WO2018155377A1 - Matériau de formation de film pour procédé de réserve, procédé de formation de motif, et polysiloxane - Google Patents
Matériau de formation de film pour procédé de réserve, procédé de formation de motif, et polysiloxane Download PDFInfo
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- WO2018155377A1 WO2018155377A1 PCT/JP2018/005727 JP2018005727W WO2018155377A1 WO 2018155377 A1 WO2018155377 A1 WO 2018155377A1 JP 2018005727 W JP2018005727 W JP 2018005727W WO 2018155377 A1 WO2018155377 A1 WO 2018155377A1
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- film
- silicon
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- 238000000034 method Methods 0.000 title claims abstract description 109
- -1 polysiloxane Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 71
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 61
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 109
- 239000010703 silicon Substances 0.000 claims abstract description 108
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 51
- 238000005530 etching Methods 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 125000000962 organic group Chemical group 0.000 claims abstract description 29
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 47
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 17
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- 239000011248 coating agent Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000059 patterning Methods 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
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- 125000004429 atom Chemical group 0.000 description 3
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- 125000003827 glycol group Chemical group 0.000 description 3
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- 239000011261 inert gas Substances 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical group C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005676 cyclic carbonates Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000001127 nanoimprint lithography Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CVCYODHOXFGRCE-UHFFFAOYSA-N propane-1,2-diol;propyl acetate Chemical compound CC(O)CO.CCCOC(C)=O CVCYODHOXFGRCE-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000008053 sultones Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SIPHWXREAZVVNS-UHFFFAOYSA-N trichloro(cyclohexyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCCC1 SIPHWXREAZVVNS-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- LMQGXNPPTQOGDG-UHFFFAOYSA-N trimethoxy(trimethoxysilyl)silane Chemical compound CO[Si](OC)(OC)[Si](OC)(OC)OC LMQGXNPPTQOGDG-UHFFFAOYSA-N 0.000 description 1
- DJYGUVIGOGFJOF-UHFFFAOYSA-N trimethoxy(trimethoxysilylmethyl)silane Chemical compound CO[Si](OC)(OC)C[Si](OC)(OC)OC DJYGUVIGOGFJOF-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- 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
-
- 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
Definitions
- the present invention relates to a film forming material for a resist process, a pattern forming method, and polysiloxane.
- the resist film laminated on the substrate to be processed through an organic antireflection film is exposed and developed, and then the substrate is microfabricated by etching using the obtained resist pattern as a mask.
- a pattern forming method is used.
- a silicon-containing film is provided between the resist film and the organic underlayer film, the pattern formed on the resist film is transferred to the silicon-containing film, and the substrate to be processed is then used with the silicon-containing film patterned by transfer as a mask.
- a multilayer resist process for etching is performed (see International Publication No. 2006-126406).
- the silicon-containing film is required to have excellent solvent resistance and resistance to etching with an oxygen-based gas or the like (hereinafter also referred to as “oxygen-based gas etching resistance”).
- the miniaturization of the resist pattern has progressed to a level of 45 nm or less, the required level of the performance is further increased, and it is used for forming a silicon-containing film in the conventional multilayer resist process.
- the resist process film forming material cannot satisfy all of these requirements.
- the present invention has been made based on the above circumstances, and can form a silicon-containing film that is excellent in oxygen-based gas etching resistance and peelability by alkaline hydrogen peroxide while maintaining solvent resistance. It is to provide a film forming material for resist process, a pattern forming method using the same, and polysiloxane.
- the invention made in order to solve the above problems is a polysiloxane having a first structural unit (hereinafter also referred to as “structural unit (I)”) represented by the following formula (1) or formula (2) (hereinafter referred to as “structural unit (I)”). It is a film forming material for a resist process containing “[A] polysiloxane” and a solvent (hereinafter also referred to as “[B] solvent”).
- L 1 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
- R 1 is an ethynediyl group or a substituted or unsubstituted ethenediyl group.
- L 2 is a single bond.
- L 2 is a single bond, n is 1.
- R 2 is a polar group.
- R X is a monovalent group not containing an ethylenic carbon-carbon double bond and carbon-carbon triple bond.
- I is an integer of 0-2.
- L 3 is an (m + 1) -valent organic group having 1 to 20 carbon atoms.
- m is an integer of 1 to 3.
- R 3 is a monovalent group containing a polar group. When m is 2 or more, the plurality of R 3 are the same or different.
- L 4 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
- R 4 is a substituted or unsubstituted ethynyl group or a substituted or unsubstituted ethenyl group.
- Another invention made in order to solve the above problems is a step of forming a silicon-containing film on the upper side of the substrate by coating the film forming material for resist process, a step of patterning the silicon-containing film, And a step of forming a pattern on a substrate using the patterned silicon-containing film as a mask.
- Still another invention made to solve the above problems is a polysiloxane having a structural unit represented by the above formula (1) or (2).
- the film forming material for resist process and the pattern forming method of the present invention it is possible to form a silicon-containing film excellent in oxygen gas etching resistance and peelability by alkaline hydrogen peroxide while maintaining solvent resistance, Furthermore, it is possible to form a resist pattern that is excellent in shape and collapse suppression.
- the polysiloxane of the present invention can be suitably used as a polysiloxane component of the resist process film-forming material. Therefore, these can be used suitably for a multilayer resist process etc., and can be used suitably for manufacture of a semiconductor device etc. in which further miniaturization is expected in the future.
- the resist process film-forming material (hereinafter also simply referred to as “film-forming material”) contains [A] polysiloxane and [B] solvent.
- the film-forming material may contain an optional component as long as the effects of the present invention are not impaired.
- the film forming material it is possible to form a silicon-containing film excellent in oxygen-based gas etching resistance and peelability by alkaline hydrogen peroxide while maintaining solvent resistance, and further excellent in shape and collapse suppression A resist pattern can be formed.
- the reason why the film-forming material has the above-described configuration and exhibits the above-mentioned effects is not necessarily clear, but can be inferred as follows, for example. That is, the structural unit (I) of [A] polysiloxane has a carbon-carbon double bond or a carbon-carbon triple bond as R 1 or R 4 . Since this carbon-carbon double bond or carbon-carbon triple bond has a high cross-linking property, a high-density cross-linked structure is formed by heating.
- the silicon-containing film formed from the film-forming material is further improved in oxygen-based gas etching resistance and peelability by alkaline hydrogen peroxide.
- the structural unit (I) of [A] polysiloxane has a monovalent group containing a polar group as R 2 or R 3 , a negative resist pattern formed on the silicon-containing film, etc. Therefore, the shape of the negative resist pattern or the like and the collapse suppression property are further improved. Since the film forming material has such an effect, it can be suitably used for a resist process.
- each component will be described.
- the polysiloxane is a polysiloxane having the structural unit (I).
- the structural unit (I) is a structural unit represented by the following formula (1) or the following formula (2).
- L 1 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
- R 1 is an ethynediyl group or a substituted or unsubstituted ethenediyl group.
- L 2 is a single bond or an (n + 1) -valent organic group having 1 to 20 carbon atoms.
- n is an integer of 1 to 3.
- R 2 is a monovalent group containing a polar group.
- R X is a monovalent group not containing an ethylenic carbon-carbon double bond and carbon-carbon triple bond.
- i is an integer of 0-2.
- L 3 is an (m + 1) -valent organic group having 1 to 20 carbon atoms.
- m is an integer of 1 to 3.
- R 3 is a monovalent group containing a polar group. When m is 2 or more, the plurality of R 3 are the same or different.
- L 4 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
- R 4 is a substituted or unsubstituted ethynyl group or a substituted or unsubstituted ethenyl group.
- Examples of the divalent organic group having 1 to 20 carbon atoms represented by L 1 and L 4 include, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms and a divalent hydrocarbon between carbon-carbon of the hydrocarbon group.
- Examples include a group ( ⁇ ) having a heteroatom-containing group, a group obtained by substituting part or all of the hydrogen atoms of the hydrocarbon group and the group ( ⁇ ) with a monovalent heteroatom-containing group.
- Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. And 20 divalent aromatic hydrocarbon groups.
- Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include alkanes such as methane, ethane, propane, and butane, alkenes such as ethene, propene, and butene, and alkynes such as ethyne, propyne, and butyne. And a group excluding individual hydrogen atoms.
- Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include alicyclic saturated carbon such as cycloalkane such as cyclopentane and cyclohexane, bridged saturated hydrocarbon such as norbornane, adamantane and tricyclodecane. Examples thereof include a group in which two hydrogen atoms of a cycloalkene such as hydrogen, cyclopentene and cyclohexene, and an alicyclic unsaturated hydrocarbon such as a bridged ring unsaturated hydrocarbon such as norbornene and tricyclodecene are removed.
- Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include hydrogen on 2 to 4 aromatic rings possessed by arenes such as benzene, toluene, ethylbenzene, xylene, naphthalene, methylnaphthalene, anthracene, and methylanthracene. Examples include a group in which a hydrogen atom on an atom or two aromatic rings and an alkyl group is removed.
- hetero atom constituting the divalent and monovalent hetero atom-containing group examples include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- divalent heteroatom-containing group examples include —O—, —CO—, —S—, —CS—, —NR′—, a group in which two or more of these are combined, and the like.
- R ' is a hydrogen atom or a monovalent hydrocarbon group. Of these, —O— and —S— are preferred.
- Examples of the monovalent heteroatom-containing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, amino group and sulfanyl group. Among these, a halogen atom is preferable, and a fluorine atom is more preferable.
- L 1 is preferably a single bond or a hydrocarbon group, more preferably a single bond or a chain hydrocarbon group, still more preferably a single bond or an alkanediyl group, and particularly preferably a single bond, a methanediyl group or an ethanediyl group.
- L 4 is preferably a single bond or a hydrocarbon group, and more preferably a single bond.
- Examples of the substituent for the ethenediyl group of R 1 and the ethenyl group of R 4 include monovalent organic groups having 1 to 10 carbon atoms.
- the substituent of the ethenediyl group of R 1 and the ethenyl group of R 4 is preferably a hydrocarbon group, more preferably a chain hydrocarbon group, still more preferably an alkyl group, and particularly preferably a methyl group and an ethyl group.
- R 1 is preferably an unsubstituted ethenediyl group.
- R 4 is preferably an unsubstituted ethenyl group.
- Examples of the divalent to tetravalent organic group having 1 to 20 carbon atoms represented by L 2 and L 3 include those exemplified as the divalent organic group having 1 to 20 carbon atoms of L 1 and L 4 , And a group obtained by removing one or two hydrogen atoms from a divalent organic group.
- N and m are preferably 1 and 2, and more preferably 1.
- L 2 is preferably a single bond or a methanediyl group.
- L 2 is preferably a trivalent or tetravalent group obtained by removing 3 or 4 hydrogen atoms from methane.
- L 3 is preferably a divalent to tetravalent group obtained by removing 2 to 4 hydrogen atoms from methane.
- Examples of the monovalent group not containing the carbon-carbon double bond and carbon-carbon triple bond represented by R X are exemplified as the divalent organic groups having 1 to 20 carbon atoms of L 1 and L 4 described above. And monovalent organic groups obtained by adding one hydrogen atom to the group.
- I is preferably 0 or 1, more preferably 0.
- Examples of the monovalent group containing the polar group represented by R 2 and R 3 include a monovalent group containing a hetero atom.
- R 2 and R 3 are preferably groups represented by the following formula (a) or the following formula (b).
- R A is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- R B is either a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R B and R a and are combined with each other ring members together with the atom chain to which they are attached 5-20 The ring structure is formed.
- R a and R b are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a ring composed of these groups combined with each other and the carbon atom to which they are bonded.
- R c and R d are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a ring composed of these groups combined with each other and the carbon atom to which they are bonded.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R A and R B and R a to R d include a divalent carbon group having 1 to 20 carbon atoms exemplified as L 1 and L 4 above. Examples thereof include a monovalent hydrocarbon group obtained by adding one hydrogen atom to a hydrogen group.
- the hydrocarbon group for RA is preferably a chain hydrocarbon group or an alicyclic hydrocarbon group, more preferably an alkyl group or a cycloalkyl group, a methyl group, an i-propyl group, a t-butyl group, or a 1-methyl group.
- a cyclohexane-1-yl group is more preferred, and a methyl group is preferred.
- the hydrocarbon group of R A also preferably tertiary hydrocarbon group, t- butyl group is particularly preferable.
- Examples of the ring structure having 3 to 20 ring members constituted by the carbon atoms to which R a and R b and R c and R d are combined and bonded to each other include, for example, 3 to 3 carbon atoms exemplified as L 1 and L 4 above. Examples thereof include an alicyclic structure contained in 20 divalent alicyclic hydrocarbon groups.
- the ring structure of R B and ring members 5-20 that the R a is formed together with the atom chain to which they are attached are combined to each other, for example 1,3-dioxacyclopentane structure, 1,3-dioxacyclohexane structure 1,3-dioxacycloalkane structures such as Of these, a 1,3-dioxacyclopentane structure is preferable.
- Examples of the group containing a ring structure having 5 to 20 ring members formed together with an atomic chain in which R B and R a are combined with each other include 1,3-dioxacyclopentyl group and 2,2-dimethyl-1 , 3-Dioxacyclopentyl group is preferred.
- mol% is preferred to 1 mol% with respect to all the structural units which constitute [A] polysiloxane, 5 mol% is still more preferred, 10 mol% is particularly preferred, and 20 mol% is even more particularly preferred.
- 80 mol% is preferable, 50 mol% is more preferable, 40 mol% is further more preferable, 30 mol% is especially preferable.
- Examples of the monomer that gives the structural unit (I) include compounds represented by the following formulas.
- R is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- R is preferably a monovalent chain hydrocarbon group, more preferably an alkyl group, and even more preferably a methyl group or an ethyl group.
- the polysiloxane may have a structural unit (II) represented by the following formula (3).
- R Y is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- j is an integer of 1 to 3.
- the plurality of R Y are the same or different.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R Y include one hydrogen atom in the divalent hydrocarbon group having 1 to 20 carbon atoms exemplified as L 1 and L 4 above. Examples thereof include a monovalent hydrocarbon group. Among these, a chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group is more preferable.
- J is preferably 1 or 2, and more preferably 1.
- Examples of the monomer giving the structural unit (II) include methyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, cyclohexyltrichlorosilane, and the like.
- the lower limit of the content ratio of the structural unit (II) is preferably 0.1 mol% with respect to all the structural units constituting the [A] polysiloxane. 1 mol% is more preferable, 10 mol% is further more preferable, 20 mol% is especially preferable, and 30 mol% is further especially preferable. As an upper limit of the said content rate, 80 mol% is preferable, 60 mol% is more preferable, 50 mol% is further more preferable, 40 mol% is further especially preferable.
- the polysiloxane may have a structural unit (III) represented by the following formula (4).
- Examples of the monomer that gives the structural unit (III) include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and tetrahalosilanes such as tetrachlorosilane and tetrabromosilane.
- the lower limit of the content ratio of the structural unit (III) is preferably 1 mol% with respect to all the structural units constituting the [A] polysiloxane. More preferably, mol% is more preferable, 30 mol% is further more preferable, and 60 mol% is especially preferable. As an upper limit of the said content rate, 95 mol% is preferable, 90 mol% is more preferable, 85 mol% is further more preferable, 80 mol% is especially preferable.
- the film-forming material can further enhance the etching resistance by the oxygen-based gas and the peelability by the alkaline hydrogen peroxide solution by setting the content ratio of the structural unit (III) in the above range.
- the polysiloxane may have structural units other than the structural units (I) to (III) as other structural units as long as the effects of the present invention are not impaired.
- Examples of other structural units include structural units derived from silane monomers containing a plurality of silicon atoms, such as hexamethoxydisilane, bis (trimethoxysilyl) methane, polydimethoxymethylcarbosilane, and the like.
- the upper limit of the content of other structural units is preferably 10 mol%, more preferably 5 mol%, still more preferably 2 mol%, and more preferably 5 mol%. Particularly preferred.
- the lower limit of the content of [A] polysiloxane in the film forming material is preferably 0.01% by mass, more preferably 0.1% by mass, further preferably 0.5% by mass, and particularly preferably 1% by mass. .
- 20 mass% is preferable, 10 mass% is more preferable, 5 mass% is further more preferable, 3 mass% is especially preferable.
- paintability of the said film formation material can be improved.
- Only 1 type of polysiloxane may be contained and 2 or more types may be contained.
- the lower limit of the weight average molecular weight (Mw) of the polysiloxane is preferably 1,000, more preferably 1,300, still more preferably 1,500, and particularly preferably 1,700.
- the upper limit of Mw is preferably 100,000, more preferably 20,000, still more preferably 7,000, and particularly preferably 3,000.
- the Mw of [A] polysiloxane in this specification uses Tosoh's GPC columns (two “G2000HXL”, one “G3000HXL” and one “G4000HXL”), flow rate: 1.0 mL / min, elution It is a value measured by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene under the analysis conditions of solvent: tetrahydrofuran, column temperature: 40 ° C.
- the film forming material contains a [B] solvent.
- the solvent include alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, and the like.
- a solvent can be used individually by 1 type or in combination of 2 or more types.
- the alcohol solvent examples include monoalcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol, ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol and the like.
- monoalcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol, ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol and the like.
- polyhydric alcohol solvents examples include polyhydric alcohol solvents.
- ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-butyl ketone, and cyclohexanone.
- ether solvents include ethyl ether, iso-propyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Tetrahydrofuran etc. are mentioned.
- ester solvent examples include ethyl acetate, ⁇ -butyrolactone, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, acetic acid
- Examples include propylene glycol monoethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethyl propionate, n-butyl propionate, methyl lactate, and ethyl lactate.
- nitrogen-containing solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
- ether solvents and ester solvents are preferable, and ether solvents and ester solvents having a glycol structure are more preferable because of excellent film-forming properties.
- ether solvents and ester solvents having a glycol structure examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl acetate
- examples include ether. Among these, propylene glycol monomethyl ether acetate is particularly preferable.
- the lower limit of the content of the ether solvent and the ester solvent having a glycol structure in the solvent is preferably 20% by mass, more preferably 60% by mass, still more preferably 90% by mass, and particularly preferably 100% by mass. preferable.
- the lower limit of the content of the [B] solvent in the film forming material is preferably 80% by mass, more preferably 90% by mass, and still more preferably 95% by mass.
- 99 mass% is preferable and 98 mass% is more preferable.
- the film forming material may contain optional components such as a basic compound and an acid generator.
- the basic compound promotes the curing reaction of the film forming material, and as a result, improves the strength and the like of the formed silicon-containing film. Further, the basic compound improves the peelability of the silicon-containing film with an acidic solution.
- the basic compound include a compound having a basic amino group and a base generator that generates a compound having a basic amino group by the action of an acid or the action of heat.
- the compound having a basic amino group include amine compounds.
- the base generator include amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like. Specific examples of the amine compound, amide group-containing compound, urea compound and nitrogen-containing heterocyclic compound include compounds described in paragraphs [0079] to [0082] of JP-A-2016-27370, for example. .
- the content of the basic compound with respect to 100 parts by mass of [A] polysiloxane is, for example, 1 part by mass or more and 50 parts by mass or less.
- the acid generator is a component that generates an acid upon exposure or heating.
- the film forming material contains an acid generator, the condensation reaction of the [A] polysiloxane compound can be promoted even at a relatively low temperature (including room temperature).
- photoacid generator examples include the acid generators described in paragraphs [0077] to [0081] of JP-A No. 2004-168748. It is done.
- thermal acid generator examples include onium salt acid generators exemplified as photoacid generators in the above-mentioned patent documents, , 4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkylsulfonates and the like.
- the lower limit of the content of the acid generator with respect to 100 parts by mass of [A] polysiloxane is preferably 0.01 parts by mass, more preferably 0.1 parts by mass. 0.5 parts by mass is more preferable, and 1 part by mass is particularly preferable.
- the upper limit of the said content 20 mass parts is preferable, 10 mass parts is more preferable, and 5 mass parts is further more preferable.
- the film forming material may contain other optional components in addition to the basic compound and the acid generator.
- other optional components include surfactants, radical generators, colloidal silica, colloidal alumina, and organic polymers.
- the said film forming material contains another arbitrary component, as an upper limit of the content, 2 mass parts is preferable with respect to 100 mass parts of [A] polysiloxane, and 1 mass part is more preferable.
- the method for preparing the film-forming material is not particularly limited.
- [A] polysiloxane, [B] solvent and, if necessary, optional components are mixed in a predetermined ratio.
- the obtained mixed solution is mixed with a pore size of 0. It can be prepared by filtering with a 2 ⁇ m filter.
- the lower limit of the solid content concentration of the film forming material is preferably 0.01% by mass, more preferably 0.1% by mass, further preferably 0.5% by mass, and particularly preferably 1% by mass.
- the upper limit of the solid content concentration is preferably 20% by mass, more preferably 10% by mass, further preferably 5% by mass, and particularly preferably 3% by mass.
- the solid content concentration of the film forming material means that the mass of the solid content in the film forming material is measured by baking the film forming material at 250 ° C. for 30 minutes, and the mass of the solid content is the mass of the film forming material. It is a value (mass%) calculated by dividing.
- the silicon-containing film obtained from the film-forming material forms a resist pattern that is excellent in oxygen gas etching resistance and alkaline hydrogen peroxide solution while maintaining solvent resistance, and is excellent in shape and collapse suppression. be able to. Therefore, the film forming material can be suitably used as a material for forming a silicon-containing film as an intermediate film in a resist process, particularly a multilayer resist process.
- the multilayer resist processes it is particularly preferably used in pattern formation using a multilayer resist process in a region finer than 90 nm (ArF, ArF in immersion exposure, F 2 , EUV, nanoimprint, etc.). it can.
- the silicon-containing film forms the coating film by applying the film-forming material described above to the surface of another lower layer film such as a substrate or an organic lower layer film, and heat-treats and cures the coating film. Can be formed.
- Examples of the method for applying the film forming material include a spin coating method, a roll coating method, and a dip method.
- a spin coating method As a minimum of the temperature of heat processing, 50 ° C is preferred and 70 ° C is more preferred.
- As an upper limit of the said temperature 450 degreeC is preferable and 300 degreeC is more preferable.
- the lower limit of the average thickness of the formed silicon-containing film is preferably 10 nm, more preferably 20 nm.
- the upper limit of the average thickness is preferably 200 nm, and more preferably 150 nm.
- the pattern forming method includes a step of forming a silicon-containing film on the upper side of the substrate by applying the film-forming material (hereinafter also referred to as “silicon-containing film forming step”), and a step of patterning the silicon-containing film ( Hereinafter, it is also referred to as a “silicon-containing film patterning step” and a step of forming a pattern on the substrate using the patterned silicon-containing film as a mask (hereinafter also referred to as “substrate pattern forming step”).
- the pattern forming method since the film forming material is used, it is possible to form a silicon-containing film that is excellent in oxygen-based gas etching resistance and peelability with alkaline hydrogen peroxide while maintaining solvent resistance. It is possible to form a resist pattern that is excellent in shape and collapse suppression.
- the silicon-containing film patterning step includes a step of forming a resist pattern on the upper side of the silicon-containing film (hereinafter also referred to as “resist pattern forming step”), and a step of etching the silicon-containing film using the resist pattern as a mask. (Hereinafter also referred to as “silicon-containing film etching step”).
- the pattern forming method may further include a step of forming an organic underlayer film on the upper side of the substrate (hereinafter, also referred to as “organic underlayer film forming step”) before the silicon-containing film forming step, if necessary. Good.
- the pattern forming method may further include a step of removing the silicon-containing film (hereinafter, also referred to as “silicon-containing film removing step”) after the silicon-containing film forming step.
- silicon-containing film removing step the silicon-containing film
- Organic underlayer formation process In this step, an organic underlayer film is formed on the upper side of the substrate.
- an organic underlayer film forming step can be performed as necessary.
- the silicon-containing film forming step is performed after the organic underlayer film forming step, and in the silicon-containing film forming step, silicon is formed using the film forming material on the organic underlayer film. A containing film is formed.
- the substrate examples include an insulating film such as silicon oxide, silicon nitride, silicon oxynitride, and polysiloxane, a resin substrate, and the like.
- an interlayer insulating film such as a wafer covered with a low dielectric insulating film formed by “Black Diamond” from AMAT, “Silk” from Dow Chemical, “LKD5109” from JSR, or the like can be used.
- a patterned substrate such as a wiring groove (trench) or a plug groove (via) may be used.
- the organic underlayer film is different from the silicon-containing film formed from the film forming material.
- the organic underlayer film has a predetermined function (for example, antireflection) that is necessary for further supplementing the function of the silicon-containing film and / or the resist film in the formation of the resist pattern, or to obtain a function that these do not have. Film, coating film flatness, and high etching resistance against fluorine-based gas).
- Examples of the organic underlayer film include an antireflection film.
- Examples of the antireflection film forming material include “NFC HM8006” manufactured by JSR Corporation.
- the organic underlayer film can be formed by applying a composition for forming an organic underlayer film by a spin coating method or the like to form a coating film, followed by heating.
- a silicon-containing film is formed on the upper side of the substrate by coating the film forming material.
- a silicon-containing film is formed on the substrate directly or via another layer such as an organic underlayer film.
- the method for forming the silicon-containing film is not particularly limited, but for example, by exposing and / or heating a coating film formed by coating the film-forming material on a substrate or the like by a known method such as a spin coating method. For example, a method of forming by curing.
- Examples of the radiation used for this exposure include electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, X-rays and ⁇ rays, particle beams such as electron beams, molecular beams and ion beams.
- the temperature at the time of heating a coating film 90 ° C is preferred, 150 ° C is more preferred, and 200 ° C is still more preferred.
- As an upper limit of the said temperature 550 degreeC is preferable, 450 degreeC is more preferable, and 300 degreeC is further more preferable.
- As a minimum of average thickness of a silicon content film formed 1 nm is preferred, 10 nm is more preferred, and 20 nm is still more preferred.
- the upper limit of the average thickness is preferably 20,000 nm, more preferably 1,000 nm, and even more preferably 100 nm.
- ⁇ Silicon-containing film patterning process> the silicon-containing film is patterned.
- the silicon-containing film formed in the silicon-containing film forming step is patterned.
- Examples of the method for patterning the silicon-containing film include a method including a resist pattern forming step and a silicon-containing film etching step.
- resist pattern formation process In this step, a resist pattern is formed on the upper side of the silicon-containing film. By this step, a resist pattern is formed on the upper side of the silicon-containing film formed in the silicon-containing film forming step.
- Examples of the method for forming a resist pattern include conventionally known methods such as a method using a resist composition and a method using a nanoimprint lithography method. This resist pattern is usually formed from an organic material.
- a step of forming a resist film on the upper side of the silicon-containing film with the resist composition for example, a step of forming a resist film on the upper side of the silicon-containing film with the resist composition (hereinafter also referred to as “resist film forming step”), and a step of exposing the resist film (hereinafter also referred to as “development step”) may be used.
- resist film formation process In this step, a resist film is formed on the upper side of the silicon-containing film with a resist composition. By this step, a resist film is formed on the upper side of the silicon-containing film.
- the resist composition examples include a radiation-sensitive resin composition (chemically amplified resist composition) containing a polymer having an acid-dissociable group and a radiation-sensitive acid generator, an alkali-soluble resin, and a quinonediazide-based photosensitizer. And a negative resist composition containing an alkali-soluble resin and a crosslinking agent.
- a radiation sensitive resin composition is preferable.
- a positive pattern can be formed by developing with an alkali developer
- a negative pattern can be formed by developing with an organic solvent developer.
- a double patterning method, a double exposure method, or the like, which is a method for forming a fine pattern may be used as appropriate.
- the polymer contained in the radiation-sensitive resin composition includes, in addition to the structural unit containing an acid dissociable group, for example, a structural unit containing a lactone structure, a cyclic carbonate structure and / or a sultone structure, or a structural unit containing an alcoholic hydroxyl group. Further, it may have a structural unit containing a phenolic hydroxyl group, a structural unit containing a fluorine atom, or the like.
- EUV extreme ultraviolet rays
- the lower limit of the solid content concentration of the resist composition is preferably 0.1% by mass, and more preferably 1% by mass.
- As an upper limit of the said solid content concentration 50 mass% is preferable and 30 mass% is more preferable.
- As the resist composition a resist composition filtered with a filter having a pore diameter of about 0.2 ⁇ m can be suitably used. In the pattern forming method, a commercially available resist composition can be used as it is as the resist composition.
- Examples of the resist film forming method include a method of coating a resist composition on a silicon-containing film.
- Examples of the resist composition coating method include conventional methods such as a spin coating method. When applying the resist composition, the amount of the resist composition to be applied is adjusted so that the resulting resist film has a predetermined thickness.
- the resist film can be formed by volatilizing the solvent in the coating film by pre-baking the coating film of the resist composition.
- the pre-baking temperature is appropriately adjusted according to the type of resist composition to be used, and the like.
- the lower limit of the pre-baking temperature is preferably 30 ° C., more preferably 50 ° C.
- 200 degreeC is preferable and 150 degreeC is more preferable.
- the resist film is exposed. This exposure is performed by selectively irradiating radiation, for example, through a photomask.
- the radiation used for the exposure includes electromagnetic waves such as visible rays, ultraviolet rays, far ultraviolet rays, X-rays, ⁇ rays, electron beams, molecular rays, ions, depending on the type of acid generator used in the resist composition.
- electromagnetic waves such as visible rays, ultraviolet rays, far ultraviolet rays, X-rays, ⁇ rays, electron beams, molecular rays, ions, depending on the type of acid generator used in the resist composition.
- a particle beam such as a beam is appropriately selected, and among these, deep ultraviolet rays and electron beams are preferable, and KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F 2 excimer laser light (wavelength 157 nm).
- the exposure method is not particularly limited, and can be performed in accordance with a conventionally known pattern formation method.
- the development may be alkali development or organic solvent development.
- alkali developer examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanol.
- alkaline aqueous solutions in which at least one of the alkaline compounds is dissolved.
- these alkaline aqueous solutions may be those obtained by adding appropriate amounts of water-soluble organic solvents such as alcohols such as methanol and ethanol, surfactants and the like.
- organic solvent developer examples include liquids mainly composed of organic solvents such as ketone solvents, alcohol solvents, amide solvents, ether solvents, ester solvents and the like.
- organic solvents such as ketone solvents, alcohol solvents, amide solvents, ether solvents, ester solvents and the like.
- these solvents include those similar to the respective solvents exemplified as the above [B] organic solvent. These solvents may be used alone or in combination.
- a predetermined resist pattern corresponding to the photomask can be formed by washing and drying.
- the silicon-containing film is etched using the resist pattern as a mask. More specifically, a silicon-containing film on which a pattern is formed is obtained by one or more etchings using the resist pattern formed in the resist pattern forming step as a mask.
- the etching may be dry etching or wet etching, but is preferably dry etching.
- Dry etching can be performed using, for example, a known dry etching apparatus.
- the etching gas used for dry etching can be selected as appropriate depending on the elemental composition of the silicon-containing film to be etched, such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6, etc.
- Fluorine gas chlorine gas such as Cl 2 , BCl 3 , oxygen gas such as O 2 , O 3 , H 2 O, H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , C 3 H 4 , C 3 H 6 , C 3 H 8 , HF, HI, HBr, HCl, NO, NH 3 , reducing gases such as BCl 3 , He, N 2 , An inert gas such as Ar is used. These gases can also be mixed and used. For dry etching of a silicon-containing film, a fluorine-based gas is usually used, and a mixture of an oxygen-based gas and an inert gas is preferably used.
- a pattern is formed on the substrate using the patterned silicon-containing film as a mask.
- This step is usually performed by etching the substrate using the patterned silicon-containing film as a mask. More specifically, the patterned substrate is obtained by performing etching one or more times using the pattern formed on the silicon-containing film obtained in the silicon-containing film etching step as a mask.
- the organic underlayer film is formed by etching the organic underlayer film using the silicon-containing film pattern as a mask, and then the substrate is etched using the organic underlayer film pattern as a mask. Thus, a pattern is formed on the substrate.
- the etching may be dry etching or wet etching, but is preferably dry etching.
- Dry etching for forming a pattern on the organic underlayer film can be performed using a known dry etching apparatus.
- the etching gas used for dry etching can be appropriately selected depending on the elemental composition of the silicon-containing film and the organic underlayer film to be etched, and for example, CHF 3 , CF 4 , C 2 F 6 , C 3 F 8.
- Fluorine gas such as SF 6 , chlorine gas such as Cl 2 and BCl 3 , oxygen gas such as O 2 , O 3 , and H 2 O, H 2 , NH 3 , CO, CO 2 , CH 4 , C Reducing gases such as 2 H 2 , C 2 H 4 , C 2 H 6 , C 3 H 4 , C 3 H 6 , C 3 H 8 , HF, HI, HBr, HCl, NO, NH 3 , BCl 3 , An inert gas such as He, N 2 , Ar, or the like is used, and these gases can be mixed and used. For dry etching of an organic underlayer film using a silicon-containing film pattern as a mask, an oxygen-based gas is usually used.
- Dry etching for forming a pattern on a substrate using an organic underlayer film pattern as a mask can be performed using a known dry etching apparatus.
- the etching gas used for the dry etching can be appropriately selected depending on the elemental composition of the organic underlayer film and the substrate to be etched, and is similar to those exemplified as the etching gas used for the dry etching of the organic underlayer film.
- ⁇ Silicon-containing film removal process> the silicon-containing film is removed after the silicon-containing film forming step.
- this step is performed after the substrate etching step, the silicon-containing film remaining on the upper side of the substrate is removed.
- This step can also be performed on a patterned or non-patterned silicon-containing film before the substrate etching step.
- Examples of the method for removing the silicon-containing film include a method of dry etching the silicon-containing film, and a method of bringing a liquid such as a basic liquid or an acidic liquid into contact with the silicon-containing film.
- a liquid such as a basic liquid or an acidic liquid.
- a basic liquid is preferable.
- the dry etching can be performed using a known dry etching apparatus. Further, as a source gas at the time of dry etching, for example, a fluorine gas such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6 , a chlorine gas such as Cl 2 , BCl 3, or the like is used. These gases can be mixed and used.
- a fluorine gas such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6
- a chlorine gas such as Cl 2 , BCl 3, or the like.
- the wet stripping method is not particularly limited as long as the silicon-containing film and the alkaline hydrogen peroxide solution can be in contact with each other for a certain period of time under heating conditions, for example, a silicon-containing film.
- substrate which has this in the heated alkaline hydrogen peroxide solution, the method of spraying alkaline hydrogen peroxide solution in a heating environment, the method of coating the heated alkaline hydrogen peroxide solution, etc. are mentioned. After each of these methods, the substrate may be washed with water and dried.
- the lower limit of the temperature when the silicon-containing film removing step is performed using alkaline hydrogen peroxide is preferably 40 ° C., more preferably 50 ° C.
- 90 degreeC is preferable and 80 degreeC is more preferable.
- the lower limit of the dipping time in the dipping method is preferably 0.2 minutes, and more preferably 0.5 minutes.
- the upper limit of the immersion time is preferably 30 minutes, more preferably 20 minutes, further preferably 10 minutes, and particularly preferably 5 minutes from the viewpoint of suppressing the influence on the substrate.
- Example shown below shows an example of the typical Example of this invention, and, thereby, the range of this invention is not interpreted narrowly.
- the measurement of the solid content concentration of the [A] polysiloxane solution and the measurement of the weight average molecular weight (Mw) of [A] polysiloxane in this example were carried out by the following methods.
- Average thickness of film The average thickness of the film was measured using a spectroscopic ellipsometer (“M2000D” from JA WOOLLAM).
- the inside of the reaction vessel was cooled to 30 ° C. or lower. After adding 379 parts by mass of propylene glycol monomethyl ether acetate to the cooled reaction solution, using an evaporator, the alcohol produced by the reaction and excess propylene glycol monomethyl ether acetate were removed to remove the propylene acetate of polysiloxane (A-1). A glycol monomethyl ether solution was obtained.
- the Mw of the polysiloxane (A-1) was 1,820.
- the solid content concentration of this polysiloxane (A-1) solution in propylene glycol monomethyl ether acetate was 11.1% by mass.
- Example 1 [A] 1.8 parts by mass of (A-1) as a polysiloxane (solid content) and 98.2 parts by mass of (B-1) as a [B] solvent (included in the solution of [A] polysiloxane Solvent (including B-1)), and the obtained solution was filtered through a filter having a pore size of 0.2 ⁇ m to prepare a film forming material (J-1) for resist process.
- Each of the prepared resist process film-forming materials was applied on a silicon wafer (substrate) by a spin coating method using a spin coater (“CLEAN TRACK ACT12” manufactured by Tokyo Electron Ltd.).
- the obtained coating film was heated on a hot plate at 220 ° C. for 1 minute, and then cooled at 23 ° C. for 60 seconds to obtain an average thickness of 30 nm shown in Examples 1 to 11 and Comparative Examples 1 to 3 in Table 2.
- a substrate on which a silicon-containing film was formed was obtained.
- SC1 mixed liquid
- the average thickness of the film before and after immersion was measured.
- the film thickness change rate (%) due to SC1 immersion was determined by the following formula.
- Film thickness change rate (%) (S 0 ⁇ S 1 ) ⁇ 100 / S 0
- the peelability by the alkaline hydrogen peroxide solution was evaluated as “A” (good) when the rate of change in film thickness was 99% or more, and “B” (bad) when it was less than 99%.
- resist pattern shape and resist pattern collapse suppression The resist pattern shape and resist pattern collapse-inhibiting property were evaluated by performing the following lithography evaluation.
- a composition for forming an organic underlayer film (“NFC HM8006” from JSR) is applied on a 12-inch silicon wafer by the above spin coater and then heated at 250 ° C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm. did.
- the obtained film forming material is applied by the spin coater, heated at 220 ° C. for 60 seconds, and cooled at 23 ° C. for 60 seconds to form a silicon-containing film having an average thickness of 30 nm. did.
- a radiation-sensitive resin composition (“ARF AR2772JN” manufactured by JSR) was coated on the silicon-containing film by the spin coater, heated at 90 ° C. for 60 seconds, and cooled at 23 ° C. for 30 seconds.
- a resist film having a thickness of 100 nm was formed.
- the exposure amount is gradually decreased and the exposure is sequentially performed, and the line width corresponding to the minimum exposure amount at which the collapse of the resist pattern is not confirmed is defined as the minimum dimension before collapse (nm). It was used as an index of pattern collapse inhibition.
- the resist pattern collapse inhibition property was evaluated as “A” (good) when the minimum dimension before collapse was 32 nm or less, and “B” (bad) when it exceeded 32 nm.
- the shape of the resist pattern was evaluated as “A” (good) when there was no tailing in the resist pattern, and “B” (bad) when there was pattern collapse or tailing.
- the film forming material for resist process and the pattern forming method of the present invention it is possible to form a silicon-containing film excellent in oxygen gas etching resistance and peelability by alkaline hydrogen peroxide while maintaining solvent resistance, Furthermore, it is possible to form a resist pattern that is excellent in shape and collapse suppression.
- the polysiloxane of the present invention can be suitably used as a polysiloxane component of the resist process film-forming material. Therefore, these can be used suitably for a multilayer resist process etc., and can be used suitably for manufacture of a semiconductor device etc. in which further miniaturization is expected in the future.
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Le but de la présente invention est de fournir : un matériau de formation de film pour un processus de réserve, à partir duquel il est possible de former un film contenant du silicium qui a une résistance à la gravure à base d'oxygène et présente d'excellentes propriétés de libération au moyen d'une solution alcaline de peroxyde d'hydrogène tout en maintenant la résistance aux solvants ; un procédé de formation de motif utilisant ledit matériau de formation de film ; et un polysiloxane. La présente invention concerne un matériau de formation de film pour un procédé de réserve, contenant : un polysiloxane ayant une première unité structurale représentée par la formule (1) ou (2) ; et un solvant. Dans la formule (1), L1 représente une liaison simple ou un groupe organique divalent ayant de 1 à 20 atomes de carbone ; R1 représente un groupe éthynediyle ou un groupe éthènediyle substitué ou non substitué ; L2 représente une liaison simple ou un groupe organique (n +1)-valent ayant de 1 à 20 atomes de carbone ; n représente un nombre entier de 1 à 3 ; et R2 représente un groupe monovalent comprenant un groupe polaire. Dans la formule (2), L4 représente une liaison simple ou un groupe organique divalent ayant de 1 à 20 atomes de carbone ; et R4 représente un groupe éthinyle substitué ou non substitué ou un groupe éthényle substitué ou non substitué.
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JP2019501309A JPWO2018155377A1 (ja) | 2017-02-24 | 2018-02-19 | レジストプロセス用膜形成材料、パターン形成方法及びポリシロキサン |
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JP2017034173 | 2017-02-24 | ||
JP2017-034173 | 2017-02-24 |
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WO2018155377A1 true WO2018155377A1 (fr) | 2018-08-30 |
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PCT/JP2018/005727 WO2018155377A1 (fr) | 2017-02-24 | 2018-02-19 | Matériau de formation de film pour procédé de réserve, procédé de formation de motif, et polysiloxane |
Country Status (3)
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JP (1) | JPWO2018155377A1 (fr) |
TW (1) | TW201835229A (fr) |
WO (1) | WO2018155377A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023136250A1 (fr) * | 2022-01-12 | 2023-07-20 | 日産化学株式会社 | Composition pour former un film de sous-couche de réserve contenant du silicium, et film de sous-couche de réserve contenant du silicium |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016011411A (ja) * | 2014-06-05 | 2016-01-21 | Jsr株式会社 | シリコン含有膜形成用組成物、パターン形成方法及びポリシロキサン化合物 |
JP2016074772A (ja) * | 2014-10-03 | 2016-05-12 | 信越化学工業株式会社 | 塗布型ケイ素含有膜形成用組成物、基板、及びパターン形成方法 |
WO2016111210A1 (fr) * | 2015-01-09 | 2016-07-14 | Jsr株式会社 | Composition pour former un film contenant du silicium et procédé de formation de motif utilisant ladite composition |
-
2018
- 2018-02-19 WO PCT/JP2018/005727 patent/WO2018155377A1/fr active Application Filing
- 2018-02-19 JP JP2019501309A patent/JPWO2018155377A1/ja active Pending
- 2018-02-22 TW TW107105924A patent/TW201835229A/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2016011411A (ja) * | 2014-06-05 | 2016-01-21 | Jsr株式会社 | シリコン含有膜形成用組成物、パターン形成方法及びポリシロキサン化合物 |
JP2016074772A (ja) * | 2014-10-03 | 2016-05-12 | 信越化学工業株式会社 | 塗布型ケイ素含有膜形成用組成物、基板、及びパターン形成方法 |
WO2016111210A1 (fr) * | 2015-01-09 | 2016-07-14 | Jsr株式会社 | Composition pour former un film contenant du silicium et procédé de formation de motif utilisant ladite composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023136250A1 (fr) * | 2022-01-12 | 2023-07-20 | 日産化学株式会社 | Composition pour former un film de sous-couche de réserve contenant du silicium, et film de sous-couche de réserve contenant du silicium |
Also Published As
Publication number | Publication date |
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TW201835229A (zh) | 2018-10-01 |
JPWO2018155377A1 (ja) | 2020-01-16 |
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