TWI434339B - 金屬材料用蝕刻劑組成物及用它之半導體裝置之製法 - Google Patents
金屬材料用蝕刻劑組成物及用它之半導體裝置之製法 Download PDFInfo
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- TWI434339B TWI434339B TW095122654A TW95122654A TWI434339B TW I434339 B TWI434339 B TW I434339B TW 095122654 A TW095122654 A TW 095122654A TW 95122654 A TW95122654 A TW 95122654A TW I434339 B TWI434339 B TW I434339B
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- Prior art keywords
- acid
- etchant composition
- mass
- metal material
- insulating material
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- 239000000203 mixture Substances 0.000 title claims description 57
- 239000007769 metal material Substances 0.000 title claims description 52
- 238000005530 etching Methods 0.000 title claims description 37
- 239000004065 semiconductor Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title description 13
- 239000003153 chemical reaction reagent Substances 0.000 title 1
- 239000011810 insulating material Substances 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 20
- 150000002222 fluorine compounds Chemical class 0.000 claims description 19
- 150000004767 nitrides Chemical class 0.000 claims description 19
- -1 Pr 2 O 3 Inorganic materials 0.000 claims description 17
- 239000002738 chelating agent Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 6
- 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 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 150000004715 keto acids Chemical class 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 229910004200 TaSiN Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 4
- 229910001632 barium fluoride Inorganic materials 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- GIXFALHDORQSOQ-UHFFFAOYSA-N 2,4,6,8-tetrahydroxy-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-N 0.000 description 1
- PTOKDFKDUYQOAK-UHFFFAOYSA-N 2-aminoethanol;hydrofluoride Chemical compound F.NCCO PTOKDFKDUYQOAK-UHFFFAOYSA-N 0.000 description 1
- CFAOOHORWCGLMC-UHFFFAOYSA-N 2-aminoethylphosphinic acid Chemical compound NCCP(O)=O CFAOOHORWCGLMC-UHFFFAOYSA-N 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- QVVDFVKPAQJOJF-UHFFFAOYSA-N 5-cyclooctylpentanoic acid Chemical compound C1C(CCCCC(=O)O)CCCCCC1 QVVDFVKPAQJOJF-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PJMTUTCWDUKQKR-UHFFFAOYSA-M C(CC(O)(C(=O)O)CC(=O)O)(=O)O.[F-].[K+] Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.[F-].[K+] PJMTUTCWDUKQKR-UHFFFAOYSA-M 0.000 description 1
- TUYRAIOYNUOFNH-UHFFFAOYSA-N CP(=O)(O)OP(=O)O Chemical compound CP(=O)(O)OP(=O)O TUYRAIOYNUOFNH-UHFFFAOYSA-N 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- KLXVFGDULWLAID-UHFFFAOYSA-N OB(O)O.N.N.N.N.F Chemical compound OB(O)O.N.N.N.N.F KLXVFGDULWLAID-UHFFFAOYSA-N 0.000 description 1
- QLDOURDNHUCYDT-UHFFFAOYSA-N P(O)(O)=O.C(CN)N Chemical compound P(O)(O)=O.C(CN)N QLDOURDNHUCYDT-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- JIMVSXSPGYTTSC-UHFFFAOYSA-J [Ba+2].[F-].[Ba+2].[F-].[F-].[F-] Chemical compound [Ba+2].[F-].[Ba+2].[F-].[F-].[F-] JIMVSXSPGYTTSC-UHFFFAOYSA-J 0.000 description 1
- QDIYZGWZTHZFNM-UHFFFAOYSA-N [F].[K] Chemical compound [F].[K] QDIYZGWZTHZFNM-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004663 bisphosphonates Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- VVRKSAMWBNJDTH-UHFFFAOYSA-N difluorophosphane Chemical compound FPF VVRKSAMWBNJDTH-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- LZCVHHFGMKXLBU-UHFFFAOYSA-N ethanamine;hydrofluoride Chemical compound [F-].CC[NH3+] LZCVHHFGMKXLBU-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- RRSMHQNLDRCPQG-UHFFFAOYSA-N methanamine;hydrofluoride Chemical compound [F-].[NH3+]C RRSMHQNLDRCPQG-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
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- 229960002799 stannous fluoride Drugs 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- POVVSDFLZJPOGC-UHFFFAOYSA-M tetraethoxyazanium;fluoride Chemical compound [F-].CCO[N+](OCC)(OCC)OCC POVVSDFLZJPOGC-UHFFFAOYSA-M 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Description
本發明係有關於一種蝕刻劑組成物及使用其之半導體裝置之製造方法,該蝕刻劑組成物在製造由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絕緣材料、以及金屬材料所構成的半導體裝置時,能夠選擇性、且有效率地蝕刻金屬材料。
近年來,隨著半導體裝體的高積體化、及閘極絕緣層的薄層化,在施加閘偏壓時會有***絕緣層的隧道體流增加、信號延遲、或驅動力降低的問題。
為了抑制隧道電流增加,有採用以介電常數10以上的絕緣材料代替介電常數3.9之矽氧化物之方法。此種高介電常數絕緣材料被檢討作為候選材料的有Al2
O3
、HfO2
、Y2
O3
及ZrO2
等稀土元素氧化物。使用此種高介電常數絕緣材料時,即使閘長度微細化亦能夠到按照比例換算而保持閘絕緣材料容量,同時閘絕緣層可以製成能夠防止隧道電流之厚度。
又,為了抑制信號延遲或驅動力降低,有檢討一種方法係將以往所使用的閘電極材料,從多晶矽變更為金屬材料。藉由將金屬材料使用作為閘電極材料,能夠降低閘電阻及源極之間的電阻,能夠減少半導體裝置的信號延遲。又,不會觀察到使用多晶矽電極時所產生的閘極耗盡化,能夠提升驅動力。而且能夠得到組合高介電常數絕緣材料與金屬材料之相乘效果,能夠抑制隧道電流,同時維持半導體裝置之高水準的性能。
此種絕緣材料在製造由絕緣材料(矽的氧化膜或氮化膜所構成)及金屬材料所構成的半導體裝置時,產生選擇性地蝕刻金屬材料之製程。可舉出的有例如在只有雙閘型電晶體的第一閘區域將金屬材料圖案化之製程,在絕緣材料上堆積高介電常數絕緣材料、及金屬材料後,只蝕刻第二閘區域的金屬材料之製程。將以往使用電漿氣體之乾蝕刻方法應用在該蝕刻製程時,因為無法得到絕緣材料及高介電常數絕緣材料與金屬材料的選擇比,絕緣材料及高介電常數絕緣材料被蝕刻掉,精確的加工變為困難。而且,亦未有報告揭示應用濕蝕刻的方法來蝕刻金屬材料之技術。
因此,迫切希望一種技術能夠以對高介電常數絕緣材料、矽氧化膜或氮化膜(以下簡稱為氧化膜或氮化膜)等絕緣材料之腐蝕性少、能夠選擇性且有效率地只蝕刻金屬材料。
本發明提供一種蝕刻劑組成物,對由高介電常數絕緣材料、氧化膜或氮化膜所構成的絕緣材料之腐蝕性小、能夠選擇性、且有效率地蝕刻金屬材料,本發明係有關於一種蝕刻劑,用以在製造抑制半導體裝置的隧道電流、減少信號延遲、提升驅動力的技術上不可缺少之由高介電常數絕緣材料、氧化膜或氮化膜所構成的絕緣材料、及金屬材料所構成的半導體裝置時,能夠選擇性、且有效率地蝕刻金屬材料。
為了解決上述課題,確立能夠選擇性地蝕刻金屬材料之技術,本發明者等專心研究的結果,發現藉由在含有氟化合物之水溶液、或在氟化合物中含有無機酸或有機酸中任一者之水溶液中,添加在分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑而成的蝕刻劑組成物,具有非常優良的特性,能夠經由蝕刻對金屬材料進行微細加工,且對由高介電常數絕緣材料、氧化膜或氮化膜所構成絕緣材料之腐蝕性小,而完成了本發明。
亦即,本發明係有關於以下的金屬材料用之蝕刻劑組成物及使用其之半導體裝置之製造方法。
1.一種蝕刻劑組成物,係在製造由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絕緣材料、以及金屬材料所構成的半導體裝置時,選擇性地蝕刻金屬材料時所使用的蝕刻劑組成物,含有氟化合物及分子結構中具有以磷元素的含氧酸作為官能基鉗合劑之水溶液。
2.一種蝕刻劑組成物,係在製造由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絕緣材料、以及金屬材料所構成的半導體裝置時,選擇性地蝕刻金屬材料時所使用的蝕刻劑組成物,含有氟化合物、分子結構中具有以磷元素的含氧酸作為官能基鉗合劑以及無機酸及/或有機酸之水溶液。
3.如上述1之蝕刻劑組成物,其中該氟化合物為0.001~10質量%,分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑為0.001~10質量%。
4.如上述2之蝕刻劑組成物,其中該氟化合物為0.001~10質量%,無機酸為50質量%以下,分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑為0.001~10質量%。
5.如上述2之蝕刻劑組成物,其中該氟化合物為0.001~10質量%,有機酸為15質量%以下,分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑為0.001~10質最%。
6.如上述1至5項中任一項之蝕刻劑組成物,其中該氟化合物係選自氫氟酸、氟化銨、氟化四甲銨、氟化鈉、及氟化鉀中至少1種。
7.如上述第2或4項之蝕刻劑組成物,其中該無機酸係選自硫酸、硝酸、鹽酸、磷酸、胺基磺酸、亞硝酸、及胺基硫酸中至少1種。
8.如上述第2或5項之蝕刻劑組成物,其中該有機酸係選甲酸、草酸、檸檬酸、丙二酸、琥珀酸、乙酸、丙酸、蘋果酸、及酒石酸中至少1種。
9.如上述第1至8項中任一項之蝕刻劑組成物,其中該金屬材料係Al、Co、Cr、Cu、Fe、Hf、Mo、Nb、Ni、Pt、Ru、Ta、Ti、W或Zr之材料,或是在該等中含有矽原子及/或氮原子之材料。
10.如上述第1至8項中任一項之蝕刻劑組成物,其中該高介電常數絶緣材料係Al2
O3
、CeO3
、Dy2
O3
、Er2
O3
、Eu2
O3
、Gd2
O3
、HfO2
、HO2
O3
、La2
O3
、Lu2
O3
、Nb2
O5
、Nd2
O3
、Pr2
O3
、ScO3
、Sm2
O3
、Ta2
O5
、Tb2
O3
、TiO2
、Tm2
O3
、Y2
O3
、Yb2
O3
或ZrO2
之材料,或是該等中含有矽原子及/或氮原子之材料。
11.一種半導體裝置之製造方法,係使用如上述第1至8項中任一項之蝕刻劑組成物,選擇性地蝕刻金屬材料,而不會腐蝕由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絶緣材料。
本發明所使用的氟化合物可舉出的有氫氟酸、氟化銨、酸性氟化銨、氟化鈰、四氟化矽、氟化矽酸、氟化氮、氟化磷、偏氟乙烯、三氟化硼、硼氟化氫酸、氟化硼酸銨、題乙醇胺氟化氫鹽、甲胺氟化氫鹽、乙胺氟化氫鹽、丙胺氟化氫鹽、氟化四甲銨、氟化四乙銨、氟化三乙基甲銨、氟化三甲基羥基乙銨、氟化四乙氧基銨、氟化甲基三乙氧基銨等氟化合物鹽、或氟化鋰、氟化鈉、酸性氟化鈉、氟化鉀、酸性氟化鉀、氟化矽酸鉀、六氟化磷酸鉀、氟化鎂、氟化鈣、氟化鍶、氟化鋇、氟化鋅、氟化鋁、氟化亞錫、氟化鉛、三氟化銻等金屬氟化合物等。其中較佳之氟化合物有氫氟酸、氟化銨、氟化四甲銨、氟化鈉及氟化鉀。
本發明所使用之上述氟化合物可單獨使用或組合2種以上使用。
蝕刻劑組成物中的氟化合物濃度以0.001~10質量%的範圍為佳。藉由在0.001質量%以上,可得到對金屬材料較快的蝕刻速度,在10質量%以下,能夠防止由腐蝕高介電常數絕緣材料、氧化膜或氮化膜所所構成的絕緣材料。
本發明所使用之在分子結構中具有磷元素的含氧酸作為官能基之鉗合劑,可舉出的有例如甲基二膦酸、胺基三亞甲基膦酸、1-羥基亞乙基-1,1-二膦酸、乙胺二亞甲基膦酸、十二烷基胺基二亞甲基膦酸、氰基三亞甲基膦酸伸乙二胺二亞甲基膦酸、伸乙二胺四亞甲基膦酸、己烯二胺四亞甲基膦酸、二伸乙三胺五亞甲基膦酸、1,2-丙二胺四亞甲基膦酸等分子中具有膦酸基之膦酸系鉗合劑、或是此等之銨鹽、有機胺鹽、鹼金屬鹽、或是此等膦酸系鉗合劑中在其分子中具有氮原子之物被氧化成為N-氧化體之氧化體、或是原磷酸、焦磷酸、偏磷酸、三偏磷酸、四偏磷酸、六偏磷酸、三聚磷酸等胺基烷基磷酸系鉗合劑、或是此等之銨鹽、有機胺鹽、鹼金屬鹽、或是此等胺基烷基磷酸系鉗合劑中在其分子中具有氮原子之物被氧化成為N-氧化體之氧化體、或是8-喹啉基次膦酸、2-胺基乙基次膦酸等分子中具有次膦酸基之次膦酸系鉗合劑、或是此等之銨鹽、有機胺鹽、鹼金屬鹽、或是此等次膦酸系鉗合劑中在其分子中具有氮原子之物被氧化成為N-氧化體之氧化體等。此等之中,以二膦酸鹽類、氰基亞甲基膦酸類、或五亞甲基膦酸類為佳。
分子結構中具有磷元素的含氧酸作為官能基之鉗合劑可單獨使用或組合2種類以上使用。分子結構中具有磷元素的含氧酸作為官能基之鉗合劑在蝕刻劑組成物中的濃度以0.001~10質量%的範圍為佳。藉由在0.001質量%以上,能夠得到添加效果,10質量%以下能夠防止在蝕蝕刻劑組成物中產生結晶析出。
本發明所使用的無機酸可舉出的有硫酸、硝酸、鹽酸、磷酸、次磷酸、碳酸、胺基磺酸、硼酸、膦酸、次膦酸、亞硝酸、醯胺硫酸等,此等之中,以硫酸、硝酸、鹽酸、磷酸、胺基磺酸、亞硝酸、及醯胺硫酸為佳。
蝕刻劑組成物中之無機酸的濃度可按照在所含有水中的溶解度而適當地決定,其中以50質量%以下為佳。藉由在50質量%以下,除了作為蝕刻對象之金屬材料以外,可防止本來不希望因蝕刻而造成損傷的材質被蝕刻。
本發明所使用的有機酸可舉出的有草酸、琥珀酸、丙二酸、丙酸、乙酸、順丁烯二酸、乙醇酸、二乙醇酸、酒石酸、衣庚酸、丙酮酸、蘋果酸、己二酸、甲酸、酞酸、苯甲酸、柳酸、胺基甲酸、硫氰酸、乳酸、檸檬酸等。其中以草酸、檸檬酸、丙二酸、琥珀酸、乙酸、丙酸、蘋果酸、及酒石酸為佳。
蝕刻液組成物中的有機酸濃度,可按照在所含有水中的溶解度而適當地決定,其中以15質量%以下為佳。藉由在15質量%以下,能防止在蝕刻劑組成物中產生結晶析出。
本發明所使用之上述無機酸、有機酸可單獨使用或組合2種以上使用。又,藉由添加上述有機酸或無機酸,不容易腐蝕由矽的氧化膜或氮化膜所構成的絕緣材料,能夠更有效率地蝕刻金屬材料。
本發明之蝕刻液組成物亦可先使用氫氟酸除去金屬材料表層部的自然氧化膜後使用。藉由使用氫氟酸進行前處理,能夠更有效率地蝕刻金屬材料。
又,本發明之蝕刻液組成物係使用來蝕刻金屬材料(蝕刻對象)之全部製程,亦可在不會對由高介電常數絕緣材料、氧化膜或氮化膜所構成的絕緣材料造成損傷的程度,藉由以往使用電漿氣體進行乾蝕刻之方法蝕刻後,使用來除去金屬材料之未蝕刻部分。
又,本發明之蝕刻液組成物的目的係改善蝕刻劑組成物的潤濕性,或是抑制晶圓處理後黏附在晶圓上的微粒或金屬污染,或對絕緣材料的損傷等提升蝕刻劑組成物的性能,亦可調配以往所使用的添加劑。此種添加劑可舉出的有具有界面活性能之化合物、水溶性高分子、及水溶性或水混合性的有機溶劑等。又,此等添加劑若可溶於本發明的蝕刻劑組成物中時即可使用,可單獨使用或組合2種以上使用。
又,本發明之蝕刻劑組成物的pH沒有特別限制,可按照蝕刻條件、所使用半導體基材的種類等來選擇。以鹼性的方式使用時,可添加例如氨、胺、氫氧化四甲銨等氫氧化第四級銨,以酸性的方式使用時,可添加無機酸、有機酸。
本發明之蝕刻劑組成物的使用溫度可按照蝕刻對象之金屬材料的種類、必要的蝕刻量,而與使用時間一同適當地決定。
本發明之蝕刻劑組成物可應用之金屬材料,若含有選自Al、Co、Cr、Cu、Fe、Hf、Mo、Nb、Ni、Pt、Ru、Ta、Ti、W或Zr之材料中至少一種即可,較佳是選自Co、Hf、Ni、Ta、Ti、W。又,亦可應用在此等中含有矽原子或氮原子材料,或在該等中含有矽原子、氮原子雙方之材料。而且,亦可應用於混合上述材料中2種而成的材料、亦可應用於層積狀態。
本發明之蝕刻劑組成物可應用之高介電常數絕緣材料若含有選自Al2
O3
、CeO3
、Dy2
O3
、Er2
O3
、Eu2
O3
、Gd2
O3
、HfO2
、Ho2
O3
、La2
O3
、Lu2
O3
、Nb2
O5
、Nd2
O3
、Pr2
O3
、ScO3
、Sm2
O3
、Ta2
O5
、Tb2
O3
、TiO2
、Tm2
O3
、Y2
O3
、Yb2
O3
或ZrO2
中至少一種即可,較佳是選自Al2
O3
、HfO2
、Ta2
O5
、ZrO2
。又,亦可應用在此等中含有矽原子或氮原子材料,或在該等中含有矽原子、氮原子雙方之材料。而且,亦可應用於混合上述材料中2種而成的材料、亦可應用於層積狀態。
藉由實施例及比較例來更具體地說明本發明,但是本發明未受到此等之任何限定。
使用在矽晶圓基板上形成有絕緣材料之th-SiO2
、並且形成有高介電常數絕緣材料之HfSiON之晶圓樣片,進行確認蝕刻性。其結果如表1所示。又,高介電常數絕緣材料之HfSiON的評價基準係如下。
○:HfSiON幾乎未被蝕刻(5/分鐘以下)△:HfSiON少許被蝕刻(5~50/分鐘)×:HfSiON被蝕刻程度大(50/分鐘以上)
又,使用在矽晶圓基板上形成有絕緣材料之th-SiO2
之晶圓樣片,進行確認蝕刻性。其結果同樣地如表1所示。
○:th-SiO2
幾乎未被蝕刻(5/分鐘以下)△:th-SiO2
少許被蝕刻(5~50/分鐘)×:th-SiO2
被蝕刻程度大(50/分鐘以上)
使用在矽晶圓基板上形成有絕緣材料之th-SiO2
、並且形成有通路的金屬材料Ti之晶圓樣片,進行確認蝕刻性。其結果如表1所示。
又,通路的金屬材料Ti的評價基準如下。
○:Ti顯明地被蝕刻△:Ti少許被蝕刻×:Ti未被蝕刻
使用表2所示組成之蝕刻組成物進行處理,進行確認高介電常數絕緣材料之HfSiON、絕緣材料之th-SiO2
的蝕刻性能。而且使用形成有HfSi(含有矽原子的金屬材料)之晶圓試片,確認蝕刻性能。其結果如表2所示。
又,含有矽原子的金屬材料之HfSi之評價基準如下。
○:HfSi顯明地被蝕刻△:HfSi少許被蝕刻×:HfSi未被蝕刻
使用表3所示組成之蝕刻組成物進行處理,進行確認高介電常數絕緣材料之HfSiON、絕緣材料之th-SiO2
的蝕刻性能。而且使用形成有HfN(含有氮原子的金屬材料)之晶圓試片,確認蝕刻性能。其結果如表3所示。
又,含有氮原子的金屬材料之HfN之評價基準如下。
○:HfN顯明地被蝕刻△:HfN少許被蝕刻×:HfN未被蝕刻
使用表4所示組成之蝕刻組成物進行處理,進行確認高介電常數絕緣材料之HfSiON、絕緣材料之th-SiO2
的蝕刻性能。而且使用形成有TaSiN(含有矽原子、氮原子雙方)之晶圓試片,確認蝕刻性能。其結果如表4所示。又,含有矽原子、氮原子雙方之TaSiN之評價基準如下。
○:TaSiN顯明地被蝕刻△:TaSiN少許被蝕刻×:TaSiN未被蝕刻
關於比較例8、比較例22、比較例36或比較例50,因為在蝕刻劑組成物中有產生結晶析出,無法進行蝕刻性能之確認。
在表1、2、3及4,藉由應用本發明的蝕刻劑組成物,能夠對希望金屬材料進行蝕刻,可確認能夠抑制對由高介電常數絕緣材料、氧化膜或氮化膜所構成的絕緣材料之蝕刻速度。
如此,使用本發明的蝕刻劑組成物來蝕刻高介電常數絕緣材料或金屬材料時,能夠抑制對HfO2
、HfSiON、Ta2
O5
、ZrO2
等高介電常數絕緣材料的蝕刻。因此,清楚地知道對由高介電常數絕緣材料、氧化膜或氮化膜所構成的絕緣材料之腐蝕性小、能夠選擇性且效率良好地蝕刻金屬材料。
藉由使用本發明之蝕刻劑組成物來蝕刻金屬材料,能夠選擇性地蝕刻以往只使用電漿氣體之蝕刻方法時係有困難之金屬材料,且能夠抑制對高介電常數絕緣材料、氧化膜或氮化膜所構成的絶緣材之腐蝕。
Claims (11)
- 一種蝕刻劑組成物,係在製造由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絕緣材料、以及金屬材料所構成的半導體裝置時,選擇性地蝕刻金屬材料時所使用的蝕刻劑組成物,其特徵為其係含有氟化合物、分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑、無機酸及/或有機酸之水溶液,且無機酸係50質量%以下,有機酸係15質量%以下。
- 一種蝕刻劑組成物,係在製造由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絕緣材料、以及金屬材料所構成的半導體裝置時,選擇性地蝕刻金屬材料時所使用的蝕刻劑組成物,其特徵為其係含有氟化合物及分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑以及無機酸及/或有機酸之水溶液。
- 如申請專利範圍第1項之蝕刻劑組成物,其中該氟化合物為0.001~10質量%,分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑為0.001~10質量%。
- 如申請專利範圍第2項之蝕刻劑組成物,其中該氟化合物為0.001~10質量%,無機酸為50質量%以下,分子結構中具有以磷元素的含氧酸作為官能基之鉗合劑為0.001~10質量%。
- 如申請專利範圍第2項之蝕刻劑組成物,其中該氟化合物為0.001~10質量%,有機酸為15質量%以下,分子結 構中具有以磷元素的含氧酸作為官能基之鉗合劑為0.001~10質量%。
- 如申請專利範圍第1至5項中任一項之蝕刻劑組成物,其中該氟化合物係選自氫氟酸、氟化銨、氟化四甲銨、氟化鈉、及氟化鉀中至少1種。
- 如申請專利範圍第2或4項之蝕刻劑組成物,其中該無機酸係選自硫酸、硝酸、鹽酸、磷酸、胺基磺酸、亞硝酸、及胺基硫酸中至少1種。
- 如申請專利範圍第2或5項之蝕刻劑組成物,其中該有機酸係選甲酸、草酸、檸檬酸、丙二酸、琥珀酸、乙酸、丙酸、蘋果酸、及酒石酸中至少1種。
- 如申請專利範圍第1至5項中任一項之蝕刻劑組成物,其中該金屬材料係Al、Co、Cr、Cu、Fe、Hf、Mo、Nb、Ni、Pt、Ru、Ta、Ti、W或Zr之材料,或是在該等中含有矽原子及/或氮原子之材料。
- 如申請專利範圍第1至5項中任一項之蝕刻劑組成物,其中該高介電常數絕緣材料係Al2 O3 、CeO3 、Dy2 O3 、Er2 O3 、Eu2 O3 、Gd2 O3 、HfO2 、Ho2 O3 、La2 O3 、Lu2 O3 、Nb2 O5 、Nd2 O3 、Pr2 O3 、ScO3 、Sm2 O3 、Ta2 O5 、Tb2 O3 、TiO2 、Tm2 O3 、Y2 O3 、Yb2 O3 或ZrO2 之材料,或是該等中含有矽原子及/或氮原子之材料。
- 一種半導體裝置之製造方法,係使用如申請專利範圍第1至8項中任一項之蝕刻劑組成物,選擇性地蝕刻金屬材 料,而不會腐蝕由高介電常數絕緣材料、矽的氧化膜或氮化膜所構成的絕緣材料。
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CN101199043B (zh) | 2010-05-19 |
TW200707573A (en) | 2007-02-16 |
WO2006137497A1 (ja) | 2006-12-28 |
JP5050850B2 (ja) | 2012-10-17 |
US20100216315A1 (en) | 2010-08-26 |
JPWO2006137497A1 (ja) | 2009-01-22 |
EP1895577A4 (en) | 2009-10-28 |
US8658053B2 (en) | 2014-02-25 |
EP1895577A1 (en) | 2008-03-05 |
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