TWI593783B - 用於移除與防止於金屬線路表面形成氧化物之組合物 - Google Patents
用於移除與防止於金屬線路表面形成氧化物之組合物 Download PDFInfo
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- TWI593783B TWI593783B TW102126148A TW102126148A TWI593783B TW I593783 B TWI593783 B TW I593783B TW 102126148 A TW102126148 A TW 102126148A TW 102126148 A TW102126148 A TW 102126148A TW I593783 B TWI593783 B TW I593783B
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- Prior art keywords
- metal
- oxide
- group
- composition
- formation
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims description 52
- 239000002184 metal Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 30
- 230000015572 biosynthetic process Effects 0.000 title claims description 11
- 230000002265 prevention Effects 0.000 title 1
- 239000002904 solvent Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012971 dimethylpiperazine Substances 0.000 claims description 6
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 5
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012972 dimethylethanolamine Substances 0.000 claims description 5
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims description 4
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 4
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 4
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001356 alkyl thiols Chemical class 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 3
- FQXRXTUXSODUFZ-UHFFFAOYSA-N 1h-imidazol-2-ylmethanethiol Chemical compound SCC1=NC=CN1 FQXRXTUXSODUFZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- -1 alkyl mercaptan Chemical compound 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 3
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 3
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 3
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 3
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical group [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 2
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 101100456571 Mus musculus Med12 gene Proteins 0.000 description 2
- QNPXWWXCLVJROL-UHFFFAOYSA-N NCCCN1CCOCC1.CN1CCN(CC1)C Chemical compound NCCCN1CCOCC1.CN1CCN(CC1)C QNPXWWXCLVJROL-UHFFFAOYSA-N 0.000 description 2
- CTGHBTYZMIKZPJ-UHFFFAOYSA-N S1N=NC=C1.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O Chemical compound S1N=NC=C1.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O CTGHBTYZMIKZPJ-UHFFFAOYSA-N 0.000 description 2
- DWLXOFBRSGIFPF-UHFFFAOYSA-N S1NN=C2C1=C1C(C=C2)=NC=2C=CC=CC21 Chemical compound S1NN=C2C1=C1C(C=C2)=NC=2C=CC=CC21 DWLXOFBRSGIFPF-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 description 1
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- NPAILDWTXUDAOR-UHFFFAOYSA-N benzo[g][1,2,3]benzothiadiazole Chemical compound C1=CC2=CC=CC=C2C2=C1N=NS2 NPAILDWTXUDAOR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- 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
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- 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
- C11D7/34—Organic compounds containing sulfur
-
- 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
- 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
- C11D7/5013—Organic solvents 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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- C—CHEMISTRY; METALLURGY
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Description
本發明係關於一種用於移除與防止於金屬線路表面產生氧化物之組合物；尤其，本發明係關於一種於製造半導體電路或製造用於液晶顯示器(LCD)、發光二極管(LED)或有機發光二極管(OLED)顯示器之電路過程中用於移除金屬線路表面上產生之氧化物的組合物，並防止氧化物之形成。
用於半導體電路或供液晶顯示器(LCD)、發光二極管(LED)或有機發光二極管(OLED)顯示器使用之電路之金屬線路電路結構，已逐漸成為越來越精細之積體電路。
作為金屬線路的材料所使用的金屬如：鋁、鈦、銅、銀、金等。其中，因為優異的導電性和相對較低的價格，銅被廣泛應用到眾多領域中。然而，由於銅很容易在環境中氧化，在單元佈線結束之後，使用銅之該線路表面將覆蓋著氧化物。換言之，使用銅之該線路表面將覆蓋著氧化物，經由熱處理程序能夠沉積低介電值之材料，相片曝光過程能利用感光材料確定金屬線路之形狀，在相片曝光過程之後的蝕刻過程中能產生金屬線路膜，脫膜過程能除去在蝕刻過程後殘留在金屬線路表面之感光材料等。但是，此等氧化物將降低銅之固有導電性且使其電阻增強，而最終難
以實現低電壓精細電路結構。因此，到目前為止，銅還沒有被用來作為有機發光二極管(OLED)顯示器電路中之金屬。
因此，如果藉由上述各種過程能除去金屬線路表面形成的氧化物，藉以維持金屬線路之固有導電性，將可使金屬線路之佈線越來越精細。然而，由於金屬氧化物和金屬膜具有非常相似的特性，因此到目前為止，還不可能選擇性地除去該金屬氧化物。
本發明之目標係提供一種能夠選擇性地移除金屬線路表面氧化物的組合物。
本發明之另一目標係提供一種能夠防止在金屬線路表面產生氧化物之組合物。
本發明之另一目標係提供一種能夠移除在金屬線路表面之氧化物且防止氧化物產生之組合物，且更能避免較低金屬膜之腐蝕。
一種根據本發明之用於移除與防止於金屬線路表面產生氧化物之組合物，包括：由下列化學式I表示之化合物，其重量百分率為0.01%到20%；有機溶劑，其重量百分率為10%到99.99%；以及水，其重量百分率為0%到70%：化學式I
在以上化學式I中，X1係為C或S。
另，X2係為CR1 2、NR2、O或S，其中R1和R2中每一者係獨立地為氫、C1-12烷基、C1-12烷基硫醇，或C1-12烷氧基、C6-12芳基或羥基。
X3和X4中每一者係獨立地為CR3或N，其中R3係各自獨立地為氫、C1-12烷基、或C1-12烷基硫醇或羥基，其中X3和X4皆為CR3，且如果R3為C1-12烷基，該取代基R3末端之碳係彼此連接，藉以形成飽和或不飽和環。
在本發明之一實施例中，由化學式I表示之化合物係選自由巰基咪唑、巰基甲基咪唑、苯基巰基四唑、巰苯並噻二唑、巰基苯並咪唑、巰苯並噻二唑、巰基苯並噁唑以及前述物質之混合物所組成之群組。
在本發明之一實施例中，前述之有機溶劑係為胺溶劑。
在本發明之一實施例中，該胺溶劑係選自由單乙醇胺、單異丙胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、二異丙胺、氨基丙醇、單甲基乙醇胺、氨乙基乙醇胺、二甲基乙醇胺、嗎啉、N-甲基嗎啉、N-乙基嗎啉、N-氨基乙基哌嗪、二甲基哌嗪、二甲基氨基丙胺、二甲基哌嗪、氨基丙基嗎啉、二甲基氨基丙胺、甲氧基丙胺、氨基丙基嗎啉、五甲基二乙烯胺、乙烯二胺、二乙烯基三胺、三乙烯基四胺、四乙烯基五胺以及由前述物質之混合物所組成之群組。
在本發明之另一實施例中，該有機溶劑係選自由醇溶劑、醯
胺溶劑、甘醇溶劑、甘醇***溶劑以及前述物質之混合物所組成之群組，且包括重量百分率0%到70%之水。
在本發明之一實施例中，該有機溶劑係選自由乙二醇單甲基醚、丙二醇丙基醚、二乙二醇單甲基醚、乙二醇單丁基醚、三乙二醇丁基醚、乙二醇單乙基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、三丙二醇甲基醚、乙二醇甲基醚乙酸酯、3-甲氧基-1-丁醇、二丙二醇單甲基醚、丙二醇二甲基醚、3-甲氧基-1-丙醇、2-乙氧基乙基乙酸酯、N-甲基-2-吡咯烷酮、乙烯基卡必醇、丙烯基卡必醇、γ-丁內酯、二甲基亞碸、環丁碸、二甲基甲醯胺、四氫糠醇、炔丙醇、三乙二醇單乙基醚、聚乙二醇單乙基醚、丙二醇單甲基醚、乙二醇單異丙醚、乙二醇單異丁基醚、二乙二醇單苯醚以及由前述物質之混合物所組成之群組。
在本發明之一實施例中，該金屬係為銅。
根據本發明所揭露之組合物係能選擇性地移除在金屬線路表面之氧化物、防止在金屬線路表面氧化物之產生，同時防止較低金屬膜之腐蝕，且藉此維持金屬線路之固有導電性，因而使金屬線路之佈線能夠越來越精細。
第1圖為銅沉積於一玻璃後之即時照片。第2圖是在第1圖之玻璃被放到170度的加熱板20分鐘後之影像圖且該氧化物被人工合成於該金屬之表面。第3圖是第2圖之玻璃被沉浸在含有根據本發明所揭露組合物之燒杯中的影像圖。第4圖是第3圖之玻璃被取出後拍攝的照片，其顯示一
滴水得以良好地散佈於許多氧化物形成之部分的結果，然而，同時顯示一滴水不會良好地散佈於該氧化物被移除之部分。第5圖顯示第1圖玻璃之X射線光電子光譜(XPS)分析結果。第6圖顯示第2圖玻璃之X射線光電子光譜分析結果。第7圖顯示使用根據本發明之組合物中除去金屬氧化物後之X射線光電子光譜分析結果。第8A圖顯示本發明金屬電路表面氧化物移除機制之步驟1之示意圖。第8B圖顯示本發明金屬電路表面氧化物移除機制之步驟2之示意圖。
根據本發明用於移除與防止於金屬線路表面產生氧化物之組合物，包括：由下列化學式I表示之化合物，其重量百分率為0.01%到20%；有機溶劑，其重量百分率為10%到99.99%；以及水，其重量百分率為0%到70%：
在以上化學式I中，X1係為C或S。
同樣地，X2係為CR1 2、NR2、O或S，其中R1和R2中每一者係獨立地為氫、C1-12烷基、C1-12烷基硫醇，或C1-12烷氧基、C6-12芳基或羥基。
X3和X4中每一者係獨立地為CR3或N，其中R3係各自獨立地為氫、C1-12烷基、或C1-12烷基硫醇或羥基，其中X3和X4皆為CR3，且如果R3
為C1-12烷基，該取代基R3末端之碳係彼此連接，藉以形成飽和或不飽和環。
在本發明之一實施例中，由化學式I表示之化合物係選自由巰基咪唑、巰基甲基咪唑、苯基巰基四唑、巰苯並噻二唑、巰基苯並咪唑、巰苯並噻二唑、巰基苯並噁唑以及前述物質之混合物所組成之群組。
在本發明之一實施例中，該前述之有機溶劑係為胺溶劑。在此情況下，無論水是否包括於其中，皆可選擇性地移除該金屬電路表面之氧化物。
在本發明之一實施例中，該胺溶劑係選自由單乙醇胺、單異丙胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、二異丙胺、氨基丙醇、單甲基乙醇胺、氨乙基乙醇胺、二甲基乙醇胺、嗎啉、N-甲基嗎啉、N-乙基嗎啉、N-氨基乙基哌嗪、二甲基哌嗪、二甲基氨基丙胺、二甲基哌嗪、氨基丙基嗎啉、二甲基氨基丙胺、甲氧基丙胺、氨基丙基嗎啉、五甲基二乙烯胺、乙烯二胺、二乙烯基三胺、三乙烯基四胺、四乙烯基五胺以及由前述物質之混合物所組成之群組。
在本發明之另一實施例中，該有機溶劑係選自由醇溶劑、醯胺溶劑、甘醇溶劑、甘醇***溶劑以及前述物質之混合物所組成之群組，且包括重量百分率0%到70%之水。換言之，於有機溶劑不包括該胺溶劑，但包括該醇溶劑、該醯胺溶劑、該甘醇溶劑、該甘醇***溶劑，且必須包含水之情況下，藉此可選擇性地移除在金屬線路表面之氧化物。
在本發明之一實施例中，該有機溶劑係選自由乙二醇單甲基醚、丙二醇丙基醚、二乙二醇單甲基醚、乙二醇單丁基醚、三乙二醇丁基醚、乙二醇單乙基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、三丙二醇
甲基醚、乙二醇甲基醚乙酸酯、3-甲氧基-1-丁醇、二丙二醇單甲基醚、丙二醇二甲基醚、3-甲氧基-1-丙醇、2-乙氧基乙基乙酸酯、n-甲基-2-吡咯烷酮、乙烯基卡必醇、丙烯基卡必醇、γ-丁內酯、二甲基亞碸、環丁碸、二甲基甲醯胺、四氫糠醇、炔丙醇、三乙二醇單乙基醚、聚乙二醇單乙基醚、丙二醇單甲基醚、乙二醇單異丙醚、乙二醇單異丁基醚、二乙二醇單苯基醚以及由前述物質之混合物所組成之群組。
在本發明之一實施例中，該金屬係為銅。
在本發明中，將金屬電路表面氧化物移除之機制如第8A圖、第8B圖所示。
步驟1：如果有水存在，將與該化合物結合的巰基之硫原子(S)以該化學式I表示，與金屬(銅)形成配位鍵，且構成由該式I表示之化合物以及具有一非共價電子對的雜原子(N、O或S)(X)，係藉由氫原子之媒介，經與該組合物內的雜原子或氫離子(H+)結合，而與該金屬氧化物中之氧原子(O)形成配位鍵。
步驟2：接下來，該氫離子(H+)和與其結合的金屬氧化物中之氧原子被結合到組合物中之氫離子(H+)上，而以水(H2O)的形式存在於該組合物中。
如果該氧原子從金屬氧化物被除去而使其露出一純金屬表面，藉由化學式I所表示、以巰基與金屬形成配位鍵之化合物，可防止額外金屬氧化物之產生。
此外，由該化學式I所表示、以巰基與金屬形成配位鍵之該化合物，係可保護該金屬電路之表面，以防止腐蝕。
此外，如果水不存在，金屬氧化物之氧原子可由該組合物中之胺基或羥基自表面移除。
最後，由於結合到金屬表面的巰基(SH)是非常弱的結合，因此極易被水的氫鍵所斷裂，而於隨後的超純清洗過程中從金屬表面被移除。
下文中，本發明將經由參考實例詳加描述。然而，應該理解的是，這些實例之目的僅用於說明，而非欲限制本發明的範圍。
實例
被金屬沉積於其上之玻璃置於170度的加熱板上20分鐘，而以人工方式於該金屬膜表面上產生氧化物。同時將溫度保持在40度，將在於其上產生有氧化物之金屬膜浸入根據本發明所揭露之組合物中20分鐘，其後取出，藉此可以肉眼觀察到具有從該金屬表面去除之氧化物之玻璃以及具有該腐蝕金屬之玻璃。於此實驗中，銅金屬膜係用作為位於該玻璃上半部之金屬膜。
表1顯示胺溶劑係用作為有機溶劑，表2則顯示以非胺溶劑作為有機溶劑使用。該組成之單位係如下列表1和表2中所示之重量百分比。實驗結果係按以下標準進行評估且顯示於表1和表2中。
[該氧化物是否被移除]
◎：在兩分鐘內除去該金屬氧化物
△：在兩分鐘後除去該金屬氧化物
X：金屬氧化物未被移除
[金屬腐蝕等級]
◎：具有與控制組基板相同之狀況
○：具有與該控制組基板相同之膜厚度，且於表面上具有輕微腐蝕。
△：與該控制組基板相比，膜厚度稍微減少，且於表面上具有腐蝕。
X：由於腐蝕之緣故，與該控制組基板相比，膜厚度減少一半或以上。
MI：巰基咪唑
MBO：巰基苯並噁唑
MBTD：巰苯並噻二唑
MEA：單乙醇胺
MIPA：單異丙胺
DEA：二乙醇胺
TEA：三乙醇胺
MDEA：n-甲基二乙醇胺
DIPA：二異丙胺
AMP：氨基丙醇
MMEA：單甲基乙醇胺
AEEA：氨乙基乙醇胺
DMEA：二甲基乙醇胺
MOR：嗎啉
NMM：N-甲基嗎啉
NEM：N-乙基嗎啉
AEP：N-氨基乙基哌嗪
DMP：二甲基哌嗪
DMAPA：二甲基氨基丙胺
MOPA：二甲基哌嗪
APM：氨基丙基嗎啉
DMCHA：二甲基氨基丙胺
MOPA：甲氧基丙胺
APM：氨基丙基嗎啉
PMDETA：五甲基二乙烯胺
EDA：乙烯二胺
DETA：二乙烯基三胺
TETA：三乙烯基四胺
TEPA：四乙烯基五胺
NMP：n-甲基-2-吡咯烷酮
EC：乙烯基卡必醇
PC：丙烯基卡必醇
GBL：γ-丁內酯
DMSO：二甲基亞碸
Sulforan：環丁碸
DMF：二甲基甲醯胺
THFA：四氫糠醇
PA：炔丙醇
MG：乙二醇單甲基醚
MDG：二乙二醇單甲基醚
EG：乙二醇單乙基醚
EDG：二乙二醇單乙基醚
ETG：三乙二醇單乙基醚
EPG：聚乙二醇單乙基醚
BDG：二乙二醇單丁基醚
MFG：丙二醇單甲基醚
IPG：乙二醇單異丁醚
IBG：乙二醇單異丁基醚
BFG：二乙二醇單苯醚
PGPE：丙二醇丙基醚
EGMEA：乙二醇單丁基醚乙酸酯
本發明係以示例性實施例描述，但本領域技術人員將理解到，可作出各種改變以及以等效元件代替，而不脫離本發明的範圍。此外，對於本發明揭露之內容可以做出許多修飾，以應用於特定的情況或材質，而不脫離其基本範圍。因此，本發明並不限於所揭露之最佳具體實施例，本發明將包括所有落入本發明之申請專利範圍中之所有實施例。
Claims (3)
- 一種用於移除與防止於金屬線路表面產生氧化物之組合物，包括：由下列化學式I表示之化合物，其重量百分率為0.01%到20%；胺溶劑，其重量百分率為10%到99.99%；以及水，其重量百分率為0%到70%：其中由化學式I表示之化合物係選自由巰基咪唑、巰基甲基咪唑、苯基巰基四唑以及前述物質之混合物所組成之群組；
- 如申請專利範圍第1項所述之用於移除與防止於金屬線路表面產生氧化物之組合物，其中該胺溶劑係選自由單乙醇胺、單異丙胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、二異丙胺、氨基丙醇、單甲基乙醇胺、氨乙基乙醇胺、二甲基乙醇胺、嗎啉、N-甲基嗎啉、N-乙基嗎啉、N-氨基乙基哌嗪、二甲基哌嗪、二甲基氨基丙胺、氨基丙基嗎啉、甲氧基丙胺、 五甲基二乙烯胺、乙烯二胺、二乙烯基三胺、三乙烯基四胺、四乙烯基五胺以及由前述物質之混合物所組成之群組。
- 如申請專利範圍第1項所述之用於移除與防止於金屬線路表面產生氧化物之組合物，其中該金屬為銅。
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| KR101697336B1 (ko) * | 2016-03-03 | 2017-01-17 | 주식회사 엘지화학 | 액정 배향막의 제조방법 |
| US11008500B2 (en) | 2018-07-12 | 2021-05-18 | Championx Usa Inc. | Alkyl lactone-derived corrosion inhibitors |
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| CN102498197A (zh) * | 2009-09-11 | 2012-06-13 | 东友Fine-Chem股份有限公司 | 清洗组成物 |
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| US7375066B2 (en) * | 2000-03-21 | 2008-05-20 | Wako Pure Chemical Industries, Ltd. | Semiconductor wafer cleaning agent and cleaning method |
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| TWI362415B (en) * | 2003-10-27 | 2012-04-21 | Wako Pure Chem Ind Ltd | Novel detergent and method for cleaning |
| US20060003910A1 (en) * | 2004-06-15 | 2006-01-05 | Hsu Jiun Y | Composition and method comprising same for removing residue from a substrate |
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| US20060063687A1 (en) * | 2004-09-17 | 2006-03-23 | Minsek David W | Composition and process for ashless removal of post-etch photoresist and/or bottom anti-reflective material on a substrate |
| KR20080059442A (ko) * | 2005-10-13 | 2008-06-27 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 금속 상용성 포토레지스트 및/또는 희생 반사방지 코팅제거 조성물 |
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| CN102498197A (zh) * | 2009-09-11 | 2012-06-13 | 东友Fine-Chem股份有限公司 | 清洗组成物 |
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| WO2014017819A1 (ko) | 2014-01-30 |
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| CN104662202B (zh) | 2017-06-20 |
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| US20150299628A1 (en) | 2015-10-22 |
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