CN101258444A - 用来在不存在氮化硅的条件下进行硅的koh蚀刻的负性光刻胶 - Google Patents
用来在不存在氮化硅的条件下进行硅的koh蚀刻的负性光刻胶 Download PDFInfo
- Publication number
- CN101258444A CN101258444A CNA2006800326654A CN200680032665A CN101258444A CN 101258444 A CN101258444 A CN 101258444A CN A2006800326654 A CNA2006800326654 A CN A2006800326654A CN 200680032665 A CN200680032665 A CN 200680032665A CN 101258444 A CN101258444 A CN 101258444A
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- China
- Prior art keywords
- silane
- substrate
- independently selected
- photosensitive layer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052710 silicon Inorganic materials 0.000 title claims description 27
- 239000010703 silicon Substances 0.000 title claims description 27
- 229920002120 photoresistant polymer Polymers 0.000 title abstract description 13
- 229910052581 Si3N4 Inorganic materials 0.000 title description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 46
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 40
- -1 Carboxyl Chemical group 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000004377 microelectronic Methods 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 15
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
- 150000002118 epoxides Chemical group 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 125000006267 biphenyl group Chemical group 0.000 claims description 7
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 6
- UBMUZYGBAGFCDF-UHFFFAOYSA-N trimethoxy(2-phenylethyl)silane Chemical compound CO[Si](OC)(OC)CCC1=CC=CC=C1 UBMUZYGBAGFCDF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- BRXDAEMGSYZHGK-UHFFFAOYSA-N (4-bromophenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(Br)C=C1 BRXDAEMGSYZHGK-UHFFFAOYSA-N 0.000 claims description 3
- GWCJNVUIVCCXER-UHFFFAOYSA-N 2-(1-phenylprop-2-enoxymethyl)oxirane Chemical compound C=1C=CC=CC=1C(C=C)OCC1CO1 GWCJNVUIVCCXER-UHFFFAOYSA-N 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 241000723346 Cinnamomum camphora Species 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Chemical group 0.000 claims description 3
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 claims description 3
- 125000005055 alkyl alkoxy group Chemical group 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229960000846 camphor Drugs 0.000 claims description 3
- 229930008380 camphor Natural products 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- NPVQBEIMNWDKEU-UHFFFAOYSA-N chloromethoxy-dimethoxy-phenylsilane Chemical compound ClCO[Si](OC)(OC)C1=CC=CC=C1 NPVQBEIMNWDKEU-UHFFFAOYSA-N 0.000 claims description 3
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 3
- HLXCYTXLQJWQFG-UHFFFAOYSA-N diphenyl(2-triethoxysilylethyl)phosphane Chemical compound C=1C=CC=CC=1P(CC[Si](OCC)(OCC)OCC)C1=CC=CC=C1 HLXCYTXLQJWQFG-UHFFFAOYSA-N 0.000 claims description 3
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical group CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- BGSBEWOQSOBCCU-UHFFFAOYSA-N trichloro(3-phenoxypropyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCOC1=CC=CC=C1 BGSBEWOQSOBCCU-UHFFFAOYSA-N 0.000 claims description 3
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 3
- SUIOPANHTSHMHP-UHFFFAOYSA-N trichloro-(3,4-dichlorophenyl)silane Chemical compound ClC1=CC=C([Si](Cl)(Cl)Cl)C=C1Cl SUIOPANHTSHMHP-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- 238000012940 design transfer Methods 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- 239000008199 coating composition Substances 0.000 description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 229920001897 terpolymer Polymers 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 238000001259 photo etching Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005059 solid analysis Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical class CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000219495 Betulaceae Species 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- G03F7/0041—Photosensitive materials providing an etching agent upon exposure
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Abstract
提供了一种用于制备半导体和MEMS器件的新颖的光刻胶。所述底涂层优选包含溶解或分散在溶剂体系中的硅烷。所述光刻胶层包含由苯乙烯、丙烯腈和含环氧的单体制备的共聚物。所述光刻胶层包含光致酸生成剂,优选是负性作用的。
Description
发明背景
相关申请
本申请要求2005年9月9日提交的名为NEGATIVE PHOTORESIST FORSILICON KOH ETCH WITHOUT SILICON NITRIDE的美国专利申请第60/715,964号的优先权,该申请通过参考结合于本文。
技术领域
本发明涉及一种新的光刻胶,其用来制造微电子器件,例如用于微电子机械系统(MEMS)中的那些微电子器件。
背景技术
在硅蚀刻工艺中通常会在硅基片上使用薄的(100-至300-纳米)氮化硅或二氧化硅涂层作为用于形成图案蚀刻的掩模,或者作为钝化层,以封闭有源电路。在现有技术中,人们主要通过使用尝试法选择用于MEMS制造工艺的蚀刻保护涂层或掩模,这是因为在市场上没有通用保护涂层。经常用蚀刻剂对各种材料的蚀刻选择性作为对MEMS工艺工程师的指导。由于氮化硅膜的蚀刻速率远低于硅,其在KOH或TMAH主体硅蚀刻中用作保护层或硬掩模。二氧化硅的蚀刻速率高于氮化硅。因此,其仅在极短的蚀刻中用作保护层/掩模层。在一些情况下人们还报道了使用金(Au),铬(Cr)和硼(B)。无图案的硬烘烤的光刻胶被用作掩模,但是它们容易在碱性溶液中被蚀刻。人们评价认为聚甲基丙烯酸甲酯也可用作KOH的蚀刻掩模。但是由于酯基的皂化反应,发现该聚合物的掩蔽时间从60℃时的165分钟迅速减至90℃时的15分钟。
不考虑所选的保护涂层或掩模,必须将待形成图案的光刻胶层施加于保护涂层或掩模,这样可以将所述图案转移到下面的基片上。但是,这仅能在施加保护涂层或掩模之后进行,因此需要时间和费用来施加和随后蚀刻所述难以除去的保护层或掩模。
发明内容
本发明通过提供了一种旋涂的光敏涂层体系克服了这些问题,该体系代替了现有技术的掩模或保护涂层,在该体系中不需要另外的光刻胶。在使用浓碱水的深蚀刻工艺中,本发明体系可保护器件的特征免于腐蚀和其它形式的破坏。
本发明提供了一种可用作保护层的光敏组合物。该组合物包含聚合物和光致酸生成剂(photoacid generator),所述聚合物包含含苯乙烯的单体、含丙烯腈的单体、以及含环氧的单体。本发明还提供了将这些光敏组合物与底涂层结合使用以形成微电子结构的方法。
具体实施方式
更具体来说,这些体系包括施涂于微电子基片表面上的底涂层,以及施涂于所述底涂层上的光敏层。
底涂层
优选的底涂层由包含分散或溶解在溶剂体系中的硅烷的底涂层组合物形成。芳族和有机硅烷是特别优选用于本发明底涂层的硅烷。另外,优选所述硅烷每分子化合物或聚合物每个重复单元包含至少一个(更优选2-3)能够与环氧基团反应形成共价键的基团,因此与硅基片的粘合性非常强。这样一种优选的基团是胺基。
优选的硅烷包括氨基烷氧基硅烷,优选约为C1-C8烷氧基,更优选约为C1-C4烷氧基,更优选约为C1-C3烷氧基。更优选,所述氨基烷氧基硅烷是氨基烷基烷氧基硅烷,优选约为C1-C8烷基,更优选约为C1-C4烷基,更优选约为C1-C3烷基。还优选苯基氨基烷基烷氧基硅烷。一些上述硅烷的例子包括氨基丙基三甲氧基硅烷,氨基丙基三乙氧基硅烷,N-苯基氨基丙基三甲氧基硅烷,N-苯基氨基丙基三乙氧基硅烷,3-环氧丙氧基丙基三甲氧基硅烷,2-(3,4-环氧基环己基)乙基三甲氧基硅烷和3-巯基丙基-三甲氧基硅烷。
其它优选的硅烷包括苯基硅烷,例如苯基三甲氧基硅烷,苯基三氯硅烷,苯基三乙氧基硅烷,苯基三乙酰氧基硅烷;以及二苯基硅烷。例如二苯基二甲氧基硅烷,二苯基二氯硅烷和二苯基硅烷二醇。最优选的硅烷包括2-苯基乙基三烷氧基硅烷,对/间-氯苯基三甲氧基硅烷,对/间-溴苯基三甲氧基硅烷,(对/间-氯甲基)苯基三甲氧基硅烷,2-(对/间-甲氧基)苯基乙基三甲氧基硅烷,2-(对/间-氯甲基)苯基乙基三甲氧基硅烷,3,4-二氯苯基三氯硅烷,3-苯氧基丙基三氯硅烷,3-(N-苯基氨基)丙基三甲氧基硅烷,以及2-(二苯基膦基)乙基三乙氧基硅烷。
用于本发明的一些优选的硅烷还可用以下通式表示:
其中:
i,j和k各自独立地选自0和1,如果i和j之一是1,则i和j的另一个是0;
各R4独立地选自氢,卤素,C1-C8(优选C1-C4)烷基,C1-C8(优选C1-C4)烷氧基,C1-C8(优选C1-C4)卤代烷基,氨基,以及C1-C8(优选C1-C4)烷基氨基;
各R5独立地选自C1-C8(优选C1-C4)脂族基团;
各R6独立地选自氢和卤代烷基(优选C1-C8,更优选C1-C4);
各X独立地选自卤素,羟基,C1-C4烷氧基和C1-C4羧基;
Y选自氧和硫;
Z选自氮和磷;
各d独立地选自0和1。
根据本发明的一种有效的底涂层组合物是二苯基二烷氧基硅烷(例如二苯基二甲氧基硅烷)和苯基三烷氧基硅烷,(例如苯基三甲氧基硅烷)的混合物,或者更优选二苯基硅烷二醇和苯基三甲氧基硅烷在含有约5-10重量%水的1-甲氧基-2-丙醇或1-丙氧基-2-丙醇溶液中的混合物。一种特别有效的用于包含聚(苯乙烯-丙烯腈)共聚物的光敏层的底涂层组合物是包含0.1-1.0重量%(优选约0.25-0.5重量%)二苯基硅烷二醇和约0.1-1.0重量%(优选约0.25-0.5重量%)苯基三甲氧基硅烷的醇和水溶液。在加热时,二苯基硅烷二醇和苯基硅烷三醇(苯基三甲氧基硅烷的水解产物)缩合形成硅氧烷键,并在基片上形成三维硅氧烷涂层。另一种优选的硅烷具有以下结构式:
其中:
各R7独立地选自氢,卤素,C1-C8(优选C1-C4)烷基,C1-C8(优选C1-C4)烷氧基,C1-C8(优选C1-C4)卤代烷基,氨基和C1-C8(优选C1-C4)烷基氨基;
各R8独立地选自C1-C8(优选C1-C4)脂族基团。
具有这种结构的硅烷不仅能够与含苯乙烯的共聚物相容,而且还能够与酯、苄基氯和/或环氧基团反应,它们是极佳的增粘剂。在此式范围内一种特别优选的硅烷是
该硅烷是3-[N-苯基氨基]丙基三甲氧基硅烷(上文所述),其可从兰卡斯特合成和格莱斯特公司(Lancaster Synthesis and Gelest Corporation)购得。
在所述底涂层组合物中,所述硅烷的含量应约为0.1-3重量%,优选约为0.2-2重量%,更优选约为0.5-1重量%(以所述底涂层组合物中固体总重量为100重量%计)。
用于所述底涂层组合物中的溶剂体系的沸点应约为100-220℃,优选约为140-180℃。该溶剂体系的用量应约为30-99.9重量%,优选约为40-80重量%(以所述底涂层组合物总重量为100重量%计)。优选的溶剂体系包括选自以下的溶剂:甲醇、乙醇、异丙醇、丁醇、1-甲氧基-2-丙醇,乙二醇单甲醚和1-丙氧基-2-丙醇,以及它们的混合物。在一个优选的实施方式中,溶剂体系中水的含量约为20-60重量%,优选约为20-40重量%(以所述底涂层组合物总重量为100重量%计)。
所述底涂层还可包含催化剂。合适的催化剂包括任意无机酸或有机酸(例如盐酸、硫酸、磷酸、乙酸)或者无机碱或有机碱(例如氢氧化钾,TMAH,氨,胺)。在所述底涂层组合物中催化剂的含量优选约为0.01-0.5重量%,更优选约为0.1-0.3重量%,更优选约为0.02-0.03重量%(以所述底涂层组合物中固体总重量为100重量%计)。
最后,所述底涂层还可包含一些任选的组分,例如表面活性剂。在一个实施方式中,可以加入约100-150ppm的表面活性剂,例如FC4430(得自3M)或TritonX-100(得自3M)以制备无缺陷的均匀的底涂层。
光敏层
所述光敏层由包含分散或溶解在溶剂体系中的聚合物的组合物形成。优选的聚合物是一种三元共聚物,其包含以下重复单元:苯乙烯单体;丙烯腈单体;以及包含能够与胺反应的官能团的单体。优选的苯乙烯单体具有以下结构式
优选的丙烯腈具有以下结构式:
包含用来与胺反应的官能团的优选单体包括含一个或多个环氧基团的单体(例如甲基丙烯酸缩水甘油酯,丙烯酸缩水甘油酯,乙烯基苄基缩水甘油基醚)。下式表示了一个例子:
在上面(I)-(III)的各式中:
各R1独立地选自氢和C1-C8(优选C1-C4)烷基;
各R2独立地选自氢,C1-C8(优选C1-C4)烷基以及C1-C8(优选C1-C4)烷氧基。
所述聚合物优选包含约35-75重量%的单体(I),更优选约40-70重量%的单体(I),更优选约50-65重量%的单体(I)。所述聚合物优选包含约20-40重量%的单体(II),更优选约25-35重量%的单体(II),更优选约25-30重量%的单体(II)。最后,所述聚合物优选包含约5-15重量%的单体(III),更优选约6-12重量%的单体(III),更优选约8-10重量%的单体(III)。上述各重量百分数是以聚合物的总重量为100重量%计。
优选所述聚合物的重均分子量约为10,000-80,000道尔顿,优选约为20,000-60,000道尔顿,更优选约为30,000-50,000道尔顿n。
如果需要,所述聚合物中还可包含除单体(I)、(II)和(III)以外的单体。当存在其它的单体时,以所述聚合物的总重量为100重量%计,所述聚合物中单体(I),(II)和(III)的总重量优选至少约为60重量%,更优选约为70-90重量%。合适的其它单体的例子包括包含能够与底涂层中的基团反应、在两层之间形成化学键的官能团的单体。这些单体可包含例如卤代烷基(例如苄基氯,甲基丙烯酸-2-氯乙酯),酯(甲基丙烯酸酯,丙烯酸酯,马来酸酯,富马酸酯,异氰酸酯),或者酸酐官能团,所述官能团能够容易地与所述底涂层中可包含的官能团(例如羟基、氨基或环氧乙烷基)反应。
以所述光敏层组合物中的固体总重量为100重量%计,所述光敏层组合物中聚合物的含量应约为90-98重量%,优选约为90-95重量%。
所述光敏组合物还可包含光致酸生成剂(PAG)。所述PAG在受到紫外光之类的光化辐射时产生强酸或过酸。合适的PAG的例子包括选自以下的那些:六氟锑酸三芳基锍,六氟磷酸三芳基锍,六氟锑酸二芳基碘鎓,六氟磷酸二芳基碘鎓,
其中各R3独立地选自:C3H7,C8H17,CH3C6H4和樟脑。式(IV)和(V)的PAG分别是希巴特殊化学品公司(Ciba Specialty Chemicals)销售的CGI 13XX类和CGI 26X类。
以所述光敏组合物中的固体总重量为100重量%计,所述光敏组合物中的PAG含量应约为2-10重量%,优选约为5-8重量%。
用于所述光敏组合物中的溶剂体系的沸点应约为120-200℃,优选约为130-180℃。以所述光敏组合物的总重量为100重量%计,所述溶剂体系的用量应约为70-95重量%,优选约为80-90重量%。优选的溶剂体系包含选自以下的溶剂:甲基异戊基酮,二(乙二醇)二甲基醚,丙二醇单甲基醚乙酸酯,乳酸乙酯,环己酮,以及它们的混合物。
施涂方法
优选用于该工艺的基片包括含硅的基片。一些特别优选的基片选自:Si基片,SiO2基片,Si3N4基片,SiO2在硅上的基片,Si3N4在硅上的基片,玻璃基片,石英基片,陶瓷基片,半导体基片,以及金属基片。
将所述硅烷和任意其它的组分溶解在所述底涂层溶剂体系中,形成所述硅烷组合物。然后以约500-5000rpm、优选约1000-3000rpm的转速将所述组合物旋涂在所述基片上约30-90秒、优选约60秒。然后在约60-110℃下烘烤约60-180秒(优选约120秒),然后在约150-250℃下烘烤约60-180秒(优选约120秒),以使得所述硅烷分子凝结成连续的膜,所述膜结合于常规微电子基片上的表面羟基。也就是说,所述水解的硅烷与所述含硅基片中的硅烷醇基反应,还通过缩合自交联。优选所述底涂层的平均厚度(在5个不同的点用椭圆偏振议测量)约小于50纳米,更优选约为20-30纳米。
对于光敏层,将聚合物,PAG和任意的其它组分溶解在所述溶剂体系中,以约1,000-5,000rpm,优选约1,000-2,000rpm的转速旋涂在基片上约30-90秒,优选约60秒。然后其在约100-120℃下烘烤约60-180秒(优选约120)。通常根据基片上的全部器件外形所需的覆盖程度,对所述聚合物固体含量和旋涂条件进行调节,以便在烘烤之后获得(在5个不同的点用椭圆偏振议测量)约500-3000纳米、优选约1000-2000纳米的平均涂层厚度。有利的是,所述光敏层聚合物中的环氧基团或其它活性基团与所述底涂层的硅烷上的胺基或其它活性基团形成共价键。
然后所述光敏层通过优选以约500毫焦/厘米2的剂量、波长约为150-500纳米(例如约248-365纳米)的紫外光曝光而进行成像。然后所述涂层优选在约110-130℃下进行约2分钟的曝光后烘烤,用溶剂显影约1分钟。最后,所述涂层在约200-250℃下烘烤约5分钟。
曝光使得PAG产生酸,所述酸引发了所述光敏层中聚合物的交联(优选通过环氧基团交联)。所述交联的环氧基团将具有以下结构:
所述曝光的区域变得基本不溶于(例如溶解度约小于1重量%,优选约小于0.05%,更优选约为0%)常规的溶剂显影剂,例如丙二醇单甲基醚乙酸酯,甲基异戊基酮,以及乙酰乙酸乙酯。未曝光的区域保持可溶于这些显影剂中,因此在显影的过程中它们很容易地除去。结果,可以很容易地转移所述图案,而无需通过另外的蚀刻步骤来除去所述保护层。
通过实施本发明将会得到在蚀刻过程中几乎不会或完全不会发生侧壁腐蚀(undercut)的保护层体系。也就是说,所述层体系在约83-87℃的温度下,在约30-35重量%的KOH水溶液中蚀刻约2小时(或甚至约3小时)时,其侧壁腐蚀约小于100微米,优选约小于70微米,更优选约小于50微米。侧壁腐蚀是通过在共焦显微镜下观察测量在蚀刻的区域边缘处伸出的保护层的宽度而测定的。
另外,本发明的保护体系在蚀刻过程中将发生极少的蚀刻剂渗透或完全没有蚀刻剂渗透。因此,在约83-87℃的温度下、在约30-35重量%的KOH水溶液中蚀刻约2小时(或甚至约3小时)之后,通过显微镜以10倍放大观察,本发明的保护体系的针孔数将约小于0.1个针孔/厘米2基片,优选约小于0.05个针孔/厘米2基片。这不同于现有技术的光敏层,现有技术的光敏层会较快地溶于KOH,因此需要有独立的保护层,例如氮化硅层。
实施例
以下实施例说明了根据本发明的优选方法。但是应当理解这些实施例仅仅是说明性的,不应看作对本发明总体范围的限制。
实施例1
1.环戊酮中的三元共聚物合成
通过将67.50克苯乙烯、25.00克丙烯腈、7.50克甲基丙烯酸缩水甘油酯和1.25克2,2’-偶氮二异丁腈溶解在400克环戊酮中,制备了一种溶液,所有这些试剂都得自阿尔德瑞奇(Aldrich)。所述溶液在进行磁力搅拌的同时,在氮气气氛下加热至65℃。使所述聚合反应在65℃温度下进行98小时。通过固体分析测定实际产率为理论产率的97%。
2.面涂层溶液配制
在此制备过程中,将25.01克丙二醇甲基醚乙酸酯(PGMEA,通用化学公司(General Chemical))和1.03克UVI-6976(购自陶氏化学公司(Dow Chemical)的光致酸生成剂,六氟锑酸三芳基锍)加入50.03克的本实施例的部分1合成的三元共聚物溶液中。所得的溶液用0.1微米的薄膜过滤器过滤。
3.底涂层溶液配制
为了制备底涂层溶液,将1.02克N-苯基氨基丙基三甲氧基硅烷(得自格莱斯特公司(Gelest))溶解在120.4克丙二醇丙基醚(得自通用化学公司)和80.2克去离子水的混合物中。该溶液用0.1微米的薄膜过滤器过滤。
4.负性光刻胶涂层的制备和形成图案
以1500rpm的转速将本实施例的部分3中的底涂层溶液旋涂在硅晶片上1分钟。然后所述底涂层在75℃烘烤2分钟,然后在180℃烘烤2分钟。然后以1500rpm的转速将本实施例的部分2的面涂层溶液旋涂到底涂层上1分钟。然后所述面涂层在100℃下烘烤2分钟。该涂层通过以下方式成像:通过用波长365纳米、剂量500mJ/cm2的紫外光曝光,在130℃下烘烤2分钟,然后用丙酮显影1分钟。最后,所述组合涂层在230℃下烘烤5分钟。得到负性图案。
5.硅晶片的蚀刻
本实施例的部分4中制备和形成图案的晶片在85℃下、在30%的KOH水溶液中蚀刻1小时。所述硅在没有聚合物涂层的区域蚀刻70微米的深度。涂敷聚合物的区域保持不变。该图案按照与现有技术的氮化硅掩模法基本相同的方式转移到硅晶片上。
实施例2
1.PGMEA中的三元共聚物合成
通过将27.07克苯乙烯、10.00克丙烯腈、3.08克甲基丙烯酸缩水甘油酯和0.51克过氧化二异丙苯(得自阿尔德瑞奇)溶解在160克PGMEA中制备溶液。在进行磁力搅拌的同时,将该溶液在氮气气氛下加热至120℃。使该聚合反应在120℃下进行24小时。通过固体分析确定实际产率是理论产率的95.5%。
2.面涂层溶液配制
在此制备过程中,将4.54克PGMEA和0.114克UVI-6976加入5.03克本实施例的部分1中合成的三元共聚物溶液中。该溶液通过0.1微米的薄膜过滤器过滤。
3.负性光刻胶涂层的制备和形成图案
以1500rpm的转速将实施例1的部分2的底涂层溶液旋涂在硅晶片上1分钟。所述底涂层在60℃烘烤5分钟,然后在180℃下烘烤2分钟。然后将得自本实施例的部分2的面涂层溶液以1500rpm的转速旋涂在晶片上1分钟。该面涂层在100℃下烘烤2分钟。该涂层通过用254纳米、500mJ/cm2的剂量的紫外光曝光而成像之后,其在130℃下烘烤2分钟,然后用PGMEA显影1分钟。最后该涂层在230℃下烘烤5分钟。得到负性图案。
4.硅晶片的蚀刻
在本实施例的部分3中制备和形成图案的晶片在80℃下、在30%的KOH水溶液中蚀刻1小时。硅晶片在没有聚合物涂层的区域蚀刻58微米深。聚合物涂敷的区域保持不变。将所述图案按照与现有技术的氮化硅掩模法基本相同的方式转移到所述硅晶片上。
实施例3
1.在PGMEA中的三元共聚物合成
通过将168.0克苯乙烯,84.0克丙烯腈,28.3克甲基丙烯酸缩水甘油酯和7.0克过氧化二异丙苯溶解在1,120克PGMEA中制备溶液。该溶液在磁力搅拌的同时,在氮气气氛下加热至120℃。使该聚合反应在120℃下进行28小时。通过固体分析发现实际的产率为理论产率的97.5%。所述三元共聚物在异丙醇中沉淀,过滤,在50℃下真空干燥过夜。
2.面涂层溶液配制
在此制备过程中,将32.8克的本实施例的部分1中合成的三元共聚物溶解在140.0克PGMEA和40.0克乙酰乙酸乙酯中。接下来,加入6.0克UVI-6976,该溶液用0.1微米的薄膜过滤器过滤。
3.底涂层溶液配制
为了制备底涂层溶液,将2.04克N-苯基氨基丙基三甲氧基硅烷溶解在77.50克丙二醇丙基醚(PnP),120.14克去离子水,0.51克乙酸和0.03克FC4430(表面活性剂)的混合物中。该溶液磁力搅拌2小时以上。其通过0.1微米的薄膜过滤器过滤。
4.负性光刻胶涂层的制备和形成图案
以1500rpm的转速将本实施例的部分3中制备的底涂层溶液旋涂在硅晶片上1分钟。所述底涂层在110℃下烘烤1分钟,然后在205℃下烘烤1分钟。然后将来自本实施例的部分2的面涂层溶液以1500rpm的转速旋涂在所述底涂层上1分钟。所述面涂层在110℃下烘烤2分钟。该涂层通过用254纳米、500mJ/cm2的剂量的紫外光曝光而成像之后,其在130℃下烘烤2分钟,然后用PGMEA显影1分钟。最后,该组合涂层在230℃下烘烤5分钟。得到负性图案。
5.硅晶片的蚀刻
在本实施例的部分4中制备和形成图案的晶片在75℃下、在30%的KOH水溶液中蚀刻4小时。硅晶片在没有聚合物涂层的区域蚀刻178微米深。聚合物涂敷的区域保持不变。将所述图案按照与现有技术的氮化硅掩模法基本相同的方式转移到所述硅晶片上。
Claims (37)
1.一种可用作保护层的光敏组合物,所述组合物包含溶解或分散在溶剂体系中的聚合物和光致酸生成剂,所述聚合物包含:
以及
(III)包含至少一个环氧基团的单体,
在(I)和(II)中:
各R1独立地选自氢和C1-C8烷基;
各R2独立地选自氢、C1-C8烷基和C1-C8烷氧基。
2.如权利要求1所述的组合物,其特征在于,所述单体(III)选自甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、以及乙烯基苄基缩水甘油基醚单体。
5.如权利要求1所述的组合物,其特征在于,所述聚合物包含约35-75重量%的(I)、约20-40重量%的(II)、以及约5-15重量%的(III),以所述聚合物的总重量为100重量%计。
7.如权利要求6所述的方法,其特征在于,所述单体(III)选自甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、以及乙烯基苄基缩水甘油基醚单体。
10.如权利要求6所述的方法,其特征在于,所述聚合物包含约35-75重量%的(I)、约20-40重量%的(II)、以及约5-15重量%的(III),以所述聚合物的总重量为100重量%计。
11.如权利要求6所述的方法,其特征在于,所述硅烷具有选自下组的结构式:
式中:
i、j和k各自独立地选自0和1,如果i和j之一是1,则i和j的另一个是0;
各R4独立地选自氢、卤素、C1-C8烷基、C1-C8烷氧基、C1-C8卤代烷基、氨基、以及C1-C8烷基氨基;
各R5独立地选自C1-C8脂族基团;
各R6独立地选自氢和卤代烷基;
各X独立地选自卤素、羟基、C1-C4烷氧基和C1-C4羧基;
Y选自氧和硫;
Z选自氮和磷;
各d独立地选自0和1;以及
其中:
各R7独立地选自氢、卤素、C1-C8烷基、C1-C8烷氧基、C1-C8卤代烷基、氨基和C1-C8烷基氨基;
各R8独立地选自C1-C8脂族基团。
12.如权利要求6所述的方法,其特征在于,所述硅烷选自氨基烷氧基硅烷、苯基硅烷和二苯基硅烷。
13.如权利要求12所述的方法,其特征在于,所述硅烷选自氨基烷基烷氧基硅烷和苯基氨基烷基烷氧基硅烷。
14.如权利要求12所述的方法,其特征在于,所述硅烷选自氨基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、N-苯基氨基丙基三甲氧基硅烷、N-苯基氨基丙基三乙氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、2-(3,4-环氧基环己基)乙基三甲氧基硅烷、3-巯基丙基-三甲氧基硅烷、苯基三甲氧基硅烷、苯基三氯硅烷、苯基三乙氧基硅烷、苯基三乙酰氧基硅烷、二苯基二甲氧基硅烷、二苯基二氯硅烷、二苯基硅烷二醇2-苯基乙基三烷氧基硅烷、对/间-氯苯基三甲氧基硅烷、对/间-溴苯基三甲氧基硅烷、(对/间-氯甲基)苯基三甲氧基硅烷、2-(对/间-甲氧基)苯基乙基三甲氧基硅烷、2-(对/间-氯甲基)苯基乙基三甲氧基硅烷、3,4-二氯苯基三氯硅烷、3-苯氧基丙基三氯硅烷、3-(N-苯基氨基)丙基三甲氧基硅烷和2-(二苯基膦基)乙基三乙氧基硅烷。
15.如权利要求6所述的方法,其特征在于,所述方法还包括在施涂所述底涂层之后,对所述底涂层进行烘烤。
16.如权利要求15所述的方法,其特征在于,所述底涂层还包含催化剂,所述底涂层的烘烤导致所述硅烷的交联。
17.如权利要求6所述的方法,其特征在于,所述方法还包括在施涂所述光敏层之后,对所述光敏层进行烘烤。
18.如权利要求17所述的方法,其特征在于,所述烘烤使得所述光敏层的聚合物与所述底涂层的硅烷共价键合。
19.如权利要求6所述的方法,其特征在于,所述方法还包括使所述光敏层的第一部分进行光化辐射曝光,而所述光敏层的第二部分不进行光化辐射曝光。
20.如权利要求19所述的方法,其特征在于,所述光敏层的第一部分在所述曝光过程中交联。
21.如权利要求20所述的方法,其特征在于,所述方法还包括在进行所述光化辐射曝光之后,对所述光敏层进行烘烤。
22.如权利要求20所述的方法,其特征在于,所述方法还包括对所述光敏层进行显影。
23.如权利要求22所述的方法,其特征在于,所述显影造成所述光敏层的第二部分在所述显影步骤过程中基本上被除去,从而形成包括其中形成有图案的光敏层的叠层。
24.如权利要求23所述的方法,其特征在于,所述方法还包括在进行所述显影之后对所述光敏层进行烘烤。
25.如权利要求23所述的方法,其特征在于,所述方法还包括用KOH对所述叠层进行蚀刻,从而将所述光敏层的图案转移到所述基片上。
26.如权利要求25所述的方法,其特征在于,所述光敏层在蚀刻过程中的侧壁腐蚀小于约100微米。
27.如权利要求25所述的方法,其特征在于,所述光敏层的针孔数小于约0.1个针孔/厘米2基片。
28.如权利要求6所述的方法,其特征在于,所述基片选自Si基片、SiO2基片、Si3N4基片、SiO2在硅上的基片、Si3N4在硅上的基片、玻璃基片、石英基片、陶瓷基片、半导体基片、以及金属基片。
31.如权利要求29所述的微电子结构,其特征在于,所述硅烷包含胺,所述光敏层的聚合物包含与所述胺共价键合的环氧基团。
32.如权利要求29所述的微电子结构,其特征在于,所述聚合物包含约35-75重量%的(I)、约20-40重量%的(II)、以及约5-15重量%的(III),以所述聚合物的总重量为100重量%计。
33.如权利要求29所述的微电子结构,其特征在于,所述硅烷具有选自下组的结构式:
式中:
i、j和k各自独立地选自0和1,如果i和j之一是1,则i和j的另一个是0;
各R4独立地选自氢、卤素、C1-C8烷基、C1-C8烷氧基、C1-C8卤代烷基、氨基、以及C1-C8烷基氨基;
各R5独立地选自C1-C8脂族基团;
各R6独立地选自氢和卤代烷基;
各X独立地选自卤素、羟基、C1-C4烷氧基和C1-C4羧基;
Y选自氧和硫;
Z选自氮和磷;
各d独立地选自0和1;以及
其中:
各R7独立地选自氢、卤素、C1-C8烷基、C1-C8烷氧基、C1-C8卤代烷基、氨基和C1-C8烷基氨基;
各R8独立地选自C1-C8脂族基团。
34.如权利要求29所述的微电子结构,其特征在于,所述硅烷选自氨基烷氧基硅烷、苯基硅烷和二苯基硅烷。
35.如权利要求34所述的微电子结构,其特征在于,所述硅烷选自氨基烷基烷氧基硅烷和苯基氨基烷基烷氧基硅烷。
36.如权利要求34所述的微电子结构,其特征在于,所述硅烷选自氨基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、N-苯基氨基丙基三甲氧基硅烷、N-苯基氨基丙基三乙氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、2-(3,4-环氧基环己基)乙基三甲氧基硅烷、3-巯基丙基-三甲氧基硅烷、苯基三甲氧基硅烷、苯基三氯硅烷、苯基三乙氧基硅烷、苯基三乙酰氧基硅烷、二苯基二甲氧基硅烷、二苯基二氯硅烷、二苯基硅烷二醇2-苯基乙基三烷氧基硅烷、对/间-氯苯基三甲氧基硅烷、对/间-溴苯基三甲氧基硅烷、(对/间-氯甲基)苯基三甲氧基硅烷、2-(对/间-甲氧基)苯基乙基三甲氧基硅烷、2-(对/间-氯甲基)苯基乙基三甲氧基硅烷、3,4-二氯苯基三氯硅烷、3-苯氧基丙基三氯硅烷、3-(N-苯基氨基)丙基三甲氧基硅烷和2-(二苯基膦基)乙基三乙氧基硅烷。
37.如权利要求29所述的微电子结构,其特征在于,所述基片选自Si基片、SiO2基片、Si3N4基片、SiO2在硅上的基片、Si3N4在硅上的基片、玻璃基片、石英基片、陶瓷基片、半导体基片、以及金属基片。
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