CN109983560A - 剥离方法 - Google Patents
剥离方法 Download PDFInfo
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- CN109983560A CN109983560A CN201780070832.2A CN201780070832A CN109983560A CN 109983560 A CN109983560 A CN 109983560A CN 201780070832 A CN201780070832 A CN 201780070832A CN 109983560 A CN109983560 A CN 109983560A
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- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000004065 semiconductor Substances 0.000 claims abstract description 32
- 238000004090 dissolution Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 125000005418 aryl aryl group Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 238000003851 corona treatment Methods 0.000 claims 1
- 125000003831 tetrazolyl group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 47
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 34
- -1 3- methyl -3- methyl butyl Chemical group 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 8
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229940116333 ethyl lactate Drugs 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000013047 polymeric layer Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 3
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 3
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920005479 Lucite® Polymers 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- LJRDOKAZOAKLDU-UDXJMMFXSA-N (2s,3s,4r,5r,6r)-5-amino-2-(aminomethyl)-6-[(2r,3s,4r,5s)-5-[(1r,2r,3s,5r,6s)-3,5-diamino-2-[(2s,3r,4r,5s,6r)-3-amino-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-6-hydroxycyclohexyl]oxy-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl]oxyoxane-3,4-diol;sulfuric ac Chemical compound OS(O)(=O)=O.N[C@@H]1[C@@H](O)[C@H](O)[C@H](CN)O[C@@H]1O[C@H]1[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](N)C[C@@H](N)[C@@H]2O)O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)O[C@@H]1CO LJRDOKAZOAKLDU-UDXJMMFXSA-N 0.000 description 1
- MEJYDZQQVZJMPP-ULAWRXDQSA-N (3s,3ar,6r,6ar)-3,6-dimethoxy-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan Chemical compound CO[C@H]1CO[C@@H]2[C@H](OC)CO[C@@H]21 MEJYDZQQVZJMPP-ULAWRXDQSA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 1
- 229940006190 2,3-dimercapto-1-propanesulfonic acid Drugs 0.000 description 1
- JLVSRWOIZZXQAD-UHFFFAOYSA-N 2,3-disulfanylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(S)CS JLVSRWOIZZXQAD-UHFFFAOYSA-N 0.000 description 1
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 1
- 229960001406 2,5-dimethylisosorbide Drugs 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JEPCLNGRAIMPQV-UHFFFAOYSA-N 2-aminobenzene-1,3-diol Chemical compound NC1=C(O)C=CC=C1O JEPCLNGRAIMPQV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
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Abstract
本发明涉及一种用于剥离图案化半导体衬底上的有机膜的方法。所述方法包括在一个步骤中以水性剥离剂组合物处理所述有机膜以移除所述有机膜。所述有机膜包括至少第一层和第二层,所述第一层在25℃在显影剂中具有至多约0.01μ/分钟的溶解速率,且所述第二层在25℃在所述显影剂中具有大于约0.01μ/分钟的溶解速率。
Description
本申请案主张于2016年11月17日提交的序号62/423,323的美国临时申请的优先权,其内容在此被完整并入以供参考。
背景技术
移动计算应用的持续扩展需要将不断增长的计算能力封装到更小的装置空间中。半导体装置设计者依赖于使用各种新芯片结构以满足新的装置要求。这些新结构包括使用铜柱的覆晶晶圆凸块以及使用通过硅过孔(TSV)的方法,诸如,三维集成电路(3D IC),其中将晶圆变薄,将形成的模堆叠,然后通过TSV及2.5D中介层设计连接。这些方法不仅为新IC结构的设计者,而且为将用于这些装置的封装材料的设计者都带来了重大挑战。
时常地,当建构这些新IC结构时,变得需要同时移除两个或更多个聚合物光刻胶层。时常地,这些聚合物层由具有截然不同的可溶性特征的材料所组成。如果要在不损害下层衬底的完整性的情况下移除两个层,充分了解每一聚合物层的特征是必要的。用于半导体产业的许多传统化学剥离剂是极度严苛的,且通常不可能使用单一剥离剂移除所有层而不会伴随损害下层衬底。此事实阻碍传统化学剥离剂及其相伴随的方法用于制造新的复杂IC结构。用于半导体封装的新先进材料的设计者要求剥离剂的作用有效且具选择性。
不可预期地发现本发明的组合物可在一个步骤中移除图案化半导体衬底上的有机膜中的具有不同溶解性质或可溶性质的多个层,且不会损害该衬底或其结构。
发明内容
本发明的特征是一种用于剥离图案化半导体衬底(例如,含图案化金属的半导体衬底)上的有机膜的方法。所述方法包括在一个步骤中以水性剥离剂组合物处理所述有机膜以移除所述有机膜。所述有机膜包括至少第一层和第二层,所述第一层在25℃在显影剂中具有至多约0.01μ/分钟的溶解速率,且所述第二层在25℃在所述显影剂中具有大于约0.01μ/分钟的溶解速率。
在某些实施例中,本发明的特征是通过上述方法形成的三维物体。在某些实施例中,本发明的特征是含有所述三维物体的半导体装置。在某些实施例中,所述半导体装置是集成电路、发光二极管、太阳能电池或晶体管。
具体实施方式
本发明的某些实施例描述一种用于在一个步骤中通过使用水性剥离剂组合物剥离图案化半导体衬底(例如,含图案化金属的半导体衬底)上的具有不同溶解性质或可溶性质的有机膜(例如,多层或多堆叠式有机膜)的方法。所述有机膜可包括至少第一层和第二层。所述第一层(例如,经高度交联的层)在25℃在显影剂中可为不可溶的。所述第二层(例如,经轻度交联的层或未经交联的层)在25℃在显影剂中可以具有比第一层更高的可溶性。在某些实施例中,所述第二层在25℃可溶于显影剂中。在某些实施例中,有机膜可含有多于两(例如,三、四、五、六或七)个层,其中一些具有与第一层相似的溶解/可溶性质,且其中一些具有与第二层相似的溶解/可溶性质。
在某些实施例中,所述第一层在25℃不溶于显影剂。例如,所述第一层可以具有在25℃在显影剂中至多约0.01μ/分钟(例如,至多约0.005μ/分钟,至多约0.001μ/分钟,至多约0.0005μ/分钟,或至多约0.0001μ/分钟)的溶解速率。所述显影剂可包括至少一种有机溶剂、至少一种水溶液(例如,pH范围为2-14的溶液)或其混合物。可作为适合显影剂的有机溶剂的例子包括,但不限于γ-丁内酯(GBL)、N-甲基-2-吡咯烷酮(NMP)、二甲基咪唑啉酮、N-甲基己内酰胺、N-甲基丙酰胺、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺、二乙基乙酰胺、甲基乙基酮(MEK)、甲基异丁基酮(MIBK)、2-庚酮、环戊酮(CP)、环己酮、乙酸正丁酯(nBA)、丙二醇甲醚乙酸酯(PGMEA)、丙二醇甲醚(PGME)、乳酸乙酯(EL)、乳酸丙酯、3-甲基-3-甲氧基丁醇、四氢化萘、异佛尔酮、乙二醇单丁醚、二乙二醇单乙醚、二乙二醇单乙醚乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、三乙二醇单乙醚、二丙二醇单甲醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙二酸二乙酯、乙二醇1,4:3,6-二脱水山梨醇、2,5-二甲醚(2,5-二甲基异山梨酯)、1,4:3,6-二脱水山梨醇2,5-二乙醚(2,5-二乙基异山梨酯)及其混合物。在某些实施例中,可作为显影剂的有机溶剂包括乙酸正丁酯(nBA)、丙二醇甲醚乙酸酯(PGMEA)、丙二醇甲醚(PGME)、乳酸乙酯(EL)、乳酸丙酯、3-甲基-3-甲氧基丁烷及其混合物。可作为显影剂的水溶液的例子包括碱性水溶液(例如,TMAH溶液)及酸性水溶液。在某些实施例中,显影剂可为本文所述的水性剥离剂组合物。在某些实施例中,所述第一层具有至少约20,000克/摩尔(例如,至少约30,000克/摩尔、至少约40,000克/摩尔、至少约50,000克/摩尔、至少约60,000克/摩尔、至少约70,000克/摩尔、至少约80,000克/摩尔、至少约90,000克/摩尔、或至少约100,000克/摩尔)的重均分子量。
在某些实施例中,所述第一层在上述显影剂中可具有在25℃在1000克显影剂中少于约1克(例如,少于约0.5克、少于约0.1克、少于约0.05克、或少于约0.01克)的溶解度。
在某些实施例中,所述第二层在上述相同显影剂中具有在25℃比第一层更高的溶解度。例如,所述第二层在25℃在显影剂中可具有大于约0.01μ/分钟(例如,大于约0.05μ/分钟、大于约0.1μ/分钟、大于约0.5μ/分钟、或大于约1μ/分钟)的溶解速率。在某些实施例中,所述第二层在上述显影剂中可具有在25℃在1000克的显影剂中大于约1克(例如,大于约5克、大于约10克、大于约50克、或大于约100克)的溶解度。在某些实施例中,所述第二层可溶于25℃的显影剂中(例如,具有大于1μ/分钟的溶解速率或具有在1000克的显影剂中大于50克的溶解度)。在某些实施例中,所述第二层具有至多约200,000克/摩尔(例如,至多约150,000克/摩尔、至多约100,000克/摩尔、至多约50,000克/摩尔、至多约25,000克/摩尔、至多约10,000克/摩尔、至多约5,000克/摩尔、或至多约3,000克/摩尔)的重均分子量。
半导体衬底可具有圆形,诸如,晶圆,或其可为板材。在某些实施例中,所述半导体衬底可为硅衬底、铜衬底、铝衬底、氧化硅衬底、氮化硅衬底、玻璃衬底、有机层压板衬底、或介电材料衬底。所述衬底可含有具有不同长度或尺寸的线、支柱、垫材或其他结构的金属图案。用于所述金属图案的金属包括,但不限于铜、铝、钨及其合金。
在某些实施例中,所述图案化半导体衬底可包括至少一个组件,所述组件具有至多约5微米(例如,至多约4微米、至多约3微米、至多约2微米、或至多约1微米)的特征尺寸。
在某些实施例中,所述图案化半导体衬底可含有多个图案。在某些实施例中,所述图案的两个图案(例如,一组图案中的两个图案)可以被至多约200微米(例如,至多约175微米、至多约150微米、至多约125微米、至多约100微米、至多约75微米、至多约50微米、至多约25微米、至多约10微米、至多约4微米、或至多约2微米)的间隔分开。
在某些实施例中,所述图案化半导体衬底可含有多组图案。在某些实施例中,两组图案可以被至多约100毫米(例如,至多约75毫米、至多约50毫米、至多约100毫米、至多约50毫米、至多约10毫米、至多约5毫米、至多约1000微米(1毫米)、至多约500微米、至多约250微米、或至多约100微米)的间隔分开。
在某些实施例中,有机膜中的第一层、第二层、或任何其他层的厚度的范围可独立地为至少约2微米(例如,至少约3微米、至少约4微米、至少约5微米、或至少约10微米)至至多约40微米(例如,至多约35微米、至多约30微米、至多约25微米、或至多约20微米)。使用的适当膜厚度可由具体应用来确定。
在某些实施例中,图案化半导体上形成的有机膜的总厚度优选为至少约20微米(例如,至少约25微米、至少约30微米、至少约35微米、或至少约40微米)至至多约100微米(例如,至多约90微米、至多约80微米、至多约70微米、或至多约60微米)。使用的适当膜厚度可由具体应用来确定。
在某些实施例中,可用于本文所述的剥离方法的水性剥离剂组合物包括:(a)按所述组合物的重量计约0.5%至约25%的量的碱性化合物;(b)按所述组合物的重量计约65%至约95%的量的水;(c)按所述组合物的重量计约0.1%至约5%的量的腐蚀抑制剂化合物;及(d)按所述组合物的重量计0至约5%的量的界面活性剂。
可用于本文所述的剥离剂组合物的碱性化合物(a)不受特别限制,且是本领域技术人员所熟知的。例如,所述碱性化合物可包括无机碱,诸如,氢氧化钾、氢氧化钠、碳酸钠、碳酸氢钠、碳酸钾、及碳酸氢钾;以及有机碱,诸如,季铵盐。在某些实施例中,碱性化合物是季铵盐。季铵盐的例子包括,但不限于季铵氢氧化物,其可选自由四甲基氢氧化铵(TMAH)、2-羟基三甲基氢氧化铵、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化铵(TBAH)和其混合物所组成的组。在某些实施例中,季铵氢氧化物是四甲基氢氧化铵和2-羟基三甲基氢氧化铵。在某些实施例中,季铵氢氧化物是四甲基氢氧化铵。
用于剥离剂组合物中的碱性化合物(a)可以相对于本发明的组合物的总量的至少约0.5重量%(例如,至少约1重量%、至少约1.5重量%、至少约2重量%、至少约2.5重量%、至少约3重量%、至少约4重量%、或至少约5重量%)至至多约25重量%(例如,至多约20重量%、至多约15重量%、或至多约10重量%)的量存在。
用于剥离剂组合物中的腐蚀抑制剂化合物包括,但不限于芳香族羟基化合物、炔醇、含羧基基团的有机化合物及其酐、四唑化合物、及三唑化合物,只要其在剥离剂组合物中具有合理的可溶性。
芳香族羟基化合物的例子包括,但不限于酚、甲酚、二甲酚、邻苯二酚、间苯二酚、氢醌、连苯三酚、1,2,4-苯三酚、水杨醇、对-羟基苯甲醇、邻-羟基苯甲醇、对-羟基苯乙醇、对-氨基酚、间-氨基酚、二氨基酚、氨基间苯二酚、对-羟基苯甲酸、邻-羟基苯甲酸、2,4-二羟基苯甲酸、2-5-二羟基苯甲酸、3,4-二羟基苯甲酸及3,5-二羟基苯甲酸。
炔醇的例子包括,但不限于2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇、及2,5-二甲基-3-己炔2,5-二醇。
含羧基基团的有机化合物及其酐的例子包括,但不限于甲酸、乙酸、丙酸、丁酸、异丁酸、草酸、丙二酸、琥珀酸、戊二酸、马来酸、福马酸、苯甲酸、邻苯二甲酸、1,2,3-苯三羧酸、乙醇酸、乳酸、苹果酸、柠檬酸、水杨酸、及其酐。
三唑化合物的例子包括,但不限于1,2,4-三唑,或任选以诸如C1-C8烷基基团、氨基基团、硫醇基团、巯基基团、亚氨基基团、羧基基团及硝基基团的取代基取代的三唑。三唑化合物的例子包括苯并三唑、甲苯三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-氨基-1,2,4-三唑-5-羧酸、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、卤基-苯并三唑(卤基=F、Cl、Br或I)、萘并三唑等。
在某些实施例中,腐蚀抑制剂化合物是结构(I)的肟化合物:
其中,R1选自由氢、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C12环烷基或杂环烷基、及经取代或未经取代的C5-C12芳基或杂芳基所组成的组;且R2至R5各自独立地选自由氢、卤素、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C12环烷基或杂环烷基、及经取代或未经取代的C5-C12芳基或杂芳基所组成的组;或R2至R5的任何两个相邻基团(例如,R2及R3、R3及R4、或R4及R5)与和其附接的环碳原子一起形成六元环。
在某些实施例中,R1是氢、经取代或未经取代的C1-C12直链或支链烷基、或者经取代或未经取代的C6-C12芳基。R1基团的例子包括,但不限于氢、甲基及苯基。在某些实施例中,R2至R5各自独立地是氢、卤素、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C10环烷基或杂环烷基、或者经取代或未经取代的C6-C12芳基或杂芳基。R2至R5基团的例子包括,但不限于氢、卤素、壬基、十二烷基、苯基、异丙基、叔丁基、环戊基、1,3-二甲基环己基及甲苯基。结构(I)的化合物上的取代基经选择以优化各种参数,包括但不限于肟化合物在给定组合物中的溶解性和活性以及所述组合物的贮存稳定性。
结构(I)的适合化合物的例子包括,但不限于
用于剥离剂组合物中的腐蚀抑制剂化合物可以相对于清洁/剥离组合物的总量的至少约0.1重量%(例如,至少约0.2重量%、至少约0.3重量%、至少约0.4重量%、至少约0.5重量%、或至少约1重量%)至至多约5重量%(例如,至多约4重量%、至多约3重量%、至多约2重量%、或至多约1.5重量%)的量存在。在某些实施例中,腐蚀抑制剂化合物的量是相对于清洁/剥离组合物的总量的0.2重量%至0.4重量%。
用于剥离剂组合物中的水(诸如,去离子水、纯水、超纯水等)的量可为相对于清洁/剥离组合物的总量的至少约65重量%(例如,至少约70重量%、至少约75重量%、或至少约78重量%)至至多约95重量%(例如,至多约90重量%、至多约85重量%、或至多约82重量%)。
可用于剥离剂组合物中的适合界面活性剂包括,但不限于氟烷基界面活性剂;聚乙二醇;聚丙二醇;聚乙二醇醚;聚丙二醇醚;羧酸盐;十二烷基苯磺酸及其盐;聚丙烯酸酯聚合物;二壬基苯基聚氧乙烯;聚硅氧聚合物;经改性的聚硅氧聚合物;炔二醇;经改性的炔二醇;烷基铵盐;经改性的烷基铵盐;烷基铵磺酸内盐,及前述的两种或更多种的组合。适合界面活性剂的例子包括,但不限于JP-A-62-36663、JP-A-61-226746、JP-A-61-226745、JP-A-62-170950、JP-A-63-34540、JP-A-7-230165、JP-A-8-62834、JP-A-9-54432及JP-A-9-5988中描述的界面活性剂。
用于剥离剂组合物中的界面活性剂的量可为相对于剥离剂组合物的总量的至少约0.001重量%(例如,至少约0.005重量%、至少约0.01重量%、至少约0.02重量%、至少约0.03重量%、至少约0.04重量%、或至少约0.05重量%)至至多约5重量%(例如,至多约2.5重量%、至多约1重量%、至多约0.5重量%、至多约0.25重量%、或至多约0.1重量%)。在某些实施例中,剥离剂组合物不包括任何界面活性剂。
本文所述的剥离剂组合物还可包括下列添加剂的一种或多种,只要这些添加剂不会不利地影响组合物的剥离性能,也不会损害下层衬底表面:螯合剂、偶联剂、化学改性剂、染料、杀生物剂和/或其他添加剂,以组合物总重量为基准,其中每种添加剂可为高达5重量%的量。
螯合剂的例子可包括,但不限于乙二胺四乙酸(EDTA)、羟基乙基乙二胺三乙酸(HEDTA)、青霉胺、2,3-二巯基-1-丙磺酸(DMPS)、二巯基琥珀酸(DMSA)、葡萄糖酸、丙烯酸、氮三乙酸(NTA)、谷氨酸、二乙酸、亚氨基二琥珀酸四钠、亚氨基琥珀酸、二乙烯三胺五乙酸五钠、及聚天冬胺酸酯。在某些实施例中,螯合剂可为EDTA。
剥离剂组合物可进一步包括偶联剂。偶联剂可有助于稳定所述组合物,诸如,维持保存期限。偶联剂的例子可包括,但不限于二甲苯磺酸钠(SXS)、异丙苯磺酸钠(SCS)及磺酸乙基己酯(EHS)。在某些实施例中,偶联剂是二甲苯磺酸钠。
在某些实施例中,下列材料的一种或多种可从本发明的组合物排除:水解而释出氟的含氟化合物(例如,潜在的HF来源,诸如,羧基氟化物);氟化盐,诸如,铵或季铵氟化物;氧化剂,诸如,过氧化物及无机氧化剂;脒盐,诸如,胍盐、乙脒盐及甲脒盐;尿素及尿素衍生物以及酚系化合物。
在某些实施例中,剥离剂组合物可具有碱性pH。例如,pH可为至少约12(例如,至少约12.2、至少约12.4、至少约12.6、至少约12.8、至少约13、至少约13.2、至少约13.4、至少约13.6、至少约13.8、或至少约14)或至多约16.0(例如,至多约15.8、至多约15.6、至多约15.4、至多约15.2、至多约15.0、至多约14.8、至多约14.6、至多约14.4、或至多约14)。在某些实施例中,pH范围为13.5至15.5(诸如,14至15.3)。
剥离剂组合物可通过使用传统混合方法以任何顺序将各种组分混合而制备。所述组分可于未添加热的情况下冷混合。
在某些实施例中,本发明的剥离剂组合物可用于移除本文所述的含有不同溶解性质或可溶性质的至少两层的有机膜的方法。
所述移除(剥离)方法可通过以一种或多种剥离剂组合物使用诸如浸渍、喷洒及超音波/兆声波浴的已知技术处理本文所述的有机膜而完成。所述方法的一个优点是本发明的水性剥离剂组合物在无需溶解可能不溶于剥离剂组合物的第一层的情况下,可以在一个步骤中剥离有机膜的所有层,包括本文所述的第一层及第二层。在某些实施例中,虽不欲受理论约束,但相信剥离剂组合物在未溶解第一层的情况下使整个有机膜从图案化半导体衬底移开,从而在一个步骤中将有机膜自衬底剥离。
在某些实施例中,在剥离方法完成后基本上没有留下有机膜残余物。在某些实施例中,相对于原始膜厚度留下的任何膜残余物的厚度少于约5%(例如,少于约4%,少于约3%,少于约2%,或少于约1%)。在某些微量的膜残余物留在图案化半导体衬底顶面上的情况,膜残余物可通过本领域技术人员已知的等离子体蚀刻步骤完全移除。
剥离方法中使用的温度可为至少约25℃(例如,至少约30℃、至少约35℃、至少约40℃、或至少约45℃)至至多约85℃(例如,至多约80℃、至多约75℃、至多约70℃、至多约65℃、至多约60℃、或至多约55℃)。剥离时间可为至少约15分钟(例如,至少约30分钟、至少约45分钟、或至少约60分钟)至至多约120分钟(例如,至多约105分钟、至多约90分钟、或至多约75分钟)。
剥离方法中的可选择步骤包括冲洗步骤、干燥步骤及等离子体蚀刻步骤,所述步骤可在以剥离剂组合物处理半导体衬底后实施。例如,以剥离剂组合物处理之后,半导体衬底可以用冲洗溶剂(例如,水或水溶液)冲洗。可用于所述方法的水溶液可为去离子水与界面活性剂的混合物、含有界面活性剂的微碱性的水溶液、或含有直链或支链C1–C4醇的水溶液,以移除剥离剂组合物及任何其他残余物。所述步骤还可通过使用已知技术,诸如,浸渍、离心喷洒、兆声波清洁及超音波清洁完成。然后,经冲洗的半导体衬底可使用本领域技术人员已知的干燥手段干燥。
实施例
合成实施例1
聚合物(Poly-1)
固体4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)(334.0克)加料至室温的NMP(2206克)中的5(6)-氨基-1-(4-氨基苯基)-1,3,3-三甲基茚烷(DAPI)(218.4克)的溶液。额外的NMP(816克)被用以将所述二酐冲洗到溶液中。反应温度增至60℃且使混合物反应3.5小时。接着,添加乙酸酐(125.7克)及吡啶(49.5克)。反应温度增至100℃后,使混合物反应12小时。然后,将反应混合物冷却至室温,且以等体积的THF稀释。经稀释的溶液缓慢添加至水(10×)中使粗制聚合物沉淀。粗制聚合物通过真空过滤分离且以水清洗。粗制的湿聚合物用甲醇形成浆液,通过真空过滤收集,在45℃在真空下干燥过夜。
组合物实施例1a
用以涂覆第一层的制剂(F-1)
向装设机械式搅拌器的3颈圆底烧瓶,添加20份的PGMEA、8份的PGME、16份的来自璐彩特国际集团(Lucite International)的聚合物(Elvacite4412-聚(甲基丙烯酸甲酯-共-甲基丙烯酸羟基丙酯)、2.4份的来自King Industries的TAG-2168E(在PGME中,25%)、3份的powderlink 1174、4份的来自奥麒化工(Arch Chemical)的poly T-305。组合物经机械式搅拌18小时。然后,所述组合物通过使用5微米过滤器过滤。
组合物实施例1b
用以产生干膜的制剂(F-2)
向装设机械式搅拌器的3颈圆底烧瓶,添加300份的环戊酮、100份的于合成实施例1获得的聚合物(Poly-1)、5份的3-(甲基丙烯酰氧基)丙基三甲氧基-硅烷、3份的NCI-831(商品名,可得自ADEKA公司)、31.75份的四乙二醇二丙烯酸酯、11.25份的季戊四醇三丙烯酸酯。组合物经机械式搅拌18小时。然后,所述组合物通过使用0.2微米过滤器(来自Meissner Filtration Product公司的Ultradyne)过滤。
制备干膜(DF-1)
经过滤的光敏性溶液(F-2)经由来自Frontier Industrial Technologies(Towanda,PA)的狭缝式涂覆机,以5英尺/分钟(150厘米/分钟)的线速度施用于作为载体衬底的具有36微米厚度的聚对苯二甲酸乙二酯(PET)膜TA 30(由Toray Plastics America,Inc.制造)上,且于180-200°F干燥以获得具有15微米厚度的聚合物层(DF-1)。在所述聚合物层上,通过辊压法制备双向拉伸聚丙烯(BOPP)膜(由IMPEX GLOBAL LLC制造,商品名80gaBOPP)作为保护层。
制备经高度交联的层(HCL-1)
用制剂(F-1)涂覆含有铜结构的四英寸晶圆,之后进行两阶段软烤程序(90℃持续3分钟及130℃持续3分钟),获得20微米的膜。然后,所述膜于160℃热固化30分钟,制造经高度交联的层。
干膜的层合实施例(L-1)
通过剥离移除DF-1保护层之后,干膜结构的聚合物层(6”x 6”)置于含有经高度交联的层(HCL-1)的4英寸结构化晶圆上。聚合物层通过在80℃真空层合及其后接受25psi的压力而层合在经高度交联的层(HCL-1)上。层合程序通过使用OPTEK,NJ制造的DPL-24A差压层合机进行。
干膜的成像实施例(I-1)
经层合的干膜(L-1)使用掩膜曝露于150mJ/cm2剂量的365nm(i-线源),印出各种线/间隔及接触孔特征。然后,使用环戊酮显影。然后,膜在120℃在真空下烘烤30分钟。
剥离聚合物膜实施例(S-1)
具有由上述两层组成的膜堆叠物的晶圆被切成1”x 2”的块,且垂直置于含有300毫升剥离剂水溶液的600毫升烧杯内,所述剥离剂水溶液含有4.78%的TMAH、94.87%的去离子水及0.35%的1H-四唑。使用磁性搅拌棒在75℃搅拌烧杯的内容物。通过使用温度控制器保持温度恒定。30分钟后,晶圆块被移除,且立即用水冲洗并使用氮气吹扫干燥。在金溅度后通过使用光学显微镜及SEM确定剥离效果。通过使用Dektak轮廓仪测量剩余膜的厚度而确定膜厚度损失程度。
Claims (19)
1.一种用于剥离图案化半导体衬底上的有机膜的方法,其包含:
在一个步骤中以水性剥离剂组合物处理所述有机膜以移除所述有机膜;
其中,所述有机膜包括至少第一层和第二层,所述第一层在25℃在显影剂中具有至多约0.01μ/分钟的溶解速率,且所述第二层在25℃在所述显影剂中具有大于约0.01μ/分钟的溶解速率。
2.如权利要求1所述的方法,其中,所述第一层是经交联的。
3.如权利要求1所述的方法,其中,所述图案化半导体衬底包含至少一个组件,所述组件具有至多约5微米的特征尺寸。
4.如权利要求1所述的方法,其中,所述图案化半导体衬底包含两个图案,所述两个图案通过至多约200微米的间隔分开。
5.如权利要求1所述的方法,其中,所述图案化半导体衬底包含两组图案,且所述两组图案通过至多约100毫米的间隔分开。
6.如权利要求1所述的方法,其中,在所述处理步骤之后,基本上没有留下所述有机膜的膜残余物。
7.如权利要求1所述的方法,其中,在所述处理步骤之后,所述有机膜的残余物具有少于原始膜厚度的约5%的厚度。
8.如权利要求1所述的方法,进一步包含在所述处理步骤之后对所述图案化半导体衬底实施等离子体处理。
9.如权利要求1所述的方法,进一步包含在所述处理步骤之后用冲洗溶剂冲洗所述图案化半导体衬底。
10.如权利要求9所述的方法,进一步包含在所述冲洗步骤之后干燥所述图案化半导体衬底。
11.如权利要求1所述的方法,其中,所述图案化半导体衬底包含金属。
12.如权利要求1所述的方法,其中,所述水性剥离剂组合物包含:
按所述组合物的重量计约0.5%至约25%的量的碱性化合物;
按所述组合物的重量计约65%至约95%的量的水;
按所述组合物的重量计约0.1%至约5%的量的腐蚀抑制剂化合物;及
按所述组合物的重量计0至约5%的量的界面活性剂。
13.如权利要求12所述的方法,其中,所述碱性化合物选自由四甲基氢氧化铵(TMAH)、2-羟基三甲基氢氧化铵、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化铵(TBAH)及其混合物所组成的组。
14.如权利要求12所述的方法,其中,所述腐蚀抑制剂是四唑、三唑、苯并三唑、经取代的三唑或经取代的苯并三唑。
15.如权利要求12所述的方法,其中,所述腐蚀抑制剂是结构(I)的化合物
其中,
R1选自由氢、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C12环烷基或杂环烷基、及经取代或未经取代的C5-C12芳基或杂芳基所组成的组;且
R2至R5各自独立地选自由氢、卤素、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C12环烷基或杂环烷基、及经取代或未经取代的C5-C12芳基或杂芳基所组成的组;或R2至R5的任何两个相邻基团和与其连接的环碳原子一起形成六元环。
16.如权利要求12所述的方法,其中,所述腐蚀抑制剂是
17.一种三维物体,其通过权利要求1-16中任一项所述的方法形成。
18.一种半导体装置,其包含权利要求17所述的三维物体。
19.如权利要求18所述的半导体装置,其中,所述半导体装置是集成电路、发光二极管、太阳能电池或晶体管。
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EP3542393A1 (en) | 2019-09-25 |
KR20190083334A (ko) | 2019-07-11 |
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TW201829656A (zh) | 2018-08-16 |
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