TWI567085B - 矽烷化合物及使用其之單分子層或多分子層形成用組成物 - Google Patents
矽烷化合物及使用其之單分子層或多分子層形成用組成物 Download PDFInfo
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- TWI567085B TWI567085B TW101105632A TW101105632A TWI567085B TW I567085 B TWI567085 B TW I567085B TW 101105632 A TW101105632 A TW 101105632A TW 101105632 A TW101105632 A TW 101105632A TW I567085 B TWI567085 B TW I567085B
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- -1 Silane compound Chemical class 0.000 title claims description 31
- 239000011254 layer-forming composition Substances 0.000 title claims 2
- 150000001875 compounds Chemical class 0.000 title description 6
- 229910000077 silane Inorganic materials 0.000 title 1
- 229920002120 photoresistant polymer Polymers 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 26
- 239000002052 molecular layer Substances 0.000 claims description 23
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 18
- 239000004065 semiconductor Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000004060 quinone imines Chemical group 0.000 claims description 3
- 125000004151 quinonyl group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005544 phthalimido group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 239000010408 film Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VHCSBTPOPKFYIU-UHFFFAOYSA-N 2-chloroethanesulfonyl chloride Chemical compound ClCCS(Cl)(=O)=O VHCSBTPOPKFYIU-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
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- 239000012043 crude product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000001914 filtration Methods 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
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001587 sorbitan monostearate Substances 0.000 description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 description 2
- 229940035048 sorbitan monostearate Drugs 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- WELKBINNNXKQQS-UHFFFAOYSA-N 1,4-benzoquinone imine Chemical group N=C1C=CC(=O)C=C1 WELKBINNNXKQQS-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
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- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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- HMWGIKRPUHMXKA-UHFFFAOYSA-N C(C)OC(CCCCCCCCCCCCN1C=NCC1)(OCC)OCC Chemical compound C(C)OC(CCCCCCCCCCCCN1C=NCC1)(OCC)OCC HMWGIKRPUHMXKA-UHFFFAOYSA-N 0.000 description 1
- CSVRRPIOLNZVNK-UHFFFAOYSA-N C(CCCCCCCCC)C(C(OCC)(OCC)OCC)(CCCCCCCC)CCC Chemical compound C(CCCCCCCCC)C(C(OCC)(OCC)OCC)(CCCCCCCC)CCC CSVRRPIOLNZVNK-UHFFFAOYSA-N 0.000 description 1
- JSGRIFNBTXDZQU-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC JSGRIFNBTXDZQU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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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- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
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- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
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- ALVGSDOIXRPZFH-UHFFFAOYSA-N [(1-diazonioimino-3,4-dioxonaphthalen-2-ylidene)hydrazinylidene]azanide Chemical compound C1=CC=C2C(=N[N+]#N)C(=NN=[N-])C(=O)C(=O)C2=C1 ALVGSDOIXRPZFH-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
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- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
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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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- G—PHYSICS
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
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- 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
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- G—PHYSICS
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- 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
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Description
本發明關於塗佈在基板表面，將單分子層或多分子層形成在光阻下層用之組成物。特別地，關於在階差(凹凸)表面上形成單分子層或多分子層用之組成物。
電場效果電晶體等半導體元件之製造中的離子注入步驟，有採用以光阻圖型為遮罩，在半導體基板中導入賦予n型或p型導電型的雜質離子之步驟的情況。於許多的情況下，該半導體基板係藉由使用多晶矽、鋁、氮化鈦等的半導體材料或金屬材料來形成閘電極及閘配線，而具有階差或凹凸表面。於該階差(凹凸)表面上形成光阻圖型的步驟中，由於光阻膜係部分地厚形成，故形成均勻膜厚者係困難。因此，對於上述光阻膜，即使經過曝光、顯像及沖洗，厚形成的部分也無法完全去除而容易殘留。結果，光阻圖型的底部形狀容易變成下端拖尾形狀，有發生殘渣的問題。
另一方面，以HMDS(六亞甲基二矽氮烷)處理半導體基板之代表例的矽晶圓之表面，使該表面成為疏水性(撥水性)的方法係以往已知。矽晶圓表面若形成自然氧化膜，則顯示親水性。於該親水性的表面上，塗佈光阻溶液，進行預烘烤而形成的光阻膜，係與矽晶圓的密接性差。
基板表面的疏水性及親水性係可藉由水的接觸角來評
價。專利文獻1中記載一種光分解性偶合劑，其在光照射的前後大幅改變接觸角，光照射前具有撥液性能，經光照射時藉由具有撥液性能的基之解離而產生具有親水性能的取代基。專利文獻2中記載一種形成有機薄膜的化合物，其為了使圖型形成步驟成為簡潔且高可靠性，可藉由光照射選擇地轉換表面物性。
專利文獻1：特開2008-050321號公報
專利文獻2：特開2006-070026號公報
本發明提供新穎的組成物，其即使在具有階差的基板表面上，也可形成沒有底部形狀為下端拖尾形狀或鄰接的圖型為在底部相連的形狀之所欲的光阻圖型，其使用於形成該光阻圖型用的基板之表面處理，用於在該基板上形成單分子層或多分子層。再者，本發明提供該組成物所用的新穎矽烷化合物。
發現藉由使用本發明的組成物在基板上形成單分子層或多分子層，在其上形成光阻圖型，而可調整該光阻圖型
的底部形狀。即，本發明的第1態樣係一種下述式(1A)或下述式(1B)所示之矽烷化合物，
[式中，R1各自獨立地表示甲基或乙基，X各自獨立地表示碳原子數1至10的連結基，Z表示可具有至少1個取代基的鄰苯二甲醯亞胺基、馬來醯亞胺基或琥珀醯亞胺基，Ar各自獨立地表示苯基或萘基，前述X所示的連結基係可在主鏈中含有至少1個氧原子或硫原子，當前述Ar表示苯基時，該苯基可具有至少1個取代基]。
前述苯二甲醯亞胺基係由下述式(2)所表示，前述馬來醯亞胺基係由下述式(3)所表示，前述琥珀醯亞胺基係由下述式(4)所表示。
前述式(2)、式(3)或式(4)所示的基之氮原子係與前述式(1A)的氧原子鍵結合。
當前述苯基具有取代基時，作為該取代基，例如可舉出甲基、第三丁基、環己基、苯基、羥基、甲氧基、氟基
、氯基。此等取代基對前述苯基的取代位置係沒有特別的限制，亦可具有2個以上或2種以上的前述取代基。當前述苯二甲醯亞胺基、前述馬來醯亞胺基、前述琥珀醯亞胺基亦具有取代基時，可自作為該取代基的上述例中選擇。
本發明的第2態樣係含有上述矽烷化合物及有機溶劑之單分子層或多分子層形成用組成物。
上述單分子層或多分子層形成用組成物更含有下述式(5)所示之矽烷化合物：
[式中，R2各自獨立地表示甲基或乙基，Y表示可具有至少1個取代基的碳原子數1至5的烷基或苯基]。
當前述碳原子數1至5的烷基具有取代基時，作為該取代基，例如可舉出胺基、咪唑基、吡啶基、巰基、磺基。此處，胺基“-NH2”之氫原子的至少1個亦可被烷基取代，例如被甲基取代。當前述苯基具有取代基時，作為該取代基，例如可舉出甲基。
本發明的第3態樣係光阻圖型之形成方法，其包含：使用本發明的第2態樣之組成物，在半導體基板上形成單分子層或多分子層之步驟；於前述單分子層或多分子層上形成光阻膜之步驟；將經前述單分子層或多分子層與前述光阻膜被覆的半導體基板曝光之步驟；及，於前述曝光後，將前述光阻膜顯像之步驟。
作為上述半導體基板，可使用表面形成有階差的基板
。該階差例如係起因於半導體元件的閘電極及閘配線。
本發明的組成物係可在基板的表面尤其形成有階差的基板之表面上形成單分子層或多分子層。此單分子層或多分子層係可調整其上所形成的光阻圖型之底部形狀，例如可成為沒有下端拖尾的形狀，而且可成為鄰接的圖型在底部沒有相連的形狀。
本發明的組成物含有前述式(1A)或式(1B)所示的矽烷化合物。矽烷化合物係藉由具有此等式所示的構造，經由曝光而產生酸，使酸擴散至上層光阻膜，而可使所形成的光阻圖型之底部形狀發生變化。式(1A)或式(1B)中，作為X所示之碳原子數1至10的連結基，例如可舉出伸烷基、伸苯基、伸環己基。當該連結基為碳原子數3以上的伸烷基，其主鏈亦可為分枝狀。
本發明的組成物，係除了式(1A)或式(1B)所示的矽烷化合物，還藉由含有式(5)所示的矽烷化合物，而可控制基板上所形成的單分子層或多分子層表面之疏水性。式(5)所示的矽烷化合物係可僅使用1種，也可組合2種以上使用。相對於式(1A)或式(1B)所示的矽烷化合物與式(5)所示的矽烷化合物之總和而言，式(5)所示
的矽烷化合物之比例例如為1質量%至99質量%，更佳為5質量%至95質量%。
本發明的組成物係除了上述矽烷化合物以外，還可含有水及有機酸。藉由含有水及有機酸，而提高本發明的組成物之保存安定性，同時在將該組成物塗佈於基板上，進行烘烤而形成單分子層或多分子層時，可促進矽烷化合物的縮合反應。作為有機酸，例如可舉出如醋酸、馬來酸、草酸、檸檬酸、蘋果酸、琥珀酸的羧酸。
本發明的組成物可含有界面活性劑。作為界面活性劑，例如可舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯油基醚等的聚氧乙烯烷基醚類、聚氧乙烯辛基苯酚醚、聚氧乙烯壬基苯酚醚等的聚氧乙烯烷基芳基醚類、聚氧乙烯．聚氧丙烯嵌段共聚物類、山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯、山梨糖醇酐單硬脂酸酯、山梨糖醇酐單油酸酯、山梨糖醇酐三油酸酯、山梨糖醇酐三硬脂酸酯等的山梨糖醇酐脂肪酸酯類、聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐單棕櫚酸酯、聚氧乙烯山梨糖醇酐單硬脂酸酯、聚氧乙烯山梨糖醇酐三油酸酯、聚氧乙烯山梨糖醇酐三硬脂酸酯等的聚氧乙烯山梨糖醇酐脂肪酸酯類等的非離子系界面活性劑、Eftop(註冊商標)EF301、同EF303、同EF352(三菱材料電子化成(股)(舊(股)JEMC)製)、Megafac(註冊商標)F171、同F173、同R30(DIC(股)製)、Fluorad FC430、同FC431(住友3M(股)製)、
Asahiguard(註冊商標)AG710、Surflon(註冊商標)S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(股)製)等的氟系界面活性劑、有機矽氧烷聚合物KP341(信越化學工業(股)製)。此等界面活性劑的配合量係在本發明的組成物的全成分中通常為0.2質量%以下，較佳為0.1質量%以下。可添加由此等界面活性劑中選出的1種類，也可以2種以上的組合添加。
本發明的組成物係可藉由將上述各成分溶解於適當的機溶劑中而調製，以均勻的溶液狀態使用。作為如此的有機溶劑，例如可舉出乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單丙基醚、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、醋酸乙酯、醋酸丁酯、乳酸乙酯、乳酸丁酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮。此等有機溶劑係可單獨或以2種以上的組合使用。
自本發明的組成物中去除有機溶劑後(含有水及有機酸時亦去除此等)的固體成分之比例例如為0.001質量%
至10質量%，較佳為0.1質量%至5質量%。
以下，說明本發明的組成物之使用。於半導體基板(例如形成有閘電極的矽晶圓，該矽晶圓亦可經氧化矽膜、氮化矽膜或氧氮化矽膜被覆)之上，藉由旋轉器、塗佈器等適當的塗佈方法來塗佈本發明的組成物，然後使用熱板等的加熱手段進行烘烤。烘烤條件係自烘烤溫度80℃至180℃、烘烤時間0.3分鐘至10分鐘中適宜選擇。代替半導體基板，亦可使用氮化矽基板、石英基板、玻璃基板(包含無鹼玻璃、低鹼玻璃、結晶化玻璃)、形成有ITO膜的玻璃基板。
然後，用溶劑去除半導體基板上所殘留之過剩的矽烷化合物，使乾燥而形成單分子層或多分子層。此處，使用本發明的組成物所形成的層係極薄，測定其厚度係困難。再者，鑑定該層為單分子層、多分子層中的任一者亦困難。
在經由上述過程於半導體基板上形成的單分子層或多分子層之上，形成光阻膜。光阻膜的形成係可藉由一般的方法，即光阻溶液的塗佈及烘烤而進行。
作為光阻溶液，只要是對曝光光線感光者，則沒有特別的限定。有由酚酸清漆樹脂與1,2-萘醌二疊氮磺酸酯所成的正型光阻，由含羥基的聚合物、胺基塑料交聯劑、光酸產生劑所成的系之因酸進行交聯而降低鹼溶解速度的負型光阻，由具有因酸進行分解而使鹼溶解速度上升之基的黏結劑與光酸產生劑所成的化學增幅型光阻，由因酸進行
分解而使光阻的鹼溶解速度上升之低分子化合物與鹼可溶性黏結劑和光酸產生劑所成的化學增幅型光阻，由具有因酸進行分解而使鹼溶解速度上升之基的黏結劑與因酸進行分解而使光阻的鹼溶解速度上升之低分子化合物和光酸產生劑所成的化學增幅型光阻等。亦可使用對電子線或EUV(極端紫外線)感應之光阻。
於形成光阻圖型之際，曝光係通過用於形成指定圖型的光罩(標線板)而進行。於曝光中，例如可使用KrF準分子雷射、ArF準分子雷射、EUV、電子線。曝光後，按照需要進行曝光後加熱(Post Exposure Bake)。作為曝光後加熱的條件，可自加熱溫度80℃至150℃、加熱時間0.3分鐘至60分鐘之中適宜選擇。對形成有光阻膜的半導體基板，通過光罩進行曝光，然後藉由鹼性顯像液來顯像。
作為鹼性顯像液，可舉出氫氧化鉀、氫氧化鈉等的鹼金屬氫氧化物之水溶液、氫氧化四甲銨、氫氧化四乙銨、膽鹼等的氫氧化四級銨之水溶液、乙醇胺、丙胺、乙二胺等之胺水溶液等的鹼性水溶液當作例子。再者，於此等顯像液中，亦可添加界面活性劑等。
作為顯像的條件，可自顯像溫度5℃至50℃、顯像時間10秒至300秒中適宜選擇。由本發明的光阻下層膜形成組成物所形成之光阻下層膜，係可使用光阻之顯像所廣用之2.38質量%的氫氧化四甲銨水溶液，在室溫下容易進行顯像。
以下，說明本發明的組成物之具體例，惟本發明不受此所限定。
於具備磁性攪拌棒的1000mL四口燒瓶中，加入N-羥基苯二甲醯亞胺15.77g及四氫呋喃(THF)450g，在冰浴下添加2-氯乙烷磺醯氯17.33g。接著，費30分鐘將三乙胺(Et3N)21.52g經四氫呋喃20g稀釋的溶液滴下。於該期間，將內溫保持在4~7℃。然後，在5~10℃攪拌2小時。反應結束後，將反應液中所析出的鹽過濾，以醋酸乙酯1000mL稀釋濾液。以純水200g洗淨濾液2次後，濃縮乾燥，而得到化合物1的粗物26.14g。於此粗物中加入1,2-二氯乙烷(DCE)60g，在30℃使溶解後，於冰冷下將所析出的結晶過濾乾燥，而得到13.29g化合物1(收率54%)。
[化5]
1H-NMR(400MHz)，CDCl3中：6.35 ppm(dd，J=9.8Hz，1.0Hz，1H)，6.59 ppm(dd，J=16.6Hz，1.0Hz，1H)，6.89 ppm(dd，J=16.6Hz，9.8Hz，1H)，7.81-7.87 ppm(m，2H)，7.90-7.94 ppm(m，2H)
於具備磁性攪拌棒的200mL四口燒瓶中，加入上述合成例1所得的化合物1 7.00g、巰基丙基三乙氧基矽烷6.26g及1,2-二氯乙烷56g，在冰浴下費2小時滴下吡啶0.55g經1,2-二氯乙烷14g稀釋的溶液。然後，於室溫下攪拌一夜。反應結束後，將反應液濃縮乾燥，而得到化合物2的粗物12.23g。藉由矽凝膠管柱將此粗物精製(展開溶劑：醋酸乙酯/己烷=1/1)，而得到5.63g化合物2(收率44%)。
[化6]
1H-NMR(400MHz)，CDCl3中：0.75-0.80 ppm(m，2H)，1.23 ppm(t，J=6.9Hz，9H)，1.74-1.80 ppm(m，2H)，2.68 ppm(t，J=7.3Hz，2H)，3.14-3.19 ppm(m，2H)，3.77-3.84 ppm(m，2H)，3.84 ppm(q，J=6.9Hz，6H)，7.83-7.87 ppm(m，2H)，7.92-7.95 ppm(m，2H)
於具備磁性攪拌棒的500mL四口燒瓶中，加入三乙胺23.04g及乙醇(EtOH)135g，進行攪拌。接著，於冰浴下滴下2-氯乙烷磺醯氯16.87g經1,2-二氯乙烷51g稀釋的溶液，在15℃攪拌1小時。反應結束後，以醋酸乙酯300mL稀釋反應液，以純水100g洗淨有機相2次，以飽和食鹽水100g洗淨1次。將前述有機相濃縮乾燥，而得到12.50g化合物3(收率89%)。
[化8]
1H-NMR(400MHz)，CDCl3中：1.40 ppm(t，J=7.0Hz，3H)，4.21 ppm(q，J=7.0Hz，2H)，6.14 ppm(d，J=9.8Hz，1H)，6.40 ppm(d，J=16.6Hz，1H)，6.54 ppm(dd，J=9.8Hz，16.6Hz，1H)
於具備磁性攪拌棒的200mL四口燒瓶中，加入上述合
成例3所得的化合物3 12.50g及二氯甲烷50g，於冰浴下添加三乙胺18.58g經二氯甲烷(DCM)10g稀釋的溶液。接著，滴下巰基丙基三乙氧基矽烷20.79g經二氯甲烷40g稀釋的溶液。然後，於室溫下攪拌一夜。反應結束後，將反應液濃縮乾燥，而得到41.07g化合物4(收率99%)。
[化9]
1H-NMR(400MHz)，CDCl3中：0.70-0.75 ppm(m，2H)，1.22 ppm(t，J=7.0Hz，9H)，1.37 ppm(t，J=7.2Hz，12H)，1.67-1.78 ppm(m，2H)，2.56 ppm(t，J=7.2Hz，2H)，2.95-3.10 ppm(m，4H)，3.39 ppm(q，J=7.2Hz，8H)，3.81 ppm(q，J=7.0Hz，6H)
於具備磁性攪拌棒的500mL四口燒瓶中，加入上述合成例4所得的化合物4 10.76g、溴化苯基鋶6.47g、純水160g及氯仿160g，在室溫攪拌2小時。反應結束後，抽出氯仿相，以硫酸鈉進行乾燥。過濾該硫酸鈉後，將濾液濃縮乾燥，而得到9.87g化合物5(收率86%)。
[化10]
1H-NMR(400MHz)，CDCl3中：0.70-0.75 ppm(m，2H)，1.22 ppm(t，J=6.9Hz，9H)，1.66-1.74 ppm(m，2H)，2.56 ppm(t，J=7.4Hz，2H)，2.96-3.11 ppm(m
，4H)，3.80 ppm(q，J=6.9Hz，6H)，7.67-7.75 ppm(m，6H)，7.73-7.78 ppm(m，3H)，7.81-7.85 ppm(m，6H)
使用下述表1中所示的矽烷化合物、水、醋酸及PGME(丙二醇單甲基醚)來製作溶液。然後，使用孔徑0.03μm的聚乙烯製微過濾器進行過濾，而調製單分子層或多分子層形成用組成物。表1中，“PhTMS”表示苯基三甲氧基矽烷(東京化成工業(股)製)，“ImTES”表示N-(3-三乙氧基矽烷基丙基)-4,5-二氫咪唑(Gelest公司製)。
使用旋塗器將實施例1所調製之組成物塗佈在矽晶圓上，於熱板上以100℃烘烤1分鐘。然後，在由丙二醇單甲基醚70質量%及丙二醇單甲基醚乙酸酯30質量%所成的OK73稀釋劑(東京應化工業(股)製)中，浸漬1分鐘，旋乾後，以100℃乾燥30秒，而在矽晶圓上形成單分子層或多分子層。於此層上，藉由旋塗器，以旋轉數1050 rpm塗佈市售的光阻溶液(JSR(股)製，商品名：V146G
)，於熱板上以110℃加熱1分鐘而形成光阻膜(膜厚0.360μm)。接著，使用(股)Nikon製NSR-S205C、KrF掃描機(波長248nm，NA：0.75，ANNULAR)，通過以顯像後光阻圖型的線寬及該線間的寬度成為0.16μm的方式所設定的遮罩，進行曝光。然後，於熱板上以110℃進行1分鐘曝光後加熱。冷卻後，使用0.26當量的氫氧化四甲銨水溶液當作顯像液來顯像。
顯像後，用掃描型電子顯微鏡(SEM)觀察所得之光阻圖型的截面。結果，觀察到光阻圖型的底部形狀不成為下端拖尾形狀，鄰接的圖型之底部亦不成為相連之形狀。
另一方面，作為比較例，藉由六甲基二矽氮烷(HMDS)來處理矽晶圓的表面，於該表面上藉由與上述同樣的方法，形成光阻膜(膜厚0.360μm)後，形成光阻圖型。圖1中顯示其結果。於比較例的情況，觀察到所得之光阻圖型的形狀係具有鄰接的圖型之底部相連的形狀。即，藉由使用本發明的組成物在矽晶圓上形成單分子層或多分子層，可使該層上所形成的光阻圖型之底部形狀產生變化。茲認為實施例1所調製的組成物中所含有的化合物5係作為光酸產生劑作用，經由曝光所產生的酸係轉移到光阻膜，故光阻圖型的底部形狀發生變化。
圖1係將以掃描型電子顯微鏡(SEM)觀察比較例所形成的光阻圖型之截面的影像拍攝而得之照片。
Claims (6)
- 一種下述式(1A)或下述式(1B)所示之矽烷化合物，
- 一種單分子層或多分子層形成用組成物，其係含有如申請專利範圍第1項之矽烷化合物及有機溶劑。
- 如申請專利範圍第2項之單分子層或多分子層形成用組成物，其係進一步含有水及有機酸。
- 如申請專利範圍第2或3項之單分子層或多分子層 形成用組成物，其係進一步含有下述式(5)所示之矽烷化合物：[化2](R2O)3Si-Y (5)[式中，R2各自獨立地表示甲基或乙基，Y表示可具有至少1個取代基的碳原子數1至5的烷基或苯基，前述碳原子數1至5的烷基具有取代基時，該取代基為胺基、咪唑基、吡啶基、巰基或磺基，前述苯基具有取代基時，該取代基為甲基]。
- 一種光阻圖型之形成方法，其係包含：使用如申請專利範圍第2至4項中任一項之組成物而在半導體基板上形成單分子層或多分子層之步驟、於前述單分子層或多分子層上形成光阻膜之步驟、將經前述單分子層或多分子層與前述光阻膜被覆的半導體基板曝光之步驟及於前述曝光後將前述光阻膜顯像之步驟。
- 如申請專利範圍第5項之光阻圖型之形成方法，其中前述半導體基板係在表面形成有階差。
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| JP2007031351A (ja) * | 2005-07-27 | 2007-02-08 | Toyobo Co Ltd | シラン誘導体および有機薄膜形成体 |
| TW200944943A (en) * | 2008-02-22 | 2009-11-01 | Renesas Tech Corp | Water repellent agent composition for substrate to be exposed, method for forming a resist pattern and electronic device produced by using the method, water repelling treatment method for substrate to be exposed, and water repellent agent set for substra |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5835593B2 (ja) | 2015-12-24 |
| JPWO2012114864A1 (ja) | 2014-07-07 |
| KR20140009395A (ko) | 2014-01-22 |
| WO2012114864A1 (ja) | 2012-08-30 |
| TW201247691A (en) | 2012-12-01 |
| KR101757170B1 (ko) | 2017-07-12 |
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