TW202136489A - 用以清除聚合物的組合物 - Google Patents
用以清除聚合物的組合物 Download PDFInfo
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- TW202136489A TW202136489A TW110107857A TW110107857A TW202136489A TW 202136489 A TW202136489 A TW 202136489A TW 110107857 A TW110107857 A TW 110107857A TW 110107857 A TW110107857 A TW 110107857A TW 202136489 A TW202136489 A TW 202136489A
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- composition
- based solvents
- amine compound
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- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 238000004140 cleaning Methods 0.000 title abstract description 3
- -1 fluorinated alkyl compound Chemical class 0.000 claims abstract description 91
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 238000009835 boiling Methods 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000005453 ketone based solvent Substances 0.000 claims description 4
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical compound CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 0.000 claims description 4
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003660 carbonate based solvent Substances 0.000 claims description 3
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 claims description 3
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- ORSUTASIQKBEFU-UHFFFAOYSA-N n,n-diethylbutan-1-amine Chemical compound CCCCN(CC)CC ORSUTASIQKBEFU-UHFFFAOYSA-N 0.000 claims description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 39
- 235000012431 wafers Nutrition 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 21
- 230000002000 scavenging effect Effects 0.000 description 19
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 239000002998 adhesive polymer Substances 0.000 description 11
- 150000002222 fluorine compounds Chemical class 0.000 description 11
- 229920005573 silicon-containing polymer Polymers 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
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- 238000000034 method Methods 0.000 description 8
- 229910001128 Sn alloy Inorganic materials 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 5
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 4
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- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
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- 239000004094 surface-active agent Substances 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
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- 229940022663 acetate Drugs 0.000 description 2
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 229940072049 amyl acetate Drugs 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012971 dimethylpiperazine Substances 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004660 morphological change Effects 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 230000002522 swelling effect Effects 0.000 description 2
- CMUTXJXHVDKYAN-UHFFFAOYSA-L tetrabutylazanium difluoride Chemical compound [F-].[F-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC CMUTXJXHVDKYAN-UHFFFAOYSA-L 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
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- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 1
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- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
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- JAWZAONCXMJLFT-UHFFFAOYSA-N 4-propylpyridine Chemical compound CCCC1=CC=NC=C1 JAWZAONCXMJLFT-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本發明公開了用以清除聚合物的組合物,組合物包含:氟化烷基化合物、極性非質子溶劑和胺化合物,其中,胺化合物包括非環狀仲胺化合物或非環狀叔胺化合物。
Description
[相關申請案的交叉參照]
本申請要求2020年3月26日提交的日本專利申請No. 10-2020-0036615的權益,此處通過引用併入的方式將此日本申請案的全部內容收載於本文中。
本發明涉及用以清除聚矽氧聚合物的組合物。
在製造半導體裝置時,在半導體晶片(以下,簡稱為「晶片」)的前表面(以下,稱為「電路表面」)上形成電子電路等之後,存在進行背研磨(這是對晶片的背表面進行研磨的過程)以減小晶片的厚度的情況。在這種情況下,為了保護晶片的電路表面或防止晶片移動,通常通過黏合聚合物(例如,聚矽氧聚合物)將支撐物黏附到晶片的電路表面。黏附到晶片的電路表面的支撐物具有以下優點:增強通過背研磨而變薄的晶片,並且允許在晶片的經研磨的背表面上形成背電極。
在執行背研磨和形成背電極之後,從晶片的電路表面去除支撐物,剝離黏合聚合物,並且對晶片進行切割以生產半導體晶片。
近年來,已經開發並使用了採用作為形成為延伸穿過晶片的電極的貫通電極(例如,矽貫通電極)的晶片堆疊技術。根據晶片堆疊技術,由於多個晶片的電子電路通過貫通電極而不是典型的導線電連接,所以實現電子電路的高密度集成和高速操作是可能的。當使用這種晶片堆疊技術時,經常執行背研磨以減小其中堆疊有多個晶片的元件的厚度。因此增加支撐物和黏合聚合物之使用。
關於此問題,通常通過黏合聚合物將支撐物黏附到晶片的電路表面,然後將黏合聚合物熱固化以將支撐物牢固地黏附到晶片。因此,當剝離黏合聚合物時,固化的黏合聚合物可能殘留在晶片的電路表面上。因此,需要一種有效清除殘留在晶片電路表面上的固化的黏合聚合物的手段。另外,當清除黏合聚合物時,存在的問題是金屬膜或凸球(bump ball)可能由於金屬腐蝕而被損壞。
專利文獻1公開了一種用於清除黏合聚合物的組合物。但是,該組合物的問題在於對於網狀聚合物的清除速率慢。
現有技術的文獻
專利文獻
(專利文獻1)韓國專利申請公佈No. 10-2014-0060389
為了解決上述現有技術中出現的問題而完成本發明,並且本發明的目的在於提供一種用以清除聚合物的組合物,該組合物能夠有效且快速地清除在半導體裝置製造過程中殘留在晶片的電路表面上的黏合聚合物,而不引起金屬腐蝕。
本發明的效果、特徵和目的不限於上述,並且本領域普通技術人員根據以下描述可以清楚地理解上文未提及的其他效果、特徵和目的。
為了實現本發明的目的,提供了一種用以清除聚合物的組合物,該組合物包括氟化烷基化合物、極性非質子溶劑和胺化合物。胺化合物包括非環狀仲胺化合物或非環狀叔胺化合物。
根據本發明,提供了一種清除聚合物的組合物,其能夠通過包括非環狀仲胺或非環狀叔胺來提高聚合物清除速率。特別地,本發明的清除聚合物的組合物能夠高速清除基於聚矽氧的聚合物,並且能夠通過防止金屬腐蝕而最小化對金屬膜或凸球的損壞。
本發明涉及一種清除聚合物的組合物,該組合物包含氟化合物、溶劑和胺化合物。氟化合物是氟化烷基化合物,溶劑是極性非質子溶劑,且胺化合物是非環狀仲胺化合物或非環狀叔胺化合物。
在本發明中,烷基是指與單鍵結合的烴基。
<用以清除聚合物的組合物>
根據本發明,用以清除聚合物的組合物包含氟化烷基化合物、極性非質子溶劑和胺化合物。組合物可以進一步包含其他添加劑,並且可以用以清除聚矽氧聚合物。
使用組合物清除的聚合物沒有特別限制,但優選為聚矽氧聚合物。具體地,聚矽氧聚合物包括線性聚合物和網狀聚合物。例如,聚矽氧聚合物包括通過固化形成網狀聚合物的基於聚有機矽氧烷的樹脂以及線性非反應性聚二甲基矽氧烷聚合物。
特別地,本發明的組合物具有不僅清除線性聚合物而且清除網狀聚合物的優點,因為氟化烷基化合物分解並溶解聚矽氧聚合物。
根據本發明,由於胺化合物將組合物的pH值調節至合適的水準,因此可以在聚合物清除期間獲得防止金屬腐蝕的效果。因此,可以防止對金屬膜或凸球的損壞。具體地,該組合物可以通過防止金屬腐蝕來保護金屬(諸如Sn、Sn/Ag合金和Sn/Au合金)。在這種情況下,可以保護的金屬不限於此。
此外,根據本發明的用以清除聚合物的組合物不包含有意添加的水。優選地,用以清除聚合物的組合物不含水。但是,如果需要,可以使用氟化烷基化合物的水合物。在這種情況下,用以清除聚合物的組合物可以包含少量水。在這種情況下,相對於組合物的總重量,組合物中水的含量按重量計可小於4%。當水的含量超過該範圍時,聚合物清除性降低並且金屬腐蝕增加。
此外,優選地,根據本發明的用以清除聚合物的組合物在其分子結構中不包含具有羥基(-OH)基團的化合物,例如基於醇的化合物。在化合物的分子結構中具有羥基基團的情況下,存在羥基基團抑制氟化合物的活性而使聚矽氧樹脂的清除性降低的問題。
(A)氟化烷基化合物
根據本發明的用以清除聚合物的組合物包含氟化烷基化合物。氟化烷基化合物通過斷開聚合物(例如聚矽氧聚合物)的環來降低分子量。
在本發明中,氟化烷基化合物的實例是烷基氟化銨。具體地,氟化烷基化合物的實例包括一種或多種由式4-1或式4-2所表示的化合物。
[式4-1]
在式4-1中,R6
至R9
各自為具有3至10個碳原子(C3至C10)的烷基。當R6
至R9
各自為具有兩個或更少個碳原子(C2或更少)的烷基時,由於氟化合物在溶劑中的溶解度降低,因此在混合後立即發生沉澱,或者在混合後經過一定時間發生沉澱。
[式4-2]
在式4-2中,R10
至R12
各自為具有1至10個碳原子(C1至C10)的烷基。
例如,作為氟化烷基化合物,單獨地或組合地使用一種或多種選自四丁基二氟化銨(TBAF.HF)、四丁基氟化銨(TBAF)、四辛基氟化銨(TOAF)、以及苄基三甲基氟化銨(BTMAF)中的化合物。
當烷基氟化銨以水合物形式存在時,烷基氟化銨的實例包括四正丁基氟化銨水合物、四正丁基氟化銨三水合物、苄基三甲基氟化銨水合物等。
相對於用以清除聚合物的組合物的總重量,組合物中氟化烷基化合物的含量按重量計可為0.1%至20%、優選為0.5%至17%。當氟化合物的含量按重量計小於0.1%時,存在不能有效地清除黏附在電子部件上的聚合物(聚矽氧樹脂)的問題。另一方面,當氟化合物的含量按重量計為20%或更多且它以水合物型烷基氟化銨的形式存在時,含水量增加,從而使清除聚合物(諸如聚矽氧樹脂)的效果變差。另外,金屬膜由於過量的氟化物而被腐蝕。
(B)極性非質子溶劑
根據本發明的用以清除聚合物的組合物包含極性非質子溶劑。極性非質子溶劑使聚矽氧聚合物溶脹並溶解氟化合物和分解的聚矽氧聚合物。
作為通常已知的溶劑,水和基於醇的化合物(例如,二甘醇單甲醚、乙二醇、異丙醇等)由於與氟離子的氫鍵結合而難以清除聚合物。因此,優選地,根據本發明的用以清除聚合物的組合物中的溶劑不包含水和基於醇的化合物。
極性非質子溶劑包括選自由基於酮的溶劑、基於乙酸酯的溶劑、基於醯胺的溶劑、基於吡啶的溶劑、基於嗎啉的溶劑、基於吡咯烷酮的溶劑、基於脲的溶劑、基於磷酸酯的溶劑、基於亞碸的溶劑、基於腈的溶劑、基於碳酸酯的溶劑、基於噁唑烷酮的溶劑、以及基於呱嗪的溶劑所組成的群組中的至少一種溶劑。
具體地,基於酮的溶劑的實例包括由式5-1所表示的化合物:
[式5-1]
在式5-1中,R13
和R14
各自獨立地為具有1至18個碳原子(C1至C18)的直鏈或支鏈的脂族烴,並且R13
和R14
的碳原子數總和優選為2或更大且小於30。
酮溶劑的實例包括2-庚酮、3-庚酮、4-庚酮、3-戊酮、2-己酮、3-己酮、4-甲基-2-戊酮、5-甲基-2-己酮和2,6-二甲基-4-己酮,但不限於此。
具體地,基於乙酸酯的溶劑的實例包括乙酸甲酯、乙酸乙酯(EA)、乙酸丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸仲丁酯、乙酸戊酯(amyl acetate / pentyl acetate)、乙酸異戊酯、乙酸辛酯、乙酸苄酯、乙酸苯酯、乙酸乙氧基乙酯、乙酸甲氧基丁酯(MBA)、丙二醇單甲醚乙酸酯(PGMEA)、乙酸乙烯酯或乙氧基丙酸乙酯(EEP)等,但不限於此。
具體地,基於醯胺的溶劑的實例包括N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N,N-二丙基乙醯胺、N-乙基-N-甲基乙醯胺、N,N-二甲基丙醯胺(N,N-dimethylpropionamide / N,N-dimethylpropanamide)、N,N-二甲基丁醯胺、N,N-二甲基異丁醯胺、N,N-二甲基戊醯胺、N,N-二乙基丙醯胺和N,N-二丁基丙醯胺,但不限於此。
具體地,基於吡啶的溶劑的實例包括由式5-2所表示的化合物:
[式5-2]
在式5-2中,R15
至R17
各自獨立地為氫、具有1至10個碳原子(C1至C10)的直鏈或支鏈的脂族烴基、鹵素(例如,F、Cl、Br、I)、醛基(-CHO)、乙醛基(-COCH3
)、具有1至4個碳原子(C1至C4)的烷氧基、乙烯基、乙炔基、氰基(-CN)或甲基硫基(-SCH3
)。
吡啶溶劑的實例包括吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、4-乙基吡啶、4-丙基吡啶、4-異丙基吡啶、4-戊基吡啶、2,3-二甲基吡啶、2,4-二甲基吡啶、2,5-二甲基吡啶、3,4-二甲基吡啶、3,5-二甲基吡啶和2,4,6-三甲基吡啶,但不限於此。
具體地,嗎啉溶劑的實例包括由式5-3所表示的化合物:
[式5-3]
在式5-3中,R18
為氫,具有1至6個碳原子(C1至C6)的直鏈或支鏈的脂族烴基,乙烯基,氰基(-CN),具有1至4個碳原子(C1至C4)且被叔胺取代的脂族烴基,或被具有1至4個碳原子(C1至C4)的烷基、氰基(-CN)、鹵素基團(例如,F、Cl、Br或I)或醛基(-CHO)取代的苯基或吡啶基;X是氧或-NR19
-;且R19
為具有1至4個碳原子(C1至C4)的脂族烴基。
基於嗎啉的溶劑的實例包括N-甲基嗎啉、N-乙基嗎啉、N-芳基嗎啉、N-丁基嗎啉、N-異丁基嗎啉等,但不限於此。
具體地,基於吡咯烷酮的溶劑的實例包括N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)和N-乙烯基吡咯烷酮(NVP),但不限於此。
具體地,基於尿素的溶劑的實例包括由式5-4所表示的化合物:
[式5-4]
在式5-4中,X為氧或-NR19
-,並且R19
和R20
各自獨立地為具有1至6個碳原子(C1至C6)的直鏈、支鏈或環狀的脂族烴基,或具有1至4個碳原子(C1至C4)且被乙烯基、苯基、乙炔基、甲氧基或二甲基氨基取代的脂族烴基。
基於尿素的溶劑的實例包括四甲基尿素、四乙基脲、四丁基脲等,但不限於此。
具體地,基於磷酸酯的溶劑的實例包括由式5-5所表示的化合物:
[式5-5]
在式5-5中,R21
至R23
各自獨立地為具有1至8個碳原子(C1至C8)的直鏈或支鏈的脂族烴基、具有3至8個碳原子(C3至C8)且與相鄰氧形成環的二價脂族烴基、未取代或被具有1至4個碳原子(C1至C4)的脂族烴基取代的苯基、具有2至4個碳原子且被鹵素(例如F、Cl、Br或I)取代的脂族烴基、或被鹵素取代的苯基。在具有1至8個碳原子(C1至C8)的直鏈或支鏈的脂族烴基中包含的基團“-CH2
-”可被氧原子取代。
基於磷酸酯的溶劑的實例包括磷酸三乙酯、磷酸三丁酯、磷酸三戊酯、三芳基磷酸酯等,但不限於此。
具體地,基於亞碸的溶劑的實例包括二甲基亞碸(DMSO)、二丁基亞碸、二苯基亞碸、二苄基亞碸和甲苯基亞碸,但不限於此。
具體地,基於腈的溶劑的實例包括丙腈、丁腈、異丁腈、乙腈、三甲基乙腈和苯乙腈,但不限於此。
具體地,基於碳酸酯的溶劑的實例包括碳酸二甲酯(DMC)、碳酸二乙酯、碳酸二苯酯、碳酸二苄酯、碳酸亞乙酯、碳酸丙烯酯(PC)和碳酸亞乙烯酯,但不限於此。
具體地,基於噁唑烷酮的溶劑的實例包括2-噁唑烷酮、3-甲基-2-噁唑烷酮等,但不限於此。
基於呱嗪的溶劑的實例包括二甲基呱嗪、二丁基呱嗪等,但不限於此。
另一方面,根據本發明,極性非質子溶劑不包括後文描述的非環狀叔胺。
相對於用以清除聚合物的組合物的總重量,組合物中極性非質子溶劑的含量按重量計可為60%至99.89%、優選地為68%至99.45%的。當組合物中極性非質子溶劑的含量按重量計小於60%時,存在金屬膜被腐蝕的問題。另一方面,當組合物中極性非質子溶劑的含量按重量計超過99.89%的量時,存在不能有效地清除黏附在電子部件上的聚矽氧樹脂的問題。
(C)胺化合物
根據本發明的用以清除聚合物的組合物包含胺化合物,並且胺化合物是非環狀仲胺化合物或非環狀叔胺化合物。胺化合物促進聚矽氧聚合物的溶脹並改善氟化烷基化合物的溶解度,從而提高聚矽氧聚合物的清除速率。在本發明中,通過將用以清除聚合物的組合物的pH值調節至適當的水準,胺化合物表現出防腐蝕作用。
為了使用以清除聚合物的組合物中的胺化合物的功能效果最大化,適合使用具有特定結構的胺化合物。例如,當胺的烷基中的碳原子數增加時,使聚矽氧聚合物溶脹的作用增強,而當胺的烷基中的碳原子數減少時,改善氟化烷基化合物的溶解度的效果增強。另外,氟化烷基化合物的游離性愈好,發生的腐蝕就愈多。為了獲得互補效果,使用胺化合物。也就是說,胺化合物改善了聚合物的清除效果並減輕了金屬的腐蝕。具體地,優選使用具有下述特定結構的胺化合物。
具體地,用於本發明的胺化合物的實例包括由式1至式3中的任一者所表示的化合物。
[式1]
在式1中,R1
和R2
各自獨立地為具有1至8個碳原子(C1至C8)的直鏈或支鏈的烷基。當R1
和R2
相同時,R1
和R2
優選為具有4個或更多個碳原子的烷基。
更優選地,R1
和R2
各自獨立地為具有2個至8個碳原子(C2至C8)的直鏈或支鏈的烷基。當R1
和R2
相同時,R1
和R2
優選為具有4個至8個碳原子(C4至C8)的直鏈或支鏈的烷基。
[式2]
在式2中,R3
至R5
各自為具有1至8個碳原子(C1至C8)的烷基。
[式3]
在式3中,n是3至6的整數。
胺化合物優選為沸點為140℃或更高的胺化合物,更優選為沸點在140℃至300℃範圍內的胺化合物。當胺化合物滿足式1至式3中的一者並且沸點為140℃或更高時,由於揮發性成分被最小化,因此根據本發明的用以清除聚合物的組合物可以容易地應用於裝置製造工藝中。當胺化合物的沸點為140℃或更高時,不僅可以預期提高聚合物清除性能的效果,還可以預期防止金屬腐蝕的效果。當胺化合物的沸點低於140℃時,預期聚合物清除性能有很大的改善,但是防止金屬腐蝕的效果不明顯。因此,難以同時獲得提高聚合物清除性能的效果和防止金屬腐蝕的效果。
例如,胺化合物包括選自由三丙胺(沸點為158℃)、三丁胺(沸點為215℃)、三戊胺(沸點為242℃)、三異丁胺(沸點為191℃)、二甲基辛胺(沸點為192℃)、二乙基丁胺(沸點為141℃)、二異丁胺(沸點為141℃)、N,N,N',N'-四甲基-1,3-二氨基丙烷(沸點為144℃)、N,N,N',N'-四甲基-1,4-二氨基丁烷(沸點為169℃)和N,N,N',N'-四甲基-1,6-二氨基己烷(沸點為209℃)所組成的群組中的一種或多種化合物。
相對於用以清除聚合物的組合物的總重量,組合物中胺化合物的含量按重量計可為0.01%至20%、優選為0.05%至15%。當組合物中胺化合物的含量按重量計小於0.01%時,難以預期清除速率的提高。另一方面,當組合物中胺化合物的含量按重量計超過20%時,聚合物溶脹效果不與胺化合物的含量成比例地增加,並且金屬腐蝕增加。
(D)添加劑
除了上述成分外,根據本發明的用以清除聚合物的組合物任選地包含其他成分,諸如本領域中常用的腐蝕抑制劑和表面活性劑。
腐蝕抑制劑用以在清除樹脂期間有效地抑制含金屬的底膜的腐蝕。腐蝕抑制劑可從各種來源商購獲得,且無需進一步純化即可使用。
表面活性劑用以增強清除聚合物的效果。例如,可以使用陰離子表面活性劑、陽離子表面活性劑和非離子型表面活性劑。其中,優選使用具有優異的潤溼性且產生少量氣泡的非離子型表面活性劑。選自這些表面活性劑中的一種或多種表面活性劑可以單獨使用或組合使用。
本發明還提供了一種使用根據本發明的用以清除聚合物的組合物以從裝置中清除聚合物的方法。根據本發明的聚合物的清除方法可應用對根據本發明的用以清除聚合物的組合物所描述的所有內容,且下文將省略重複部分的詳細描述。即便省略描述,仍可應用相同的內容。
具體地,聚合物的清除方法是用於清除在晶片薄化處理中使用的聚合物(諸如矽黏合劑)的方法。晶片薄化處理包括在載體晶片和裝置晶片之間形成聚矽氧分離層和聚矽氧黏合劑層的步驟以及使裝置晶片變薄的步驟。聚矽氧分離層用作分離位置,在該分離位置處去除載體晶片,而不損壞裝置晶片。聚矽氧黏合劑將裝置晶片黏合到載體晶片上,並進行固化過程。在這樣的處理步驟之後,使用根據本發明的用以清除聚合物的組合物清除固化的聚合物。
將參考下面描述的實施例更詳細地描述本發明。實施例旨在更詳細地描述本發明,但是本發明的範圍不限於這些實施例。
實施例和比較例:製備清除聚合物的組合物
根據表1和表2中列出的成分和組成比例製備用以清除聚合物的組合物。
[表1]
單位: 重量% | (A)氟化合物 | (B)溶劑 | (C)胺化合物 | |||
種類 | 含量 | 種類 | 含量 | 種類 | 含量 | |
實施例1 | A-1 | 5 | B-1 | 90 | C-1 | 5 |
實施例2 | A-2 | 5 | B-2 | 85 | C-2 | 10 |
實施例3 | A-2 | 6 | B-3 | 91 | C-3 | 3 |
實施例4 | A-3 | 4 | B-4 | 84 | C-3 | 10 |
實施例5 | A-2 | 5 | B-4 | 90 | C-3 | 5 |
實施例6 | A-2 | 7 | B-5 | 92 | C-4 | 1 |
實施例7 | A-2 | 7 | B-6/B-7 | 40/52.5 | C-5 | 0.5 |
實施例8 | A-1 | 4 | B-8 | 94 | C-4 | 2 |
實施例9 | A-1 | 4 | B-9 | 95 | C-1 | 1 |
實施例10 | A-2 | 1 | B-2 | 99 | C-2 | 2 |
實施例11 | A-3 | 15 | B-2 | 85 | C-2 | 2 |
實施例12 | A-2 | 0.5 | B-2 | 99.5 | C-2 | 2 |
實施例13 | A-2 | 17 | B-2 | 83 | C-2 | 2 |
實施例14 | A-2 | 6 | B-3 | 79 | C-3 | 20 |
實施例15 | A-2 | 6 | B-3 | 93.99 | C-3 | 0.01 |
實施例16 | A-2 | 6 | B-3 | 93.95 | C-3 | 0.05 |
實施例17 | A-1 | 5 | B-6/B-3 | 50/44 | C-3 | 1 |
實施例18 | A-2 | 8 | B-10 | 88 | C-2 | 4 |
實施例19 | A-2 | 8 | B-11 | 77 | C-2 | 15 |
實施例20 | A-2 | 8 | B-3 | 67 | C-3 | 25 |
實施例21 | A-1 | 5 | B-4 | 90 | C-6 | 5 |
[表2]
單位: 重量% | (A)氟化合物 | (B)溶劑 | (C)胺化合物 | |||
種類 | 含量 | 種類 | 含量 | 種類 | 含量 | |
比較例1 | - | - | B-1 | 100 | - | - |
比較例2 | - | - | B-5 | 100 | - | - |
比較例3 | A-20 | 5 | B-3 | 95 | - | - |
比較例4 | A-2 | 5 | B-7 | 95 | - | - |
比較例5 | A-2 | 5 | B-22 | 85 | C-1 | 10 |
比較例6 | A-2 | 5 | B-23 | 85 | C-1 | 10 |
比較例7 | A-1 | 6 | B-2 | 89 | C-20 | 5 |
比較例8 | A-1 | 7 | B-20 | 88 | C-1 | 5 |
比較例9 | A-2 | 5 | B-21 | 90 | C-1 | 5 |
比較例10 | A-1 | 5 | B-4 | 85 | C-21 | 10 |
比較例11 | A-1 | 5 | B-4 | 85 | C-22 | 10 |
比較例12 | A-1 | 5 | B-4 | 85 | C-23 | 10 |
實施例22 | A-1 | 5 | B-1 | 90 | C-24 | 5 |
實施例23 | A-1 | 5 | B-1 | 90 | C-25 | 5 |
<氟化合物>
(A-1)TBAF.HF:四丁基二氟化銨;
(A-2)TBAF:四丁基氟化銨;
(A-3)BTMAF:苄基四甲基氟化銨;
(A-20)氟化銨(NH4
HF2
)
<溶劑>
(B-1)2-庚酮;(B-2)N,N-二乙基乙醯胺;
(B-3)N,N-二甲基丙醯胺;(B-4)N-乙基吡咯烷酮;
(B-5)N-甲基嗎啉;(B-6)乙酸正丁酯;
(B-7)PGMEA:丙二醇單甲醚乙酸酯;
(B-8)4-甲基吡啶;(B-9)二甲基呱嗪;
(B-10)三乙基磷酸酯;(B-11)四乙基脲;
(B-20)乙二醇;(B-21)異丙醇
(B-22)水;(B-23)二乙二醇單甲醚
<胺化合物>
(C-1)三丙胺(沸點158℃);
(C-2)二異丁胺(沸點141℃);
(C-3)三丁胺(沸點215℃);
(C-4)二甲基辛胺(沸點192℃);
(C-5)N,N,N',N'-四甲基-1,3-二氨基丙烷(沸點144℃);
(C-6)三乙基胺(沸點89℃);
(C-20)辛胺(沸點176℃);
(C-21)單乙醇胺(沸點174℃);
(C-22)羥胺(沸點58℃);
(C-23)四甲基氫氧化銨水溶液(20%)(沸點102℃)
(C-24)二丙胺
(C-25)N-甲基丁胺
(測試實施例1)聚合物清除性評估1—網狀聚合物
為了評價網狀聚合物的清除性,將塗覆固化聚矽氧聚合物至80 μm厚度的晶片切成尺寸為2 cm x 2 cm的小塊,並將小塊用作樣品。將根據實施例和比較例的各個組合物的溶液加熱至25℃並以400 rpm旋轉。將製備的樣品在各個組合物溶液中浸泡1分鐘,用異丙醇(IPA)洗滌,並乾燥。在將樣品浸入組合物溶液中之前,通過掃描電子顯微鏡(SEM)測量每個樣品的固化聚矽氧聚合物的膜厚度。在將樣品浸泡、洗滌和乾燥後,用掃描電子顯微鏡(SEM)測量每個樣品中殘留的聚矽氧樹脂的厚度,並計算每種組合物溶液的清除速率,並匯總在表3和表4中。
清除速率(μm/min)= [測試前厚度(μm)-測試後厚度(μm)]/測試時間(分鐘)
(測試實施例2)聚合物清除性評估2—線性PDMS
為了評估線性聚二甲基矽氧烷(PDMS)的清除性,將通過以預定的品質比混合聚二甲基矽氧烷(PDMS)的預聚物和固化劑而獲得的混合物旋塗在矽晶片上且切成尺寸為2 cm x 2 cm的小塊,將小塊用作樣品。將根據實施例和比較例的組合物溶液加熱至25℃並以400 rpm旋轉。將樣品在各個組合物溶液中浸泡1分鐘,用IPA洗滌,並乾燥。測試後,用光學顯微鏡和SEM觀察每個樣品表面上的殘留物。表3和表4中標出了每個樣品上是否存在殘留物。
O:不存在 / X:存在
(測試實施例3)金屬腐蝕評估1—凸球
為了評估金屬腐蝕,將具有1011個由Sn、Sn/Ag合金或Sn/Au合金製成的凸球的晶片切成尺寸為2 cm x 2 cm的小塊,並將小塊用作樣品。將製備的樣品在根據實施例和比較例的各個組合物溶液中浸泡30分鐘,同時將組合物溶液加熱至25℃並以400 rpm旋轉,用IPA洗滌,並乾燥。用SEM觀察各個樣品。將每個樣品中損壞的凸球的數量計數並匯總在表3和表4中。
(測試實施例4)金屬腐蝕評估2—金屬膜
將塗覆有鋁薄膜的晶片切成尺寸2 cm x 2 cm的小塊,並將小塊用作樣品。將根據實施例和比較例的各個組合物的溶液加熱至25℃並以400 rpm旋轉。將製備的樣品在各個組合物溶液中浸泡10分鐘,用異丙基醇(IPA)洗滌,並乾燥。洗滌後,各個樣品上的薄膜用SEM檢查缺陷,並且根據下述標準將結果匯總在表3和表4中。
良好:未觀察到表面形態學變化或變色。
發生:觀察到表面形態學變化和變色。
[表3]
清除速率(μm/min) | 存在/不存在 殘留物 | 凸球損壞 計數(個/1011個) | Al損壞 | |
實施例1 | 34 | O | 3 | 良好 |
實施例2 | 30 | O | 4 | 良好 |
實施例3 | 31 | O | 3 | 良好 |
實施例4 | 25 | O | 0 | 良好 |
實施例5 | 24 | O | 1 | 良好 |
實施例6 | 28 | O | 1 | 良好 |
實施例7 | 26 | O | 3 | 良好 |
實施例8 | 25 | O | 0 | 良好 |
實施例9 | 24 | O | 0 | 良好 |
實施例10 | 23 | O | 0 | 良好 |
實施例11 | 46 | O | 3 | 良好 |
實施例12 | 23 | O | 0 | 良好 |
實施例13 | 32 | O | 4 | 良好 |
實施例14 | 48 | O | 4 | 良好 |
實施例15 | 30 | O | 0 | 良好 |
實施例16 | 29 | O | 3 | 良好 |
實施例17 | 31 | O | 0 | 良好 |
實施例18 | 27 | O | 0 | 良好 |
實施例19 | 30 | O | 2 | 良好 |
實施例20 | 30 | O | 23 | 良好 |
實施例21 | 24 | O | 21 | 良好 |
[表4]
清除速率 (μm/min) | 存在/不存在 殘留物 | 凸球損壞 計數(個/1011個) | Al損壞 | |
比較例1 | 0 | X | 0 | 良好 |
比較例2 | 0 | X | 0 | 良好 |
比較例3 | 無法評估 | 無法評估 | 無法評估 | 無法評估 |
比較例4 | 12 | O | 25 | 良好 |
比較例5 | 0 | X | 675 | 發生 |
比較例6 | 0 | X | 243 | 發生 |
比較例7 | 4 | O | 32 | 發生 |
比較例8 | 2 | X | 0 | 良好 |
比較例9 | 3 | X | 0 | 良好 |
比較例10 | 8 | X | 41 | 發生 |
比較例11 | 12 | O | 67 | 發生 |
比較例12 | 5 | X | 1011 | 發生 |
實施例22 | 18.7 | O | 43 | 良好 |
實施例23 | 19 | O | 50 | 良好 |
參見表3,根據本發明的用以清除聚合物的組合物(實施例1至實施例21)對於網狀的基於聚矽氧的聚合物表現出23 μm/min或更大的高清除速率,並且對於線性的基於聚矽氧的聚合物表現出優異的清除性能。另外,根據本發明的組合物表現出良好的抗腐蝕作用。當使用具有低沸點的胺化合物時(實施例21),或者當以過量添加胺化合物時(實施例20),性能略有降低,但是明顯優於比較例的性能。
另一方面,參考表4,在均沒有使用根據本發明的胺化合物的比較例7和比較例10至比較例12對於網狀聚合物表現出12 μm/min或更小的清除速率。也就是說,與使用根據實施例的組合物的情況相比,清除速率顯著降低且金屬的腐蝕也顯著增加。
另外,即使在使用根據本發明的胺化合物時,但當在使用水或基於醇的化合物作為溶劑的情況下(比較例5和比較例6),證實了聚合物清除是困難的且金屬腐蝕非常高。在均使用質子溶劑的比較例8和比較例9中,聚合物清除速率低,並且在清除聚合物之後仍有殘留物。
另一方面,當單獨使用極性非質子溶劑時,沒有清除聚合物(比較例1和比較例2)。當使用氟化銨作為氟化合物時(比較例3),在組合物的製備過程中發生沉澱,使得不能進行評估。另外,在分別使用二丙胺和N-甲基丁胺作為胺化合物的實施例22和實施例23中,網狀聚合物的清除速率降低至20 μm/min或更少,且在由Sn、Sn/Ag合金或Sn/Au合金製成的1011個凸球中,有40個或更多個凸球被損壞。
Claims (8)
- 一種用以清除聚合物的組合物,該組合物包含:氟化烷基化合物、極性非質子溶劑和胺化合物,其中,該胺化合物包括非環狀仲胺化合物或非環狀叔胺化合物。
- 如請求項1所述之組合物,其中,該極性非質子溶劑包括選自由基於酮的溶劑、基於乙酸酯的溶劑、基於醯胺的溶劑、基於吡啶的溶劑、基於嗎啉的溶劑、基於吡咯烷酮的溶劑、基於脲的溶劑、基於磷酸酯的溶劑、基於亞碸的溶劑、基於腈的溶劑、基於碳酸酯的溶劑、基於噁唑烷酮的溶劑、以及基於呱嗪的溶劑所組成的群組中的至少一種溶劑。
- 如請求項1所述之組合物,其中,該胺化合物包括選自由三丙胺、三丁胺、三戊胺、三異丁胺、二甲基辛胺、二乙基丁胺、二異丁胺、N,N,N',N'-四甲基-1,3-二氨基丙烷、N,N,N',N'-四甲基-1,4-二氨基丁烷、以及N,N,N',N'-四甲基-1,6-二氨基己烷所組成的群組中的至少一種化合物。
- 如請求項1所述之組合物,其中,該胺化合物的沸點在140℃至300℃的範圍內。
- 如請求項1所述之組合物,其中,該組合物用以清除基於聚矽氧的聚合物。
- 如請求項1所述之組合物,其中,相對於該組合物的總重量,該組合物包含按重量計0.1%至20%的該氟化烷基化合物、按重量計60%至99.89%的該極性非質子溶劑和按重量計0.01%至20%的該胺化合物。
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US20230339843A1 (en) | 2023-10-26 |
CN113444589A (zh) | 2021-09-28 |
KR102192954B1 (ko) | 2020-12-18 |
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