Patent Application
20240294855
The present invention relates to an electronic device manufacturing aqueous solution, a method for manufacturing a resist pattern and a method for manufacturing a device.
In recent years, needs for high integration of LSI has been increasing, and refining of patterns is required. In order to respond such needs, lithography processes using KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV; 13 nm), X-ray of short wavelength, electron beam or the like have been put to practical use. In order to respond to such refining of resist patterns, also for photosensitive resin compositions to be used as a resist during refining processing, those having high resolution are required. Finer patterns can be formed by exposing with light of short wavelength, but since an extremely fine structure is formed, a yield becomes a problem due to fine pattern collapse or the like.
Under such circumstances, in Patent Document 1, a rinse liquid for lithography, which has good performance such as pattern collapse margin, defect, and LWR as in the conventional system containing a surfactant, and also has good characteristics in melting, has been studied.
Further, as another attempt there are studies to use a fluorine-containing surfactant (Patent Document 2 and Patent Document 3).
The present inventors considered that there are one or more problems still need improvements. Examples of these include the followings: reducing defects in fine resist patterns; suppressing bridge formation in resist patterns; preventing resist pattern collapse in fine resist patterns; suppressing resist pattern width non-uniformity; reducing the residue after removing an electronic device manufacturing aqueous solution; reducing the surface tension of an electronic device manufacturing aqueous solution; providing an electronic device manufacturing aqueous solution with less environmental impact; providing an electronic device manufacturing aqueous solution with low handling risk; providing an electronic device manufacturing aqueous solution having good storage stability (for example, long-term storage); and providing an electronic device manufacturing aqueous solution with less impact given to resist patterns.
The present invention has been made based on the technical background as described above, and provides an electronic device manufacturing aqueous solution.
The electronic device manufacturing aqueous solution comprises an alkylcarboxylic acid compound (A); and a solvent (B)
A1-COOH (a)
The method for manufacturing a resist pattern according to the present invention uses the above-mentioned electronic device manufacturing aqueous solution.
The method for manufacturing a device according to the present invention comprises the above-mentioned method for manufacturing a resist pattern.
Using the electronic device manufacturing aqueous solution according to the present invention, it is possible to expect one or more of the following effects.
It is possible to reduce defects in fine resist patterns. It is possible to suppress the formation of bridges in the resist patterns. It is possible to prevent the resist pattern collapse in fine resist patterns. It is possible to suppress the resist pattern width non-uniformity. It is possible to reduce the residue after removing an electronic device manufacturing aqueous solution. It is possible to reduce the surface tension of an electronic device manufacturing aqueous solution. It is possible to reduce the environmental impact of an electronic device manufacturing aqueous solution. It is possible to reduce the handling risk of an electronic device manufacturing aqueous solution. It is possible to make good storage stability of an electronic device manufacturing aqueous solution. It is possible to reduce the impact that an electronic device manufacturing aqueous solution gives to resist patterns.
Embodiments of the present invention are described below in detail.
Unless otherwise specified in the present specification, the definitions and examples described in this paragraph are followed.
The singular form includes the plural form and “one” or “that” means “at least one”. An element of a concept can be expressed by a plurality of species, and when the amount (for example, mass % or mol %) is described, it means sum of the plurality of species.
“And/or” includes a combination of all elements and also includes single use of the element.
When a numerical range is indicated using “to” or “-”, it includes both endpoints and units thereof are common. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.
The descriptions such as “Cx-y”, “Cx-Cy” and “Cx” mean the number of carbons in a molecule or substituent. For example, C1-6 alkyl means an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl etc.).
When polymer has plural types of repeating units, these repeating units copolymerize. These copolymerization may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When polymer or resin is represented by a structural formula, n, m or the like that is attached next to parentheses indicate the number of repetitions.
Celsius is used as the temperature unit. For example, 20 degrees means 20 degrees Celsius.
The additive refers to a compound itself having a function thereof (for example, in the case of a base generator, a compound itself that generates a base). An embodiment in which a compound is dissolved or dispersed in a solvent and added to a composition is also possible. As one embodiment of the present invention, it is preferable that such a solvent is contained in the composition according to the present invention as the solvent (B) or another component.
The electronic device manufacturing aqueous solution according to the present invention comprises an alkylcarboxylic acid compound (A) and a solvent (B).
The electronic device manufacturing aqueous solution is one used in the process of manufacturing an electronic device. It can be one used in the manufacturing process of an electronic device and can be one being removed or lost in the course of the process. Examples of the electronic device include display devices, LED and semiconductor devices.
The electronic device manufacturing aqueous solution is preferably a semiconductor substrate manufacturing aqueous solution; more preferably a semiconductor substrate manufacturing process cleaning liquid; further preferably a lithography cleaning liquid; and further more preferably a resist pattern cleaning liquid. The electronic device manufacturing aqueous solution that is a semiconductor substrate manufacturing aqueous solution can also be said to be a semiconductor substrate manufacturing aqueous solution consisting only of the electronic device manufacturing aqueous solution of the present invention.
As another embodiment of the present invention, the electronic device manufacturing aqueous solution can be a rinse composition used for rinsing an exposed and developed resist pattern.
The alkylcarboxylic acid compound (A) used in the present invention is represented by the formula (a):
A1-COOH (a)
Exemplified embodiments of the alkylcarboxylic acid compound (A) include 2-methylpropionic acid, n-butanoic acid, 2-methylbutanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid, 2-methylheptanoic acid, 4-methyl-n-octanoic acid, 2-ethylhexanoic acid, 2-propylpentanoic acid, 2,2-dimethylpentanoic acid and 3,5,5-trimethyl-hexanoic acid.
The content of the alkylcarboxylic acid compound (A) is preferably 0.01 to 10 mass % (more preferably 0.02 to 5 mass %; and further preferably 0.02 to 1 mass %), based on the electronic device manufacturing aqueous solution.
One of the effects of the alkylcarboxylic acid compound (A) in the electronic device manufacturing aqueous solution according to the present invention is to contribute to the prevention of pattern collapse after development of the resist pattern. Although not to be bound by theory, it is considered that the low affinity between the alkylcarboxylic acid compound of the present invention and the resist wall can increase the contact angle of the electronic device manufacturing aqueous solution during the process of drying the rinse. In particular, it is considered that the alkyl in the formula (a) can reduce the surface tension of the composition, and the carboxyl can improve the solubility of the electronic device manufacturing aqueous solution, thereby being capable of making the balance between the solubility and the low surface tension improved.
The solvent (B) comprises water. The water is preferably deionized water.
Considering that it is used in the electronic device manufacturing process, the solvent (B) is preferably one having few impurities. The impurity concentration of the solvent (B) is preferably 1 ppm or less (more preferably 100 ppb or less, and further preferably 10 ppb or less).
The content of water based on the solvent (B) is preferably 90 to 100 mass % (more preferably 98 to 100 mass %; further preferably 99 to 100 mass %; and further more preferably 99.9 to 100 mass %). In a preferred embodiment of the present invention, the solvent (B) consists substantially only of water. However, an embodiment in which an additive is dissolved and/or dispersed in a solvent other than water (for example, a surfactant) and contained in the electronic device manufacturing aqueous solution of the present invention is accepted as a preferred embodiment of the present invention. In a further preferred embodiment of the present invention, the content of the water contained in the solvent (B) is 100 mass %.
As exemplified embodiments of the solvent (B) excluding water, for example, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, or any mixture of any of these are preferable. These are preferable in terms of storage stability of the solution. These solvents can be also used as any mixture of any two or more.
The content of the solvent (B) is preferably 80 to 99.99 mass % (more preferably 90 to 99.99 mass %; further preferably 95 to 99.99 mass %; and further more preferably 98 to 99.99 mass %), based on the electronic device manufacturing aqueous solution.
Further, the content of the water contained in the solvent (B) is preferably 80 to 99.99 mass % (more preferably 90 to 99.99 mass %; further preferably 95 to 99.99 mass %; and further more preferably 98 to 99.99 mass %), based on the electronic device manufacturing aqueous solution.
The electronic device manufacturing aqueous solution according to the present invention essentially comprises the above-mentioned components (A) and (B), but can comprise further compounds, if necessary. Details thereof are described below. The components other than (A) and (B) (in the case of a plurality, the sum thereof) in the entire composition are preferably 0 to 10 mass % (more preferably 0 to 5 mass %; and further preferably 0 to 3 mass %), based on the electronic device manufacturing aqueous solution. The embodiment in which the electronic device manufacturing aqueous solution according to the present invention contains no component other than (A) and (B) (0 mass %) is also a preferred embodiment of the present invention.
The electronic device manufacturing aqueous solution according to the present invention comprises a nitrogen-containing compound (C). The nitrogen-containing compound (C) may have 1 or more nitrogen in the compound.
As mentioned above, by containing the alkylcarboxylic acid compound (A) in the electronic device manufacturing aqueous solution according to the present invention, pattern collapse is suppressed, but by combining the nitrogen-containing compound (C), pattern collapse can be further suppressed. Further, other defects such as pattern melting and resist residue can be also suppressed. Although not to be bound by theory, it is considered possible to reduce the impact of the alkylcarboxylic acid compound (A) to resist patterns by containing the nitrogen-containing compound (C).
Examples of the nitrogen-containing compound (C) include the followings:
The nitrogen-containing compound (C) is preferably selected from the group consisting of (i), (ii) and (iv), and more preferably selected from the group consisting of ammonia, n-butylamine, ethylenediamine, triethylamine, tripropylamine and N,N,N′,N′-tetraethyl-ethylenediamine.
The molecular weight of the nitrogen-containing compound (C) is preferably 17 to 500 (more preferably 17 to 150; and further more preferably 60 to 143).
The content of the nitrogen-containing compound (C) is preferably 0.0001 to 10 mass % (more preferably 0.0005 to 0.5 mass %; further preferably 0.0005 to 0.05 mass %; and further more preferably 0.0005 to 0.01 mass %), based on the electronic device manufacturing aqueous solution.
The electronic device manufacturing aqueous solution according to the present invention can further comprise a hydroxy-containing compound (D). The hydroxy-containing compound (D) may have 1 or more hydroxy in the compound, and is preferably a C3-30 compound, which has 1 to 3 hydroxy and may be fluorine-substituted. The fluorine substitution in this case substitutes the H of the compound with F, but this substitution does not substitute the H in the hydroxy.
It is considered that further including the hydroxy-containing compound (D) makes it possible to further reduce the limit size that does not collapse.
As a preferred embodiment, the hydroxy-containing compound (D) is represented by the formula (d).
It is possible to obtain the effects of the present invention without using any fluorine-containing component. As such an embodiment, Ld1 and Ld2 are each independently C1-5 alkylene, C2-4 alkynylene or phenylene (more preferably, each independently C2-4 alkylene, acetylene or phenylene; and further more preferably, each independently C2-4 alkylene or acetylene).
h is 0, 1 or 2 (preferably 0 or 1; and more preferably 0).
Exemplified embodiments of the hydroxy-containing compound (D) include 3-hexyne-2,5-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octine-3,6-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, cis-1,4-dihydroxy-2-butene, 1,4-benzenedimethanol, and any combination of any of these.
The content of the hydroxy-containing compound (D) is preferably 0.001 to 10 mass % (more preferably 0.005 to 5 mass %, further preferably 0.01 to 1 mass %), based on the electronic device manufacturing aqueous solution.
It is also a preferred embodiment of the present invention to contain no hydroxy-containing compound.
The electronic device manufacturing aqueous solution according to the present invention can further comprise a surfactant (E). The surfactant (E) is useful for improving coatability and solubility. The surfactant (E) is different one from the alkylcarboxylic acid compound (A) and the hydroxy-containing compound (D).
Examples of the surfactant (E) include polyoxyethylene alkyl ether compounds, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ether compounds, such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenol ether, polyoxyethylene/polyoxypropylene block copolymer compounds, sorbitan fatty acid ester compounds, such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan fatty acid ester compounds, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan tristearate. Fluorosurfactants such as trade names Eftop EF301, EF303, EF352 (Tohkem Products), trade names Megaface F171, F173, R-08, R-30, R-2011 (DIC), Fluorad FC430, FC431 (Sumitomo 3M), and trade names AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC); and organosiloxane polymer KP341 (Shin-Etsu Chemical) or the like are exemplified.
The content of the surfactant (E) is preferably 0.01 to 5 mass %, more preferably 0.02 to 0.5 mass %, based on the electronic device manufacturing aqueous solution.
It is also a preferred embodiment of the present invention to contain no surfactant (E).
The electronic device manufacturing aqueous solution according to the present invention can further comprise an additive (F). In the present invention, the additive (F) comprises an acid, a base, a germicide, an antibacterial agent, a preservative or a fungicide. The acid in the additive (F) is different from the alkylcarboxylic acid compound (A). The base in the additive (F) is different from the nitrogen-containing compound (C).
The acid or base can be used to adjust the pH value of the treating liquid and improve the solubility of additive components. Examples of the acid include aromatic carboxylic acids.
The additive (F) can comprise an antibacterial agent, a bactericidal agent, a preservative or a germicide, if necessary. These chemicals are used to prevent bacteria or fungi from propagating over time. Examples of these chemicals include alcohols such as phenoxyethanol, and isothiazolone. Bestcide (Nippon Soda) is a particularly effective antibacterial agent, bactericidal agent and germicide.
The content of the additive (F) is preferably 0.0001 to 10 mass % (more preferably 0.0005 to 0.1 mass %), based on the electronic device manufacturing aqueous solution. It is also a preferred embodiment of the present invention to contain no additive (F).
The electronic device manufacturing aqueous solution according to the present invention can be filtered with a filter to remove impurities and/or insolubles after dissolving its components.
The present invention also provides a method for producing a resist pattern using the above-mentioned electronic device manufacturing aqueous solution. The photosensitive resin composition (resist composition) used in the method may be either a positive type or a negative type; the positive type is more preferable. A typical method for manufacturing a resist pattern to which the electronic device manufacturing aqueous solution according to the present invention is applied comprises the following steps:
Hereinafter, details are explained. First, a photosensitive resin composition is applied (for example, laminated) above a substrate such as a silicon substrate or a glass substrate, which has been pretreated as necessary, thereby forming a photosensitive resin layer. Any publicly known method can be used for laminating, but a coating method such as spin coating is suitable. The photosensitive resin composition can be laminated directly on the substrate or can be laminated with one or more intervening layers (for example, BARC). Further, an anti-reflective coating (for example, TARC) may be laminated above the photosensitive resin layer (opposite to the substrate). Layers other than the photosensitive resin layer are described later. Forming an anti-reflective coating above or under the photosensitive resin film makes it possible to improve the cross-sectional shape and the exposure margin.
Typical examples of the positive type or negative type photosensitive resin composition used in the method for manufacturing a resist pattern of the present invention include one comprising a quinonediazide-based photosensitizer and an alkali-soluble resin, and a chemically amplified type photosensitive resin composition. From the viewpoint of forming a fine resist pattern having high resolution, a chemically amplified type photosensitive resin composition is preferable, and examples thereof include a chemically amplified type PHS-acrylate hybrid-based EUV resist composition. It is more preferable that these are positive type photosensitive resin compositions.
Examples of the quinonediazide-based photosensitizer used in the positive type photosensitive resin composition comprising the quinonediazide-based photosensitizer and the alkali-soluble resin include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinone diazido-5-sulfonic acid, esters or amides of these sulfonic acids, or the like, and examples of the alkali-soluble resin include novolak resin, polyvinyl phenol, polyvinyl alcohol, copolymer of acrylic acid or methacrylic acid, or the like. Preferable examples of novolac resin include those produced from one or more phenols such as phenol, o-cresol, m-cresol, p-cresol and xylenol, and one or more aldehydes such as formaldehyde and paraformaldehyde.
Further, as the chemically amplified type photosensitive resin composition, a positive type chemically amplified photosensitive resin composition comprising a compound (photoacid generator) that generates an acid by irradiation with radiation and resin whose polarity is increased by the action of an acid generated from the photoacid generator and whose solubility in a developer changes between the exposed portion and the unexposed portion, or a negative type chemically amplified photosensitive resin composition comprising an alkali-soluble resin, a photoacid generator and a crosslinking agent, in which crosslinking of the resin occurs by the action of the acid and the solubility in a developer changes between the exposed portion and the unexposed portion can be mentioned.
As the resin whose polarity is increased by the action of the acid and whose solubility in a developer changes between the exposed portion and the unexposed portion, resin having a group at the main chain or side chain of the resin, or both the main chain and the side chain of the resin, which decomposes by the action of the acid to generate an alkali-soluble group can be mentioned. Typical examples thereof include polymer in which an acetal group or a ketal group is introduced as a protective group into a hydroxystyrene-based polymer (PHS) (for example, JP H2-19847 A), and a similar polymer in which a t-butoxy carbonyloxy group or a p-tetrahydropyranyloxy group is introduced as an acid-decomposable group (JP H2-209977 A, etc.), and the like.
Further, the photoacid generator may be any compound that generates an acid by irradiating radiation, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts, organic halogen compounds, organometallic compounds/organic halides, photoacid generators having an o-nitrobenzyl type protective group, compounds capable of photolysis to generate a sulfonic acid represented by iminosulfonate or the like, disulfon compounds, diazoketosulfone compounds, diazodisulfone compounds, and the like.
Further, compounds in which these groups or compounds capable of generating an acid by light are introduced into the main chain or the side chain of polymer can also be used.
Additionally, the above-mentioned chemically amplified type photosensitive resin composition can further comprise, if necessary, an acid-decomposable and dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like.
For example, the photosensitive resin composition is applied on a substrate by a suitable coating apparatus such as a spinner or coater by means of a suitable coating method, and is heated on a hot plate to remove the solvent in the photosensitive resin composition, thereby forming a photosensitive resin layer. The heating temperature varies depending on the solvent or resist composition used, but is generally performed at 70 to 150° C., preferably 90 to 150° C., and the heating can be performed for 10 to 180 seconds, preferably 30 to 120 seconds in the case of hot plate, or for 1 to 30 minutes in the case of clean oven.
In the method for manufacturing a resist pattern of the present invention, the presence of film(s) or layer(s) other than the photosensitive resin layer is also accepted. Without direct contact of the substrate with the photosensitive resin layer, intervening layer(s) may be interposed. The intervening layer is a layer to be formed between a substrate and a photosensitive resin layer and is referred also to as underlayer film. As the underlayer film, a substrate modifying film, a planarization film, a bottom anti-reflective coating (BARC), an inorganic hard mask intervening layer (silicon oxide film, silicon nitride film and silicon oxynitride film), and an adhesion film can be referred. As to the formation of the inorganic hard mask intervening layer, JP 5,336,306 B can be referenced. The intervening layer may be composed of one layer or a plurality of layers. A top anti-reflective coating (TARC) may be formed on the photosensitive resin layer.
For the layer constitution in the process for manufacturing a resist pattern of the present invention, any publicly known technique can be used in accordance with process conditions. For example, the following layer constitution can be referred.
These layers can be formed by coating and thereafter heating and/or exposing to cure, or by employing any publicly known method such as CVD method. These layers can be removed by any publicly known method (etching or the like) and can be patterned using the upper layer as a mask.
The photosensitive resin layer is exposed through a predetermined mask. When other layers (TARC or the like) are also included, they may be exposed together. The wavelength of the radiation (light) used for exposure is not particularly limited, but it is preferable to perform exposure with light having a wavelength of 13.5 to 248 nm. In particular, KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), extreme ultraviolet ray (wavelength: 13.5 nm) and the like can be used, and extreme ultraviolet ray is more preferable. These wavelengths allow a range of ±5%, and preferably a range of ±1%. After the exposure, post exposure bake (PEB) may be performed, if needed. The temperature for post exposure baking is appropriately selected from 70 to 150° C., preferably 80 to 120° C., and the heating time is appropriately selected from 0.3 to 5 minutes, preferably 0.5 to 2 minutes.
Thereafter, development is performed with a developer. For the development in the method for manufacturing a resist pattern of the present invention, a 2.38 mass % (±1% is accepted) tetramethylammonium hydroxide (TMAH) aqueous solution is preferably used. Further, a surfactant or the like may also be added to the developer. The temperature of the developer is appropriately selected from generally 5 to 50° C., preferably 25 to 40° C., and the developing time is appropriately selected generally from 10 to 300 seconds, preferably 20 to 60 seconds. As the developing method, any publicly known method such as paddle development can be used.
As described above, the resist pattern of the present invention includes not only one obtained by exposing/developing a resist film but also one having a wall thickened by further covering a resist film with other layer(s) or film(s).
The resist pattern (the developed photosensitive resin layer) formed up to the above steps is in a non-cleaned state. This resist pattern can be cleaned with the electronic device manufacturing aqueous solution of the present invention. The time for bringing the electronic device manufacturing aqueous solution into contact with the resist pattern, that is, the processing time is preferably 1 second or more. The processing temperature may be also freely determined. The method for bringing the electronic device manufacturing aqueous solution into contact with the resist is also freely selected, and it can be performed, for example, by immersing a resist substrate in the electronic device manufacturing aqueous solution or dropping the electronic device manufacturing aqueous solution on a rotating resist substrate surface.
In the method for manufacturing a resist pattern according to the present invention, the resist pattern after being developed can be cleaned with other cleaning liquid before and/or after the cleaning processing with the electronic device manufacturing aqueous solution. The other cleaning liquid is preferably water, and more preferably pure water (DW, deionized water, or the like). The cleaning before the present processing is useful for cleaning the developer that has adhered to the resist pattern. The cleaning after the present processing is useful for cleaning the electronic device manufacturing aqueous solution. One preferred embodiment of the manufacturing method according to the present invention is a method comprising cleaning the pattern after being developed while substituting the developer by pouring pure water on the resist pattern, and further cleaning the pattern while substituting pure water by pouring the electronic device manufacturing aqueous solution while keeping the pattern immersed in pure water.
The cleaning with the electronic device manufacturing aqueous solution may be carried out by any publicly known method. It can be performed, for example, by immersing a resist substrate in the electronic device manufacturing aqueous solution, or by dropping the electronic device manufacturing aqueous solution on a rotating resist substrate surface. These methods may be also carried out in appropriate combination thereof.
As one of the conditions under which pattern collapse is likely to occur, there is a place where the distance between a wall and a wall of a resist pattern is the narrowest. At a place where a wall and a wall of a resist pattern are aligned in parallel, this becomes a severe condition. In the present specification, the distance of the interval at the place where the interval is the smallest on one circuit unit is defined as the minimum space size. It is preferable that one circuit unit becomes one semiconductor in a later process. Further, it is also a preferred embodiment that one semiconductor includes one circuit unit in the horizontal direction and a plurality of circuit units in the vertical direction. Of course, unlike the test sample, if the occurrence frequency of the place where the interval between a wall and a wall is narrow is low, the occurrence frequency of defects decreases, so that the occurrence frequency of defective products decreases.
In the present invention, the minimum space size of the resist pattern in one circuit unit is preferably 10 to 30 nm, more preferably 10 to 20 nm, and further preferably 10 to 17 nm.
The method for manufacturing a device of the present invention comprises the method for manufacturing a resist pattern using the electronic device manufacturing aqueous solution. Preferably, the method for manufacturing a device according to the present invention further comprising etching using the resist pattern manufactured by the above-mentioned method as a mask and processing a substrate. After processing, the resist film is peeled off, if necessary. Preferably, the device is a semiconductor.
In the manufacturing method of the present invention, the intervening layer and/or the substrate can be processed by etching using the resist pattern as a mask. For etching, any publicly known method such as dry etching and wet etching can be used, and dry etching is more suitable. For example, the intervening layer can be etched using the resist pattern as an etching mask, and the substrate can be etched using the obtained intervening layer pattern as an etching mask to process the substrate. Further, while etching the layer(s) under the resist layer (for example, an intervening layer) using the resist pattern as an etching mask, the substrate can also be uninterruptedly etched. The processed substrate becomes, for example, a patterned substrate. A wiring can be formed on the substrate by utilizing the formed pattern.
These layers can be removed preferably by performing dry etching with O2, CF4, CHF3, Cl2 or BCl3, and preferably, O2 or CF4 can be used.
As a preferred embodiment, the method for manufacturing a device according to the present invention further comprises forming a wiring on a processed substrate.
As described in Namatsu et al., Appl. Phys. Lett. 1995 (66), p 2655-2657 and schematically illustrated in
These lengths can be measured by a known method (for example, SEM photograph).
As can be seen from the above formula, the shorter D or W is, the more stress is caused. In the present specification, “pitch size” means, as described in
This means that the finer (narrower pitch size) the required resist pattern is, the greater the stress applied to the resist pattern becomes. As the pattern becomes finer in this way, the conditions become stricter, and more improvements are required for the electronic device manufacturing aqueous solution (for example, a rinse composition).
The present invention is described below with reference to various examples. Further, the embodiments of the present invention are not limited to these examples.
Into deionized water, 2-methyl propionic acid as the alkylcarboxylic acid compound (A) and n-butylamine as the nitrogen-containing compound (C) are added so that their concentration become respectively 1.0 mass % and 0.01 mass %, and the mixture are stirred. Visually, its complete dissolvement is confirmed. This is filtered (pore size=10 nm) to obtain an aqueous solution of Example 101.
In the same manner as in Preparation Example of Example 101 above, using the alkylcarboxylic acid compound (A) and the nitrogen-containing compound (C) as shown in Table 1, aqueous solutions of Examples 102 to 112 and Comparative Examples 101 to 104 are prepared so as to have the concentrations as shown in Table 1.
Further, Comparative Example 101 is one, in which deionized water to which nothing is added, is filtered.
A BARC composition (AZ Kr-F17B, Merck Electronics K.K. (hereinafter referred to as ME)) is applied on a silicon substrate by spin coating, and heating is performed on a hot plate at 180° C. for 60 seconds to obtain a BARC having a film thickness of 80 nm. A PHS-acrylate-based chemically amplified type resist (DX6270P, ME) is applied on this and heating is performed on a hot plate at 120° C. for 90 seconds to obtain a resist film having a film thickness of 620 nm. This substrate is exposed using a KrF stepper (FPA3000 EX5, Canon) through a mask (250 nm, line/space=1:1). At this time, the exposure amount is changed from 25 mJ/cm2 to 40 mJ/cm2 so that the line width to be obtained is changed.
After that, PEB is performed on a hot plate at 100° C. for 60 seconds, a developer that is a 2.38 mass % TMAH aqueous solution is poured in, and thereafter this state is held for 60 seconds (paddle). In the state that the developer is paddled, water pouring is started. While rotating the substrate, the developer is replaced with water, this treatment is stopped in the state of being paddled with water, and this state is left standing for 60 seconds. After that, the aqueous solution of Example 101 prepared above is poured into the state of being paddled with water, the water is replaced while rotating with the aqueous solution of Example 101, the pouring of the aqueous solution of Example 101 is stopped for 10 seconds in the state of being paddled with the aqueous solution of Example 101. The substrate is dried by spin drying for 30 seconds.
For Examples 102 to 112 and Comparative Examples 102 to 104, the evaluation substrate productions are performed in the same manner as the above using the respective aqueous solutions.
Comparative Example 101 is different from the above Example 101 in that the substrate is immediately spin-dried after the state of being paddled with water, but is the same as Example 101 excluding that.
Using the evaluation substrates of Production 1, evaluation of the pattern collapse prevention performance is carried out. The resist pattern is observed using an SEM equipment S-9220 (Hitachi High-Technologies), and the presence or absence of pattern collapse is observed. The evaluation criteria are shown below. In Comparative Example 101, pattern collapse of a resist pattern is confirmed when the line width becomes thinner than 190 nm. The results are as shown in Table 1.
In the same manner as in Preparation Example of Example 101 above, using the alkylcarboxylic acid compound (A) and the nitrogen-containing compound (C) as shown in Table 2, aqueous solutions of Examples 201 to 206 and Comparative Examples 201 and 202 are prepared so as to have the concentrations as shown in Table 2. Further, Comparative Example 201 is one, in which deionized water to which nothing is added, is filtered.
A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90° C. for 30 seconds. A PHS-acrylate-based chemically amplified type resist for EUV is applied thereon by spin coating and heating is performed on a hot plate at 110° C. for 60 seconds to obtain a resist film having a film thickness of 50 nm. This substrate is exposed using an EUV stepper (NXE: 3300B, ASML) through a mask (18 nm, line/space=1:1). At this time, the exposure amount is changed so that the line width to be obtained is changed. After that, PEB is performed on a hot plate at 100° C. for 60 seconds, a developer that is a 2.38 mass % TMAH aqueous solution is poured in, and thereafter this state is held for 30 seconds (paddle). In the state that the developer is paddled, water pouring is started. While rotating the substrate, the developer is replaced with water, this treatment is stopped in the state of being paddled with water, and this state is left standing for 60 seconds. After that, the aqueous solution of Example 201 is poured into the state of being paddled with water, the water is replaced while rotating the substrate with the aqueous solution of Example 201, the pouring of the aqueous solution of Example 201 is stopped for 10 seconds in the state of being paddled with the aqueous solution of Example 201. This substrate is dried by spin drying.
For the solutions of Examples 202 to 206 and Comparative Example 202, the evaluation substrate production is performed in the same manner as the above using the respective aqueous solutions.
Comparative Example 201 is different from the above Example 201 in that the substrate is immediately spin-dried after the state of replacing the developer with water and being paddled with water, but is the same as Example 201 excluding that.
Using a length measuring SEM CG5000 (Hitachi High-Technologies), line width and existence or absence of pattern collapse of the resist pattern formed on the evaluation substrates of Production 2 are observed. As the amount of exposure increases, the line width decreases. The minimum line width size at which no pattern collapse occurs is defined as “limit pattern size”.
In the case of the aqueous solution of Comparative Example 201, pattern collapse is confirmed at a line size of 20.3 nm. On the other hand, since no collapse is confirmed at 20.8 nm, the limit pattern size is set to 20.8 nm. The results are as shown in Table 2.
Each evaluation substrate is produced in the same manner as in the above Evaluation Substrate Production 2, except that the mask is changed to one with a narrower pitch of 17 nm, line/space=1:1.
With respect to the resist pattern formed on the evaluation substrates of Production 3, the limit pattern size is measured in the same manner as in the above evaluation of limit pattern size (18 nm, line/space). The results are as shown in Table 2.
In Comparative Examples 201 and 202, since the pattern was not formed in Production 3, measurement is not possible.
The LWR of the resist pattern formed on the evaluation substrates of Production 2 is evaluated. Using a length measuring SEM CG5000, the LWR (Line Width Roughness) of the resist pattern having a line width of 18 nm is measured. The results are as shown in Table 2.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-117253 | Jul 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/069365 | 7/12/2022 | WO |
