WO2013080929A1 - 多層レジストプロセスに用いられるレジスト下層膜形成用組成物、レジスト下層膜及びその形成方法、並びにパターン形成方法 - Google Patents
多層レジストプロセスに用いられるレジスト下層膜形成用組成物、レジスト下層膜及びその形成方法、並びにパターン形成方法 Download PDFInfo
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- WO2013080929A1 WO2013080929A1 PCT/JP2012/080518 JP2012080518W WO2013080929A1 WO 2013080929 A1 WO2013080929 A1 WO 2013080929A1 JP 2012080518 W JP2012080518 W JP 2012080518W WO 2013080929 A1 WO2013080929 A1 WO 2013080929A1
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- underlayer film
- resist
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- forming
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- DRWVEDRBGUMYHG-UHFFFAOYSA-N CC(OCc(c(COC(C)=O)c1COC(C)=O)c(COC(C)=O)c2c1c(C#N)c(c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c1COC(C)=O)c1c2C#N)=O Chemical compound CC(OCc(c(COC(C)=O)c1COC(C)=O)c(COC(C)=O)c2c1c(C#N)c(c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c1COC(C)=O)c1c2C#N)=O DRWVEDRBGUMYHG-UHFFFAOYSA-N 0.000 description 1
- ZTDKWAJBUSIRDF-UHFFFAOYSA-N CC(OCc1c(COC(C)=O)c2c(COC(C)=O)c(c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c3O)c3c(O)c2c(O)c1COC(C)=O)=O Chemical compound CC(OCc1c(COC(C)=O)c2c(COC(C)=O)c(c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c3O)c3c(O)c2c(O)c1COC(C)=O)=O ZTDKWAJBUSIRDF-UHFFFAOYSA-N 0.000 description 1
- ZZAVGZCAFOJMQO-UHFFFAOYSA-N CCOCc1cccc2cccc(-c3c(c(COCC)cc(-c4ccc(cc(c(CO)c5)-c6c(CO)cc(cccc7)c7c6)c5c4)c4)c4ccc3)c12 Chemical compound CCOCc1cccc2cccc(-c3c(c(COCC)cc(-c4ccc(cc(c(CO)c5)-c6c(CO)cc(cccc7)c7c6)c5c4)c4)c4ccc3)c12 ZZAVGZCAFOJMQO-UHFFFAOYSA-N 0.000 description 1
- JYENOFFZPPXWOL-UHFFFAOYSA-N CCc(c1c2c(O)c(CO)cc1CO)c(c(CO)cc(CO)c1O)c1c2O Chemical compound CCc(c1c2c(O)c(CO)cc1CO)c(c(CO)cc(CO)c1O)c1c2O JYENOFFZPPXWOL-UHFFFAOYSA-N 0.000 description 1
- NYXSCXJXDOBCAD-UHFFFAOYSA-N CCc1c(c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c2COC(C)=O)c2c(CC)c2c1c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c2COC(C)=O Chemical compound CCc1c(c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c2COC(C)=O)c2c(CC)c2c1c(COC(C)=O)c(COC(C)=O)c(COC(C)=O)c2COC(C)=O NYXSCXJXDOBCAD-UHFFFAOYSA-N 0.000 description 1
- RNRFGFQJBQSMLH-UHFFFAOYSA-N COCc(c1c2c(O)c3c(O)c(COC)cc(COC)c3c1COC)cc(COC)c2O Chemical compound COCc(c1c2c(O)c3c(O)c(COC)cc(COC)c3c1COC)cc(COC)c2O RNRFGFQJBQSMLH-UHFFFAOYSA-N 0.000 description 1
- RREBXENSENADQE-UHFFFAOYSA-N COCc(cc(cccc1)c1c1-c2c(cccc3)c3cc(COC)c2O)c1O Chemical compound COCc(cc(cccc1)c1c1-c2c(cccc3)c3cc(COC)c2O)c1O RREBXENSENADQE-UHFFFAOYSA-N 0.000 description 1
- 0 COCc1c(COC)c(cccc2)c2c(COC)c1C* Chemical compound COCc1c(COC)c(cccc2)c2c(COC)c1C* 0.000 description 1
- MAUZKHFBUMFTEH-UHFFFAOYSA-N COCc1c(c(COC)ccc2COC)c2c(COC)cc1 Chemical compound COCc1c(c(COC)ccc2COC)c2c(COC)cc1 MAUZKHFBUMFTEH-UHFFFAOYSA-N 0.000 description 1
- NZNIIFYEGQOOHD-UHFFFAOYSA-N COCc1ccc-2c3c1c(COC)ccc3-c1ccc(COC)c3c(COC)ccc-2c13 Chemical compound COCc1ccc-2c3c1c(COC)ccc3-c1ccc(COC)c3c(COC)ccc-2c13 NZNIIFYEGQOOHD-UHFFFAOYSA-N 0.000 description 1
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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
-
- 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
- G03F7/094—Multilayer resist systems, e.g. planarising layers
Definitions
- the present invention relates to a resist underlayer film forming composition used in a multilayer resist process, a resist underlayer film, a method for forming the resist underlayer film, and a pattern forming method.
- a multilayer resist process is used to obtain a high degree of integration.
- a resist underlayer film forming composition is applied on a substrate to be processed to form a resist underlayer film, and the resist composition is applied onto the resist underlayer film to form a resist film.
- the resist film is exposed through a mask pattern with a reduction projection exposure apparatus (stepper) or the like, and developed with an appropriate developer to form a resist pattern.
- the resist underlayer film is dry-etched using the resist pattern as a mask, and the substrate to be processed is further dry-etched using the obtained resist underlayer film pattern as a mask, whereby a desired pattern can be formed on the substrate to be processed.
- the resist underlayer film used in such a multilayer resist process is required to have general characteristics such as optical characteristics and etching resistance.
- the resist underlayer film using the above conventional composition has difficulty in heat resistance, and due to the low heat resistance, the resist underlayer film component is heated by the resist underlayer film formation. May sublimate, and the sublimated components may reattach to the substrate and deteriorate the manufacturing yield of semiconductor devices.
- the resist underlayer film is also required to improve solvent resistance and bending resistance.
- the present invention has been made based on the above circumstances, and its purpose is to sufficiently satisfy general characteristics such as etching resistance and to form a resist underlayer film having high heat resistance and solvent resistance.
- Another object of the present invention is to provide a resist underlayer film forming composition used in such a multilayer resist process, a resist underlayer film using this composition, a method for forming the resist underlayer film, and a pattern forming method using the composition.
- composition for forming a resist underlayer film used in a multilayer resist process containing a polymer having a structural unit (I) represented by the following formula (1) (hereinafter also referred to as “[A] polymer”) (Hereinafter also simply referred to as “resist underlayer film forming composition” or “composition”).
- [A] polymer a polymer having a structural unit (I) represented by the following formula (1)
- resist underlayer film forming composition hereinafter also simply referred to as “resist underlayer film forming composition” or “composition”.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently a divalent aromatic hydrocarbon group or a divalent heteroaromatic group, provided that the above aromatic carbonization is performed.
- R 1 is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that Some or all of the hydrogen atoms of the divalent hydrocarbon group having 1 to 20 carbon atoms may be substituted, and the divalent hydrocarbon group having 1 to 20 carbon atoms may be an ester group or an ether group.
- a carbonyl group may be present in the structure, Y is a carbonyl group or a sulfonyl group, m is 0 or 1, and n is 0 or 1.
- the resist underlayer film forming composition contains the [A] polymer, so that the resist underlayer film formed from the composition sufficiently satisfies general characteristics such as optical characteristics and etching resistance, and additionally has high heat resistance. Property, solvent resistance and bending resistance.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 in the above formula (1) are preferably each independently represented by the following formula (2).
- Q 1 is a (k + 2) -valent aromatic hydrocarbon group or a (k + 2) -valent heteroaromatic group.
- R 2 is a halogen atom, a hydroxy group, a cyano group, a formyl group, or A monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that a part or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms are a halogen atom, a hydroxy group, a cyano group, or (It may be substituted with a formyl group.
- K is an integer of 0 to 6. However, when k is 2 or more, a plurality of R 2 may be the same or different.
- R 1 in the above formula (1) is preferably represented by a single bond or the following formula (3).
- Q 2 is an (a + 2) -valent aromatic hydrocarbon group or an (a + 2) -valent heteroaromatic group.
- Q 3 is a (b + 2) -valent aromatic hydrocarbon group or ( b + 2) -valent heteroaromatic group
- R 3 and R 4 each independently represents a halogen atom, a hydroxy group or a cyano group, a is an integer of 0 to 4, and b is 0 to 4 is an integer .
- R 3 and optionally R 4 is plural respective plurality of R 3 and R 4 may each be the same or different.
- the structural unit (I) contains the specific group, the heat resistance of the resist underlayer film formed from the resist underlayer film forming composition can be further enhanced.
- the resist underlayer film forming composition preferably further contains a [B] solvent.
- paintability can be improved because the said composition for resist lower layer film formation contains a [B] solvent further.
- the resist underlayer film of the present invention is formed from the resist underlayer film forming composition.
- the resist underlayer film sufficiently satisfies general characteristics such as etching resistance and has high heat resistance, solvent resistance and bending resistance.
- the resist underlayer film forming method of the present invention comprises: (1) The process which forms a coating film on a to-be-processed substrate using the said composition for resist underlayer film formation, (2) It has the process of heating the said coating film and forming a resist underlayer film.
- the resist underlayer film forming method can form a resist underlayer film having the above-mentioned specific steps, sufficiently satisfying general characteristics such as etching resistance, and additionally having high heat resistance, solvent resistance and bending resistance. .
- the pattern forming method of the present invention comprises: (1) forming a resist underlayer film on a substrate to be processed using the resist underlayer film forming composition; (2) forming a resist film on the upper surface side of the resist underlayer film using a resist composition; (3) a step of exposing the resist film by selective irradiation; (4) a step of developing the exposed resist film to form a resist pattern; and (5) a step of sequentially dry-etching the resist underlayer film and the substrate to be processed using the resist pattern as a mask.
- the pattern forming method has the above specific steps to sufficiently satisfy general characteristics such as etching resistance and to easily and reliably form a resist underlayer film having high heat resistance, solvent resistance and bending resistance. Can do. As a result, the pattern forming method contributes to the formation of a finer pattern on the substrate to be processed.
- (1 ′) further includes a step of forming an intermediate layer on the resist underlayer film.
- the intermediate layer may be dry etched.
- the pattern forming method further includes the above specific step, whereby, for example, an intermediate layer having a desired function such as an antireflection function and etching resistance can be formed. As a result, it contributes to the formation of a finer pattern on the substrate to be processed.
- the composition for forming a resist underlayer film used in the multilayer resist process of the present invention it is possible to form a resist underlayer film that sufficiently satisfies general characteristics such as etching resistance and has high heat resistance and solvent resistance. it can. Therefore, the composition for forming a resist underlayer film, the resist underlayer film, a method for forming the resist underlayer, and a pattern forming method are suitably used for a pattern forming process using a multilayer resist process in a semiconductor device in which further miniaturization of the pattern proceeds. be able to.
- composition for forming a resist underlayer film used in the multilayer resist process of the present invention contains a [A] polymer.
- the said composition for resist lower layer film formation may contain a [B] solvent as a suitable component.
- the resist underlayer film forming composition is not limited to the effects of the present invention, and other such as [C] acid generator, [D] cross-linking agent, [E] surfactant and [F] adhesion aid. These optional components may be contained.
- the said composition for resist lower layer film formation may contain 2 or more types of [A] polymers. Hereinafter, each component will be described in detail.
- the polymer is a polymer having the structural unit (I).
- the polymer may contain other structural units as long as the effects of the present invention are not impaired.
- the [A] polymer may have 2 or more types of each structural unit, and the [A] polymer in this case may be any of a random copolymer and a block copolymer.
- each structural unit will be described in detail.
- the structural unit (I) is a structural unit represented by the above formula (1).
- the resist underlayer film formed from the resist underlayer film forming composition sufficiently satisfies general characteristics such as etching resistance, and additionally has high heat resistance and resistance. Solvent resistance and bending resistance.
- the high heat resistance and the like are stabilized by the two bonds of the ether group being directly bonded to the aromatic hydrocarbon group or heteroaromatic group in the main chain of the [A] polymer. It is presumed to be caused by
- Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently a divalent aromatic hydrocarbon group or a divalent heteroaromatic group. However, part or all of the hydrogen atoms of the aromatic hydrocarbon group and heteroaromatic group may be substituted.
- R 1 is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. However, part or all of the hydrogen atoms of the divalent hydrocarbon group having 1 to 20 carbon atoms may be substituted.
- the divalent hydrocarbon group having 1 to 20 carbon atoms may have an ester group, an ether group or a carbonyl group in the structure.
- Y is a carbonyl group or a sulfonyl group.
- m is 0 or 1.
- n is 0 or 1.
- the divalent aromatic hydrocarbon group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 is preferably a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenylene group or naphthylene. Group, anthranylene group and the like.
- the divalent heteroaromatic group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 is preferably a divalent heteroaromatic group having 3 to 20 carbon atoms, such as furan, pyrrole, thiophene, Examples include groups obtained by removing two hydrogen atoms from a heteroaromatic compound such as phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, quinoline and acridine.
- Examples of the substituent that may be substituted with the divalent aromatic hydrocarbon group and the divalent heteroaromatic group include, for example, a halogen atom, a hydroxy group, a cyano group, a nitro group, a formyl group, or a monovalent organic group. Etc.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the monovalent organic group include a group consisting of —CO—, —COO—, —OCO—, —O—, —NR—, —CS—, —S—, —SO— and —SO 2 —.
- the thing which the hydrogen atom which group has is substituted by the substituent is mentioned.
- R is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.
- Examples of the substituent include a hydroxy group, a cyano group, a carboxy group, and an ethynyl group.
- the monovalent aromatic group having 3 to 20 carbon atoms is preferably a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a monovalent heteroaromatic group having 3 to 20 carbon atoms.
- the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthranyl group.
- the monovalent heteroaromatic group having 3 to 20 carbon atoms include furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, quinoline. And groups obtained by removing one hydrogen atom from a heteroaromatic compound such as acridine.
- Examples of the monovalent group in combination with the monovalent aromatic group of 3 to 20 include a phenoxy group, a naphthyloxy group, an anthranyloxy group, and an anilino group.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 in the above formula (1) are preferably each independently a group represented by the above formula (2).
- Ar 1 , Ar 2 , Ar 3 and Ar 4 into the specific groups, respectively the heat resistance and the like of the resist underlayer film can be further improved.
- Q 1 is a (k + 2) -valent aromatic hydrocarbon group or a (k + 2) -valent heteroaromatic group.
- R 2 is a halogen atom, a hydroxy group, a cyano group, a formyl group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. However, part or all of the hydrogen atoms contained in the monovalent hydrocarbon group having 1 to 20 carbon atoms may be substituted with a halogen atom, a hydroxy group, a cyano group, or a formyl group.
- k is an integer of 0 to 6. However, when k is 2 or more, the plurality of R 2 may be the same or different.
- Examples of the (k + 2) -valent aromatic hydrocarbon group represented by Q 1 include a group obtained by removing k hydrogen atoms from a divalent aromatic hydrocarbon group.
- the divalent aromatic hydrocarbon group for example, the divalent aromatic hydrocarbon group exemplified for Ar 1 , Ar 2 , Ar 3 and Ar 4 can be applied.
- Examples of the (k + 2) -valent heteroaromatic group represented by Q 1 include a group in which k hydrogen atoms have been removed from a divalent heteroaromatic group.
- the divalent heteroaromatic group for example, the divalent heteroaromatic groups exemplified for Ar 1 , Ar 2 , Ar 3 and Ar 4 can be applied.
- Examples of the halogen atom represented by R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 2 include, for example, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and carbon. Examples thereof include monovalent aromatic hydrocarbon groups of 6 to 20.
- alkyl group having 1 to 20 carbon atoms examples include linear alkyl groups such as methyl group, ethyl group, n-propyl group, and n-butyl group; i-propyl group, i-butyl group, sec- Examples thereof include branched alkyl groups such as a butyl group and a t-butyl group.
- Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, ethyl Monocyclic saturated hydrocarbon group such as cyclohexyl group; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclo Monocyclic unsaturated hydrocarbon group such as decadienyl group; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] oc
- Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group.
- Q 1 in Ar 1 and Ar 2 each independently has a benzene ring or a naphthalene ring.
- Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include, for example, an alkanediyl group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Examples thereof include a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent group obtained by combining two or more of these groups.
- alkanediyl group having 1 to 20 carbon atoms examples include methanediyl group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, and hexanediyl group.
- Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as cyclopropanediyl group, cyclobutanediyl group, and cyclopentanediyl group; cyclobutenediyl group, cyclopentene Monocyclic unsaturated hydrocarbon group such as diyl group, cyclohexenediyl group; bicyclo [2.2.1] heptanediyl group, bicyclo [2.2.2] octanediyl group, tricyclo [5.2.1.0 2 , 6 ] decanediyl group and other polycyclic saturated hydrocarbon groups; bicyclo [2.2.1] heptenediyl group, bicyclo [2.2.2] octenediyl group, tricyclo [5.2.1.0 2,6 ] And polycyclic unsaturated hydrocarbon groups such as decenediyl groups.
- monocyclic saturated hydrocarbon groups such as cyclo
- Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, a naphthylene group, and an anthranylene group.
- divalent group in which two or more of these groups are combined include, for example, the above alkanediyl group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 to 6 carbon atoms.
- Examples of the substituent that may be substituted with the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include, for example, the above divalent aromatic hydrocarbon group and divalent heteroaromatic group.
- the group illustrated as a substituent which may be substituted can be applied.
- M in the above formula (1) is 0, or m in the above formula (1) is 1 and R 1 in the above formula (1) is preferably represented by a single bond or the above formula (3).
- structural unit (I ′) the structural unit (I ′) having this structure is also referred to as “structural unit (I ′”).
- Q 2 is an (a + 2) -valent aromatic hydrocarbon group or an (a + 2) -valent heteroaromatic group.
- Q 3 is a (b + 2) -valent aromatic hydrocarbon group or a (b + 2) -valent heteroaromatic group.
- R 3 and R 4 are each independently a halogen atom, a hydroxy group or a cyano group.
- a is an integer of 0 to 4.
- b is an integer of 0 to 4. If R 3 and R 4 are a plurality of each of the plurality of R 3 and R 4 may each be the same or different.
- Examples of the (a + 2) -valent aromatic hydrocarbon group represented by Q 2 include a group obtained by removing a hydrogen atom from a divalent aromatic hydrocarbon group.
- the divalent aromatic hydrocarbon group for example, the divalent aromatic hydrocarbon groups exemplified for Ar 1 , Ar 2 , Ar 3 and Ar 4 can be applied.
- Examples of the (a + 2) -valent heteroaromatic group represented by Q 2 include a group obtained by removing a hydrogen atom from a divalent heteroaromatic group.
- the divalent heteroaromatic group for example, the divalent heteroaromatic groups exemplified for Ar 1 , Ar 2 , Ar 3 and Ar 4 can be applied.
- Examples of the (b + 2) -valent aromatic hydrocarbon group represented by Q 3 include groups obtained by removing b hydrogen atoms from a divalent aromatic hydrocarbon group.
- the divalent aromatic hydrocarbon group for example, the divalent aromatic hydrocarbon groups exemplified for Ar 1 , Ar 2 , Ar 3 and Ar 4 can be applied.
- Examples of the (b + 2) -valent heteroaromatic group represented by Q 3 include a group obtained by removing b hydrogen atoms from a divalent heteroaromatic group.
- the divalent heteroaromatic group for example, the divalent heteroaromatic groups exemplified for Ar 1 , Ar 2 , Ar 3 and Ar 4 can be applied.
- halogen atom represented by R 3 and R 4 for example, those exemplified as the halogen atom represented by R 2 can be applied.
- Examples of the structural unit (I) include structural units represented by the following formulas (1-1) to (1-15).
- the structural units (I ′) are preferably the formulas (1-1) to (1-14).
- the content ratio of the structural unit (I) to the total structural unit in the polymer is preferably 60 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% or less. Furthermore, it is particularly preferable that the content ratio of the structural unit (I ′) with respect to all the structural units in the [A] polymer is 80 mol% or more and 100 mol% or less.
- the polymer may contain other structural units as long as the effects of the present invention are not impaired.
- the component (A) containing a compound represented by the following formula (4) is reacted with an alkali metal or an alkali metal compound in an organic solvent to react with the alkali of the component (A).
- the obtained alkali metal salt is reacted with a component (B) containing a compound represented by the following formula (5).
- the alkali metal salt of a component (A) and a component (B) can also be made to react by performing reaction with a component (A) and an alkali metal or an alkali metal compound in presence of a component (B).
- the polymer obtained by the reaction can be recovered by a reprecipitation method.
- the reprecipitation solvent an alcohol solvent or the like can be used.
- Ar 1, Ar 2, R 1 and m are as defined in the above formula (1).
- Ar ⁇ 3 >, Ar ⁇ 4 >, Y and n are synonymous with the said Formula (1).
- X is each independently a halogen atom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.
- alkali metal used in the reaction examples include lithium, potassium, sodium and the like.
- alkali metal compound used in the reaction examples include alkali metal hydrides such as lithium hydride, potassium hydride and sodium hydride; alkali metal hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide; lithium carbonate Alkali metal carbonates such as potassium carbonate and sodium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.
- the amount of the metal atom in the alkali metal or the alkali metal compound is usually 1 to 3 times equivalent to all —OH in the component (A). It is used in an amount of 1 to 2 equivalents, more preferably 1.2 to 1.5 equivalents.
- Examples of the organic solvent used in the reaction include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -butyrolactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl
- Examples include sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (alkoxy group having 1 to 4 carbon atoms), trialkoxybenzene (alkoxy group having 1 to 4 carbon atoms), and the like.
- polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are preferable.
- the said organic solvent can be used individually or in combination of 2 or more types.
- a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, phenetole and the like can be further used. These can be used alone or in combination of two or more.
- component (A) includes at least one compound represented by the following formula from the viewpoint of improving solubility in a solvent as a part of the compound represented by formula (4). May be.
- the proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) and component (B) are 100 mol% in total. 48 mol% or more and 50 mol% or less is more preferable, and 48 mol% or more and less than 50 mol% is particularly preferable.
- Component (B) is preferably 45 mol% or more and 55 mol% or less, more preferably 50 mol% or more and 52 mol% or less, and particularly preferably more than 50 mol% and 52 mol% or less.
- the reaction temperature is preferably 60 ° C to 250 ° C, more preferably 80 ° C to 200 ° C.
- the reaction time is preferably 15 minutes to 100 hours, more preferably 1 hour to 24 hours.
- the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 20,000, more preferably 1,500 to 15,000, and more preferably 2,000 to 12,000 is particularly preferred.
- the solvent is a suitable component that the resist underlayer film forming composition may contain.
- the solvent is not particularly limited as long as it can dissolve or disperse the [A] polymer and optional components contained as necessary.
- coatability can be improved.
- solvents examples include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and the like.
- a [B] solvent can be used individually or in combination of 2 or more types.
- Examples of the alcohol solvent include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, t-butanol, n-pentanol, iso-pentanol and sec-pen.
- Monoalcohol solvents such as tanol and t-pentanol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,
- polyhydric alcohol solvents such as 5-hexanediol and 2,4-heptanediol.
- ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl- aliphatic ketone solvents such as n-hexyl ketone, di-iso-butyl ketone and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone; 2,4-pentane Examples include dione, acetonyl acetone, diacetone alcohol, acetophenone, methyl n-amyl ketone, and the like.
- amide solvent examples include 1,3-dimethyl-2-imidazolidinone, N-methylformamide, dimethylformamide, diethylformamide, acetamide, N-methylacetamide, dimethylacetamide, N-methylpropionamide, N- And methyl-2-pyrrolidone.
- ether solvent examples include alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether Alkyl ether acetates of polyhydric alcohols such as acetate; aliphatic ethers such as diethyl ether, dipropyl ether, dibutyl ether, butyl methyl ether, butyl ethyl ether and diisoamyl ether; aliphatics such as anisole and phenyl ethyl ether Aromatic ethers; cyclic ethers such as tetrahydrofuran, tetrahydropyran, dioxane, etc.
- alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol
- ester solvent examples include diethyl carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, n-propyl acetate, iso-propyl acetate, and n-butyl acetate.
- cyclohexanone propylene glycol methyl ether acetate, cyclopentanone, ⁇ -butyrolactone, ethyl lactate, methyl n-amyl ketone, and a mixed solvent thereof are preferable.
- the composition for forming a resist underlayer film is an optional component other than the [A] polymer that is an essential component and the [B] solvent that is a suitable component within a range not impairing the effects of the present invention (for example, [C] Acid generator, [D] cross-linking agent, [E] surfactant, [F] adhesion aid and the like). Further, the content of other optional components can be appropriately determined according to the purpose.
- the acid generator is a component that generates an acid by the action of heat or light and promotes crosslinking of the polymer [A].
- the composition for forming a resist underlayer film contains a [C] acid generator, the crosslinking reaction of the [A] polymer is promoted, and the hardness of the resist underlayer film can be further increased.
- a [C] acid generator can be used individually or in combination of 2 or more types.
- Examples of the acid generator include onium salt compounds and sulfonimide compounds. Of these, onium salt compounds are preferred.
- onium salt compounds examples include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and the like.
- sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept.
- triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate
- triphenylphosphonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) -hexane-1 -Sulfonate triphenylphosphonium 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) -hexane-1 -Sulfonate
- 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate is preferred.
- tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium.
- Nonafluoro-n-butanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoro Lomethanesulfonate, 1- (6-n-butoxynaphthalene) 2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxy)
- iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl.
- sulfonimide compound examples include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5 Examples include ene-2,3-dicarboximide.
- the content when the acid generator is contained is 100 parts by weight of the [A] polymer (however, when the polymer further contains a polymer other than the [A] polymer, the total weight 1 mass part or more and 20 mass parts or less are preferable, and 3 mass parts or more and 10 mass parts or less are more preferable. [C] By making content of an acid generator into the said specific range, a crosslinking reaction can be promoted effectively.
- the crosslinking agent is a component that forms a bond with a compounded composition such as a resin or other crosslinking agent molecules by the action of heat or acid.
- a [D] crosslinking agent can be used individually or in combination of 2 or more types.
- Examples of the [D] crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, alkoxyalkyl group-containing phenol compounds, compounds having an alkoxyalkylated amino group, acenaphthylene and hydroxy And random copolymers with methyl acenaphthylene, compounds represented by the following formulas (6-1) to (6-12), and the like.
- polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol.
- epoxy compound examples include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.
- hydroxymethyl group-substituted phenol compound examples include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6 -Bis (hydroxymethyl) -p-cresol] and the like.
- alkoxyalkyl group-containing phenol compound examples include methoxymethyl group-containing phenol compounds and ethoxymethyl group-containing phenol compounds.
- Examples of the compound having an alkoxyalkylated amino group include, for example, (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea in one molecule.
- the compound having an alkoxyalkylated amino group may be a mixture in which a plurality of substituted compounds are mixed, or may include an oligomer component that is partially self-condensed.
- Me represents a methyl group
- Et represents an ethyl group
- Ac represents an acetyl group
- the compounds represented by the above formulas (6-1) to (6-12) can be synthesized by referring to the following documents, respectively.
- Compound represented by formula (6-1) Guo, Qun-Shen; Lu, Yong-Na; Liu, Bing; Xiao, Jian; Li, Jin-Shan Journal of Organometallic Chemistry, 2006, vol. 691, # 6 p. 1282-1287
- crosslinking agents methoxymethyl group-containing phenol compounds, compounds having an alkoxyalkylated amino group, and random copolymers of acenaphthylene and hydroxymethylacenaphthylene are preferred.
- the content in the case of containing a crosslinking agent is as follows: 100 parts by mass of [A] polymer (provided that when other polymer other than [A] polymer is further contained, the total polymer 0.5 parts by weight or more and 50 parts by weight or less, preferably 1 part by weight or more and 40 parts by weight or less, and more preferably 2 parts by weight or more and 35 parts by weight or less. [D] By making content of a crosslinking agent into the said specific range, a crosslinking reaction can be caused effectively.
- [E] surfactant is a component which improves applicability
- [E] surfactant can be used individually or in combination of 2 or more types.
- Surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, polyethylene Nonionic surfactants such as glycol dilaurate and polyethylene glycol distearate, and commercially available products such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
- the content when the surfactant is contained is 100 parts by weight of the [A] polymer (provided that when the polymer further contains a polymer other than the [A] polymer, the total weight 0.001 to 5 parts by mass is preferable, and 0.005 to 1 part by mass is more preferable. [E] By making content of surfactant into the said specific range, applicability
- paintability can be improved effectively.
- Adhesion aid is a component that improves adhesion to the substrate.
- the resist underlayer film forming composition contains [F] adhesion assistant, so that a substrate as a base (if there is another film between the resist underlayer film and the substrate, another film in contact with the resist underlayer film) ) Can be improved.
- adhesion assistant for example, a known adhesion assistant can be used.
- the content of the adhesion assistant is 100 parts by mass of the polymer (A) (provided that the polymer further contains another polymer other than the polymer [A], 100 parts by mass of the whole polymer). ), Preferably 0.01 parts by weight or more and 10 parts by weight or less, more preferably 0.01 parts by weight or more and 5 parts by weight or less.
- the resist underlayer film forming composition includes an essential component [A] polymer, suitable components [B] solvent, [C] acid generator and [D] cross-linking agent, and [E] as necessary. It can be prepared by mixing other optional components such as a surfactant and [F] adhesion aid in a predetermined ratio.
- the resist underlayer film forming method of the present invention comprises: (1) The process which forms a coating film on a to-be-processed substrate using the said composition for resist underlayer film formation, (2) It has the process of heating the said coating film and forming a resist underlayer film.
- the substrate to be processed examples include a silicon wafer and a wafer coated with aluminum.
- coating method of the said composition for resist underlayer film formation to a to-be-processed substrate is not specifically limited, For example, it can implement by appropriate methods, such as spin coating, cast coating, and roll coating.
- the heating of the coating film is usually performed in the atmosphere.
- the heating temperature is usually 150 ° C. to 500 ° C., preferably 200 ° C. to 450 ° C. When the heating temperature is less than 150 ° C., the oxidative crosslinking does not proceed sufficiently, and there is a possibility that the characteristics necessary for the resist underlayer film are not exhibited.
- the heating time is usually 30 seconds to 1,200 seconds, preferably 60 seconds to 600 seconds.
- the oxygen concentration during heating is preferably 5% by volume or more.
- the oxygen concentration at the time of heating is low, the oxidative crosslinking of the resist underlayer film does not proceed sufficiently, and there is a possibility that the characteristics necessary for the resist underlayer film cannot be expressed.
- the coating film Before heating the coating film at a temperature of 150 ° C. to 500 ° C., it may be preheated at a temperature of 60 ° C. to 250 ° C.
- the heating time in the preheating is not particularly limited, but is preferably 10 seconds to 300 seconds, and more preferably 30 seconds to 180 seconds.
- the coating film is heated to form a resist underlayer film, but when the resist underlayer film forming composition contains a photoacid generator,
- the resist underlayer film can also be formed by curing the coating film by combining exposure and heating.
- the radiation used for this exposure is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, ⁇ -rays, molecular beams, ion beams, etc., depending on the type of photoacid generator.
- the resist underlayer film of the present invention is formed from the resist underlayer film forming composition by, for example, the resist underlayer film forming method described above. Since the resist underlayer film is formed from the resist underlayer film forming composition, the resist underlayer film sufficiently satisfies general characteristics such as etching resistance required for the resist underlayer film, and additionally has high heat resistance, solvent resistance, and bending resistance. Have Therefore, the resist underlayer film can be suitably applied to a pattern formation process using a multilayer resist process in a semiconductor device in which the pattern is further miniaturized.
- the pattern forming method of the present invention comprises: (1) A step of forming a resist underlayer film on a substrate to be processed using the resist underlayer film forming composition (hereinafter, also referred to as “step (1)”), (2) a step of forming a resist film on the upper surface side of the resist underlayer film using the resist composition (hereinafter also referred to as “step (2)”), (3) a step of exposing the resist film by selective irradiation (hereinafter also referred to as “step (3)”), (4) a step of developing the exposed resist film to form a resist pattern (hereinafter also referred to as “step (4)”), and (5) using the resist pattern as a mask, A process of sequentially dry-etching the substrate to be processed (hereinafter also referred to as “process (5)”).
- the pattern forming method is also referred to as (1 ′) a step of forming an intermediate layer on the resist underlayer film (hereinafter referred to as “step (1 ′)”) between the step (1) and the step (2).
- the intermediate layer may be further dry etched.
- Step (1) a resist underlayer film is formed on the substrate to be processed using the resist underlayer film forming composition.
- the above-mentioned formation method of a resist underlayer film can be applied as it is.
- the thickness of the resist underlayer film formed in this step (1) is usually 0.05 ⁇ m to 5 ⁇ m.
- the pattern forming method may further include a step (1 ′) of forming an intermediate layer (intermediate layer coating) on the resist underlayer film, if necessary, after the step (1).
- This intermediate layer is a layer to which these functions are added in order to further supplement the functions of the resist underlayer film and / or resist film in the formation of the resist pattern, or to give them the functions that they do not have. That is.
- the antireflection film is formed as an intermediate layer, the antireflection function of the resist underlayer film can be further supplemented.
- This intermediate layer can be formed of an organic compound or an inorganic oxide.
- the organic compound include commercially available products such as “DUV-42”, “DUV-44”, “ARC-28”, “ARC-29” (above, manufactured by Brewer Science); “AR-3”, “ AR-19 “(above, manufactured by Rohm and Haas).
- As said inorganic oxide "NFC SOG01”, “NFC SOG04”, “NFC SOG080” (above, JSR make) etc. are mentioned as a commercial item, for example.
- polysiloxane, titanium oxide, alumina oxide, tungsten oxide, or the like formed by a CVD method can be used.
- the method for forming the intermediate layer is not particularly limited, and for example, a coating method, a CVD method, or the like can be used. Among these, a coating method is preferable.
- the intermediate layer can be formed continuously after forming the resist underlayer film.
- the film thickness of the intermediate layer is not particularly limited, and is appropriately selected according to the function required for the intermediate layer, but is preferably 10 nm to 3,000 nm, and more preferably 20 nm to 300 nm.
- Step (2) a resist film is formed on the upper surface side of the resist underlayer film using a resist composition. Specifically, after applying the resist composition so that the obtained resist film has a predetermined thickness, the resist film is formed by volatilizing the solvent in the coating film by pre-baking.
- the resist composition examples include a positive or negative chemically amplified resist composition containing a photoacid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin.
- examples thereof include a negative resist composition composed of a crosslinking agent.
- the total solid concentration of the resist composition is usually 1% by mass to 50% by mass.
- the resist composition is generally filtered through a filter having a pore diameter of about 0.2 ⁇ m and provided for forming a resist film. In this step, a commercially available resist composition can be used as it is.
- the coating method of the resist composition is not particularly limited, and examples thereof include a spin coating method.
- the pre-baking temperature is appropriately adjusted according to the type of resist composition used and the like, but is usually 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.
- Step (3) the resist film is exposed by selective irradiation.
- the radiation used for the exposure is appropriate from visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, ⁇ rays, molecular beams, ion beams, etc., depending on the type of photoacid generator used in the resist composition. Selected.
- the resist pattern may be formed without a development step such as a nanoimprint method.
- post-baking can be performed to improve resolution, pattern profile, developability, and the like.
- the post-baking temperature is appropriately adjusted according to the type of resist composition used, but is usually 50 ° C. to 200 ° C., preferably 70 ° C. to 150 ° C.
- Step (4) the exposed resist film is developed to form a resist pattern.
- the developer used in this step is appropriately selected according to the type of resist composition used. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanol.
- An appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, a surfactant, and the like can be added to these alkaline aqueous solutions.
- the resist pattern is formed by washing and drying.
- Step (5) when the resist pattern is used as a mask and the step (1 ′) is included, the intermediate layer, the resist underlayer film, and the substrate to be processed are sequentially dry-etched in this order, and the step (1 ′)
- dry etching is sequentially performed in the order of the resist underlayer film and the substrate to be processed, and a predetermined pattern is formed on the substrate to be processed through a multilayer resist process.
- gas plasma such as oxygen plasma is used.
- examples of the pattern forming method using the resist underlayer film forming composition include a pattern forming method using a nanoimprint method or the like in addition to the pattern forming method described above.
- the polystyrene conversion weight average molecular weight (Mw) of [A] polymer used the Tosoh GPC column (G2000HXL: 2 pieces, G3000HXL: 1 piece), flow volume: 1.0 mL / min, elution solvent: tetrahydrofuran, Column temperature: It was measured by a gel permeation chromatograph (detector: differential refractometer) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C. Each film thickness was measured using a spectroscopic ellipsometer (M2000D, manufactured by JA WOOLLAM).
- Synthesis Example 1 Synthesis of (A-1) In a separable flask equipped with a thermometer, in a nitrogen atmosphere, 30 parts by mass of M-1 and 100 parts by mass of M-5, potassium carbonate as an alkali metal compound 260 parts by mass and 500 parts by mass of dimethylacetamide as a solvent were blended, and a reaction solution was obtained by performing a condensation polymerization reaction at 140 ° C. for 4 hours while stirring. The reaction solution was filtered, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain a polymer (A-1) having a structural unit represented by the following formula. The Mw of (A-1) was 4,000.
- Synthesis Example 2 Synthesis of (A-2) In a separable flask equipped with a thermometer, 130 parts by mass of M-2 and 100 parts by mass of M-5 and potassium carbonate as an alkali metal compound in a nitrogen atmosphere 260 parts by mass and 500 parts by mass of dimethylacetamide as a solvent were blended, and a reaction solution was obtained by performing a condensation polymerization reaction at 140 ° C. for 4 hours while stirring. The reaction solution was filtered, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain a polymer (A-2) having a structural unit represented by the following formula. The Mw of (A-2) was 5,000.
- Synthesis Example 6 Synthesis of (A-6) In a separable flask equipped with a thermometer, 65 parts by mass of M-1, 65 parts by mass of M-2, and 100 parts by mass of M-5 were added in a nitrogen atmosphere. Part by mass, 140 parts by mass of potassium carbonate as an alkali metal compound and 500 parts by mass of dimethylacetamide as a solvent were blended and subjected to a condensation polymerization reaction at 130 ° C. for 4 hours while stirring to obtain a reaction solution. After filtering this reaction liquid, a methanol random copolymer (A-6) was obtained. The Mw of (A-6) was 3,800.
- composition for forming resist underlayer film [A] Each component other than the polymer is shown below.
- Example 1 [A] 10 parts by mass of (A-1) as a polymer and 100 parts by mass of (B-1) as a [B] solvent were mixed to obtain a solution. And the composition for resist lower layer film formation was prepared by filtering this solution with a membrane filter with a hole diameter of 0.1 micrometer.
- Examples 2 to 11 and Comparative Example 1 Each composition for forming a resist underlayer film was prepared in the same manner as in Example 1 except that the types and amounts (parts by mass) of the components to be mixed were as described in Table 1. In Table 1, the column labeled “-” indicates that the component is not blended.
- Each of the prepared resist underlayer film forming compositions was spin-coated on the surface of a silicon wafer having a diameter of 8 inches to be a substrate to be processed, and then heated at 350 ° C. for 2 minutes to form a resist underlayer film having a thickness of 250 nm. . Then, using a spectroscopic ellipsometer (M2000D, manufactured by JA WOOLLAM), the refractive index and extinction coefficient of the formed resist underlayer film at a wavelength of 193 nm were measured. At this time, the case where the refractive index was 1.3 or more and 1.6 or less and the extinction coefficient was 0.2 or more and 0.8 or less was judged good, and the case outside the above range was regarded as bad.
- a resist underlayer film was formed in the same manner as in the above evaluation of [refractive index and absorption coefficient].
- the substrate on which the resist underlayer film was formed was immersed in cyclohexanone at room temperature for 10 seconds.
- the film thickness before and after the immersion was measured using the above spectroscopic ellipsometer, and the rate of change in film thickness was calculated from the measured value as an index of solvent resistance.
- the solvent resistance is “A” (good), when it is 1% or more and less than 5%, “B” (slightly good), and when it is 5% or more, “C”. (Poor).
- a resist underlayer film was formed in the same manner as in the above evaluation of [refractive index and extinction coefficient].
- an interlayer composition solution for a three-layer resist process (NFC SOG508, manufactured by JSR) is spin-coated on this resist underlayer film, and then heated at 200 ° C. for 60 seconds, and subsequently heated at 300 ° C. for 60 seconds to obtain a film thickness.
- a 0.04 ⁇ m interlayer coating was formed.
- a commercially available resist composition was spin-coated on this intermediate layer coating and pre-baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 0.1 ⁇ m.
- the resist film was developed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Thereafter, it was washed with water and dried to form a positive resist pattern.
- the intermediate layer film is dry-etched with carbon tetrafluoride gas using a reactive ion etching type etching apparatus (Telius SCCM, manufactured by Tokyo Electron). The etching process was stopped when the intermediate layer film located under the resist film opening disappeared, and the resist pattern was transferred to the intermediate layer film.
- etching apparatus dry etching treatment is performed with a mixed gas of oxygen and nitrogen, and a resist underlayer film located under the intermediate layer film opening is formed. When it disappeared, the etching process was stopped and the pattern of the intermediate layer film was transferred to the resist underlayer film.
- dry etching is performed with a mixed gas of carbon tetrafluoride and argon using the above-described etching apparatus, and below the resist underlayer film opening. The etching process was stopped when the positioned silicon oxide film was removed by 0.1 ⁇ m.
- the shape of a so-called line and space pattern in which linear patterns are arranged at equal intervals was observed with an SEM (scanning electron microscope).
- the repetition interval is fixed at 84 nm and 100 linear patterns are arranged at equal intervals, and this is regarded as one set.
- the pattern width referred to here is the width of one linear pattern arranged at equal intervals formed by the resist underlayer film.
- the pattern of each pattern width was observed with the SEM at five arbitrary locations, and the observation result was regarded as bending resistance. At this time, if all the patterns of the resist underlayer film were vertical, the bending resistance was evaluated as “A”, and if it was bent even at one place, it was evaluated as defective “B”. *
- the resist underlayer films formed from the resist underlayer film forming compositions of Examples 1 to 11 have good refractive index and extinction coefficient, excellent etching resistance, and comparative examples. Compared with the resist underlayer film formed from the resist underlayer film forming composition of No. 1, it has high heat resistance. In the examples, the solvent resistance and the bending resistance were also good.
- the present invention provides a composition for forming a resist underlayer film that is used in a multilayer resist process that can form a resist underlayer film that sufficiently satisfies general characteristics such as etching resistance and that has high heat resistance, solvent resistance, and bending resistance.
- a resist underlayer film using the composition, a method for forming the resist underlayer film, and a pattern forming method using the composition can be provided. Therefore, the resist underlayer film forming composition, resist underlayer film and method for forming the same, and pattern forming method used in the multilayer resist process of the present invention use the multilayer resist process in a semiconductor device in which further miniaturization of the pattern proceeds. It can be suitably used for the conventional pattern forming process.
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Abstract
Description
[A]下記式(1)で表される構造単位(I)を有する重合体(以下、「[A]重合体」ともいう)を含有する多層レジストプロセスに用いられるレジスト下層膜形成用組成物(以下、単に「レジスト下層膜形成用組成物」又は「組成物」ともいう)である。
(1)当該レジスト下層膜形成用組成物を用いて被加工基板上に塗膜を形成する工程、及び
(2)上記塗膜を加熱してレジスト下層膜を形成する工程
を有する。
(1)当該レジスト下層膜形成用組成物を用いて被加工基板上にレジスト下層膜を形成する工程、
(2)レジスト組成物を用いて上記レジスト下層膜の上面側にレジスト膜を形成する工程、
(3)選択的な放射線照射により上記レジスト膜を露光する工程、
(4)上記露光されたレジスト膜を現像してレジストパターンを形成する工程、及び
(5)上記レジストパターンをマスクとして用い、上記レジスト下層膜及び上記被加工基板を順次ドライエッチングする工程
を有する。
本発明の多層レジストプロセスに用いられるレジスト下層膜形成用組成物は、[A]重合体を含有する。また、当該レジスト下層膜形成用組成物は、好適成分として、[B]溶媒を含有してもよい。さらに、当該レジスト下層膜形成用組成物は、本発明の効果を損なわない限り、[C]酸発生剤、[D]架橋剤、[E]界面活性剤及び[F]密着助剤等のその他の任意成分を含有してもよい。なお、当該レジスト下層膜形成用組成物は、[A]重合体を2種以上含有してもよい。以下、各成分について詳述する。
[A]重合体は、構造単位(I)を有する重合体である。また、[A]重合体は、本発明の効果を損なわない限り、その他の構造単位を含んでいてもよい。なお、[A]重合体は、各構造単位を2種以上有していてもよく、この場合の[A]重合体は、ランダム共重合体及びブロック共重合体のいずれであってもよい。以下、各構造単位について詳述する。
構造単位(I)は、上記式(1)で表される構造単位である。[A]重合体が上記特定の構造単位を有することで、当該レジスト下層膜形成用組成物から形成されるレジスト下層膜は、エッチング耐性等の一般特性を十分満たし、加えて高い耐熱性、耐溶剤性及び曲がり耐性を有する。なお、この高い耐熱性等は、[A]重合体の主鎖中において、エーテル基の2つの結合手が、芳香族炭化水素基又はヘテロ芳香族基に直接結合することにより安定化していることに起因するものと推察される。
[A]重合体は、本発明の効果を損なわない限り、その他の構造単位を含んでいてもよい。
[A]重合体の合成方法としては、例えば、下記式(4)で表される化合物を含む成分(A)を有機溶媒中でアルカリ金属又はアルカリ金属化合物と反応させて成分(A)のアルカリ金属塩を得た後、得られたアルカリ金属塩と下記式(5)で表される化合物を含む成分(B)とを反応させる。なお、成分(A)とアルカリ金属又はアルカリ金属化合物との反応を成分(B)の存在下で行うことにより、成分(A)のアルカリ金属塩と成分(B)とを反応させることもできる。反応により得られた重合体は、再沈殿法により回収することができる。再沈溶媒としては、アルコール系溶媒等を使用できる。
[B]溶媒は、当該レジスト下層膜形成用組成物が含有してもよい好適成分である。[B]溶媒としては、[A]重合体及び必要に応じて含有する任意成分を溶解又は分散することができれば特に限定されない。当該レジスト下層膜形成用組成物が[B]溶媒をさらに含有することで、塗布性を向上させることができる。
当該レジスト下層膜形成用組成物は、本発明の効果を損なわない範囲で、必須成分である[A]重合体、好適成分である[B]溶媒以外のその他の任意成分(例えば、[C]酸発生剤、[D]架橋剤、[E]界面活性剤、[F]密着助剤等)を含有してもよい。また、その他の任意成分の含有量は、その目的に応じて適宜決定することができる。
[C]酸発生剤は、熱や光の作用により酸を発生し、[A]重合体の架橋を促進する成分である。当該レジスト下層膜形成用組成物が[C]酸発生剤を含有することで[A]重合体の架橋反応が促進され、レジスト下層膜の硬度をより高めることができる。なお、[C]酸発生剤は、単独で又は2種以上を組み合わせて用いることができる。
[D]架橋剤は、熱や酸の作用により、樹脂等の配合組成物や他の架橋剤分子との結合を形成する成分である。当該レジスト下層膜形成用組成物が[D]架橋剤を含有することで、レジスト下層膜の硬度を高めることができる。なお、[D]架橋剤は、単独で又は2種以上を組み合わせて用いることができる。
式(6-1)で表される化合物:
Guo,Qun-Sheng;Lu,Yong-Na;Liu,Bing;Xiao,Jian;Li,Jin-Shan Journal of Organometallic Chemistry,2006,vol.691,#6 p.1282-1287
式(6-2)で表される化合物:
Badar,Y.et al. Journal of the Chemical Society,1965,p.1412-1418
式(6-3)で表される化合物:
Hsieh,Jen-Chieh;Cheng,Chien-Hong Chemical Communications(Cambridge,United Kingdom),2008,#26 p.2992-2994
式(6-4)で表される化合物:
特開平5-238990号公報
式(6-5)で表される化合物:
Bacon,R.G.R.;Bankhead,R. Journal of the Chemical Society,1963,p.839-845
式(6-6)、(6-8)、(6-11)及び(6-12)で表される化合物:
Macromolecules 2010,vol43,p2832-2839
式(6-7)、(6-9)及び(6-10)で表される化合物:
Polymer Journal 2008,vol.40,No.7,p645-650、及びJournal of Polymer Science:Part A,Polymer Chemistry,Vol 46,p4949-4968
[E]界面活性剤は、塗布性を向上させる成分である。当該レジスト下層膜形成用組成物が[E]界面活性剤を含有することで、塗布されるレジスト下層膜の塗布面均一性を向上し、かつ塗布斑の発生を防止することができる。なお、[E]界面活性剤は、単独で又は2種以上を組み合わせて用いることができる。
[F]密着助剤は、下地との密着性を向上させる成分である。当該レジスト下層膜形成用組成物が[F]密着助剤を含有することで、下地としての基板(レジスト下層膜と基板との間に他の膜がある場合はレジスト下層膜が接する他の膜)との密着性を向上させることができる。なお、[F]密着助剤は単独で又は2種以上を組み合わせて用いてもよい。
当該レジスト下層膜形成用組成物は、必須成分である[A]重合体、好適成分である[B]溶媒、[C]酸発生剤及び[D]架橋剤、必要に応じて、[E]界面活性剤、[F]密着助剤等のその他の任意成分を所定の割合で混合することにより調製できる。
本発明のレジスト下層膜形成方法は、
(1)当該レジスト下層膜形成用組成物を用いて被加工基板上に塗膜を形成する工程、及び
(2)上記塗膜を加熱してレジスト下層膜を形成する工程を有する。
本発明のレジスト下層膜は、当該レジスト下層膜形成用組成物から、例えば、上述のレジスト下層膜形成方法により形成される。当該レジスト下層膜は、当該レジスト下層膜形成用組成物から形成されているため、レジスト下層膜に要求されるエッチング耐性等の一般特性を十分満たし、加えて高い耐熱性、耐溶剤性及び曲がり耐性を有する。従って、当該レジスト下層膜は、パターンの更なる微細化が進む半導体デバイスでの多層レジストプロセスを用いたパターン形成プロセスに好適に適用することができる。
本発明のパターン形成方法は、
(1)当該レジスト下層膜形成用組成物を用いて被加工基板上にレジスト下層膜を形成する工程(以下、「工程(1)」ともいう)、
(2)レジスト組成物を用いて上記レジスト下層膜の上面側にレジスト膜を形成する工程(以下、「工程(2)」ともいう)、
(3)選択的な放射線照射により上記レジスト膜を露光する工程(以下、「工程(3)」ともいう)、
(4)上記露光されたレジスト膜を現像してレジストパターンを形成する工程(以下、「工程(4)」ともいう)、及び
(5)上記レジストパターンをマスクとして用い、上記レジスト下層膜及び上記被加工基板を順次ドライエッチングする工程(以下、「工程(5)」ともいう)を有する。
本工程では、当該レジスト下層膜形成用組成物を用いて被加工基板上にレジスト下層膜を形成する。なお、このレジスト下層膜の形成方法については、上述のレジスト下層膜の形成方法をそのまま適用することができる。この工程(1)で形成されるレジスト下層膜の膜厚は、通常0.05μm~5μmである。
本工程では、レジスト組成物を用いて上記レジスト下層膜の上面側にレジスト膜を形成する。具体的には、得られるレジスト膜が所定の膜厚となるようにレジスト組成物を塗布した後、プレベークすることによって塗膜中の溶媒を揮発させることにより、レジスト膜が形成される。
本工程では、選択的な放射線照射により上記レジスト膜を露光する。露光に用いられる放射線としては、レジスト組成物に使用される光酸発生剤の種類に応じて、可視光線、紫外線、遠紫外線、X線、電子線、γ線、分子線、イオンビーム等から適切に選択される。これらの中で、遠紫外線が好ましく、KrFエキシマレーザー光(248nm)、ArFエキシマレーザー光(193nm)、F2エキシマレーザー光(波長157nm)、Kr2エキシマレーザー光(波長147nm)、ArKrエキシマレーザー光(波長134nm)、極紫外線(波長13nm等)等がより好ましい。なお、このレジストパターンの形成は、ナノインプリント法等の現像工程を経ないものであってもよい。
本工程では、露光されたレジスト膜を現像してレジストパターンを形成する。本工程で用いられる現像液は、使用されるレジスト組成物の種類に応じて適宜選択される。現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウム、メタ珪酸ナトリウム、アンモニア、エチルアミン、n-プロピルアミン、ジエチルアミン、ジ-n-プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、コリン、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン、1,5-ジアザビシクロ[4.3.0]-5-ノネン等のアルカリ性水溶液が挙げられる。これらのアルカリ性水溶液には、例えば、メタノール、エタノール等のアルコール類などの水溶性有機溶媒、界面活性剤等を適量添加することもできる。
本工程では、レジストパターンをマスクとして用い、上記工程(1’)を有する場合にあっては上記中間層、上記レジスト下層膜、上記被加工基板の順に順次ドライエッチングし、上記工程(1’)を有しない場合にあっては上記レジスト下層膜、上記被加工基板の順に順次ドライエッチングし、多層レジストプロセスを経ることにより上記被加工基板に所定のパターンを形成する。このドライエッチングには、例えば、酸素プラズマ等のガスプラズマ等が用いられる。上記ドライエッチングの後、所定のパターンを有する被加工基板が得られる。
下記式(M-1)~(M-6)で表される化合物を用いて、各重合体を合成した。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、M-1を30質量部及びM-5を100質量部、アルカリ金属化合物としての炭酸カリウムを260質量部並びに溶媒としてのジメチルアセトアミドを500質量部配合し、攪拌しつつ、140℃で4時間縮合重合反応を行い反応液を得た。この反応液をろ過後、メタノールを加えて再沈殿を行い、得られた沈殿物を乾燥させて下記式で表される構造単位を有する重合体(A-1)を得た。(A-1)のMwは、4,000であった。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、M-2を130質量部及びM-5を100質量部、アルカリ金属化合物としての炭酸カリウムを260質量部並びに溶媒としてのジメチルアセトアミドを500質量部配合し、攪拌しつつ、140℃で4時間縮合重合反応を行い反応液を得た。この反応液をろ過後、メタノールを加えて再沈殿を行い、得られた沈殿物を乾燥させて下記式で表される構造単位を有する重合体(A-2)を得た。(A-2)のMwは、5,000であった。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、M-3を130質量部及びM-5を100質量部、アルカリ金属化合物としての炭酸カリウムを260質量部並びに溶媒としてのジメチルアセトアミドを500質量部配合し、攪拌しつつ、140℃で4時間縮合重合反応を行い反応液を得た。この反応液をろ過後、メタノールを加えて再沈殿を行い、得られた沈殿物を乾燥させて下記式で表される構造単位を有する重合体(A-3)を得た。(A-3)のMwは、4,500であった。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、M-4を140質量部及びM-5を100質量部、アルカリ金属化合物としての炭酸カリウムを260質量部並びに溶媒としてのジメチルアセトアミドを500質量部配合し、攪拌しつつ、140℃で4時間縮合重合反応を行い反応液を得た。この反応液をろ過後、メタノールを加えて再沈殿を行い、得られた沈殿物を乾燥させて下記式で表される構造単位を有する重合体(A-4)を得た。(A-4)のMwは、2,500であった。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、M-1を130質量部及びM-6を100質量部、アルカリ金属化合物としての炭酸カリウムを260質量部並びに溶媒としてのジメチルアセトアミドを500質量部配合し、攪拌しつつ、140℃で4時間縮合重合反応を行い反応液を得た。この反応液をろ過後、メタノールを加えて再沈殿を行い、得られた沈殿物を乾燥させて下記式で表される構造単位を有する重合体(A-5)を得た。(A-5)のMwは、3,500であった。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、M-1を65質量部、M-2を65質量部、及びM-5を100質量部、アルカリ金属化合物としての炭酸カリウムを140質量部並びに溶媒としてのジメチルアセトアミドを500質量部配合し、攪拌しつつ、130℃で4時間縮合重合反応を行い反応液を得た。この反応液をろ過後、メタノーるランダム共重合体(A-6)を得た。(A-6)のMwは、3,800であった。
温度計を備えたセパラブルフラスコに、窒素雰囲気下で、2,7-ジヒドロキシナフタレン100質量部、ホルマリン30質量部、p-トルエンスルホン酸1質量部、及び、プロピレングリコールモノメチルエーテル150質量部を仕込み、攪拌しつつ80℃で6時間重合させて反応液を得た。その後、反応液を酢酸n-ブチル100質量部で希釈し、多量の水/メタノール(質量比:1/2)混合溶媒で有機層を洗浄した。その後、溶媒を留去して下記式で表される構造単位を有する重合体(a-1)を得た。得られた重合体(a-1)の重量平均分子量(Mw)は、1,800であった。
[A]重合体以外の各成分について以下に示す。
B-1:シクロヘキサノン
下記式(C-1)~(C-3)で表される化合物
下記式(D-1)で表される化合物(ニカラックN-2702、三和ケミカル製)
下記式(D-2)で表される化合物(Journal of Polymer Science Part A:2008,Vol 46,p4949を参考に合成した。)
下記式(D-3)で表される化合物(MW-100LM、三和ケミカル製)
下記式(D-4)で表される化合物(アセナフチレンとヒドロキシメチルアセナフチレンとのランダム共重合体、Mw=3,000)(特開2004-168748号公報を参考に合成した。)
[A]重合体として(A-1)10質量部及び[B]溶媒として(B-1)100質量部を混合して溶液を得た。そして、この溶液を孔径0.1μmのメンブランフィルターでろ過することによりレジスト下層膜形成用組成物を調製した。
混合する各成分の種類及び配合量(質量部)を表1に記載した通りとした以外は、実施例1と同様に操作して、各レジスト下層膜形成用組成物を調製した。なお、表1中、「-」で表記した欄は、その成分を配合していないことを示している。
屈折率、吸光係数、エッチング耐性、耐熱性、耐溶剤性、及び曲がり耐性を測定し、その結果を表2に示す。
上記調製した各レジスト下層膜形成用組成物を、被加工基板となる直径8インチのシリコンウエハ表面にスピンコートした後、350℃で2分間加熱を行い、膜厚250nmのレジスト下層膜を形成した。そして、分光エリプソメータ(M2000D、J.A.WOOLLAM製)を用い、形成されたレジスト下層膜の波長193nmにおける屈折率及び吸光係数を測定した。このとき、屈折率が1.3以上1.6以下かつ吸光係数が0.2以上0.8以下の場合を良好、上記範囲外の場合を不良とした。
まず、スピンコート法により、直径8インチのシリコンウエハ上に、レジスト下層膜形成用組成物をスピンコートして、膜厚300nmのレジスト下層膜を形成した。その後、このレジスト下層膜を、エッチング処理(圧力:0.03Torr、高周波電力:3000W、Ar/CF4=40/100sccm、基板温度:20℃)し、エッチング処理後のレジスト下層膜の膜厚を測定した。そして、膜厚の減少量と処理時間との関係からエッチングレート(nm/分)を算出し、比較例に対する比率を算出した。この値が小さいほど、エッチング耐性が良好である。
直径8インチのシリコンウエハ上に、各レジスト下層膜形成用組成物をスピンコートして塗膜(レジスト下層膜)を形成し、この塗膜の膜厚を上記分光エリプソメータを用いて測定した(この測定値をXとする)。次に、このレジスト下層膜を350℃で120秒間加熱し、加熱後のレジスト下層膜の膜厚を上記分光エリプソメータを用いて測定した(この測定値をYとする)。そして、加熱前後のレジスト下層膜の膜厚減少率△FT(%)(△FT(%)=100×(X-Y)/X)を算出し、この算出値を耐熱性(%)とした。なお、耐熱性(%)の値が小さいほど、レジスト下層膜の加熱時に発生する昇華物や膜分解物が少なく、良好(高い耐熱性)であることを表している。
上記[屈折率及び吸光係数]の評価と同様の方法でレジスト下層膜を形成した。次いで、レジスト下層膜が形成された基板を、シクロヘキサノン中に室温で10秒間浸漬した。浸漬前後の膜厚を上記分光エリプソメータを用いて測定し、その測定値から膜厚変化率を算出して耐溶剤性の指標とした。膜厚変化率が1%未満の場合、耐溶剤性は「A」(良好)と、1%以上5%未満の場合は「B」(やや良好)と、5%以上の場合は「C」(不良)と評価した。
上記[屈折率及び吸光係数]の評価と同様の方法でレジスト下層膜を形成した。次いで、このレジスト下層膜上に3層レジストプロセス用中間層組成物溶液(NFC SOG508、JSR製)をスピンコートした後、200℃で60秒間加熱し、引き続き300℃で60秒間加熱して膜厚0.04μmの中間層被膜を形成した。次に、この中間層被膜上に市販のレジスト組成物をスピンコートし、100℃で60秒間プレベークして膜厚0.1μmのレジスト膜を形成した。
Claims (8)
- [A]下記式(1)で表される構造単位(I)を有する重合体を含有する多層レジストプロセスに用いられるレジスト下層膜形成用組成物。
- [B]溶媒をさらに含有する請求項1に記載のレジスト下層膜形成用組成物。
- 請求項1に記載のレジスト下層膜形成用組成物から形成されるレジスト下層膜。
- (1)請求項1に記載のレジスト下層膜形成用組成物を用いて被加工基板上に塗膜を形成する工程、及び
(2)上記塗膜を加熱してレジスト下層膜を形成する工程
を有するレジスト下層膜形成方法。 - (1)請求項1に記載のレジスト下層膜形成用組成物を用いて被加工基板上にレジスト下層膜を形成する工程、
(2)レジスト組成物を用いて上記レジスト下層膜の上面側にレジスト膜を形成する工程、
(3)選択的な放射線照射により上記レジスト膜を露光する工程、
(4)上記露光されたレジスト膜を現像してレジストパターンを形成する工程、及び
(5)上記レジストパターンをマスクとして用い、上記レジスト下層膜及び上記被加工基板を順次ドライエッチングする工程
を有するパターン形成方法。 - 上記工程(1)と上記工程(2)との間に、
(1’)上記レジスト下層膜上に中間層を形成する工程
をさらに有し、
上記工程(5)において、さらに上記中間層をドライエッチングする請求項7に記載のパターン形成方法。
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US20150198882A9 (en) | 2015-07-16 |
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