WO2015129405A1 - レジストパターンに塗布されるポリマー含有塗布液 - Google Patents
レジストパターンに塗布されるポリマー含有塗布液 Download PDFInfo
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- WO2015129405A1 WO2015129405A1 PCT/JP2015/052970 JP2015052970W WO2015129405A1 WO 2015129405 A1 WO2015129405 A1 WO 2015129405A1 JP 2015052970 W JP2015052970 W JP 2015052970W WO 2015129405 A1 WO2015129405 A1 WO 2015129405A1
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- LUKAQXLDLPZULO-UHFFFAOYSA-O CO[SH+](CCC1CC2OC2CC1)(OC)OC Chemical compound CO[SH+](CCC1CC2OC2CC1)(OC)OC LUKAQXLDLPZULO-UHFFFAOYSA-O 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
- G03F7/0041—Photosensitive materials providing an etching agent upon exposure
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- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
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- 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
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
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- 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
- G03F7/322—Aqueous alkaline compositions
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- 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
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- 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
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- 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
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/3086—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
- H01L21/31138—Etching organic layers by chemical means by dry-etching
Definitions
- the present invention relates to a polymer-containing coating liquid (rinsing liquid) applied to a resist pattern used in a lithography process.
- the present invention also relates to a method for forming a reversal pattern using the coating solution.
- Patent Document 1 as a pattern forming method that suppresses the occurrence of defects due to resist pattern collapse, a process of forming a resist film on a substrate, and an energy beam on the resist film to form a latent image on the resist film are disclosed.
- a coating film material including a step of supplying the rinsing liquid onto the substrate, and at least a part of the rinsing liquid on the substrate includes a solvent and a solute different from the resist film.
- a solvent in the coating film material is volatilized in order to supply the coating film material onto the substrate and to form a coating film covering the resist film on the substrate.
- Using the mask pattern to expose at least a portion of the upper surface of the resist pattern and to retreat at least a portion of the surface of the coating film to form a mask pattern composed of the coating film.
- a pattern forming method is disclosed.
- Patent Document 2 discloses a developer containing a curable resin different from the curable resin forming the resist film and an organic solvent as a developer that does not cause pattern collapse when forming a fine pattern. ing. And novolak resin and polysiloxane resin are illustrated as curable resin contained in the said developing solution.
- Patent Document 3 a silicon compound or a condensate thereof is brought into contact with a water-soluble compound having one or more hydroxyl groups or amino groups in the molecule, and then brought into contact with an acidic substance, whereby highly stable water-solubility.
- a production method for obtaining a silicon compound is disclosed. And glycols are illustrated as said water-soluble compound.
- Patent Document 1 Since the invention described in Patent Document 1 includes a step of supplying a rinsing liquid onto the substrate, the problem that the resist pattern collapses still cannot be solved.
- the invention described in Patent Document 2 is a developer, and is not used in place of a conventional rinse solution in a rinsing process after developing a resist film after exposure to form a resist pattern. Furthermore, a solution containing a polysiloxane resin, such as the developer, has a problem that storage stability at room temperature is not good when the polymer molecule of the polysiloxane resin has a plurality of hydroxy groups bonded to Si atoms. .
- Patent Document 3 brings a silicon compound or a condensate thereof into contact with a water-soluble compound, and does not intend to cause the silicon compound or a condensate thereof to react with the water-soluble compound. Furthermore, in the invention described in Patent Document 3, it is essential for obtaining a water-soluble compound that an acidic substance is contacted at the end, and thereafter the acidic substance is not removed. If the acidic substance is not contacted, the desired effect is obtained. Cannot be obtained.
- the present inventors use a composition containing a polymer having a specific structural unit and a solvent containing water and / or alcohols as a coating solution. Therefore, even if the coating solution is stored at room temperature, it is possible to solve the problem that the resist pattern collapses in the rinsing process for the resist pattern, and to form a reverse pattern used as a mask in the etching process. I found it.
- the present invention is a coating solution applied to a resist pattern, which includes a polymer having a structural unit represented by the following formula (1) and a solvent containing water and / or alcohols.
- R 1 represents an organic group having 1 to 12 carbon atoms
- X represents an organic group represented by the following formula (2).
- R 2 and R 3 each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, and R 2 is bonded to the oxygen atom in the formula (1);
- R 4 represents an alkoxy group having 1 to 4 carbon atoms, an allyloxy group or a hydroxy group, and p represents 0, 1 or 2)
- the polymer may further have a structural unit represented by the following formula (3). (In the formula, two Xs have the same definitions as in the formula (1)).
- the polymer having the structural unit represented by the formula (1) and the structural unit represented by the formula (3) is represented by, for example, a compound represented by the following formula (4) and the following formula (5). It is a product obtained by reacting a compound represented by the following formula (6) with a co-hydrolysis condensate of a compound.
- R 1 has the same definition as in the formula (1), Y and Z each independently represent a methyl group or an ethyl group, and R 2 , R 3 , R 4, and p each represent the formula (2 It is synonymous with the definition in).
- the compound represented by the formula (4) is, for example, ⁇ - (2-triethoxysilylethyl) - ⁇ -butyrolactone.
- the organic group having 1 to 12 carbon atoms defining R 1 is a linear, branched or cyclic alkyl group, vinyl group, allyl group, phenyl group, and the following formulas (7) to (13). Selected from the group consisting of represented groups. In particular, when a group represented by the following formula (11), formula (12) or formula (13) is selected as the organic group having 1 to 12 carbon atoms, it is highly effective in improving the storage stability of the coating solution. Indicates.
- R 5 represents a linear or branched alkylene group having 1 to 3 carbon atoms
- R 5 is bonded to the Si atom in the formula (1)
- R 6 is a hydrogen atom or Represents a methyl group
- R 7 and R 8 each independently represents a hydrogen atom or an allyl group.
- the group represented by the formula (11) is, for example, a group represented by the following formula (11 ′).
- linear or branched alkylene group having 1 to 3 carbon atoms a methylene group (—CH 2 — group), an ethylene group (—CH 2 CH 2 — group), a trimethylene group (—CH 2 CH 2 CH 2 -group) and propylene group (-CH (CH 3 ) CH 2 -group).
- alkoxy group having 1 to 4 carbon atoms examples include methoxy group (-OCH 3 group), ethoxy group (-OCH 2 CH 3 groups), n-propoxy group (—OCH 2 CH 2 CH 3 group), isopropoxy group (—OCH (CH 3 ) 2 group), n-butoxy group (—OCH 2 CH 2 CH 2 CH 3 group), Examples include isobutoxy group (—OCH 2 CH (CH 3 ) 2 group), sec-butoxy group (—OCH (CH 3 ) CH 2 CH 3 group) and tert-butoxy group (—OC (CH 3 ) 3 group). .
- R 2 is bonded to R 4 through a single bond.
- the alcohol in the solvent containing water and / or alcohol is, for example, a compound represented by the following formula (6).
- R 2 , R 3 , R 4 and p are the same as defined in the formula (2).
- the water of the solvent containing water and / or alcohols include pure water and ultrapure water.
- the solvent containing water and / or alcohols may be any of water, alcohols, and a mixture of water and alcohols, and the alcohols may be only one type or a mixture of two or more types.
- the content ratio of the alcohols in the mixture is, for example, 10% by mass to 70% by mass, preferably 30% by mass to 50%. % By mass.
- the content ratio of the alcohol is a numerical value with respect to 100% by mass of the mixture of water and alcohol.
- the concentration of the polymer in the coating liquid of the present invention is, for example, 0.5% by mass to 20% by mass.
- the concentration of this polymer is a numerical value with respect to 100% by mass of the coating liquid of the present invention.
- the film thickness of the formed coating film can be increased as the concentration is increased with the upper limit being 40% by mass.
- the coating liquid of the present invention can be used in place of the conventional rinse liquid, it can be referred to as a rinse liquid.
- Another aspect of the present invention includes a step of applying a positive resist solution on a substrate on which a lower layer film is formed, prebaking to form a resist film, a step of exposing the resist film, and a resist film after the exposure Is heated (PEB: Post Exposure Bake), and then the resist film is developed with an alkaline developer to form a resist pattern on the substrate on which the lower layer film is formed, at least between the patterns of the resist pattern is filled.
- PEB Post Exposure Bake
- a method for forming a reverse pattern comprising: exposing a surface of a resist pattern; and removing the resist pattern.
- the substrate coated with the coating solution is spin-dried, or spin-dried and then heated. Achieved.
- the spin dry is to dry while rotating the substrate.
- components other than the said polymer contained in the said coating liquid are a solvent and the additive added as needed.
- the step of removing the resist pattern is performed, for example, by dry etching or ashing.
- dry etching or ashing.
- ashing it is necessary to perform under the condition that the lower layer film is not removed except the resist pattern.
- Still another embodiment of the present invention is a method for manufacturing a semiconductor device, which includes forming a reverse pattern by the method of the present invention and then etching the substrate on which the lower layer film is formed using the reverse pattern as a mask.
- the step of etching the substrate on which the lower layer film is formed is performed, for example, by dry etching.
- the coating liquid of the present invention is excellent in storage stability because at least a part of the hydrogen atoms of the hydroxy group in the polymer molecule contained is substituted with the organic group represented by the formula (2). Therefore, it can be stored at room temperature. Moreover, the coating liquid of the present invention exhibits excellent storage stability even when no organic acid is added. By using the coating liquid of the present invention, a conventional rinsing process using a rinsing liquid is not required, so that the resist pattern can be prevented from collapsing.
- FIG. 1 is a cross-sectional SEM image showing a pattern shape of a reverse pattern obtained after forming a coating film on a resist pattern using the coating liquid of Preparation Example 3 and dry etching the coating film.
- FIG. 2 is a cross-sectional SEM image showing a pattern shape of an inverted pattern obtained by forming a coating film on a resist pattern using the coating liquid of Preparation Example 7 and dry etching the coating film.
- FIG. 3 is a cross-sectional SEM image showing the pattern shape of the reverse pattern obtained after forming a coating film on the resist pattern using the coating liquid of Preparation Example 10 and dry etching the coating film.
- FIG. 1 is a cross-sectional SEM image showing a pattern shape of a reverse pattern obtained after forming a coating film on a resist pattern using the coating liquid of Preparation Example 3 and dry etching the coating film.
- FIG. 2 is a cross-sectional SEM image showing a pattern shape of an inverted pattern obtained by forming a
- FIG. 4 is a cross-sectional SEM image showing the pattern shape of the reverse pattern obtained after forming a coating film on the resist pattern using the coating liquid of Preparation Example 11 and dry etching the coating film.
- FIG. 5 is a cross-sectional SEM image showing the pattern shape of the resist pattern after rinsing after development using pure water as a rinse solution.
- the polymer having the structural unit represented by the formula (1) is obtained by dissolving the compound represented by the formula (4) in a solvent containing water and subjecting it to a hydrolytic condensation reaction in the presence of a catalyst.
- the compound represented by the formula (6) is added to the solution, and the solvent, catalyst and the like containing water are distilled off under reduced pressure.
- the polymer having the structural unit represented by the formula (1) and the structural unit represented by the formula (3) is represented by the formula (5) in addition to the compound represented by the formula (4). Using a compound, it can be obtained by the same method as described above.
- Examples of the compound represented by the formula (6) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol monoallyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol Bruno ether, ethylene glycol, 1,2-propanediol or 1,3-propanediol, diethylene glycol, dipropylene glycol, and di isopropylene glycol and triethylene glycol.
- Preferred examples of the catalyst include inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as formic acid, oxalic acid, fumaric acid, maleic acid, glacial acetic acid, acetic anhydride, propionic acid, and n-butyric acid.
- the amount of the catalyst used is, for example, 0.001 based on the mass of the compound represented by the formula (4) or the total mass of the compound represented by the formula (4) and the compound represented by the formula (5). % By mass to 1% by mass.
- the hydrolytic condensation reaction and the cohydrolytic condensation reaction are performed under a temperature condition of 30 ° C. to 80 ° C., for example.
- the structural unit represented by the formula (1) and the structural unit represented by the formula (3) of the polymer contained in the coating solution of the present invention are a random copolymer, a block copolymer, and an alternating copolymer. Any of these structures may be formed.
- organic group defining X in the structural unit represented by the formula (1) and the structural unit represented by the formula (3) include the following formulas (2-1) to (2-25). Shown in In the following formulae, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, and Bu represents an n-butyl group.
- An organic acid may be added to the coating solution of the present invention.
- the organic acid include maleic acid, formic acid, acetic acid, maleic anhydride, oxalic acid, citric acid, and phosphoric acid.
- the content rate is 0.1 mass% thru
- An organic acid as an additive can also be expressed as a pH adjuster.
- a surfactant may be added to the coating solution of the present invention.
- the said surfactant is an additive for improving the applicability
- Known surfactants such as nonionic surfactants and fluorine surfactants can be used, and the content thereof is, for example, 0.1% by mass or more with respect to the polymer contained in the coating liquid of the present invention. 5% by mass or less.
- surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkylaryl ethers such as nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristea
- the reverse pattern forming method of the present invention includes a step of applying a positive resist solution onto a substrate on which a lower layer film is formed, and prebaking to form a resist film.
- a substrate used for manufacturing a precision integrated circuit element for example, a semiconductor substrate such as a silicon substrate coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, an alkali-free substrate
- the organic film and / or inorganic film which have antireflection ability are formed as a lower layer film.
- a positive resist solution is applied onto the lower layer film by an appropriate application method such as a spinner or a coater, and prebaked at a temperature of about 80 ° C. to 180 ° C., for example.
- a resist film is formed by drying.
- the thickness of the resist film at this time is, for example, 10 nm to 1000 nm.
- the positive resist solution include PAR710, PAR855 manufactured by Sumitomo Chemical Co., Ltd., and AR2772JN manufactured by JSR Co., Ltd.
- the exposure is performed through a mask having a predetermined pattern, visible light (g-line), ultraviolet (i-line, KrF excimer laser, ArF excimer laser), extreme ultraviolet (EUV), This is performed using a light source such as an electron beam.
- a light source such as an electron beam.
- the alkali developer includes sodium hydroxide, potassium hydroxide, Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, triethylamine, methyldiethylamine Tertiary amines such as alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, cyclic amines such as pyrrole and piperidine, etc.
- Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia
- primary amines such as ethylamine and n-propylamine
- secondary amines such as diethyl
- alkaline Solution Of alkaline Solution, and the like. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
- a preferred developer is an aqueous solution of a quaternary ammonium salt, more preferably an aqueous solution of tetramethylammonium hydroxide. In the case of the present invention, there is no need for a step of developing with the alkaline developer and then washing and drying with a conventional rinse solution.
- the coating solution of the present invention is applied so as to fill at least the space between the resist patterns, and components other than the polymer and the alkaline developer contained in the coating solution are removed or reduced to form a coating film.
- the coating liquid of the present invention is applied by an appropriate application method such as a spinner or a coater.
- the solvent in the coating film is rapidly volatilized by heating at 80 ° C. to 180 ° C., for example. Can do.
- the heating time at this time is, for example, 10 seconds to 300 seconds.
- the film thickness of the said coating film is not specifically limited, For example, it is 10 nm to 1000 nm.
- the etch back is, for example, dry etching using a fluorine-based gas such as CF 4 , an aqueous solution of an organic acid or an organic base, or an organic solvent.
- a fluorine-based gas such as CF 4
- an aqueous solution of an organic acid or an organic base or an organic solvent.
- the etching is performed by wet etching using a CMP method, and the processing conditions can be adjusted as appropriate.
- a mixed gas of O 2 and N 2 or O 2 gas is used.
- a desired reverse pattern is formed by the coating film remaining after the resist pattern is removed.
- the weight average molecular weight shown to the following synthesis example of this specification is a measurement result by gel permeation chromatography (henceforth GPC).
- the measuring equipment and measuring conditions used are as follows.
- GPC device HLC-8220GPC (manufactured by Tosoh Corporation)
- GPC column Shodex [registered trademark] KF803L, KF802, KF801 (manufactured by Showa Denko KK) Column temperature: 40 ° C
- Solvent tetrahydrofuran (THF)
- Flow rate 1.0 mL / min Standard sample: Polystyrene (manufactured by Showa Denko KK)
- reaction solution is cooled to room temperature, 60.0 g of propylene glycol monomethyl ether is added to the reaction solution, acetone, water, hydrochloric acid, and ethanol as a reaction byproduct are distilled off from the reaction solution under reduced pressure and concentrated.
- a propylene glycol monomethyl ether solution of the hydrolysis condensate (polymer) was obtained.
- the solid content concentration was adjusted to 15% by mass in terms of solid residue at 140 ° C.
- the weight average molecular weight Mw by GPC was 700 in terms of polystyrene.
- the flask was transferred to an oil bath adjusted to 40 ° C. and reacted for 240 minutes under heating and reflux. Thereafter, the reaction solution is cooled to room temperature, 24.0 g of propylene glycol monomethyl ether is added to the reaction solution, and acetone, water, hydrochloric acid, and ethanol as a reaction byproduct are distilled off from the reaction solution under reduced pressure and concentrated. A propylene glycol monomethyl ether solution of the hydrolysis condensate (polymer) was obtained. The solid content concentration was adjusted to 15% by mass in terms of solid residue at 140 ° C. The weight average molecular weight Mw by GPC was 1000 in terms of polystyrene.
- reaction solution is cooled to room temperature, 24.0 g of propylene glycol monomethyl ether is added to the reaction solution, and acetone, water, hydrochloric acid, and ethanol as a reaction byproduct are distilled off from the reaction solution under reduced pressure and concentrated.
- a propylene glycol monomethyl ether solution of the hydrolysis condensate (polymer) was obtained.
- the solid content concentration was adjusted to 15% by mass in terms of solid residue at 140 ° C.
- the weight average molecular weight Mw by GPC was 800 in terms of polystyrene.
- reaction solution is cooled to room temperature, 24.0 g of propylene glycol monomethyl ether is added to the reaction solution, and acetone, water, hydrochloric acid, and ethanol as a reaction byproduct are distilled off from the reaction solution under reduced pressure and concentrated.
- a propylene glycol monomethyl ether solution of the hydrolysis condensate (polymer) was obtained.
- the solid content concentration was adjusted to 15% by mass in terms of solid residue at 140 ° C.
- the weight average molecular weight Mw by GPC was 2000 in terms of polystyrene.
- reaction solution is cooled to room temperature, 24.0 g of propylene glycol monomethyl ether is added to the reaction solution, and acetone, water, hydrochloric acid, and ethanol as a reaction byproduct are distilled off from the reaction solution under reduced pressure and concentrated.
- a propylene glycol monomethyl ether solution of the hydrolysis condensate (polymer) was obtained.
- the solid content concentration was adjusted to 15% by mass in terms of solid residue at 140 ° C.
- the weight average molecular weight Mw by GPC was 2000 in terms of polystyrene.
- a commercially available resist underlayer film forming composition (resin component is a methacrylate copolymer) is applied onto a silicon substrate using a spinner, and heated at 205 ° C. for 60 seconds to form a resist underlayer film having a thickness of 28 nm.
- An ArF resist solution (manufactured by JSR Corporation, trade name: AR2772JN) was applied onto the film using a spinner.
- a resist film having a thickness of 210 nm was formed by heating at 110 ° C. for 90 seconds on a hot plate.
- an exposure apparatus for ArF excimer laser (Nikon Corporation, S307E)
- the resist film was exposed under predetermined conditions.
- the coating solution of the present invention can be used for, for example, a rinsing solution for an ultraviolet or extreme ultraviolet resist solution, and a composition for forming a reverse pattern.
Abstract
Description
(式中、R1は炭素原子数1乃至12の有機基を表し、Xは下記式(2)で表される有機基を表す。
(式中、R2及びR3はそれぞれ独立に直鎖状又は分岐鎖状の炭素原子数1乃至3のアルキレン基を表し、該R2は前記式(1)中の酸素原子と結合し、R4は炭素原子数1乃至4のアルコキシ基、アリルオキシ基又はヒドロキシ基を表し、pは0、1又は2を表す。))
(式中、R1は前記式(1)における定義と同義であり、Y及びZはそれぞれ独立にメチル基又はエチル基を表し、R2、R3、R4及びpはそれぞれ前記式(2)における定義と同義である。)
(式中、R5は直鎖状又は分岐鎖状の炭素原子数1乃至3のアルキレン基を表し、当該R5は前記式(1)中のSi原子と結合し、R6は水素原子又はメチル基を表し、R7及びR8はそれぞれ独立に水素原子又はアリル基を表す。)
(式中、R2、R3、R4及びpはそれぞれ前記式(2)における定義と同義である。)
前記水及び/又はアルコール類を含有する溶剤の水として、例えば、純水及び超純水が挙げられる。前記水及び/又はアルコール類を含有する溶剤は、水、アルコール類、水とアルコール類との混合物、のいずれでもよく、前記アルコール類は、1種のみ、2種以上の混合物のいずれでもよい。前記水及び/又はアルコール類を含有する溶剤が水とアルコール類との混合物である場合、当該混合物中のアルコール類の含有割合は、例えば10質量%乃至70質量%、好ましくは30質量%乃至50質量%である。このアルコール類の含有割合は、水とアルコール類との混合物100質量%に対する数値である。
<ポリマー>
前記式(1)で表される構造単位を有するポリマーは、前記式(4)で表される化合物を、水を含有する溶剤に溶解させ、触媒の存在下、加水分解縮合反応させて得られた溶液に、式(6)で表される化合物を加え、水を含有する溶剤、触媒等を減圧留去して得ることができる。前記式(1)で表される構造単位及び前記式(3)で表される構造単位を有するポリマーは、前記式(4)で表される化合物に加えて前記式(5)で表される化合物を用い、上記同様の方法で得ることができる。式(6)で表される化合物として、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノアリルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコール、1,2-プロパンジオール又は1,3-プロパンジオール、ジエチレングリコール、ジプロピレングリコール、ジイソプロピレングリコール及びトリエチレングリコールを挙げることができる。好ましい触媒として、例えば、塩酸、硝酸等の無機酸、及びギ酸、シュウ酸、フマル酸、マレイン酸、氷酢酸、無水酢酸、プロピオン酸、n-酪酸等の有機酸を挙げることができる。使用する触媒の量は、式(4)で表される化合物の質量、又は式(4)で表される化合物及び式(5)で表される化合物の全質量に対して、例えば0.001質量%乃至1質量%である。上記加水分解縮合反応及び共加水分解縮合反応は、例えば、30℃乃至80℃の温度条件にて実施される。
本発明の塗布液は、有機酸が添加されていてもよい。当該有機酸として、例えば、マレイン酸、ギ酸、酢酸、無水マレイン酸、シュウ酸、クエン酸及びリン酸が挙げられる。本発明の塗布液が有機酸を含む場合、その含有割合は、本発明の塗布液に対して、例えば0.1質量%乃至10質量%である。添加剤としての有機酸は、pH調製剤と表現することもできる。
本発明の反転パターンの形成方法は、前述のとおり、下層膜が形成された基板上にポジ型のレジスト溶液を塗布し、プリベークしてレジスト膜を形成する工程を有する。前記基板として、精密集積回路素子の製造に使用される基板(例えば、酸化珪素膜、窒化珪素膜又は酸化窒化珪素膜で被覆されたシリコン基板等の半導体基板、窒化珪素基板、石英基板、無アルカリガラス基板、低アルカリガラス基板、結晶化ガラス基板、ITO膜が形成されたガラス基板)を挙げることができる。そして、前記基板には、下層膜として、反射防止能を有する有機膜及び/又は無機膜が形成されている。
[GPC条件]
GPC装置:HLC-8220GPC(東ソー(株)製)
GPCカラム:Shodex〔登録商標〕KF803L,KF802,KF801(昭和電工(株)製)
カラム温度:40℃
溶媒:テトラヒドロフラン(THF)
流量:1.0mL/分
標準試料:ポリスチレン(昭和電工(株)製)
テトラエトキシシラン16.7g(30mol%)、メチルトリエトキシシラン33.3g(70mol%)、アセトン100g及び超純水100gを500mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら、0.01mol/Lの塩酸4.8gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、反応溶液を室温まで冷却し、その反応溶液にプロピレングリコールモノメチルエーテル60.0gを加え、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)のプロピレングリコールモノメチルエーテル溶液を得た。固形分濃度は140℃における固形残物換算で15質量%となるように調整した。GPCによる重量平均分子量Mwはポリスチレン換算で700であった。
テトラエトキシシラン16.7g(30mol%)、メチルトリエトキシシラン33.3g(70mol%)、アセトン100g及び超純水100gを500mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら0.01mol/Lの塩酸4.8gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、反応溶液に1質量%のマレイン酸水溶液4.8gを添加し、さらにプロピレングリコールモノメチルエーテル100gを加え、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)のプロピレングリコールモノメチルエーテル溶液を得た。固形分濃度は140℃における固形残物換算で15質量%となるように調整した。GPCによる重量平均分子量Mwはポリスチレン換算で1200であった。
テトラエトキシシラン5.8g(30mol%)、メチルトリエトキシシラン6.7g(40mol%)、下記式(4-1)で表される化合物である5-(トリエトキシシリル)ノルボルナン-2,3-ジカルボン酸無水物9.2g(30mol%)、アセトン43g及び超純水43gを200mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら0.01mol/Lの塩酸1.7gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、反応溶液を室温まで冷却し、その反応溶液にプロピレングリコールモノメチルエーテル24.0gを加え、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)のプロピレングリコールモノメチルエーテル溶液を得た。固形分濃度は140℃における固形残物換算で15質量%となるように調整した。GPCによる重量平均分子量Mwはポリスチレン換算で1000であった。
テトラエトキシシラン5.8g(30mol%)、メチルトリエトキシシラン6.7g(40mol%)、下記式(4-2)で表される化合物であるβ-(2-トリエトキシシリルエチル)-γ-ブチロラクトン7.7g(30mol%)、アセトン40g及び超純水40gを200mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら0.01mol/Lの塩酸1.7gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、反応溶液を室温まで冷却し、その反応溶液にプロピレングリコールモノメチルエーテル24.0gを加え、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)のプロピレングリコールモノメチルエーテル溶液を得た。固形分濃度は140℃における固形残物換算で15質量%となるように調整した。GPCによる重量平均分子量Mwはポリスチレン換算で800であった。
テトラエトキシシラン5.8g(30mol%)、メチルトリエトキシシラン6.7g(40mol%)、下記式(4-3)で表される化合物である2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン6.9g(30mol%)、アセトン43g及び超純水43gを200mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら0.01mol/Lの塩酸1.7gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、反応溶液を室温まで冷却し、その反応溶液にプロピレングリコールモノメチルエーテル24.0gを加え、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)のプロピレングリコールモノメチルエーテル溶液を得た。固形分濃度は140℃における固形残物換算で15質量%となるように調整した。GPCによる重量平均分子量Mwはポリスチレン換算で2000であった。
テトラエトキシシラン5.8g(30mol%)、メチルトリエトキシシラン6.7g(40mol%)、下記式(4-4)で表される化合物である3-グリシジルオキシプロピルトリメトキシシラン6.6g(30mol%)、アセトン43g及び超純水43gを200mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら0.01mol/Lの塩酸1.7gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、反応溶液を室温まで冷却し、その反応溶液にプロピレングリコールモノメチルエーテル24.0gを加え、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)のプロピレングリコールモノメチルエーテル溶液を得た。固形分濃度は140℃における固形残物換算で15質量%となるように調整した。GPCによる重量平均分子量Mwはポリスチレン換算で2000であった。
テトラエトキシシラン16.7g(30mol%)、メチルトリエトキシシラン33.3g(70mol%)、アセトン100g及び超純水100gを500mlのフラスコに入れ、そのフラスコ内の混合溶液をマグネチックスターラーにて撹拌しながら0.01mol/Lの塩酸4.8gをその混合溶液に滴下した。滴下後、40℃に調整されたオイルバスにフラスコを移し、加温還流下で240分反応させた。その後、アセトン、水及び塩酸、並びに反応副生物であるエタノールを反応溶液から減圧留去し濃縮して、共加水分解縮合物(ポリマー)の水溶液を得た。GPCによる重量平均分子量Mwはポリスチレン換算で600であった。
上記合成例1乃至合成例6及び比較合成例1で得られたポリマー溶液に、プロピレングリコールモノメチルエーテル及び水を下記表1に示す割合で含有する溶剤を加え、塗布液をそれぞれ調製した。水として超純水を用いた。表1に示すポリマーの含有割合は、ポリマー溶液ではなく、ポリマー溶液から溶剤を除いた固形分の含有割合を示す。各成分の含有割合は質量部で表す。表1中では、プロピレングリコールモノメチルエーテルをPGMEと略記する。
〔塗布液の保存安定性〕
上記調製例1乃至調製例11及び比較調製例1の塗布液を、23℃の恒温槽で1ヶ月間保管し、これらの塗布液の1ヶ月後の保存安定性を目視により観察した。その結果を下記表2にまとめた。表2において、「良好」とは塗布液が透明な溶液を維持していることを表し、「不良」とは塗布液中に白色の沈殿物が生成し半透明な溶液に変化したことを表す。調製例1乃至調製例11の塗布液を用いた実施例1乃至実施例11のみ、「良好」と評価することができた。
シリコン基板上に市販のレジスト下層膜形成組成物(樹脂成分はメタクリレート共重合体)を、スピナーを用いて塗布し、205℃で60秒間加熱することにより膜厚28nmのレジスト下層膜を形成し、その膜上にArF用レジスト溶液(JSR(株)製、商品名:AR2772JN)を、スピナーを用いて塗布した。ホットプレート上で、110℃で90秒間加熱することにより、膜厚210nmのレジスト膜を形成した。ArFエキシマレーザー用露光装置((株)ニコン製、S307E)を用い、そのレジスト膜に対し所定の条件で露光した。目的の線幅を65nm、スペース幅を195nmとした上記露光後、110℃で90秒間加熱(PEB)を行い、クーリングプレート上で上記シリコン基板を室温まで冷却した。その後、2.38質量%テトラメチルアンモニウム水溶液を用いて現像して、レジストパターンが形成された。続いて、このレジストパターンに調製例3、調製例7、調製例10又は調製例11の塗布液を塗布し、現像に用いた2.38質量%テトラメチルアンモニウム水溶液をこの塗布液に置き換えた。その後、上記シリコン基板を1500rpmで60秒間スピンして塗布液中の溶剤を乾燥させた後、100℃で60秒間加熱して塗膜を形成し、上記レジストパターンの埋め込みを行った。
Claims (14)
- 前記式(4)で表される化合物はβ-(2-トリエトキシシリルエチル)-γ-ブチロラクトンである、請求項3に記載の塗布液。
- 前記水及び/又はアルコール類を含有する溶剤が水とアルコール類との混合物であり、該混合物中のアルコール類の含有割合は10質量%乃至70質量%である、請求項7に記載の塗布液。
- 前記ポリマーの濃度が0.5質量%乃至20質量%である請求項1乃至請求項8のいずれか一項に記載の塗布液。
- 前記塗布液はリンス液に該当する請求項1乃至請求項9のいずれか一項に記載の塗布液。
- 下層膜が形成された基板上にポジ型のレジスト溶液を塗布し、プリベークしてレジスト膜を形成する工程、
前記レジスト膜を露光する工程、
前記露光後のレジスト膜を加熱し、その後当該レジスト膜をアルカリ現像液で現像して前記下層膜が形成された基板上にレジストパターンを形成する工程、
少なくとも前記レジストパターンのパターン間を充填するように請求項1乃至請求項10のいずれか一項に記載の塗布液を塗布し、当該塗布液に含まれる前記ポリマー以外の成分及び前記アルカリ現像液を除去し又は減少させて塗膜を形成する工程、
前記塗膜をエッチバックして前記レジストパターンの表面を露出させる工程、及び
前記レジストパターンを除去する工程、
を含む反転パターンの形成方法。 - 前記塗布液が塗布された前記基板をスピンドライし、又はスピンドライした後加熱することにより、当該塗布液に含まれる前記ポリマー以外の成分及び前記アルカリ現像液を除去し又は減少させる、請求項11に記載の反転パターンの形成方法。
- 前記レジストパターンを除去する工程はドライエッチング又はアッシングにより行われる請求項11又は請求項12に記載の反転パターンの形成方法。
- 請求項11乃至請求項13のいずれか一項に記載の方法で反転パターンを形成した後、該反転パターンをマスクとして前記下層膜が形成された基板をエッチングする工程を含む半導体装置の作製方法。
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