactive group A and the reactive group B.
In General formula (A), R1 to R4 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. Here, at least one of R1 to R3 represents a fluorine atom or an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom. * represents a bonding site.
The alkyl group may be linear or branched.
All of R1 to R3 are preferably fluorine atoms.
Specific examples of the group represented by General formula (A) include —C(CF3)2OH, —C(C2F5)2OH, —C(CF3)(CH3)OH, and —CH(CF3)OH.
In the case of the above combination, the reactive group A and the reactive group B react with each other to form a covalent bond. Alternatively, as described above, the reactive group A and the reactive group B may react with each other to form a non-covalent bond.
A combination for forming a non-covalent bond is preferably, for example, a combination in which one of the reactive group A and the reactive group B is an acidic group (for example, a carboxylic group, a sulfonic group, or a phosphoric group) and the other is a basic group (for example, an amino group, an imino group, an imidazoline group, a pyrrole group, an imidazole group, a benzimidazole group, a pyrazole group, a pyridine group, a pyrimidine group, a pyrazine group, a pyrrolidine group, a piperidine group, or a piperazine group). The amino group includes a primary amino group, a secondary amino group, and a tertiary amino group.
With this combination, an ionic bond is formed between the acidic group and the basic group, and this bond is broken by action of acid.
A first preferred embodiment of the resin X1 will be described below.
The resin X1 preferably includes a repeating unit having a polarity-decreasing group. Examples of the polarity-decreasing group include those described above.
Examples of the repeating unit having a polarity-decreasing group include repeating units represented by any one of Formulae (I) to (III) below.
In Formula (I),
R41, R42, and R43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R42 may be bonded to Ar4 to form a ring, and in such a case, R42 represents a single bond or an alkylene group.
X4 represents a single bond, —COO—, or —CONR64—, where R4 represents a hydrogen atom or an alkyl group.
L4 represents a single bond or an alkylene group.
Ar4 represents an (n+1)-valent aromatic ring group or alicyclic group, and when Ar4 is bonded to R42 to form a ring, Ar4 represents an (n+2)-valent aromatic ring group or alicyclic group.
W represents a group represented by Formula (KD1) above (polarity-decreasing group).
n represents an integer of 1 to 5.
In R41, R42, and R43 in Formula (I), the alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, still more preferably an alkyl group having 3 or less carbon atoms.
In R41, R42, and R43 in Formula (I), the cycloalkyl group may be monocyclic or polycyclic. In particular, monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, are preferred.
In R41, R42, and R43 in Formula (I), the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom.
The alkyl group included in the alkoxycarbonyl group in R41, R42, and R43 in Formula (I) is preferably the same as the alkyl group in R41, R42, and R43 above.
Each of the groups represented by R41, R42, and R43 may have a substituent.
Ar4 represents an (n+1)-valent aromatic ring group or alicyclic group.
The divalent aromatic ring group in the case where n is 1 is preferably, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group including a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Of these, an arylene group is preferred, and a phenylene group or a naphthalene group is more preferred. The aromatic ring group may have a substituent.
Specific examples of the (n+1)-valent aromatic ring group in the case where n is an integer of 2 or more include groups provided by removing any (n−1) hydrogen atoms from any of the foregoing specific examples of the divalent aromatic ring group.
The (n+1)-valent alicyclic group represented by Ar4 may be, for example, a group provided by removing any (n+1) hydrogen atoms from a polycyclic cycloalkane such as norbornene, tetracyclodecane, tetracyclododecane, or adamantane.
The (n+1)-valent aromatic ring group and alicyclic group may further have a substituent.
Examples of substituents that the above alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group or alicyclic group can have include the alkyl groups described in R41, R42, and R43 in Formula (I); alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; aryl groups such as a phenyl group; and halogen atoms.
The alkyl group in R64 in —CONR64—(where R64 represents a hydrogen atom or an alkyl group) represented by X4 may be an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, and is preferably an alkyl group having 8 or less carbon atoms.
X4 is preferably a single bond, —COO—, or —CONH—, more preferably a single bond or —COO—.
The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group.
Examples of the repeating unit represented by Formula (I) are as follows. In the formulae, a represents 1 or 2. W represents a group represented by Formula (KD1) above (polarity-decreasing group).
L5 represents a divalent linking group.
Examples of the divalent linking group represented by L5 include —CO—, —O—, —S—, —SO—, —SO2—, hydrocarbon groups (such as an alkylene group, a cycloalkylene group, an alkenylene group, and an arylene group), and a linking group provided by linking a plurality of these together. The hydrocarbon groups may have a substituent. The substituent is not particularly limited, and may be, for example, a fluorine atom or an iodine atom.
In particular, the divalent linking group represented by L5 is preferably —CO—, an arylene group, or -arylene group-alkylene group-, more preferably —CO— or an -arylene group.
The arylene group is preferably a phenylene group.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
R44 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The alkyl group and the aryl group represented by R44 may have a substituent. The substituent is not particularly limited, and may be, for example, a fluorine atom or an iodine atom.
R45 represents a leaving group that leaves due to action of acid.
Examples of the leaving group that leaves due to action of acid and represented by R45 include the above-described leaving groups represented by Formulae (Y1) to (Y4).
A preferred embodiment of L5, R44, and R45 is an embodiment in which at least one of L5, R44, or R45 has a fluorine atom or an iodine atom.
Here, when the repeating unit represented by Formula (II) includes an acid-decomposable group having a structure in which a polar group is protected with a leaving group, the polar group generated after acid decomposition is more hydrophobic than the acid-decomposable group before acid decomposition. Specifically, the log P of the acid-decomposable group is smaller than the log P of the polar group after the protective group leaves.
R46 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The alkyl group and the aryl group represented by R46 may have a substituent. The substituent is not particularly limited, and may be, for example, a fluorine atom or an iodine atom.
L6 represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by L6 include —CO—, —O—, —S—, —SO—, —SO2—, hydrocarbon groups (such as an alkylene group, a cycloalkylene group, an alkenylene group, and an arylene group), and a linking group provided by linking a plurality of these together. The hydrocarbon groups may have a substituent. The substituent is not particularly limited, and may be, for example, a fluorine atom or an iodine atom.
The divalent linking group represented by L6 is preferably —COO—.
Rd4 and Rd9 to Rd11 have the same definitions and preferred embodiments as in the above-described Rd4 and Rd9 to Rd11, respectively, in Formula (KD2).
Rt represents a substituent. The substituent is not particularly limited, and may be, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorine atom, or an iodine atom.
p represents an integer of 0 to 3.
In the resin X1, one or more repeating units having a polarity-decreasing group may be included, or two or more of such repeating units may be included.
In the resin X1, the content of the repeating unit having a polarity-decreasing group is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 100 mol % or less, more preferably 90 mol % or less, still more preferably 80 mol % or less.
It is also preferable that the resin X1 include a repeating unit having one or more selected from the group consisting of an interactive group, an onium salt group, and a polar group.
The interactive group, the onium salt group, and the polar group are as described above.
The repeating unit having one or more selected from the group consisting of an interactive group, an onium salt group, and a polar group may be, for example, a repeating unit represented by Formula (T1) below.
In Formula (T1) above, R50 represents a hydrogen atom, a halogen atom, or an alkyl group that may have a substituent.
X5 represents a single bond, —COO—, or —CONR52—, where R52 represents a hydrogen atom or an alkyl group.
L5 represents a single bond or a divalent linking group.
Ar5 represents an (r+1)-valent aromatic ring group or alicyclic group.
R51 represents an interactive group, an onium salt group, or a polar group.
q represents 0 or 1.
When q is 0, r represents 1. When q is 1, r represents an integer of 1 to 4.
The alkyl group represented by R50 may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3. The alkyl group represented by R50 may have a substituent. The substituent is not particularly limited, but may be, for example, a halogen atom or a hydroxy group.
The alkyl group in R64 in —CONR64— (where R64 represents a hydrogen atom or an alkyl group) represented by X5 may be an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, and is preferably an alkyl group having 8 or less carbon atoms.
X5 is preferably a single bond, —COO—, or —CONH—, more preferably a single bond or —COO—.
Examples of the divalent linking group represented by L5 include, but are not particularly limited to, —CO—, —O—, —SO—, —SO2—, —NRA—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group provided by combining a plurality of these. The alkylene group may have a substituent. The substituent may be, for example, a halogen atom or a hydroxy group. RA may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Ar5 represents an (r+1)-valent aromatic ring group or alicyclic group.
The divalent aromatic ring group in the case where r is 1 is preferably, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group including a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Of these, an arylene group is preferred, and a phenylene group or a naphthalene group is more preferred. The aromatic ring group may have a substituent other than R51.
Specific examples of the (r+1)-valent aromatic ring group in the case where r is an integer of 2 or more include groups provided by removing any (r−1) hydrogen atoms from any of the foregoing specific examples of the divalent aromatic ring group.
The (r+1)-valent alicyclic group represented by Ar5 may include a heteroatom such as an oxygen atom and a carbonyl carbon. Examples of the (r+1)-valent alicyclic group represented by Ar5 include groups provided by removing any r+1 hydrogen atoms from a polycyclic cycloalkane such as norbornene, tetracyclodecane, tetracyclododecane, or adamantane. The (r+1)-valent alicyclic group represented by Ar5 may be a group provided by removing any r+1 hydrogen atoms from a lactone ring or a sultone ring. The lactone ring or the sultone ring is preferably a five- to seven-membered lactone ring, more preferably a five- to seven-membered lactone ring or sultone ring to which another ring structure is fused so as to form a bicyclo structure or a spiro structure.
The (r+1)-valent aromatic ring group and alicyclic group may further have a substituent. Examples of the substituent include the alkyl groups described in R51 in Formula (T1); alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; aryl groups such as a phenyl group; and halogen atoms.
In Formula (T1) above, R51 represents an interactive group, an onium salt group, or a polar group. The interactive group, the onium salt group, and the polar group are as described above.
In the resin X1, one or more repeating units having one or more selected from the group consisting of an interactive group, an onium salt group, and a polar group may be included, or two or more of such repeating units may be included.
In the resin X1, the content of the repeating unit having an interactive group is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 90 mol % or less, more preferably 80 mol % or less.
In the resin X1, the content of the repeating unit having an onium salt group is preferably 1 mol % or more, more preferably 2 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 50 mol % or less, more preferably 40 mol % or less.
In the resin X1, the content of the repeating unit having a polar group is preferably 10 mol % or more, more preferably 20 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 90 mol % or less, more preferably 80 mol % or less.
It is also preferable that the resin X1 include a repeating unit having a reactive group A.
The reactive group A is as described above.
The repeating unit having a reactive group A is, for example, an embodiment of “the repeating unit having an interactive group, an onium salt group, or a polar group” described as an example of the repeating unit that the resin X1 in the upper part may have, where R1 represents a reactive group A.
When the resin X1 includes a repeating unit having a reactive group A, the resin X1 further includes a repeating unit having a reactive group B, or the resist composition further includes a crosslinking agent (a crosslinking agent including a reactive group B that reacts (that is subjected to a crosslinking reaction) with the reactive group A), which will be described later.
When the resin X1 further includes a repeating unit having a reactive group B, the repeating unit having a reactive group B is, for example, an embodiment of “the repeating unit having an interactive group, an onium salt group, or a polar group” described as an example of the repeating unit that the resin X1 in the upper part may have, where R1 represents a reactive group B.
The reactive group B is as described above.
In the resin X1, one or more repeating units having a reactive group A may be included, or two or more of such repeating units may be included.
In the resin X1, the content of the repeating unit having the reactive group A is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 90 mol % or less, more preferably 80 mol % or less.
In the resin X1, one or more repeating units having a reactive group B may be included, or two or more of such repeating units may be included.
When the resin X1 includes a repeating unit having a reactive group B, the content of the repeating unit is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 90 mol % or less, more preferably 80 mol % or less.
The resin X1 also preferably includes a repeating unit having at least one selected from the group consisting of a lactone group and a sultone group.
The lactone group or the sultone group at least has a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a five- to seven-membered lactone structure or a five- to seven-membered sultone structure. In particular, a five- to seven-membered lactone structure to which another ring structure is fused so as to form a bicyclo structure or a spiro structure, or a five- to seven-membered sultone structure to which another ring structure is fused so as to form a bicyclo structure or a spiro structure is more preferred.
The resin X1 preferably has a repeating unit having a lactone group or a sultone group provided by abstracting one or more hydrogen atoms from ring member atoms of a lactone structure represented by any one of Formulae (LC1-1) to (LC1-21) below or a sultone structure represented by any one of Formulae (SL1-1) to (SL1-3) below.
The lactone group or the sultone group may be directly bonded to the main chain. For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of the resin XL.
The lactone or sultone structural moiety may have a substituent (Rb2). Preferred examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a halogen atom. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb2's may be different and a plurality of Rb2's may be bonded together to form a ring.
The repeating unit having a group having the lactone structure represented by any one of Formulae (LC1-1) to (LC1-21) or the sultone structure represented by any one of Formulae (SL1-1) to (SL1-3) is. for example. a repeating unit represented by Formula (AI) below.
In Formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
A preferred substituent that the alkyl group in Rb0 may have is, for example, a halogen atom.
Examples of the halogen atom in Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group provided by combining these. In particular, a single bond or a linking group represented by -Ab1—CO2— is preferred. Abi is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group provided by abstracting one hydrogen atom from a ring member atom of the lactone structure represented by any one of Formulae (LC1-1) to (LC1-21) or a group provided by abstracting one hydrogen atom from a ring-member atom of the sultone structure represented by any one of Formulae (SL1-1) to (SL1-3).
When the repeating unit having a lactone group or a sultone group has an optical isomer, any optical isomer may be used. A single optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When a single optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
The content of the repeating unit having a lactone group or a sultone group is preferably 1 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 85 mol % or less, more preferably 80 mol % or less, still more preferably 70 mol % or less, particularly preferably 60 mol % or less.
Repeating Unit Represented by Formula (V-1) below or Formula (V-2) below
The resin X1 may have a repeating unit represented by Formula (V-1) below or Formula (V-2) below.
The repeating units represented by Formula (V-1) below and Formula (V-2) below are preferably repeating units different from the repeating units described above.
In the formulae,
R6 and R7 each independently represent a substituent.
The substituent is, for example, an alkyl group, an alkoxy group, a cyano group, a nitro group, a halogen atom, or an ester group (—OCOR or —COOR: R is an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms).
The alkyl group and the alkyl group moiety (which may be linear, branched, or cyclic) in the alkoxy group preferably have 1 to 10 carbon atoms.
n3 represents an integer of 0 to 6.
n4 represents an integer of 0 to 4.
X4 is a methylene group, an oxygen atom, or a sulfur atom.
Examples of the repeating unit represented by Formula (V-1) or (V-2) are as follows.
Examples of the repeating unit represented by Formula (V-1) or (V-2) include the repeating units described in paragraph [0100] of WO2018/193954A.
The resin X1 preferably has a high glass transition temperature (Tg) from the viewpoint that excessive diffusion of the generated acid or pattern collapse during development can be suppressed. Tg is preferably higher than 90° C., more preferably higher than 100° C., still more preferably higher than 110° C., particularly preferably higher than 125° C. Note that since an excessively high Tg leads to a decrease in the dissolution rate in developers, Tg is preferably 400° C. or lower, more preferably 350° C. or lower.
In the present specification, the glass transition temperature (Tg) of a polymer such as the resin X1 is calculated by the following method. First, Tg's of homopolymers composed only of the repeating units included in the polymer are calculated by the Bicerano method. Hereinafter, the calculated Tg's are referred to as “Tg's of repeating units”. Next, the mass ratios (%) of the repeating units relative to all the repeating units in the polymer are calculated. Next, Tg's at the mass ratios are calculated using the Fox equation (described in, for example, Materials Letters 62 (2008) 3152), and the sum total of the Tg's is defined as the Tg (° C.) of the polymer.
The Bicerano method is described in, for example, Prediction of polymer properties, Marcel Dekker Inc., New York (1993). The calculation of Tg by the Bicerano method can be performed using software for estimating physical properties of polymers, MDL Polymer (MDL Information Systems, Inc.).
In order to increase Tg of the resin X1 (preferably, to make Tg higher than 90° C.), the mobility of the main chain of the resin X1 is preferably decreased. Examples of the method for decreasing the mobility of the main chain of the resin X1 include the following methods (a) to (e):
The resin X1 preferably has a repeating unit whose homopolymer has a Tg of 130° C. or higher.
The type of the repeating unit whose homopolymer has a Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit whose homopolymer has a Tg of 130° C. or higher as calculated by the Bicerano method. Note that repeating units represented by Formula (A) to Formula (E) described later may, depending on the types of functional groups, correspond to the repeating unit whose homopolymer has a Tg of 130° C. or higher.
An example of specific means for achieving (a) above is a method of introducing a repeating unit represented by Formula (A) into the resin X1.
In Formula (A), RA represents a group having a polycyclic structure. RA represents a hydrogen atom, a methyl group, or an ethyl group. The group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may be fused together or may not be fused together.
Specific examples of the repeating unit represented by Formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954A.
An example of specific means for achieving (b) above is a method of introducing a repeating unit represented by Formula (B) into the resin X1.
In Formula B), Rb1 to Rb4 each independently represent a hydrogen atom or an organic group, and at least two or more of Rb1 to Rb4 represent organic groups.
When at least one of the organic groups is a group whose ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited.
When none of the organic groups is a group whose ring structure is directly linked to the main chain in the repeating unit, at least two or more of the organic groups are substituents in which the number of constituent atoms excluding hydrogen atoms is 3 or more.
Specific examples of the repeating unit represented by Formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954A.
An example of specific means for achieving (c) above is a method of introducing a repeating unit represented by Formula (C) into the resin X1.
In Formula (C), Rc1 to Rc4 each independently represent a hydrogen atom or an organic group, and at least one of Rc1 to Rc4 is a group having a hydrogen-bond-forming hydrogen atom positioned within three atoms from a carbon atom in the main chain. In particular, from the viewpoint of inducing the interaction between the main chains of the resin X1, it is preferable to have a hydrogen-bond-forming hydrogen atom positioned within two atoms (closer to the main chain).
Specific examples of the repeating unit represented by Formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954A.
An example of specific means for achieving (d) above is a method of introducing a repeating unit represented by Formula (D) into the resin X1.
In Formula (D), “Cyclic” represents a group that forms the main chain with a ring structure. The number of atoms constituting the ring is not particularly limited.
Specific examples of the repeating unit represented by Formula (D) include those described in paragraphs [0126] and [0127] of WO2018/193954A.
An example of specific means for achieving (e) above is a method of introducing a repeating unit represented by Formula (E) into the resin X1.
In Formula (E), each Re independently represents a hydrogen atom or an organic group. The organic group may be, for example, an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group that may have a substituent.
“Cyclic” is a cyclic group including a carbon atom of the main chain. The number of atoms included in the cyclic group is not particularly limited.
Specific examples of the repeating unit represented by Formula (E) include those described in paragraphs [0131] to [0133] of WO2018/193954A.
The resin X1 may have a repeating unit having a fluorine atom or an iodine atom.
Note that herein, the repeating unit having a fluorine atom or an iodine atom is a repeating unit different from each of the repeating units described above.
The repeating unit having a fluorine atom or an iodine atom is preferably a repeating unit represented by Formula (C).
L5 represents a single bond or an ester group.
R9 represents a hydrogen atom or an alkyl group that may have a fluorine atom or an iodine atom.
R10 represents a hydrogen atom, an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a group provided by combining these.
Examples of the repeating unit having a fluorine atom or an iodine atom are as follows.
The content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 mol % or more, more preferably 5 mol % or more, still more preferably 10 mol % or more relative to all the repeating units in the resin X1. The upper limit value thereof is preferably 50 mol % or less, more preferably 45 mol % or less, still more preferably 40 mol % or less.
The resin X1 of the first preferred embodiment can be synthesized by an ordinary method (for example, radical polymerization).
The resin X1 of the first preferred embodiment preferably has a weight-average molecular weight of 1,000 to 200,000, more preferably 2,500 to 150,000, still more preferably 3,000 to 50,000 in terms of polystyrene as determined by the GPC method. When the weight-average molecular weight is within the above numerical range, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, deterioration of developing performance and deterioration of film-forming properties due to an increase in viscosity can also be further suppressed.
The dispersity (molecular weight distribution) of the resin X1 of the first preferred embodiment is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, still more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and the resist shape.
A second preferred embodiment of the resin X1 will be described below.
The resin X1 of the second preferred embodiment is preferably a resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating, more preferably a resin that undergoes a decrease in molecular weight caused by the decomposition of a structure (e.g., a main chain structure or a side chain structure) in the resin due to action of exposure, acid, base, or heating, still more preferably a resin that undergoes a decrease in molecular weight caused by the scission of the main chain in the resin due to action of exposure, acid, base, or heating (a so-called main chain scission resin).
Examples of the form of the resin X1 which is a main chain scission-type resin include resins having the following configurations. In the resins having the configurations described below, a resin X1-I corresponds to a resin that undergoes a decrease in molecular weight caused by the scission of the main chain due to action of exposure, and resins X1-II and X1-III correspond to a resin that undergoes a decrease in molecular weight caused by the scission of the main chain due to action of acid.
Of these, the resin X1-I is preferred from the viewpoint of providing a better effect of the present invention.
A resin including a repeating unit represented by Formula (XP) below and a repeating unit represented by Formula (XQ) below:
In Formula (XP), XP represents a halogen atom. L represents a single bond or a divalent linking group. RP represents a substituent.
In Formula (XQ), Rq1 represents an alkyl group that may have a substituent. Lqrepresents a single bond or a divalent linking group. Rq2 represents a substituent.
The resin X1-I includes at least the above-described polarity-decreasing group.
In the resin X1-I, at least one of the substituent represented by Rp in Formula (XP) or the substituent represented by Rq2 in Formula (XQ) preferably has the above-described polarity-decreasing group.
The substituent represented by Rp in Formula (XP) and the substituent represented by Rq2 in Formula (XQ) preferably also include the interactive group, the onium salt group, the polar group, the reactive group A, or the reactive group B. Note that when the resin X1I -includes the reactive group B, the reactive group A is also included in the resin X1-I.
Preferred forms of the resin X1-I will be described in detail below.
The resin X1-I includes a repeating unit represented by Formula (XP) above and a repeating unit represented by Formula (XQ) above.
In the resin X1-I, the total content of the repeating unit represented by Formula (XP) above and the repeating unit represented by Formula (XQ) above is preferably 90 mol % or more, more preferably 95 mol % or more relative to all the repeating units. The upper limit value is preferably 100 mol % or less.
In the resin X1-I, the repeating unit represented by Formula (XP) above and the repeating unit represented by Formula (XQ) above may be in any form of a random copolymer, a block copolymer, an alternating copolymer (ABAB . . . ), and the like, and among these, an alternating copolymer is preferred.
A preferred embodiment of the resin X1-I is, for example, an embodiment in which the presence ratio of the alternating copolymer in the resin X1 is 90 mass % or more (preferably 100 mass % or more) relative to the total mass of the resin X1.
In the resin X1-I, the content of the repeating unit represented by Formula (XP) above is preferably 5 to 95 mol %, more preferably 10 to 90 mol % relative to all the repeating units. Furthermore, in the resin X1-I, the content of the repeating unit represented by Formula (XQ) above is preferably 5 to 95 mol %, more preferably 10 to 90 mol % relative to all the repeating units.
In Formula (XP) above, the halogen atom represented by XP is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom from the viewpoint of providing a better effect of the present invention.
In Formula (XP) above, examples of the divalent linking group represented by Lp include, but are not particularly limited to, —CO—, —O—, —SO—, —SO2—, —NRA—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a six- to ten-membered ring, more preferably a six-membered ring), and a divalent linking group provided by combining a plurality of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. The substituent is, for example, an alkyl group, a halogen atom, or a hydroxy group. RA may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A preferred embodiment of the divalent linking group represented by Lp is, for example, an embodiment in which —COO— is located at a position at which the divalent linking group represented by Lp is bonded to the main chain.
In Formula (XP) above, the substituent represented by RP is not particularly limited, and may be, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, a halogen atom, an ester group (—OCOR″ or —COOR″: R″ represents an alkyl group or a fluorinated alkyl group), a lactone group, a polarity-decreasing group, an interactive group, an onium salt group, a polar group, a reactive group A, or a reactive group B.
The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group, the alkoxy group, the acyloxy group, the ester group, and the lactone group may further have a substituent, and the substituent is, for example, a halogen atom, a polarity-decreasing group, an interactive group, an onium salt group, a polar group, a reactive group A, or a reactive group B. When the alkyl group has a fluorine atom, the alkyl group may be a perfluoroalkyl group.
The alkyl group may be linear or branched. The number of carbon atoms is not particularly limited, but is, for example, preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6.
The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is, for example, preferably 5 to 15, more preferably 5 to 10. Examples of the cycloalkyl group include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
The aryl group may be monocyclic or polycyclic. The number of carbon atoms is not particularly limited, but is, for example, preferably 6 to 15, more preferably 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, more preferably a phenyl group.
The aralkyl group preferably has a structure in which one of hydrogen atoms in the above-mentioned alkyl group is substituted with the above-mentioned aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 20, more preferably 7 to 15.
The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms is not particularly limited, but is, for example, preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 6.
The alkoxy group may be linear, branched, or cyclic, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6.
The acyloxy group may be linear, branched, or cyclic, and the number of carbon atoms thereof is preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 6.
The number of carbon atoms of the alkyl group or fluorinated alkyl group represented by R″ above is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6.
The lactone group is preferably a five- to seven-membered lactone group, more preferably a five- to seven-membered lactone ring to which another ring structure is fused so as to form a bicyclo structure or a spiro structure.
The polarity-decreasing group, the interactive group, the onium salt group, the polar group, the reactive group A, and the reactive group B are as described above.
The repeating unit represented by Formula (XP) is preferably one or more selected from the group consisting of a repeating unit represented by Formula (XP1) below and a repeating unit represented by Formula (XP2) below.
In Formula (XP1), Xp1 has the same definition and preferred embodiments as in Xp in Formula (XP) above.
Yp1 represents a single bond or —COO—.
Lp1 represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Lp1 include, but are not particularly limited to, —CO—, —O—, —SO—, —SO2—, —NRA—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group provided by combining a plurality of these. The alkylene group may have a substituent. The substituent may be, for example, a halogen atom or a hydroxy group. RA may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Arp1 represents a (p2+1)-valent aromatic ring group or alicyclic group.
The divalent aromatic ring group in the case where P2 is 1 is preferably, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group including a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Of these, an arylene group is preferred, a phenylene group, a naphthalene group, or an anthracenylene group is more preferred, and a phenylene group or a naphthalene group is still more preferred.
Specific examples of the (p2+1)-valent aromatic ring group in the case where p2 is an integer of 2 or more include groups provided by removing any (p2−1) hydrogen atoms from any of the foregoing specific examples of the divalent aromatic ring group.
The (p2+1)-valent alicyclic group represented by Arp1 may include a heteroatom such as an oxygen atom and a carbonyl carbon. Examples of the (p2+1)-valent alicyclic group represented by Arp1 include groups provided by removing any p2+1 hydrogen atoms from a polycyclic cycloalkane such as norbornene, tetracyclodecane, tetracyclododecane, or adamantane. The (p2+1)-valent alicyclic group represented by Arp1 may be a group provided by removing any p2+1 hydrogen atoms from a lactone ring or a sultone ring. The lactone ring or the sultone ring is preferably a five- to seven-membered lactone ring or sultone ring, more preferably a five- to seven-membered lactone ring or sultone ring to which another ring structure is fused so as to form a bicyclo structure or a spiro structure.
The (p2+1)-valent aromatic ring group and alicyclic group may have a substituent other than Rp1.
p1 represents 0 or 1.
When p1 is 0, p2 represents 1. When p1 is 1, p2 represents an integer of 0 to 4.
Rp1 represents a substituent. Rp1 may be the same as Rp in Formula (XP) above and is particularly preferably an alkyl group that may have a substituent, a polarity-decreasing group, an interactive group, an onium salt group, a polar group, a reactive group A, or a reactive group B. The substituent is preferably a halogen atom.
As an embodiment of the substituent represented by Rp1, an embodiment represented by *-LN-RpA is also preferred. LN represents a single bond or a divalent linking group. The divalent linking group represented by LN may be the same as the divalent linking group represented by Lp in Formula (XP) above and is particularly preferably an alkylene group having 1 to 6 carbon atoms. RpA represents the polarity-decreasing group, interactive group, onium salt group, polar group, reactive group A, or reactive group B described above.
In Formula (XP2), Xp2 has the same definition as in X P in Formula (XP) above.
Yp2 represents a single bond or —COO—.
Lp2 represents a divalent linking group.
Examples of the divalent linking group represented by Lp2 include —CO—, —O—, —S—, —SO—, —SO2—, hydrocarbon groups (such as an alkylene group, a cycloalkylene group, an alkenylene group, and an arylene group), and a linking group provided by linking a plurality of these together. The hydrocarbon groups may have a substituent. The substituent is not particularly limited, and may be, for example, a fluorine atom or an iodine atom.
In particular, the divalent linking group represented by Lp2 is preferably an arylene group, an arylene group-CO—, an alkylene group-CO—, or an alkylene group-arylene group-, more preferably an arylene group.
The arylene group is preferably a phenylene group.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
Rp2 represents a leaving group that leaves due to action of acid.
Examples of the leaving group that leaves due to action of acid and represented by Rp2 include the above-described leaving groups represented by Formulae (Y1) to (Y4).
Here, when the repeating unit represented by Formula (XP2) includes an acid-decomposable group having a structure in which a polar group is protected with a leaving group, the polar group generated after acid decomposition is more hydrophobic than the acid-decomposable group before acid decomposition. Specifically, the log P of the acid-decomposable group is smaller than the log P of the polar group after the protective group leaves.
In Formula (XQ), the alkyl group represented by Rq1 may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3.
The alkyl group represented by Rq1 may have a substituent. The substituent is not particularly limited, but may be, for example, a halogen atom or a hydroxy group.
In Formula (XQ), the divalent linking group represented by Lq may be the same as the divalent linking group represented by Lp in Formula (XP) above.
In Formula (XQ), the substituent represented by Rq2 may be the same as the substituent represented by Rp in Formula (XP) above.
The repeating unit represented by Formula (XQ) is preferably one or more selected from the group consisting of a repeating unit represented by Formula (XQ1) below and a repeating unit represented by Formula (XQ2) below.
In Formula (XQ1), Rq11 has the same definition and preferred embodiments as in Rq1 in Formula (XQ) above.
Yq1 represents a single bond or —COO—.
Lq1 represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Lq1 include, but are not particularly limited to, —CO—, —O—, —SO—, —SO2—, —NRA—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group provided by combining a plurality of these. The alkylene group may have a substituent. The substituent may be, for example, a halogen atom or a hydroxy group. RA may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Arq1 represents a (q2+1)-valent aromatic ring group or alicyclic group.
The divalent aromatic ring group in the case where q2 is 1 is preferably, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group including a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Of these, an arylene group is preferred, and a phenylene group or a naphthalene group is more preferred.
Specific examples of the (q2+1)-valent aromatic ring group in the case where q2 is an integer of 2 or more include groups provided by removing any (q2−1) hydrogen atoms from any of the foregoing specific examples of the divalent aromatic ring group.
The (q2+1)-valent alicyclic group represented by Arq1 may include a heteroatom such as an oxygen atom and a carbonyl carbon. Examples of the (q2+1)-valent alicyclic group represented by Arq1 include groups provided by removing any q2+1 hydrogen atoms from a polycyclic cycloalkane such as norbornene, tetracyclodecane, tetracyclododecane, or adamantane. The (q2+1)-valent alicyclic group represented by Arq1 may be a group provided by removing any q2+1 hydrogen atoms from a lactone ring or a sultone ring. The lactone ring or the sultone ring is preferably a five- to seven-membered lactone ring or sultone ring, more preferably a five- to seven-membered lactone ring or sultone ring to which another ring structure is fused so as to form a bicyclo structure or a spiro structure.
The (q2+1)-valent aromatic ring group and alicyclic group may have a substituent other than Rq12
q1 represents 0 or 1.
When q1 is 0, q2 represents 1. When q1 is 1, q2 represents an integer of 0 to 4.
Rq12 represents a substituent. Rq12 may be the same as Rp in Formula (XP) above and is particularly preferably an alkyl group that may have a substituent, a polarity-decreasing group, an interactive group, an onium salt group, a polar group, a reactive group A, or a reactive group B. The substituent is preferably a halogen atom.
As an embodiment of the substituent represented by Rq12, an embodiment represented by *-LN-RpA is also preferred. LN represents a single bond or a divalent linking group. The divalent linking group represented by LN may be the same as the divalent linking group represented by Lp in Formula (XP) above and is particularly preferably an alkylene group having 1 to 6 carbon atoms. RpA represents the polarity-decreasing group, interactive group, onium salt group, polar group, reactive group A, or reactive group B described above.
In Formula (XQ2), Rq13 has the same definition and preferred embodiments as in Rq1 in Formula (XQ) above.
Yq2 represents a single bond or —COO—.
Lq2 represents a divalent linking group.
Examples of the divalent linking group represented by Lq2 include —CO—, —O—, —S—, —SO—, —SO2—, hydrocarbon groups (such as an alkylene group, a cycloalkylene group, an alkenylene group, and an arylene group), and a linking group provided by linking a plurality of these together. The hydrocarbon groups may have a substituent. The substituent is not particularly limited, and may be, for example, a fluorine atom or an iodine atom.
In particular, the divalent linking group represented by Lq2 is preferably an arylene group, an arylene group-CO—, an alkylene group-CO—, or an alkylene group-arylene group-, more preferably an arylene group.
The arylene group is preferably a phenylene group.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
Rq14 represents a leaving group that leaves due to action of acid.
Examples of the leaving group that leaves due to action of acid and represented by Rq14include the above-described leaving groups represented by Formulae (Y1) to (Y4).
Here, when the repeating unit represented by Formula (XQ2) includes an acid-decomposable group having a structure in which a polar group is protected with a leaving group, the polar group generated after acid decomposition is more hydrophobic than the acid-decomposable group before acid decomposition. Specifically, the log P of the acid-decomposable group is smaller than the log P of the polar group after the protective group leaves.
The above-described resin X1-I may include a repeating unit other than the above-described repeating units as long as the effects of the present invention are not inhibited.
A resin including a moiety represented by Formula (XR0) below in a main chain structure:
In Formula (XR0), Rr1 to Rr4 each independently represent a hydrogen atom or a substituent. Rr2 and Rr3 may be bonded together to form a ring. * represents a bonding site.
The resin X1-II has the above-described polarity-decreasing group.
In the resin X1-II, preferably, at least one or more of Rr1 to Rr4 in Formula (XR0) represent substituents, and at least one or more of the substituents have the above-described polarity-decreasing group; or Rr2 and Rr3 in Formula (XR0) are bonded together to form a ring, and at least one or more of substituents on the ring have the above-described polarity-decreasing group. From the viewpoint of providing a better effect of the present invention, in the resin X1-II, more preferably, Rr2 and Rr3 in Formula (XR0) are bonded together to form a ring, and at least one or more of substituents on the ring have the above-described polarity-decreasing group.
More preferably, at least two or more of Rrl to Rr4 in Formula (XR0) represent substituents, and at least one or more of the substituents have the above-described polarity-decreasing group, and at least one or more of the substituents have one or more selected from the group consisting of the interactive group, the onium salt group, the polar group, the reactive group A, and the reactive group B; or Rr2 and Rr3 in Formula (XR0) are bonded together to form a ring, and at least one or more of substituents on the ring have the above-described polarity-decreasing group, and at least one or more of the other substituents on the ring have one or more selected from the group consisting of the interactive group, the onium salt group, the polar group, the reactive group A, and the reactive group B.
Note that when the resin X1-II includes the reactive group B, the reactive group A is also included in the resin X1-II.
The resin X1-II may include the moiety represented by Formula (XR0) as apart thereof or as a repeating unit thereof. From the viewpoint of providing a better effect of the present invention, the resin X1-II is preferably a resin including Formula (XR0) as a repeating unit (specifically, a resin including a repeating unit represented by Formula (XR) below).
In Formula (XR), Rrl to Rr have the same definitions and preferred embodiments as in the above-described Rr1 to Rr4 in Formula (XR0).
Preferred forms of the resin X1-II will be described in detail below.
In the resin X1-II, the content of the repeating unit represented by Formula (XR) above is preferably 90 mol % or more, more preferably 95 mol % or more relative to all the repeating units. The upper limit value is preferably 100 mol % or less.
In Formula (XR) and Formula (XR0), the substituents represented by Rrl to Rr4 may each be the same as the substituent represented by Rp in Formula (XP) above, and preferred embodiments are also the same.
As an embodiment of the substituents represented by Rr1 to Rr4, an embodiment represented by *-LN-RpA is also preferred. LN represents a single bond or a divalent linking group. The divalent linking group represented by LN may be the same as the divalent linking group represented by Lp in Formula (XP) above and is particularly preferably an alkylene group having 1 to 6 carbon atoms. RpA represents the polarity-decreasing group, interactive group, onium salt group, polar group, reactive group A, or reactive group B described above.
In Formula (XR) and Formula (XR0), the ring formed by bonding R2 and Rr3 together is not particularly limited, and may be an alicyclic ring or an aromatic ring. The ring may further have a substituent, and the substituent represents, for example, a polarity-decreasing group, an interactive group, an onium salt group, a polar group, a reactive group A, or a reactive group B. Alternatively, the substituent is also preferably a group of an embodiment represented by *-LN-RpA described as one embodiment of the substituents represented by Rr1 to Rr4 above.
In Formula (XR), when Rr2 and Rr3 are bonded together, the repeating unit represented by Formula (XR) is also preferably a repeating unit represented by Formula (XRA) below.
In the formula, Rrl and Rr4 have the same definitions and preferred embodiments as in Rr1 and Rr4, respectively, in Formula (XR) above. RT represents a substituent. Each substituent represented by RT may be the same as the substituent represented by Rp in Formula (XP) above, and preferred embodiments are also the same.
However, at least one of the substituents represented by RT represents a polarity-decreasing group, an interactive group, or a polar group. m represents an integer of 0 to 4.
The above-described resin X1-II may include a repeating unit other than the above-described repeating units as long as the effects of the present invention are not inhibited.
A resin including a repeating unit represented by Formula (XS) below:
In Formula (XS), L5l represents a linking group represented by *—C(Rs1)(Rs2)-*. Rs1 and Rs2 each independently represent a hydrogen atom or a monovalent organic group. * represents a bonding site. However, at least one of Rs1 or Rs2 represents a monovalent organic group. Ls2 represents a single bond or a divalent linking group,
The resin X1-III has the above-described polarity-decreasing group.
In the resin X1-III, one or more of the monovalent organic group represented by Rs1 and Rs2 and the divalent linking group represented by Ls2 in Formula (XS) preferably have the above-described polarity-decreasing group.
From the viewpoint of providing a better effect of the present invention, in the resin X1-III, more preferably, at least one of Rs1 or Rs2 in Formula (XS) represents a monovalent organic group, and the monovalent organic group has the above-described polarity-decreasing group.
It is also preferable that one or more of the monovalent organic group represented by Rs1 and Rs2 and the divalent linking group represented by Ls2 in Formula (XS) further have one or more groups selected from the group consisting of the interactive group, the onium salt group, the polar group, the reactive group A, and the reactive group B.
Note that when the resin X1-III includes the reactive group B, the reactive group A is also included in the resin X1-III.
Preferred forms of the resin X1-III will be described in detail below.
In the resin X1-III, the content of the repeating unit represented by Formula (XS) above is preferably 90 mol % or more, more preferably 95 mol % or more relative to all the repeating units. The upper limit value is preferably 100 mol % or less.
In Formula (XS), L5l represents a linking group represented by *—C(Rs1)(Rs2)-*
Rs1 and Rs2 each independently represent a hydrogen atom or a monovalent organic group. * represents a bonding site.
However, in Formula (XS), at least one of Rs1 or Rs2 represents a monovalent organic group.
The monovalent organic group represented by Rs1 and Rs2 is preferably an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), or an aryl (monocyclic or polycyclic) group, more preferably an alkyl group.
The alkyl group in Rs1 and Rs2 is preferably an alkyl group having 1 to 4 carbon atoms.
The cycloalkyl group in Rs1 and Rs2 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
The aryl group in Rs1 and Rs2 is preferably a phenyl group.
Rs1 and Rs2 are each preferably an alkyl group, each more preferably an alkyl group having 1 to 4 carbon atoms, each still more preferably a methyl group.
The divalent linking group represented by Ls2 in Formula (XS) may be the same as the divalent linking group represented by Lp in Formula (XP) above.
In particular, Ls2 is preferably a group represented by *i-LO1-ph-LO2—O—*2. ph represents a phenylene group that may have a substituent. *1 represents a bonding site to Ls1, and *2 represents another bonding site. LO1 and LO2 represent a single bond or a divalent linking group.
The substituent that ph may have is not particularly limited, but is preferably, for example, a group represented by *-LN-RpA. LN represents a single bond or a divalent linking group. The divalent linking group represented by LN may be the same as the divalent linking group represented by Lp in Formula (XP) above and is particularly preferably an alkylene group having 1 to 6 carbon atoms. RpA represents the polarity-decreasing group, interactive group, onium salt group, polar group, reactive group A, or reactive group B described above.
Examples of the divalent linking group represented by LO1 and LO2 include —CO—, —O—, —SO—, —SO2—, —NRA—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group provided by combining a plurality of these. The alkylene group may have a substituent. The substituent may be, for example, a halogen atom or a hydroxy group. RA may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
An embodiment of the divalent linking group represented by LO1 and LO2 may be a divalent linking group represented by an -alkylene group-O.
The above-described resin X1-III may include a repeating unit other than the above-described repeating units as long as the effects of the present invention are not inhibited.
The resin X1 of the second preferred embodiment can be synthesized by an ordinary method (for example, radical polymerization).
The resin X1 preferably has a weight-average molecular weight of 1,000 to 200,000, more preferably 2,500 to 150,000, still more preferably 3,000 to 50,000 in terms of polystyrene as determined by the GPC method. When the weight-average molecular weight is within the above numerical range, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, deterioration of developing performance and deterioration of film-forming properties due to an increase in viscosity can also be further suppressed.
The dispersity (molecular weight distribution) of the resin X1 of the second preferred embodiment is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, still more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and the resist shape.
In the resist composition, the content of the resin X1 (the resin X1 of the first preferred embodiment or the second preferred embodiment) is preferably 50.0 to 99.9 mass %, more preferably 60.0 to 99.0 mass %, still more preferably 70.0 to 99.0 mass % relative to the total solid content of the composition.
Such resins X1 may be used alone or in combination of two or more thereof. When two or more resins are used, the total content thereof is preferably within the above preferred content range.
Hereinafter, the resin X2 included in the resist composition will be described.
The resin X2 may be any resin having a polar group.
An example of preferred embodiments of the resin X2 will be described below.
An embodiment (Embodiment 1) of the resin X2 is, for example, an embodiment in which the resin has a polar group and has an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating (interactive group).
An embodiment (Embodiment 2) of the resin X2 is, for example, an embodiment in which the resin has a polar group and has an onium salt group that is decomposed due to action of exposure.
An embodiment (Embodiment 3) of the resin X2 is, for example, an embodiment in which the resin has a polar group and undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating. One form of Embodiment 3 may be an embodiment in which the decrease in molecular weight is caused by the decomposition of the main chain due to action of exposure.
An embodiment (Embodiment 4) of the resin X2 is, for example, an embodiment in which the resin has a polar group and has a reactive group A.
An embodiment (Embodiment 5) of the resin X2 is, for example, an embodiment in which the resin has a polar group and has a reactive group A and a reactive group B that reacts with the reactive group A.
An embodiment (Embodiment 6) of the resin X2 is, for example, an embodiment in which the resin has a polar group and has a polarity-decreasing group.
An embodiment (Embodiment 7) of the resin X2 is, for example, an embodiment to which at least two or more of Embodiments 1 to 6 above correspond.
Such an embodiment may be, for example, an embodiment in which the resin has a polar group, an onium salt group that is decomposed due to action of exposure, and an interactive group. Alternatively, such an embodiment may be, for example, an embodiment in which the resin has a polar group, an onium salt group that is decomposed due to action of exposure, and an interactive group and undergoes a decrease in molecular weight due to action of exposure, acid, or base.
The polar group, the onium salt group, the interactive group, the polarity-decreasing group, the reactive group A, and the reactive group B are as described above.
The resin X2 may be any resin having a polar group, but preferably includes a repeating unit having a polar group from the viewpoint of providing a better effect of the present invention.
When the resist composition includes the resin X2, the resist composition further includes a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent).
In Embodiment 5, since the resin X2 has the reactive group B in its molecule, the composition may not include a crosslinking agent including the reactive group B.
Note that when the resin X2 has a polarity-decreasing group, the resin X2 may have, before the action of exposure, acid, base, or heating, both the polarity-decreasing group and a group after the decrease in polarity, the group being generated from the polarity-decreasing group by the action of exposure, acid, base, or heating.
A first preferred embodiment of the resin X2 will be described below.
The resin X2 preferably includes a repeating unit having a polar group.
Examples of the polar group include those described above.
Examples of the repeating unit having a polar group include embodiments of the above-described repeating unit represented by Formula (T1) described in the section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”, where R51 represents a polar group.
In the resin X2, one or more repeating units having a polar group may be included, or two or more of such repeating units may be included.
In the resin X2, the content of the repeating unit having a polar group is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin X2. The upper limit value thereof is preferably 100 mol % or less, more preferably 90 mol % or less, still more preferably 80 mol % or less.
The resin X2 may include a repeating unit other than the repeating unit having a polar group. Examples of the other repeating unit include the repeating units described in the above section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”. When the resin X2 optionally includes repeating units described in the above section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”, the contents thereof are also the same as the corresponding contents described in the above section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”. Second Preferred Embodiment of Resin X2 (Main Chain Decomposition-Type Resin)
A second preferred embodiment of the resin X2 will be described below.
The resin X2 of the second preferred embodiment is preferably a resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating, more preferably a resin that undergoes a decrease in molecular weight caused by the decomposition of a structure (e.g., a main chain structure or a side chain structure) in the resin due to action of exposure, acid, base, or heating, still more preferably a resin that undergoes a decrease in molecular weight caused by the scission of the main chain in the resin due to action of exposure, acid, base, or heating (a so-called main chain scission resin).
Examples of the form of the resin X2 which is a main chain scission-type resin include the resins described in the section “Second Preferred Embodiment of Resin X1 (Main Chain Decomposition-Type Resin)” in which “polarity-decreasing groups” are replaced by “polar groups” and “polar groups” are replaced by “polarity-decreasing groups”.
The resins X2 of the first preferred embodiment and the second preferred embodiment can be synthesized by an ordinary method (for example, radical polymerization).
The resins X2 of the first preferred embodiment and the second preferred embodiment preferably have a weight-average molecular weight of 1,000 to 200,000, more preferably 2,500 to 150,000, still more preferably 3,000 to 50,000 in terms of polystyrene as determined by the GPC method. When the weight-average molecular weight is within the above numerical range, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, deterioration of developing performance and deterioration of film-forming properties due to an increase in viscosity can also be further suppressed.
The dispersity (molecular weight distribution) of each of the resins X2 of the first preferred embodiment and the second preferred embodiment is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, still more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and the resist shape.
In the resist composition, the content of the resin X2 (the resin X2 of the first preferred embodiment or the second preferred embodiment) is preferably 50.0 to 99.9 mass %, more preferably 60.0 to 99.0 mass %, still more preferably 70.0 to 99.0 mass % relative to the total solid content of the composition.
Such resins X2 may be used alone or in combination of two or more thereof. When two or more resins are used, the total content thereof is preferably within the above preferred content range.
The resist composition preferably includes a compound that generates acid upon irradiation with an actinic ray or a radiation (photoacid generator).
A preferred embodiment of the photoacid generator may be a compound (I) or a compound (II) described below.
The compound (I) and the compound (II) (hereinafter, the “compound (I) and compound (II)” are also referred to as “photoacid generator PG1”) will be described below.
The compound (I) is a compound having one or more of the following moiety X and one or more of the following moiety Y and is a compound that generates an acid including the following first acidic moiety derived from the following moiety X and the following second acidic moiety derived from the following moiety Y upon irradiation with an actinic ray or a radiation.
Moiety X: A moiety that is constituted by an anionic moiety A1− and a cationic moiety M1+ and that forms the first acidic moiety represented by HA1 upon irradiation with an actinic ray or a radiation
Moiety Y: A moiety that is constituted by an anionic moiety A2− and a cationic moiety M2+ and that forms the second acidic moiety represented by HA2 upon irradiation with an actinic ray or a radiation
Here, the compound (I) satisfies the following condition I.
Condition I: A compound PI in which, in the compound (I), the cationic moiety M1+ in the moiety X and the cationic moiety M2+ in the moiety Y are replaced by H+ has an acid dissociation constant a1 derived from an acidic moiety represented by HA1 in which the cationic moiety M1+ in the moiety X is replaced by H+ and an acid dissociation constant a2 derived from an acidic moiety represented by HA2 in which the cationic moiety M2+ in the moiety Y is replaced by H+, and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
The condition I will be more specifically described below.
When the compound (I) is, for example, a compound that generates an acid having a single first acidic moiety derived from the moiety X and a single second acidic moiety derived from the moiety Y, the compound PI corresponds to a “compound having HA1 and HA2”.
The acid dissociation constant a1 and the acid dissociation constant a2 of such a compound PI are more specifically described as follows. In determination of the acid dissociation constants of the compound PI, the pKa determined when the compound PI is turned into a “compound having A1− and HA2” is the acid dissociation constant a1, and the pKa determined when the “compound having A1− and HA2” is turned into “compound having A1− and A2−” is the acid dissociation constant a2.
When the compound (I) is, for example, a compound that generates an acid having two first acidic moieties derived from the moiety X and a single second acidic moiety derived from the moiety Y, the compound PI corresponds to a “compound having two HA1 and a single HA2”.
In determination of the acid dissociation constants of such a compound PI, the acid dissociation constant determined when the compound PI is turned into a “compound having a single A1−, a single HA1, and a single HA2” and the acid dissociation constant determined when the “compound having a single A1−, a single HA1, and a single HA2” is turned into a “compound having two A1− and a single HA2” correspond to the above-described acid dissociation constant a1. The acid dissociation constant determined when the “compound having two A1− and a single HA2” is turned into a “compound having two A1− and A2−” corresponds to the acid dissociation constant a2. That is, as in such a compound PI, when there are a plurality of acid dissociation constants derived from acidic moieties represented by HA1 in which the cationic moiety M1+ in the moiety X is replaced by H+, the value of the acid dissociation constant a2 is larger than the maximum value of the plurality of acid dissociation constants a1. Note that, when the acid dissociation constant determined when the compound PI is turned into a “compound having a single A1−, a single HA1, and a single HA2” is defined as aa and the acid dissociation constant determined when the “compound having a single A1−, a single HA1, and a single HA2” is turned into a “compound having two A1− and a single HA2” is defined as ab, the relation between aa and ab satisfies aa<ab.
The acid dissociation constant a1 and the acid dissociation constant a2 can be determined by the above-described method of measuring an acid dissociation constant.
The compound PI corresponds to an acid generated when the compound (I) is irradiated with an actinic ray or a radiation.
When the compound (I) has two or more moieties X, the moieties X may be the same or different. The two or more A1− and the two or more M1+ may be individually the same or different.
In the compound (I), the A1− and the A2−, and the M1+ and the M2+ may be individually the same or different, but the A1− and the A2− are preferably different.
From the viewpoint of a better LWR performance of the pattern to be formed, in the compound PI, the difference between the acid dissociation constant a1 (in the case where there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more. The upper limit value of the difference between the acid dissociation constant a1 (in the case where there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
From the viewpoint of a better LWR performance of the pattern to be formed, in the compound PI, the acid dissociation constant a2 is, for example, 20 or less, preferably 15 or less. The lower limit value of the acid dissociation constant a2 is preferably −4.0 or more.
From the viewpoint of a better LWR performance of the pattern to be formed, in the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less. The lower limit value of the acid dissociation constant a1 is preferably -20.0 or more.
The anionic moiety A1− and the anionic moiety A2− are moieties including a negatively charged atom or atomic group and are, for example, moieties selected from the group consisting of Formulae (AA-1) to (AA-3) and Formulae (BB-1) to (BB-6) below. The anionic moiety A1− is preferably one that can form an acidic moiety having a small acid dissociation constant, particularly preferably any one of Formulae (AA-1) to (AA-3). The anionic moiety A2− is preferably one that can form an acidic moiety having a larger acid dissociation constant than the anionic moiety A1− and is preferably selected from the group consisting of Formulae (BB-1) to (BB-6). In Formulae (AA-1) to (AA-3) and Formulae (BB-1) to (BB-6) below, * represents a bonding site. RA represent a monovalent organic group. The monovalent organic groups represented by RA may be, for example, a cyano group, a trifluoromethyl group, or a methanesulfonyl group.
The cationic moiety M1+ and the cationic moiety M2+ are moieties including a positively charged atom or atomic group and are, for example, organic cations having a charge number of 1. The organic cations are not particularly limited, but may be, for example, the same organic cations as those represented by M11+ and M12+ in Formula (Ia-1) described below.
The specific structure of the compound (I) is not particularly limited, and examples of the compound (I) include compounds represented by Formula (Ia-1) to Formula (Ia-5) described below.
First, the compound represented by Formula (Ia-1) will be described below. The compound represented by Formula (Ia-1) is as follows.
M
11
+
A
11
−-L1-A12−M12+ (Ia-1)
The compound (Ia-1) generates an acid represented by HA11-L1-A12H upon irradiation with an actinic ray or a radiation.
In Formula (Ia-1), M11+ and M12+ each independently represent an organic cation.
A11− and A12− each independently represent a monovalent anionic functional group.
L1 represents a divalent linking group.
M11+ and M12+ may be the same or different.
A11− and A12− may be the same or different, but are preferably different from each other.
Note that, in a compound PIa (HA11-L1-A12H) in which, in Formula (Ia-1) above, the organic cations represented by M11− and M12+ are replaced by H+, the acid dissociation constant a2 derived from the acidic moiety represented by A12H is larger than the acid dissociation constant a1 derived from the acidic moiety represented by HA11. Preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are the same as those described above. The compound PIa is the same as the acid generated from the compound represented by Formula (Ia-1) upon irradiation with an actinic ray or a radiation.
At least one of M1+, M12+, A11−, A12−, or L1 may have an acid-decomposable group as a substituent.
In Formula (Ia-1), the organic cations represented by M11+ and M12+ are as described below.
The monovalent anionic functional group represented by A11− means a monovalent group including the above-described anionic moiety A1−. The monovalent anionic functional group represented by A12− means a monovalent group including the above-described anionic moiety A2−.
The monovalent anionic functional groups represented by A11− and A12− are preferably monovalent anionic functional groups including the anionic moiety of any one of Formulae (AA-1) to (AA-3) and Formulae (BB-1) to (BB-6), more preferably monovalent anionic functional groups selected from the group consisting of Formulae (AX-1) to (AX-3) and Formulae (BX-1) to (BX-7). In particular, the monovalent anionic functional group represented by A11− is preferably the monovalent anionic functional group represented by any one of Formulae (AX-1) to (AX-3). In particular, the monovalent anionic functional group represented by A12− is preferably the monovalent anionic functional group represented by any one of Formulae (BX-1) to (BX-7), more preferably the monovalent anionic functional group represented by any one of Formulae (BX-1) to (BX-6).
In Formulae (AX-1) to (AX-3), RA1 and RA2 each independently represent a monovalent organic group. * represents a bonding site.
The monovalent organic groups represented by RA1 may be, for example, a cyano group, a trifluoromethyl group, or a methanesulfonyl group.
The monovalent organic group represented by RA2 is preferably a linear, branched, or cyclic alkyl group or an aryl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 6.
The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, the alkyl group may be a perfluoroalkyl group.
The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or a cyano group, more preferably a fluorine atom, an iodine atom, or a perfluoroalkyl group.
In Formulae (BX-1) to (BX-4) and Formula (BX-6), RB represent a monovalent organic group. * represents a bonding site.
The monovalent organic groups represented by RB are preferably a linear, branched, or cyclic alkyl group or an aryl group.
The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 6.
The alkyl group may have a substituent. The substituent is not particularly limited, but the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, the alkyl group may be a perfluoroalkyl group.
Note that, in the alkyl group, when a carbon atom serving as a bonding site (which corresponds to, for example, in the case of Formulae (BX-1) and (BX-4), the carbon atom directly bonded to —CO— clearly shown in the formula of such an alkyl group; in the case of Formulae (BX-2) and (BX-3), the carbon atom directly bonded to —SO2— clearly shown in the formula of such an alkyl group; and in the case of Formula (BX-6), the carbon atom directly bonded to —N−— clearly shown in the formula of the alkyl group) has a substituent, the substituent is also preferably a substituent other than a fluorine atom and a cyano group.
In the alkyl group, a carbon atom may be replaced by a carbonyl carbon.
The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
In Formula (Ia-1), examples of the divalent linking group represented by L1 include, but are not particularly limited to, —CO—, —NR—, —O—, —S—, —SO—, —SO2—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (which is preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic heterocyclic group (which is preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), and a divalent aromatic hydrocarbon ring group (which is preferably a six- to ten-membered ring, more preferably a six-membered ring), and a divalent linking group provided by combining a plurality of these. R above is, for example, a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. The substituent is, for example, a halogen atom (preferably a fluorine atom).
The divalent linking group represented by L1 is particularly preferably a divalent linking group represented by Formula (L1).
In Formula (L1), L111 represents a single bond or a divalent linking group.
The divalent linking group represented by L111 is not particularly limited, and may be, for example, —CO—, —NH—, —O—, —SO—, —SO2—, an alkylene group that may have a substituent (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group that may have a substituent (preferably having 3 to 15 carbon atoms), an arylene group that may have a substituent (preferably having 6 to 10 carbon atoms), or a divalent linking group provided by combining a plurality of these. The substituent is not particularly limited, and may be, for example, a halogen atom.
p represents an integer of 0 to 3, and preferably represents an integer of 1 to 3.
Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Each Xf2 independently represents a hydrogen atom, an alkyl group that may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. In particular, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group.
In particular, Xf1 and Xf2 are preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, Xf1 and Xf2 are each still more preferably a fluorine atom.
* represents a bonding site.
When L1 in Formula (Ia-1) represents a divalent linking group represented by Formula (L1), the direct bond (*) on the L111-side in Formula (L1) is preferably bonded to A12− in Formula (Ia-1).
In Formula (Ia-1), the organic cations represented by M11− and M12+ are, for example, the same as the organic cation represented by MA+ in the group represented by Formula (O1) described in the above section “Onium Salt Group” and preferred embodiments thereof are also the same.
Specific examples of the organic cations represented by M11+ and M11+ are as follows; however, the present invention is not limited to these.
Next, Formulae (Ia-2) to (Ia-4) will be described.
In Formula (Ia-2), A21a− and A21− each independently represent a monovalent anionic functional group. Here, each of the monovalent anionic functional groups represented by A21a− and A21b− means a monovalent group including the above-described anionic moiety A1−. The monovalent anionic functional groups represented by A21a− and A21b− are not particularly limited, but each may be, for example, a monovalent anionic functional group selected from the group consisting of Formulae (AX-1) to (AX-3) above.
A22− represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A22− means a divalent group including the above-described anionic moiety A2−. Examples of the divalent anionic functional group represented by A22− include divalent anionic functional groups represented by Formulae (BX-8) to (BX-11) below.
M21a+, M21b+, and M22+ each independently represent an organic cation. The organic cations represented by M21a+, M21b+, and M22+ have the same definitions and preferred embodiments as in M1+ described above.
L21 and L22 each independently represent a divalent organic group.
In a compound PIa-2 in which, in Formula (Ia-2) above, the organic cations represented by M21a+, M21b+, and M22+ are replaced by H+, the acid dissociation constant a2 derived from the acidic moiety represented by A22H is larger than the acid dissociation constant a1-1 derived from the acidic moiety represented by A21aH and the acid dissociation constant a1-2 derived from the acidic moiety represented by A21bH. Note that the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the above-described acid dissociation constant a1.
A21a− and A21− may be the same or different. M21a+, M21b+, and M22+ may be the same or different.
At least one of M21a+, M21b+, M22+, A21a−, A21b−, A22−, L21, or L22 may have an acid-decomposable group as a substituent.
In Formula (Ia-3), A31a− and A32− each independently represent a monovalent anionic functional group. The monovalent anionic functional group represented by A31a− has the same definition and preferred embodiments as in the above-described A21a− and A21b− in Formula (Ia-2).
The monovalent anionic functional group represented by A32− means a monovalent group including the above-described anionic moiety A2−. The monovalent anionic functional group represented by A32− is not particularly limited, but may be, for example, a monovalent anionic functional group selected from the group consisting of Formulae (BX-1) to (BX-7) above.
A31b− represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A31b− means a divalent group including the above-described anionic moiety A1−. The divalent anionic functional group represented by A31b− may be, for example, a divalent anionic functional group represented by Formula (AX-4) below.
M31a+, M31b+, and M32+ each independently represent a monovalent organic cation. The organic cations represented by M31a+, M31b+, and M32+ have the same definitions and preferred embodiments as in M1+ described above.
L31 and L32 each independently represent a divalent organic group.
In a compound PIa-3, in which, in Formula (Ia-3) above, the organic cations represented by M31a+, M31b+, and M32+ are replaced by H+, the acid dissociation constant a2 derived from the acidic moiety represented by A32H is larger than the acid dissociation constant a1-3 derived from the acidic moiety represented by A31aH and the acid dissociation constant a1-4 derived from the acidic moiety represented by A31bH. Note that the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the above-described acid dissociation constant a1.
A31a− and A32− may be the same or different. M31a+, M31b+, and M32+ may be the same or different.
At least one of M31a+, M31b+, M32+, A31a−, A31b−, A32−, L31, or L32 may have an acid-decomposable group as a substituent.
In Formula (Ia-4), A41a−, A41b−, and A42− each independently represent a monovalent anionic functional group. The definition of the monovalent anionic functional groups represented by A41a− and A41b− is the same as that of the above-described A21a− and A21b− in Formula (Ia-2). The monovalent anionic functional group represented by A42− has the same definition and preferred embodiments as in the above-described A32− in Formula (Ia-3).
M41a+, M41b+, and M42+ each independently represent an organic cation.
L41 represents a trivalent organic group.
In a compound PIa-4 in which, in Formula (Ia-4) above, the organic cations represented by M41a+, M41b+, and M42+ are replaced by H+, the acid dissociation constant a2 derived from the acidic moiety represented by A42H is larger than the acid dissociation constant a1-5 derived from the acidic moiety represented by A41aH and the acid dissociation constant a1-6 derived from the acidic moiety represented by A41bH. Note that the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the above-described acid dissociation constant a1.
A41a−, A41b−, and A42− may be the same or different. M41a+, M41b+, and M42+ may be the same or different.
At least one of M41a+, M41b+, M42+, A41a−, A41b−, A42−, or L41 may have an acid-decomposable group as a substituent.
Examples of the divalent organic groups represented by L21 and L22 in Formula (Ia-2) and L31 and L32 in Formula (Ia-3) include, but are not particularly limited to, —CO—, —NR—, —O—, —S—, —SO—, —SO2—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (which is preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic heterocyclic group (which is preferably a five-to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic hydrocarbon ring group (which is preferably a six- to ten-membered ring, more preferably a six-membered ring), and a divalent organic group provided by combining a plurality of these. R above is, for example, a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. The substituent is, for example, a halogen atom (preferably a fluorine atom).
The divalent organic groups represented by L21 and L22 in Formula (Ia-2) and L31 and L32 in Formula (Ia-3) are also preferably, for example, divalent organic groups represented by Formula (L2) below.
In Formula (L2), q represents an integer of 1 to 3. * represents a bonding site.
Xf's each independently represent a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Each Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, both of Xf's are still more preferably fluorine atoms.
LA represents a single bond or a divalent linking group.
The divalent linking group represented by LA is not particularly limited, but may be, for example, —CO—, —O—, —SO—, —SO2—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon cyclic group (preferably a six- to ten-membered ring, more preferably a six-membered ring), or a divalent linking group provided by combining a plurality of these.
The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. The substituent is, for example, a halogen atom (preferably a fluorine atom).
Examples of the divalent organic group represented by Formula (L2) include *—CF2—*, *—CF2—CF2—*, *—CF2—CF2—CF2—*, *-Ph-O—SO2—CF2—*, *-Ph-O—SO2—CF2—CF2—*, *-Ph-O—SO2—CF2—CF2—CF2—*, and *-Ph-OCO—CF2—*. Note that Ph is a phenylene group that may have a substituent, and preferably a 1,4-phenylene group. The substituent is not particularly limited, but is preferably an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms).
When L21 and L22 in Formula (Ia-2) represent a divalent organic group represented by Formula (L2), the direct bond (*) on the LA-side in Formula (L2) is preferably bonded to A22− in Formula (Ia-2).
When L32 in Formula (Ia-3) represents a divalent organic group represented by Formula (L2), the direct bond (*) on the LA-side in Formula (L2) is preferably bonded to A32− in Formula (Ia-3).
The trivalent organic group represented by L41 in Formula (Ia-4) is not particularly limited, and may be, for example, a trivalent organic group represented by Formula (L3) below.
In Formula (L3). LB represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents a bonding site.
The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms included in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocycle is preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure.
Of these, LB is preferably a trivalent hydrocarbon ring group, more preferably a benzene ring group or an adamantane ring group. The benzene ring group or the adamantane ring group may have a substituent. The substituent is not particularly limited, but is, for example, a halogen atom (preferably a fluorine atom).
In Formula (L3), LB1 to LB3 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group represented by LB1 to LB3 include, but are not particularly limited to, —CO—, —NR—, —O—, —S—, —SO—, —SO2—, an alkylene group (which preferably has 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (which is preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic heterocyclic group (which is preferably a five- to ten-membered ring, more preferably a five- to seven-membered ring, still more preferably a five- or six-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure), a divalent aromatic hydrocarbon ring group (which is preferably a six- to ten-membered ring, more preferably a six-membered ring), and a divalent linking group provided by combining a plurality of these. R above is, for example, a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. The substituent is, for example, a halogen atom (preferably a fluorine atom).
Among these, the divalent linking group represented by LB1 to LB3 is preferably —CO—, —NR—, —O—, —S—, —SO—, —SO2—, an alkylene group that may have a substituent, and a divalent linking group provided by combining a plurality of these.
In particular, the divalent linking group represented by LB1 to LB3 is more preferably a divalent linking group represented by Formula (L3-1).
In Formula (L3-1), LB11 represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by LB11 include, but are not particularly limited to, —CO—, —O—, —SO—, —SO2—, an alkylene group that may have a substituent (which preferably has 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group provided by combining a plurality of these. The substituent is not particularly limited, and may be, for example, a halogen atom.
r represents an integer of 1 to 3.
Xf's have the same definition and preferred embodiments as in the above-described Xf's in Formula (L2). * represents a bonding site.
Examples of the divalent linking group represented by LB1 to LB3 include *—O—*, *—O— SO2—CF2—*, *—O—SO2—CF2—CF2—*, *—O—SO2—CF2—CF2—CF2—*, and *—COO—CH2—CH2—*.
When L41 in Formula (Ia-4) includes a divalent linking group represented by Formula (L3-1) and the divalent linking group represented by Formula (L3-1) is bonded to A42−, the direct bond (*) on the carbon-atom-side clearly shown in Formula (L3-1) is preferably bonded to A42− in Formula (Ia-4).
When L41 in Formula (Ia-4) includes a divalent linking group represented by Formula (L3-1) and the divalent linking group represented by (L3-1) is bonded to A41a− and A41b−, the direct bond (*) on the carbon-atom-side clearly shown in Formula (L3-1) is also preferably bonded to A41a− and A41b− in Formula (Ia-4).
Next, Formula (Ia-5) will be described.
In Formula (Ia-51, A51−, A51−, and A51c− each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional groups represented by A51a−, A51b−, and A51c− each mean a monovalent group including the above-described anionic moiety A1−. The monovalent anionic functional groups represented by A51a−, A51b−, and A51c− are not particularly limited, but each may be, for example, a monovalent anionic functional group selected from the group consisting of Formulae (AX-1) to (AX-3) above.
A52a− and A52b− represent a divalent anionic functional group. Here, the divalent anionic functional groups represented by A52a− and A52b− each mean a divalent group including the above-described anionic moiety A2−. The divalent anionic functional group represented by A52a− and A52b− may be, for example, a divalent anionic functional group selected from the group consisting of Formulae (BX-8) to (BX-11) above.
M51a+, M51b+, M51c+, M52a+, and M52b+ each independently represent an organic cation. The organic cations represented by M51a+, M51b+, M51c+, M52a+, and M52b+ have the same definitions and preferred embodiments as in M1+ described above.
L51 and L53 each independently represent a divalent organic group. The divalent organic groups represented by L51 and L53 have the same definitions and preferred embodiments as in the above-described L21 and L22 in Formula (Ia-2). When L51 in Formula (Ia-5) represents a divalent organic group represented by Formula (L2), the direct bond (*) on the LA-side in Formula (L2) is also preferably bonded to A52a− in Formula (Ia-5). When L53 in Formula (Ia-5) represents a divalent organic group represented by Formula (L2), the direct bond (*) on the LA-side in Formula (L2) is also preferably bonded to A52b− in Formula (Ia-5).
L52 represents a trivalent organic group. The trivalent organic group represented by L52 has the same definition and preferred embodiments as in the above-described L41 in Formula (Ia-4). When L52 in Formula (Ia-5) includes a divalent linking group represented by Formula (L3-1) and the divalent linking group represented by (L3-1) is bonded to A51c−, the direct bond (*) on the carbon-atom-side clearly shown in Formula (L3-1) is also preferably bonded to A51c− in Formula (Ia-5).
In a compound PIa-5 in which, in Formula (Ia-5) above, the organic cations represented by M51a+, M51b+, M51c+, M52a+, and M52b+ are replaced by H+, the acid dissociation constant a2-1 derived from the acidic moiety represented by A52aH and the acid dissociation constant a2-2 derived from the acidic moiety represented by A52bH are larger than the acid dissociation constant a1-1 derived from the acidic moiety represented by A51aH, the acid dissociation constant a1-2 derived from the acidic moiety represented by A51bH, and the acid dissociation constant a1-3 derived from the acidic moiety represented by A51cH. Note that the acid dissociation constants a1-1 to a1-3 correspond to the above-described acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the above-described acid dissociation constant a2.
A51a−, A51b−, and A51c− may be the same or different. A52a− and A52b− may be the same or different. M51a+, M51b+, M51c+, M52a+, and M52b+ may be the same or different.
At least one of M51b+, M51c+, M52a+, M52b+, A51a−, A51b−, A51c−, L51, L52, or L53 may have an acid-decomposable group as a substituent.
The compound (II) is a compound having two or more moieties X described above and one or more moieties Z described below and is a compound that generates an acid including two or more first acidic moieties derived from the moiety X and the moiety Z upon irradiation with an actinic ray or a radiation.
Moiety Z: nonionic moiety that can neutralize acid
In the compound (II), the moiety X, A1−, and M1+ have the same definitions and preferred embodiments as in the above-described moiety X, A1−, and M1+, respectively, in the compound (I).
In a compound PII in which, in the compound (II), the cationic moiety M1+ in the moiety X is replaced by H+, the acid dissociation constant a1 derived from the acidic moiety represented by HA1 in which the cationic moiety M1+ in the moiety X is replaced by H+ has the same preferred range as in the acid dissociation constant a1 in the compound PI.
When the compound (II) is, for example, a compound that generates an acid having two first acidic moieties derived from the moiety X and the moiety Z, the compound PII corresponds to a “compound having two HA1”. When the acid dissociation constant of this compound PII is determined, the acid dissociation constant determined when the compound PII is turned into a “compound having a single A1− and a single HA1” and the acid dissociation constant determined when the “compound having a single A1− and a single HA1” is turned into a “compound having two A1−” correspond to the acid dissociation constant a1 .
The acid dissociation constant a1 can be determined by the method of measuring an acid dissociation constant described above.
The compound PII corresponds to an acid generated when the compound (II) is irradiated with an actinic ray or a radiation.
The two or more moieties X may be the same or different. The two or more A1− and the two or more M1+ may be individually the same or different.
The nonionic moiety that can neutralize acid in the moiety Z is not particularly limited, and is preferably, for example, a moiety including a group that can electrostatically interact with a proton or a functional group having an electron.
The group that can electrostatically interact with a proton or the functional group having an electron may be, for example, a functional group having a macrocyclic structure such as a cyclic polyether or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. Examples of the nitrogen atom having an unshared electron pair that does not contribute to π conjugation include nitrogen atoms having moieties represented by formulae below.
Unshared electron pair
Examples of the moiety of the group that can electrostatically interact with a proton or the functional group having an electron include a crown ether moiety, an azacrown ether moiety, primary to tertiary amine moieties, a pyridine moiety, an imidazole moiety, and a pyrazine moiety. Of these, primary to tertiary amine moieties are preferred.
The compound (II) is not particularly limited, and examples thereof include compounds represented by Formula (IIa-1) and Formula (IIa-2) below.
In Formula (IIa-1) above, A61a− and A61b− have the same definitions and preferred embodiments as in the above-described A11− in Formula (Ia-1). M61a+ and M61b+ have the same definitions and preferred embodiments as in the above-described M1l+ in Formula (Ia-1).
In Formula (IIa-1) above, L61 and L62 have the same definitions and preferred embodiments as in the above-described L1 in Formula (Ia-1).
When L61 in Formula (IIa-1) represents a divalent linking group represented by Formula (L1), the direct bond (*) on the L111-side in Formula (L1) is preferably bonded to the nitrogen atom clearly shown in Formula (IIa-1). When L62 in Formula (IIa-1) represents a divalent linking group represented by Formula (L1), the direct bond (*) on the L111-side in Formula (L1) is preferably bonded to the nitrogen atom clearly shown in Formula (IIa-1).
In Formula (IIa-1), R2x represents a monovalent organic group. The monovalent organic group represented by R2x is not particularly limited, and may be, for example, an alkyl group (which preferably has 1 to 10 carbon atoms and may be linear or branched), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an alkenyl group (preferably having 2 to 6 carbon atoms), in which —CH2— may be substituted with one or a combination of two or more selected from the group consisting of —CO—, —NH—, —O—, —S—, —SO—, and —SO2—.
The alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. The substituent is not particularly limited, but is, for example, a halogen atom (preferably a fluorine atom).
In a compound PIIa-1 in which, in Formula (IIa-1) above, the organic cations represented by M61a+ and M61b+ are replaced by H+, the acid dissociation constant a1-7 derived from the acidic moiety represented by A61aH and the acid dissociation constant a1-8 derived from the acidic moiety represented by A61aH correspond to the above-described acid dissociation constant a1 .
The compound PIIa-1 in which, in the compound (IIa-1), the cationic moieties M61a+ and M61b+ in the moiety X are replaced by H+ corresponds to HA61a-L61—N(R2X)-L62-A61bH. The compound PIIa-1 is the same as the acid generated from the compound represented by Formula (IIa-1) upon irradiation with an actinic ray or a radiation.
At least one of M61a+, M61b+, A61a−, A61b−, L61, L62, or R2X may have an acid-decomposable group as a substituent.
In Formula (IIa-2) above, A71a−, A71b−, and A71− have the same definitions and preferred embodiments as in the above-described A11− in Formula (Ia-1). M71a+, M71b+, and M71c+ have the same definitions and preferred embodiments as in the above-described M11+ in Formula (Ia-1).
In Formula (IIa-2) above, L71, L72, and L73 have the same definitions and preferred embodiments as in the above-described L1 in Formula (Ia-1).
When L71 in Formula (IIa-2) represents a divalent linking group represented by Formula (L1), the direct bond (*) on the L111-side in Formula (L1) is preferably bonded to the nitrogen atom clearly shown in Formula (IIa-2). When L72 in Formula (IIa-2) represents a divalent linking group represented by Formula (L1), the direct bond (*) on the L111-side in Formula (L1) is preferably bonded to the nitrogen atom clearly shown in Formula (IIa-2). When L73 in Formula (IIa-2) represents a divalent linking group represented by Formula (L1), the direct bond (*) on the L111-side in Formula (L1) is preferably bonded to the nitrogen atom clearly shown in Formula (IIa-2).
In a compound PIIa-2 in which, in Formula (IIa-2) above, the organic cations represented by M71a+, M71b+, and M71c+ are replaced by H+, the acid dissociation constant a1-9 derived from the acidic moiety represented by A71aH, the acid dissociation constant a1-10 derived from the acidic moiety represented by A71bH, and the acid dissociation constant a1-11 derived from the acidic moiety represented by A71cH correspond to the above-described acid dissociation constant a1.
The compound PIIa-2 in which, in the compound (IIa-2), the cationic moieties M71a+, M71b+, and M71c+ in the moieties X are replaced by H+ corresponds to HA71a-L71—N(L73-A71cH)—L72-A71bH. The compound PIIa-2 is the same as the acid generated from the compound represented by Formula (IIa-2) upon irradiation with an actinic ray or a radiation.
At least one of M71a+, M71b+, M71c+, A71a−, A71b−, A71c−, L71, L72, or L73 may have an acid-decomposable group as a substituent.
The molecular weight of the photoacid generator PG1 is preferably 100 to 10,000, more preferably 100 to 2,500, still more preferably 100 to 1,500.
Another preferred embodiment of the photoacid generator may be a photoacid generator (hereinafter, also referred to as “photoacid generator PG2”) other than the above-described photoacid generator PG1.
The photoacid generator PG2 is preferably, for example, a compound that is represented by “M+ X−” (onium salt compound) and that generates an organic acid due to exposure.
Examples of the organic acid include sulfonic acids (such as aliphatic sulfonic acids, aromatic sulfonic acids, and camphorsulfonic acid), carboxylic acids (such as aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids), carbonylsulfonylimidic acid, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.
In the compound represented by “M+ X−”, M+ represents an organic cation.
The organic cation is, for example, the same as the organic cation represented by MA+ in the group represented by Formula (O1) described in the above section “Onium Salt Group”. Specifically, a cation represented by Formula (ZaI) (cation (ZaI)) or a cation represented by Formula (ZaII) (cation (ZaII)) is preferred.
In the compound represented by “M+ X−”, X− represents an organic anion.
The organic anion is, for example, the same as the organic anion represented by XB− in the group represented by Formula (O2) described in the above section “Onium Salt Group”.
It is also preferable to use, as the photoacid generator PG2, for example, photoacid generators disclosed in paragraphs [0135] to [0171] of WO2018/193954A, paragraphs [0077] to [0116] of WO2020/066824A, and paragraphs [0018] to [0075] and [0334] and [0335] of WO2017/154345A.
The molecular weight of the photoacid generator PG2 is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the resist composition includes a photoacid generator (for example, the photoacid generator PG1 and the photoacid generator PG2), the content thereof is not particularly limited, but is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, still more preferably 5.0 mass % or more relative to the total solid content of the composition. The content is preferably 40.0 mass % or less, more preferably 30.0 mass % or less.
Such photoacid generators may be used alone or in combination of two or more thereof. When two or more photoacid generators are used, the total content thereof is preferably within the above preferred content range.
The resist composition may include an acid diffusion control agent.
The acid diffusion control agent serves as a quencher that traps acid generated from the photoacid generator or the like upon exposure and that suppresses a reaction of the resin X1 or the resin X2 in an unexposed region due to an excess of the generated acid. Examples of the acid diffusion control agent that can be used include a basic compound (CA), a basic compound (CB) that undergoes a decrease or loss of the basicity upon irradiation with an actinic ray or a radiation, a low-molecular-weight compound (CD) having a nitrogen atom and having a group that leaves due to action of acid, and an onium salt compound (CE) having a nitrogen atom in a cationic moiety. In the resist composition, publicly known acid diffusion control agents can be appropriately used. For example, the publicly known compounds disclosed in paragraphs [0627] to [0664] of US2016/0070167A1, paragraphs [0095] to [0187] of US2015/0004544A1, paragraphs [0403] to [0423] of US2016/0237190A1, and paragraphs [0259] to [0328] of US2016/0274458A1 can be suitably used as acid diffusion control agents.
Specific examples of the basic compound (CA) include those described in paragraphs [0132] to [0136] of WO2020/066824A. Specific examples of the basic compound (CB) that undergoes a decrease or loss of the basicity upon irradiation with an actinic ray or a radiation include those described in paragraphs [0137] to [0155] of WO2020/066824A. Specific examples of the low-molecular-weight compound (CD) having a nitrogen atom and having a group that leaves due to action of acid include those described in paragraphs [0156] to [0163] of WO2020/066824A. Specific examples of the onium salt compound (CE) having a nitrogen atom in a cationic moiety include those described in paragraph [0164] of WO2020/066824A.
An onium salt compound that serves as a weak acid relative to a photoacid-generating component (the photoacid generator PG1 and the photoacid generator PG2 are also collectively referred to as a photoacid-generating component) can also be used as the acid diffusion control agent.
In the case where a photoacid-generating component is used in combination with an onium salt compound that generates an acid weaker than the acid generated from the photoacid-generating component, upon collision between the acid generated from the photoacid-generating component upon irradiation with an actinic ray or a radiation and the onium salt compound having an unreacted weak-acid anion, the weak acid is released by salt exchange to generate an onium salt compound having a strong-acid anion. In this process, since the strong acid is exchanged with the weak acid having a lower catalytic ability, the acid is apparently deactivated and acid diffusion can be controlled.
The onium salt compound that serves as a weak acid relative to a photoacid-generating component is preferably a compound represented by any of Formulae (d1-1) to (d1-3) below.
In the formula, R51 is an organic group. The number of carbon atoms is preferably 1 to 30.
Z2c is an organic group. The number of carbon atoms of the organic group is preferably 1 to 30. However, in the organic group represented by Z2c, when a carbon atom is adjacent to SO3− clearly shown in the formula, this carbon atom (a-carbon atom) does not have a fluorine atom and/or a perfluoroalkyl group as a substituent. The a-carbon atom is other than a ring member atom of a ring structure, and is preferably a methylene group. In Z2c, when the atom at the β-position with respect to SO3 is a carbon atom (β-carbon atom), the β-carbon atom also does not have a fluorine atom and/or a perfluoroalkyl group as a substituent.
R52 is an organic group (such as an alkyl group), Y3 is —SO2—, a linear, branched, or cyclic alkylene group, or an arylene group, Y4 is —CO— or —SO2—, and Rf is a hydrocarbon group having a fluorine atom (such as a fluoroalkyl group).
Each M+ is independently an ammonium cation, a sulfonium cation, or an iodonium cation. M+ in Formulae (d1-1) to (d1-3) is, for example, the same as the organic cation represented by MA+ in the group represented by Formula (O1) described in the above section “Onium Salt Group”.
In one embodiment, these cations also preferably have an acid-decomposable group.
A zwitterion may be used as the acid diffusion control agent. The acid diffusion control agent which is a zwitterion preferably has a carboxylate anion, and also preferably has a sulfonium cation or an iodonium cation.
When the resist composition includes an acid diffusion control agent, the content of the acid diffusion control agent (the total content in the case where a plurality of acid diffusion control agents are present) is preferably 0.1 mass % or more, more preferably 1.0 mass % or more relative to the total solid content of the composition. The upper limit value is not particularly limited, but is preferably 30.0 mass % or less, more preferably 20.0 mass % or less, still more preferably 10.0 mass % or less.
In the resist composition, such acid diffusion control agents may be used alone or in combination of two or more thereof.
Compound That Reacts with Polar Group in Resin Due to Action of Exposure, Acid, Base, or Heating (Capping Agent)
When the resist composition includes the resin X2 or includes a resin that is the resin X1 and that has a polar group, the resist composition preferably includes a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent). The polarity of the polar group in the resin decreases due to reaction with the capping agent.
The capping agent may be a compound that itself can bind to the polar group in the resin due to action of exposure, acid, base, or heat, or may be a compound that undergoes a change in structure due to action of exposure, acid, base, or heating and can bind to the polar group in the resin after the structural change.
The capping agent is preferably a compound having a functional group that reacts with the polar group in the resin X1, such as an alcoholic hydroxy group, a phenolic hydroxy group, or a carboxyl group.
The reaction mechanism between the capping agent and the polar group is not particularly limited as long as the reaction proceeds by the action of exposure, acid, base, or heating.
The compound that can react with a polar group such as an alcoholic hydroxy group, a phenolic hydroxy group, or a carboxyl group may be, for example, a tertiary alcohol, a tertiary ether, an epoxide, a vinyl ether, an olefin, a benzyl ether, benzyl alcohol, and a carboxylic acid.
Regarding an example of an embodiment of specific combinations of the polar group and the capping agent, for example, when the polar group is an alcoholic hydroxy group or a carboxyl group, an epoxide or the like is preferred, and when the polar group is a phenolic hydroxy group, a tertiary alcohol, a tertiary ether, an epoxide, a vinyl ether, a benzyl ether, or the like is preferred.
The tertiary alcohol is preferably a compound represented by C(R1)(R2)(R3)OH.
R1 to R3 each independently represent a monovalent organic group.
The monovalent organic group is not particularly limited, but is preferably an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic) in view of a better hydrophobization property after capping. The alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group may further have a substituent. The substituent is, for example, a fluorine atom, an iodine atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group.
The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group may have, as a substituent, a fluorine atom, an iodine atom, a cycloalkyl group, an alkenyl group, an aryl group, or the like. Specific examples of the cycloalkyl group, the alkenyl group, and the aryl group serving as the substituent that the alkyl group may have include the same cycloalkyl group, alkenyl group, and aryl group as those represented by R1 to R3.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, still more preferably a cycloalkyl group having 3 to 10 carbon atoms.
The cycloalkyl group may have, as a substituent, a fluorine atom, an iodine atom, an alkyl group, an alkenyl group, an aryl group, or the like. Specific examples of the alkyl group, the alkenyl group, and the aryl group serving as the substituent that the cycloalkyl group may have include the same alkyl group, alkenyl group, and aryl group as those represented by R1 to R3.
The alkenyl group may be linear or branched and is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 15 carbon atoms, still more preferably an alkenyl group having 2 to 10 carbon atoms.
The alkenyl group may have, as a substituent, a fluorine atom, an iodine atom, an alkyl group, a cycloalkyl group, an aryl group, or the like. Specific examples of the alkyl group, the cycloalkyl group, and the aryl group serving as the substituent that the alkenyl group may have include the same alkyl group, cycloalkyl group, and aryl group as those represented by R1 to R3.
The aryl group may be monocyclic or polycyclic, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably an aryl group having 6 to 10 carbon atoms.
The aryl group may have, as a substituent, a fluorine atom, an iodine atom, an alkyl group, a cycloalkyl group, an alkenyl group, or the like. Specific examples of the alkyl group, the cycloalkyl group, and the alkenyl group serving as the substituent that the aryl group may have include the same alkyl group, cycloalkyl group, and alkenyl group as those represented by R1 to R3.
The tertiary ether is preferably a compound represented by C(R4)(R5)(R6)—O—R7. R4 to R7 each independently represent a monovalent organic group.
Examples of the monovalent organic group represented by R4 to R7 include, but are not particularly limited to, those specifically described as the groups R1 to R3 of the tertiary alcohol.
The epoxide is preferably a compound represented by R8-X.
R8 represents a monovalent organic group.
Examples of the monovalent organic group represented by R8 include, but are not particularly limited to, those specifically described as the groups R1 to R3 of the tertiary alcohol.
X represents an oxiranyl group.
The vinyl ether is a compound represented by CH2CH—O—CHCH2. A hydrogen atom in the vinyl ether may be substituted with a fluorine atom or an iodine atom.
The olefin is not particularly limited, and may be, for example, an unsaturated hydrocarbon compound having 2 to 10 carbon atoms, and specific examples thereof include ethylene, propylene, butylene, butadiene, and pentene. A hydrogen atom in the olefin may have a substituent. The substituent may be, for example, a fluorine atom, an iodine atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Specific examples of the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group serving as the substituent that the olefin may have include the same alkyl group, cycloalkyl group, alkenyl group, and aryl group as those represented by R1 to R3.
The benzyl ether is preferably a compound represented by R8—O—CH2-ph. ph represents a phenyl group that may have a substituent (such as an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 4 carbon atoms).
R8 represents a monovalent organic group.
Examples of the monovalent organic group represented by R8 include, but are not particularly limited to, those specifically described as the groups R1 to R3 of the tertiary alcohol.
One form of the benzyl ether may be a compound having a benzyl ether group as a substituent.
The benzyl ether group is preferably a group formed by removing one of hydrogen atoms on a ring member atom of ph of the compound represented by R8—O—CH2-ph.
The compound having a benzyl ether group as a substituent may be, for example, a compound in which a benzyl ether group is substituted on a polycyclic aromatic ring (such as a 9H-fluorene ring).
Benzyl alcohol is represented by ph-CH2—OH. ph represents a phenyl group.
The carboxylic acid is preferably a compound represented by R9—COOH.
R9 represents a monovalent organic group.
Examples of the monovalent organic group represented by R9 include, but are not particularly limited to, those specifically described as the groups R1 to R3 of the tertiary alcohol.
Whether or not the polarity of the polar group in the resin has decreased after capping with the capping agent can be determined by determining log P (octanol/water partition coefficient) based on the chemical structures of the polar group before and after being subjected to the action of exposure, acid, base, or heating, and determining whether or not there is an increase in log P after reaction with the capping agent. The log P can be calculated using, for example, ChemBioDraw Ultra (Version16.0.14).
When the resist composition includes a capping agent, the content of the capping agent (total content in the case where a plurality of capping agents are present) is preferably 3 mass % or more, more preferably 5 mass % or more relative to the total solid content of the composition. The upper limit value is not particularly limited, but is preferably 60 mass % or less, more preferably 50 mass % or less, still more preferably 40 mass % or less.
In the resist composition, such capping agents may be used alone or in combination of two or more thereof.
Crosslinking Agent (Compound Including Reactive Group B That Reacts with Reactive Group A)
The crosslinking agent may be a low-molecular-weight compound or a high-molecular-weight compound. Note that the low-molecular-weight compound means a compound having a molecular weight of 2,000 or less, and the high-molecular-weight compound means a compound having a molecular weight of more than 2,000.
Note that, when the molecular weight of the crosslinking agent is polydisperse, whether the crosslinking agent is a low-molecular-weight compound or a high-molecular-weight compound is determined depending on whether the weight-average molecular weight is 2,000 or less or more than 2,000.
The crosslinking agent may be a polymer including a predetermined repeating unit.
The type of the reactive group B included in the crosslinking agent is not particularly limited as long as it is a group that reacts with the reactive group A. Examples thereof include the above-described groups, specifically, a hydroxy group, an isocyanate group, a carboxylic group, an epoxy group, a carboxylic anhydride group, an amino group, a vinyl ether group, a sulfonic group, and a group represented by General formula (A) above.
The number of reactive groups in the crosslinking agent is not particularly limited, but is usually 2 or more, preferably 2 to 8, more preferably 2 to 4 from the viewpoint of reactivity.
A preferred embodiment of the crosslinking agent is, for example, a compound represented by General formula (E).
Z—(—L-Y)m General formula (E)
In General formula (E), Y represents a reactive group B. L represents a single bond or a divalent linking group.
The structure of the divalent linking group represented by L is not particularly limited, but may be, for example, a divalent hydrocarbon group (which may be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof, where the divalent saturated hydrocarbon group may be linear, branched, or cyclic, preferably has 1 to 20 carbon atoms, and may be, for example, an alkylene group, and the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and may be, for example, a phenylene group, or which may be an alkenylene group or an alkynylene group), a divalent heterocyclic group, —O—, —S—, —SO2—, —NRc—, —CO—, —COO—, —SO3—, or a group provided by combining two or more of these. Rc represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Z represents an m-valent linking group. Examples of the m-valent linking group include a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom, an m-valent aliphatic hydrocarbon group, an m-valent aromatic hydrocarbon group, and an m-valent heterocyclic group.
Examples of the m-valent aromatic hydrocarbon group include divalent to hexavalent aromatic hydrocarbon groups, such as a group represented by General formula (L1). In General formula (L1), * represents a bonding site, Y-L-groups are bonded to two to six *'s among six *'s, and a hydrogen atom or an organic group is bonded to the remaining *'s. For example, in the case of a valence of 3, Y-L-groups are bonded to three *'s, and a hydrogen atom or an organic group is bonded to each of the remaining three *'s. The type of the organic group is not particularly limited, and the organic group may be a publicly known group (such as an alkyl group).
Examples of the m-valent heterocyclic group include groups represented by General formula (L2) to General formula (L4).
General formula (L1) General formula (L2) General formula (L3) General formula (L4)
When the crosslinking agent is a polymer, the polymer preferably has a repeating unit having the reactive group B.
Such crosslinking agents may be used alone or in combination of two or more thereof.
The content of the crosslinking agent is preferably 2 to 50 mass %, more preferably 5 to 40 mass % relative to the total solid content of the composition.
The mixing mass ratio between the resin containing the reactive group A and the crosslinking agent (mass of resin containing reactive group A/mass of crosslinking agent) is not particularly limited, but is preferably 0.1 to 10, and more preferably 0.2 to 4, from the viewpoint of more excellent effects of the present invention.
The resist composition may include, in addition to the resin X1 and the resin X2, a hydrophobic resin different from the resin X1 and the resin X2.
The hydrophobic resin is preferably designed so as to be localized in the surface of a resist film. However, unlike surfactants, the hydrophobic resin does not necessarily need to have a hydrophilic group in the molecule, and does not necessarily contribute to homogeneous mixing of a polar substance and a nonpolar substance.
Advantages due to the addition of the hydrophobic resin are, for example, the control of static and dynamic contact angles at the surface of the resist film for water, and the suppression of outgassing.
From the viewpoint of localization in the surface layer of the film, the hydrophobic resin preferably has one or more, more preferably two or more selected from the group consisting of a “fluorine atom”, a “silicon atom”, and a “CH3 moiety included in a side chain moiety of the resin”. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. The resin may have such a group in the main chain or, as a substituent, in a side chain.
Examples of the hydrophobic resin include compounds described in paragraphs [0275] to [0279] of WO2020/004306A.
When the resist composition includes a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass % relative to the total solid content of the composition.
The resist composition may include a surfactant. The resist composition including a surfactant enables the formation of a pattern having higher adhesiveness and less development defects.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Examples of the fluorine-based and/or silicon-based surfactant include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954A.
Such surfactants may be used alone or in combination of two or more thereof.
When the resist composition includes a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass % relative to the total solid content of the composition.
The resist composition may include a solvent.
The solvent preferably includes at least one of (M1) a propylene glycol monoalkyl ether carboxylate or (M2) at least one selected from the group consisting of a propylene glycol monoalkyl ether, a lactate, an acetate, an alkoxypropionate, a chain ketone, a cyclic ketone, a lactone, and an alkylene carbonate. The solvent may further include a component other than the components (M1) and (M2).
The inventors of the present invention have found that, in the case of using such a solvent and the above-described resin in combination, coatability of the resulting composition is improved, and a pattern having a smaller number of development defects can be formed. The reason for this is not necessarily clear; however, the inventors of the present invention consider that this is due to the fact that such solvents are well-balanced in terms of solubility of the resin described above, boiling point, and viscosity, and thus, for example, unevenness of the film thickness of the composition film and the generation of precipitates during spin coating can be suppressed.
Details of the component (M1) and the component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306A.
When the solvent further includes a component other than the components (M1) and (M2), the content of the component other than the components (M1) and (M2) is preferably 5 to 30 mass % relative to the total amount of the solvent.
In the resist composition, the content of the solvent is determined such that the concentration of solid content becomes preferably 0.5 to 30 mass %, more preferably 1 to 20 mass %. In such a case, the resist composition has further improved coatability.
The resist composition may further include a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorbent, and/or a compound that improves solubility in developers (for example, a phenolic compound having a molecular weight of 1,000 or less or an alicyclic or aliphatic compound including a carboxylic group).
The resist composition may further include a dissolution-inhibiting compound. Herein, the “dissolution-inhibiting compound” refers to a compound that has a molecular weight of 3,000 or less and that is decomposed due to action of acid to undergo a decrease in the degree of solubility in organic-based developers.
The resist composition is suitably used as a photosensitive composition for EUV light.
The EUV light has a wavelength of 13.5 nm, which is shorter than the wavelength of ArF (wavelength 193 nm) light and the like, and thus provides a smaller number of incident photons when exposure is performed with the same sensitivity. Therefore, “photon shot noise”, which is stochastic variations in the number of photons, exerts a great influence, resulting in degradation of LER and bridge defects. In order to reduce the photon shot noise, a method of increasing the exposure dose to increase the number of incident photons may be employed; however, this method is a trade-off with the demand for higher sensitivity.
When a value A determined by Expression (1) below is large, a resist film formed from the resist composition has high absorption efficiency for EUV light and electron beams, which is effective to reduce the photon shot noise. The value A represents the absorption efficiency of the resist film for EUV light and electron beams based on mass proportions.
A=([H]x0.04+[C]×1.0+[N]×2.1+[0]×3.6+[F]×5.6+[S]×1.5+[I]×39.5)/([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) Expression (1)
The value A is preferably 0.120 or more. The upper limit is not particularly limited; however, if the value A is excessively large, the transmittances of the resist film for EUV light and electron beams decrease, the optical image profile in the resist film deteriorates, and as a result, a good pattern shape is less likely to be obtained. Thus, the value A is preferably 0.240 or less, more preferably 0.220 or less.
In Expression (1), [H] represents the molar ratio of hydrogen atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content, [C] represents the molar ratio of carbon atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content, [N] represents the molar ratio of nitrogen atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content, [O] represents the molar ratio of oxygen atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content, [F] represents the molar ratio of fluorine atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content, [S] represents the molar ratio of sulfur atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content, and [I] represents the molar ratio of iodine atoms derived from the whole solid content in the actinic ray-sensitive or radiation-sensitive resin composition relative to all the atoms of the whole solid content.
For example, when the resist composition includes a resin X1, a photoacid generator, an acid diffusion control agent, and a solvent, the resin X1, the photoacid generator, and the acid diffusion control agent correspond to the solid content. That is, all the atoms of the whole solid content correspond to the total of all the atoms derived from the resin X1, all the atoms derived from the photoacid generator, and all the atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the whole solid content relative to all the atoms of the whole solid content, and, in the description based on the above example, [H] represents the molar ratio of the total of the hydrogen atoms derived from the resin X1, the hydrogen atoms derived from the photoacid generator, and the hydrogen atoms derived from the acid diffusion control agent relative to the total of all the atoms derived from the resin X1, all the atoms derived from the photoacid generator, and all the atoms derived from the acid diffusion control agent.
When the structures and contents of constituent components of the whole solid content in the resist composition are known, the value A can be determined by calculating the ratio of the numbers of atoms contained. Even when the constituent components are not known, for a resist film formed by evaporating the solvent component of the resist composition, the ratio of the numbers of constituent atoms can be calculated by an analytical method such as elemental analysis.
It is also preferable that the resist composition further include a resin Y1 different from the resin X1 and the resin X2. That is, it is also preferable that the resist composition satisfy the requirement A1 or the requirement A2 described above and include a resin Y1.
The resin X1 and the resin X2 have the same definitions and preferred embodiments as in the resin X1 and the resin X2, respectively, included in the resist composition (resist composition of the first exemplary embodiment) described above.
Components other than the resin X1 and the resin X2, the contents thereof, and the like are the same as those of the resist composition (resist composition of the first exemplary embodiment) described above, and preferred embodiments thereof are also the same.
Preferred embodiments of the resin Y1 will be described below.
An embodiment (Embodiment 1) of the resin Y1 is, for example, an embodiment in which the resin has an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating (interactive group).
An embodiment (Embodiment 2) of the resin Y1 is, for example, an embodiment in which the resin has an onium salt group that is decomposed due to action of exposure.
An embodiment (Embodiment 3) of the resin Y1 is, for example, an embodiment in which the resin undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating. One form of Embodiment 3 may be an embodiment in which the decrease in molecular weight is caused by the decomposition of the main chain due to action of exposure.
An embodiment (Embodiment 4) of the resin Y1 is, for example, an embodiment in which the resin has a reactive group A.
An embodiment (Embodiment 5) of the resin Y1 is, for example, an embodiment in which the resin has a reactive group A and a reactive group B that reacts with the reactive group A.
An embodiment (Embodiment 6) of the resin Y1 is, for example, an embodiment to which at least two or more of Embodiments 1 to 5 above correspond. Such an embodiment may be, for example, an embodiment in which the resin has an interactive group and undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating.
The onium salt group, the interactive group, the reactive group A, and the reactive group B are as described above.
Preferably, the resin Y1 does not include a polar group (provided that when used in combination with a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent)) or a polarity-decreasing group. Note that when a component corresponding to the capping agent is not included in the composition, the resin Y1 also preferably includes a polar group.
In Embodiment 5, since the resin Y1 has the reactive group B in its molecule, the composition may not include a crosslinking agent including the reactive group B.
Preferred embodiments of the resin Y1 will be described below.
A first preferred embodiment of the resin Y1 may include resins having the following configurations.
Resin Y1A: A resin including one or more repeating units selected from the group consisting of a repeating unit having an onium salt group, a repeating unit having an interactive group, a repeating unit having a reactive group A, and a repeating unit having a reactive group B (provided that when a repeating unit having a reactive group B is included, a repeating unit having a reactive group A is also included).
Resin Y1B: A resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating.
Resin Y1C: A resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heat and that has one or more groups selected from the group consisting of an onium salt group, an interactive group, a reactive group A, and a reactive group B (provided that when the resin has a reactive group B, the resin also has a reactive group A).
The resins Y1A to Y1C will be described below.
The resin Y1A includes one or more repeating units selected from the group consisting of a repeating unit having an onium salt group, a repeating unit having an interactive group, a repeating unit having a reactive group A, and a repeating unit having a reactive group B.
Examples of the repeating unit having an onium salt group include embodiments of the above-described repeating unit represented by Formula (T1) described in the section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”, where R51 represents an onium salt group.
Examples of the repeating unit having an interactive group include embodiments of the above-described repeating unit represented by Formula (T1) described in the section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”, where R51 represents an interactive group.
Examples of the repeating unit having a reactive group A include embodiments of the above-described repeating unit represented by Formula (T1) described in the section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”, where R51 represents a reactive group A.
Examples of the repeating unit having a reactive group B include embodiments of the above-described repeating unit represented by Formula (T1) described in the section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”, where R51 represents a reactive group B.
When the resin Y1A includes a repeating unit having an onium salt group, a repeating unit having an interactive group, a repeating unit having a reactive group A, and/or a repeating unit having a reactive group B, the content of the repeating unit (total content in the case of a plurality of repeating units) is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin Y1A. The upper limit value thereof is, for example, 100 mol % or less, preferably 90 mol % or less, more preferably 80 mol % or less.
When the resin Y1A includes a repeating unit having an onium salt group, the content of the repeating unit is preferably 2 mol % or more, more preferably 5 mol % or more relative to all the repeating units in the resin Y1A. The upper limit value thereof is, for example, 100 mol % or less, preferably 90 mol % or less, more preferably 80 mol % or less.
When the resin Y1A includes a repeating unit having an interactive group, the content of the repeating unit is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin Y1A. The upper limit value thereof is, for example, 100 mol % or less, preferably 90 mol % or less, more preferably 80 mol % or less.
When the resin Y1A includes a repeating unit having a reactive group A, the content of the repeating unit is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin Y1A. The upper limit value thereof is, for example, 100 mol % or less, preferably 90 mol % or less, more preferably 80 mol % or less.
When the resin Y1A includes a repeating unit having a reactive group B, the content of the repeating unit is preferably 5 mol % or more, more preferably 10 mol % or more relative to all the repeating units in the resin Y1A. The upper limit value thereof is preferably 90 mol % or less, more preferably 80 mol % or less.
When the composition does not include the compound that reacts with a polar group due to action of exposure, acid, base, or heating (capping agent), the resin Y1A also preferably includes a repeating unit having a polar group.
The resin Y1A may include a repeating unit other than the above-described repeating units. Examples of the other repeating unit include the other repeating units excluding “the repeating unit having an interactive group, an onium salt group, or a polar group” and “the repeating unit having a reactive group A or a reactive group B” described in the above section “Other Repeating Units” of the section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”. When the resin Y1A optionally includes the repeating units described above, the contents thereof are also the same as the corresponding contents described in the above section “First Preferred Embodiment of Resin X1 (Main Chain Non-Decomposition-Type Resin)”.
The resin Y1B is a resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating.
The resin Y1B preferably corresponds to a so-called main chain scission-type resin that undergoes a decrease in molecular weight caused by the scission of the main chain due to action of exposure, acid, base, or heating.
Examples of the form of the resin Y1B which is a main chain scission-type resin include the resins described in the section “Second Preferred Embodiment of Resin X1 (Main Chain Decomposition-Type Resin)”, in which each substituent does not include a polarity-decreasing group, an interactive group, an onium salt group, a polar group, a reactive group A, or a reactive group B.
The resin Y1C is a resin that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heat and that has one or more groups selected from the group consisting of an interactive group, an onium salt group, a reactive group A, and a reactive group B.
The resin Y1C preferably corresponds to a so-called main chain scission-type resin that undergoes a decrease in molecular weight caused by the scission of the main chain due to action of exposure, acid, base, or heating.
Examples of the form of the resin Y1C which is a main chain scission-type resin include the resins described in the section “Second Preferred Embodiment of Resin X1 (Main Chain Decomposition-Type Resin)”, in which each substituent does not include a polarity-decreasing group or a polar group (provided that when used in combination with a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent)), and at least one substituent of the resin is one selected from the group consisting of an interactive group, an onium salt group, a reactive group A, and a reactive group B.
Note that when a component corresponding to the capping agent is not included in the composition, the resin Y1C also preferably includes a polar group.
The resin Y1 can be synthesized by an ordinary method (for example, radical polymerization).
The resin Y1 preferably has a weight-average molecular weight of 1,000 to 200,000, more preferably 2,500 to 150,000, still more preferably 3,000 to 50,000 in terms of polystyrene as determined by the GPC method. When the weight-average molecular weight is within the above numerical range, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, deterioration of developing performance and deterioration of film-forming properties due to an increase in viscosity can also be further suppressed.
The dispersity (molecular weight distribution) of the resin Y1 is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, still more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and the resist shape.
In the resist composition, the content of the resin Y1 is preferably 5 to 95 mass %, more preferably 10 to 90 mass %, still more preferably 20 to 80 mass % relative to the total solid content of the composition.
Such resins Y1 may be used alone or in combination of two or more thereof. When two or more resins are used, the total content thereof is preferably within the above preferred content range.
In the resist composition, the content of the resin Y1 is preferably 5 to 95 mass %, more preferably 10 to 90 mass %, still more preferably 20 to 80 mass % relative to the total content of the resin X1, the resin X2, and the resin Y1.
A pattern forming method according to the present invention has steps below:
The procedure of each of the steps will be described in detail below.
The step 1 is a step of forming a resist film on a substrate using a resist composition.
The resist composition corresponds to the above-described resist composition.
The method for forming a resist film on a substrate using a resist composition is, for example, a method of applying a resist composition onto a substrate.
Prior to the application, the resist composition is preferably subjected to filtration through a filter, if necessary. The filter preferably has a pore size of 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. The filter is preferably formed of polytetrafluoroethylene, polyethylene, or nylon.
The resist composition can be applied onto a substrate (for example, formed of silicon and covered with silicon dioxide) as used in the production of an integrated circuit element by a suitable coating method using a spinner, a coater, or the like. The coating method is preferably spin-coating using a spinner. The rotational speed during spin coating using a spinner is preferably 1,000 to 3,000 rpm.
After the application of the resist composition, the substrate may be dried to form a resist film. Note that, as needed, an underlying film (an inorganic film, an organic film, or an antireflection film) may be formed as an underlayer of the resist film.
The drying method may be, for example, a method of performing drying by heating. The heating can be performed using means included in an ordinary exposure apparatus and/or an ordinary developing apparatus, or may be performed using a hot plate or the like. The heating temperature is preferably 80° C. to 150° C., more preferably 80° C. to 140° C., still more preferably 80° C. to 130° C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, still more preferably 60 to 600 seconds.
The film thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint that a fine pattern with higher accuracy can be formed. In particular, in the case of EUV exposure, the film thickness of the resist film is more preferably 10 to 65 nm, still more preferably 15 to 50 nm. In the case of ArF liquid immersion exposure, the film thickness of the resist film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.
As an upper layer of the resist film, a topcoat may be formed using a topcoat composition.
The topcoat composition preferably does not mix with the resist film and can be uniformly applied as an upper layer of the resist film. The topcoat is not particularly limited, a publicly known topcoat can be formed by a publicly known method, and, for example, a topcoat can be formed on the basis of the description of paragraphs [0072] to [0082] of JP2014-059543A.
For example, a topcoat including a basic compound and described in JP2013-61648A is preferably formed on the resist film. Specific examples of the basic compound that can be included in the topcoat include basic compounds that may be included in the resist composition.
The topcoat also preferably includes a compound including at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxy group, a thiol group, a carbonyl bond, and an ester bond.
The step 2 is a step of exposing the resist film.
The exposure method may be a method of irradiating the formed resist film with an actinic ray or a radiation through a predetermined mask.
Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far-ultraviolet light, extreme ultraviolet light, X-rays, and an electron beam. The actinic ray or radiation is preferably far-ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, particularly preferably 1 to 200 nm, and specific examples thereof include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and an electron beam.
After the exposure, before development, post-exposure heat treatment (also referred to as post-exposure bake) is preferably performed. The post-exposure heat treatment accelerates the reaction in exposed regions to provide higher sensitivity and a better pattern shape.
The heating temperature is preferably 80° C. to 150° C., more preferably 80° C. to 140° C., still more preferably 80° C. to 130° C.
The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, still more preferably 30 to 120 seconds.
The heating can be performed using means included in an ordinary exposure apparatus and/or an ordinary developing apparatus, or may be performed using a hot plate or the like.
The step 3 is a step of developing the exposed resist film with a developer to form a pattern.
The developer is a developer including an organic solvent (hereinafter, also referred to as an organic-based developer).
Examples of the developing method include a method of immersing the substrate for a predetermined time in a tank filled with a developer (dipping method), a method of puddling a developer over a surface of the substrate using surface tension and allowing the developer to stand for a predetermined time to perform development (puddling method), a method of spraying a developer onto a surface of the substrate (spraying method), and a method of continuously ejecting a developer over the substrate rotating at a constant rate, while scanning a developer ejection nozzle at a constant rate, (dynamic dispensing method).
After the step of performing development, a step of stopping the development by performing replacement with another solvent may be performed.
The development time is not particularly limited as long as the resin in unexposed regions is sufficiently dissolved within the time, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developer is preferably 0° C. to 50° C., more preferably 15° C. to 35° C.
The organic-based developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
A plurality of such solvents may be mixed together, or such a solvent may be mixed with a solvent other than those described above or water. The developer as a whole preferably has a moisture content of less than 50 mass %, more preferably less than 20 mass %, still more preferably less than 10 mass %, and particularly preferably contains substantially no moisture.
In the organic-based developer, the content of the organic solvent relative to the total amount of the developer is preferably 50 mass % or more and 100 mass % or less, more preferably 80 mass % or more and 100 mass % or less, still more preferably 90 mass % or more and 100 mass % or less, particularly preferably 95 mass % or more and 100 mass % or less.
The pattern forming method preferably includes, after the step 3, a step of performing washing with a rinsing liquid.
The rinsing liquid used in the rinsing step after the developing step using an organic-based developer is not particularly limited as long as it does not dissolve the pattern, and may be a solution including a typical organic solvent. The rinsing liquid used is preferably a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents.
The method of performing the rinsing step is not particularly limited, and examples thereof include a method of continuously ejecting a rinsing liquid onto the substrate rotating at a constant rate (spin-coating method), a method of immersing the substrate for a predetermined time in a tank filled with a rinsing liquid (dipping method), and a method of spraying a rinsing liquid onto a surface of the substrate (spraying method).
The pattern forming method according to the present invention may include a heating step (Post Bake) performed after the rinsing step. In this step, the developer and the rinsing liquid remaining between patterns and inside patterns are removed by baking. In addition, this step also provides an effect of annealing the resist pattern to suppress roughening of surfaces of the patterns. The heating step after the rinsing step is performed usually at 40° C. to 250° C. (preferably 90° C. to 200° C.) for usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
The formed pattern may be used as a mask to perform etching treatment of the substrate. Specifically, the pattern formed in the step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate), thereby forming a pattern in the substrate.
The method of processing the substrate (or the underlayer film and the substrate) is not particularly limited, but is preferably a method of subjecting the substrate (or the underlayer film and the substrate) to dry etching using the pattern formed in the step 3 as a mask, thereby forming a pattern in the substrate. The dry etching is preferably oxygen plasma etching.
The resist composition and various materials used in the pattern forming method according to the present invention (for example, the solvent, the developer, the rinsing liquid, the antireflection film-forming composition, and the topcoat-forming composition) preferably do not include impurities such as metal. The content of impurities included in such materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, most preferably 1 mass ppt or less. Examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
The method of removing impurities, such as metal, from the various materials may be, for example, filtration using a filter. Details of filtration using a filter are described in paragraph [0321] of WO2020/004306A.
Examples of the method of reducing the amount of impurities such as metal included in the various materials include a method of selecting, as raw materials constituting the various materials, raw materials having low metal contents, a method of subjecting raw materials constituting the various materials to filter filtration, and a method of performing distillation under conditions in which contamination is minimized by, for example, lining the interior of apparatuses with Teflon (registered trademark).
Instead of filter filtration, an adsorbing material may be used to remove impurities. Alternatively, filter filtration and an adsorbing material may be used in combination. Publicly known adsorbing materials can be used as such adsorbing materials, and, for example, inorganic adsorbing material such as silica gel and zeolite, and organic adsorbing materials such as activated carbon can be used. In order to reduce the amount of impurities such as metal included in the various materials, mixing of metal impurities in the production process needs to be prevented. Whether or not metal impurities are sufficiently removed from the production apparatuses can be determined by measuring the content of metal components included in a washing liquid that has been used for washing the production apparatuses. The content of metal components included in the washing liquid that has been used is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, still more preferably 1 mass ppt or less.
A conductive compound may be added to an organic treatment liquid such as a rinsing liquid in order to prevent failure of a chemical liquid pipe and various parts (such as a filter, an O-ring, and a tube) caused by electrostatic charging and subsequent electrostatic discharging. The conductive compound is not particularly limited, but may be, for example, methanol. The amount of addition is not particularly limited, but is preferably 10 mass % or less, more preferably 5 mass % or less from the viewpoint of maintaining preferred developing performance or rinsing performance.
Examples of the chemical liquid pipe that can be used include various pipes made of SUS (stainless steel) or a material coated with polyethylene, polypropylene, or a fluororesin (such as polytetrafluoroethylene or a perfluoroalkoxy resin) subjected to antistatic treatment. Similarly, for the filter and the O-ring, polyethylene, polypropylene, or a fluororesin (such as polytetrafluoroethylene or a perfluoroalkoxy resin) subjected to antistatic treatment can be used.
The present invention also relates to a method for producing an electronic device, the method including the above-described pattern forming method, and an electronic device produced by the production method.
The electronic device according to the present invention is suitably mounted on electric or electronic devices (such as household appliances, OA (Office Automation), media-related devices, optical devices, and communication devices).
The present invention also relates to a resist composition.
The resist composition according to the present invention corresponds to one form of the resist composition described above. Accordingly, specific embodiments of components and specific contents of the components are respectively the same as specific embodiments of components and specific contents of the components described in the above resist composition.
Resist compositions according to the present invention will be described below.
A resist composition satisfying any one of requirements A11 to A14 below.
Requirement A11: The composition includes a resin X 11 having a group that decreases polarity due to action of exposure, acid, base, or heating and an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating, and
Requirement A12: The composition includes a resin X12 having a polar group and an interactive group that forms an interaction with an onium salt compound and that is released from the interaction due to action of exposure, acid, base, or heating,
Requirement A13: The composition includes a resin X1 having a group that decreases polarity due to action of exposure, acid, base, or heating,
Requirement A14: The composition includes a resin X2 having a polar group,
A resist composition satisfying any one of requirements A21 to A23 below.
Requirement A21: The composition includes a resin X21 having a group that decreases polarity due to action of exposure, acid, base, or heating and an onium salt group that is decomposed due to action of exposure.
Requirement A22: The composition includes a resin X22 having a polar group and an onium salt group that is decomposed due to action of exposure, and a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent).
Requirement A23: The composition satisfies a requirement A1 or a requirement A2 below and includes a resin Y21 having an onium salt group that is decomposed due to action of exposure.
Requirement A1: The composition includes a resin X1 having a group that decreases polarity due to action of exposure, acid, base, or heating.
Requirement A2: The composition includes a resin X2 having a polar group, and a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent).
A resist composition satisfying a requirement A1 or a requirement A2 below and including a resin Y31 that undergoes a decrease in molecular weight due to action of exposure, acid, base, or heating.
Requirement A1: The composition includes a resin X1 having a group that decreases polarity due to action of exposure, acid, base, or heating.
Requirement A2: The composition includes a resin X2 having a polar group, and a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent).
A resist composition satisfying any one of requirements A41 to A45 below.
Requirement A41: The composition includes a resin X41 having a group that decreases polarity due to action of exposure, acid, base, or heating and a reactive group A, and
Requirement A42: The composition includes a resin X42 having a group that decreases polarity due to action of exposure, acid, base, or heating, a reactive group A, and a reactive group B that reacts with the reactive group A, and
Requirement A43: The composition includes a resin X43 having a polar group and a reactive group A,
Requirement A44: The composition is a composition including a resin X44 having a polar group, a reactive group A, and a reactive group B that reacts with the reactive groups A, and
Requirement A45: The composition satisfies a requirement A1 or a requirement A2 below and satisfies a requirement A46 or a requirement A47 below.
Requirement A1: The composition includes a resin X1 having a group that decreases polarity due to action of exposure, acid, base, or heating.
Requirement A2: The composition includes a resin X2 having a polar group, and a compound that reacts with the polar group due to action of exposure, acid, base, or heating (capping agent).
Requirement A46: The composition includes a resin Y41 having a reactive group A, and
Requirement A47: The composition includes a resin Y42 having a reactive group A and a reactive group B that reacts with the reactive group A, and
Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, amounts used, ratios, details of processes, procedures of processes, and the like described in the following Examples may be appropriately changed without departing from the spirit and scope of the present invention. Accordingly, the scope of the present invention should not be construed as being limited to the following Examples.
Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition Resin
Resins P-1 to 15 shown in Table 2 will be described below.
The resins P-1 to P-11 correspond to specific resins having a polarity-decreasing group. The resin P-14 used together with a capping agent corresponds to a resin having a polar group.
The resins P-1 to P-15 used were resins synthesized in accordance with a method for synthesizing the resin P-1 (Synthesis Example 1) described later or by a known method. Table 1 shows the compositional ratio of repeating units shown below (mol % ratio, corresponding to the order from the left), the weight-average molecular weight (Mw), and the dispersity (Mw/Mn).
The weight-average molecular weight (Mw) and the dispersity (Mw/Mn) of each of the resins P-1 to P-15 were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene-equivalent values). The compositional ratio (mol % ratio) of the resin was measured by 13C-NMR (Nuclear Magnetic Resonance).
In a nitrogen stream, 194.3 g of cyclohexanone was placed in a three-necked flask and heated to 80° C. Subsequently, a solution prepared by dissolving, sequentially from the left, 12.0 g and 40.7 g of monomers corresponding to the repeating units of the resin P-1 shown below and a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation, 3.17 g) in 105 g of cyclohexanone was added dropwise thereto over six hours. After completion of the dropwise addition, the resulting reaction solution was further reacted at 80° C. for two hours. The reaction solution was left to cool and then added dropwise to a liquid mixture of methanol:water over 20 minutes. Subsequently, a powder precipitated by the dropwise addition was collected by filtration and dried to obtain the resin P-1 (31.6 g). The compositional ratio (molar ratio) of the repeating units as determined by NMR (Nuclear Magnetic Resonance) was 30/70. The obtained resin P-1 was found to have a weight-average molecular weight of 8,000 in terms of standard polystyrene, and a dispersity (Mw/Mn) of 1.6.
The structural formulae of the resins P-1 to P-15 listed in Table 1 are as follows.
The structures of photoacid generators (PAG-1 to PAG-7) shown in Table 2 are as follows.
The structures of quenchers (Q-1 to Q-3) shown in Table 2 are as follows.
Additives (X-1 and X-2) shown in Table 2 are as follows.
Surfactants shown in Table 2 are as follows.
Solvents shown in Table 2 are as follows.
The components shown in Table 2 below were mixed. Subsequently, the resulting liquid mixtures were each filtered through a polyethylene filter having a pore size of 0.03 μm to prepare resin compositions (resist compositions). The concentration of solid content of each resist composition was appropriately adjusted such that the resist composition could be applied in a film thickness shown in Tables 3 and 4 below. The solid content means all components other than the solvents. The obtained resist compositions were used in Examples and Comparative Examples.
Table 2 is shown below.
In Table 2, in the column “Remarks (Configuration of resin)”, the column “Presence or absence of interactive group or onium salt group” indicates whether or not the resist composition includes a resin having an interactive group that is released from an interaction with an onium salt compound due to action of exposure, acid, base, or heating or a resin having an onium salt group that is decomposed due to exposure, “A” indicates the case where the resist composition includes such a resin, and “B” indicates the case where the resist composition does not include such a resin. Note that even when the resin X1 has a group corresponding to an interactive group (for example, a phenolic hydroxy group), the case where the composition does not include an onium salt compound that can interact with the interactive group is denoted by “B”.
“Presence or absence of polar group” of the Remarks column in Table 2 indicates whether or not the resist composition includes a resin having a polar group, “A” indicates the case where the resist composition includes such a resin, and “B” indicates the case where the resist composition does not include such a resin. Note that even when the resin has a group corresponding to a polar group (for example, a phenolic hydroxy group), the case where the composition does not include a capping agent that can react with the polar group is denoted by “B”.
“Presence or absence of reactive group A” of the Remarks column in Table 2 indicates whether or not the resist composition includes a resin having a reactive group A, “A” indicates the case where the resist composition includes such a resin, and “B” indicates the case where the resist composition does not include such a resin. Note that even when the resin has a group corresponding to a reactive group A, the case where the composition does not include a crosslinking agent that can react with the reactive group A is denoted by “B”.
The column “Presence or absence of resin that undergoes decrease in molecular weight” indicates whether or not the resist composition includes a resin that undergoes a decrease in molecular weight caused by decomposition due to action of exposure, acid, base, or heating, “A” indicates the case where the resist composition includes such a resin, and “B” indicates the case where the resist composition does not include such a resin.
The column “Whether or not corresponding to resin mixture type” indicates whether or not the resist composition corresponds to a resin mixture type including a resin other than the specific resin (corresponding to the resin (A) in Table 2), “A” indicates the case where the resist composition corresponds to such a resin mixture type, and “B” indicates the case where the resist composition does not correspond to such a resin mixture type.
An underlayer film-forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a film thickness of 20 nm. A resist film was formed thereon under the conditions (film thickness and PreBake) described in Table 3 using the resist composition shown in Table 2. Thus, a silicon wafer having a resist film was formed.
The silicon wafer having the resist film obtained by the above-described procedure was subjected to pattern irradiation using an EUV exposure apparatus (manufactured by Exitech Ltd., Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). A mask having a line size of 20 nm and line:space=1:1 was used as a reticle. Subsequently, only in the case where there is a description, baking (Post Exposure Bake; PEB) was performed under the conditions shown in Table 3 below; development was then performed with a developer shown in Table 3 below by puddling for 30 seconds; only in the case where there is a description, rinsing was performed by pouring a rinsing liquid shown in Table 3 below for 10 seconds while the wafer was rotated at a rotational speed of 1,000 rpm; and the wafer was then rotated at a rotational speed of 4,000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 40 nm.
The line width of the line-and-space pattern was measured with a critical dimension-scanning electron microscope (SEM: Scanning Electron Microscope (CG-4100, manufactured by Hitachi High-Tech Corporation)) while changing the exposure dose, and an exposure dose at which the line width became 20 nm was determined, and this was defined as an optimum exposure dose (mJ/cm2). Note that this evaluation was conducted so that the interval from the end of exposure to the start of development treatment was controlled to be three minutes.
Evaluation of Change in Line Width When Waiting Time before Development Varies
Wafer processing was performed by the method described above except that the interval from the end of exposure to the start of developing treatment was controlled to be 60 minutes, and the line width of the obtained line-and-space pattern was measured and defined as CD1. A change in the line width ΔCD1 when the waiting time before development varied was calculated by the following formula.
ΔCD1(nm)=CD1(nm)−20(nm)
A smaller absolute value of ΔCD1 indicates a better performance.
From the results shown in Table 3, it is apparent that the patterns formed from the resist compositions of Examples are excellent in terms of change in line width when the waiting time before development varies.
In comparison with Examples 1 and 2 using resist compositions including none of a resin having an interactive group that is released from an interaction with an onium salt compound due to action of exposure, acid, base, or heating, a resin having an onium salt group that is decomposed due to exposure, a resin that undergoes a decrease in molecular weight caused by decomposition due to action of exposure, acid, base, or heating, and a resin having a reactive group A in which a bond formed by a reactive group B included in a crosslinking agent and the reactive group A is broken by action of exposure, acid, base, or heating, Examples 3 to 16 using resist compositions including at least one of a resin having an interactive group that is released from an interaction with an onium salt compound due to action of exposure, acid, base, or heating, a resin having an onium salt group that is decomposed due to exposure, a resin that undergoes a decrease in molecular weight caused by decomposition due to action of exposure, acid, base, or heating, or a resin having a reactive group A in which a bond formed by a reactive group B included in a crosslinking agent and the reactive group A is broken by action of exposure, acid, base, or heating were confirmed to further suppress the variation in the development waiting time.
An antireflection film-forming composition DUV44 (manufactured by Brewer Science, Inc.) was applied onto a mask blank having an outermost surface made of Cr and a size of 152 mm square using ACT™ (manufactured by Tokyo Electron Ltd.) and baked at 205° C. for 60 seconds to form an underlayer film having a film thickness of 60 nm. A resist film was formed thereon under the conditions (film thickness and PreBake) described in Table 4 using the resist composition described in Table 2. Thus, a mask blank having a resist film was formed.
The mask blank having the resist film obtained by the above procedure was subjected to pattern irradiation using an electron beam exposure apparatus (manufactured by NuFlare Technology, Inc., EBM-9000, accelerating voltage: 50 kV). At this time, patterning was performed so as to form a line-and-space of 1:1. Subsequently, only in the case where there is a description, baking (Post Exposure Bake; PEB) was performed under the conditions shown in Table 4 below; development was then performed with a developer shown in Table 4 below by puddling for 30 seconds; only in the case where there is a description, rinsing was performed by pouring a rinsing liquid shown in Table 4 below for 10 seconds while the wafer was rotated at a rotational speed of 1,000 rpm; and the wafer was then rotated at a rotational speed of 4,000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 40 nm.
The line width of the line-and-space pattern was measured with a critical dimension-scanning electron microscope (SEM: Scanning Electron Microscope (E3630, manufactured by ADVANTEST CORPORATION)) while changing the exposure dose, and an exposure dose at which the line width became 20 nm was determined, and this was defined as an optimum exposure dose (μC/cm2). Note that this evaluation was conducted so that the interval from the end of patterning to the start of development treatment was controlled to be three minutes.
Evaluation of Change in Line Width When Waiting Time before Development Varies
Blanks processing was performed by the method described above except that the interval from the end of patterning to the start of developing treatment was controlled to be 60 minutes, and the line width of the obtained line-and-space pattern was measured and defined as CD2. A change in the line width ΔCD2 when the waiting time before development varied was calculated by the following formula.
ΔCD2(nm)=CD2(nm)−20(nm)
A smaller absolute value of ΔCD2 indicates a better performance.
From the results shown in Table 4, it is apparent that the patterns formed from the resist compositions of Examples are excellent in terms of change in line width when the waiting time before development varies.
In comparison with Examples 17 and 18 using resist compositions including none of a resin having an interactive group that is released from an interaction with an onium salt compound due to action of exposure, acid, base, or heating, a resin having an onium salt group that is decomposed due to exposure, and a resin that undergoes a decrease in molecular weight caused by decomposition due to action of exposure, acid, base, or heating, Examples 19 to 22 using resist compositions including at least one of a resin having an interactive group that is released from an interaction with an onium salt compound due to action of exposure, acid, base, or heating, a resin having an onium salt group that is decomposed due to exposure, or a resin that undergoes a decrease in molecular weight caused by decomposition due to action of exposure, acid, base, or heating were confirmed to further suppress the variation in the development waiting time.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-116511 | Jul 2021 | JP | national |
This application is a Continuation of PCT International Application No. PCT/JP2022/027383 filed on Jul. 12, 2022, which claims priority under 35 U.S.C. § 119(a) to Japanese Patent Application No. 2021-116511 filed on Jul. 14, 2021. The above applications are hereby expressly incorporated by reference, in their entirety, into the present application.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP22/27383 | Jul 2022 | WO |
| Child | 18412068 | US |
