TWI575013B - And a composition for forming an underlayer film - Google Patents
And a composition for forming an underlayer film Download PDFInfo
- Publication number
- TWI575013B TWI575013B TW104100383A TW104100383A TWI575013B TW I575013 B TWI575013 B TW I575013B TW 104100383 A TW104100383 A TW 104100383A TW 104100383 A TW104100383 A TW 104100383A TW I575013 B TWI575013 B TW I575013B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- underlayer film
- photoresist
- film
- forming
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 112
- 229920002120 photoresistant polymer Polymers 0.000 claims description 232
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- 125000001424 substituent group Chemical group 0.000 claims description 21
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- SSXKOJOYOWVNRL-UHFFFAOYSA-M ethyl [4-(thiolan-1-ium-1-yl)naphthalen-1-yl] carbonate;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OC(=O)OCC)=CC=C1[S+]1CCCC1 SSXKOJOYOWVNRL-UHFFFAOYSA-M 0.000 description 1
- HONACFWHXHOMHL-UHFFFAOYSA-N ethyl acetate methyl acetate Chemical compound C(C)(=O)OC.C(C)(=O)OCC.C(C)(=O)OC HONACFWHXHOMHL-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- MEEWSBNOBXBASQ-UHFFFAOYSA-M fluoromethanesulfonate Chemical compound [O-]S(=O)(=O)[CH]F MEEWSBNOBXBASQ-UHFFFAOYSA-M 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 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
- XKYICAQFSCFURC-UHFFFAOYSA-N isoamyl formate Chemical compound CC(C)CCOC=O XKYICAQFSCFURC-UHFFFAOYSA-N 0.000 description 1
- JSLCOZYBKYHZNL-UHFFFAOYSA-N isobutyric acid butyl ester Natural products CCCCOC(=O)C(C)C JSLCOZYBKYHZNL-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 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
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- LYLUAHKXJUQFDG-UHFFFAOYSA-N methyl 3-methoxy-2-methylpropanoate Chemical compound COCC(C)C(=O)OC LYLUAHKXJUQFDG-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- WEBFLHSTQYJFHU-UHFFFAOYSA-M methyl [4-(thiolan-1-ium-1-yl)naphthalen-1-yl] carbonate;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OC(=O)OC)=CC=C1[S+]1CCCC1 WEBFLHSTQYJFHU-UHFFFAOYSA-M 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000004002 naphthaldehydes Chemical class 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-L naphthalene-1,8-dicarboxylate Chemical compound C1=CC(C([O-])=O)=C2C(C(=O)[O-])=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-L 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- OGLOUCVTUZYEGZ-UHFFFAOYSA-N octadecyl trifluoromethanesulfonate Chemical compound CCCCCCCCCCCCCCCCCCOS(=O)(=O)C(F)(F)F OGLOUCVTUZYEGZ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 description 1
- ZZRBEZSPVWPQQX-UHFFFAOYSA-M propan-2-yl [4-(thiolan-1-ium-1-yl)naphthalen-1-yl] carbonate;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OC(=O)OC(C)C)=CC=C1[S+]1CCCC1 ZZRBEZSPVWPQQX-UHFFFAOYSA-M 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- PTDFYTRMUCOFBP-UHFFFAOYSA-M propyl [4-(thiolan-1-ium-1-yl)naphthalen-1-yl] carbonate;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OC(=O)OCCC)=CC=C1[S+]1CCCC1 PTDFYTRMUCOFBP-UHFFFAOYSA-M 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- GDISDVBCNPLSDU-UHFFFAOYSA-N pyrido[2,3-g]quinoline Chemical compound C1=CC=NC2=CC3=CC=CN=C3C=C21 GDISDVBCNPLSDU-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- UACVJSDAGHJPNP-UHFFFAOYSA-M tert-butyl [4-(thiolan-1-ium-1-yl)naphthalen-1-yl] carbonate;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OC(=O)OC(C)(C)C)=CC=C1[S+]1CCCC1 UACVJSDAGHJPNP-UHFFFAOYSA-M 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76807—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics for dual damascene structures
- H01L21/76808—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics for dual damascene structures involving intermediate temporary filling with material
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明,係關於一種光阻下層膜形成用組成物,係用於形成可成為光阻膜基底層之光阻下層膜。具體而言,係關於一種光阻下層膜形成用組成物,係在適用於長寬比大之基板(例如,形成多層配線構造時所使用之具有微細孔或溝渠之基板等)時,對於基板間隙容易充填之特性(埋入性)優異。
半導體之製造程序,係具備在矽晶圓上依序層合而形成由特性相異之複數物質所構成之被加工膜之層,並使該等之被加工膜圖案化成為所希望之圖案之步驟。被加工膜之圖案化,係藉由以下之方式進行:首先,於被加工膜之表面形成由感光性物質(光阻)所構成之光阻膜,對此光阻膜之既定區域實施曝光,其次,藉由將光阻膜之曝光部或未曝光部作顯像處理而除去以形成光阻圖案,更進一步,將此光阻圖案當作蝕刻光罩,對被加工膜作乾式蝕刻。
在如此之程序中,係使用ArF準分子雷射等之紫外光作為用於對光阻膜實施曝光之曝光光源。現在,對於大型
積體電路(LSI)之微細化之要求日益提高,必要之解像度成為曝光光線之波長以下之情況亦逐漸出現。如此一來解像度若成為曝光光線之波長以下,則曝光量裕度、聚焦裕度等之曝光程序裕度不足,因此為不適合。就彌補曝光程序裕度不足之方案而言,使光阻膜之膜厚變薄以提升解像性為有效。但是,若使光阻膜之膜厚變薄,則難以確保被加工膜之蝕刻所必要之光阻膜厚。
於是檢討出一種程序,係在被加工膜之表面形成光阻下層膜(以下,有簡單記為「下層膜」之情況)。將光阻圖案暫時轉寫於下層膜而形成下層膜圖案之後,再將此下層膜圖案當作蝕刻光罩而轉寫於被加工膜。由於在此程序所使用之下層膜,係以具有耐蝕刻性為佳,因而提案了藉由含有具有苊烯骨架之聚合物(係可吸收蝕刻中之能量而發揮耐蝕刻性)之組成物以形成下層膜(例如參照專利文獻1~3)。
然而,若成為具有0.13μm以下之微細度之LSI圖案規則,則配線延遲對LSI高速化造成之影響變大,藉由現在之LSI程序技術,LSI之高性能化之進展逐漸變為困難。於是,為了使配線延遲變小,檢討出將配線材由Al變更為Cu之方法。
就用於將配線材由Al變更為Cu之技術而言,已知有雙鑲嵌程序(例如參照專利文獻4)。在此程序中,與使用Al作為配線材之情況相比,有必要使用長寬比(凹凸)較大之基板,而需要使光阻下層膜形成用組成物對基板間
隙容易充填之特性(埋入性)優異。
就提升光阻下層膜形成用組成物之埋入性之方案而言,已知有例如將組成物所含之樹脂之分子量定為3000以下之方法(例如參照專利文獻5)、將組成物之以[黏度(mPas)之對數變化]/[固體成分濃度(質量%)之變化]表示之係數H定為0.06以下,且將以固體成分濃度25質量%所測定之黏度定為1~80mPas之方法(例如參照專利文獻6)、以及於組成物中配合分子量800以下之含氮化合物(交聯劑)之方法等(例如參照專利文獻7)。
[專利文獻1]特開2000-143937號公報
[專利文獻2]特開2001-40293號公報
[專利文獻3]特開2004-168748號公報
[專利文獻4]美國專利第6057239號公報
[專利文獻5]特開2000-294504號公報
[專利文獻6]特開2003-057828號公報
[專利文獻7]特開2002-329781號公報
然而,專利文獻5所記載之方法,為了使組成物之埋入性提升,有必要將樹脂之玻璃轉移溫度定為130℃以下。特別是,對於長寬比為3以上之基板而言,玻璃轉移溫度為130℃以上之樹脂,即使降低其分子量亦無法使埋入性提升。
另一方面,在使用玻璃轉移溫度為130℃以下之樹脂
之情況下,雖然組成物之埋入性提升,然而卻有埋入性與重要特性之下層膜耐蝕刻性為不充分之課題。另外,對於混有孔與溝渠之基板而言,僅降低樹脂之分子量,則難以對孔與溝渠兩者發揮充分之埋入性。
另外,於專利文獻6所記載之方法,係有下層膜之耐蝕刻性為不充分之課題。畢竟此方法係關於一種與光阻相比有必要降低耐蝕刻性之抗反射膜(BARC=Bottom Anti Reflective Coating)之發明。
再者,於專利文獻7所記載之方法,係有下層膜之耐蝕刻性為不充分之課題。另外,形成下層膜時,亦有含氮化合物或其分解物昇華,污染成膜裝置之不適合情形。
如此,以現在之時間點,並無揭示兼具對基板間隙之埋入性與下層膜之耐蝕刻性,並且可防止成膜裝置之污染之光阻下層膜形成用組成物。本發明係鑑於如此先前技術之課題而完成者,提供一種光阻下層膜形成用組成物,係兼具對基板間隙之埋入性與下層膜之耐蝕刻性,並且可有效地防止成膜裝置之污染。
本發明人等為了解決上述課題反覆努力檢討之結果,發現藉由在光阻下層膜形成用組成物配合具有丁醚基之交聯劑,可解決上述先前技術之課題,而完成了本發明。具體而言,藉由本發明,可提供以下之光阻下層膜形成用組成物。
[1]一種光阻下層膜形成用組成物,係含有(A)樹脂、(B)具有丁醚基之交聯劑及(C)溶劑。
[2]如上述[1]所記載之光阻下層膜形成用組成物,其中,上述(B)具有丁醚基之交聯劑係具有至少2個丁醚基之含氮環狀化合物。
[3]如上述[2]所記載之光阻下層膜形成用組成物,其中,上述含氮環狀化合物係具有甘脲骨架或三嗪骨架之化合物。
[4]如上述[1]所記載之光阻下層膜形成用組成物,其中,上述(B)具有丁醚基之交聯劑係選自以下述式(1)及(2)所表示之化合物之群中至少1種之化合物。
[5]如上述[1]~[4]中任一者所記載之光阻下層膜形成用組成物,其中,上述(A)樹脂係由具有選自以下述式(3)~(5)所表示之構造單位之群中至少1個之構造單位之聚合物所構成者。
本發明之光阻下層膜形成用組成物,係兼具對基板間隙之埋入性與下層膜之耐蝕刻性,而且,可有效地防止成膜裝置之污染。
1‧‧‧基板
2‧‧‧第一之低介電絕緣膜
3,13‧‧‧光阻下層膜
4‧‧‧配線溝(溝渠)
5,15‧‧‧障壁金屬
6‧‧‧下層銅配線層
7‧‧‧第二之低介電絕緣膜
8‧‧‧第一之蝕刻停止層
9‧‧‧第三之低介電絕緣膜
10‧‧‧第二之蝕刻停止層
11‧‧‧光阻下層膜
12‧‧‧通孔
14‧‧‧溝渠
16‧‧‧通孔配線
17‧‧‧上層銅配線層
圖1係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖2係說明使用本發明之光阻下層膜形成用組成物之
雙鑲嵌構造之形成方法之一步驟之模式圖。
圖3係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖4係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖5係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖6係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖7係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖8係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖9係說明使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一步驟之模式圖。
圖10係表示施加配線於使用本發明之光阻下層膜形成用組成物所形成之雙鑲嵌構造後之狀態之剖面圖。
以下,對於本發明之實施形態作說明,而本發明並非受到以下之實施形態所限定者。亦即,可理解為在不逸脫本發明之趣旨之範圍,根據業界人士之通常知識,對以下之實施形態加以適宜變更、改良等而成者亦屬於本發明之範圍。
本發明之光阻下層膜形成用組成物,係含有(A)樹脂、(B)具有丁醚基之交聯劑及(C)溶劑。
本發明之光阻下層膜形成用組成物,係含有樹脂(以下,有記為「樹脂(A)」之情況)。本發明之組成物中,樹脂(A)係為了發揮充分之耐蝕刻性,因此以玻璃轉移溫度為130℃以上之樹脂為佳,由具有萘、尤其苊烯骨架之聚合物所構成者為更佳,由具有選自以下述式(3)~(6)所表示之構造單位之群中至少1個之構造單位之聚合物所構成者為特佳。
以上述式(3)所表示之構造單位(構造單位(3))中,就以R3所表示之1價之有機基而言,係以碳數1~10之基
為佳。具體而言,可列舉苯基、烷基、烯基、醯基、或該等之基之一部分被鹵素原子、羥基、巰基、羧基、硝基、磺酸基等之官能基取代之官能基。上述被取代之官能基,係亦可被以2種以上之官能基取代。
就上述烷基而言,係以碳數1~6之直鏈狀或分枝狀之烷基為佳。
具體而言,可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基等。另外,就上述烯基而言,可列舉碳數2~6之直鏈狀或分枝狀之烯基為佳。具體而言,乙烯基、丙烯基、甲基烯丙基、1-丁烯基、2-丁烯基等。再者,就上述醯基而言,係以碳數2~6之脂肪族或芳香族之醯基為佳。具體而言,可列舉乙醯基、丙醯基、丁醯基、苯甲醯基等。
於構造單位(3)中,就以R4或R5所表示之1價之原子而言,除了可列舉例如氫原子之外,還有氟原子、氯原子、溴原子等之鹵素原子等。
另外,就以R4或R5所表示之1價之有機基而言,可列舉作為以R3所表示之1價之有機基所例示之基。
於構造單位(3)中,就以R3所表示之基而言,係以氫原子、甲基、乙醯基為佳。另外,就以R4或R5所表示之基而言,係以氫原子、甲基、苯基為佳。
具有構造單位(3)之聚合物,係可藉由例如單獨使對應於構造單位(3)之苊烯類,或因應目的與其他之共聚合性不飽和化合物一起,進行自由基聚合、陰離子聚合、陽
離子聚合等而得到。該等之聚合,係可藉塊狀聚合、溶液聚合等以往周知之聚合形態進行。
另外,具有R3為氫原子之構造單位(3)之聚合物,亦可藉由將具有R3為乙醯基之構造單位(3)之聚合物之乙醯氧基以常法水解而製造。另外,具有R3為乙醯基之構造單位(3)之聚合物,亦可藉由將具有R3為氫原子之構造單位(3)之聚合物之羥基以常法乙醯化而製造。
對應於構造單位(3)之苊烯類而言,可列舉例如3-羥甲基苊烯、4-羥甲基苊烯、5-羥甲基苊烯、1-甲基-3-羥甲基苊烯、1-甲基-4-羥甲基苊烯、1-甲基-5-羥甲基苊烯、1-甲基-6-羥甲基苊烯、1-甲基-7-羥甲基苊烯、1-甲基-8-羥甲基苊烯、1,2-二甲基-3-羥甲基苊烯、1,2-二甲基-4-羥甲基苊烯、1,2-二甲基-5-羥甲基苊烯、1-苯基-3-羥甲基苊烯、1-苯基-4-羥甲基苊烯、1-苯基-5-羥甲基苊烯、1-苯基-6-羥甲基苊烯、1-苯基-7-羥甲基苊烯、1-苯基-8-羥甲基苊烯、1,2-二苯基-3-羥甲基苊烯、1,2-二苯基-4-羥甲基苊烯、1,2-二苯基-5-羥甲基苊烯等之羥甲基苊烯類;3-乙醯氧基甲基苊烯、4-乙醯氧基甲基苊烯、5-乙醯氧基甲基苊烯、1-甲基-3-乙醯氧基甲基苊烯、1-甲基-4-乙醯氧基甲基苊烯、1-甲基-5-乙醯氧基甲基苊烯、1-甲基-6-乙醯氧基甲基苊烯、1-甲基-7-乙醯氧基甲基苊烯、1-甲基-8-乙醯氧基甲基苊烯、1,2-二甲基-3-乙醯氧基甲基苊烯、1,2-二甲基-4-乙醯氧基甲基苊烯、1,2-二甲基-5-乙醯氧基甲基苊烯、1-苯基-3-乙醯氧基甲基苊烯、1-苯基-
4-乙醯氧基甲基苊烯、1-苯基-5-乙醯氧基甲基苊烯、1-苯基-6-乙醯氧基甲基苊烯、1-苯基-7-乙醯氧基甲基苊烯、1-苯基-8-乙醯氧基甲基苊烯、1,2-二苯基-3-乙醯氧基甲基苊烯、1,2-二苯基-4-乙醯氧基甲基苊烯、1,2-二苯基-5-乙醯氧基甲基苊烯等之乙醯氧基甲基苊烯類;3-甲氧基甲基苊烯、4-甲氧基甲基苊烯、5-甲氧基甲基苊烯、1-甲基-3-甲氧基甲基苊烯、1-甲基-4-甲氧基甲基苊烯、1-甲基-5-甲氧基甲基苊烯、1-甲基-6-甲氧基甲基苊烯、1-甲基-7-甲氧基甲基苊烯、1-甲基-8-甲氧基甲基苊烯、1,2-二甲基-3-甲氧基甲基苊烯、1,2-二甲基-4-甲氧基甲基苊烯、1,2-二甲基-5-甲氧基甲基苊烯、1-苯基-3-甲氧基甲基苊烯、1-苯基-4-甲氧基甲基苊烯、1-苯基-5-甲氧基甲基苊烯、1-苯基-6-甲氧基甲基苊烯、1-苯基-7-甲氧基甲基苊烯、1-苯基-8-甲氧基甲基苊烯、1,2-二苯基-3-甲氧基甲基苊烯、1,2-二苯基-4-甲氧基甲基苊烯、1,2-二苯基-5-甲氧基甲基苊烯等之甲氧基甲基苊烯類;其他3-苯氧基甲基苊烯、4-苯氧基甲基苊烯、5-苯氧基甲基苊烯、3-乙烯基氧甲基苊烯、4-乙烯基氧甲基苊烯、5-乙烯基氧甲基苊烯等。
該等之苊烯類之內、特別是,3-羥甲基苊烯、4-羥甲基苊烯、5-羥甲基苊烯、3-乙醯氧基甲基苊烯、4-乙醯氧基甲基苊烯、5-乙醯氧基甲基苊烯、3-甲氧基甲基苊烯、4-甲氧基甲基苊烯、5-甲氧基甲基苊烯等為佳。上述苊烯類,係可單獨使用或混合2種以上使用。
具有構造單位(3)之聚合物,係具有藉由加熱或曝光,於分子鏈間形成交聯之特性。除了適合使用作為如本發明之光阻下層膜形成用組成物之外,亦可以其單獨或與其他硬化性樹脂或硬化性橡膠混合,而使用作為塗料、接著劑、絕緣劑等。
以上述式(4)所表示之構造單位(構造單位(4))中,就以R6或R7所表示之1價之原子、1價之有機基而言,可列舉在構造單位(3)之項目中,作為以R4或R5所表示之1價之原子、1價之有機基所例示之基。構造單位(4)中,就R4或R5而言,係以氫原子、甲基為佳。
以上述式(5)所表示之構造單位(構造單位(5))中,就R8之1價之有機基而言,可列舉例如與關於構造單位(3)中之R3之1價之有機基所例示之基相同者,另外,就R9之1價之原子及1價之有機基而言,可列舉例如與關於構造單位(3)中之R4及R5各自之1價之原子及1價之有機基之例示相同者。
於構造單位(5)中,就R8而言尤其以氫原子、甲基等為佳。另外,就R9而言,尤其以氫原子、甲基等為佳。
具有構造單位(5)之聚合物,係可藉由例如單獨使對應於構造單位(5)之芳香族乙烯基系化合物,或因應目的與其他共聚合性不飽和化合物一起,進行自由基聚合、陰離子聚合、陽離子聚合等而得到。該等之聚合,係可藉塊狀聚合、溶液聚合等以往周知之聚合形態進行。
另外,具有R8為氫原子之構造單位(5)之聚合物,亦
可藉由將具有R8為乙醯基之構造單位(5)之聚合物之乙醯氧基以常法水解而製造。另外,具有R8為乙醯基之構造單位(5)之聚合物亦可藉由將具有R8為氫原子之構造單位(5)之聚合物之羥基以常法乙醯化而製造。
就對應於構造單位(5)之芳香族乙烯基系化合物而言,可列舉例如2-羥甲基苯乙烯、3-羥甲基苯乙烯、4-羥甲基苯乙烯、2-羥甲基-α-甲基苯乙烯、3-羥甲基-α-甲基苯乙烯、4-羥甲基-α-甲基苯乙烯等之羥甲基苯乙烯系化合物;2-甲氧基甲基苯乙烯、3-甲氧基甲基苯乙烯、4-甲氧基甲基苯乙烯、2-甲氧基甲基-α-甲基苯乙烯、3-甲氧基甲基-α-甲基苯乙烯、4-甲氧基甲基-α-甲基苯乙烯等之甲氧基甲基苯乙烯系化合物;4-苯氧基甲基苯乙烯、4-苯氧基甲基-α-甲基苯乙烯、4-乙烯基氧甲基苯乙烯、4-乙烯基氧甲基-α-甲基苯乙烯、4-乙醯氧基甲基苯乙烯、4-乙醯氧基甲基-α-甲基苯乙烯等之其他之苯乙烯系化合物;
4-羥甲基-1-乙烯基萘、7-羥甲基-1-乙烯基萘、8-羥甲基-1-乙烯基萘、4-羥甲基-1-異丙烯基萘、7-羥甲基-1-異丙烯基萘、8-羥甲基-1-異丙烯基萘等之羥甲基-1-乙烯基萘系化合物;4-甲氧基甲基-1-乙烯基萘、7-甲氧基甲基-1-乙烯基萘、8-甲氧基甲基-1-乙烯基萘、4-甲氧基甲基-1-異丙烯基萘、7-甲氧基甲基-1-異丙烯基萘、8-甲氧基甲基-1-異丙烯基萘等之甲氧基甲基-1-乙烯基萘系化合物;4-苯氧基甲基-1-乙烯基萘、4-乙烯基氧甲基-1-乙烯基萘、4-乙醯氧基甲基-1-乙烯基萘、4-苯氧基甲基-1-異丙
烯基萘、4-乙烯基氧甲基-1-異丙烯基萘、4-乙醯氧基甲基-1-異丙烯基萘等之其他之乙烯基萘系化合物等。
於該等之芳香族乙烯基系化合物之中,係以4-羥甲基苯乙烯、4-甲氧基甲基苯乙烯為特佳。上述芳香族乙烯基系化合物,係可單獨使用或混合2種以上使用。
另外,就得到具有構造單位(3)~(5)之聚合物時所使用之其他共聚合性不飽和化合物而言,可列舉例如苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、1-乙烯基萘、2-乙烯基萘、9-乙烯基蔥、9-乙烯基咔唑等之其他之芳香族乙烯基系化合物;醋酸乙烯酯、丙酸乙烯酯、己酸乙烯酯等之乙烯酯系化合物;(甲基)丙烯腈、α-氯丙烯腈、氰化亞乙烯等之氰化乙烯基系化合物;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸縮水甘油酯等之不飽和羧酸酯系化合物;乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、(甲基)丙烯酸乙烯基、二甲基.乙烯基.(甲基)丙烯醯基氧甲基矽烷等含不飽和基之不飽和羧酸酯系化合物;2-氯乙基乙烯醚、氯醋酸乙烯酯、氯醋酸烯丙酯等含鹵素之乙烯基系化合物;2-羥乙基(甲基)丙烯酸酯、(甲基)丙烯酸2-羥丙酯、(甲基)烯丙醇等含羥基之乙烯基系化合物;(甲基)丙烯醯胺、巴豆酸醯胺等含醯胺基之乙烯基系化合物;琥珀酸單[2-(甲基)丙烯醯基氧乙基]、馬來酸單
[2-(甲基)丙烯醯基氧乙基]、苯二甲酸單[2-(甲基)丙烯醯基氧乙基]等含羧基之有乙烯基系化合物等。上述其他之共聚合性不飽和化合物,係可單獨使用或混合2種以上使用。
以上述式(6)所表示之構造單位(構造單位(6))中,就取代基R10之可具有碳數1~6之取代基之烷基而言,可列舉甲基、乙基、正丙基、異丙基、正丁基、1-甲基丙基、2-甲基丙基、第三丁基、正戊基、正己基等。其中,尤其以甲基、乙基為佳。
就可具有碳數1~6之取代基之烷氧基而言,可列舉甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、1-甲基丙氧基、2-甲基丙氧基、第三丁氧基、正戊氧基、正己氧基等。其中,尤其以甲氧基、第三丁氧基為佳。
就可具有碳數2~10之取代基之烷氧羰基而言,可列舉甲氧羰基、乙氧羰基、正丙氧羰基、異丙氧羰基、正丁氧羰基、1-甲基丙氧羰基、2-甲基丙氧羰基、第三丁氧羰基、正戊氧羰基、正己氧羰基等。其中,尤其以甲氧羰基、乙氧羰基、第三丁氧羰基為佳。
就可具有碳數6~14之取代基之芳香基而言,可列舉苯基、萘基、蔥基、芘基等。其中,尤其以苯基、萘基為佳。
就以上述X所表示之可具有碳數1~20之取代基之伸烷基而言,可列舉亞甲基、伸乙基、甲基亞甲基、2-糠基亞甲基、苯亞甲基、萘亞甲基、蔥基亞甲基、芘基亞甲基
等。其中,尤其以亞甲基、甲基亞甲基、2-糠基亞甲基為佳。
另外,就可具有碳數6~14之取代基之伸芳香基而言,可列舉伸苯基、伸萘基、亞聯苯基、伸茬基等。其中,尤其以伸苯基、伸萘基為佳。
就伸烷基而言,係以碳數為1~20並且可取代者為佳,可列舉例如亞甲基、伸乙基等。
就上述伸芳香基而言,係以碳數6~14並且可取代者為佳,可列舉例如伸苯基、伸萘基等。
具有構造單位(6)之聚合物,係可藉由例如以下所述之合成法(i)或合成法(ii)合成。合成法(i),係使對應於構造單位(6)之萘衍生物與醛類在酸觸媒之存在下,進行單獨縮合或與其他可共縮合之成分進行共縮合之方法。另一方面,合成法(ii),係使對應於構造單位(6)之萘衍生物與二乙烯基化合物類在酸觸媒之存在下進行單獨縮合或與其他可共縮合之成分進行共縮合之方法。
就醛類而言,可列舉例如甲醛、三聚甲醛、乙醛、丙醛等之飽和脂肪族醛類;丙烯醛、甲基丙烯醛等之不飽和脂肪族醛類;呋喃甲醛等之雜環式醛類;苯甲醛、萘甲醛、蔥甲醛等之芳香族醛類等。其中,尤其以甲醛、三聚甲醛或呋喃甲醛為特佳。該等係可單獨使用1種,或混合2種以上使用。
就二乙烯基化合物類而言,可列舉例如二乙烯苯、二環戊二烯、四氫茚、4-乙烯基環己烯、5-乙烯基降冰片-2-
烯、α-蒎烯、β-蒎烯、薴烯、5-乙烯基降冰片二烯等。其中,尤其以二乙烯苯為特佳。該等係可單獨使用1種,或混合2種以上使用。
該等之縮合反應中,亦可添加芳香族烴類(以下,有簡單記為「芳香族類」之情況)。作為其他共縮合成分。在此情況下,使用萘衍生物以及該芳香族類作為反應成分。此情況之縮合反應,係藉由將上述萘衍生物、芳香族類及醛類混合,在酸觸媒之存在下,於無溶劑或溶劑中加熱而進行。
就芳香族類而言,只要可與萘衍生物進行共縮合聚合之芳香族類,使用任一者皆可。可列舉例如、苯、萘、蔥、菲、苊等之無取代芳香族烴類;甲苯、m-二甲苯、p-二甲苯、1-甲萘、1,5-二甲基萘等之烷基取代芳香族烴類;酚、甲酚、1-萘酚、雙酚類、多價酚類等之羥取代芳香族烴類;安息香酸、1-萘羧酸、9-蔥羧酸等之羧基取代芳香族烴類;苯胺等之胺基取代芳香族烴類;氯苯、溴苯等之鹵化芳香族烴類等。該等係可單獨使用1種,或混合2種以上使用。
樹脂(A)之中,構造單位(3)之含有率,相對於全構造單位係以5~80莫耳%為佳,10~60莫耳%為更佳,30~60莫耳%為特佳。構造單位(4)之含有率,相對於全構造單位係以5~95莫耳%為佳,10~90莫耳%為更佳,20~90莫耳%為特佳。構造單位(5)之含有率,相對於全構造單位,係以5~80莫耳%為佳,5~60莫耳%為更佳,5~
40莫耳%為特佳。構造單位(6)之含有率,相對於全構造單位,係以5~100莫耳%為佳,10~90莫耳%為更佳,30~80莫耳%為特佳。來自其他共聚合性不飽和化合物、或其他之共縮合成分之構造單位之含有率,相對於全構造單位係以50莫耳%以下為佳,30莫耳%以下為更佳。
樹脂(A)之藉由凝膠透過層析所測定之聚苯乙烯換算質量平均分子量(以下有記為「Mw」之情況)。,係因應組成物所需要之特性適當地決定即可,而以500~5,000為佳,800~3,000為佳。藉由將質量平均分子量定為500以上,光阻下層膜形成用組成物之塗佈性成為良好。另外,藉由將質量平均分子量定為5,000以下,可提升埋入性。
光阻下層膜形成用組成物中之樹脂(A)之含量,係依照所形成之光阻下層膜之膜厚而有所不同,而通常為5~30質量%,宜為8~15質量%。藉由將樹脂之含量定為5質量%以上,可形成膜厚充分之光阻下層膜。另外,藉由將樹脂之含量定為30質量%以下,可使黏性降低、提升對基板間隙之埋入性。
於光阻下層膜形成用組成物中,為了防止暈光而添加交聯劑為一般的情形,而以往所使用之交聯劑係容易昇華,在形成光阻下層膜之時,有污染成膜裝置之不適合情形。另外,即使使用難以昇華之交聯劑,亦有由於其分解
物昇華,而導致成膜裝置受到污染之情況。
於是,於本發明之光阻下層膜形成用組成物,係定為含有具有丁醚基之交聯劑(以下,有記為「交聯劑(B)」之情況)。具有丁醚基之交聯劑係昇華性低,另外,由分解所生成之1-丁烯、2-丁烯、異丁烯等,在標準條件下係氣態之物質。因此,在形成光阻下層膜時,可有效地防止污染成膜裝置之不適合情形。
就「丁醚基」而言,可列舉例如正丁醚基、異丁醚基、第三丁醚基等。其中,尤其以正丁醚基為佳。
就具有丁醚基之交聯劑而言,可列舉例如丁醚基變性多核酚、丁醚基變性胺基樹脂等。
就丁醚基變性多核酚而言,可列舉例如4,4'-聯苯二酚、4,4'-亞甲基雙酚、4,4'-亞乙基雙酚、雙酚A等之2核酚類;4,4',4"-亞甲基三苯酚、4,4'-[1-{4-(1-[4-羥苯基]-1-甲基乙基)苯基}亞乙基]雙酚等之3核酚類;酚醛等之將丁醚基導入於多酚類等者。
就上述丁醚基變性胺基樹脂而言,可列舉將尿素、硫脲、乙烯尿素、三聚氰胺苯胍胺等與甲醛之共縮合物之胺基樹脂,以正丁醇或異丁醇進行處理,而導入丁醚基者等。
但,在本發明之光阻下層膜形成用組成物中,就交聯劑而言,係以配合具有至少2個丁醚基之含氮環狀化合物者為佳。「含氮環狀化合物」係只要在環構造中含有氮原子之複素環化合物即足夠,關於其環構造等並無特別限
制。例如、5員環、6員環、員數更高之環,除此之外亦可為該等之縮合環。其中,尤其以二個5員環縮合之縮合環或6員環為佳。
關於環構造中所含之氮原子之數亦無特別限制,而以每一個環含2~3個之氮原子之環構造為佳,就環全體而言以含3~4個之氮原子之環構造為佳。另外,就化合物全體而言以含4~6個之氮原子之構造為佳。
若將該等之條件總合地考慮,則上述含氮環狀化合物係以具有甘脲骨架之化合物為佳。就具有至少2個丁醚基,進一步具有甘脲骨架之化合物而言,可列舉以下述式(1)所表示之化合物。亦即,在本發明之光阻下層膜形成用組成物中,就交聯劑而言,係以配合以下述式(1)所表示之化合物者為佳。此化合物係於甘脲之4個之氮原子,分別導入烷氧基甲基,而該等之烷氧基甲基之中至少2個為丁氧基甲基之化合物。
另外,上述含氮環狀化合物,係具有三嗪骨架之化合物亦為適合形態之一種。三嗪骨架係以1,3,5-三嗪骨架為較佳,三聚氰胺骨架為更佳。就具有至少2個之丁醚基、進一步具有三嗪骨架之化合物而言,可列舉以下述式(2)所表示之化合物。亦即,本發明之光阻下層膜形成用組成物中,交聯劑係以配合以下述式(2)所表示之化合物為佳。此化合物,係六羥甲三聚氰胺之6個羥基各自受到烷醚化,該等之烷醚基中至少2個為丁醚基之化合物。
以上述式(1)或(2)所表示之化合物,由於R1或R2之至少2個以上係丁基,交聯劑之昇華性受到抑制,進而可
防止由光阻下層膜形成用組成物之昇華物導致之成膜裝置之污染。
以式(1)或(2)所表示之化合物係丁基之數目愈多,則愈可抑制交聯劑之昇華。就以式(1)或(2)所表示之化合物而言,係以R1或R2之全部為正丁基之化合物為佳。
光阻下層膜形成用組成物中之交聯劑(B)之含量,係依照所含有之聚合物之種類而有所不同,而通常係相對於樹脂100質量份為1~50質量份,宜為5~30質量份。藉由將交聯劑之含量定為1質量份以上,可提升交聯性能,並有效地防止光阻下層膜之暈光。另外,藉由將交聯劑之含量定為50質量份,可有效地防止起因於未反應之交聯劑(並未與樹脂進行反應之自由交聯劑)殘存於光阻下層膜中而造成之耐蝕刻性降低。
就本發明之光阻下層膜形成用組成物所使用之溶劑而言,只要為可溶解樹脂(A)及交聯劑(B)、及後述之添加劑者,係並未受到特別限定。
適當地選擇使用例如,乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單正丁醚等之乙二醇單烷醚類;乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單正丙醚乙酸酯、乙二醇單正丁醚乙酸酯等之乙二醇單烷醚乙酸酯類;二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二正丙醚、二乙二醇二正丁醚等之二乙二醇二烷醚類;
三乙二醇二甲醚、三乙二醇二乙醚等之三乙二醇二烷醚類;丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單正丁醚等之丙二醇單烷醚類;丙二醇二甲醚、丙二醇二乙醚、丙二醇二正丙醚、丙二醇二正丁醚等之丙二醇二烷醚類;丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單正丙醚乙酸酯、丙二醇單正丁醚乙酸酯等之丙二醇單烷醚乙酸酯類;乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸異丙酯、乳酸正丁酯、乳酸異丁酯等之乳酸酯類;蟻酸甲酯、蟻酸乙酯、蟻酸正丙酯、蟻酸異丙酯、蟻酸正丁酯、蟻酸異丁酯、蟻酸正戊酯、蟻酸異戊酯、醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、醋酸正戊酯、醋酸異戊酯、醋酸正己酯、丙酸甲酯、丙酸乙酯、丙酸正丙酯、丙酸異丙酯、丙酸正丁酯、丙酸異丁酯、酪酸甲酯、酪酸乙酯、酪酸正丙酯、酪酸異丙酯、酪酸正丁酯、酪酸異丁酯等之脂肪族羧酸酯類;羥醋酸乙酯、2-羥-2-甲基丙酸乙酯、3-甲氧基-2-甲基丙酸甲酯、2-羥-3-甲基酪酸甲酯、甲氧基醋酸乙酯、乙氧基醋酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸乙酯、3-甲氧基丙基乙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、3-甲基-3-甲氧基丁基丁酸酯、乙醯醋酸甲酯、丙酮酸甲酯、丙酮酸乙酯等之其他之酯類;甲苯、二
甲苯等之芳香族烴類;甲基乙基酮、甲基正丙基酮、甲基正丁基酮、2-庚酮、3-庚酮、4-庚酮、環己酮等之酮類;N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮等之醯胺類;γ-丁內酯等之內酯類等即可。
該等之溶劑之內,宜為、乙二醇單乙醚乙酸酯、乳酸乙酯、醋酸正丁酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮等。上述溶劑,係可單獨使用或混合2種以上使用。
溶劑之使用量係通常為使所得到之組成物之固體成分濃度成為0.01~70質量%之範圍,宜為0.05~60質量%、更佳為0.1~50質量%。
對於本發明之光阻下層膜形成用組成物而言,只要不損及本發明之效果,可因應必要配合酸產生劑、黏結劑、放射線吸收劑、界面活性劑、保存安定劑、消泡劑、接著助劑等之各種添加劑。
就酸產生劑而言,可使用藉由化學刺激或物理刺激產生酸之物質。
可列舉例如藉由曝光產生酸之光酸產生劑或藉由加熱產生酸之熱酸產生劑。
就光酸產生劑而言,可列舉例如二苯錪鎓三氟甲烷磺酸鹽、二苯錪鎓九氟正丁烷磺酸鹽、二苯錪鎓芘磺酸鹽、
二苯錪鎓正十二基苯磺酸鹽、二苯錪鎓10-樟腦磺酸鹽、二苯錪鎓萘磺酸鹽、二苯錪鎓六氟銻酸鹽、雙(4-第三丁基苯基)錪鎓三氟甲烷磺酸鹽、雙(4-第三丁基苯基)錪鎓九氟正丁烷磺酸鹽、雙(4-第三丁基苯基)錪鎓正十二基苯磺酸鹽、雙(4-第三丁基苯基)錪鎓10-樟腦磺酸鹽、雙(4-第三丁基苯基)錪鎓萘磺酸鹽、雙(4-第三丁基苯基)錪鎓六氟銻酸鹽、三苯鋶三氟甲烷磺酸鹽、三苯鋶九氟正丁烷磺酸鹽、三苯鋶正十二基苯磺酸鹽、三苯鋶萘磺酸鹽、三苯鋶10-樟腦磺酸鹽、三苯鋶六氟銻酸鹽、4-羥苯基.苯基.甲基鋶P-甲苯磺酸鹽、4-羥苯基.苄基.甲基鋶p-甲苯磺酸鹽、環己基.甲基.2-氧代環己基鋶三氟甲烷磺酸鹽、2-氧代環己基二環己基鋶三氟甲烷磺酸鹽、2-氧代環己基二甲基鋶三氟甲烷磺酸鹽、1-萘二甲基鋶三氟甲烷磺酸鹽、1-萘二乙基鋶三氟甲烷磺酸鹽、4-氰-1-萘二甲基鋶三氟甲烷磺酸鹽、4-氰-1-萘二乙基鋶三氟甲烷磺酸鹽、4-硝基-1-萘二甲基鋶三氟甲烷磺酸鹽、4-硝基-1-萘二乙基鋶三氟甲烷磺酸鹽、4-甲基-1-萘二甲基鋶三氟甲烷磺酸鹽、4-甲基-1-萘二乙基鋶三氟甲烷磺酸鹽、4-羥-1-萘二甲基鋶三氟甲烷磺酸鹽、4-羥-1-萘二乙基鋶三氟甲烷磺酸鹽、1-(4-羥萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-甲氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-乙氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-甲氧基甲氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-乙氧基甲氧基萘-
1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-[4-(1-甲氧基乙氧基)萘-1-基]四氫噻吩鎓三氟甲烷磺酸鹽、1-[4-(2-甲氧基乙氧基)萘-1-基]四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-甲氧基羰氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-乙氧基羰氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-正丙氧基羰氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-異丙氧基羰氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-正丁氧基羰氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-第三丁氧基羰氧基萘-1-基)四氫噻吩鎓三氟甲烷磺酸鹽、1-[4-(2-四氫呋喃氧基)萘-1-基]四氫噻吩鎓三氟甲烷磺酸鹽、1-[4-(2-四氫吡喃氧基)萘-1-基]四氫噻吩鎓三氟甲烷磺酸鹽、1-(4-苄氧基)四氫噻吩鎓三氟甲烷磺酸鹽、1-(萘乙醯甲基)四氫噻吩鎓三氟甲烷磺酸鹽等之鎓鹽系光酸產生劑;苯基雙(三氯甲基)-s-三嗪、4-甲氧基苯基雙(三氯甲基)-s-三嗪、1-萘雙(三氯甲基)-s-三嗪等之鹵素含有化合物系光酸產生劑;1,2-萘醌二疊氮-4-磺醯氯、1,2-萘醌二疊氮-5-磺醯氯、2,3,4,4'-四羥二苯基酮之1,2-萘醌二疊氮-4-磺酸酯或1,2-萘醌二疊氮-5-磺酸酯等之重氮酮化合物系光酸產生劑;4-參苯甲醯甲基碸、均三甲苯基苯甲醯甲基碸、雙(苯磺醯基)甲烷等之碸化合物系光酸產生劑;苯偶姻甲苯磺酸酯、五倍子酚之參(三氟甲烷磺酸鹽)、硝基苄基-9,10-二乙氧基蔥-2-磺酸鹽、三氟甲烷磺醯基雙環[2,2,1]庚-5-烯-2,3-二碳二醯亞胺、N-羥基琥珀醯亞胺三氟
甲烷磺酸鹽、1,8-萘二羧酸醯亞胺三氟甲烷磺酸鹽等之磺酸化合物系光酸產生劑;等。
該等之光酸產生劑之內、二苯錪鎓三氟甲烷磺酸鹽、二苯錪鎓九氟正丁烷磺酸鹽、二苯錪鎓芘磺酸鹽、二苯錪鎓正十二基苯磺酸鹽、二苯錪鎓10-樟腦磺酸鹽、二苯錪鎓萘磺酸鹽、雙(4-第三丁基苯基)錪鎓三氟甲烷磺酸鹽、雙(4-第三丁基苯基)錪鎓九氟正丁烷磺酸鹽、雙(4-第三丁基苯基)錪鎓正十二基苯磺酸鹽、雙(4-第三丁基苯基)錪鎓10-樟腦磺酸鹽、雙(4-第三丁基苯基)錪鎓萘磺酸鹽為佳。該等之光酸產生劑,係可單獨使用或混合2種以上使用。
另外,就藉由加熱產生酸之酸產生劑(以下,稱為「熱酸產生劑」)。而言,可列舉例如2,4,4,6-四溴環己二烯酮、苯偶姻甲苯磺酸酯、2-硝基苄基甲苯磺酸酯、烷基磺酸鹽類等。該等之熱酸產生劑,係可單獨使用或混合2種以上使用。另外,酸產生劑亦可併用光酸產生劑與熱酸產生劑。
酸產生劑,係通常以相對於光阻下層膜形成用組成物之固體成分100質量份為5,000質量份以下作配合,而宜為0.1~1,000質量份、更佳為0.1~100質量份。本發明之光阻下層膜形成用組成物,係藉由含有光酸產生劑及/或熱酸產生劑,於包含常溫之較低溫度可在各聚合物之分子鏈間有效地使交聯形成。
另外,就黏結劑而言,可使用各種之熱塑性樹脂或熱固性樹脂。就上述熱塑性樹脂而言,可列舉例如聚乙烯、
聚丙烯、聚-1-丁烯、聚-1-戊烯、聚-1-己烯、聚-1-庚烯、聚-1-辛烯、聚-1-癸烯、聚-1-十二烯、聚-1-十四烯、聚-1-十六烯、聚-1-十八烯、聚乙烯基環烷烴等之α-烯烴系聚合物;聚-1,4-戊二烯、聚-1,4-己二烯、聚-1,5-己二烯等之非共軛二烯系聚合物;α,β-不飽和醛系聚合物;聚(甲基乙烯基酮)、聚(芳香族乙烯基酮)、聚(環狀乙烯基酮)等之α,β-不飽和酮系聚合物;(甲基)丙烯酸、α-氯丙烯酸、(甲基)丙烯酸鹽、(甲基)丙烯酸酯、(甲基)丙烯酸鹵化物等之α,β-不飽和羧酸或其衍生物之聚合物;聚(甲基)丙烯酸酐、無水馬來酸之共聚物等之α,β-不飽和羧酸酐之聚合物;亞甲基丙二酸二酯、伊康酸二酯等之不飽和多鹼性羧酸酯之聚合物;
山梨酸酯、黏康酸酯等之二烯烴羧酸酯之聚合物;(甲基)丙烯酸硫酯、α-氯丙烯酸硫酯等之α,β-不飽和羧酸硫酯之聚合物;(甲基)丙烯腈、α-氯丙烯腈等之(甲基)丙烯腈或其衍生物之聚合物;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺等之(甲基)丙烯醯胺或其衍生物之聚合物;苯乙烯基金屬化合物之聚合物;乙烯氧基金屬化合物之聚合物;聚亞胺;聚苯醚、聚-1,3-二噁戊烷、聚環氧乙烷、聚四氫呋喃、聚四氫吡喃等之聚醚;聚硫醚;聚磺醯胺;聚胜肽;耐綸66、耐綸1~耐綸12等之聚醯胺;脂肪族聚酯、芳香族聚酯、脂環族聚酯、聚碳酸酯等之聚酯;聚尿素;聚碸;聚吖嗪;聚胺;聚芳香族酮;聚醯亞胺;聚苯并咪唑;聚苯並噁唑;聚苯并噻唑;聚胺基三
唑;聚噁二唑;聚吡唑;聚四唑;聚喹惡啉;聚三嗪;聚苯并噁嗪酮;聚喹啉;聚蔥唑啉(Anthrazoline);等。
另外,熱固性樹脂,係藉由加熱而硬化,變成不溶於溶劑,具有防止所得到之光阻下層膜、與形成於其上之光阻被膜間之互混作用之成分,可適合使用作為黏結劑。就如此之熱固性樹脂而言,可列舉例如熱硬化性丙烯酸系樹脂、酚樹脂、尿素樹脂、三聚氰胺樹脂、胺基系樹脂、芳香族烴樹脂、環氧樹脂、醇酸樹脂等。該等之熱固性樹脂之內、尿素樹脂、三聚氰胺樹脂、芳香族烴樹脂等為佳。
黏結劑係可單獨使用或混合2種以上使用。黏結劑之配合量,相對於樹脂(A)100質量份,通常為20質量份以下,宜為10質量份以下。
另外,就上述放射線吸收劑而言,可列舉例如油溶性染料、分散染料、鹼性染料、次甲基系染料、吡唑系染料、咪唑系染料、羥基偶氮系染料等之染料;胭脂木酯(bixin)衍生物、降胭脂木酯(norbixin)、茋、4,4'-二胺基茋衍生物、香豆素衍生物、吡唑啉衍生物等之螢光增白劑;羥基偶氮系染料、TINUVIN 234(商品名,CIBA-GEIGY公司製)、TINUVIN 1130(商品名,CIBA-GEIGY公司製)等之紫外線吸收劑;蔥衍生物、蔥醌衍生物等之芳香族化合物等。該等之放射線吸收劑,係可單獨使用或混合2種以上使用。放射線吸收劑之配合量,係相對於光阻下層膜形成用組成物之固體成分100質量份,通常為100質量份以下,宜為50質量份以下。
另外,界面活性劑係具有改良塗佈性、條紋、潤濕性、顯像性等作用之成分。就如此之界面活性劑而言,可列舉例如聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油烯基醚、聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等之非離子性界面活性劑或以下商品名:KP341(信越化學工業公司製)、POLY-FLOW No.75、同型之No.95(以上,共榮社油脂化學工業公司製)、F-TOP EF101、同型之EF204、同型之EF303、同型之EF352(以上,Tochem Products公司製)、MEGAFAC F171、同型之F172、同型之F173(以上、大日本墨水化學工業公司製)、Fluorad FC430、同型之FC431、同型之FC135、同型之FC93(以上,住友3M公司製)、Asahiguard AG710、Surflon S382、同型之SC101、同型之SC102、同型之SC103、同型之SC104、同型之SC105、同型之SC106(以上,旭硝子公司製)等。
該等之界面活性劑,係可單獨使用或混合2種以上使用。界面活性劑之配合量,相對於光阻下層膜形成用組成物之固體成分100質量份,通常為15質量份以下,宜為10質量份以下。
本發明之光阻下層膜形成用組成物,其製造方法並無特別限制。例如,藉由於樹脂(A)及交聯劑(B)添加上述溶劑、調整成為既定之固體成分濃度,其後以孔徑0.1μm程
度之過濾器過濾,可得到光阻下層膜形成用組成物。
若使用本發明之光阻下層膜形成用組成物,則可形成雙鑲嵌構造。以下,對於使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法進行說明。
雙鑲嵌構造,係可藉由具備下述步驟之方法形成:將配置於光阻下層膜(係藉由本發明之光阻下層膜形成用組成物所形成)之表面、形成有光阻圖案之光阻膜作為光罩使用,使光阻膜之光阻圖案藉由蝕刻轉寫於光阻下層膜之步驟(第一轉寫步驟)、將轉寫有光阻膜之光阻圖案之光阻下層膜作為光罩使用,使光阻下層膜之光阻圖案轉寫於低介電絕緣膜(係配置於光阻下層膜下)之步驟(第二轉寫步驟)、與將光阻下層膜之光阻圖案轉寫於低介電絕緣膜之後,使光阻下層膜藉由電漿灰化除去之步驟(下層膜除去步驟)。
本發明之光阻下層膜形成用組成物,係可形成良好之光阻圖案,且由於對基板之間隙之埋入性良好,故可形成無機被膜損傷小之雙鑲嵌構造。
首先,配置於光阻下層膜(係藉由上述之光阻下層膜形成用組成物所形成)表面、形成有光阻圖案之光阻膜作
為光罩使用,使光阻膜之光阻圖案藉由蝕刻轉寫於光阻下層膜。
光阻膜只要為配置於光阻下層膜(係藉由上述之光阻下層膜形成用組成物所形成)上,並形成光阻圖案者,係並無特別限制,而以藉由可形成光阻膜之光阻組成物所形成者為佳。就此光阻組成物而言,可列舉例如含有光酸產生劑之正型或負型之化學增幅型光阻組成物、由鹼可溶性樹脂與醌二疊氮系感光劑所構成之正型光阻組成物、由鹼可溶性樹脂與交聯劑所構成之負型光阻組成物等。將上述光阻膜配置於光阻下層膜之方法,係並無特別限制,例如可藉由旋轉塗佈法進行。
具體而言,可藉由以旋轉塗佈法將光阻組成物塗佈於光阻下層膜上,其後,進行預烘,使塗膜中之溶劑揮發進行。預烘之溫度,係依照使用之光阻組成物之種類等而有所不同,而係以30~200℃為佳,50~150℃為更佳。
光阻膜其膜厚係以100~20000nm為佳,100~200nm為更佳。
本發明之光阻下層膜形成用組成物,係由於成膜裝置污染之原因物質之交聯劑之昇華性低,故可不污染成膜裝置而形成光阻下層膜。
由上述光阻組成物所形成之光阻膜,係藉由上述之旋轉塗佈法等配置於光阻下層膜上之後,可藉由具有光阻程序(經過放射線之照射(曝光步驟)、顯像等之步驟)之光微影形成光阻圖案。
上述光阻程序之曝光步驟,係隔著於光阻膜描繪有元件設計之光罩(標線),藉由照射放射線,形成對應於元件設計之光阻圖案之步驟。此曝光步驟所使用之放射線,係因應光阻膜所含有之光酸產生劑之種類,可由可見光、紫外線、遠紫外線、X射線、電子射線、γ射線、分子射線、離子束等適當地作選擇。宜為遠紫外線,尤其以KrF準分子雷射(248nm)、ArF準分子雷射(193nm)、F2準分子雷射(波長157nm)、Kr2準分子雷射(波長147nm)、ArKr準分子雷射(波長134nm)、極紫外線(波長13nm等)等為佳。
上述光阻程序之顯像所使用之顯像液,係因應光阻組成物之種類適當地作選擇。就使用正型光阻組成物(含有正型化學增幅型光阻組成物或鹼可溶性樹脂)之顯像液而言,可列舉例如含氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、甲基二乙胺、二甲基.乙醇胺、三乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、吡咯、哌啶、膽鹼、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,5-二氮雜雙環[4.3.0]-5-壬烯等之鹼性水溶液。另外,於該等之鹼性水溶液,亦可適量添加水溶性有機溶劑,例如甲醇、乙醇等之醇類,或界面活性劑。
光阻下層膜之膜厚,係並無特別限制,而以100~2000nm為佳,200~1000nm為更佳,200~500nm為特佳。藉由將光阻下層膜之膜厚定為100nm以上,可形成
將基板加工所需之充分厚度之光罩。另外,藉由定為2000nm以下,可防止後述之經圖案化之下層膜之縱/橫比(長寬比)變為過大,經圖案化之下層膜崩壞之不適合情形。
然後,將上述光阻膜當作光罩使用,使光阻膜之光阻圖案藉由蝕刻轉寫於光阻下層膜。蝕刻係並無特別限制,乾式蝕刻或濕式蝕刻之任一者皆可,可藉由以往周知之方法進行。例如就乾式蝕刻之來源氣體而言,可使用例如O2、CO、CO2等含氧原子之分子所構成之氣體、He、N2、Ar等之惰性氣體、Cl2、BCl2等之氯系氣體,其他還有H2、NH3等。另外,將該等氣體混合使用亦可。
其次,藉由上述第一轉寫步驟,將轉寫有光阻膜之光阻圖案之光阻下層膜當作光罩使用,使光阻下層膜之光阻圖案轉寫於低介電絕緣膜(係配置於光阻下層膜之下)。
低介電絕緣膜(Low-k膜),係配置於光阻下層膜之下之膜,可列舉例如無機被膜,較具體而言,為藉由氧化矽、氮化矽、酸氮化矽、聚矽氧烷等所形成之絕緣膜。亦可使用藉由市售品之「BLACK DIAMOND(商品名,AMAT公司製)」、「SiLK(商品名,Dow Chemical公司製)」、「LKD5109(商品名,JSR公司製)」等所形成之膜。
上述低介電絕緣膜,係以被覆例如晶圓等基板之方式所形成之膜,其形成方法係並無特別限制,可藉由周知之
方法形成。例如,可藉由塗佈法(SOD:Spin On Dielectric)或化學氣相蒸著法(CVD:Chernical Vapor Deposition)等形成。
使用本發明之光阻下層膜形成用組成物,使光阻下層膜形成於以上述之方式形成之低介電絕緣膜之表面。配置光阻下層膜之方法並無特別限制,而可列舉例如將本發明之光阻下層膜形成用組成物,藉由旋轉塗佈法塗佈於低介電絕緣膜之表面,形成光阻下層膜之方法。
然後,將形成於光阻下層膜之光阻圖案轉寫於低介電絕緣膜。將光阻圖案轉寫之方法,係並無特別限制,可藉由先前所述之蝕刻進行。
本發明之光阻下層膜形成用組成物由於埋入性良好,因此若使用於雙鑲嵌構造之形成,則可防止在蝕刻時低介電絕緣膜曝露於電漿。因此,不會對低介電絕緣膜造成損害而可形成雙鑲嵌構造。
然後,藉由第二轉寫步驟,將光阻下層膜之光阻圖案轉寫於低介電絕緣膜之後,藉由電漿灰化除去光阻下層膜。
電漿灰化,係指為了除去在對基板作乾式蝕刻加工後殘留在基板上之光罩(例如、光阻下層膜、光阻膜),使主要為氧電漿等之反應氣體之電漿產生,於氣相中,使有機物(例如光阻下層膜、光阻膜)分解為COx或H2O等而除去
之操作。
電漿灰化之條件係以例如施加於晶座之高頻電力為100~1000W者為佳,100~500W為更佳。另外,晶座溫度係以20~100℃為佳,20~60℃為更佳。處理容器內之壓力係以1~300mtoor為佳,30~100mtoor為更佳。
電漿灰化所使用之氣體,係以可抑制灰化導致之低介電絕緣膜之比介電率上昇,而含選自氮、氫、氨、及氬所構成之群中至少一種之氣體者為佳。另外,在使用氮與氫之混合氣體之情況下,容量比係以相對於氮100,氫為0~20者為佳,氫為1~10者為更佳。另外,在使用氨與氬之混合氣體之情況下,容量比係以相對於氨100,氬為0~10者為佳。藉由如此之混合氣體之電漿,可較為有效率地除去光阻下層膜。另外,氨、氮及氫之混合氣體亦佳。
以使曝光後之光阻膜顯像之後,將此光阻膜洗淨、乾燥為佳。另外,為了提升解像度、圖案輪廓、顯像性等,亦可於曝光後、顯像前進行後烘。
另外,在光阻膜與光阻下層膜之間,可形成中間層。
中間層係意指於光阻圖案形成中,具有光阻下層膜、光阻膜、及該等之兩者所不足之機能之層。例如,於光阻下層膜抗反射機能為不足之情況下,則中間層可適用具有抗反射機能之膜。此中間層之材質,係可依照必要之機能
適宜地選擇有機化合物或無機氧化物。例如光阻膜為有機化合物之情況下,中間層亦可適用無機氧化物。
由有機化合物所構成之中間層,係可藉由以下全部商品名「DUV-42」、「DUV-44」、「ARC-28」、「ARC-29」(任一者皆為Brewer Science公司製)、AR-3」、「AR-19」(任一者皆為Rohm and Haas公司製)等形成。另外,由無機氧化物所構成之中間層,係可使用聚矽氧烷、氧化鈦、氧化氧化鋁、氧化鎢等形成。亦可使用市售品之「NFC SOG01」、「NFC SOG04」(商品名,任一者皆為JSR公司製)等形成。
就中間層之形成方法而言,可使用塗佈法或CVD法等,而宜為塗佈法。在塗佈法之情況,形成光阻下層膜之後,可連續形成中間層,而在CVD法不可連續形成。
中間層之膜厚,係依照中間層所需要之機能適宜選擇即可。但以10~3000nm為佳,20~300nm為更佳。藉由將中間層之膜厚定為10nm以上,可防止在光阻下層膜之蝕刻途中中間層被削除之不適合情形。另一方面,藉由定為3000nm以下,將光阻膜之光阻圖案轉寫於中間層時,可有效地防止發生加工變換差異之事態。
對於使用本發明之光阻下層膜形成用組成物之雙鑲嵌構造之形成方法之一實施形態,於以下具體地說明。
圖1係表示於基板1上形成低介電絕緣膜2,再於此低介電絕緣膜2上形成之光阻下層膜3,然後使用乾式蝕刻法將光阻膜之光阻圖案轉寫於該光阻下層膜3之步驟之
圖。
若使用本發明之光阻下層膜形成用組成物,則光阻下層膜之耐蝕刻性良好,可將光阻圖案良好地轉寫於光阻下層膜3。
將光阻圖案轉寫至光阻下層膜之後,如圖2所示般,將此光阻下層膜3當作光罩而於低介電絕緣膜2形成光阻圖案(溝渠)。低介電絕緣膜之光阻圖案之形成,係藉由以反應性離子蝕刻除去對應於光阻圖案部分之低介電絕緣膜而進行。圖3係表示於介電絕緣膜2形成光阻圖案之後,藉由電漿灰化將光阻下層膜3除去之步驟之圖。
另外,可因應必要,於低介電絕緣膜上形成障壁金屬膜。圖4係表示形成溝渠(配線溝)4,並在形成有配線溝4之低介電絕緣膜2之表面使障壁金屬5堆積之步驟之圖。若形成障壁金屬(障壁金屬膜),則可提升埋入配線溝內之銅與低介電絕緣膜之接著性,此外還加上可防止銅往低介電絕緣膜中擴散(遷移)。
其後,於配線溝內藉由銅電鍍等可將銅埋入而形成下層銅配線層。另外,形成光阻圖案之低介電絕緣膜,係不限為一層之情況,亦可為複數之低介電絕緣膜成為層合狀之多層。圖5係表示於配線溝4內藉由銅電鍍將銅埋入,而形成下層銅配線層6,將附著於低介電絕緣膜2之表面之銅與障壁金屬5藉由化學研磨(CMP)除去,在使低介電絕緣膜2之表面平坦化之後,於低介電絕緣膜2上,依序以層合狀之方式形成第1之低介電絕緣膜7、第1之蝕刻
停止膜8、第2之低介電絕緣膜9、及第2之蝕刻停止膜10,於最上層之蝕刻停止膜10上之光阻下層膜11形成光阻圖案之步驟之圖。
其後,如圖6所示般,將光阻下層膜11當作光罩藉由反應性離子蝕刻,使第2之蝕刻停止膜10、第2之低介電絕緣膜9、第1之蝕刻停止層8、及第1之低介電絕緣膜7貫通,形成通達下層配線層6之表面之通孔(光阻圖案)12,其後,藉由電漿灰化處理除去光阻下層膜。
藉由電漿灰化處理除去光阻下層膜之後,如圖7所示般,以將通孔12填埋之方式充填光阻下層膜形成用組成物、且以將第2之蝕刻停止10(積層體之最上面層)覆蓋之方式塗佈光阻下層膜形成用組成物,再度於光阻下層膜13形成光阻圖案。
於光阻下層膜13形成光阻圖案之後,如圖8所示般,將光阻下層膜13之光阻圖案當作光罩,藉由反應性離子蝕刻,對第2之蝕刻停止膜10與第2之低介電絕緣膜9進行蝕刻而形成溝渠(光阻圖案)14。
形成溝渠(光阻圖案)14之後,藉由電漿灰化除去光阻下層膜13。圖9係表示藉由灰化處理將通孔12內之光阻下層膜、及蝕刻停止膜10上之光阻下層膜之光阻圖案13完全除去而形成具有通孔12與溝渠14之雙鑲嵌構造之步驟之圖。
如以上之方式形成雙鑲嵌構造之後,如圖10所示般,藉由於通孔12與溝渠14形成障壁金屬15,並將銅
埋入,再進行CMP,可同時形成通孔配線16與上層銅配線層17。
另外,雙鑲嵌構造,係不限於藉由上述通孔優先(via first)而形成,亦可藉由溝渠優先(trench first)而形成。另外,藉由將以上之程序依序重覆進行可形成各式各樣之多層配線構造。
以下,列舉實施例,對本發明實施之形態作更具體地說明。但本發明完全沒有受到該等之實施例所制約。於以下「份」及「%」若沒有特別表記係以質量基準。
於以下之各合成例中所得到之聚合物(A-1)、(A-2)、(A-3)之質量平均分子量(Mw)與數平均分子量(Mn),係藉由使用東曹公司製之GPC管柱(G2000HXL:2根、G3000HXL:1根),以流量:1.0ml/分、溶出溶劑:四氫呋喃、管柱溫度:40℃之分析條件,將單分散聚苯乙烯定為標準之凝膠透過層析(偵測器:示差折射計)進行測定。
於具備溫度計之可拆式燒瓶,在氮環境氣氛下,裝入苊烯8份、5-羥甲基苊烯4份、醋酸正丁酯50份及偶氮
二異丁腈4份,攪拌同時於80℃聚合7小時。其後,將反應溶液以醋酸正丁酯100份稀釋,以大量之水/甲醇(質量比=1/2)混合溶劑洗淨有機層之後,將溶劑餾除,得到Mw為1,000之聚合物(A-1)。
於具備溫度計之可拆式燒瓶,在氮環境氣氛下,裝入苊烯5份、4-羥甲基苯乙烯5份、醋酸正丁酯48份及偶氮二異丁腈4份,攪拌同時於75℃聚合7小時。其後,將反應溶液以醋酸正丁酯100份稀釋,以大量之水/甲醇(質量比=1/2)混合溶劑洗淨有機層之後,將溶劑餾除,得到Mw為1,200之聚合物(A-2)。
於具備溫度計之可拆式燒瓶,在氮環境氣氛下,裝入2,7-二羥萘100份、丙二醇單甲醚乙酸酯100份及三聚甲醛50份,添加草酸2份之後、脫水同時昇溫至120℃,使其反應5小時。其後,將反應溶液以醋酸正丁酯100份稀釋,以大量之水/甲醇(質量比=1/2)混合溶劑洗淨有機層之後,將溶劑餾除,得到Mw為1,500之聚合物(A-3)。
使上述聚合物(A-1)10份、作為交聯劑之四丁氧基甲基甘脲(以下述式(7)表示。表1中以「B-1」表示)0.5份、作為酸產生劑之雙(4-第三丁基苯基)錪鎓九氟正丁烷磺酸鹽(以下述式(7)表示。表1中以「D-1」表示)0.5份溶解於作為溶劑之乳酸乙酯(表1中以「C-1」表示)89份而得到混合溶液。其後,將藉由以孔徑0.1μm之膜過濾器過濾此混合溶液所得到者定為光阻下層膜形成用組成物。將此光阻下層膜形成用組成物當作塗佈液,使用於以下所示之各種評估。
對於所得到之光阻下層膜形成用組成物是否良好地浸入通孔內、良好地埋入,評估往通孔之埋入性。往通孔之埋入性之評估,係藉由以下之方法進行。
首先,將光阻下層膜形成用組成物旋轉塗佈於以形成通孔(通孔大小:100nm、通孔間距:1H/1.2S、深度:1000nm)之方式加工之正矽酸四乙酯(TEOS)基板上。旋轉塗佈後,於180℃加熱60秒鐘,其後,進一步於250℃熱板上加熱60秒鐘。以如此之方式,在通孔內與TEOS表面上,製作膜厚300nm之光阻下層膜。對於所製作之光阻下層膜,藉由掃描式電子顯微鏡觀察往通孔內之埋入狀態並作評估。將光阻下層膜形成於通孔內之情況(埋入之情況)定為良好(「○」),將並未埋入之情況定為不良(「×」)。
藉由以下之方法對由光阻下層膜形成用組成物所形成之光阻下層膜之圖案轉寫性能及耐蝕刻性作評估。首先,藉由旋轉塗佈法形成膜厚300nm之光阻下層膜。其後,對光阻下層膜進行蝕刻處理(壓力:0.03Torr、高頻電力:3000W、Ar/CF4=40/100sccm、基板溫度:20℃),測定蝕刻處理後之光阻下層膜之膜厚。由膜厚之減少量與處理時間之關係算出蝕刻速率(nm/分)。蝕刻速率為80nm/分以下之情況,定為良好(「○」),超過80nm/分之情況,定為
不良(「×」)。
將光阻下層膜形成用組成物旋轉塗佈於直徑8英吋之矽晶圓上。旋轉塗佈後,以180℃加熱60秒鐘,其後,進一步在250℃熱板上加熱60秒鐘製作膜厚300nm之光阻下層膜,測定此時之昇華物量。為了捕集昇華物而使8英吋矽晶圓附著於熱板之天花板,並對塗佈光阻下層膜形成用組成物100枚之後堆積於8英吋晶圓之昇華物重量作測定,確認昇華物量之大小。昇華物量為2.5mg以下之情況定為良好(「○」),而超過2.5mg之情況,定為不良(「×」)。
除了定為表1所示之配合處方以外,係與實施例1同樣之方式,調製光阻下層膜形成用組成物。另外,表1中之「A-4」係聚羥苯乙烯(商品名:Maruka Lyncur,丸善石油化學公司製)、「B-2」係正丁醚化六羥甲三聚氰胺(以下述式(8)表示)。
除了定為表1所示之配合處方以外,係與實施例1同樣之方式,調製光阻下層膜形成用組成物。另外在表1中,「B-3」係四甲氧基甲基甘脲(以下述式(9)表示)、「B-4」係羥甲基化六羥甲三聚氰胺(以下述式(10)表示)。
對於實施例1~12之光阻下層膜形成用組成物、及比較例1~7之光阻下層膜形成用組成物,進行上述各評估。將評估結果示於表1。
如表1所示般,由實施例1~12之光阻下層膜形成用組成物所形成之光阻下層膜,係由於含有具有丁醚基之交聯劑,不僅含有耐蝕刻性之良好之樹脂作為組成物,埋入性亦優異、昇華物量亦少。
由比較例1~2之光阻下層膜形成用組成物所形成之光阻下層膜,係由於與實施例1~12同樣地含有耐蝕刻性之良好之樹脂作為組成物,故具有良好之耐蝕刻性,而由於不含有交聯劑,故埋入性為不良。另一方面,由比較例3~6之光阻下層膜形成用組成物所形成之光阻下層膜,係由於與實施例1~12之光阻下層膜形成用組成物同樣地,含有耐蝕刻性之良好之樹脂作為組成物,故具有良好之耐蝕刻性,埋入性亦為良好,而由於不含具有丁醚基之
交聯劑作為組成物,故與實施例1~12之光阻下層膜形成用組成物相比昇華物量為較多。
另外,比較例7之光阻下層膜形成用組成物,係使用玻璃轉移溫度低之樹脂,故埋入性以及昇華物量皆良好,然而並不具有作為光阻下層膜所必要之耐蝕刻性。
本發明之光阻下層膜形成用組成物,係由於藉由使用具有丁醚基之交聯劑,而具有良好之埋入性與昇華物量少,而且具有良好之耐蝕刻性,故可形成優異之光阻下層膜。亦即,本發明之光阻下層膜形成用組成物,可適合在高集積之電路中之雙鑲嵌構造之形成時使用。
Claims (5)
- 一種光阻下層膜形成用組成物,其係含有(A)含羥基之樹脂、(B)具有丁醚基之交聯劑及(C)溶劑,其特徵為前述(A)樹脂係由具有下述式(3)或(6)中任一項之構造單位之聚合物所構成者,式(3)之-OR3或式(6)之-R10之至少一方為羥基;
- 如申請專利範圍第1項之光阻下層膜形成用組成物,其中,前述(A)含羥基之樹脂係由具有上述式(6)之構造單位之聚合物所構成者。
- 如申請專利範圍第1項之光阻下層膜形成用組成物,其中,該(B)具有丁醚基之交聯劑係具有至少2個丁醚基之含氮環狀化合物。
- 如申請專利範圍第3項之光阻下層膜形成用組成物,其中,該含氮環狀化合物係具有甘脲骨架之化合物。
- 如申請專利範圍第1項之光阻下層膜形成用組成物,其中,該(B)具有丁醚基之交聯劑係選自以下述式(1)所表示之化合物,
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