WO2013054803A1 - 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 - Google Patents
微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 Download PDFInfo
- Publication number
- WO2013054803A1 WO2013054803A1 PCT/JP2012/076167 JP2012076167W WO2013054803A1 WO 2013054803 A1 WO2013054803 A1 WO 2013054803A1 JP 2012076167 W JP2012076167 W JP 2012076167W WO 2013054803 A1 WO2013054803 A1 WO 2013054803A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pattern
- composition
- forming
- resist pattern
- photoresist
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
- G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
Definitions
- the present invention relates to a composition for obtaining a resist pattern having a fine size by forming a resist pattern in a manufacturing process of a semiconductor or the like and further thickening the resist pattern, and a pattern forming method using the composition. is there.
- a resist pattern is exposed using an optical developer technique, for example, a positive resist that becomes highly soluble in an alkaline developer when exposed, and after exposing the resist, using an alkaline developer. The portion is removed to form a positive pattern.
- an optical developer technique for example, a positive resist that becomes highly soluble in an alkaline developer when exposed, and after exposing the resist, using an alkaline developer. The portion is removed to form a positive pattern.
- the part that depends on the exposure light source and the exposure method is large, and expensive and special equipment and peripheral materials that can provide the light source and method are necessary, which is a huge investment Is required.
- a practical method is to cover a resist pattern formed in a range that can be stably obtained by conventional methods with a composition containing a water-soluble resin and additives as necessary, and thicken the resist pattern.
- the hole diameter or the separation width is made finer.
- the following techniques are known as such methods.
- the resist pattern is thickened by removing the non-crosslinked portion with a developer, and the hole diameter or separation width of the resist pattern is refined (see Patent Documents 1 and 2).
- Patent Document 6 When a negative pattern is formed using the positive resist, a higher resolution pattern can be obtained by applying a composition containing a crosslinking agent on the negative pattern, heating and rinsing. There is technology (Patent Document 6).
- Japanese Patent Laid-Open No. 10-73927 Japanese Patent Laid-Open No. 2005-300853 JP 2003-84459 A JP 2008-518260 A JP 2010-139996 A Japanese Patent No. 4558064
- the cross-linking reaction occurs vigorously, or the amount of the composition for forming a fine pattern penetrating into the pattern becomes excessive.
- defects such as coating unevenness, surface roughness, and unresolved to occur.
- the conventional fine pattern forming composition often contains a basic substance such as a primary amine, and the composition is generally basic. For this reason, the pattern containing many acids is often dissolved. As a result, it is considered that defects such as surface roughness, bridge defects, or non-resolution occur.
- the present invention covers a negative resist pattern formed by developing a chemically amplified positive photoresist using an organic solvent developer, and thickens the pattern to make fine patterns. It is an object of the present invention to provide a composition capable of stably forming a pattern and a pattern forming method using the composition.
- a composition for forming a fine pattern according to the present invention is used to make a pattern fine by thickening the resist pattern in a method of forming a negative resist pattern using a chemically amplified resist composition. , During the repeating unit, A polymer containing any of the structures And a solvent.
- the method for forming a negative resist pattern includes: Forming a photoresist layer by applying a chemically amplified photoresist composition on a semiconductor substrate; Exposing the semiconductor substrate coated with the photoresist layer; A step of developing with an organic solvent developer after the exposure to form a photoresist pattern; On the surface of the photoresist pattern, During the repeating unit, A step of applying a composition for forming a fine pattern comprising a polymer comprising any of the following structures and a solvent; It is characterized by comprising a step of heating a coated photoresist pattern and a step of washing and removing an excessive fine pattern forming composition.
- a fine negative photoresist pattern free from defects such as surface roughness, bridge defects, or unresolved can be obtained.
- composition for forming a fine pattern comprises a polymer having a specific structure and a solvent.
- the polymer containing a specific structure used in the present invention is contained in a repeating unit. One of the structures is included.
- the composition for forming a fine pattern containing such a polymer comprises an amine having no highly reactive nitrogen-hydrogen bond under the present process and an amide group-containing polymer having a very low reactivity.
- the polymer may infiltrate the resist pattern or the fine pattern forming composition containing the polymer may adhere to the resist pattern surface, etc. Refined.
- the polymer shows a certain basicity by including a specific structure, and an excessive reaction with a hydroxyl group or the like contained in a resin or the like in the photoresist pattern is suppressed, thereby improving problems such as surface roughness. It is considered a thing.
- the structure represented by (A) is a structure in which three carbon atoms are bonded to a nitrogen atom by a single bond.
- examples of such a structure include a tertiary amine.
- the carbon bonded to the nitrogen atom may be bonded to each other via a hydrocarbon chain to have a cyclic structure.
- This cyclic structure may include an unsaturated bond between atoms constituting the ring, and a carbon atom constituting the ring may be substituted with an oxygen atom or another nitrogen atom to constitute a heterocyclic ring.
- Such a structure is also included in polymers obtained by polymerizing N, N-dimethylvinylamine, N, N-dimethylallylamine, N-vinylpyrrolidone, N-vinylcaprolactam, and the like.
- the structure represented by (B) is a structure in which one carbon atom is bonded to a nitrogen atom by a single bond and the other carbon atom is bonded by a double bond. It may exist between hydrogen and may be contained in a heterocyclic ring.
- This heterocyclic ring may contain an unsaturated bond different from the unsaturated bond contained in (B).
- Examples of the heterocyclic ring having such a structure include an imidazole ring, an oxazole ring, a pyridine ring, and a bipyridine ring. Among these, those containing an imidazole ring or an oxazole ring are preferred, and those containing an imidazole ring are particularly preferred because of their excellent coatability and a large pattern reduction effect.
- the amide bond may be present in the middle or the end of the chain hydrocarbon group bonded as a side chain of the polymer main chain, or may be contained in a lactam ring bonded as a side chain.
- the polymer containing a specific structure used in the present invention contains any one of the structures (A) to (C) as a repeating unit. These structures are appropriately selected from the viewpoint of the type of resist pattern to be applied and the availability of the polymer. Among these structures, advantageous results are obtained in the coating property and the pattern reduction amount. ) Or (C) is preferred.
- the polymer that can be used in the composition for forming a fine pattern according to the present invention has a monomer having a substituent as described above as a polymerization unit.
- monomers include vinyl imidazole, vinyl oxazole, vinyl caprolactam, N, N-dialkylallylamine, N-alkylpyrroline and the like.
- a copolymer produced by combining these monomers with a monomer that does not contain the specific structure as long as the scope of the present invention is not impaired can also be used in the composition for forming a fine pattern according to the present invention.
- a copolymer containing polyacrylic acid, polymethacrylic acid, polyvinyl alcohol and the like as copolymerized units can be mentioned.
- a monomer containing a primary amine structure or a secondary amine structure can be used as a polymerization unit within a range not impairing the scope of the present invention.
- the affinity between the resin and the polymer in the photoresist cannot be maintained properly, and the effects of the present invention may not be exhibited. This was expected to be due to the high basicity of the polymer itself, but surprisingly it cannot be solved by adjusting the pH of the composition, for example.
- the repeating unit containing a primary amine structure or a secondary amine structure is preferably 40 mol% or less, more preferably 30 mol% or less of the polymer unit constituting the polymer. .
- the molecular weight of the polymer having a specific structure used in the present invention is not particularly limited, but the weight average molecular weight is generally selected from the range of 3,000 to 200,000, preferably 5,000 to 150,000. .
- a weight average molecular weight means the polystyrene conversion average weight molecular weight measured using gel permeation chromatography.
- water is generally used as the solvent.
- the water used is preferably water from which organic impurities, metal ions, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like, particularly pure water.
- a small amount of an organic solvent may be used as a cosolvent in order to improve wettability and the like.
- examples of such a solvent include alcohols such as methyl alcohol, ethyl alcohol, and propylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl lactate and ethyl acetate.
- the solvent should be selected from those which do not dissolve or modify the resist film to which the composition is applied.
- the composition for forming a fine pattern according to the present invention contains a polymer having a specific structure as described above, but the concentration of the polymer is arbitrary depending on the type and size of the target resist pattern, the target pattern size, etc. Can be selected. However, the concentration of the polymer containing the specific structure is generally 0.1 to 10% by weight, preferably 1.0 to 7.0% by weight, based on the total weight of the composition.
- the fine pattern forming composition according to the present invention may further contain an acid.
- the type of acid is not particularly limited as long as it does not adversely affect the resist pattern, and can be selected from inorganic acids and organic acids. Specifically, acetic acid, malonic acid, citric acid, glycine, glutamic acid, p-toluenesulfonic acid, or camphorsulfonic acid can be used as the organic acid, and hydrochloric acid, sulfuric acid, nitric acid, or the like can be used as the inorganic acid.
- the pattern is refined using the composition for forming a fine pattern, the surface of the photoresist pattern may be roughened, but the surface roughness may be improved by adding an acid to the composition. However, if the amount of acid added is excessive, the coatability and the pattern thickness may be reduced. In general, it is generally 0.5 to 50% by weight, preferably 2.5 to 30% by weight, based on the total weight of the polymer containing the specific structure in the composition.
- the pH of the composition for forming a fine pattern is generally preferably 2 or more and 11 or less, more preferably 3 or more and 10 or less.
- the pH is less than 2 or more than 11, dissolution of the photoresist pattern may occur, and the surface of the photoresist resist pattern may be roughened. Therefore, it is preferable to adjust the pH appropriately.
- the fine pattern forming composition according to the present invention may contain other additives as required.
- Such additives include surfactants, bactericides, antibacterial agents, preservatives, and fungicides.
- a composition contains surfactant from a viewpoint of the applicability
- surfactant from a viewpoint of the applicability
- These additives in principle do not affect the performance of the composition for forming a fine pattern, and are usually 1% or less, preferably 0.1% or less, and preferably, based on the total weight of the composition. The content is 0.001% or less.
- the effect of application property improvement can also be acquired by apply
- a typical pattern forming method to which the composition for forming a fine pattern of the present invention is applied includes the following method.
- a chemically amplified photoresist layer is formed by applying a chemically amplified photoresist to a surface of a substrate such as a silicon substrate, which has been pretreated as necessary, by a conventionally known coating method such as a spin coating method.
- a conventionally known coating method such as a spin coating method.
- an antireflection film may be formed on the substrate surface. Such an antireflection film can improve the cross-sectional shape and the exposure margin.
- a chemically amplified photoresist generates an acid upon irradiation with light such as ultraviolet rays, and forms a pattern by increasing the solubility of the light irradiated portion in an alkaline developer by a chemical change caused by the catalytic action of this acid.
- An acid-generating compound that generates an acid upon irradiation with light; and an acid-sensitive group-containing resin that decomposes in the presence of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group; an alkali-soluble resin;
- an alkali-soluble resin The thing which consists of a crosslinking agent and an acid generator is mentioned.
- a photoresist pattern formed by a method of removing a portion where an alkali-soluble group is not generated using an organic solvent developer is used. Therefore, a negative photoresist pattern in which an exposed portion remains as a pattern is formed using a chemically amplified photoresist that functions as a positive type when developed with a normal alkaline developer.
- the chemically amplified photoresist layer formed on the substrate is pre-baked, for example, on a hot plate as necessary to remove the solvent in the chemically amplified photoresist, and the photoresist has a thickness of typically about 50 nm to 500 nm. It is made a film.
- the pre-baking temperature varies depending on the solvent used or the chemically amplified photoresist, but is usually 50 to 200 ° C., preferably about 70 to 150 ° C.
- the photoresist film is then used with a known irradiation device such as a high-pressure mercury lamp, a metal halide lamp, an ultra-high pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, a soft X-ray irradiation device, an electron beam drawing device, and through a mask as necessary. Exposure is performed.
- a known irradiation device such as a high-pressure mercury lamp, a metal halide lamp, an ultra-high pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, a soft X-ray irradiation device, an electron beam drawing device, and through a mask as necessary. Exposure is performed.
- the resist is developed using an organic solvent developer.
- Any organic solvent developer may be used as long as it does not dissolve the photoresist film portion solubilized in the alkaline aqueous solution by exposure, and has the effect of dissolving the unexposed photoresist film portion insoluble in the alkaline aqueous solution. Can be used.
- a photoresist film portion insoluble in an alkaline aqueous solution is easily dissolved in an organic solvent, and therefore, an organic solvent developer can be selected from a relatively wide range.
- the organic solvent that can be used as the organic solvent developer that can be used can be selected from polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
- ketone solvents include 1-octanone, 2-octanone, 2-nonanone, 2-nonanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone. Can do.
- the ester solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxybutyl Examples include ester solvents such as acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate.
- Alcohol solvents include alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, etc.
- Examples include glycol solvents and glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethyl butanol.
- ether solvent examples include di-n-propyl ether, di-n-butyl ether, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
- amide solvent N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used.
- hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
- organic solvents can be used in combination of two or more kinds, and can be used in combination with an inorganic solvent such as water as long as the effects of the present invention are not impaired.
- the resist pattern is rinsed (washed) using a rinse solution after the development treatment.
- cleaning is performed using a rinsing liquid containing at least one organic solvent selected from alkane solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. It is preferable to do.
- Examples of the rinsing liquid used in the rinsing step after development include n-hexyl alcohol, n-heptyl alcohol, and benzyl alcohol. A plurality of these solvents may be mixed, or may be used by mixing with other solvents or water.
- the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained. An appropriate amount of a surfactant can be further added to the rinse solution.
- the composition for forming a fine pattern according to the present invention is applied to refine the pattern.
- water or an organic solvent that does not dissolve the resist pattern can be applied to the surface of the resist pattern.
- the applicability of the composition can be improved and the composition can be applied uniformly. That is, coatability can be improved without using an additive for improving coatability such as a surfactant in the composition.
- Such a process is sometimes called a pre-wet process.
- the composition for forming a fine pattern according to the present invention is applied so as to cover the resist pattern, and the resist pattern is thickened by the interaction between the resist pattern and the composition for forming a fine pattern.
- the interaction that occurs here is thought to be that the polymer permeates or adheres to the resist, thereby causing the resist pattern to thicken.
- the fine pattern forming composition according to the present invention permeates or adheres to the inner wall of the groove or hole formed on the surface of the resist pattern, and the pattern becomes thicker. As a result, the width between the resist patterns is reduced, and the pitch of the resist pattern is reduced. It is possible to effectively reduce the size or the hole opening size to below the limit resolution.
- any method such as a spin coating method conventionally used when applying a photoresist resin composition may be used. it can.
- the resist pattern after the fine pattern forming composition is applied is pre-baked as necessary.
- Pre-baking may be performed by heating at a constant temperature or by heating while raising the temperature stepwise.
- the conditions for the heat treatment after applying the composition for forming a fine pattern are, for example, a temperature of 40 to 200 ° C., preferably 80 to 160 ° C., 10 to 300 seconds, and preferably about 30 to 120 seconds. Such heating promotes penetration and adhesion of the polymer to the resist pattern.
- the resist pattern After applying and heating the composition for forming a fine pattern, the resist pattern is thickened, the line width of the resist pattern is thickened, and the hole pattern has a small hole diameter.
- Such a change in size can be appropriately adjusted according to the temperature and time of the heat treatment, the type of the photoresist resin composition to be used, and the like. Therefore, if these conditions are set depending on how fine the resist pattern is to be made, in other words, how much the line width of the resist pattern is increased and how small the hole diameter of the hole pattern is required. Good.
- the difference before and after the application of the fine pattern forming composition is generally 5 to 30 nm.
- an excessive fine pattern forming composition that did not act on the resist can be removed by rinsing with water or a solvent as necessary.
- water or a solvent used for such rinsing treatment, an excessive composition that has low solubility and does not penetrate or adhere to the fine pattern forming composition that penetrates or adheres to the resist pattern. Is selected so as to have high solubility.
- the solvent used for the composition for forming a fine pattern, particularly pure water is preferably used for the rinsing treatment.
- the resist pattern obtained in this manner is substantially miniaturized because the pattern size of the resist pattern immediately after development is changed by the action of the composition for forming a fine pattern.
- the resist pattern manufactured using the composition for fine pattern formation by this invention is useful for manufacture of the semiconductor element etc. which have a finer pattern in manufacture of a semiconductor element.
- Resist pattern formation example 1 Apply a lower antireflection film AZ ArF-1C5D (trade name, manufactured by AZ Electronic Materials Co., Ltd.) to an 8-inch silicon wafer with a spin coater (manufactured by Tokyo Electron Co., Ltd.), and bake at 200 ° C. for 60 seconds. The antireflection film having a thickness of 37 nm was obtained.
- a photosensitive resin composition AZ AX2110P (trade name, manufactured by AZ Electronic Materials Co., Ltd.) was baked at 110 ° C. for 60 seconds to obtain a film thickness of 120 nm.
- the mask was rotated in a direction orthogonal to the first exposure, and a second exposure was performed.
- development treatment negative development
- 2-heptanone for 30 seconds to obtain a resist pattern having a pitch of 160 nm and a hole size of 80 nm.
- composition for forming a fine pattern The following were prepared as polymers used for the composition for forming a fine pattern.
- the prepared composition was applied to the resist pattern 1 using a spin coater, heated at 120 ° C. for 60 seconds, washed with pure water, and dried.
- the dimension of the obtained hole pattern was measured, and the reduction amount of the hole pattern by the fine pattern forming composition was measured. Further, the pattern surface after development was evaluated visually or by a scanning electron microscope.
- the obtained results were as shown in Table 1.
- the evaluation criteria for the fine pattern surface are as follows. A: Color unevenness cannot be visually confirmed on the resist pattern surface, and the surface of the resist pattern after processing is not rough compared to the original photoresist pattern surface even by observation with an SEM.
- B Although the color unevenness can be visually confirmed on the resist pattern surface, the processed resist pattern surface is not rough as compared with the original photoresist pattern surface in the observation by SEM, and is in a good state.
- C Color unevenness is visually confirmed on the resist pattern surface, and the surface of the resist pattern after processing is slightly rougher than the original photoresist pattern surface even by observation with an SEM, but there is no practical problem.
- D Color unevenness and white turbidity were confirmed by visual observation on the resist pattern surface, the resist pattern surface after processing was significantly rougher than the original photoresist pattern even by observation with SEM, and part of the hole pattern was blocked, Unpractical state.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
(1)形成されたレジストパターンを酸によって架橋しえる組成物でレジストパターンを覆い、加熱によりレジストパターン中に存在する酸を拡散させ、レジストとの界面に架橋層をレジストパターンの被覆層として形成させ、現像液で非架橋部分を取り除くことでレジストパターンを太らせ、レジストパターンのホール径または分離幅が微細化される方法(特許文献1および2参照)。
(2)形成されたレジストパターンに、(メタ)アクリル酸モノマーと水溶性ビニルモノマーとからなるコポリマーの水溶液をレジストパターンに塗布し、熱処理により、レジストパターンを熱収縮させてパターンを微細化させる方法(特許文献3参照)。
(3)アミノ基、特に1級アミンを含むポリマーを含有する、フォトレジストパターンを被覆するための水溶性被覆用組成物(特許文献4参照)。
繰り返し単位中に、
溶剤と
を含んでなることを特徴とするものである。
本発明による微細パターン形成用組成物は、特定の構造を含むポリマーと溶剤とを含んでなる。本発明においてもちいられる、特定の構造を含むポリマーは、繰り返し単位中に
次に、本発明による微細なレジストパターンの形成方法について説明する。本発明の微細パターン形成用組成物が適用される代表的なパターン形成方法をあげると、次のような方法が挙げられる。
アミド系溶剤としては、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド等が使用できる。
スピンコーター(東京エレクトロン株式会社製)にて、下層反射防止膜AZ ArF-1C5D(商品名、AZエレクトロニックマテリアルズ株式会社製)を8インチシリコンウェハーに塗布し、200℃にて、60秒間ベークを行い、膜厚37nmの反射防止膜を得た。その上に感光性樹脂組成物AZ AX2110P(商品名、AZエレクトロニックマテリアルズ株式会社製)を、110℃にて60秒間ベークを行い120nmの膜厚を得た。得られたウエハーをArF線(193nm)の露光波長を有する露光装置(株式会社ニコン製)を用いて、マスク(ライン/スペース=1/1)を用いて、1回目のパターン露光を行った。次に、同マスクを、1回目の露光と直交する方向に回転し、2回目の露光を行った。その後110℃にて、60秒間ベークした後、2-ヘプタノンにて30秒間現像処理(ネガ型現像)を行い、ピッチ160nm、ホールサイズ80nmのレジストパターンを得た。
A:レジストパターン表面に目視により色ムラが確認できず、SEMによる観察でも元のフォトレジストパターン表面に比べて処理後のレジストパターン表面が荒れておらず、非常に良好な状態。
B:レジストパターン表面に目視により色ムラが確認できるが、SEMによる観察では元のフォトレジストパターン表面に比べて処理後のレジストパターン表面が荒れておらず、良好な状態。
C:レジストパターン表面に目視により色ムラが確認され、SEMによる観察でも処理後のレジストパターン表面が元のフォトレジストパターン表面に比べわずかに荒れているが、実用上問題ない状態。
D:レジストパターン表面に目視により色ムラや白濁化が確認され、SEMによる観察でも処理後のレジストパターン表面が元のフォトレジストパターンに比べ著しく荒れていて、一部ホールパターンが閉塞しており、実用不能な状態。
Claims (7)
- 前記ポリマーが、前記構造(B)または(C)を含むものである、請求項1に記載の組成物。
- 酸をさらに含んでなる、請求項1または2に記載の組成物。
- 前記溶剤が水を含むことでなる、請求項1~3のいずれか1項に記載の組成物。
- 界面活性剤をさらに含んでなる、請求項1~4のいずれか1項に記載の組成物。
- 前記フォトレジスト組成物が、光酸発生剤をさらに含んでなる、請求項6に記載の微細化されたネガ型レジストパターンの形成方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/344,943 US9448485B2 (en) | 2011-10-11 | 2012-10-10 | Composition for forming fine resist pattern and pattern forming method using same |
SG11201400460WA SG11201400460WA (en) | 2011-10-11 | 2012-10-10 | Composition for forming fine resist pattern and pattern forming method using same |
CN201280049610.XA CN103858058B (zh) | 2011-10-11 | 2012-10-10 | 细微抗蚀图案形成用组合物以及使用其的图案形成方法 |
KR1020147012384A KR101681524B1 (ko) | 2011-10-11 | 2012-10-10 | 미세 레지스트 패턴 형성용 조성물 및 이를 사용한 패턴 형성 방법 |
US15/216,288 US20160327867A1 (en) | 2011-10-11 | 2016-07-21 | Composition for forming fine resist pattern and pattern forming method using same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-224030 | 2011-10-11 | ||
JP2011224030A JP5758263B2 (ja) | 2011-10-11 | 2011-10-11 | 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/344,943 A-371-Of-International US9448485B2 (en) | 2011-10-11 | 2012-10-10 | Composition for forming fine resist pattern and pattern forming method using same |
US15/216,288 Division US20160327867A1 (en) | 2011-10-11 | 2016-07-21 | Composition for forming fine resist pattern and pattern forming method using same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013054803A1 true WO2013054803A1 (ja) | 2013-04-18 |
Family
ID=48081858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/076167 WO2013054803A1 (ja) | 2011-10-11 | 2012-10-10 | 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 |
Country Status (7)
Country | Link |
---|---|
US (2) | US9448485B2 (ja) |
JP (1) | JP5758263B2 (ja) |
KR (1) | KR101681524B1 (ja) |
CN (1) | CN103858058B (ja) |
SG (1) | SG11201400460WA (ja) |
TW (1) | TWI617880B (ja) |
WO (1) | WO2013054803A1 (ja) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6134619B2 (ja) * | 2013-09-13 | 2017-05-24 | 富士フイルム株式会社 | パターン形成方法、及び、電子デバイスの製造方法 |
JP6340304B2 (ja) * | 2013-11-29 | 2018-06-06 | 富士フイルム株式会社 | パターン形成方法、及び電子デバイスの製造方法 |
JP6286227B2 (ja) * | 2014-02-21 | 2018-02-28 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、感活性光線性又は感放射線性膜を備えたマスクブランクス、パターン形成方法、及び電子デバイスの製造方法 |
JP6531397B2 (ja) * | 2014-03-07 | 2019-06-19 | Jsr株式会社 | パターン形成方法及びこれに用いられる組成物 |
US9529265B2 (en) | 2014-05-05 | 2016-12-27 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method of preparing and using photosensitive material |
JP6459759B2 (ja) * | 2014-05-26 | 2019-01-30 | 信越化学工業株式会社 | パターン形成方法及びシュリンク剤 |
US9448483B2 (en) * | 2014-07-31 | 2016-09-20 | Dow Global Technologies Llc | Pattern shrink methods |
KR101994793B1 (ko) * | 2014-09-02 | 2019-07-01 | 후지필름 가부시키가이샤 | 패턴 형성 방법, 전자 디바이스의 제조 방법, 레지스트 조성물, 및 레지스트막 |
US9696625B2 (en) | 2014-10-17 | 2017-07-04 | Tokyo Ohka Kogyo Co., Ltd. | Method of forming resist pattern |
JP6503206B2 (ja) | 2015-03-19 | 2019-04-17 | 東京応化工業株式会社 | レジストパターン修復方法 |
WO2016158507A1 (ja) * | 2015-03-31 | 2016-10-06 | 日産化学工業株式会社 | レジストパターン被覆用塗布液及びパターンの形成方法 |
US9909050B2 (en) | 2015-10-14 | 2018-03-06 | Cnpc Usa Corporation | High density and high temperature emulsifier for use in an oil based drilling fluid system |
US10280357B2 (en) | 2015-10-14 | 2019-05-07 | CNPC USA Corp. | High density and high temperature emulsifier for use in an oil based drilling fluid system |
US9963630B2 (en) | 2015-11-18 | 2018-05-08 | Cnpc Usa Corporation | Method for a fracturing fluid system at high temperatures |
WO2017084741A1 (en) | 2015-11-19 | 2017-05-26 | AZ Electronic Materials (Luxembourg) S.à.r.l. | Composition for forming fine resist pattern and pattern forming method using same |
JP2017165846A (ja) * | 2016-03-15 | 2017-09-21 | アーゼッド・エレクトロニック・マテリアルズ(ルクセンブルグ)ソシエテ・ア・レスポンサビリテ・リミテ | 微細パターン形成用組成物およびそれを用いた微細パターン形成方法 |
KR101730838B1 (ko) * | 2016-05-04 | 2017-04-28 | 영창케미칼 주식회사 | 네가톤 포토레지스트를 이용한 패터닝 공정에서 lwr 개선 방법과 조성물 |
KR101819992B1 (ko) | 2016-06-24 | 2018-01-18 | 영창케미칼 주식회사 | 포토레지스트 패턴 축소 조성물과 패턴 축소 방법 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004212967A (ja) * | 2002-12-30 | 2004-07-29 | Hynix Semiconductor Inc | フォトレジスト用オーバーコーティング組成物及びこれを利用したフォトレジストパターン形成方法 |
WO2005008340A1 (ja) * | 2003-07-17 | 2005-01-27 | Az Electronic Materials (Japan) K.K. | 微細パターン形成材料およびそれを用いた微細パターン形成方法 |
JP2006307179A (ja) * | 2005-03-29 | 2006-11-09 | Jsr Corp | 重合体 |
JP2008102348A (ja) * | 2006-10-19 | 2008-05-01 | Az Electronic Materials Kk | 微細化されたパターンの形成方法およびそれに用いるレジスト基板処理液 |
JP2008310314A (ja) * | 2007-05-15 | 2008-12-25 | Fujifilm Corp | パターン形成方法 |
JP2010524040A (ja) * | 2007-04-09 | 2010-07-15 | エイゼット・エレクトロニック・マテリアルズ・ユーエスエイ・コーポレイション | フォトレジストパターン上にコーティングするためのラクタム含有組成物 |
JP2011524930A (ja) * | 2008-06-18 | 2011-09-08 | エイゼット・エレクトロニック・マテリアルズ・ユーエスエイ・コーポレイション | フォトレジストパターン上にコーティングするための水性組成物 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5729046A (en) * | 1980-07-29 | 1982-02-16 | Mitsubishi Paper Mills Ltd | Processing method for lithographic plate |
US4612346A (en) * | 1983-06-14 | 1986-09-16 | Toray Industries, Inc. | Resinous composition |
DE3903001A1 (de) * | 1989-02-02 | 1990-08-16 | Hoechst Ag | Lichtempfindliches gemisch und damit hergestelltes lichtempfindliches aufzeichnungsmaterial |
US5398092A (en) * | 1992-07-08 | 1995-03-14 | Mitsubishi Paper Mills Limited | Method and apparatus for developing lithographic offset printing plate |
DE19533217A1 (de) * | 1995-09-08 | 1997-03-13 | Basf Ag | Verfahren zur Herstellung von Polymerisaten auf Basis basischer Vinylmonomere |
JP3071401B2 (ja) | 1996-07-05 | 2000-07-31 | 三菱電機株式会社 | 微細パターン形成材料及びこれを用いた半導体装置の製造方法並びに半導体装置 |
DE19732902A1 (de) * | 1997-07-30 | 1999-02-04 | Sun Chemical Corp | Deckschicht für lichtempfindliche Materialien umfassend ein (1-Vinylimidazol)-Polymer oder -Copolymer |
US6899994B2 (en) * | 2001-04-04 | 2005-05-31 | Kodak Polychrome Graphics Llc | On-press developable IR sensitive printing plates using binder resins having polyethylene oxide segments |
JP3662870B2 (ja) | 2001-07-05 | 2005-06-22 | 東京応化工業株式会社 | レジストパターン微細化用被覆形成剤及びそれを用いた微細レジストパターン形成方法 |
JP3485182B1 (ja) * | 2002-06-28 | 2004-01-13 | 東京応化工業株式会社 | パターン微細化用被覆形成剤およびそれを用いた微細パターンの形成方法 |
US7282291B2 (en) * | 2002-11-25 | 2007-10-16 | California Institute Of Technology | Water free proton conducting membranes based on poly-4-vinylpyridinebisulfate for fuel cells |
JP4485241B2 (ja) | 2004-04-09 | 2010-06-16 | Azエレクトロニックマテリアルズ株式会社 | 水溶性樹脂組成物およびそれを用いたパターン形成方法 |
US7595141B2 (en) | 2004-10-26 | 2009-09-29 | Az Electronic Materials Usa Corp. | Composition for coating over a photoresist pattern |
US7833683B2 (en) * | 2007-08-14 | 2010-11-16 | Xerox Corporation | Photosensitive member having an overcoat |
US20100028803A1 (en) * | 2008-08-01 | 2010-02-04 | Fujifilm Corporation | Surface treating agent for resist pattern formation, resist composition, method of treating surface of resist pattern therewith and method of forming resist pattern |
JP5183449B2 (ja) * | 2008-12-15 | 2013-04-17 | 富士フイルム株式会社 | ネガ型現像用レジスト組成物を用いたパターン形成方法 |
JP5664509B2 (ja) * | 2011-09-16 | 2015-02-04 | 信越化学工業株式会社 | パターン形成方法 |
-
2011
- 2011-10-11 JP JP2011224030A patent/JP5758263B2/ja active Active
-
2012
- 2012-10-09 TW TW101137188A patent/TWI617880B/zh active
- 2012-10-10 US US14/344,943 patent/US9448485B2/en active Active
- 2012-10-10 SG SG11201400460WA patent/SG11201400460WA/en unknown
- 2012-10-10 CN CN201280049610.XA patent/CN103858058B/zh active Active
- 2012-10-10 KR KR1020147012384A patent/KR101681524B1/ko active IP Right Grant
- 2012-10-10 WO PCT/JP2012/076167 patent/WO2013054803A1/ja active Application Filing
-
2016
- 2016-07-21 US US15/216,288 patent/US20160327867A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004212967A (ja) * | 2002-12-30 | 2004-07-29 | Hynix Semiconductor Inc | フォトレジスト用オーバーコーティング組成物及びこれを利用したフォトレジストパターン形成方法 |
WO2005008340A1 (ja) * | 2003-07-17 | 2005-01-27 | Az Electronic Materials (Japan) K.K. | 微細パターン形成材料およびそれを用いた微細パターン形成方法 |
JP2006307179A (ja) * | 2005-03-29 | 2006-11-09 | Jsr Corp | 重合体 |
JP2008102348A (ja) * | 2006-10-19 | 2008-05-01 | Az Electronic Materials Kk | 微細化されたパターンの形成方法およびそれに用いるレジスト基板処理液 |
JP2010524040A (ja) * | 2007-04-09 | 2010-07-15 | エイゼット・エレクトロニック・マテリアルズ・ユーエスエイ・コーポレイション | フォトレジストパターン上にコーティングするためのラクタム含有組成物 |
JP2008310314A (ja) * | 2007-05-15 | 2008-12-25 | Fujifilm Corp | パターン形成方法 |
JP2011524930A (ja) * | 2008-06-18 | 2011-09-08 | エイゼット・エレクトロニック・マテリアルズ・ユーエスエイ・コーポレイション | フォトレジストパターン上にコーティングするための水性組成物 |
Also Published As
Publication number | Publication date |
---|---|
TW201324037A (zh) | 2013-06-16 |
SG11201400460WA (en) | 2014-05-29 |
CN103858058B (zh) | 2018-03-13 |
CN103858058A (zh) | 2014-06-11 |
JP2013083818A (ja) | 2013-05-09 |
TWI617880B (zh) | 2018-03-11 |
KR20140090189A (ko) | 2014-07-16 |
US20160327867A1 (en) | 2016-11-10 |
US9448485B2 (en) | 2016-09-20 |
KR101681524B1 (ko) | 2016-12-01 |
JP5758263B2 (ja) | 2015-08-05 |
US20150017587A1 (en) | 2015-01-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5758263B2 (ja) | 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 | |
JP6239833B2 (ja) | 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 | |
CN105103053B (zh) | 微细抗蚀图案形成用组合物以及使用了其的图案形成方法 | |
JP6075724B2 (ja) | 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 | |
JP5306755B2 (ja) | 基板処理液およびそれを用いたレジスト基板処理方法 | |
WO2013183686A1 (ja) | 上層膜形成用組成物およびそれを用いたレジストパターン形成方法 | |
TWI748998B (zh) | 細微圖案的製造方法及使用該方法之裝置的製造方法 | |
JP2018537703A (ja) | 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 | |
JPWO2015178387A1 (ja) | 上層膜形成用組成物およびそれを用いたレジストパターン形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12839487 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14344943 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147012384 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12839487 Country of ref document: EP Kind code of ref document: A1 |