WO2012083587A1 - 一种厚膜光刻胶清洗液 - Google Patents
一种厚膜光刻胶清洗液 Download PDFInfo
- Publication number
- WO2012083587A1 WO2012083587A1 PCT/CN2011/002135 CN2011002135W WO2012083587A1 WO 2012083587 A1 WO2012083587 A1 WO 2012083587A1 CN 2011002135 W CN2011002135 W CN 2011002135W WO 2012083587 A1 WO2012083587 A1 WO 2012083587A1
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- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- acrylate
- cleaning solution
- group
- solution according
- Prior art date
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- 238000004140 cleaning Methods 0.000 title claims abstract description 63
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- 150000002989 phenols Chemical class 0.000 claims abstract description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- -1 alcohol amine Chemical class 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001897 terpolymer Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 9
- 150000003457 sulfones Chemical class 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- 229920006027 ternary co-polymer Polymers 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 4
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical group CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940102253 isopropanolamine Drugs 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 claims description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- BPHYZRNTQNPLFI-UHFFFAOYSA-N 2,4,6-trihydroxytoluene Chemical group CC1=C(O)C=C(O)C=C1O BPHYZRNTQNPLFI-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JLNDHRCFOWTTQO-UHFFFAOYSA-N 2-butylbenzene-1,3,5-triol Chemical compound CCCCC1=C(O)C=C(O)C=C1O JLNDHRCFOWTTQO-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- XOIZPYZCDNKYBW-UHFFFAOYSA-N 5-tert-butylbenzene-1,3-diol Chemical compound CC(C)(C)C1=CC(O)=CC(O)=C1 XOIZPYZCDNKYBW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003000 phloroglucinols Chemical class 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 239000010949 copper Substances 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 15
- 238000005530 etching Methods 0.000 abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- 150000001412 amines Chemical class 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 6
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 abstract description 3
- 229960001553 phloroglucinol Drugs 0.000 abstract description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000003989 dielectric material Substances 0.000 abstract 1
- 229910001092 metal group alloy Inorganic materials 0.000 abstract 1
- 238000004377 microelectronic Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 230000007797 corrosion Effects 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 11
- 239000004005 microsphere Substances 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 150000002576 ketones Chemical class 0.000 description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000012459 cleaning agent Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical compound NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- OBUPVPZCSVEBQN-UHFFFAOYSA-N 1-pyridin-2-ylpropan-1-ol Chemical compound CCC(O)C1=CC=CC=N1 OBUPVPZCSVEBQN-UHFFFAOYSA-N 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- GTZBNACEDVMNPG-UHFFFAOYSA-N 2-aminoethanol;benzene Chemical compound NCCO.C1=CC=CC=C1 GTZBNACEDVMNPG-UHFFFAOYSA-N 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 1
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 description 1
- 125000004811 3-methylpropylene group Chemical group [H]C([H])([H])C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- QHBLUIPWHUJCEC-UHFFFAOYSA-N C1=CC=CC=C1.CCCCCCC1=CC=CC=C1 Chemical compound C1=CC=CC=C1.CCCCCCC1=CC=CC=C1 QHBLUIPWHUJCEC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229960002170 azathioprine Drugs 0.000 description 1
- LMEKQMALGUDUQG-UHFFFAOYSA-N azathioprine Chemical compound CN1C=NC([N+]([O-])=O)=C1SC1=NC=NC2=C1NC=N2 LMEKQMALGUDUQG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DNBHVMRIHKHYIN-UHFFFAOYSA-N benzene;4,5-dihydro-1,3-oxazole Chemical compound C1CN=CO1.C1=CC=CC=C1 DNBHVMRIHKHYIN-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
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- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the invention relates to a cleaning liquid, in particular to a thick film photoresist cleaning liquid.
- a mask of a photoresist is formed on a surface of a metal such as silicon dioxide, Cu (copper), or a low-k material, and the pattern is transferred after exposure to obtain a desired circuit pattern.
- the remaining photoresist needs to be stripped off before the next process.
- a photoresist is required to form a mask, which needs to be removed after the microsphere is successfully implanted, but since the photoresist is thick, it is completely removed. More difficult.
- a more common method for improving the removal is to extend the soaking time, increase the soaking temperature, and use a more aggressive solution, but this often results in corrosion of the wafer substrate and corrosion of the microspheres, resulting in a significant reduction in wafer yield.
- the photoresist cleaning liquid is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning liquid or rinsing the semiconductor wafer with the cleaning liquid.
- the strong bases commonly used are mainly inorganic metal hydroxides (such as potassium hydroxide and the like) and organic hydroxides such as tetramethylammonium hydroxide.
- JP1998239865 consists of an alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO) 1,3'-dimethyl-2-imidazoline (DMI) and water.
- TMAH tetramethylammonium hydroxide
- DMSO dimethyl sulfoxide
- DI 1,3'-dimethyl-2-imidazoline
- water water
- TMAH tetramethylammonium hydroxide
- DMSO dimethyl sulfoxide
- DI 1,3'-dimethyl-2-imidazoline
- Glue insufficient cleaning ability
- WO2006/056298A1 utilizes tetramethylammonium hydroxide ( ⁇ ), dimethyl A sulfoxide (DMSO), ethylene glycol (EG) and water alkaline cleaning solution for cleaning 50 ⁇ 100 micron thick photoresist, while basically no corrosion to metallic copper
- US6040117 utilizes TMAH, dimethyl An alkaline cleaning solution consisting of sulfoxide (DMSO), 1,3'-dimethyl-2-imidazolium (DMI) and water, the wafer is introduced into the cleaning solution, and the metal is removed at 50 to 100 ° C.
- a thick film photoresist of 20 ⁇ M or more on a dielectric substrate.
- US 5529887 consists of an alkaline cleaning solution consisting of potassium hydroxide (hydrazine), mercapto diol monodecyl ether, water-soluble fluoride and water, and the wafer is immersed in the cleaning solution to remove the metal at 40 to 90 ° C. And a thick film photoresist on a dielectric substrate. It has a high corrosion to the semiconductor wafer substrate.
- the requirements for the cleaning solution are further improved, and the corrosion rate required to control the metal aluminum is proposed, which is advantageous for overcoming the wafer microsphere implantation.
- the position of the microspheres in the process slightly deviates from the problem of not completely covering the underlying metal aluminum pad. If the cleaning solution has a high rate of corrosion to aluminum, it will corrode the metal aluminum pad, resulting in a decrease in yield.
- the technical problem to be solved by the present invention is to provide a defect that the existing thick film photoresist cleaning liquid has insufficient cleaning ability or is highly corrosive to semiconductor wafer patterns and substrates (especially corrosion of metal aluminum).
- a photoresist cleaning solution that has strong cleaning ability for thick film photoresist and low corrosivity to semiconductor wafer patterns and substrates.
- the technical solution adopted by the present invention to solve the above technical problems is: a low etching property suitable for
- the thicker photoresist cleaning solution comprises: potassium hydroxide, a solvent, pentaerythritol, an alcoholamine and a phenolic compound, wherein the phenolic compound is selected from the group consisting of resorcinol and its derivatives, and phloroglucinol and its derivatives. One or several of them.
- the solvent is one or more selected from the group consisting of sulfoxide, sulfone, imidazolium, pyrrolidone, imidazolidinone, ether, and amide.
- the sulfoxide is dimethyl sulfoxide; the sulfone is sulfolane; the imidazolium is 1, 3-dimethyl-2-imidazolium; the pyrrolidone Is N-methylpyrrolidone and/or hydroxyethylpyrrolidone; the imidazolinone is 1,3-dimethyl-2-imidazolidinone; the amide is dimethylformamide, dimethyl The acetamide; the ether is propylene glycol monomethyl ether and / or dipropylene glycol monomethyl ether.
- the alcohol amine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanolamine and diglycolamine. One or several.
- the resorcinol derivative is selected from the group consisting of 5-methyl-resorcinol, 5-methoxy-resorcinol and 5-tert-butyl-resorcinol. Or a plurality of; the phloroglucinol derivative is methyl phloroglucinol and/or butyl phloroglucinol.
- the presence of resorcinol and its derivatives or phloroglucin and its derivatives facilitate the inhibition of corrosion of metals, especially metallic copper, in this system; and its isomer, catechol or pyrogallol Corrosion of metallic copper is not effectively inhibited in the cleaning liquid system.
- the potassium hydroxide content is 0.1-6 wt%; the solvent content is 14-95 wt%; the pentaerythritol content is 0.1-15 wt% ; and the alkanolamine content is 0.1-55.
- the wt%; the content of the phenolic compound is 0.0001 to 10% by weight.
- the content of the solvent is preferably from 30 to 90% by weight, and the content of the phenolic compound is preferably from 0.01 to 1% by weight.
- the cleaning liquid further includes a polymer containing a pigment affinity group.
- the pigment-containing group-containing polymer is a hydroxyl group, a carboxyl group or an amino group. Polymer.
- the pigment-containing group-containing polymer is a polyacrylate-based polymer.
- the pigment-containing group-containing polymer is a copolymer selected from the group consisting of an acrylate monomer and a hydroxyethyl acrylate monomer, and an acrylate monomer and a hydroxyethyl methacrylate monomer.
- Copolymer copolymer of acrylate monomer and acrylamide monomer, acrylate monomer, hydroxyethyl acrylate monomer and ternary copolymer containing vinyl monomer, acrylate monomer a hydroxyethyl methacrylate monomer and a terpolymer containing a vinyl monomer, and one of an acrylate monomer, an acrylamide monomer, and a vinyl monomer-containing terpolymer or A variety.
- the acrylate monomer, the hydroxyethyl acrylate monomer, and the ternary copolymer containing a vinyl monomer are terpolymers of methyl acrylate, hydroxyethyl acrylate, and styrene;
- the ternary copolymer of the acrylate monomer, the acrylamide monomer and the vinyl monomer is a terpolymer of 'butyl acrylate, acrylamide and acrylic acid.
- the acrylate monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate or methacrylic acid. Butyl ester.
- the pigment-containing group-containing polymer is contained in an amount of from 0.01 to 2% by weight.
- a photoresist having a thickness of ⁇ or more can be washed at room temperature to 90 °C.
- the specific method is as follows: The photoresist wafer-containing semiconductor wafer is immersed in the low-etching photoresist cleaning agent of the present invention, and after being immersed at room temperature to 90 ° C for a suitable period of time, it is taken out and washed, and then subjected to high-purity nitrogen gas blowing.
- the alcohol amine described in the present invention is monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, One or more of isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanolamine, and diglycolamine.
- the presence of an alcoholamine is beneficial to increase the solubility of potassium hydroxide and pentaerythritol in the system and to protect the metal microspheres.
- the low-etching photoresist cleaning agent of the present invention can wash a photoresist having a thickness of ⁇ or more at room temperature to 90 ° C, and also contains resorcinol and its derivatives and/or Pyrogallol and its derivatives can form a protective film on the surface of various metals such as aluminum, copper, tin, and lead, thereby reducing the corrosion of the substrate.
- the specific method is as follows: The photoresist wafer-containing semiconductor wafer is immersed in the low-etching photoresist cleaning agent of the present invention, and after being immersed at room temperature to 90 ° C for a suitable period of time, it is taken out and washed, and then dried by high-purity nitrogen gas.
- the low-etching photoresist cleaning agent of the present invention is particularly suitable for cleaning thicker (thickness greater than 100 micrometers) photoresist, has a lower etching rate for metals such as Cu (copper), and is effective at the same time. Inhibits corrosion of copper, aluminum and metal microspheres.
- N-ring 2- (di. propyl acrylate and hexyl benzene benzene)
- the present invention adopts the following technical means: a semiconductor wafer containing a negative acrylate-based photoresist (having a thickness of about 120 ⁇ m and exposed and etched) (bump package) Wafer) Dip into the cleaning agent, soak 15 ⁇ at 25 ⁇ 90 °C! After 20 minutes, the semiconductor wafer was taken out and washed with deionized water and then dried with high purity nitrogen.
- Example 4 (min) Cu substrate A1 substrate photoresist metal microspheres, corrosion condition corrosion condition cleaning result corrosion condition Example 4 25 120 ⁇ : ⁇ ⁇ ⁇ Example 5 85 60 ⁇ ⁇ ⁇ ⁇ Example 6 80 1 10 ⁇ ⁇ ⁇ ⁇ Example 7 75 90 ⁇ ⁇ ⁇ ⁇ Example 8 70 75 ⁇ ⁇ ⁇ Example 12 . 65 60 ⁇ . ⁇ ⁇
- Example 13 60 15 ⁇ ⁇ . ⁇
- Example 23 45 100 ⁇ ⁇ ⁇ ⁇ Example 24 40 75 ⁇ ⁇ ⁇ Example 25 35 ⁇ 20 ⁇ ⁇ ⁇ ⁇ Example 26 25 120 ⁇ ⁇ ⁇ ⁇ Example 22 30 120 . ⁇ ⁇ ⁇ ⁇
- Example 25 70 90 ⁇ ⁇ ⁇ . . ⁇ Comparative Example 1 70 90 ⁇ ⁇ ⁇ Corrosion: ⁇ Basically non-corrosive; ⁇ Completely removed;
- the cleaning liquid of the present invention has a good cleaning effect on the thick film photoresist, has a wide temperature range of use, and has good corrosion inhibition effect on the metal microspheres and the metal aluminum and copper.
- the effect data of Comparative Example 1 when the phenolic compound in the cleaning solution is catechol or pyrogallol, the corrosion of the metal copper is not effectively inhibited in the cleaning liquid system, that is, the invention is not selected. The technical effect that phenolic compounds can achieve.
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Description
一种厚膜光刻胶清洗液
技术领域
本发明涉及一种清洗液, 尤其涉及一种厚膜光刻胶清洗液。 技术背景
在通常的半导体制造工艺中, 通过在二氧化硅、 Cu (铜)等金属以及低 k材料等表面上形成光刻胶的掩膜, 曝光后进行图形转移, 在得到需要的电 路图形之后, 进行下一道工序之前, 需要剥去残留的光刻胶。 例如, 在晶圆 微球植入工艺(bumping technology) 中, 需要光刻胶形成掩膜, 该掩膜在微 球成功植入后同样需要去除, 但由于该光刻胶较厚, 完全去除常较为困难。 改善去除效果较为常用的方法是采用延长浸泡时间、提高浸泡温度和采用更 富有攻击性的溶液, 但这常会造成晶片基材的腐蚀和微球的腐蚀, 从而导致 晶片良率的显著降低。
目前,光刻胶清洗液主要由极性有机溶剂、强碱和 /或水等组成, 通过将 半导体晶片浸入清洗液中或者利用清洗液冲洗半导体晶片, 去除半导体晶片 上的光刻胶。 其中其常用的强碱主要是无机金属氢氧化物 (如氢氧化钾等) 和有机氢氧化物如四甲基氢氧化胺等。
如 JP1998239865由四甲基氢氧化铵 (TMAH)、 二甲基亚砜 (DMSO) 1 ,3'-二甲基 -2-咪唑烧酮(DMI)和水等组成碱性清洗液, 将晶片浸入该清洗 液中, 于 50~10(TC下除去金属和电介质基材上的 20μπι以上的厚膜光刻胶。 其对半导体晶片基材的腐蚀略高, 且不能完全去除半导体晶片上的光刻胶, 清洗能力不足; WO2006/056298A1利用由四甲基氢氧化铵 (ΤΜΑΗ)、 二甲
基亚砜 (DMSO), 乙二醇 (EG) 和水组成碱性清洗液, 用于清洗 50〜100 微米厚的光刻胶, 同时对金属铜基本无腐蚀; US6040117利用由 TMAH、二 甲基亚砜 (DMSO)、 1,3'-二甲基 -2-咪唑垸酮 (DMI ) 和水等组成碱性清洗 液,将晶片进入该清洗液中,于 50~100°C下除去金属和电介质基材上的 20μΐΏ 以上的厚膜光刻胶。 又例如 US5529887由氢氧化钾 (ΚΟΗ)、 垸基二醇单垸 基醚、 水溶性氟化物和水等组成碱性清洗液, 将晶片浸入该清洗液中, 在 40~90°C下除去金属和电介质基材上的厚膜光刻胶。 其对半导体晶片基材的 腐蚀较高。
近来, 随着半导体工业对良率的进一步追求, 在晶圆微球植入工艺中, 对清洗液的要求进一步提高, 提出了要求控制金属铝的腐蚀速率, 这有利于 克服晶圆微球植入工艺中微球位置稍微偏离未能完全覆盖住下层金属铝垫 的问题。 如果清洗液对铝的腐蚀速率大, 则会腐蚀金属铝垫, 从而导致良率 降低。
由此可见, 寻找在溶解更多光刻胶同时对多种金属 (包括铝) 的腐蚀速 率较小的清洗液是该类光刻胶清洗液努力改进的方向。 发明概要
本发明要解决的技术问题就是针对现有的厚膜光刻胶清洗液存在的清 洗能力不足或者对半导体晶片图案和基材腐蚀性较强 (特别是金属铝的腐 蚀)的缺陷, 而提供的一种对厚膜光刻胶清洗能力强且对半导体晶片图案和 基材腐蚀性较低的光刻胶清洗液。
本发明解决上述技术问题所采用的技术方案是: 一种低蚀刻性的适用于
较厚光刻胶的清洗液, 包含: 氢氧化钾、 溶剂、 季戊四醇、 醇胺及酚类化合 物,所述酚类化合物选自间苯二酚及其衍生物和间苯三酚及其衍生物中的一 种或几种。
本发明中, 所述的溶剂选自亚砜、砜、 咪唑垸酮、 吡咯烷酮、 咪唑啉酮、 醚、 酰胺中的一种或多种。
本发明中, 所述的亚砜为二甲基亚砜; 所述的砜为环丁砜; 所述的咪唑 垸酮为 1 ,3-二甲基 -2-咪唑垸酮; 所述的吡咯垸酮为 N-甲基吡咯垸酮和 /或羟 乙基吡咯烷酮; 所述的咪唑啉酮为 1,3-二甲基 -2-咪唑啉酮; 所述的酰胺为二 甲基甲酰胺、二甲基乙酰胺;所述的醚为丙二醇单甲醚和 /或二丙二醇单甲醚。
本发明中, 所述的醇胺选自单乙醇胺、二乙醇胺、三乙醇胺、正丙醇胺、 异丙醇胺、 2- (二乙氨基)乙醇、 乙基二乙醇胺和二甘醇胺中的一种或几种。
本发明中, 所述的间苯二酚衍生物选自 5-甲基 -间苯二酚、 5-甲氧基-间 苯二酚和 5-叔丁基-间苯二酚中的一种或多种; 所述的间苯三酚衍生物为甲 基间苯三酚和 /或丁基间苯三酚。间苯二酚及其衍生物或间苯三酚及其衍生物 的存在有利于在该体系中抑制金属特别是金属铜的腐蚀; 而其同分异构体邻 苯二酚或邻苯三酚在该清洗液体系中并不能有效抑制金属铜的腐蚀。
本发明中, 所述氢氧化钾的含量为 0.1-6wt% ; 所述溶剂的含量为 14-95wt%; 所述季戊四醇的含量为 0.1-15 wt%; 所述醇胺的含量为 0.1-55 wt%; 所述酚类化合物的含量为 0.0001-10wt%。 其中, 所述溶剂的含量优选 为 30-90wt%, 所述酚类化合物的含量优选为 0.01-lwt%。
本发明中, 所述清洗液还包括含颜料亲和基团的聚合物。
本发明中, 所述的含颜料亲和基团的聚合物为含有羟基、 羧基或氨基的
聚合物。
本发明中, 所述的含颜料亲和基团的聚合物为聚丙烯酸酯类聚合物。 本发明中,所述的含颜料亲和基团的聚合物为选自丙烯酸酯类单体与丙 烯酸羟乙酯类单体的共聚物, 丙烯酸酯类单体与甲基丙烯酸羟乙酯类单体的 共聚物, 丙烯酸酯类单体与丙烯酰胺类单体的共聚物, 丙烯酸酯类单体、 丙 烯酸羟乙酯类单体和含乙烯基单体的三元共聚物, 丙烯酸酯类单体、 甲基丙 烯酸羟乙酯类单体和含乙烯基单体的三元共聚物, 以及丙烯酸酯类单体、 丙 烯酰胺类单体和含乙烯基单体的三元共聚物中的一种或多种。
本发明中, 所述的丙烯酸酯类单体、 丙烯酸羟乙酯类单体和含乙烯基单 体的三元共聚物为丙烯酸甲酯、 丙烯酸羟乙酯和苯乙烯的三元共聚物; 所述.. 的丙烯酸酯类单体、丙烯酰胺类单体和含乙烯基单体的三元共聚物为丙烯酸' 丁酯、 丙烯酰胺和丙烯酸的三元共聚物。
本发明中, 所述的丙烯酸酯类单体为丙烯酸甲酯、 丙烯酸乙酯、 丙烯酸 丙酯、 丙烯酸丁酯、 甲基丙烯酸甲酯、 甲基丙烯酸乙酯、 甲基丙烯酸丙酯或 甲基丙烯酸丁酯。
本发明中, 所述含颜料亲和基团的聚合物的含量为 0.01-2wt%。
本发明中的低蚀刻性光刻胶清洗液, 可以在室温至 90°C下清洗 ΙΟΟμηι 以上厚度的光刻胶。 具体方法如下: 将含有光刻胶的半导体晶片浸入本发明 中的低蚀刻性的光刻胶清洗剂,在室温至 90°C下浸泡合适的时间后,取出洗 涤后用高纯氮气吹千。
本发明相对现有技术的有益效果是:
1 )本发明中所述的醇胺为单乙醇胺、 二乙醇胺、 三乙醇胺、 正丙醇胺、
异丙醇胺、 2- (二乙氨基)乙醇、 乙基二乙醇胺和二甘醇胺中的一种或几种。 醇胺的存在有利于提高氢氧化钾和季戊四醇在体系中的溶解度, 并有利于金 属微球 (bump) 的保护。
2 ) 本发明所述的低蚀刻性光刻胶清洗剂, 可以在室温至 90°C下清洗 ΙΟΟμπι 以上厚度的光刻胶, 而且由于其中含有的间苯二酚及其衍生物和 /或 间苯三酚及其衍生物, 可以在多种金属如铝、 铜、 锡、 铅表面形成一层保护 膜, 从而降低基材的腐蚀。 具体方法如下: 将含有光刻胶的半导体晶片浸入 本发明中的低蚀刻性的光刻胶清洗剂, 在室温至 90°C下浸泡合适的时间后, 取出洗涤后用高纯氮气吹干。
3 ) 本发明所述的低蚀刻性光刻胶清洗剂, 尤其适用于较厚 (厚度大于 100微米) 光刻胶的清洗, 对 Cu (铜) 等金属具有较低的蚀刻速率, 能同时 有效抑制铜、 铝及金属微球的腐蚀。
4) 含颜料亲和基团的聚合物, 抑制了金属铝的腐蚀。
5)季戊四醇的存在有利于提高 KOH的溶解度, 同时对铜的腐蚀有抑制 作用。 发明内容
下面通过本发明优选的效果实施例来进一步说明本发明的有益效果,但 并不因此将本发明限制在所述的实施例范围之中。 下述实施例中, 百分比均
表 1各实施例 (Examples) 中的清洗剂的组分和含量
氢氧 含颜料亲和基团的 溶剂 季戊四 醇胺 酚类化合物 实 化 聚合物 醇, 含
施 钾, m.
里
例 含量 含
含量 % 名 含量
wt% 名称 Wt 含量 名称
wt% 里 名称
称 wt% wt% wt%
间
环丁 单乙醇
1 6 苯
14 】5 55 10
砜 1 1 胺
酚
5-
1 ,3-二 甲
甲基
三乙醇
2 0.1 -2-咪 95 0.1 0.1 间 2.7 1 1 胺
唑垸 苯
酮
酚
5- 甲
氧
二甲
3 0.5 基亚 36.5 12.9999 50 0.0001 1 1 胺 - 间
砜
苯
酚
5- 叔
N-甲' 丁
基吡 正丙醇'
■4 1 44 9.9995 45 0.0005
咯垸 胺 间」 7 ■ 1
. 酮 ■■苯 .
酚
羟乙 间
基吡 异丙醇
5 1.5 51.5 苯
6.999 40 0.001 • · / I 咯垸 胺
酮' . 酚
甲
■1 ,3-二
2- (二
甲基
乙氨
2 间
6 -2-咪. 78 4.995 15 0.005
基) 乙 1 1 唑啉 苯
酮
酚
丁
二甲
7 间
2.5 基甲 62 0.49 35 0.01 1 1 乙醇胺 苯
酰胺
1 ,3-二 甲基丙烯
酸乙酯与 甲基 间
乙醇
2 -2-咪 87.4 5 5 0.3 甲基丙烯
0.3 胺 苯 酸羟乙酯 唑垸
的共聚物 酮
Mn=l 5000 酚
丁
丙烯酸甲 酯、 丙烯酸 二甲 间 羟乙酯和
单乙醇
2.6 基亚 77 5 15 0.3 苯乙烯的 0.1 胺 苯
砜 三元共聚
物
Mn=30000 酚
丙烯酸丁
N-乙 间 酯、 丙烯酰 基吡 正丙醇 苯
3 30 ] 2 53.8 1 胺和丙烯
0. 2 咯垸 胺 酸的三元 . 酮 酚 共聚物
Mn= 10000 丙烯酸乙 丁
N-羟 酯、 甲基丙
烯酸羟乙 异丙醇
4 间
25.3 15 55 0.5
吡咯 酯和苯乙 0. 2 胺 苯
烷酮 烯的三元
共聚物 酚
Mn=30000
. 甲基丙烯
N-环 2- (二 间 . 酸丙酯与 已基 乙氨 苯
0.3 85 2.6 1 1 1 甲基丙烯
0: 1 吡咯 基) 乙 酸羟乙酯 烷酮 . 醇■ : 酚 ' 的共聚物
Mn=3000
】,3-二
间
甲基
0.8 苯
-2-咪 90 3.2 5 1 / .
乙醇胺 . :1 唑烷
酚 .
. 酮
1 ,3-二 丙烯酸丙
间
- 甲基 酯与丙烯
二甘醇
1.79 -2-咪 80 8 10 苯 0.01 酰胺的共 0. 2 胺 .
唑啉 . 聚物
酚
酮 Mn=5000
间
二甲
二甘醇
2 苯
基亚 81 .9 6 ] 0 0.1 1 1 胺
砜
酚
N-羟 间
^乙酚
25 7 85.95 6 6 苯
0.05
吡咯 胺 /
垸酮 酚
间
二甲
单乙醇
26 3 基亚 75.99 6 】5 苯
0.01
胺 / 1 砜
酚
羟 邻
对 单乙醇
比 2 85.95 6 6 苯
0.05
吡咯 胺 / 1 例 1
垸酮 酚
为了进一步考察该类清洗液的清洗情况, 本发明采用了如下技术手段: 即将含有负性丙烯酸酯类光刻胶 (厚度约为 120微米, 且经过曝光和刻蚀) 的半导体晶片 (凸点封装晶圆) 浸入清洗剂中, 在 25〜90°C下浸泡 15〜! 20 分钟, 然后取出半导体晶片经去离子水洗涤后用高纯氮气吹干。 光刻胶的清 洗效果和清洗液对晶片的腐蚀情况如表 2所示。 表 2部分实施例对晶圆清洗情况
: 清洗 光刻胶
晶片清洗结果
温度 清洗时间
实施例
C ) (min) Cu基材 A1基材 光刻胶 金属微球 , 腐蚀情况 腐蚀情况 清洗结果 腐蚀情况 实施例 4 25 120 ◎ :◎ ◎ ◎ 实施例 5 85 60 ◎ ◎ ◎ ◎ 实施例 6 80 1 10 ◎ ◎ ◎ © 实施例 7 75 90 ◎ © ◎ ◎ 实施例 8 70 75 ◎ ◎ ◎ 实施例 12 . 65 60 ◎ . ◎ ◎
实施例 13 60 15 ◎ ■ . 〇
实施例】3 60 45 ◎ ◎ ◎ 实施例〗6 55 30 ◎ ◎ ◎ ◎ 实施例 Π 50 80 ◎ © ◎ ◎ 实施例 19 90 90 ◎ ◎ ◎ 〇 实施例 20 55 30 ◎ © ◎ 实施例 22 50 120 ◎ ◎ ◎
实施例 23 45 100 ◎ ◎ ◎ ◎ 实施例 24 40 75 ◎ ◎ ◎
实施例 25 35 Ϊ 20 ◎ ◎ ◎ ◎ 实施例 26 25 120 ◎ ◎ ◎ ◎ 实施例 22 30 120 . ◎ ◎ ◎ ◎
'实施例 25 70 90 ◎ ◎ ◎ . . ◎ 对比例 1 70 90 Δ ◎ 〇 腐蚀情况: ◎ 基本无腐蚀; ◎ 完全去除;
o 略有腐烛; 〇 少量残余;
△ 中等腐蚀; Δ 较多残余;
X 严重腐蚀。 X 大量残余。
从表 2可以看出, 本发明的清洗液对厚膜光刻胶具有良好的清洗效果, 使用温度范围广, 同时对金属微球和金属铝、 铜等有较好的腐蚀抑制作用。 此外, 从对比例 1的效果数据来看, 清洗液中酚类化合物为邻苯二酚或邻苯 三酚时, 该清洗液体系中并不能有效抑制金属铜的腐蚀, 即不具备本发明选 用的酚类化合物所能达到的技术效果。
以上对本发明的具体实施例进行了详细描述, 但其只是作为范例, 本发 明并不限制于以上描述的具体实施例。 对于本领域技术人员而言, 任何对本 发明进行的等同修改和替代也都在本发明的范畴之中。 因此, 在不脱离本发 明的精神和范围下所作的均等变换和修改, 都应涵盖在本发明的范围内。
Claims
1、 一种厚膜光刻胶的清洗液, 包含: 氢氧化钾、 溶剂、 季戊四醇、 醇 胺及酚类化合物, 其中, 所述酚类化合物选自间苯二酚及其衍生物和间苯三 酚及其衍生物中的一种或几种。
2、 如权利要求 1 所述的清洗液, 其特征在于, 所述的溶剂选自亚砜、 砜、 咪唑垸酮、 吡咯烷酮、 咪唑啉酮、 醚、 酰胺中的一种或多种。
3、 如权利要求 2所述的清洗液, 其特征在于, 所述的亚砜为二甲基亚 砜; 所述的砜为环丁砜; 所述的咪唑烷酮为 1,3-二甲基 -2-咪唑烷酮; 所述的 吡咯烷酮为 N-甲基吡咯垸酮和 /或羟乙基吡咯垸酮; 所述的咪唑啉酮为 1 ,3- 二甲基 -2-咪唑啉酮; 所述的酰胺为二甲基甲酰胺、 二甲基乙酰胺; 所述的醚 为丙二醇单甲醚和 /或二丙二醇单甲醚。
4、 如权利要求 1所述的清洗液, 其特征在于, 所述的醇胺选自单乙醇 胺、 二乙醇胺、 三乙醇胺、 正丙醇胺、 异丙醇胺、 2- (二乙氨基) 乙醇、 乙 基二乙醇胺和二甘醇胺中的一种或几种。
5、 如权利要求 1 所述的清洗液, 其特征在于, 所述的所述的间苯二酚 衍生物选自 5-甲基 -间苯二酚、 5-甲氧基 -间苯二酚和 5-叔丁基-间苯二酚中的 一种或多种; 所述的间苯三酚衍生物为甲基间苯三酚和 /或丁基间苯三酚。
6、 如权利要求 1 所述的清洗液, 其特征在于, 所述氢氧化钾的含量为 0.1 -6wt%;所述溶剂的含量为 14-95wt%;所述季戊四醇的含量为 0J -15 wt%; 所述醇胺的含量为 0.1-55 wt%; 所述酚类化合物的含量为 0.0001-10wt%。
7、 如权利要求 6 所述的清洗液, 其特征在于, 所述溶剂的含量为 30-90wt%, 所述酚类化合物的含量为 0.01 -l wt%。
8、 如权利要求 1 7任一项所述的清洗液, 其特征在于, 所述清洗液 ¾ 包括含颜料亲和基团的聚合物。
9、 如权利要求 8所述的清洗液, 其特征在于, 所述的含颜料亲和基团 的聚合物为含有羟基、 羧基或氨基的聚合物。
10、 如权利要求 9所述的清洗液, 其特征在于, 所述的含颜料亲和基团 的聚合物为聚丙烯酸酯类聚合物。
11、 如权利要求 10所述的清洗液, 其特征在于, 所述的含颜料亲和基 团的聚合物为选自丙烯酸酯类单体与丙烯酸羟乙酯类单体的共聚物,丙烯酸 酯类单体与甲基丙烯酸羟乙酯类单体的共聚物,丙烯酸酯类单体与丙烯酰胺 类单体的共聚物, 丙烯酸酯类单体、丙烯酸羟乙酯类单体和含乙烯基单体的 三元共聚物, 丙烯酸酯类单体、 甲基丙烯酸羟乙酯类单体和含乙烯基单体的 三元 聚物, 以及丙烯酸酯类单体、 丙烯酰胺类单体和含乙烯基单体的三元 共聚物中的一种或多种。
12、 如权利要求 11所述的清洗液, 其特征在于, 所述的丙烯酸酯类单 体、丙烯酸羟乙酯类单体和含乙烯基单体的三元共聚物为丙烯酸甲酯、 丙烯 酸羟乙酯和苯乙烯的三元共聚物; 所述的丙烯酸酯类单体、 丙烯酰胺类单体 和含乙烯基单体的三元共聚物为丙烯酸丁酯、丙烯酰胺和丙烯酸的三元共聚 物。
13、 如权利要求 11所述的清洗液, 其特征在于, 所述的丙烯酸酯类单 体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、 甲基丙烯酸甲酯、 甲基丙烯酸乙酯、 甲基丙烯酸丙酯或甲基丙烯酸丁酯。
14、 如权利要求 8所述的清洗液, 其特征在于, 所述含颜料亲和基团的 聚合物的含量为 0.01-2wt%。
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