CN115407607A - Application of zinc oxide cluster compound in field of photoresist - Google Patents
Application of zinc oxide cluster compound in field of photoresist Download PDFInfo
- Publication number
- CN115407607A CN115407607A CN202210843159.4A CN202210843159A CN115407607A CN 115407607 A CN115407607 A CN 115407607A CN 202210843159 A CN202210843159 A CN 202210843159A CN 115407607 A CN115407607 A CN 115407607A
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- China
- Prior art keywords
- photoresist
- zinc oxide
- film
- oxide cluster
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Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 93
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 238000001459 lithography Methods 0.000 claims description 9
- 239000000523 sample Substances 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000609 electron-beam lithography Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 238000000206 photolithography Methods 0.000 claims description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000001900 extreme ultraviolet lithography Methods 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001127 nanoimprint lithography Methods 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 13
- 238000001259 photo etching Methods 0.000 abstract description 7
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- 238000003860 storage Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
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- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000004925 denaturation Methods 0.000 abstract 1
- 230000036425 denaturation Effects 0.000 abstract 1
- 239000003504 photosensitizing agent Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010894 electron beam technology Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
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- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006552 photochemical reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- -1 acrylic compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- JFSLZPVIISMPIO-UHFFFAOYSA-N C(C)(=O)O.C=O.C(C(C)O)O Chemical compound C(C)(=O)O.C=O.C(C(C)O)O JFSLZPVIISMPIO-UHFFFAOYSA-N 0.000 description 1
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 101100460147 Sarcophaga bullata NEMS gene Proteins 0.000 description 1
- XRKIHUXCUIFHAS-UHFFFAOYSA-N [4-(3-methoxy-3-oxopropyl)phenyl]boronic acid Chemical compound COC(=O)CCC1=CC=C(B(O)O)C=C1 XRKIHUXCUIFHAS-UHFFFAOYSA-N 0.000 description 1
- UCTRNAGFHFQNSI-UHFFFAOYSA-N acetaldehyde propane-1,2-diol Chemical compound CC=O.CC(O)CO UCTRNAGFHFQNSI-UHFFFAOYSA-N 0.000 description 1
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- 239000002318 adhesion promoter Substances 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- LZCLXQDLBQLTDK-BYPYZUCNSA-N ethyl (2S)-lactate Chemical compound CCOC(=O)[C@H](C)O LZCLXQDLBQLTDK-BYPYZUCNSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005329 nanolithography Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007141 radiochemical reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Images
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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The invention discloses an application of a zinc oxide cluster compound in the field of photoresist, wherein the general structural formula of the zinc oxide cluster compound is shown as A; the zinc oxide cluster compound or the composition thereof is used for preparing the photoresist, the integrated photoresist molecule is a photosensitizer and resin, the synthesis method is simple, the raw materials are simple and easy to obtain, the product can be obtained in high yield by one step of reaction, the product is pure, the benzene and the derivative ligand thereof greatly improve the solubility of the zinc oxide cluster in various solvents or developers, especially the molecule of the 4-trifluorophenyl ligand is suitable for most solvents, has strong process compatibility, and is very suitable for preparing photoresist films with different thicknesses of 15-100 nm and uniformity. Any auxiliary agent can be not added in the production, the implementation is convenient, and the cost is greatly reduced. The synthesized photoresist molecules have high thermal stability and storage stability, no precipitation during baking, no easy denaturation during photoetching, good film forming property, low viscosity and the like, and are suitable for different types of lightAnd (4) engraving technology.
Description
Technical Field
The invention belongs to the technical field of materials/photoetching, and particularly relates to construction and application of a photoresist composition of a spatially symmetrical zinc-oxygen cluster compound molecule modified by a monocarboxylic ligand.
Background
Photolithography is a key process in integrated circuit fabrication, which uses the photo-chemical reaction (photo-chemical reaction) principle to transfer a pattern prepared on a mask to a substrate (wafer), so that selective etching and ion implantation are possible. Photoetching is a key link in the preparation process of the micro-nano device; the fabrication of semiconductor devices, optoelectronic devices, and micro/nano-electro-mechanical systems (M/NEMS) is not straightforward to the photolithographic process. Particularly, in ultra-large scale integrated circuits, the devices on the integrated circuits can be made smaller and smaller due to the development of photoresist materials and processes, the integration level of chips is higher and higher, and the average cost of a single transistor is lower and lower.
The photolithographic materials refer to adhesion promoting materials, anti-reflection coatings, photoresists, chemical solvents and developers used in photolithography. These materials are mounted on a track developer and are either spun or sprayed onto the wafer according to the process flow arrangement. The anti-reflection layer is used for absorbing or eliminating reflection light from the wafer substrate and eliminating standing wave effect. The photoresist is one of the most important components in the photoresist material, and is a thin film material with a chemical structure changed to generate solubility change after being irradiated by energy such as light beams, electron beams, ion beams or x-rays. Photoresists are sensitive to a broad spectrum of such radiation sources, i.e., have energies above the bond energy, the ionization energy of any component of the photoresist, and thus, nearly all chemical bonds of the photoresist are broken when exposed to such radiation sources. This property of high-energy radiation is detrimental to the choice of chemical functional groups, but the high-energy beam, when interacting with the photoresist, does not rely on the molecular structure of the photoresist, but rather on the trapping cross-section of the atoms, generating a large number of secondary and auger electrons of low energy that further induce chemical changes at the same molecular level as conventional exposure modes.
Structurally, it is a photosensitive polymer, or small molecule. Such as molecular glass-type structures with high glass transition temperatures, and metal-containing clusters, complexes or nanoparticles. Under the irradiation of light or radiation with certain wavelength, a series of photochemical reactions or radiochemical reactions occur, so that the structure of the photoresist is changed. The structure determines the property, so that the exposed part and the unexposed part generate the solubility change in the developing solution, and the glue generates a pattern after being developed, baked and the like. The method is widely applied to the micro-processing of integrated circuit semiconductor devices.
With the higher integration level in the semiconductor industry, the chemically amplified photoresist can cause uncontrolled acid diffusion in the photoresist according to the formula of the Edge Roughness (Line Edge Roughness) of the photoresist Line
The resulting acid concentration gradient affects the final roughness; in contrast to the chemically amplified resist, the polymer is prone to causing molecular entanglement, so that in the design of the resist, small molecules are selected as resist molecules, and the requirements of future advanced lithography are met. Compared with CAR (Chemical amplification Hotoresist) which contains various components such as a photoacid generator, a polymer, an alkaline additive and the like, the composite material has great advantages in practical production and application.
Most of the zinc oxide photoresists reported so far are produced by a sol-gel method (Advanced Materials Interfaces,2016,3 (19): 1600373.) (Journal of Materials C)Chemistry C,2017,5 (10): 2611-2619.) this type of photoresist is nano system, has no definite chemical molecular structure, and the larger size is not beneficial to the advanced photolithography process; the literature published in the Sonia Castellanos topic group of the Netherlands (Journal of micro/Nanolithography, MEMS, and MOEMS,2019,18 (4): 043504.) is an indirect preparation of zinc-oxygen clusters by stirring the displaced ligands, which in the structural schematic should consist of 4 metal 6 ligands, but the literature gives the structure Zn by characterization 4 O 18 C 31 H 37.5 F 4.5 Resolved as 4 metals, 8.5 ligands, ligand ratio 7:1.5, the preparation method cannot obtain pure products, and has the disadvantages of difficult raw material obtaining, high cost, low yield and poor thermal stability through the illustration of literature authors and repeated literature experiments. Such mixtures result in poor batch stability, and the same number of products will contain different numbers of reactive groups, resulting in different light doses required for each batch of synthesized product. In its most recent publication (Fluorine-Rich As Extreme Ultraviolet catalysts and catalysts J]ACS Materials Au, 2022.) work, the same ligand ratios were 2.4:2.9:0.8, and a total of 6.1 ligands close to the target structure 6, but still in admixture, and the film-forming properties are greatly reduced compared to before.
In view of the good lithographic properties of zinc oxide, there is a need for a preparation strategy that has a definite structure, and has excellent thermal stability, storage stability, etc., and is easy to implement and cost-effective.
Disclosure of Invention
In order to solve the above technical problems, according to the reference (Inorganica Chimica acta,186 (1991) 51-60), zinc oxide and 4-trifluoromethylbenzoic acid or benzoic acid are first used to directly synthesize the target molecule in one step. The zinc oxide cluster compound based on an organic/inorganic hybrid system is applied to the field of photoresist; the structural general formula of the zinc oxide cluster compound is shown as A:
wherein: r is selected from one of the following substituents:
the zinc oxide cluster compound III is commonly applied to the catalysis field in the prior art, but cannot be applied to the photoresist field due to the limited solubility of the zinc oxide cluster compound III. The zinc oxide cluster compounds I and II are used as the analogs of the minimum structural unit of the MOF-5 structure, are less applied in the prior art, are innovatively applied to the field of photoresist, and belong to a new application. The method is a new way related to the development of the zinc-oxygen cluster photoresist, can solve the problem of the purity of the zinc-oxygen cluster, and has a definite structure; but also can solve the problem of poor thermal stability; the implementation is convenient, the repeatability is good, and the stability is good; but also greatly reduces the cost.
One of the applications is that the compound with the structural formula shown as I or II is used as the only component to be directly used as the photoresist.
The second application is to use a zinc oxide cluster compound shown as a structural formula I or II as a photoresist composition, wherein:
1-15 parts by weight, more preferably 2-4 parts by weight of a zinc oxide cluster compound represented by the structural formula I or II;
the organic solvent accounts for 85 to 99 parts by weight, more preferably 96 to 98 parts by weight;
0 to 0.05 part by weight of a leveling agent, more preferably 0.02 part by weight;
0 to 0.05 parts by weight, more preferably 0.02 parts by weight of a dispersant;
0 to 0.05 parts by weight of a tackifier, more preferably 0.01 parts by weight;
0 to 0.1 part by weight, more preferably 0.05 part by weight, of other additives;
preferably, the organic solvent includes, but is not limited to, one of esters, alcohols, ethers, cyclic ethers, benzenes, carboxylic acids, alkanes, and the like; further preferred are tetrahydrofuran, 1,4-dioxane, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, chlorobenzene, fluorobenzene, propylene glycol monomethyl ether acetate, propylene glycol diethyl ether, propylene glycol monoacetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, chloroform and a mixture of one or more of dichloromethane, methanol, ethanol, 1,2 dichloroethane. The type and proportion of the organic solvent affect the coating performance of the photoresist composition, so that the solubility of the organic solvent on matrix molecules can be improved by adjusting the proportion and proportion of the organic solvent. Meanwhile, the polarity of the organic solvent itself also affects the effect of the coating film.
Preferably, the leveling agent may include, but is not limited to, an acrylic compound, a fluorocarbon-based compound, and the like. The leveling agent has the functions of adjusting the viscosity and the fluidity of a photoresist system and increasing the film forming uniformity of the photoresist.
Preferably, the dispersant may be a lignosulfonate, such as sodium lignosulfonate, calcium lignosulfonate, ammonium lignosulfonate, and the like.
Preferably, the adhesion promoter may include, but is not limited to, hexamethyldisilazane, hydroxymethyl cellulose, polyacrylamide, etc., and the micro-thickener may be uniformly dispersed on the substrate material by spraying, and the force between the photoresist and the substrate material may be increased by changing the hydrophilicity and hydrophobicity.
Preferably, said other additives are, for example, photoinitiators, radical quenchers, etc.
Applications of the third aspect of the invention further include: preparing a photoresist coating by using the zinc oxide cluster compound with the structure shown in the formula I or II, wherein the photoresist coating is prepared by applying the zinc oxide cluster compound with the structure shown in the formula I or II or a photoresist composition on a substrate to form a film; the photoresist coating is a smooth and compact uniform film, namely a zinc-oxygen cluster film.
Preferably, the substrate may be selected from a silicon wafer or a quartz wafer, and may also include a silicon wafer or a quartz wafer formed with a sensor, a circuit, a transistor, and the like. The photoresist coating and the like are obtained by film forming methods such as spraying, evaporation, deposition and the like, and the application method is a spin coating method.
The invention also discloses a method for optimizing the roughness of the zinc-oxygen cluster film, which comprises the following steps: the film forming property of the photoresist film is adjusted by adjusting parameters of solid content, a glue preparation solvent, glue homogenizing time, glue homogenizing rotating speed, baking temperature and time; specifically, photoresist films of different roughness are prepared by a spin coating process. The data are obtained by probe scanning measurement (10 μm × 10 μm wide area scanning) of an atomic force microscope (hereinafter abbreviated as AFM), the film roughness behavior can be evaluated by Ra and Rq, the smaller the roughness, the smoother the fluctuation of the film, and the better quality of the film roughness Ra and Rq is controlled below 0.3 nm.
R a -the arithmetic mean (mean) of the absolute values of the deviations in height measured with respect to the central plane, nm, over the sampling area;
R q -the root mean square value of the deviation of the profile from the mean line, in nm, over the sampling area, which is the root mean square parameter (variance) corresponding to Ra;
l-sample length, nm;
Z j -calculating the sampling height in Ra, nm;
Z i -calculating the sampling height in Rq, nm;
the use of the fourth aspect of the invention further comprises: the use of the photoresist coating in film science or lithography. Because the zinc oxide cluster compound with the structure of formula I or II has high thermal decomposition temperature, the zinc oxide cluster compound can be used for photoetching processing.
Preferably, the photoresist coating may be used in modern lithography techniques such as 248nm lithography, 193nm lithography, extreme Ultraviolet (EUV) lithography, extreme ultraviolet (BEUV) lithography, nanoimprint lithography or electron beam lithography, preferably in electron beam lithography or extreme ultraviolet lithography.
An electron beam lithography method comprises the steps of carrying out spin coating, soft baking, exposure, post baking, development and hard baking on a film prepared from the zinc-oxygen cluster photoresist with the structure of the formula I or II or a composition thereof; the glue homogenizing is preferably: the speed is 500rpm to 5000rpm, the time is 10s to 300s, for example, 90s at 2000 rpm. The soft-baking temperature is preferably 60 ℃ to 160 ℃ for 10s to 300s, for example, 100 ℃ for 180s. The exposure dose is preferably 20 mu C/cm at 25kV 2 ～800μC/cm 2 . The postbaking temperature is preferably from 40 ℃ to 150 ℃ for from 10s to 300s, for example for 60s at 90 ℃. The development time is preferably 10s to 300s.
The developer is compatible with the photoresist described above and is used to dissolve the unexposed negative tone photoresist. In some embodiments, the developer is selected from one or more of toluene, o-xylene, m-xylene, p-xylene, mesitylene, ethyl acetate, butyl acetate, 4-methyl 2-pentanol, 4-methyl-2-pentanone, methyl ethyl ketone, propylene glycol mono-formaldehyde acetate, propylene glycol acetaldehyde, propylene glycol mono-acetate, ethylene glycol formaldehyde acetate, 2-butanone, 2-heptanone, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ultra-pure water, n-hexane, and cyclohexane, and the temperature of development is room temperature, e.g., 20 ℃ to 30 ℃.
Advantageous effects
The selected raw materials are cheap and easy to obtain, the referenced synthesis method is simple, and the prepared product is pure.
The designed photoresist molecules are non-chemically amplified, so that no photoacid generator is required, and no acid sensitive groups are required on the ligand units. Can be in a non-composition form, is an integrated photoresist, is convenient to implement and saves cost.
The zinc oxide cluster compound adopts a multi-metal site as a core structure, has good chemical stability and a high melting point similar to MOF-5, and can meet the requirements of different advanced photoetching technologies.
The zinc-oxygen cluster belongs to a molecular level, has the advantage of definite structure, and is particularly suitable for component analysis before and after exposure to research an exposure mechanism. X-ray photoelectron spectroscopy (XPS) research shows that the binding mode of the ligand and the metal is coordination bond binding, and molecules can be subjected to chemical bond fracture after exposure to generate insoluble fragment metal oxides.
The zinc oxide cluster compound is a space symmetric compound, the cost required by the used raw materials is reduced by 30 times compared with the cost of the zinc oxide cluster photoresist in the background technology, and the zinc oxide cluster photoresist is economic and environment-friendly; the purity of the zinc-oxygen cluster is improved to 100%, the zinc-oxygen cluster can be dissolved in an organic solvent commonly used by photoresist, and compared with the traditional zinc-oxygen cluster, the solubility of the zinc-oxygen cluster is improved by more than 1 time.
The photoresist composition can be used for preparing uniform films, and the roughness of the films can be reduced to be below 0.3nm, so that the industrial front is achieved. Compared with the traditional metal cluster molecules, the thermal decomposition temperature is improved by 3 times, so that the film has stronger temperature regulation performance in the process of prebaking, postbaking and hard baking, the zinc oxide cluster compound serving as a main component in the film making process is not precipitated by high-temperature heating, and the film structure is not changed in the high-temperature baking. The traditional zinc oxide cluster compound is deteriorated in 60 days, the structure of the zinc oxide cluster compound is unchanged after the zinc oxide cluster compound is placed for 270 days under common conditions, and a film prepared from the photoresist composition has good solubility, film forming property, adhesion and thermal stability, is easy to store and stable in structure, and can meet the requirements of different types of photoetching technologies.
Drawings
FIG. 1A is a simulated theoretical value of TBA as a target compound; FIG. 1B shows the experimental values of TBA as a target compound
FIG. 2A, FIG. 2B, FIG. 2C, FIG. 2D are mass spectra of the product obtained in the repeated experiments of the background art work
FIG. 3A shows the calculation of the spatial structure optimization of the target compound TBA, and FIG. 3B shows the analysis of the x-ray single crystal structure of the target compound TBA
FIG. 4 shows TBA zinc oxygen cluster 1 H NMR spectrum
FIG. 5 shows TBA zinc oxygen cluster 13 C NMR spectrum
FIG. 6 shows TBA zinc-oxygen cluster 19 F NMR spectrum
FIG. 7 shows the calculation of the spatial structure optimization of the target compound BA
FIG. 8 shows a BA zinc oxygen cluster 1 HNMR spectrogram
FIG. 9 shows zinc oxygen cluster BA 13 C NMR spectrum
FIG. 10A is a high roughness film of TBA photoresist under AFM in comparative example two; FIG. 10C is a three-dimensional image
FIG. 10B is the TBA photoresist densified low roughness film under AFM in EXAMPLE III; FIG. 10D is a three-dimensional image
FIG. 11A is a high roughness film of TBA photoresist under AFM in comparative example three; FIG. 11B is a three-dimensional image
FIG. 12A is a thermogravimetric image referencing work in the background;
FIG. 12B is a thermogravimetric image of zinc-oxygen clusters prepared according to the present invention
FIG. 13A is an Atomic Force Microscope (AFM) image of a mechanical scratch measured film thickness of a negative photoresist of an example three; FIG. 13C is a three-dimensional image
FIG. 13B is a line profile of film thickness derived by software;
FIG. 14A is a graph showing the dose distribution of a square pattern obtained by electron beam exposure of a negative photoresist in example III;
FIG. 14B is a Scanning Electron Microscope (SEM) image of a square pattern of a negative photoresist of example three that was exposed to an electron beam;
FIG. 14C is an SEM image of the thickness of a square pattern of a negative photoresist in example III as a function of dose by electron beam exposure;
FIG. 14D is a Scanning Electron Microscope (SEM) image of a square pattern of a negative photoresist of example three obtained by electron beam exposure to an inappropriate developer
FIG. 15A is an Atomic Force Microscope (AFM) image of a square pattern obtained by electron beam exposure of a negative photoresist in example III;
FIG. 15B is a three-dimensional Atomic Force Microscope (AFM) image of a square pattern of negative photoresist obtained by electron beam exposure in EXAMPLE three
FIG. 16A is a Scanning Electron Microscope (SEM) image of a square and stripe pattern of a negative photoresist of example three as exposed by an electron beam;
FIG. 16B is a Scanning Electron Microscope (SEM) image of a 500nm stripe pattern of a negative photoresist in example three shown by E-beam exposure;
FIG. 16C is a Scanning Electron Microscope (SEM) image of a 300nm stripe pattern of a negative photoresist in example three of the invention obtained by electron beam exposure;
FIG. 16D Scanning Electron Microscopy (SEM) image of a 100nm stripe pattern of a negative tone photoresist of example three using electron beam exposure
FIG. 17A is a Fourier infrared spectrum of a negative photoresist molecule TBA and of a TBA film prepared by spin coating in example III after baking at high temperature
FIG. 17B is a Fourier infrared spectrum of a negative photoresist molecule TBA;
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example one
As shown in FIG. 1, compound I readily adds anions in the negative mode of ESI mode, and is represented by [ M + L ]] - Experimental value [ (CF) 3 C 6 H 4 COO) 6 OZn 4 +CF 3 C 6 H 4 COO] - =1600.7, theoretical 1600.8.
Comparative example 1
Mass spectrometry of the products obtained in repeated experiments on work in the background art is shown in FIG. 2, and mass spectrometry results are selectedAll structures consisting of 4 metals are illustrated, and the mass spectrometry results indicate that the compound is actually a mixture, represented by [ M + L [ ]] - The experimental value is as follows:
[(C 3 H 5 COO) 6 (O)Zn 4 +CF 3 COO] - =901.03, theoretical 901.03
[(C 3 H 5 COO) 5 (CF 3 COO)(O)Zn 4 +CF 3 COO] - =928.99, theoretical 928.96
[(C 3 H 5 COO) 4 (CF 3 COO) 2 (O)Zn 4 +CF 3 COO] - =956.97, theoretical 956.90
[(C 3 H 5 COO) 3 (CF 3 COO) 3 (O)Zn 4 +CF 3 COO] - =984.90, theoretical 984.83.
Example two
The prepared zinc-oxygen cluster structure I is subjected to simulated space optimization calculation as shown in a figure 3A, under the state of lowest and most stable energy, the chemical environments of six R are completely the same and are in a space-symmetrical octahedral structure, the X-ray single crystal structure is analyzed as shown in a figure 3B and is consistent with the figure 3A, and the distance between two symmetrical fluorine atoms is measured to be about 1.97nm by Diamond software.
Example two
And (3) testing the solubility: the prepared pure zinc-oxygen cluster is used for a comparative solubility experiment. In the conventional solvent, the former is dissolved in most organic solvents commonly used in laboratories, such as dichloromethane, methanol, ethanol, acetone, ethyl acetate and the like, and the solubility of the former is obviously superior to that of the latter. Both are not soluble in water, but both are preferably soluble in benzene solvents, such as toluene, xylene, chlorobenzene, and the like. In all examples and comparative examples, a relatively flat and uniform film was obtained by baking the process screen, preferably at 110 ℃ for 60 seconds, under the conditions used in the following examples and comparative examples.
EXAMPLE III
A negative photoresist formulation: pure zinc-oxygen cluster I (abbreviated as TBA) prepared according to the reference was dissolved in chlorobenzene to prepare a solution with a mass concentration of 40mg/ml, filtered with a microporous filter having a pore size of 0.4 μm to obtain a spin-on solution, subjected to spin-coating on a silicon substrate to prepare a film, and baked at 110 ℃ for 60 seconds. Basic characterization of the prepared zinc-oxygen cluster TBA:
FIG. 4: 1 H NMR(400MHz,Chloroform-d)δ8.35(d,J＝8.1Hz,12H),7.73(d,J＝ 8.2Hz,12H).
FIG. 5: 13 C NMR(126MHz,CDCl 3 )δ174.98,135.64,134.73(q,J＝32.5Hz)., 131.24,125.30,123.79(q,J＝272.1Hz).
FIG. 6: 19 F NMR(376MHz,CDCl 3 )δ-63.06.
elemental analysis: c: anal.40.82. Measureure 41.98, H: anal.1.71. Measurere 1.68, zn: anal.18.52. measureure 15.90.
Comparative example No. two
Representative comparative examples were selected by controlling the remaining variables constant in all failed experimental examples: a negative photoresist formulation: TBA prepared according to the reference was dissolved in L (-) -ethyl lactate to give a solution with a mass concentration of 40mg/ml, filtered through a millipore filter with a pore size of 0.4 μm to give a spin-on solution, spin-coated on a silicon substrate to form a film, and baked at 110 ℃ for 60s.
Comparative example No. three
For the prepared zinc-oxygen cluster structure II, a comparison molecule BA is selected as a comparison example by simulation space optimization calculation (shown in figure 7 (abbreviated as BA), because the solubility of BA is inferior to TBA, in order to obtain a film with lower roughness, the mass concentration is set to be 40mg/ml, and the formula of the negative photoresist comprises the following components: zinc oxide clusters (abbreviated as BA) prepared according to the reference were dissolved in chlorobenzene to prepare a solution having a mass concentration of 20mg/ml, filtered with a microporous filter having a pore size of 0.4 μm to obtain a spin-on solution, subjected to spin-coating on a silicon substrate to prepare a film, and baked at 110 ℃ for 60 seconds. Basic characterization of the prepared zinc-oxygen cluster BA:
FIG. 8: 1 H NMR(400MHz,Chloroform-d)δ8.24–8.19(m,12H),7.52(t,J＝7.4 Hz,6H),7.42(t,J＝7.6Hz,12H).
FIG. 9: 13 C NMR(101MHz,DMSO)δ171.84,134.75,130.99,129.57,127.94.
elemental analysis: c: anal.50.23. Measurere 50.52, H: anal.3.01. Measuree 2.82, zn: anal.26.04. Measureure 22.16.
Comparative example No. four
For all the above examples and comparative examples, in order to improve the uniformity of the film, the film quality was not improved by the roughness measured by AFM of the formulated photoresist added with 0.02 part by weight of vinyltrimethoxysilane, and certain additives, such as photoacid generator N-hydroxynaphthoylimide trifluoromethanesulfonic acid, had poor solubility, affected the film quality to some extent, and were added as needed. No additives were added and no treatment was performed on the wafers in all subsequent experiments.
Example four
In order to determine the quality of the spin-coated film, the film morphology was collected by AFM probe scanning in the range of 10 μm by 10 μm. Taking comparative example two as a representative failure example (comparative data), the high roughness film of TBA photoresist under AFM is as shown in fig. 10A, and fig. 10C is a three-dimensional image. Roughness R a ＝10.06nm， R q =17.06nm. Through a large number of failure case summaries which are not written in specific embodiments, the quality of the film is optimized finally by improving the spin coating process, adjusting the rotating speed, improving the baking temperature and replacing the solvent. The roughness is reduced from nanometer to picometer. Example three above resulted in a low roughness film under AFM that was very dense as shown in FIGS. 10B and 10D, where R is a ＝191.7pm，R q =245.8pm. In addition, although the BA structure also has a certain solubility, but the roughness of the BA photoresist does not achieve the effect of the TBA photoresist, the images of the thin film in comparative example three under AFM are shown in FIGS. 11A and 11B, in which the thickness is coarseRoughness R a ＝2.386nm， R q =2.993nm is higher than the roughness of the TBA photoresist shown in example three (fig. 10B). The third embodiment meets the film thickness requirement of the future advanced lithography technology and has very high-quality film properties.
EXAMPLE five
FIG. 12A is a thermogravimetric image incorporating work in the background art with ligand loss around 100 ℃ due to the product being a mixture and a portion of unreacted ligand suspended over the bulk structure; fig. 12B is a thermogravimetric image of a zinc-oxygen cluster prepared by the reference of the present invention, and no thermogravimetric effect is reported in the literature, wherein the weight loss residual amounts of TBA and BA are 23.27% and 30.35%, respectively, which indicates that zinc oxide or zinc hydroxide is generated after vaporization. The pure zinc oxide cluster is firstly found to have higher thermal decomposition temperature, the thermogravimetric images are similar, the thermal decomposition temperature is increased by 3 times, the higher temperature regulation performance is facilitated in the processes of pre-drying, post-drying and hard-drying, and the zinc oxide cluster compound serving as a main component in the film making process is not precipitated by high-temperature heating.
EXAMPLE six
Fig. 7 is a study of film thickness. FIG. 13A is a three-dimensional image of a spin-on resist wafer scratched with a utility knife in a low roughness thin film prepared in example III (FIG. 13C), and the thickness of the film is measured by AFM probe scanning. FIG. 13B shows the measurement of the film thickness, which was 56.0nm.
EXAMPLE seven
FIG. 14 shows the exposure results of the exposure experiment of the photoresist prepared in example three on an electron beam exposure machine, which is used for the sensitivity measurement experiment. Scanning Electron Microscope (SEM) images of the photoresist at different doses in fig. 14A are shown in fig. 14B and 14D. The developing conditions include the kind, formulation, developing time, baking time and temperature of the developer, etc., under inappropriate developing conditions, such as in MIBK: IPA =1: the contrast pattern obtained by developing at 3 ℃ for 30 seconds is shown in FIG. 14D, and the result shows that well-developed square patterns are not obtained, and thus the method cannot be applied to sensitivity measurement experiments. Finally, the developing conditions are determined to be n-hexane developing for 30s, ultrapure water fixing for 2s, drying at 150 ℃ after nitrogen dryingBaking for 30s. FIG. 14B is a Scanning Electron Microscope (SEM) image of an exposure result of a sensitivity experiment of the Zn-TBA photoresist by an electron beam exposure machine under the optimal development condition, the relationship of the film thickness after AFM probe type scanning and the change of the dose is shown in FIG. 14C, and the result shows that the optimal dose of the prepared photoresist film is 550 μ C/cm 2 。
Example eight
FIG. 15 is a partial image of a photoresist processed by photolithography to obtain a pattern of 10 μm, and FIG. 15B is a three-dimensional image of FIG. 15A. The film thickness can be characterized by the negative film after development by exposure, and the AFM probe scan result is about 54nm, which is basically consistent with the value measured by six scratch failures in the example.
Example nine
FIG. 16 shows the exposure results of the exposure experiment performed on the E-beam exposure machine for the film prepared in example III at the optimum dose of example 16, and the developing conditions are as follows: n-hexane solution for 30s, fixing with ultrapure water for 2s, blowing with nitrogen for 2s, and baking at 90 deg.C for 30s. Wherein fig. 16A is a 10 μm square, 5 100nm lines, 5 300nm lines, 5 500nm lines, and 5 duty ratio L: s =1:2. FIGS. 16B-16D illustrate that the lines develop well, a lithographic pattern with a maximum fringe width of 100nm and a period of 300nm can be obtained, and that the prepared photoresist has high-resolution imaging capability. In view of the excellent physicochemical property of the zinc-oxygen cluster used in the invention, the photoetching effect is expected to be further explored and verified.
Comparative example seven
Repeated exposure experiments on the zinc-oxygen clusters in the background art show that the dosage required by each exposure is different, which shows that the batch stability of the zinc-oxygen clusters synthesized by each time is poor, so that the same number of products contain different numbers of reactive groups, and the light dosage required by the synthesized products of each batch is different, therefore, the proportion of the mixture generated by each reaction is random. The zinc-oxygen cluster is accurately weighed to be pure and prepared into gel, and the exposure dose used each time has good repeatability.
Example ten
FIG. 17A illustrates elevated temperature at 150 deg.CThe film structure is unchanged after baking for 5 min. FIG. 17B is a Fourier infrared spectrum of a pure TBA sample placed in a sealed glass bottle under natural conditions for six months and nine months, zn-O-Zn stretching vibration is near 516s, 711 m-869 m are mainly C-H out-of-plane bending vibration replacing benzene rings, 1020 m-1168 m are C-H in-plane bending vibration of the benzene rings and stretching vibration of C-O, C-F bonds, 1326s and 1430s are C-F strong stretching vibration, and 1517 m-1619 s are C = C stretching vibration of the benzene ring skeleton. 3000cm -1 The gray area marked nearby has no typical-OH broad peak of carboxyl, which indicates no decarboxylation, and 3500cm -1 The peak type of the zinc oxide cluster compound is a typical water peak, the water peak signal is gradually enhanced along with the increase of the standing time, the wave number of other characteristic peaks has no obvious displacement and no obvious change of the signal, the photoresist molecule has good storage stability, the traditional zinc oxide cluster compound is deteriorated in 60 days, the structure of the zinc oxide cluster compound used in the invention is not changed after the zinc oxide cluster compound is placed for 270 days under the common condition, and the zinc oxide cluster compound is improved by 3 times compared with the traditional zinc oxide cluster which is unstable in storage.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (11)
1. The application of the zinc oxide cluster compound in the field of photoresist is characterized in that: the structural general formula of the zinc oxide cluster compound is shown as A:
wherein: r is selected from one of the following substituents:
2. use according to claim 1, characterized in that: the application comprises the step of directly using the zinc oxide cluster compound I or II with the structural general formula shown as A as the only component as the photoresist
3. Use according to claim 1, characterized in that: the applications include as photoresist compositions.
4. Use according to claim 1, characterized in that: the application comprises a photoresist composition prepared by using the zinc oxide cluster compound with the structural formula shown as I or II, wherein the composition comprises the following components in parts by weight:
1-15 parts by weight of zinc oxide cluster compound with a structural formula shown as I or II;
85 to 99 parts by weight of an organic solvent;
0 to 0.05 weight portion of flatting agent;
0 to 0.05 weight portion of dispersant;
0 to 0.05 weight portion of tackifier;
0 to 0.1 weight portion of other additives;
the organic solvent comprises one of esters, alcohols, ethers, cyclic ethers, benzenes, carboxylic acids and alkanes;
the further additives are selected from photoinitiators and/or free radical quenchers.
5. Use according to claim 4, characterized in that: the organic solvent comprises tetrahydrofuran, 1,4-dioxane, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, chlorobenzene, fluorobenzene, propylene glycol monomethyl ether acetate, propylene glycol diethyl ether, propylene glycol monoacetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, chloroform and a mixture of one or more of dichloromethane, methanol, ethanol and 1,2 dichloroethane.
6. Use according to claim 1, characterized in that: the application comprises applying a film-forming photoresist coating on a substrate by using the zinc oxide cluster compound or the photoresist composition with the structural formula shown in I or II.
7. Use according to claim 6, characterized in that: the application comprises a method for optimizing a zinc-oxygen cluster photoresist coating, and the method comprises the following steps: the film forming characteristics are adjusted by adjusting parameters of solid content, glue preparation solvent, glue homogenizing time, glue homogenizing rotating speed, baking temperature and time, and the zinc-oxygen cluster film is obtained.
8. Use according to claim 7, characterized in that: the application is that the data of the zinc-oxygen cluster film is obtained by probe type scanning measurement of an atomic force microscope, the roughness behavior of the film is evaluated by Ra and Rq, and the prepared film R a And R q The roughness Ra and the Rq of the film with better quality are both below 0.3nm and are controlled below 0.3 nm;
R a -the arithmetic mean of the absolute values of the height deviations measured with respect to the central plane, nm, in the area of the sampling zone;
R q -the root mean square value of the profile deviation from the mean line, which is the root mean square parameter corresponding to Ra, nm, over the sampling area;
l-sample length, nm;
Z j -calculating R a Time-sampled height, nm;
Z i -calculating R q Sampling height in time, nm.
9. Use according to claim 6, characterized in that: the applications include the use of the photoresist coating in film science or photolithography.
10. Use according to claim 6, characterized in that: the applications include use of the photoresist coating for 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography, or electron beam lithography.
11. Use according to claim 6, characterized in that: the application comprises an electron beam lithography method, which is characterized in that: spin coating, soft baking, exposing, post baking, developing, hard baking the photoresist coating of claim 4; the glue homogenizing process comprises the following steps: the speed is 500rpm to 5000rpm, the time is 10s to 300s, the soft drying temperature is 60 ℃ to 160 ℃, and the time is 10s to 300s; the developing time is 10 s-300 s.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304521A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院化学研究所 | Molecular glass photoresist of taking tetraphenyl furan, tetraphenyl pyrrole, tetraphenylthiophene and quinary phenylpyridine as cores |
| CN104145217A (en) * | 2012-02-27 | 2014-11-12 | 国际商业机器公司 | Metal peroxo compounds with organic co-ligands for electron beam, deep uv and extreme uv photoresist applications |
| CN105463564A (en) * | 2015-11-30 | 2016-04-06 | 东南大学 | ZnO nanorod and ZnO cluster composite structure and preparation method thereof |
| CN110443345A (en) * | 2019-07-31 | 2019-11-12 | 华中科技大学 | A method of regulation nano molecular neural network electric pulse provides behavior |
| CN111948904A (en) * | 2020-08-13 | 2020-11-17 | 清华大学 | Photoresist composition, method for forming photolithographic pattern using the same, and use thereof |
| CN113004291A (en) * | 2019-12-20 | 2021-06-22 | 中国科学院化学研究所 | Metalloporphyrin-based molecular glass chemical amplification photoresist and preparation method and application thereof |
-
2022
- 2022-07-18 CN CN202210843159.4A patent/CN115407607B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104145217A (en) * | 2012-02-27 | 2014-11-12 | 国际商业机器公司 | Metal peroxo compounds with organic co-ligands for electron beam, deep uv and extreme uv photoresist applications |
| CN103304521A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院化学研究所 | Molecular glass photoresist of taking tetraphenyl furan, tetraphenyl pyrrole, tetraphenylthiophene and quinary phenylpyridine as cores |
| CN105463564A (en) * | 2015-11-30 | 2016-04-06 | 东南大学 | ZnO nanorod and ZnO cluster composite structure and preparation method thereof |
| CN110443345A (en) * | 2019-07-31 | 2019-11-12 | 华中科技大学 | A method of regulation nano molecular neural network electric pulse provides behavior |
| CN113004291A (en) * | 2019-12-20 | 2021-06-22 | 中国科学院化学研究所 | Metalloporphyrin-based molecular glass chemical amplification photoresist and preparation method and application thereof |
| CN111948904A (en) * | 2020-08-13 | 2020-11-17 | 清华大学 | Photoresist composition, method for forming photolithographic pattern using the same, and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| KOU YANG ET AL: "Radical sensitive Zinc-based nanoparticle EUV photoresists", SPIE ADVANCED LITHOGRAPHY, 25 March 2019 (2019-03-25) * |
| ROBERTO FALLICA ET AL: "Absorption coefficient of metal-containing photoresists in the extreme ultraviolet", JOURNAL OF MICRO/NANOLITHOGRAPHY, MEMS, AND MOEMS, vol. 17, no. 2, 30 June 2018 (2018-06-30) * |
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