TWI500751B - Surface treatment agent and surface treatment methods - Google Patents
Surface treatment agent and surface treatment methods Download PDFInfo
- Publication number
- TWI500751B TWI500751B TW099138664A TW99138664A TWI500751B TW I500751 B TWI500751 B TW I500751B TW 099138664 A TW099138664 A TW 099138664A TW 99138664 A TW99138664 A TW 99138664A TW I500751 B TWI500751 B TW I500751B
- Authority
- TW
- Taiwan
- Prior art keywords
- substrate
- surface treatment
- treatment agent
- cyclic
- compound
- Prior art date
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- 239000012756 surface treatment agent Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 22
- 238000004381 surface treatment Methods 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims description 85
- -1 cyclic triazane compound Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 125000004122 cyclic group Chemical group 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 229910000062 azane Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229940100198 alkylating agent Drugs 0.000 description 5
- 239000002168 alkylating agent Substances 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 229960004042 diazoxide Drugs 0.000 description 4
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HPCIXPCAAKYXOL-UHFFFAOYSA-N CN(C)C(C(C)(C)C)CCCCCCCC Chemical compound CN(C)C(C(C)(C)C)CCCCCCCC HPCIXPCAAKYXOL-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 2
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
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- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 229960002050 hydrofluoric acid Drugs 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- IFZHGQSUNAKKSN-UHFFFAOYSA-N 1,1-diethylhydrazine Chemical compound CCN(N)CC IFZHGQSUNAKKSN-UHFFFAOYSA-N 0.000 description 1
- KDTWXGUXWNBYGS-UHFFFAOYSA-N 1,2,3,3,4,4-hexamethyl-5H-diazepine Chemical compound CC1(C(N(N(C=CC1)C)C)(C)C)C KDTWXGUXWNBYGS-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- AZLXQBNSOMJQEJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)imidazolidin-2-one Chemical compound CC(C)N1CCN(C(C)C)C1=O AZLXQBNSOMJQEJ-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- PJEXUIKBGBSHBS-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrolidin-2-one Chemical compound OCN1CCCC1=O PJEXUIKBGBSHBS-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- ODZYMSKQIROSOC-UHFFFAOYSA-N 1h-imidazole-4,5-dione Chemical compound O=C1NC=NC1=O ODZYMSKQIROSOC-UHFFFAOYSA-N 0.000 description 1
- VCLJODPNBNEBKW-UHFFFAOYSA-N 2,2,4,4,6,8,8-heptamethylnonane Chemical compound CC(C)(C)CC(C)CC(C)(C)CC(C)(C)C VCLJODPNBNEBKW-UHFFFAOYSA-N 0.000 description 1
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
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- KXVSZAQJBQHRHE-UHFFFAOYSA-N 2-[1-(2-hydroxyethyl)-9h-fluoren-2-yl]ethanol Chemical compound C1=CC=C2C3=CC=C(CCO)C(CCO)=C3CC2=C1 KXVSZAQJBQHRHE-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- IEAJQNJSHYCMEK-UHFFFAOYSA-N 5-methoxy-2,5-dimethylhexanoic acid Chemical compound COC(C)(C)CCC(C)C(O)=O IEAJQNJSHYCMEK-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
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- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- FJAKCEHATXBFJT-UHFFFAOYSA-N ethyl 2-oxobutanoate Chemical compound CCOC(=O)C(=O)CC FJAKCEHATXBFJT-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
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- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 150000002628 limonene derivativess Chemical class 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- GOQRKXBLBLOWLQ-UHFFFAOYSA-N methyl 2-acetyloxyacetate Chemical compound COC(=O)COC(C)=O GOQRKXBLBLOWLQ-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/265—Selective reaction with inorganic or organometallic reagents after image-wise exposure, e.g. silylation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
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Description
本發明係關於一種可使用於基板表面之疏水化處理的表面處理劑及使用其之表面處理方法。
在半導體裝置等之製造中係於基板形成無機圖型時使用光微影蝕刻技術。此光微影蝕刻技術係使用感光性樹脂組成物而於基板上設有感光性樹脂層,然後,再選擇性照射(曝光)活性輻射線,進行顯像處理以於基板上形成樹脂圖型(光阻圖型)。繼而,以其樹脂圖型作為掩罩而蝕刻基板俾形成無機圖型。
近年,半導體裝置之高積體化、微細化之傾向提高,無機圖型之微細化、高長寬比化正進展。但,其一者,產生所謂圖型傾倒之問題。此圖型傾倒係於基板上排列多數之無機圖型而形成時,相鄰之圖型間亦互相傾倒接近,視情形係圖型從基部折損的現象。若產生如此之圖型傾倒,無法得到所希望的製品,故引起製品之良率或信賴性之降低。
可知此圖型傾倒係在圖型形成後之清洗處理中,乾燥清洗液時,受其清洗液之表面張力所產生。亦即,在乾燥過程除去清洗液時,於圖型間發揮清洗液之表面張力的應力作用,產生圖型傾倒。
因此,至今,常於清洗液中添加降低表面張力之物質(異丙醇、氟系界面活性劑等),防止圖型傾倒之嘗試(例如參照專利文獻1、2),但在如此之清洗液的努力中圖型傾倒的防止係不充分。
[先前技術文獻]
[專利文獻]
[專利文獻1]特開平6-163391號公報
[專利文獻2]特開平7-142349號公報
[專利文獻3]特表平11-511900號公報
與圖型傾倒相異,但為提昇成為掩罩之樹脂圖型與基板表面之密著性,而防止以顯像液造成的樹脂圖型之一部分損失,於基板設有感光性樹脂層之前,對於基板表面進行使用六甲基二矽氮烷(HMDS)等之甲矽烷基化劑的疏水化處理(甲基烷基化處理)(參照例如專利文獻3之「發明的背景」)。
本發明人等係認為若藉甲矽烷基化劑使無機圖型之表面疏水化,是否在清洗處理後之乾燥過程於圖型間作用的應力降低,可防止圖型傾倒,使用HMDS、N,N-二甲基胺基三甲基矽烷(DMATMS)等之一些甲矽烷基化劑而對各種之基板嘗試疏水化處理。但,基板表面之材質為Si時,可高度地疏水化,但基板表面之材質為TiN時或SiN時,即使藉由任一者的甲矽烷基化劑,疏水化之程度亦不充分。
本發明係有鑑於如此之習知實情而成者,目的在於提供一種基板表面之材質為TiN或SiN時,可高度地疏水化之表面處理劑、及使用其表面處理劑之表面處理方法。
本發明人等係為解決上述課題,累積專心研究。其結果,發現藉由於表面處理劑使用環狀矽氮烷化合物,可解決上述課題,終完成本發明。具體上係本發明提供以下者。
本發明之第一態樣係可使用於基板表面之疏水化處理,且含有環狀矽氮烷化合物之表面處理劑。
本發明之第二態樣係於基板表面使本發明之表面處理劑曝露,使上述基板表面疏水化之表面處理方法。
若依本發明,即使基板表面之材質為TiN或SiN時,亦可使基板表面高度地疏水化。
首先,說明有關本發明之表面處理劑。本發明之表面處理劑係可適宜使用於使基板表面疏水化之時。此處,「基板」係可舉例如用以製造半導體裝置所使用的基板。又,「基板表面」係可舉例如基板本身之表面外,設於基板上之無機圖型的表面、或未被圖型化之無機層的表面等。
設於基板上之無機圖型係可舉例如於存在於基板之無機層的表面使用光微影蝕刻技術而形成樹脂圖型(光阻圖型),以其樹脂圖型作為掩罩而於無機層實施蝕刻處理所製作之圖型。無機層係基板本身之外,可舉例如形成於基板表面之無機物的膜等。
尤其,本發明之表面處理劑係適宜使用於基板表面之材質為TiN或SiN之情形。以往,在基板表面之疏水化被使用起來之六甲基二矽氮烷(HMDS)等的甲矽烷基化劑中,基板表面之材質為TiN或SiN之時係疏水化之程度不充分,但若依本發明之表面處理劑,表面之材質為TiN或SiN之時可使基板表面高度地疏水化。
本發明之表面處理劑係藉由加熱或起泡等之方法而氣化後,可使已氣化之表面處理劑接觸於基板的表面而進行表面處理所使用,亦可藉旋塗法或浸漬法等之手段而液體直接塗佈於基板之表面以進行表面處理所使用。
本發明之表面處理劑係含有環狀矽氮烷化合物作為甲矽烷基化劑。以下,詳細說明有關表面處理劑所含有的成分。
本發明之表面處理劑係含有環狀矽氮烷化合物作為甲矽烷基化劑。此環狀矽氮烷化合物係使基板表面甲矽烷基化,用以提高基板表面之疏水性的成分。
此環狀矽氮烷化合物係可舉例如2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷、2,2,6,6-四甲基-2,6-二矽-1-氮雜環己烷等的環狀二矽氮烷化合物;2,2,4,4,6,6-六甲基環三矽氮烷、2,4,6-三甲基-2,4,6-三乙烯基環三矽氮烷等的環狀三矽氮烷化合物;2,2,4,4,6,6,8,8-八甲基環四矽氮烷等的環狀四矽氮烷化合物等。
其中,基板表面之材質為TiN時,宜為環狀二矽氮烷化合物,尤其宜為2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷及2,2,6,6-四甲基-2,6-二矽-1-氮雜環己烷之至少一種。環狀二矽氮烷化合物係具有2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷之5員環構造者,或2,2,6,6-四甲基-2,6-二矽-1-氮雜環己烷的6員環構造者,更宜為5員環構造。
另外,基板表面之材質為SiN時,係宜為稀釋於後述之有機溶劑的環狀二矽氮烷化合物、或環狀三矽氮烷化合物。稀釋於有機溶劑的環狀二矽氮烷化合物尤宜為2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷及2,2,6,6-四甲基-2,6-二矽-1-氮雜環己烷之至少一種。又環狀三矽氮烷化合物尤宜為2,2,4,4,6,6-六甲基環三矽氮烷及2,4,6-三甲基-2,4,6-三乙烯基環三矽氮烷之至少一種。
此等之環狀矽氮烷化合物係可單體或組合2種以上而使用。
本發明之表面處理劑係亦可進一步含有有機溶劑。藉由以有機溶劑稀釋環狀矽氮烷化合物,俾可提昇對於基板表面之塗佈作業性、操作性、與清洗液之取代性等。又,基板表面之材質為SiN時係藉由使環狀二矽氮烷化合物稀釋於有機溶劑,可提高疏水化之程度。
此有機溶劑係不與上述環狀矽氮烷化合物反應,而可溶解上述環狀矽氮烷化合物,且若為對於基板表面的損傷少者,無特別限定而可使用以往公知之有機溶劑。
具體上,可舉例如二甲基亞碸等之亞碸類;二甲基碸、二乙基碸、雙(2-羥乙基)碸、四亞甲基碸等之碸類;N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等之醯胺類;N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、N-羥甲基-2-吡咯烷酮、N-羥乙基-2-吡咯烷酮等之內醯胺類;1,3-二甲基-2-咪唑啉二酮、1,3-二乙基-2-咪唑啉二酮、1,3-二異丙基-2-咪唑啉二酮等之咪唑啉二酮類;乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、三丙二醇單甲基醚、乙二醇二甲基醚、乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、三乙二醇二甲基醚等之(聚)烯烴二醇烷基醚類;乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等之(聚)烯烴二醇烷基醚乙酸酯類;四氫呋喃等之其他醚類;甲乙酮、環己酮、2-庚酮、3-庚酮等之酮類;2-羥基丙酸甲酯、2-羥基丙酸乙酯等之乳酸烷酯類;3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基醋酸乙酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、蟻酸正戊酯、醋酸異戊酯、丙酸正丁酯、酪酸乙酯、酪酸正丙酯、酪酸異丙酯、酪酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯基醋酸甲酯、乙醯基醋酸乙酯、2-氧丁酸乙酯等之其他酯類;β-丙內酯、γ-丁內酯、δ-戊內酯等之內酯類;正己烷、正庚烷、正辛烷、正壬烷、甲基辛烷、正癸烷、正十一碳烷、正十二碳烷、2,2,4,6,6-五甲基庚烷、2,2,4,4,6,8,8-七甲基壬烷、環己烷、甲基環己烷等之直鏈狀、分枝鏈狀、或環狀之烴類;苯、甲苯、萘、1,3,5-三甲基苯等之芳香族烴類;對薄荷烷、二苯基薄荷烷、檸檬烯、商品烯、茨烷、降冰片烷、蒎烷等之萜烯類。此等之有機溶劑係可單獨或混合2種以上而使用。
以有機溶劑稀釋環狀矽氮烷化合物時,環狀矽氮烷化合物之濃度係表面處理劑中,宜為0.1~99.9質量%,更宜為1~50質量%,最宜為1~30質量%,尤宜為3~20質量%。藉由形成上述範圍,保持表面處理之效果上,可提昇對於基板表面之塗佈作業性、操作性、與清洗液之取代性等。又,使用環狀三矽氮烷化合物作為環狀矽氮烷化合物時係較使用環狀二矽氮烷化合物時一般更宜形成高濃度。
以有機溶劑稀釋環狀矽氮烷化合物之時機,並無特別限定。例如,亦可預先以有機溶劑稀釋環狀矽氮烷化合物之狀態進行保管,使用表面處理劑而處理基板表面之前,亦可以有機溶劑稀釋環狀矽氮烷化合物。
繼而,說明有關本發明之表面處理方法。本發明之表面處理方法係於基板表面曝露本發明之表面處理劑,處理其基板之表面者。
本發明之表面處理方法係使基板表面疏水化者,其處理之目的可為任一者,但其處理之目的的代表例,可舉例如(1)使基板表面疏水化,提昇對於樹脂圖型等的密著性,(2)在清洗後之乾燥過程中,防止基板表面之無機圖型的圖型傾倒。
以上述(1)為目的時,例如於基板表面的形成感光性樹脂層之前,只要對於基板表面使本發明之表面處理劑曝露即可。於基板表面使本發明之表面處理劑曝露之方法係無特別限制,可使用以往公知的方法。例如,使本發明之表面處理劑氣化而形成蒸氣,使其蒸氣接觸於基板表面之方法,使本發明之表面處理劑藉旋塗法或浸漬法等接觸於基板表面之方法等。藉由如此之操作,基板表面之疏水性會提高,故對於感光性樹脂層等之密著性提高。
以上述(2)為目的時,進行形成無機圖型後之清洗處理後的乾燥之前,只要對於基板表面使本發明之表面處理劑曝露即可。
藉由實施如此之表面處理,而說明有關可防止清洗後之乾燥過程中的基板表面之無機圖型的圖型傾倒之理由。
於基板表面形成無機圖型時,例如進行乾式蝕刻、濕式蝕刻。以乾式蝕刻形成圖型係藉鹵素系氣體等進行乾式蝕刻,繼而,以SC-1(氨/過氧化氫水)、SC-2(鹽酸/過氧化氫水)等洗淨微粒或金屬雜質等的蝕刻殘渣。然後,以水或異丙醇等之清洗液進行清洗後,使無機圖型的表面藉自然乾燥或旋乾等進行乾燥。另外,以濕式蝕刻形成圖型中係藉DHF(稀氟酸)、BHF(氟酸、氟化氨)、SPM(硫酸/過氧化氫水)、APM(氨、過氧化氫水)等進行濕式蝕刻,以水或異丙醇等之清洗液進行的清洗後,使無機圖型的表面藉自然乾燥或旋乾等進行乾燥。
又,乾燥處理係例如以專利第3866130號公報的段落[0030]以後記載的方法亦無妨。
在本發明之表面處理方法中係於乾燥如此之無機圖型之前,使無機圖型表面以本發明之表面處理劑進行處理而疏水化。
此處,以清洗後之乾燥過程中於無機圖型之圖型間作用之力F,係如以下之式(I)表示。但,γ表示清洗液之表面張力,θ表示清洗液之接觸角,A表示無機圖型之長寬比,D表示無機圖型側壁間的距離。
F=2γ‧cosθ‧A/D…(I)
因此,若可使無機圖型之表面疏水化,提高清洗液之接觸角(減少cosθ),可降低以清洗後之乾燥過程中於無機圖型間作用之力,可防止圖型傾倒。
此表面處理係使形成無機圖型之基板浸漬於表面處理劑中,或使表面處理劑塗佈或吹向無機圖型而進行。處理時間係宜為10秒鐘~60分鐘。又,此表面處理後係宜在無機圖型表面中之水的接觸角成為60~120度,更宜為75~105度,最宜為80~100度。
以下,藉實施例更具體地說明本發明,但本發明係不限定於以下之實施例。
使表面之材質為TiN之基板以0.1%氟化氫水溶液洗淨3分鐘後,於2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷(TDACP)、六甲基二矽氮烷(HMDS)、或N,N-二甲基胺基三甲基矽烷(DMATMS)在室溫下浸漬30秒。繼而,使基板表面以甲乙酮清洗,藉氮氣流乾燥。其後,使用Dropmaster 700(協和界面科學股份公司製),於基板表面滴下純水液滴(1.8μL),測定滴下10秒後之接觸角。結果表示於表1中。又,表1中,就「TiN對照」而記載之接觸角係在未實施表面處理之基板表面的接觸角之數值。
使表面之材質為SiN之基板以0.1%氟化氫水溶液洗淨3分鐘後,於2,2,4,4,6,6-六甲基環三矽氮烷(HMCTS)、六甲基二矽氮烷(HMDS)、或N,N-二甲基胺基三甲基矽烷(DMATMS)在室溫下浸漬30秒。繼而,使基板表面以甲乙酮清洗,藉氮氣流乾燥。其後,使用Dropmaster 700(協和界面科學股份公司製),於基板表面滴下純水液滴(1.8μL),測定滴下10秒後之接觸角。結果表示於表1中。又,表1中,就「SiN對照」而記載之接觸角係在未實施表面處理之基板表面的接觸角之數值。
除使用表面之材質為Si的基板外,其餘係與上述相同做法而測定基板表面的接觸角。結果表示於表1中。又,表1中,就「Si對照」而記載之接觸角係在未實施表面處理之基板表面的接觸角之數值。
從表1可知,在使用環狀矽氮烷化合物之TDACP作為表面處理劑的實施例1中係基板表面之材質為TiN時,亦可實現所謂83度之高接觸角。另外,使用HMDS作為表面處理劑之比較例1中係接觸角為69度,使用DMATMS作為表面處理劑的比較例2中係接觸角為59度,任一者均較實施例1還更差。
又,在使用環狀矽氮烷化合物之HMCTS作為表面處理劑的實施例2中係基板表面之材質為SiN時,亦可實現所謂85度之高接觸角。另外,使用HMDS作為表面處理劑之比較例3中係接觸角為53度,使用DMATMS作為表面處理劑的比較例4中係接觸角為65度,任一者均較實施例2還更差。
基板表面之材質為Si時,係藉由任一者之表面處理劑均可實現79度以上之高接觸角。
使表面之材質為Si、SiN、或TiN之基板以0.1%氟化氫水溶液洗淨3分鐘後,以異丙醇進一步洗淨。其後,使2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷(TDACP)、2,2,4,4,6,6-六甲基環三矽氮烷(HMCTS)、六甲基二矽氮烷(HMDS)、或N,N-二甲基胺基三甲基矽烷(DMATMS)適當稀釋於有機溶劑的表面處理劑中以室溫浸漬30秒。繼而,使基板表面以異丙醇、繼而以水進行洗淨,藉氮氣流乾燥。其後,使用Dropmaster 700(協和界面科學股份公司製),於基板表面滴下純水液滴(1.8μL),測定滴下10秒後之接觸角。結果表示於表2中。
從表2可知,使用將環狀矽氮烷化合物之TDACP或HMCTS稀釋於有機溶劑之表面處理劑的實施例4~17中係基板表面的材質為SiN或TiN時,亦可使基板表面高度地疏水化。尤其,比較實施例3與實施例4~16可知,使環狀二矽氮烷化合物之TDACP稀釋於有機溶劑時,係較不稀釋於有機溶劑時更可高度地使SiN之基板表面疏水化。
另外,在使用將HMDS或DMATMS稀釋於有機溶劑之表面處理劑的比較例6~11中係基板表面之材質為Si時,可高度地疏水化,但基板表面的材質為SiN或TiN時,疏水化之程度不充分。又,比較比較例5與比較例6、7而可知,即使HMDS稀釋於有機溶劑,亦未提高對於SiN之基板表面的疏水化之程度。
Claims (5)
- 一種表面處理劑,其係可使用於TiN或SiN之疏水化處理,且含有環狀矽氮烷化合物。
- 如申請專利範圍第1項之表面處理劑,其中前述環狀矽氮烷化合物為環狀二矽氮烷化合物或環狀三矽氮烷化合物。
- 如申請專利範圍第2項之表面處理劑,其中前述環狀二矽氮烷化合物為2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷及2,2,6,6-四甲基-2,6-二矽-1-氮雜環己烷的至少一種。
- 如申請專利範圍第2項之表面處理劑,其中前述環狀三矽氮烷化合物為2,2,4,4,6,6-六甲基環三矽氮烷及2,4,6-三甲基-2,4,6-三乙烯基環三矽氮烷的至少一種。
- 一種表面處理方法,係於基板表面使如申請專利範圍第1~4項中任一項之表面處理劑曝露,使前述基板表面疏水化之表面處理方法,其中前述基板表面之材質為TiN或SiN。
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