Patent Application
20240242967
The present invention relates to: a composition for forming a metal-containing film that can be used for fine patterning according to a multilayer resist method in a semiconductor device manufacturing process; a patterning process using the composition; and a polymer for forming a metal-containing film.
As LSIs advance toward higher integration and higher processing speed, miniaturization of pattern rule is progressing rapidly. As a cutting-edge technology for miniaturization, ArF immersion lithography has been adopted for mass-producing 45-nm node devices and smaller. In addition to ArF immersion exposure, double exposure (double patterning) processes have been put to practical use in generations of 28-nm node devices and smaller, so that the formation of narrow-pitch patterns that exceed the optical limit has also become possible.
Furthermore, in the production of 20-nm node and smaller devices, studies have been carried out on multiple exposure (multi-patterning) processes for forming a pattern with a narrower pitch by repeating exposure and etching three or more times. However, multiple exposure processes have an increased number of steps, and are faced with the situation that costs rise considerably due to degradation in productivity caused by longer time spent in manufacturing and more frequent generation of defects.
In recent years, extreme ultraviolet ray (EUV) lithography with a wavelength of 13.5 nm is attracting attention as an effective technology to replace a combination of ArF immersion lithography and multiple exposure process. By using this technology, it has become possible to form a fine pattern with a half pitch of 25 nm or less in one exposure.
Meanwhile, in EUV lithography, resist materials are strongly required to have higher sensitivity to compensate for insufficient output of a light source. However, increase in shot noise accompanying higher sensitization leads to increase in edge roughness (LER and LWR) of line patterns, and compatibility of higher sensitization and low edge roughness is given as an important problem in EUV lithography.
As an attempt to achieve higher sensitivity of a resist or to lower the influence of shot noise, it has been considered in recent years to use a metal material in a resist material. A compound that contains a metallic element such as barium, titanium, hafnium, zirconium, or tin has a higher absorbance of EUV light compared to an organic material that does not contain metal, and improvement of photosensitivity of resists and suppression of the influence of shot noise can be expected. Furthermore, a metal-containing resist pattern is expected to achieve a high-selectivity etching process by combining with an underlayer film made from a non-metal material.
For example, resist materials with added metal salt or organometallic complex disclosed in Patent Documents 1 and 2 or non-chemically amplified resist materials that use nanoparticles of metal oxide disclosed in Patent Documents 3 and 4 are considered.
In particular, molecules containing tin are excellent in the absorption of an electron beam and an extreme ultraviolet ray, and are actively researched. In the case of an organotin polymer, which is one such molecule, alkyl ligand is dissociated by light absorption or secondary electrons produced thereby and a resultant is crosslinked with adjacent chains through an oxo bond, and thus this enables the negative tone patterning which may not be removed by an organic developing solution. This organic tin polymer can improve sensitivity while maintaining a resolution and line edge roughness, but has not yet reached the standards for commercial availability (Patent Document 5). In addition, many problems still remain, such as insufficient storage stability regarding change in resist sensitivity.
To solve the problems, there is also consideration of development of the use of a material containing a metal element, such as titanium, hafnium, zirconium, and tin, for a resist underlayer film. There is no need for the improvement for performance, such as the enhancement of exposure sensitivity and the suppression of change in sensitivity in storage environment, which is an issue in resist materials containing metal. In addition, it may be possible to provide a resist underlayer film excellent in dry etching resistance when the metal element is contained. Patent Document 6 reports that a material containing a Ti compound exhibits excellent dry etching resistance to CHF3/CF4-based gas and CO2/N2-based gas.
On the other hand, filling property is a problem when using a metal compound for a resist underlayer film. Although there is no mention of filling property in Patent Document 6, a metal oxide compound generally has large thermal shrinkage during baking and induces remarkable degradation of filling after baking at a high temperature. Therefore, there is a concern that such a compound is insufficient as a resist underlayer film material for which high planarizing and filling properties and heat resistance are required. Patent Document 7 reports that a metal compound modified with a particular ligand has excellent filling property. However, the baking temperature in the performed filling property evaluation is a low temperature of 150° C., and there is a concern that the compound is insufficient as a resist underlayer film, which requires heat resistance (for example, resistance to a heat treatment that is performed after the formation of a resist underlayer film in some cases). Patent Document 8 provides a resist underlayer film material excellent in filling property after baking at 400° C. by mixing the metal compound reported in Patent Document 7 and an organic polymer having a particular structure. However, since the material is a mixed composition of a metal compound which is inorganic and a polymer which is organic, there are concerns for film formation defects, degradation of storage stability, degradation of dry etching resistance, etc. caused by compatibility failure.
The present invention has been made in view of the above-described circumstances. An object of the present invention is to provide: a polymer for forming a metal-containing film having better dry etching resistance than conventional organic underlayer film materials and also having high filling and planarizing properties; a composition for forming a metal-containing film containing the polymer; and a patterning process in which the composition is used as a resist underlayer film material or the like.
To achieve the object, the present invention provides a polymer for forming a metal-containing film comprising
a repeating unit represented by the following general formula (1A),
wherein W1 represents a divalent organic group having 1 to 31 carbon atoms; and each Q independently represents a group selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and having one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.
Such a polymer for forming a metal-containing film has the repeating structural unit represented by the general formula (1A), and therefore, has excellent heat resistance property. Moreover, the general formula (1A) consists of a repeating unit of a structure including a Sn atom, and therefore, when the polymer is contained in a composition for forming a metal-containing film, the Sn content in the film is high. Thus, it is possible to provide a resist (upper layer, underlayer, etc.) film material having excellent etching resistance. That is, the present invention can provide a polymer for forming a metal-containing film having better dry etching resistance than conventional organic underlayer film materials and also having high filling and planarizing properties.
The polymer can be used in a composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor production.
The polymer can further comprise a condensation polymer of an organotin compound SnOQ2, wherein the Q is as defined above.
Such a polymer for forming a metal-containing film has a high Sn content, and when the polymer is contained in a composition for forming a metal-containing film, it is possible to provide a resist upperlayer and underlayer film material having better etching resistance.
The polymer preferably comprises a structure represented by the following general formula (1B) at an end,
wherein Tx represents a monovalent organic group having a hydroxy group or a structure represented by one of the following general formulae (a-1) to (a-3) or an unsaturated hydrocarbon group having 2 to 10 carbon atoms; and a broken line represents an attachment point to the polymer,
wherein R1 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; “q” represents 0 or 1; and “*” represents an attachment point.
A polymer for forming a metal-containing film having excellent solvent solubility and excellent thermosetting property can be achieved by the polymer having a structure represented by the general formula (1B) at an end of the polymer.
The polymer is preferably represented by the following general formula (2),
wherein W1 and Q are as defined above; T's are identical to or different from one another and each represent an unsaturated hydrocarbon group having 2 to 10 carbon atoms or a monovalent organic group represented by the following general formula (2A); and “a” represents 1 to 30,
wherein X1 represents a saturated divalent organic group having 1 to 20 carbon atoms and optionally containing a heteroatom or an unsaturated divalent organic group having 2 to 20 carbon atoms and optionally containing a heteroatom; W2 represents the following general formula (2B); and “*” represents an attachment point to a carbon atom of a carbonyl group,
wherein Y represents a saturated organic group having a valency of 1+h, having 1 to 20 carbon atoms, and optionally containing a heteroatom or an unsaturated organic group having a valency of 1+h, having 2 to 20 carbon atoms, and optionally containing a heteroatom; RA represents a hydroxy group or a structure represented by one of the general formulae (a-1) to (a-3); and “h” represents 1 to 3.
When the polymer has the structure represented by the general formula (2), it is possible to achieve a polymer for forming a metal-containing film having excellent dry etching resistance, high filling and planarizing properties and also having better solvent solubility, heat resistance, and thermosetting property.
In the inventive polymer for forming a metal-containing film, the T is preferably one of structures represented by the following general formulae (2Aa),
wherein X1a represents a saturated divalent organic group having 1 to 20 carbon atoms and optionally containing a heteroatom or an unsaturated divalent organic group having 2 to 20 carbon atoms and optionally containing a heteroatom; and W2a represents one of structures represented by the following general formulae (2C),
wherein RA1 represents a structure represented by the general formula (a-1); RA2 represents a hydroxy group or one of the structures represented by the general formula (a-2) or (a-3); Z represents an oxygen atom or a secondary amino group; L represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R2 represents a saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms; “t” represents 1 to 6 and “s” represents 0 to 5, provided that t+s is 1 or more and 6 or less; “r” represents 1 to 10; “u” represents 0 or 1; “m” represents 0 or 1; and “*” represents an attachment point.
When the T has a structure represented by the general formulae (2Aa), the thermal flowability of the polymer for forming a metal-containing film can be improved further.
In the inventive polymer for forming a metal-containing film, the W1 preferably represents a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms.
When the W1 is a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, the thermosetting property of the polymer for forming a metal-containing film can be improved further.
In the inventive polymer for forming a metal-containing film, the W1 preferably represents one of structures represented by the following general formulae (b-1) to (b-3),
wherein Ra, Rb, and RC each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, Ra and Rb optionally being bonded to each other to form a cyclic substituent; and “*1” and “*2” each represent an attachment point to a carbonyl group, “*1” and “*2” optionally being reversed.
When the W1 is one of the structures represented by the general formulae (b-1) to (b-3), both high thermal flowability and high thermosetting property can be achieved. When such a polymer is contained in a composition for forming a metal-containing film, it is possible to provide a resist underlayer film material that exhibits better planarizing and filling properties.
In the inventive polymer for forming a metal-containing film, the X1a preferably represents an unsaturated divalent organic group having 2 to 20 carbon atoms.
When the X1a is an unsaturated divalent organic group having 2 to 20 carbon atoms, the thermosetting property of the polymer for forming a metal-containing film can be improved further.
In the inventive polymer for forming a metal-containing film, the X1a preferably represents one of structures represented by the following general formulae (c-1) to (c-2),
wherein Ra, Rb, and RC each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, Ra and Rb optionally being bonded to each other to form a cyclic substituent; and “*1” and “*2” each represent an attachment point to a carbonyl group, “*1” and “*2” optionally being reversed.
When the X1a is one of the structures represented by the general formulae (c-1) to (c-2), both high thermal flowability and high thermosetting property can be achieved. When the above-described polymer is contained in a composition for forming a metal-containing film, better planarizing and filling properties can be exhibited.
In addition, the present invention provides a composition for forming a metal-containing film, the composition functioning as a resist underlayer film material and a resist material used in manufacturing a semiconductor, the composition comprising: (A) the above-described polymer for forming a metal-containing film; and (B) an organic solvent.
Such a composition for forming a metal-containing film contains an organotin polymer excellent in heat resistance and thermal flowability, and therefore, can provide a resist underlayer film material having better dry etching resistance than conventional resist underlayer film materials and also having high filling and planarizing properties.
In the present invention, the composition may be usable as a resist underlayer film used in a multilayer resist method, the composition further comprising one or more of (C) a crosslinking agent, (D) a high-boiling-point solvent, (E) a surfactant, and (F) a flowability accelerator.
A composition for forming a metal-containing film containing such additives can achieve a composition for forming a resist underlayer film having better coating property, dry etching resistance, and filling and planarizing properties.
In the present invention, the high-boiling-point solvent (D) is preferably one or more kinds of organic solvent having a boiling point of 180° C. or higher.
By the compound for forming a metal-containing film being provided with thermal flowability by containing a high-boiling-point solvent, the composition for forming a resist underlayer film can have both high filling and planarizing properties.
The composition for forming a metal-containing film can further comprise (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less.
The metal oxide nanoparticles (G) are preferably selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.
When such metal oxide nanoparticles are contained, it is possible to increase easily the metal content in the composition, and thus, it is possible to improve the dry etching resistance of the composition for forming a resist underlayer film further.
In addition, the present invention provides a patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
The patterning process by way of the two-layer resist process makes it possible to form fine patterns on the body to be processed (substrate to be processed).
The present invention also provides a patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
The patterning process by way of the three-layer resist process makes it possible to form fine patterns on the body to be processed with a high degree of accuracy.
The present invention also provides a patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
Alternatively, the present invention provides a patterning process comprising the steps of:
The patterning process by way of the four-layer resist process makes it possible to form fine patterns on the body to be processed with a high degree of accuracy.
In this case, the inorganic hard mask middle layer film is preferably formed by a CVD method or an ALD method.
When the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a body to be processed with higher accuracy.
The present invention also provides a patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
The patterning process by way of the multilayer resist process makes it possible to form fine patterns on the body to be processed with a high degree of accuracy.
The present invention also provides a tone-reversal patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
The patterning process by way of the reverse process makes it possible to form fine patterns on the body to be processed with a higher degree of accuracy.
As described above, the inventive polymer for forming a metal-containing film has a repeating structural unit represented by the general formula (1A), and therefore, has excellent heat resistance. In addition, since the general formula (1A) includes a repeating unit of a structure containing an Sn atom, it is possible to provide a material for a resist upperlayer and underlayer film having a high Sn content in the film and having excellent etching resistance when the polymer is contained in a composition for forming a metal-containing film.
In particular, in a fine patterning process using a multilayer resist method in a semiconductor device manufacturing process, filling is possible without causing defects such as voids and peeling even after high-temperature baking, since the above-described material has excellent heat resistance even on a substrate to be processed having a portion that is difficult to fill and planarize, such as a dense portion of a fine pattern structure having a high aspect ratio exemplified by increasingly miniaturized DRAM. In addition, the inventive polymer has better dry etching resistance than conventional coating-type organic resist underlayer film materials, and therefore, a fine pattern can be formed on a body to be processed with even higher precision compared with an organic resist underlayer film.
A composition for forming a metal-containing film containing the compound of the present invention for forming a metal-containing film contains tin atoms, which have high light absorbance, and therefore, has a sensitizing effect caused by secondary electrons generated from the tin atoms during exposure. Furthermore, tin atoms have a great atomic weight, and therefore, have a high effect of suppressing the diffusion of acid from an upper layer resist to a resist underlayer film, and have an effect that higher sensitivity can be achieved while sustaining the LWR performance that the resist upper layer film originally has.
As stated above, there have been demands for the development of: a composition for forming a metal-containing film, excellent in filling property and planarization property, used for forming a resist underlayer film that makes it possible to transfer a resist pattern to a substrate to be processed with higher precision in a fine patterning process according to a multilayer resist method; and a material for forming a metal-containing film useful for the composition.
The present inventors have focused on organotin materials, which are expected to play an active role in the EUV-exposure generation, and studied earnestly. As stated above, tin atoms, which greatly absorb light, have a sensitizing effect due to secondary electrons generated from the atoms during exposure, and have a characteristic that higher sensitivity can be achieved while maintaining the LWR performance that a resist upper layer film originally has. On the other hand, organotin compounds, which are considered as resist upper layer films, have poor heat resistance, and undergo rapid volume shrinkage during baking. Therefore, it is difficult to fill and planarize the steps of a substrate to be processed after high-temperature baking. The present inventors have considered that a polymer having a repeating unit excellent in heat resistance can reduce rapid volume shrinkage at the time of baking, so that steps of a substrate to be processed can be filled without voids being generated even after baking at a high temperature.
The present inventors have studied earnestly further, and found out that a polymer for forming a metal-containing film having a repeating unit represented by the general formula (1A) gives a composition for forming a metal-containing film that can reduce sudden volume shrinkage during baking since the composition has excellent heat resistance, can contribute to the improvement of sensitivity while maintaining the LWR of an upper layer resist since the composition contains tin atoms, and has excellent dry etching resistance since alkyl ligand is dissociated after high-temperature baking and a resultant forms SnO2 by crosslinking with adjacent chains through an oxo bond.
That is, the present invention is a polymer for forming a metal-containing film comprising
a repeating unit represented by the following general formula (1A),
wherein W1 represents a divalent organic group having 1 to 31 carbon atoms; and each Q independently represents a group selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and having one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.
Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
The inventive polymer for forming a metal-containing film includes a repeating unit represented by the following general formula (1A).
In the general formula (1A), W1 represents a divalent organic group having 1 to 31 carbon atoms; and each Q independently represents a group selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and having one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.
In the general formula (1A), W1 represents a divalent organic group having 1 to 31 carbon atoms, more preferably a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms. Q represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and having one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms. A combination of the above groups is also favorable, an unsubstituted alkyl group having 1 to 20 carbon atoms is more preferable, and from the viewpoint of the availability of raw materials, an n-butyl group and an n-octyl group are preferable. From the viewpoint of thermal shrinkage, an n-butyl group is further preferable.
When a repeating unit represented by the general formula (1A) is contained, it is possible to provide a polymer for forming a metal-containing film having excellent heat resistance. When such a polymer is contained in a composition for forming a metal-containing film, volume shrinkage during baking is small, and unlike tin-containing compounds for forming a resist upper layer film reported in Patent Document 5, it is possible to provide a resist underlayer film material having excellent film-formability and excellent planarizing and filling properties even after high-temperature baking.
As the above-described polymer, a polymer for forming a metal-containing film having a structure represented by the following general formula (1B) at an end of the polymer is preferable.
In the general formula (1B), Tx represents a monovalent organic group having a hydroxy group or a structure represented by any of the following general formulae (a-1) to (a-3) or an unsaturated hydrocarbon group having 2 to 10 carbon atoms. A broken line represents an attachment point to the polymer.
In the general formulae (a-1) to (a-3), R1 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; “q” represents 0 or 1; and “*” represents an attachment point.
In the general formulae (a-1) to (a-3), R1 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In further preferable structures, R1 represents a hydrogen atom, a methyl group, or a phenyl group optionally having a substituent, and from the viewpoints of thermal flowability and thermosetting property, a hydrogen atom is particularly preferable.
In the general formula (1B), when Tx represents an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 carbon atoms (a vinyl group) is more preferable in view of the availability of raw materials.
A polymer for forming a metal-containing film having such a structure has excellent solvent solubility and excellent thermosetting property by the polymer (1A) having, on an end, a structure represented by the general formula (1B). When the Tx has a hydroxy group, it is possible to provide a polymer for forming a metal-containing film having excellent adhesiveness to a substrate or the like, and when the Tx has the general formulae (a-1) to (a-3) or an unsaturated hydrocarbon group having 2 to 10 carbon atoms, it is possible to provide a polymer for forming a metal-containing film having excellent thermal flowability. It is also possible for a different Tx to be present on each of the two ends of the polymer, and in such a case, the structure preferably includes a hydroxy group on one end. When the structure is as described, it is possible to provide a compound for forming a metal-containing film that has both high adhesiveness to a substrate and high thermal flowability.
An organotin compound generates radicals, while organic groups bonded to Sn atoms via C atoms are dissociated during baking. Radicals generated in this manner form —Sn—O—Sn— bonds and initiate a condensation polymerization reaction. Thus, curing of a metal-containing film formed by using the compound progresses. Meanwhile, since organic groups are removed at the time of the reaction, great film shrinkage occurs during baking. However, since the above-described polymer includes, at an end, a monovalent organic group having a hydroxy group or a structure represented by any of the following general formulae (a-1) to (a-3) or an unsaturated hydrocarbon group having 2 to 10 carbon atoms, and has excellent thermosetting property, pyrolysis can be suppressed, and it is possible to provide a resist underlayer film material having better filling property.
The inventive polymer for forming a metal-containing film, the polymer having a repeating unit represented by the general formula (1A), can be obtained as a co-condensation product of a hydrolysable organotin compound, a dicarboxylic acid or an ester thereof, and a monocarboxylic acid or an ester thereof. For example, by using TCOOH or an ester thereof as the monocarboxylic acid, a monovalent organic group T described below can be introduced to an end of the polymer as shown by the following general formula (I). In this case, the structure represented by the general formula (1B) corresponds to the terminal structure —O(C═O)T of the polymer represented by the formula (I), and the Tx in the formula (1B) corresponds to the T of the formula (I).
In the general formula (I), W1 and Q are as defined above, and T's are identical to or different from each other and represent an unsaturated hydrocarbon group having 2 to 10 carbon atoms or a monovalent organic group represented by the following general formula (2A). “x” represents 1 to 30, and “y” represents 1.
In particular, the above polymer is preferably a polymer for forming a metal-containing film represented by the following general formula (2).
In the general formula (2), W1 and Q are as defined above, and T's are identical to or different from each other and each represent an unsaturated hydrocarbon group having 2 to 10 carbon atoms or a monovalent organic group represented by the following general formula (2A). “a” represents 1 to 30.
In the general formula (2A), X1 represents a saturated divalent organic group having 1 to 20 carbon atoms and optionally containing a heteroatom or an unsaturated divalent organic group having 2 to 20 carbon atoms and optionally containing a heteroatom; W2 represents the following general formula (2B); and “*” represents an attachment point to a carbon atom of a carbonyl group.
In the general formula (2B), Y represents a saturated organic group having a valency of 1+h, having 1 to 20 carbon atoms, and optionally containing a heteroatom or an unsaturated organic group having a valency of 1+h, having 2 to 20 carbon atoms, and optionally containing a heteroatom; RA represents a hydroxy group or a structure represented by one of the general formulae (a-1) to (a-3); and “h” represents 1 to 3.
The W1 in the general formula (2) is preferably contained in an amount of 50 mol % to 95 mol %, more preferably 60 mol % to 90 mol % of the total of W1 and T. The T in the general formula (2) is preferably contained in an amount of 5 mol % to 50 mol %, more preferably 10 mol % to 40 mol % of the total of W1 and T. The inventive polymer for forming a metal-containing film may also be a mixture of polymers in which the W1 and the T in the general formula (2) are within the above ranges.
For example, the above-described polymer may further include a condensation polymer of an organotin compound SnOQ2, the Q being as described above.
Such a polymer for forming a metal-containing film has a high Sn content, and therefore, when the polymer is contained in a composition for forming a metal-containing film, it is possible to provide a resist upperlayer and underlayer film material having better etching resistance.
When it is desired to improve the etching resistance and heat resistance of the polymer for forming a metal-containing film, the proportion of the repeating unit of the general formula (1) can be increased, that is, W1>T can be satisfied in the general formula (2). Meanwhile, when it is desired to improve thermosetting property and thermal flowability, the proportion of the repeating unit of the general formula (1) can be decreased, that is, W1<T can be satisfied in the general formula (2). W1 and T can be adjusted to any proportion in accordance with the required performance.
In the general formula (I), “x” represents 1 to 30 and “y” represents 1. Preferably, “x” represents 2 to 20, further preferably 2 to 10. In the general formula (2), “a” represents 1 to 30, preferably 2 to 20, and further preferably 2 to 10. The values of “x”, “y”, and “a” are preferably values at which the proportion of W1 and T in each formula is as described above.
A polymer for forming a metal-containing film having such a structure has a repeating unit having the structure represented by the general formula (1A) and has, at an end, the general formula (1B), including a crosslinkable group. Therefore, such a polymer for forming a metal-containing film has excellent heat resistance and thermosetting property.
A polymer for forming a metal-containing film, where the T in the general formula (2) is any of the structures represented by the following general formulae (2Aa), is preferable.
In the general formulae (2Aa), X1a represents a saturated divalent organic group having 1 to 20 carbon atoms and optionally containing a heteroatom or an unsaturated divalent organic group having 2 to 20 carbon atoms and optionally containing a heteroatom; and W2a represents any of the structures represented by the following general formulae (2C).
In the general formulae (2C), RA1 represents a structure represented by the general formula (a-1); RA2 represents a hydroxy group or one of the structures represented by the general formula (a-2) or (a-3); Z represents an oxygen atom or a secondary amino group; L represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R2 represents a saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms; “t” represents 1 to 6 and “s” represents 0 to 5, provided that t+s is 1 or more and 6 or less; “r” represents 1 to 10; “u” represents 0 or 1; “m” represents 0 or 1; and “*” represents an attachment point.
In the general formulae (2C), when “m” is 1, L is preferably methylene. In a more preferable structure of the general formulae (2C), “r” is 1 to 4, “t” is 1 to 2, “s” is 0 to 1, and “m” is 0. Furthermore, in view of solvent solubility, “u” is preferably 1.
When the structure shown by the general formula (1B) corresponds to the terminal structure —O(C═O)T of the general formula (2), the Tx of the formula (1B) corresponds to the T of the formula (I). Specific examples of the structures in which the T is one of the structures shown by the general formulae (2Aa) and the W2a in the formulae (2Aa) is one of structures shown by the general formulae (2C) include the following structures, but are not limited thereto.
“*” represents an attachment point.
When T has a structure shown by the general formulae (2Aa), the solvent solubility, thermosetting property, and thermal flowability of the polymer for forming a metal-containing film can be more improved.
When the T is a structure shown by one of the following formulae, the solvent solubility, thermosetting property, and thermal flowability of the inventive polymer for forming a metal-containing film can be further improved.
In the general formula (1A) and the general formula (2), W1 is preferably an unsaturated hydrocarbon group having 2 to 20 carbon atoms.
A polymer for forming a metal-containing film having such a structure can have further improved thermosetting property.
In the general formula (1A), the general formula (I), and the general formula (2), the W1 is preferably one of the structures shown by the following general formulae (b-1) to (b-3).
In the general formulae (b-1) and (b-2), Ra, Rb, and RC each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, Ra and Rb optionally being bonded to each other to form a cyclic substituent. “*1” and “*2” each represent an attachment point to a carbonyl group, “*1” and “*2” optionally being reversed.
In view of thermosetting property, the W1 in the general formula (2) is more preferably one of the structures shown by the following general formulae (b-1) and (b-2).
Specific examples of the structures represented by the general formulae (b-1) and (b-2) include the following structures, but are not limited thereto.
Depending on the structures represented by the general formulae (b-1) and (b-2), geometrical isomers (cis isomer and trans isomer) regarding a double bond may exist in some cases, and in such a case, the isomers will be represented by a single formula. No inconvenience arises regarding the thermal flowability and thermosetting property of the compound of the present invention for forming a metal-containing film, either when one of the isomers is used or when the isomers are used in combination.
In the general formulae (2Aa), X1a preferably represents an unsaturated divalent organic group having 2 to 20 carbon atoms.
A polymer for forming a metal-containing film having such a structure can have further improved thermosetting property.
In the general formulae (2Aa), X1a preferably represents one of the structures shown by the following general formulae (c-1) and (c-2).
In the general formulae (c-1) and (c-2), Ra, Rb, and RC each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, Ra and Rb optionally being bonded to each other to form a cyclic substituent. “*1” and “*2” each represent an attachment point to a carbonyl group, “*1” and “*2” optionally being reversed.
Specific examples of the structures shown by the general formulae (c-1) and (c-2) include the following structures, but are not limited thereto.
Depending on the structures represented by the general formulae (c-1) and (c-2), geometrical isomers (cis isomer and trans isomer) regarding a double bond may exist in some cases, and in such a case, the isomers will be represented by a single formula. No inconvenience arises regarding the thermal flowability and thermosetting property of the compound of the present invention for forming a metal-containing film, either when one of the isomers is used or when the isomers are used in combination.
The Mw/Mn (that is, the dispersity) of the compound (polymer) for forming a metal-containing film is preferably more than 1.30, further preferably more than 1.50, where Mw is a weight-average molecular weight and Mn is a number-average molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene. From the definition, Mw/Mn is 1.00 in the case of a monomolecular compound, but because of separation in GPC, the measured value exceeds 1.00 in some cases. Generally, it is extremely difficult to bring the Mw/Mn of a polymer having a repeating unit close to 1.00 unless a special polymerization method is used. Such a polymer has a distribution of Mw, and Mw/Mn exceeds 1. The range of 1.00≤Mw/Mn≤1.30, for example, may be adopted as an index to indicate monomerism in order to distinguish between monomolecular compounds and polymers so that they can be distinct from each other more clearly. A compound for forming a metal-containing film having dispersity of more than 1.30 may have better balance of the heat resistance, thermosetting property, and thermal fluidity of the compound, and thus, when the compound is contained in the composition for forming a metal-containing film, not only is it possible to fill favorably fine structures formed on a substrate, it is also possible to form a resist underlayer film to planarize the entire substrate.
The compound for forming a metal-containing film preferably has a weight-average molecular weight of 1,000 to 20,000, more preferably 1,500 to 10,000. Such compound can form a metal-containing film excellent in the heat resistance, thermosetting property, and thermal fluidity.
To determine molecular weight and dispersity in the present invention, weight-average molecular weight and number-average molecular weight in terms of polystyrene are measured by GPC with using tetrahydrofuran as an eluent, and dispersity is calculated from these values.
Furthermore, the present invention can provide a composition for forming a metal-containing film, the composition functioning as a resist underlayer film material and a resist material used in manufacturing a semiconductor, the composition containing: (A) the above-described polymer for forming a metal-containing film; and (B) an organic solvent.
Such a composition for forming a metal-containing film contains an organotin polymer having excellent heat resistance, and therefore, can provide a resist underlayer film material having better dry etching resistance than conventional organic underlayer film materials and also having excellent film-formability and excellent filling and planarizing properties even after baking at a high temperature, unlike organotin-containing compounds for forming a resist upper layer film.
In the following, the components contained in the inventive composition for forming a metal-containing film other than the compound (A) for forming a metal-containing film will be described.
The organic solvent (B) usable in the inventive composition for forming a metal-containing film is not particularly limited as long as the solvent can dissolve or disperse the polymer (A) for forming a metal-containing film and, when contained, (C) a crosslinking agent, (D) a high-boiling-point solvent, (E) a surfactant, (F) a flowability accelerator, (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less, and also additives or the like such as an acid generator and a plasticizer described below.
Specifically, an organic solvent disclosed in paragraphs [0091] and [0092] in JP2007-199653A may be contained. Furthermore, it is preferable to use propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, or a mixture containing one or more of these solvents.
The organic solvent is preferably contained in an amount of 200 to 10,000 parts by mass, more preferably 250 to 5,000 parts by mass relative to 100 parts by mass of the polymer (A) for forming a metal-containing film.
When the composition is a composition for forming a metal-containing film usable as a resist underlayer film used in a multilayer resist method, at least one kind of the polymer (A) for forming a metal-containing film and the organic solvent (B) is contained, and as necessary, the composition may contain additives such as a crosslinking agent (C), a high-boiling-point solvent (D), a surfactant (E), a flowability accelerator (F), and metal oxide nanoparticles (G) having an average primary particle size of 100 nm or less.
In the following, the components contained in the composition of the present invention for forming a resist underlayer film other than the polymer (A) for forming a metal-containing film and the organic solvent (B) will be described.
In the composition of the present invention for forming a resist underlayer film, the organic solvent (B) may be a mixture of one or more kinds of organic solvent having a boiling point of lower than 180° C. and one or more kinds of organic solvent having a boiling point of 180° C. or higher ((D) a high-boiling-point solvent).
The high-boiling-point solvent (D) is not particularly limited to hydrocarbons, alcohols, ketones, esters, ethers, or chlorine-based solvents as long as the solvent is capable of dissolving or dispersing the components of the inventive composition for forming a metal-containing film. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, and the like. One of the solvents may be used or a mixture of two or more kinds may be used.
The high-boiling-point solvent (D) may be selected suitably from the solvents above, for example, depending on the temperature at which the inventive composition for forming a metal-containing film is heat-treated, etc. The boiling point of the high-boiling-point solvent is preferably 180° C. to 300° C., further preferably 200° C. to 300° C. It is considered that when the boiling point is as described, sufficient thermal flowability can be achieved at the time of film formation, since there is no risk of excessive evaporation rate at the baking (heating). Thus, it is possible to form a resist underlayer film excellent in filling and planarizing properties. Moreover, a solvent having such a boiling point does not remain in the film without evaporating even after the baking. Therefore, there is no risk of the solvent adversely affecting the physical properties, such as etching resistance, of the film.
Furthermore, when the high-boiling-point solvent (D) is used, the contained amount is preferably 1 to 30 parts by mass per 100 parts by mass of the organic solvent, having a boiling point lower than 180° C. When the contained amount is as described, sufficient thermal flowability can be imparted at the time of baking, so that the solvent does not remain in the film and cause degradation in the physical properties, such as etching resistance, of the film. Therefore, such an amount is preferable.
To increase the curability of the polymer for forming a metal-containing film and further inhibit intermixing with the resist upper layer film, the inventive composition for forming a metal-containing film may also contain a crosslinking agent (C). The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents (e.g. polynuclear phenol-based crosslinking agents as methylol- or alkoxymethyl-modified). The crosslinking agent (C) is preferably contained in an amount of 5 to 50 parts by mass, more preferably 10 to 40 parts by mass relative to 100 parts by mass of the compound for forming a metal-containing film (A).
Specific examples of the melamine-based crosslinking agents include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and/or hydroxy-substituted derivatives thereof, and partial self-condensates thereof.
Specific examples of the acrylate-based crosslinking agents include dipentaerythritol hexaacrylate.
Specific examples of the glycoluril-based crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy- and/or hydroxy-substituted derivatives thereof, and partial self-condensates thereof.
Specific examples of the benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and/or hydroxy-substituted derivatives thereof, and partial self-condensates thereof.
Specific examples of the urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, alkoxy- and/or hydroxy-substituted derivatives thereof, and partial self-condensates thereof.
Specific examples of the β-hydroxyalkylamide-based crosslinking agent include N,N,N′,N′-tetra(2-hydroxyethyl)adipic acid amide.
Specific examples of the isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate.
Specific examples of the aziridine-based crosslinking agents include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].
Specific examples of the oxazoline-based crosslinking agents include 2,2′-isopropylidene bis(4-benzyl-2-oxazoline), 2,2′-isopropylidene bis(4-phenyl-2-oxazoline), 2,2′-methylene bis-4,5-diphenyl-2-oxazoline, 2,2′-methylene bis-4-phenyl-2-oxazoline, 2,2′-methylene bis-4-tert-butyl-2-oxazoline, 2,2′-bis(2-oxazoline), 1,3-phenylene bis(2-oxazoline), 1,4-phenylene bis(2-oxazoline), and a 2-isopropenyloxazoline copolymer.
Specific examples of the epoxy-based crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.
Specific examples of the polynuclear phenol-based crosslinking agents include compounds represented by the following general formula (XL-1). Note that the Q here applies only to the following formula.
In the formula, Q represents a single bond or q-valent hydrocarbon group having 1 to 20 carbon atoms. R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. “q” represents an integer of 1 to 5.
Q represents a single bond or a hydrocarbon group having a valency of “q” and having 1 to 20 carbon atoms. “q” represents an integer of 1 to 5, more preferably 2 or 3. Specific examples of Q include groups obtained by removing “q” hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group. Among these, a hydrogen atom or a methyl group is preferable.
Specific examples of the compounds represented by the general formula (XL-1) include the following compounds. Among these, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and a hexamethoxymethylated derivative of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferable from the viewpoint of improving the curability and film thickness uniformity of the organic film. R3 is as defined above.
A surfactant (E) may be contained in the composition for forming a resist underlayer film of the present invention in order to improve coating property in spin-coating. Examples of the surfactant include those disclosed in paragraphs [0142] to [0147] of JP2009-269953A. When the surfactant is contained, the contained amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass per 100 parts by mass of the compound (A) for forming a metal-containing film.
Another compound or polymer may be further blended in the composition for forming a resist underlayer film of the present invention. The flowability accelerator is mixed with the inventive compound for forming a metal-containing film and serves to improve the film-formability by spin-coating and the filling property for a stepped substrate. Furthermore, as the flowability accelerator, a material having a high density of carbon atoms and high etching resistance is preferable.
Examples of such a material include novolak resins of phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethyl phenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4′-(9H-fluorene-9-ylidene)bisphenol, 2,2′-dimethyl-4,4′-(9H-fluorene-9-ylidene)bisphenol, 2,2′-diallyl-4,4′-(9H-fluorene-9-ylidene)bisphenol, 2,2′-difluoro-4,4′-(9H-fluorene-9-ylidene)bisphenol, 2,2′-diphenyl-4,4′-(9H-fluorene-9-ylidene)bisphenol, 2,2′-dimethoxy-4,4′-(9H-fluorene-9-ylidene)bisphenol, 2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 3,3,3′,3′,4,4′-hexamethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, 2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-5,5′-diol, 5,5′-dimethyl-3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol, naphthol such as 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, and 7-methoxy-2-naphthol, dihydroxynaphthalene such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, methyl-3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, or limonene; polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly(meth)acrylate, and copolymers thereof. In addition, the composition may contain a naphthol dicyclopentadiene copolymer disclosed in JP2004-205685A, a fluorene bisphenol novolak resin disclosed in JP2005-128509A, an acenaphthylene copolymer disclosed in JP2005-250434A, fullerene having a phenolic group disclosed in JP2006-227391A, a bisphenol compound and a novolak resin thereof disclosed in JP2006-293298A, a novolak resin of an adamantane phenol compound disclosed in JP2006-285095A, a bisnaphthol compound and a novolak resin thereof disclosed in JP2010-122656A, a fluorene compound disclosed in JP2017-119671A, a fullerene resin compound disclosed in JP2008-158002A, a fluorene resin disclosed in JP2020-183480A, and the like. The flowability accelerator is preferably contained in an amount of 0.001 to 100 parts by mass, more preferably 0.01 to 50 parts by mass based on 100 parts by mass of the compound of the present invention for forming a metal-containing film.
In addition, in the composition for forming a resist underlayer film of the present invention, it is preferable to use, as an additive for imparting filling and planarizing properties, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermo-decomposable polymer having a weight reduction rate of 40% by mass or more in the range of 30° C. to 250° C. and a weight-average molecular weight of 300 to 200,000. This thermo-decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a). Note that the Y in the following formula applies only in this formula.
In the formula, R6 represents a hydrogen atom or a substituted or unsubstituted, saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y represents a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.
In the formula, R6a represents an alkyl group having 1 to 4 carbon atoms. Ya represents a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms and optionally having an ether bond. “n” represents an average repeating unit number of 3 to 500.
The composition for forming a resist underlayer film of the present invention can also contain metal oxide nanoparticles (G) in order to improve dry etching resistance further. Specifically, metal oxide nanoparticles selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles are preferable.
By selecting such a metal oxide, it is possible to form a metal-containing film having better dry etching resistance.
The metal oxide nanoparticles (G) preferably has an average primary particle size of 100 nm or less, more preferably an average primary particle size of 50 nm or less, further preferably an average primary particle size of 30 nm or less, and particularly preferably 15 nm or less. The lower limit is not particularly limited, but it could be, for example, 0.1 nm or more. The average primary particle size of the metal oxide nanoparticles before being dispersed in an organic solvent can be determined by a method of measuring the size of primary particles directly from an electron microscope photograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average of the values is defined as the particle size of the particle. Then, for 100 or more particles, the volume (mass) of each particle is approximated to a cuboid of the determined particle size, and this volume average particle size is determined as the average particle size. Identical results can be obtained when any of a transmission type electron microscope (TEM), a scanning type electron microscope (SEM), and a scanning transmission type electron microscope (STEM) are used.
When the particle size is within such ranges, the particles can exhibit excellent dispersity in a composition for forming a metal-containing film, and can enhance the dry etching resistance of a metal-containing film without causing the degradation of filling and planarizing properties in dense portions of a fine pattern structure.
In the present invention, a component to be a precursor of a tin oxide is contained in the composition for forming a metal-containing film, and therefore, the component (G) does not need to be contained.
An acid generator may be contained in the composition for forming a resist underlayer film of the present invention in order to promote the curing reaction of the polymer (A) for forming a metal-containing film further. The acid generator can be classified into those that generate an acid by thermal decomposition and those that generate an acid by optical irradiation; however, any acid generator can be added. Specific examples of the acid generator include the materials disclosed in paragraphs [0061] to [0085] of JP2007-199653A, but are not limited thereto.
One kind of the acid generator can be used, or two or more kinds can be used in combination. When an acid generator is contained, the contained amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the compound (A) for forming a metal-containing film.
The present invention provides a method of forming, by using the above-described composition for forming a metal-containing film, a resist underlayer film of a multilayer resist film used in lithography or a filling film that serves as a planarizing film for the manufacture of semiconductor.
In the method for forming a metal-containing film, such as a resist underlayer film, by using the inventive composition for forming a metal-containing film, the substrate to be processed is coated with the above-described composition for forming a metal-containing film by a spin-coating method or the like. Using the spin-coating method or the like ensures a desirable filling property. After spin-coating, baking (heating) is performed so as to evaporate the solvent and promote a crosslinking reaction to prevent mixing of the resist upper layer film and the resist middle layer film. The baking is preferably performed at a temperature of 100° C. or higher and 600° C. or lower for 10 to 600 seconds, more preferably at a temperature of 200° C. or higher and 500° C. or lower for 10 to 300 seconds. In consideration of influences on device damage, wafer deformation, and the like, the upper limit of the heating temperature in the wafer process of lithography is preferably not more than 600° C., and more preferably not more than 500° C.
In the method for forming a metal-containing film where the inventive composition for forming a metal-containing film is used, a substrate to be processed may also be coated with the inventive composition for forming a metal-containing film by spin-coating or the like in the same manner as described above, and then the composition for forming a metal-containing film may be baked and cured under an atmosphere having an oxygen concentration of 0.1 volume % or more and 21 volume % or less to form a metal-containing film.
By baking the inventive composition for forming a metal-containing film in such an oxygen atmosphere, a sufficiently cured film can be obtained. The atmosphere during baking may be air; however, to prevent oxidation of the metal-containing film, it is preferable to enclose an inert gas, such as N2, Ar, or He, therein to reduce the amount of oxygen. Control of oxygen concentration is necessary to prevent oxidation; the oxygen concentration is preferably 1000 ppm or less, more preferably 100 ppm or less (volumetric basis). By thus preventing oxidation of the metal-containing film during the baking, the absorption does not increase and the etching resistance does not decrease, which is preferable.
The present invention provides, as a patterning process according to a two-layer resist process using the above-described composition for forming a metal-containing film, the patterning process including:
The resist upper layer film in the two-layer resist process described above exhibits etching resistance with respect to chlorine-based gas. Therefore, the dry etching of the metal-containing film that is performed while using the resist upper layer film as a mask in the two-layer resist process is preferably performed using an etching gas mainly containing a chlorine-based gas.
The present invention provides, as a patterning process according to a three-layer resist process using the above-described composition for forming a metal-containing film, the patterning process including:
An example of a three-layer resist process specifically described with reference to
Next, as shown in
The silicon-containing resist middle layer film in the three-layer resist process exhibits etching resistance with respect to a chlorine-based gas and a hydrogen-based gas. Therefore, the dry etching of the metal-containing film that is performed while using the silicon-containing resist middle layer film as a mask in the three-layer resist process is preferably performed using an etching gas mainly containing a chlorine-based gas or a hydrogen-based gas.
As the silicon-containing resist middle layer film in the three-layer resist process, a polysiloxane-based middle layer film is also preferably used. This allows the silicon-containing resist middle layer film to possess an effect as an antireflective film, thereby suppressing reflection. When a material containing many aromatic groups and having a high etching selectivity with respect to the substrate is used as the organic film especially for 193-nm exposure, the k-value increases and thus the substrate reflection increases; however, the reflection can be suppressed by imparting absorption so that the silicon-containing resist middle layer film has an appropriate k-value. In this manner, the substrate reflection can be reduced to 0.5% or less. Preferably used as the silicon-containing resist middle layer film having an antireflective effect is a polysiloxane, which has a pendant anthracene for exposure at 248 nm or 157 nm, or a pendant phenyl group or a pendant light-absorbing group having a silicon-silicon bond for 193 nm exposure, and which is crosslinked by an acid or heat.
In addition, the present invention provides a patterning process by way of a four-layer resist process using such a composition for forming a metal-containing film, the patterning process including the steps of:
Alternatively, an inorganic hard mask (inorganic hard mask middle layer film) may be formed instead of the silicon-containing resist middle layer film. In this case, a semiconductor device circuit pattern can be formed on a substrate, at least, by:
As described above, when the inorganic hard mask is formed on the metal-containing film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, etc. The method for forming the silicon nitride film is disclosed, for example, in JP2002-334869A and WO2004/066377A1. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. The SiON film, which has a high function as an antireflective film, is the most preferably used as the inorganic hard mask. Since the substrate temperature increases to 300 to 500° C. when the SiON film is formed, the metal-containing film needs to withstand a temperature of 300 to 500° C. The composition for forming a metal-containing film used in the present invention has high heat resistance and can withstand a high temperature of 300 to 500° C. Thus, the metal-containing film formed by spin-coating and the inorganic hard mask formed by the CVD method or the ALD method can be combined.
A photoresist film may be formed on the inorganic hard mask as the resist upper layer film as described above. Alternatively, an organic antireflective film (BARC) or an adhesive film may be formed on the inorganic hard mask by spin-coating, and a photoresist film may be formed thereon. In particular, when a SiON film is used as the inorganic hard mask, the reflection can be suppressed by the two antireflective films, i.e., the SiON film and the BARC film, even in liquid immersion exposure at a high NA exceeding 1.0. Another merit of forming BARC resides in that it has an effect to reduce a footing profile of a photoresist pattern immediately above the SiON film.
In addition, the present invention provides a patterning process according to a multilayer resist process using such a composition for forming a metal-containing film. In this case, a semiconductor device circuit pattern can be formed on a substrate in the following manner:
A photoresist film may be formed on the metal-containing film as a resist upper layer film as described above. Alternatively, an organic adhesive film may be formed on the metal-containing film by spin-coating, and a photoresist film may be formed thereon.
As described above, when the resist underlayer film is formed on the substrate to be processed, the resist underlayer film can be formed by a method using a coating-type organic underlayer film material, a CVD method, an ALD method, or the like. Examples of the coating-type organic underlayer film material include resins and compositions disclosed in JP2012-001687A, JP2012-077295A, JP2004-264710A, JP2005-043471A, JP2005-250434A, JP2007-293294A, JP2008-065303A, JP2004-205685A, JP2007-171895A, JP2009-014816A, JP2007-199653A, JP2008-274250A, JP2010-122656A, JP2012-214720A, JP2014-029435A, WO2012/077640A1, WO2010/147155A1, WO2012/176767A1, JP2005-128509A, JP2006-259249A, JP2006-259482A, JP2006-293298A, JP2007-316282A, JP2012-145897A, JP2017-119671A, JP2019-044022A, etc.
The resist upper layer film in the multilayer resist process described above may be either a positive type or a negative type, and it is possible to use a film similar to the typically used photoresist composition. The prebaking, which is conducted after the spin-coating with the photoresist composition, is preferably performed at 60 to 180° C. for 10 to 300 seconds. Thereafter, exposure is conducted according to a usual manner, followed by post-exposure baking (PEB) and development, thereby obtaining a resist pattern. Although the thickness of the resist upper layer film is not particularly limited, the thickness is preferably 30 to 500 nm, particularly preferably 50 to 400 nm.
Furthermore, examples of light for exposure include high-energy beams at wavelengths of 300 nm or less, specifically excimer lasers at 248 nm, 193 nm, and 157 nm, soft X-rays at 3 to 20 nm, an electron beam, X-rays, and the like.
As the method for forming a pattern in the resist upper layer film, it is preferable to use a patterning process using a photolithography with a wavelength of 5 nm or more and 300 nm or less, a direct drawing using an electron beam, nanoimprinting, or a combination thereof.
The development method in the patterning process is preferably alkali development or development using an organic solvent.
Next, etching is performed while using the obtained resist pattern as a mask. The etching of a silicon-containing resist middle layer film or an inorganic hard mask in the three-layer resist process is performed while using the upper layer resist pattern as a mask by using a fluorocarbon-based gas. In this manner, a silicon-containing resist middle layer film pattern or an inorganic hard mask pattern is formed.
Next, the metal-containing film is etched while using the obtained silicon-containing resist middle layer film pattern or inorganic hard mask pattern as a mask. The etching of the metal-containing film is preferably performed using an etching gas mainly containing a chlorine-based gas.
The subsequent etching of a body to be processed may also be performed according to a usual manner. For example, in the case of a body to be processed made of SiO2, SiN or silica-based low dielectric constant insulating film, the etching is performed mainly based on a fluorocarbon-based gas. When the substrate is processed by way of etching with a fluorocarbon-based gas, the silicon-containing resist middle layer film pattern in the three-layer resist process is stripped simultaneously with the substrate processing.
The metal-containing film obtained by using the inventive composition for forming a metal-containing film is characterized by its excellent etching resistance at the time of etching of the body to be processed.
Examples of the body to be processed (substrate to be processed) include, but are not particularly limited to, substrates made of Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., those in which the layers to be processed are formed on the substrate, and the like. Examples of the layers to be processed include various low-k films such as those made of Si, SiO2, SiON, SiN, p-Si, α-Si, W, W—Si, Al, Cu, Al—Si, and the like, and stopper films therefor, which can each be typically formed into a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When the layer to be processed is formed, the substrate and the layer to be processed are made of different materials.
In the patterning process using the composition of the present invention for forming a resist underlayer film, it is preferable to use a substrate to be processed having a structure or step having a height of 30 nm or more. As described above, the inventive composition for forming a metal-containing film has excellent filling and planarizing properties, so that a flat cured film can be formed even when the substrate to be processed has a step (irregularities) or structure having a height of 30 nm or more. The height of the structure or step of the substrate to be processed is preferably 30 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. In the method of processing a stepped substrate having a pattern of the above-described height, filling and planarizing by forming a film of the inventive composition for forming a metal-containing film makes it possible to achieve a uniform film thickness in the subsequently formed resist middle layer film and resist upper layer film. Therefore, it is easy to ensure the exposure depth margin (DOF) at the time of photolithography, which is very desirable.
The present invention also provides, as a tone-reversal patterning process using such a composition for forming a metal-containing film, a tone-reversal patterning process including the steps of:
An example of formation of a tone-reversal pattern is specifically explained below by referring to
Next, as shown in
After applying the inventive composition for forming a metal-containing film onto the resist underlayer film pattern 7a formed of a coating-type organic underlayer film composition, heating is performed to cover the resist underlayer film pattern with a metal-containing film 8, thereby filling a space between the resist underlayer film patterns 7a formed of a coating-type organic underlayer film composition with the metal-containing film (
As described above, when the resist underlayer film is formed on the substrate to be processed, the resist underlayer film can be formed by a method using a coating-type organic underlayer film material, a CVD method, an ALD method, or the like. Examples of the coating-type organic underlayer film material include resins and compositions disclosed in JP2012-1687A, JP2012-77295A, JP2004-264710A, JP2005-043471A, JP2005-250434A, JP2007-293294A, JP2008-65303A, JP2004-205685A, JP2007-171895A, JP2009-14816A, JP2007-199653A, JP2008-274250A, JP2010-122656A, JP2012-214720A, JP2014-29435A, WO2012/077640A1, WO2010/147155A1, WO2012/176767A1, JP2005-128509A, JP2006-259249A, JP2006-259482A, JP2006-293298A, JP2007-316282A, JP2012-145897A, JP2017-119671A, JP2019-44022A, etc.
In the tone-reversal patterning process, after the obtained resist underlayer film pattern is coated with the composition for forming a metal-containing film, it is preferable to remove the metal-containing film by using a dry etching gas mainly containing a chlorine-based gas so as to expose the upper surface of the resist underlayer film pattern. Thereafter, the resist middle layer film or the hard mask middle layer film remaining on the resist underlayer film is removed by dry etching using a fluorocarbon-based gas, and the resist underlayer film pattern having an exposed surface is removed by dry etching using an oxygen-based gas to form a metal-containing film pattern.
In the tone-reversal patterning process described above, the resist underlayer film pattern preferably has a step or a structure with a height of 30 nm or more. As described above, the inventive composition for forming a metal-containing film has excellent filling and planarizing properties. Thus, even when the film to be processed has a step (irregularities) or a structure with a height of 30 nm or more, a flat cured film can be formed. The height of the structure or the step of the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and still more preferably 100 nm or more. In the method of reversing the resist underlayer film pattern having a pattern with the above-described height, by performing filling and planarization by forming a film from the inventive composition for forming a metal-containing film, inversion/transfer of the pattern can be performed with a high degree of accuracy, which is very desirable. Reversing the resist underlayer film pattern by using the composition for forming a metal-containing film allows a desired resist pattern to be formed on a film to be processed with a high degree of accuracy due to the excellence in resistance in dry etching using a fluorocarbon-based gas relative to the resist underlayer film using a previously-known coating-type organic underlayer film material.
The present invention is more specifically described below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples. However, the present invention is not limited to these Examples. To obtain molecular weight and dispersity, weight-average molecular weight (Mw) and number-average molecular weight (Mn) on polystyrene basis were measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and dispersity (Mw/Mn) was calculated from these values.
In the following Synthesis Examples and Comparative Examples, the starting material group W1: (w1) to (w3), starting material group T: (T1) to (T9), and starting material group Sn: (Sn-1) and (Sn-2) shown below were used.
Sn-1: dibutyltin oxide
Sn-2: dioctyltin oxide
10.0 g of dibutyltin oxide Sn-1, 3.9 g of the (w1) from the compound group W1, and 100 g of toluene were added together, and refluxed for 3 hours while removing water. Subsequently, the temperature was returned to room temperature, and then 1.4 g of the (T1) from the compound group T was added to the mixture, and refluxed for 4 hours while removing water. After the reaction, the solvent was removed under reduced pressure to give a compound (A-1).
The compounds (A-2) to (A-10) and the compounds (R-1) to (R-3) for the Comparative Examples shown in Tables 1 and 2 were obtained under the same reaction conditions as in Synthesis Example 1, except that the compound group W1, the compound group T, and the starting material group Sn were used at the charging amounts shown in Tables 1 and 2. The weight-average molecular weight (Mw) and the dispersity (Mw/Mn) of these compounds were determined. Table 3 shows the results.
8.0 g of butyltin trichloride was stirred at room temperature, and 10 g of acrylic acid was dropped thereto. After that, the temperature was raised to 80° C., and the mixture was stirred for 7 hours. After the completion of the reaction, the acrylic acid was removed under reduced pressure, and (R-4) was obtained.
As a compound having a different metal from the compound of the present invention for forming a metal-containing film, a titanium compound reported in [Synthesis Example A-II] of JP6189758B2 was synthesized.
An IPA solution (500 g) of deionized water (27 g) was agitated with an IPA solution (500 g) of a titanium tetraisopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) (284 g) and dropped at room temperature for 2 hours. 2-methyl-2,4-pentanediol (120 g) was added to a solution obtained and agitated at room temperature for 30 minutes. After the solution was concentrated under reduced pressure at 30° C., it was heated to 60° C. and heating was continued under reduced pressure to generate no distillate. Then, PGMEA (1,200 g) was added thereto and heated under reduced pressure at 40° C. until no IPA was distilled to obtain a PGMEA solution of a titanium-containing compound (R-5) (1,000 g) (compound concentration: 20 mass %). The molecular weight of the compound measured in terms of polystyrene was Mw=1,100.
Under a nitrogen atmosphere, 160.2 g of 1,5-dihydroxynaphthalene, 56.8 g of formaldehyde, and 300 g of PGME (propylene glycol monomethyl ether) were added, and homogenized at an internal temperature of 100° C. After that, a mixed solution of 8.0 g of p-toluenesulfonic acid monohydrate and 8.0 g of PGME that had been mixed and homogenized beforehand was added dropwise slowly, and a reaction was allowed to take place at an internal temperature of 80° C. for 8 hours. After the reaction was completed, the resultant was cooled to room temperature, and 2,000 ml of MIBK was added thereto. The resultant was washed six times with 500 ml of pure water, and the organic layer was evaporated under reduced pressure to dryness. After adding 300 g of THF to the residue to yield a homogeneous solution, a crystal was precipitated in 2,000 g of hexane. The precipitated crystal was separated by filtration, washed twice with 500 g of hexane, and collected. The collected crystal was vacuum-dried at 70° C., thereby obtaining a resin (R-6).
The weight-average molecular weight (Mw) and the dispersity (Mw/Mn) were determined by GPC, and the following results were obtained.
The compound (A-1) for forming a metal-containing film was dissolved at a ratio shown in Table 4 in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CyHO) containing 0.5 mass % of a surfactant FC-4430 (manufactured by Sumitomo 3M Limited), and the solution was filtered through a 0.2-μm membrane filter to prepare a composition (UDL-1) for forming a metal-containing film.
Each chemical liquid was prepared in the same manner as UDL-1, except that the type and the contained amount of each component were as shown in Table 4. In Table 4, “−” indicates that the component was not used. The following formulae (C-1) and (C-2) were used for the crosslinking agent, the following formula (F-1) was used for the acid generator (TAG), 1,6-diacetoxyhexane (boiling point: 260° C.) was used as the high-boiling-point solvent (D-1), ZrO2 nanoparticles (5 nm core, 915505, Sigma-Aldrich Corp) were used as the metal nanoparticles (G-1), and a compound (BP-1) for a flowability accelerator was used as the flowability accelerator.
The crosslinking agent (C-1) used in a composition for forming a metal-containing film is shown below. Dipentaerythritol Hexaacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the crosslinking agent (C-2).
The thermal acid generator (F-1) used in a composition for forming a metal-containing film is shown below.
The flowability accelerator (BP-1) used in a composition for forming a metal-containing film is shown below.
Each of the compositions (UDL-1 to -15 and comparative UDL-1 to -5) for forming a metal-containing film prepared as described above was respectively applied onto a silicon substrate and baked at 100° C. for 60 seconds, and then the film thickness (a [nm]) was measured. Subsequently, after baking at the baking temperature shown in Table 5 for 60 seconds, the film thickness (b [nm]) was measured, and the difference between the film thicknesses (film remaining percentage: (b/a)×100) before and after the additional baking was determined.
Furthermore, a PGMEA solvent was dispensed thereon, left to stand for 30 seconds, spin-dried, and baked at 100° C. for 60 seconds to evaporate the PGMEA. The film thickness (c [nm]) was then measured. The difference between the film thicknesses (film remaining percentage: (c/b)×100) before and after the PGMEA treatment was determined. The following Table 5 shows the results.
As shown in Table 5, the inventive composition for forming a metal-containing film (Examples 1-1 to 1-15) had a film remaining percentage ((b/a)×100) of 50% or more after the additional high-temperature baking, and it was shown that the compositions had the high-temperature baking resistance required in resist underlayer films. In addition, the films subjected to additional high-temperature baking had a film remaining percentage ((c/b)×100) of 99% or more after the PGMEA rinsing, and it can be seen that a crosslinking reaction took place and sufficient solvent resistance was exhibited. On the other hand, comparative UDL-1, used in Comparative Example 1-1, did not have a crosslinking group, and therefore, had insufficient heat resistance. Therefore, the film remaining percentage ((b/a)×100) after the additional high-temperature baking was less than 5%. Meanwhile, in Comparative Example 1-2, where terminal crosslinkable groups were present but a compound (R-2) was used rather than a polymer, and in Comparative Example 1-4, where a compound (R-4) was used, the heat resistance was similarly insufficient, and the film remaining after the high-temperature baking was less than 5 nm. In the case of the compound (R-3), which had a crosslinkable group having the same structure as the T of the polymer (A-7), there was film remaining even after the additional high-temperature baking and there was no problem with film-formability. However, it was found that the film remaining percentage after the additional high-temperature baking was less than 50%, and that heat resistance was poor compared to the polymers of the present invention (Comparative Example 1-3). From these results, it can be said that in order to form a metal-containing film having excellent heat resistance, it is preferable to use a polymer. It is preferable for the composition to have excellent heat resistance at the time of high-temperature baking from the viewpoint of the productivity of semiconductor devices, since the amount of generated sublimation products is small.
In Comparative Example 1-5, the used composition comparative UDL-5 contained, as a compound having a different metal from the compound of the present invention for forming a metal-containing film, the titanium compound reported in [Synthesis Example A-II] of JP6189758B2. In this case, sufficient solvent resistance was exhibited, but the difference between the film thicknesses before and after the additional high-temperature baking was large, and it was shown that volume shrinkage due to high-temperature baking was greater than in the compound of the present invention for forming a metal-containing film.
Each of the compositions (UDL-1 to -15 and comparative UDL-5) for forming a metal-containing film that had favorable film-formability after the additional baking in the solvent resistance evaluation was respectively applied onto an SiO2 wafer substrate having a dense line-and-space pattern (line width=40 nm, line depth=120 nm, distance between the centers of two adjacent lines=80 nm), followed by heating at the temperature shown in Table 6 for 60 seconds by using a hot plate to form a metal-containing film having a film thickness of 100 nm. The substrate used was a base substrate 9 (SiO2 wafer substrate) having a dense line-and-space pattern shown in
It was successfully confirmed that, as shown in Table 6, in Examples 2-1 to 2-15 using the compositions (UDL-1 to -15) of the present invention for forming a resist metal-containing film, it was possible to fill the dense line-and-space pattern without the generation of voids, and excellent filling property was provided. On the other hand, voids were observed at the bottom of the pattern in Comparative Example 2-1, using comparative UDL-5 containing the titanium compound reported in [Synthesis Example A-II] of JP6189758B2. It is conjectured that voids were generated because volume shrinkage due to high-temperature baking was great, as observed in the solvent resistance evaluation.
Regarding base substrates 11 (SiO2 wafer substrates) each having a dense line-and-space pattern shown in
As shown in Table 7, it was observed that the step in the film between the patterned portion and the non-patterned portion was small and the planarization property was better in Examples 3-1 to 3-15, where the compositions (UDL-1 to -15) of the present invention for forming a resist metal-containing film were used, than in Comparative Example 3-1, where the organic resist underlayer film material, comparative UDL-5, was used. Comparing Example 3-1 and Example 3-2, better results were achieved in Example 3-2 regarding flatness. It is conjectured that this is because the amount of the component T in the general formula (2) was greater in UDL-2 than in UDL-1, and thermal flowability was better.
Furthermore, UDL-13, which contained a high-boiling-point solvent (D-1), and UDL-15, which contained a flowability accelerator (BP-1), showed particularly excellent planarizing property. It can be observed that the thermal flowability of a compound for forming a metal-containing film can be improved further by using these additives.
Meanwhile, in Comparative Example 3-1, where comparative UDL-5 was used, flatness was poor, since thermal flowability was insufficient.
Each of the compositions (UDL-1 to -15 and comparative UDL-6) for forming a metal-containing film that had good film-formability after the additional baking in the solvent resistance evaluation was respectively applied onto a silicon substrate and heated by using a hot plate at the temperature shown in Table 8 for 60 seconds to form a metal-containing film having a film thickness of 100 nm, and the film thickness A was measured. Subsequently, etching was performed with CF4 gas, O2 gas, and Cl2 gas under the following conditions for the specified number of seconds by using an etching apparatus CE-300I manufactured by ULVAC, Inc., and the film thickness B was measured. Then, the film thickness etched in 1 minute (etching rate, nm/min) was calculated from the film thickness etched in the respective number of seconds (“film thickness B”−“film thickness A”). Table 8 shows the results.
Conditions of Dry Etching with CF4 Gas
As shown in Table 8, it was shown that better CF4 etching resistance and O2 etching resistance were exhibited in Examples 4-1 to 4-15, where the inventive compositions (UDL-1 to -15) for forming a metal-containing film were used, than in Comparative Example 4-1, where comparative UDL-6, which was an organic resist underlayer film material, was used. In addition, it was revealed that, while the compositions showed excellent resistance to etching with CF4 gas and O2 gas, the compositions exhibited excellent removability by etching with Cl2 gas.
Comparing Example 4-1 and Example 4-2, etching resistance regarding CF4 gas was better in Example 4-1. It is conjectured that this is because the amount of the component W1 in the general formula (2) was greater in UDL-1 than in UDL-2, that is, the amount of a Sn-containing repeating unit was large, and it was possible to form a cured film containing a large amount of a SnO2 structure.
Each of the compositions (UDL-1 to -15 and comparative UDL-5 and -6) for forming a metal-containing film that had favorable film-formability after the additional baking in the solvent resistance evaluation was respectively applied onto an SiO2 wafer substrate having a trench pattern (trench width: 10 μm, trench depth: 0.10 μm), and baked at 250° C. for 60 seconds in the atmosphere to form a metal-containing film having a thickness of 100 nm. A silicon-containing resist middle layer film material (SOG-1) was applied thereto, followed by baking at 220° C. for 60 seconds to form a resist middle layer film having a thickness of 30 nm. A monolayer resist for ArF as a resist upper layer film material was applied thereto, followed by baking at 105° C. for 60 seconds to form a photoresist film having a thickness of 100 nm. A liquid immersion top coat composition (TC-1) was applied to the photoresist film, followed by baking at 90° C. for 60 seconds to form a top coat having a thickness of 50 nm.
The silicon-containing resist middle layer film material (SOG-1) was prepared by dissolving a polymer represented by an ArF silicon-containing middle layer film polymer (SiP1) and a crosslinking catalyst (CAT1) in an organic solvent containing 0.1 mass % of FC-4430 (manufactured by Sumitomo 3M Limited) in the proportion shown in Table 9; and filtering the solution through a filter made of a fluororesin and having a pore size of 0.1 μm.
The structural formulae of the of the ArF silicon-containing middle layer film polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.
The resist upper layer film material (monolayer resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1), each in the proportion shown in Table 10, in a solvent containing 0.1% by mass of a surfactant FC-4430 (manufactured by Sumitomo 3M Limited), and filtering the solution through a 0.1-μm filter made of a fluororesin.
The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used for the resist upper layer film material (monolayer resist for ArF) are shown below.
The liquid immersion top coat composition (TC-1) was prepared by dissolving a top coat polymer (PP1) in an organic solvent at the proportion shown in Table 11, and filtering the solution through a 0.1-μm filter made of a fluororesin.
The polymer (PP1) used for the liquid immersion top coat composition (TC-1) is shown below.
Then, the substrate was exposed to light with an ArF liquid immersion exposure apparatus (NSR-S610C manufactured by Nikon Corporation, NA: 1.30, σ: 0.98/0.65, 35° s-polarized dipole illumination, 6% halftone phase shift mask), baked at 100° C. for 60 seconds (PEB), and developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, thereby obtaining a 55 nm 1:1 positive line-and-space pattern (a resist pattern).
Subsequently, the silicon-containing resist middle layer film material (SOG-1) was etched by dry etching while using the resist pattern as a mask to form a hard mask pattern. The metal-containing film was then etched while using the obtained hard mask pattern as a mask to form a metal-containing film pattern, and the SiO2 film was etched while using the obtained metal-containing film pattern as a mask. The etching conditions were as follows.
Conditions of Dry Etching with CF4 Gas
Conditions of Dry Etching with CF4 Gas
Table 12 shows the results obtained by observation of the pattern cross section with an electron microscope (S-4700) manufactured by Hitachi, Ltd.
As shown in Table 12, in Examples 5-1 to 5-15, where the inventive compositions (UDL-1 to -15) for forming a metal-containing film were used, the resist upper layer film pattern was successfully transferred to the substrate in the end in every case. Thus, it was confirmed that the inventive composition for forming a metal-containing film can be used suitably for fine processing using a multilayer resist method. On the other hand, in Comparative Example 5-1, where the performance in the filling property evaluation and the planarizing property evaluation was found to be insufficient, pattern collapse occurred during patterning, and it was not possible to obtain a favorable pattern in the end. Meanwhile, in Comparative Example 5-2, where there were no problems in the filling property and planarizing property evaluations but insufficient performance was observed in the dry etching resistance evaluation, distortion of the pattern profile occurred at the time of pattern processing, and it was not possible to obtain a favorable pattern in the end.
From the above, the inventive polymer for forming a metal-containing film is an organotin polymer having both high thermal flowability and high thermosetting property, so that a composition for forming a metal-containing film containing the polymer can provide a resist underlayer film material having better dry etching resistance than conventional organic underlayer film materials and also having high filling and planarizing properties. Therefore, such a composition is extremely useful as a resist underlayer film material used in a multilayer resist method and an inverting agent used in a tone-reversal etching method.
The present description includes the following embodiments.
[1]: A polymer for forming a metal-containing film comprising
a repeating unit represented by the following general formula (1A),
wherein W1 represents a divalent organic group having 1 to 31 carbon atoms; and each Q independently represents a group selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and having one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 31 carbon atoms.
[2]: The polymer for forming a metal-containing film of the above [1], further comprising a condensation polymer of an organotin compound SnOQ2, wherein the Q is as defined above.
[3]: The polymer for forming a metal-containing film of the above [1] or [2], comprising a structure represented by the following general formula (1B) at an end,
wherein Tx represents a monovalent organic group having a hydroxy group or a structure represented by one of the following general formulae (a-1) to (a-3) or an unsaturated hydrocarbon group having 2 to 10 carbon atoms; and a broken line represents an attachment point to the polymer,
wherein R1 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; “q” represents 0 or 1; and “*” represents an attachment point.
[4]: The polymer for forming a metal-containing film of the above [3], represented by the following general formula (2),
wherein W1 and Q are as defined above; T's are identical to or different from one another and each represent an unsaturated hydrocarbon group having 2 to 10 carbon atoms or a monovalent organic group represented by the following general formula (2A); and “a” represents 1 to 30,
wherein X1 represents a saturated divalent organic group having 1 to 20 carbon atoms and optionally containing a heteroatom or an unsaturated divalent organic group having 2 to 20 carbon atoms and optionally containing a heteroatom; W2 represents the following general formula (2B); and “*” represents an attachment point to a carbon atom of a carbonyl group,
wherein Y represents a saturated organic group having a valency of 1+h, having 1 to 20 carbon atoms, and optionally containing a heteroatom or an unsaturated organic group having a valency of 1+h, having 2 to 20 carbon atoms, and optionally containing a heteroatom; RA represents a hydroxy group or a structure represented by one of the general formulae (a-1) to (a-3); and “h” represents 1 to 3.
[5]: The polymer for forming a metal-containing film of the above [4], wherein the T is one of structures represented by the following general formulae (2Aa),
wherein X1a represents a saturated divalent organic group having 1 to 20 carbon atoms and optionally containing a heteroatom or an unsaturated divalent organic group having 2 to 20 carbon atoms and optionally containing a heteroatom; and W2a represents one of structures represented by the following general formulae (2C),
wherein RA1 represents a structure represented by the general formula (a-1); RA2 represents a hydroxy group or one of the structures represented by the general formula (a-2) or (a-3); Z represents an oxygen atom or a secondary amino group; L represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R2 represents a saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms; “t” represents 1 to 6 and “s” represents 0 to 5, provided that t+s is 1 or more and 6 or less; “r” represents 1 to 10; “u” represents 0 or 1; “m” represents 0 or 1; and “*” represents an attachment point.
[6]: The polymer for forming a metal-containing film of any one of the above [1] to [5], wherein the W1 represents a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms.
[7]: The polymer for forming a metal-containing film of the above [6], wherein the W1 represents one of structures represented by the following general formulae (b-1) to (b-3),
wherein Ra, Rb, and RC each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, Ra and Rb optionally being bonded to each other to form a cyclic substituent; and “*1” and “*2” each represent an attachment point to a carbonyl group, “*1” and “*2” optionally being reversed.
[8]: The polymer for forming a metal-containing film of the above [5], wherein the X1a represents an unsaturated divalent organic group having 2 to 20 carbon atoms.
[9]: The polymer for forming a metal-containing film of the above [8], wherein the X1a represents one of structures represented by the following general formulae (c-1) to (c-2),
wherein Ra, Rb, and RC each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, Ra and Rb optionally being bonded to each other to form a cyclic substituent; and “*1” and “*2” each represent an attachment point to a carbonyl group, “*1” and “*2” optionally being reversed.
[10]: A composition for forming a metal-containing film, the composition functioning as a resist underlayer film material and a resist material used in manufacturing a semiconductor, the composition comprising: (A) the polymer for forming a metal-containing film of any one of the above [1] to [9]; and (B) an organic solvent.
[11]: The composition for forming a metal-containing film of the above [10], wherein the composition is usable as a resist underlayer film used in a multilayer resist method, the composition further comprising one or more of (C) a crosslinking agent, (D) a high-boiling-point solvent, (E) a surfactant, and (F) a flowability accelerator.
[12]: The composition for forming a metal-containing film of the above [11], wherein the high-boiling-point solvent (D) is one or more kinds of organic solvent having a boiling point of 180° C. or higher.
[13]: The composition for forming a metal-containing film of any one of the above [10] to [12], further comprising (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less.
[14]: The composition for forming a metal-containing film of the above [13], wherein the metal oxide nanoparticles (G) are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.
[15]: A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
[16]: A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
[17]: A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
[18]: The patterning process of the above [17], wherein the inorganic hard mask middle layer film is formed by a CVD method or an ALD method.
[19]: A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
[20]: A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
[21]: A tone-reversal patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
It should be noted that the present invention is not limited to the above-described embodiments. The embodiments are just examples, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept disclosed in claims of the present invention are included in the technical scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-204797 | Dec 2022 | JP | national |
