TWI680206B - 矽基材之活化方法 - Google Patents
矽基材之活化方法 Download PDFInfo
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- TWI680206B TWI680206B TW105108607A TW105108607A TWI680206B TW I680206 B TWI680206 B TW I680206B TW 105108607 A TW105108607 A TW 105108607A TW 105108607 A TW105108607 A TW 105108607A TW I680206 B TWI680206 B TW I680206B
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- Prior art keywords
- acid
- aromatic
- silicon substrate
- acids
- metal
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 92
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 70
- 239000010703 silicon Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000004913 activation Effects 0.000 title claims description 27
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 230000003213 activating effect Effects 0.000 claims abstract description 57
- 159000000032 aromatic acids Chemical class 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 81
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 229910052759 nickel Inorganic materials 0.000 claims description 39
- 229910052763 palladium Inorganic materials 0.000 claims description 31
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 28
- -1 palladium ions Chemical class 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 22
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 22
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 16
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 13
- 229910021332 silicide Inorganic materials 0.000 claims description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 11
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003376 silicon Chemical class 0.000 claims description 6
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000531 Co alloy Inorganic materials 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 4
- LDQMZKBIBRAZEA-UHFFFAOYSA-N 2,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(N)=C1 LDQMZKBIBRAZEA-UHFFFAOYSA-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- MKWJZTFMDWSRIH-UHFFFAOYSA-N (4-fluoro-3-nitrophenyl)methanol Chemical compound OCC1=CC=C(F)C([N+]([O-])=O)=C1 MKWJZTFMDWSRIH-UHFFFAOYSA-N 0.000 claims description 2
- YKMDNKRCCODWMG-UHFFFAOYSA-N 2,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC=C1[N+]([O-])=O YKMDNKRCCODWMG-UHFFFAOYSA-N 0.000 claims description 2
- HKKWSIQQYJTJLW-UHFFFAOYSA-N 2,6-dinitrobenzoic acid Chemical compound OC(=O)C1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O HKKWSIQQYJTJLW-UHFFFAOYSA-N 0.000 claims description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims description 2
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 2
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 claims description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 2
- DQNAQOYOSRJXFZ-UHFFFAOYSA-N 5-Amino-1-naphthalenesulfonic acid Chemical compound C1=CC=C2C(N)=CC=CC2=C1S(O)(=O)=O DQNAQOYOSRJXFZ-UHFFFAOYSA-N 0.000 claims description 2
- UWPJYQYRSWYIGZ-UHFFFAOYSA-N 5-aminonaphthalene-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(N)=CC=CC2=C1 UWPJYQYRSWYIGZ-UHFFFAOYSA-N 0.000 claims description 2
- ZIIGSRYPZWDGBT-UHFFFAOYSA-N 610-30-0 Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O ZIIGSRYPZWDGBT-UHFFFAOYSA-N 0.000 claims description 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 2
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 2
- IGMNYECMUMZDDF-UHFFFAOYSA-N homogentisic acid Chemical compound OC(=O)CC1=CC(O)=CC=C1O IGMNYECMUMZDDF-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims 4
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 claims 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 claims 1
- KIHFFINCXFGABP-UHFFFAOYSA-N Cl.[I] Chemical compound Cl.[I] KIHFFINCXFGABP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 abstract description 6
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- 238000007747 plating Methods 0.000 description 38
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- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 2
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 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
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-UHFFFAOYSA-N 0.000 description 1
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- FEBFYWHXKVOHDI-UHFFFAOYSA-N [Co].[P][W] Chemical compound [Co].[P][W] FEBFYWHXKVOHDI-UHFFFAOYSA-N 0.000 description 1
- AQQVTZBWWYVEGR-UHFFFAOYSA-N [NH4+].[O-][PH2]=O Chemical compound [NH4+].[O-][PH2]=O AQQVTZBWWYVEGR-UHFFFAOYSA-N 0.000 description 1
- AXFKVYBBROZOGA-UHFFFAOYSA-N [P].[Mo].[Co] Chemical compound [P].[Mo].[Co] AXFKVYBBROZOGA-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- LAQNYYDYGVSPNQ-UHFFFAOYSA-N formaldehyde;hydrazine Chemical compound O=C.NN LAQNYYDYGVSPNQ-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NMUOATVLLQEYHI-UHFFFAOYSA-N iminoaspartic acid Chemical compound OC(=O)CC(=N)C(O)=O NMUOATVLLQEYHI-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- LRPCLTPZMUIPFK-UHFFFAOYSA-N methane;sulfuric acid Chemical compound C.OS(O)(=O)=O LRPCLTPZMUIPFK-UHFFFAOYSA-N 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 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 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/32051—Deposition of metallic or metal-silicide layers
- H01L21/32053—Deposition of metallic or metal-silicide layers of metal-silicide layers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
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Abstract
本發明係關於一種用於活化矽基材之活化組合物,其係包含鈀離子源、氟離子源及至少兩種芳香族酸之水溶液。本發明進一步係關於其使用及視情況用於此等經處理之基材之隨後金屬化之方法。該方法可用於半導體及太陽能電池製造中。
Description
本發明係關於太陽能電池及電子裝置之製造,具體而言係關於在無電金屬化及矽化物互連之形成之前矽基材之活化方法,該等互連可用於電晶體(MOS、CMOS)、記憶條、MS及SD卡中。
一般而言,矽化物互連係藉由將諸如鎳等金屬無電沈積於適宜矽基材上且隨後熱處理以形成金屬矽化物來形成。此熱處理通常稱為快速熱退火(RTA)。通常,此熱處理需要基材經受300℃至750℃範圍內之升高之溫度,藉此在金屬矽化物形成之後金屬擴散至矽基材中。對於欲沈積於矽基材上之金屬,該等矽基材需要經活化。此情形尤其針對p型摻雜之多晶矽。n型摻雜之基材可直接使用強鹼性無電鎳電鍍浴來電鍍。然而,強鹼性介質可損壞製造半導體中所用之基材,例如焊料遮罩。因此,業內不期望使用強鹼性電鍍浴。因此,使用包含鈀離子及氫氟酸或如GB 976,656中所揭示之其他氟離子源之組合物來活化矽基材係常用技術。此類型之活化之可能機制揭示於US 4,297,393中。
US 6,406,743 B1係關於多晶矽互連上之矽化鎳形成。其中所揭示之方法教示使用含有鈀鹽及高濃度之氫氟酸及乙酸之溶液作為在鎳或鎳合金沈積之前多晶矽之活化組合物。不管與使用此濃氫氟酸溶液相關之高毒性如何,此組合物之使用導致獲得極粗糙鈀晶種。為了在
此等粗糙鈀晶種上提供均勻矽化鎳覆蓋,需要在其上提供厚鎳沈積物,此進而導致結構太大而不能用於現代半導體技術中(參見實例1及2)。
US 5,753,304報導了具體而言用於鋁表面之活化溶液。該活化溶液尤其包含鈀鹽、鹼金屬氟化物或氟化氫及作為錯合劑之羧酸。該等羧酸係以約10ml/l活化溶液至100ml/l活化溶液之量使用。
US 2005/0161338 A1揭示使用包含鈀源及至少一種酸之水溶液來活化矽表面之方法。本揭示內容中可用之酸有多種,例如礦酸,如硫酸、硝酸及鹽酸;或有機硫酸,例如甲烷硫酸;或芳香族磺酸,例如對甲苯磺酸。然而,使用一種脂肪族或芳香族酸導致所處理表面之覆蓋極不均勻(參見實例2至4)。
WO 2014/128420揭示包含陰離子或非離子表面活性劑、金離子及氟離子之組合物用於活化半導體基材之用途。表面活性劑之採用改良了結果且使得形成較薄鎳層。根據此揭示內容,含有鈀及氟離子之組合物導致不均勻沈積且隨後鎳層擴散於基材上及基材中(第2、14及15頁及表1,條目1)。由於若干原因(例如成本),在電子裝置之製造中使用金離子係不期望的。
儘管該等方法能夠提供用於活化矽基材及隨後矽化鎳形成之方法,但其不能滿足現代半導體製造之需要。所採用之貴金屬之晶種層太粗糙且個別晶種於矽基材表面上之分佈不夠均勻,且導致必須於基材上沈積極厚的鎳層。此外,若貴金屬分佈太粗糙,則個別貴金屬粒子亦較大,從而因貴金屬之價格通常較高而導致成本增加。甚至更重要地,矽基材上之金屬或金屬層需要極薄且具有均勻高度。因此,其需要平坦並光滑。因此,前提條件係下伏鈀晶種層極均勻且實質上不含較大聚集粒子。若鈀晶種與欲於其上形成之期望之金屬或金屬合金層一樣大(或甚至更大),則此尤其不利。於其上形成之金屬或金屬合
金層將另外於彼等大粒子上形成且將形成需要拋光步驟之極粗糙(產生如山谷及丘陵之結構)表面,尤其在欲形成在5nm、10nm、20nm或50nm範圍內之金屬或金屬合金層之情形下。此與半導體製造工業中之持續小型化以及成本及環境意識不相容。
因此,本發明之目標係克服如上文所提及之缺點以提供活化組合物及其使用方法,該方法尤其使得於矽基材上形成具有優良表面覆蓋之極薄鈀晶種層。
因此,本發明之另一目標係提供上面均勻覆蓋有鈀晶種層之矽基材,其可用於無電金屬化。
本發明之另一目標係提供金屬矽化物互連形成、具體而言矽化鎳互連形成之方法,其符合如今半導體工業中之小型化要求。
該等目標係藉由使用本發明活化組合物而解決。本發明之用於活化矽基材之活化組合物係包含鈀離子源及氟離子源之水溶液,其特徵在於其包含至少兩種(彼此獨立)選自由以下組成之群之芳香族酸:芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸。
該等目標進一步藉由用於活化至少一種矽基材之本發明方法而解決,該方法以給定順序包含以下步驟:(i)提供至少一種矽基材;(ii)使用包含以下之水溶液作為活化組合物來活化該至少一種矽基材之表面之至少一部分:鈀離子源、氟離子源及至少兩種至少兩種(彼此獨立)選自由以下組成之群之芳香族酸:芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸。
圖1係使用由氫氟酸及鈀離子組成之比較水性活化組合物處理之n型摻雜之矽基材之SEM圖片(對應實例1)。
圖2係使用由氫氟酸、乙酸及鈀離子組成之比較水性活化組合物處理之n型摻雜之矽基材之SEM圖片(對應實例2)。
圖3至7係使用含有氫氟酸、鈀離子及一或多種芳香族酸之本發明水性活化組合物處理之多晶矽基材之SEM圖片。圖3至7與實例4a至4e相關。
圖8係使用本發明活化溶液處理、隨後使用無電鎳電鍍浴處理之n型摻雜之多晶矽基材之AFM圖片(與實例5a相關)。
本發明之用於活化矽基材之活化組合物係包含鈀離子源、氟離子源及至少兩種選自由以下組成之群之芳香族酸之水溶液:芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸。在本發明之較佳實施例中,至少兩種芳香族酸選自由以下組成之群:芳香族羧酸、芳香族磺酸及芳香族膦酸。
應理解,在本發明之上下文中芳香族羧酸係包含至少一個羧酸部分(-CO2H)之芳香族化合物。類似地,芳香族磺酸係包含至少一個磺酸部分(-SO3H)之芳香族化合物。芳香族亞磺酸係包含至少一個亞磺酸部分(-SO2H)之芳香族化合物,芳香族膦酸係包含至少一個膦酸部分(-PO3H2)之芳香族化合物且芳香族次膦酸係包含至少一個次膦酸部分(-PO2H2)之芳香族化合物。
芳香族化合物進一步包含至少一個環狀烴基,例如苯基或萘基,其中個別環碳原子可由N、O及/或S替代,例如苯并噻唑基或吡啶基(例如通常稱為菸鹼酸之3-吡啶甲酸中)。此外,鍵結至芳香族化合物之個別氫原子可在每一情形下藉由官能基取代,該官能基係例如胺基、羥基、硝基、烷基、芳基、鹵化物(例如氟化物、氯化物、溴
化物、碘化物)、羰基、衍生自上文所提及之酸部分中任一者之酯等。芳香族化合物亦可包含至少一個由兩個或更多個縮合環組成之烴基(如菲或蒽),只要足夠官能基附接至其以保證足夠高濃度之水溶解性即可。術語「羥基(hydroxy及hydroxyl)」作為有機部分在本文中可互換使用。業內有時將部分稱為殘基或基團。
就用於此說明書及申請專利範圍中之術語「烷基」而言,其係指具有化學通式CmH2m+1之烴基,m係自1至約50之整數。本發明烷基部分可係直鏈及/或具支鏈的且其可係飽和及/或不飽和的。若烷基部分不飽和,則對應的化學通式必須相應調整。較佳地,m在1至12、更佳1至8、甚至更佳1至4範圍內。C1-C8-烷基尤其包括(例如)甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、新戊基、己基、庚基及辛基。此一烷基之一或多個氫原子亦可藉由以下官能基取代:例如胺基、羥基、硫醇、鹵化物(例如氟化物、氯化物、溴化物、碘化物)、羰基、羧基、羧酸酯、膦酸酯等。
較佳地,酸部分中之至少一者經由碳-碳、碳-硫或碳-磷單鍵直接鍵結至芳香族化合物之芳基。更佳地,所有酸部分直接鍵結至芳基。
其中R1至R14彼此獨立選自由以下組成之群:氫(-H)、烷基、芳基、諸如氯化物(-Cl)等鹵化物、胺基(-NH2)、羧酸部分(-CO2H)、磺酸部分(-SO3H)、亞磺酸部分(-SO2H)、膦酸部分(-PO3H2)、次膦酸部分(-PO2H2)、硝基(-NO2)及羥基(-OH),前提係R1至R14中之至少一者係羧酸部分(-CO2H)、磺酸部分(-SO3H)、亞磺酸部分(-SO2H)、膦酸部分(-PO3H2)或次膦酸部分(-PO2H2)、較佳磺酸部分、羧酸部分或膦酸部分。羧酸部分(-CO2H)、磺酸部分(-SO3H)、亞磺酸部分(-SO2H)、膦酸部分(-PO3H2)及次膦酸部分(-PO2H2)在本文中統稱為「酸部分」。
較佳地,僅一種類型之酸部分包含於單一芳香族酸中。此意味著(例如)若芳香族酸包含一或多個羧酸部分,則其較佳不含如磺酸、亞磺酸、膦酸及次膦酸部分等其他酸部分。
式(I)至(II)之芳香族酸通常充分溶於水中以用於本發明活化組合物中。若芳香族酸之溶解性不夠,則可採用熟習此項技術者已知之共溶劑及表面活性劑以增加芳香族酸於活化組合物中之溶解性。
在甚至更佳實施例中,至少兩種式(I)至(II)之芳香族酸包含彼此獨立選自由以下組成之群之R1至R14:氫、烷基、芳基、胺基、磺酸部分、羧酸部分、硝基及羥基,前提係至少兩種芳香族酸中之每一者包含獨立選自由羧酸部分及磺酸部分組成之群之R1至R14中之一者。
在本發明之又一甚至更佳實施例中,活化組合物中之至少兩種芳香族酸之至少一種芳香族酸包含磺酸部分。在本發明之第二甚至更佳實施例中,活化組合物包含包括羧酸部分之至少兩種芳香族酸中之至少一種芳香族酸。在本發明之第三甚至更佳實施例中,活化組合物含有至少一種包含磺酸部分之芳香族酸及至少一種包含羧酸部分之芳香族酸。
在如式(I)至(II)之包含至少一個磺酸部分之芳香族磺酸中,較佳
R1至R14中之至少一者係羥基及/或胺基,更佳不為磺酸部分之R1至R14全部均選自氫、胺基及羥基。活化組合物中之此等酸似乎可改良如此處理之矽基材之表面覆蓋。
在另一甚至更佳實施例中,欲用於本發明活化組合物中之至少兩種芳香族酸選自由以下組成之群:苯甲酸、1,2-苯二甲酸(鄰苯二甲酸)、1,3-苯二甲酸(間苯二甲酸)、1,4-苯二甲酸(對苯二甲酸)、1,2,3-苯三甲酸(半蜜臘酸)、1,2,4-苯三甲酸(偏苯三酸)、1,3,5-苯三甲酸(苯均三酸)、1,2,4,5-苯四甲酸(焦蜜石酸)、1,2,3,4,5-苯五甲酸、1,2,3,4,5,6-苯六甲酸(蜜臘酸)、2-硝基苯甲酸、3-硝基苯甲酸、4-硝基苯甲酸、2,5-二硝基苯甲酸、2,6-二硝基苯甲酸、3,5-二硝基苯甲酸、2,4-二硝基苯甲酸、3,4-二硝基苯甲酸、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、3,4-二胺基苯甲酸、3,5-二胺基苯甲酸、2,3-胺基苯甲酸、2,4-二胺基苯甲酸、柳酸、對甲苯磺酸、1-萘甲酸、2-萘甲酸、2,6-萘二甲酸、2-萘磺酸、5-胺基-1-萘磺酸、5-胺基-2-萘磺酸、7-胺基-4-羥基-2-萘磺酸及苯基膦酸。
芳香族酸可以游離酸形式、以各別鹽形式(例如鹼金屬鹽或銨鹽)、以其水合物形式或以上文所提及者之任何適宜組合形式添加至活化組合物中。若適用,其亦可以酸酐形式添加(例如鄰苯二甲酸酐能夠在水性介質中形成鄰苯二甲酸)。
本發明活化組合物中兩種或更多種芳香族酸之使用有利地使得較精細鈀粒子(亦稱為晶種)形成於如此處理之矽基材表面上。兩種或更多種芳香族酸之添加亦得到矽基材表面上如此沈積之鈀粒子之經改良均勻性。在僅具有一種芳香族酸或沒有任何芳香族酸下,鈀粒子極其粗糙且較不均勻地分佈於矽基材表面上(參見比較實例)。
因此,活化組合物包含兩種或更多種芳香族酸。發明者已發現當在活化組合物中使用兩種或更多種芳香族酸時,矽基材之表面覆蓋
更均勻且個別粒子更小。
活化組合物中之芳香族酸之濃度(在此背景中此意指所用之所有芳香族酸之總濃度)在較佳0.1mg/L至1000mg/L、更佳1mg/L至750mg/L、甚至更佳10mg/L或40mg/L至500mg/L範圍內。在一些情形下在該等範圍之外之濃度使得獲得較少本發明之有益效應,例如使用鈀晶種處理之表面之均勻覆蓋。另外,可出現一些芳香族酸之溶解性問題。
本發明活化組合物係水溶液。術語「水溶液」意指為溶液中之溶劑的優勢液體介質係水。可添加可與水混溶之其他液體,例如醇及可與水混溶之其他極性有機液體。較佳地,活化組合物僅包含水作為溶劑。
本發明活化組合物包含鈀離子源。鈀離子源可係任何水溶性鈀鹽或鈀錯合物。較佳地,鈀離子源選自由以下組成之群:氯化鈀、硫酸鈀、硫酸錯合物形式之硫酸鈀、硝酸鈀及乙酸鈀,更佳選自由以下組成之群:氯化鈀、硫酸鈀、硝酸鈀及乙酸鈀。
本發明活化組合物中之鈀離子之濃度較佳在0.001g/L至1g/L、更佳0.005g/L至0.5g/L、甚至更佳0.05g/L至0.25g/L範圍內。
本發明活化組合物進一步包含氟離子源。此氟離子源可係任何水溶性氟化物鹽或任何水溶性氟化物錯合物。較佳地,氟離子源選自氫氟酸、氟化銨及諸如氟化鉀、氟化鈉及氟化鋰等鹼金屬氟化物。
存在於活化組合物中之氟離子之濃度較佳在0.075wt.%至4wt.%、更佳0.1wt.%至2wt.%、甚至更佳0.15wt.%至1wt.%範圍內。業內已知較高濃度之氟離子將導致來自欲使用本發明活化組合物處理之基材之矽原子的溶解增加。為處理極薄及易碎矽基材,因此在本發明活化組合物中使用較低濃度之氟離子係有利的。
本發明活化組合物較佳具有7或更低、更佳低於3、甚至更佳0至
2.5之pH。
本發明活化組合物視情況包含選自由以下組成之群之甲烷磺酸及/或礦酸:硫酸、鹽酸、硝酸、磷酸、甲烷磺酸、氫溴酸、碘化氫、過氯酸、王水、次氯酸、碘酸及亞硝酸。較佳地,可選礦酸選自硫酸、鹽酸及硝酸。可選礦酸(或甲烷磺酸)之濃度在0.01wt.%至20wt.%或較佳0.1wt.%至10wt.%範圍內。
本發明活化組合物視情況包含選自由以下組成之群之氧化劑:分子氧、諸如硝酸鉀等硝酸鹽源及過氧化氫。分子氧可以氣體進料形式添加至活化組合物中。業內已知氧化劑、甲烷磺酸及/或礦酸之可選添加可引起加速之活化製程。然而,並不總期望如此。
本發明活化組合物視情況包含選自由陽離子、非離子及陰離子表面活性劑組成之群之表面活性劑(業內亦稱為潤濕劑)。
本發明活化組合物可藉由將所有組份溶於水性液體介質(較佳水)中來製備。
本發明之用於活化至少一種矽基材之方法以給定順序包含以下步驟:(i)提供至少一種矽基材;(ii)使用本發明活化組合物活化該至少一種矽基材之表面之至少一部分。
欲用於本發明方法中之至少一種矽基材包含由諸如多晶矽(包括摻雜之多晶矽,例如p型摻雜之多晶矽及n型摻雜之多晶矽)及單晶矽等矽、氧化矽、氮化矽及氧氮化矽製得之表面。矽基材之整體可由上文所提及之材料或其組合中之任一者製得或其可僅包含由一或多種上文所提及之材料製得之表面。
多晶矽之摻雜通常使用產生n型摻雜之多晶矽之供體(例如砷或磷)及產生p型摻雜之多晶矽之受體(例如硼或鋁)來進行。通常,該等
供體/受體以介於10-4-10-9wt.%之間之含量使用。若使用極高量之摻雜劑(通常介於10-3wt.%與10-4wt.%之間),則獲得n及p型摻雜之多晶矽。在本發明之上下文中,n及p型摻雜之多晶矽亦理解為n及p型摻雜之多晶矽。可以如上文所述之類似方式摻雜氧化矽、氮化矽及氧氮化矽。
較佳地,在本發明方法中使用多晶矽、p型摻雜之多晶矽及n型摻雜之多晶矽;更佳使用p型摻雜之多晶矽。
藉由業內已知方式使該至少一種矽基材之表面之至少一部分與本發明活化組合物接觸(在步驟(ii)中)且藉此該至少一種矽基材之表面經活化。在矽基材表面與活化組合物之間之此接觸方式尤其包括將矽基材浸沒於組合物中或擦拭、噴霧或以其他方式將活化組合物引至該表面上。
在矽基材與本發明活化組合物接觸之後,將於矽基材之表面上形成薄且均勻分散之鈀晶種層。此步驟在業內係稱為活化。因此,如此處理之基材稱為「經活化」。
將基材與活化組合物接觸1秒至30分鐘、較佳30秒至10分鐘、更佳40秒至5分鐘、最佳45秒至2分鐘。端視經活化基材之期望性質,可應用在上文所述範圍外之接觸持續時間。
當與矽基材接觸時,活化溶液較佳具有在10℃至90℃、更佳15℃至50℃範圍內之溫度。
應理解,在本發明之上下文中,可使用於矽基底上包含許多摻雜區(例如源極及汲極,S/D)、絕緣層(例如摻雜及未摻雜之氧化矽)及傳導層(例如摻雜及未摻雜之多晶矽、金屬)之半導體基材。該方法亦可應用於用於製造太陽能電池之單晶或多晶矽。
本發明之用於活化矽基材之方法可在步驟(ii)之後包含另一步驟(iii)於經活化之矽基材上無電電鍍金屬或金屬合金。
無電電鍍係在無外部電子供應幫助之情形下之連續金屬膜之受控自催化沈積。無電金屬電鍍浴之主要組份係金屬離子源、錯合劑、還原劑及作為可選成份之穩定劑、細晶劑及pH調節劑(酸、鹼、緩衝劑)。錯合劑(業內亦稱為螯合劑)係用於螯合欲沈積之金屬且防止金屬自溶液沈澱(即,作為氫氧化物及諸如此類)。螯合金屬使得金屬為將金屬離子轉化為其金屬形式之還原劑可用。金屬沈積之另一形式係浸鍍。浸鍍係在無外部供應電子之幫助且無化學還原劑之情形下之金屬之另一沈積。該機制依賴於來自下伏基材之金屬代替為存在於浸鍍溶液中之金屬離子。在本發明之上下文中,無電電鍍應主要理解為在化學還原劑(本文係指「還原劑」)之幫助下自催化沈積。
為調節當使用此一無電電鍍浴時無電金屬電鍍浴及欲形成金屬或金屬合金沈積物之性質,故將添加劑添加至無電電鍍浴中以改良無電電鍍浴及所形成金屬或金屬合金沈積物二者之性質。通常,對於許多金屬及金屬合金,無電金屬電鍍浴均為業內已知。
在步驟(iii)中金屬或金屬合金係沈積於經活化之矽基材上。較佳在步驟(iii)中沈積之金屬或金屬合金選自銅、鈷、鎳、銅合金、鈷合金及鎳合金。本發明之更佳實施例為欲沈積之金屬係鎳或其合金,此乃因矽化鎳係晶片製造中矽化鉭或矽化鈦之適宜替代。本文中能夠沈積鎳或鎳合金之無電金屬電鍍浴係稱為無電鎳電鍍浴。
無電鎳電鍍浴含有至少一種鎳離子源,其可係任何水溶性鎳鹽或其他水溶性鎳化合物。較佳鎳離子源選自包含氯化鎳、硫酸鎳、乙酸鎳、甲烷磺酸鎳及碳酸鎳之群。無電鎳電鍍浴中之鎳離子濃度較佳在0.1g/l至60g/l(0.0017mol/l至1.022mol/l)、更佳2g/l至50g/l(0.034mol/l至0.852mol/l)、甚至更佳4g/l至10g/l(0.068mol/l至0.170mol/l)範圍內。
無電鎳電鍍浴進一步含有選自以下之還原劑:次膦酸鹽化合
物,例如次膦酸鈉、次膦酸鉀及次膦酸銨;基於硼之還原劑,例如胺基硼烷(如二甲基胺基硼烷(DMAB))、鹼金屬硼氫化物(如NaBH4、KBH4);甲醛;肼及其混合物。無電鎳電鍍浴中之還原劑濃度(在此處其意指還原劑之總量)通常在0.01mol/l至1.5mol/l範圍內。
無電鎳電鍍浴之pH值較佳在3.5至8.5、更佳4至6之範圍內。因為電鍍溶液在其操作期間由於H3O+離子形成從而傾向於變得酸性更強,故可藉由添加浴溶性且浴相容之鹼性物質(例如鈉、鉀或銨之氫氧化物、碳酸鹽及碳酸氫鹽)來定期或連續調整pH。可藉由以最高30g/l、更佳2g/l至10g/l之量添加多種緩衝化合物(例如乙酸、丙酸、硼酸或諸如此類)來改良電鍍溶液之操作pH之穩定性。
在本發明之一實施例中,選擇羧酸、多胺及磺酸或其混合物作為錯合劑。可用羧酸包括單-、二-、三-及四-羧酸。羧酸可經多種取代基部分(例如羥基或胺基)取代,且該等酸可以其鈉、鉀或銨鹽形式引入無電鎳電鍍浴中。一些錯合劑(例如乙酸)亦可用作緩衝劑,且此等添加組份之適當濃度可針對任一電鍍溶液鑒於該等組份之雙重功能來最佳化。
此等用作錯合劑之羧酸之實例包括:如WO 2013/113810中所揭示之亞胺基琥珀酸、亞胺基二琥珀酸、其衍生物及其鹽;單羧酸,例如乙酸、羥基乙酸、胺基乙酸、2-胺基丙酸、2-羥基丙酸(乳酸);二羧酸,例如琥珀酸、胺基琥珀酸、羥基琥珀酸、丙二酸、羥基丁二酸、酒石酸、蘋果酸;三羧酸,例如2-羥基-1,2,3-丙烷三甲酸;及四羧酸,例如乙二胺四乙酸(EDTA)。最佳錯合劑選自由單羧酸及二羧酸組成之群。在一實施例中,利用上述錯合劑中之兩者或更多者之混合物。存在於無電鎳電鍍浴中之錯合劑濃度或(在使用多於一種錯合劑之情形下)所有錯合劑一起之濃度較佳在0.01mol/l至2.5mol/l、更佳0.05mol/l至1.0mol/l之範圍內。
無電鎳電鍍浴視情況含有至少一種穩定劑。需要此穩定劑以提供足夠的浴壽命、合理的電鍍速率並控制如此沈積之鎳合金中之磷或硼含量。適宜可選穩定劑係(但不限於)重金屬離子,例如鎘、鉈、鉍、鉛及銻離子;含碘化合物,例如碘化物及碘酸鹽;含硫化合物,例如硫氰酸鹽、硫脲及巰基烷烴磺酸(如3-巰基丙烷磺酸)或如WO 2013/013941中所揭示之自其衍生之各別二硫化物;及不飽和有機酸,例如馬來酸及伊康酸(itaconic acid);或如藉由EP 2 671 969 A1所教示之彼等之適宜經取代之炔烴。使用穩定劑之組合亦在本發明之範圍內,如藉由WO 2013/113810所教示,該等組合例如鉍離子與巰基苯甲酸、巰基羧酸及/或巰基磺酸。無電鎳電鍍浴可包含電鍍速率調節劑(例如揭示於歐洲專利申請案EP 14198380.9中之彼等)以有利地降低電鍍速率並使電鍍浴穩定。無電鎳電鍍浴中之至少一種可選穩定劑之濃度在0.1mg/l至100mg/l、較佳0.5mg/l至30mg/l範圍內。
無電鎳電鍍浴可包含(但不必需包含)其他調節劑,例如潤濕劑、表面活性劑、加速劑、增亮劑、晶粒細化添加劑等。該等組份為業內所已知。
在次膦酸鹽化合物用作鎳之還原劑之情形下,獲得含有鎳及磷之合金沈積物。該合金沈積物中之磷之量尤其取決於無電鎳電鍍浴中之次膦酸鹽及鎳離子及可選穩定劑之濃度。較佳地,該合金沈積物中之磷之量在5wt.%至15wt.%範圍內,餘量為鎳。
在基於硼之還原劑用作鎳之還原劑之情形下,獲得含有鎳及硼之合金沈積物。該合金沈積物中硼之量尤其取決於無電鎳電鍍浴中之基於硼之還原劑及鎳離子及可選穩定劑之濃度或pH值。較佳地,該合金沈積物中硼之量在1wt.%至10wt.%範圍內,餘量為鎳。
在肼及甲醛中之一或多者用作鎳之還原劑之情形下,獲得純鎳沈積物。
無電鎳電鍍浴可視情況包含第二金屬離子源,例如鉬、錸或鎢離子。該等第二金屬離子可較佳以水溶性鹽或諸如MoO2(OH)2、ReO2(OH)2、WO2(OH)2、Na2MoO4、Na2ReO4及Na2WO4等化合物及其各別水合物形式來添加。
添加至無電鎳電鍍浴中之第二金屬離子之量較佳在0.01mol/l至0.2mol/l、更佳0.05mol/l至0.15mol/l範圍內。無電鎳電鍍浴中之第二金屬離子之量可足以達到經沈積鎳合金中第二金屬之4wt.%至20wt.%之濃度。
或者,在步驟(iii)中,銅或銅合金可以金屬或金屬合金形式沈積於經活化之矽基材上。在太陽能電池之製造中,銅或其合金通常沈積於矽基材上。無電銅或銅合金浴包含銅離子源、還原劑、錯合劑及通常穩定劑。US 7,220,296;WO 2014/154702;G.O.Mallory,J.B.Hajdu,Electroless Plating:Fundamentals And Applications,重印版,American Electroplaters and Surface Finishers Society,第289-295頁;US 4,617,205;US 2008/0223253及具體而言歐洲專利申請案EP 14198380.9係以引用方式全部併入本文中並闡述無電銅或銅合金沈積中所用之該等上文所提及之化合物及其他適宜添加劑(以可適用的濃度及可用的參數)。
鈷及其合金可用作矽基材上之障壁層。此等障壁層用於晶片製造中。其置於(例如)銅線與矽層之間且欲抑制銅至矽層之遷移。具體而言,三元鈷-鎢-磷及鈷-鉬-磷合金可用於此目的。無電鈷或鈷合金浴包含銅離子源、還原劑、錯合劑及通常穩定劑。US 2005/0161338、WO 2013/135396及歐洲專利申請案EP 14198380.9闡述用於無電鈷或鈷合金沈積中之該等上文所提及之化合物及其他適宜添加劑(以可適用的濃度及可用參量)且以引用方式全部併入本文中。
所沈積之金屬或金屬合金層較佳具有低於150nm之厚度,其更
佳在1nm至50nm範圍內,其甚至更佳在2nm至20nm範圍內。
至少一種矽基材或至少一部分之其表面可藉助噴霧、擦拭、浸泡、浸沒或藉由其他適宜方式來與無電金屬電鍍浴及活化組合物接觸。本發明製程中之步驟(iii)之無電金屬電鍍可以水平、捲到捲、垂直、垂直輸送或噴鍍設備來實施。可用於實施本發明製程之尤其適宜電鍍工具揭示於US 2012/0213914 A1中。
矽基材可與無電金屬電鍍浴接觸1秒至30min、較佳30秒至10分鐘、更佳40秒至3分鐘、最佳45秒至3分鐘。矽基材與活化組合物及經活化之矽基材與無電金屬或金屬合金電鍍浴之接觸時間影響所獲得金屬或金屬合金層厚度。因此,熟習此項技術者可確定兩個步驟中達成某一金屬或金屬合金層厚度所需之接觸持續時間。
本發明之用於活化矽基材之方法可在步驟(iii)之後包含另一步驟(iv)熱處理矽基材且從而形成金屬矽化物。
至少一種矽基材可在介於300℃與750℃之間之溫度下在諸如氮或氬等惰性氣體中熱處理30秒至60秒。在熱處理表面上沈積有金屬或金屬合金層之矽基材之後,金屬擴散至矽基材中且形成金屬矽化物。此熱處理已在業內充分確立且有時稱為快速熱退火(通常縮寫為RTA)。US 6,406,743 B1教示可用於本發明之上下文中之各種熱處理方案。
在熱處理之後之任何留在矽基材表面上之剩餘金屬或金屬合金可藉由濕化學蝕刻、化學機械平坦化(或任何其他適宜方式)來移除,從而在矽基材表面上留下金屬矽化物。移除金屬或金屬合金之方式為業內已知。鎳或合其金可藉由兩步蝕刻來移除,如US 6,406,743 B1中所揭示。
本發明方法可包含進一步沖洗、清洗、蝕刻及預處理步驟,其
皆為業內所已知。
本發明方法具體而言適宜形成由金屬矽化物製得之互連,例如矽化鎳互連。該等互連可例示性用於MOS電晶體、CMOS電晶體、IC基材(VLSI)之製造中。含有此等互連之產品可係記憶條(USB條)、MS卡、SD卡、功率二極體及功率電晶體。或者,本發明方法可用於在矽基材上形成障壁層,例如鈷合金障壁層。其亦可用於矽基材之金屬化中以用於生產太陽能電池。
本發明之優點係可獲得具有小於10nm或甚至小於5nm之層厚度之極薄且均勻分佈之鈀晶種層。然後,該等鈀晶種層使得50nm或25nm或甚至15nm或更薄之超薄金屬或金屬合金層(例如鎳或鎳合金層)沈積於其上。由於極薄且均勻分佈之鈀晶種層,形成於其上之金屬或金屬合金層較為平整、平坦且光滑(其可分別藉由例如原子力顯微術及XRF來量測;參見實例5)。然後,如此形成之金屬或金屬合金層可不需要或僅需要減少之化學機械平坦化步驟而轉化為金屬矽化物。
現將藉由參照以下非限制性實例來對本發明加以說明。
藉由SEM(Zeiss Ultra Plus,SE2檢測器,加速電壓3.0kV或5.0kV,數據在個別圖中給出)目測分析基材。使用來自Olympus之Stream軟體來測定表面覆蓋率以量化所量測之SEM圖片。
在各基材之5個點處藉由XRF使用XRF儀器Fischerscope XDV-SDD(Helmut Fischer GmbH,Germany)來量測金屬(合金)沈積厚度。藉由假設沈積物之層狀結構,可自此XRF數據計算出層厚度。
藉由掃描原子力顯微鏡(Digital Instruments,NanoScope,配備有來自Nanosensors之具有小於7nm之尖部半徑之PointProbe®)來測定表面之光滑度(或粗糙度),掃描大小:5倍2×2μm,以輕敲模式掃描。藉由該等量測獲得平均粗糙度(SA)、最大高度差(ST)及RSAI值(相對表
面積增加)且利用以下各別實例提供。
在室溫下將n型摻雜之多晶矽基材浸沒於含有0.1g/l Pd2+離子(來自PdSO4)及1wt.% HF之水溶液中持續120秒。表面由鈀粒子不均勻覆蓋,其中平均表面覆蓋率為(32.0±1.3)%(參見圖1)。
在室溫下將n型摻雜之多晶矽基材浸沒於含有0.1g/l Pd2+離子(來自PdSO4)、1wt.% HF及0.5ml/l冰乙酸之水溶液中持續120秒。表面由鈀粒子不均勻覆蓋,其中平均表面覆蓋率為(32.0±1.2)%(參見圖2)。
在室溫下將n型摻雜之多晶矽基材浸沒於0.1g/l Pd2+離子(來自PdSO4),1wt.% HF之水溶液(其進一步包含如表I中所給出之芳香族酸)中持續120秒。結果及處理條件亦於該表中給出。
1比較實例;2本發明實例
與不含有芳香族酸之比較實例1及2相比,比較實例a.、c.及d.均顯示顯著改良之含有鈀之矽表面之表面覆蓋。然而,使用對甲苯磺酸之比較實例b.甚至導致比彼等實例更差的表面覆蓋。與其相比,當在本發明實例e.中使用多於一種芳香族酸時,表面覆蓋優良至幾乎完全覆蓋。應考慮到在此情形下浸沒時間比在許多比較實例中更短且總濃度與在大多比較實例中相同。因此,兩種或更多種芳香族酸之組合協同促進製程且使得獲得經改良之表面覆蓋。
將多晶矽基材浸沒於各自含有0.1g/l Pd2+離子(來自PdSO4)、1wt.% HF及如下表II中可見之各別濃度之一或多種芳香族酸之水溶液中持續60秒或120秒。
1比較實例;2本發明實例
與比較實例1及2相比,表1之活化溶液均改良了基材表面之覆蓋。如SEM圖片中所見之個別粒子大多較小且相當均勻地分散於基材之整個表面上。可看到在活化組合物中兩種或更多種芳香族酸之使用
引起表面上之甚至更顯著均勻覆蓋及粒子分佈(表1中之條目d.及e.)。亦可看到,當與比較實例4a.至4c.相比時,自本發明實例4d.及4e.所獲得之個別粒子較小且實質上在表面上未形成較大聚集粒子。
因此,發現協同效應起因於活化溶液中兩種或更多種芳香族酸之使用。
將n型摻雜之多晶矽基材浸沒於實例3e之水性活化組合物中分別持續60秒(實例5a)及120秒(實例5b)。在65℃下將如此活化之矽基材浸沒至各自具有4.3之pH且含有6g/l鎳離子(以硫酸鎳形式提供)、二羧酸、三羧酸及羥基羧酸作為錯合劑以及0.25g/l二甲基胺基硼烷作為還原劑之無電鎳電鍍浴中持續600秒。
矽基材經鎳硼合金均勻覆蓋。厚度及粗糙度可參見表III。
藉由本發明處理獲得鈀及鎳硼二者之極薄層。該等層亦極光滑且顯示極小粗糙度偏差,此在當製造目前的半導體裝置時係非常合意的。實例5a之AFM圖片顯示於圖8中。
Claims (14)
- 一種用於活化矽基材之活化組合物,其中該活化組合物係包含鈀離子源及氟離子源之水溶液,其特徵在於其包含至少兩種選自由以下組成之群之芳香族酸:芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸,其中該活化組合物中之該至少兩種芳香族酸之總濃度在0.1mg/L至1000mg/L範圍內。
- 如請求項1之活化組合物,其中該至少兩種芳香族酸選自由以下組成之群:芳香族羧酸、芳香族磺酸及芳香族膦酸。
- 如請求項3之活化組合物,其中該至少兩種芳香族酸中之一者包含磺酸部分。
- 如請求項3之活化組合物,其中該至少兩種芳香族酸中之一者包含羧酸部分。
- 如請求項3之活化組合物,其中該至少兩種芳香族酸中之一者包含磺酸部分且該至少兩種芳香族酸中之另一者包含羧酸部分。
- 如請求項1或2中任一項之活化組合物,其中該至少兩種芳香族酸選自由以下組成之群:苯甲酸、1,2-苯二甲酸(鄰苯二甲酸)、1,3-苯二甲酸(間苯二甲酸)、1,4-苯二甲酸(對苯二甲酸)、1,2,3-苯三甲酸(半蜜臘酸)、1,2,4-苯三甲酸(偏苯三酸)、1,3,5-苯三甲酸(苯均三酸)、1,2,4,5-苯四甲酸(焦蜜石酸)、1,2,3,4,5-苯五甲酸、1,2,3,4,5,6-苯六甲酸(蜜臘酸)、2-硝基苯甲酸、3-硝基苯甲酸、4-硝基苯甲酸、2,5-二硝基苯甲酸、2,6-二硝基苯甲酸、3,5-二硝基苯甲酸、2,4-二硝基苯甲酸、3,4-二硝基苯甲酸、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、3,4-二胺基苯甲酸、3,5-二胺基苯甲酸、2,3-二胺基苯甲酸、2,4-二胺基苯甲酸、柳酸、對甲苯磺酸、1-萘甲酸、2-萘甲酸、2,6-萘二甲酸、2-萘磺酸、5-胺基-1-萘磺酸、5-胺基-2-萘磺酸、7-胺基-4-羥基-2-萘磺酸及苯基膦酸。
- 如請求項1或2之活化組合物,其中該活化組合物中之該至少兩種芳香族酸之總濃度在1mg/L至750mg/L範圍內。
- 如請求項1或2之活化組合物,其中該活化組合物包含選自由以下組成之群之甲烷磺酸及/或礦酸:硫酸、鹽酸、硝酸、磷酸、甲烷磺酸、氫溴酸、碘化氫、過氯酸、王水(aqua regia)、次氯酸、碘酸及亞硝酸。
- 一種用於活化至少一種矽基材之方法,其以給定順序包含以下步驟(i)提供該至少一種矽基材;(ii)使用如請求項1至9中任一項之活化組合物活化該至少一種矽基材之表面之至少一部分。
- 如請求項10之方法,其中該等矽基材包含由以下製得之表面:氧化矽、多晶矽、p型摻雜之多晶矽、n型摻雜之多晶矽、氮化矽及氧氮化矽。
- 如請求項10或11中任一項之方法,其中該方法在步驟(ii)後包含另一步驟(iii)在該經活化之矽基材上無電電鍍金屬或金屬合金。
- 如請求項12之方法,其中該欲沈積之金屬選自銅、鈷、鎳、銅合金、鈷合金及鎳合金。
- 如請求項12之方法,其中該方法在步驟(iii)後進一步包含(iv)熱處理該矽基材並從而形成金屬矽化物。
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JP7080781B2 (ja) * | 2018-09-26 | 2022-06-06 | 株式会社東芝 | 多孔質層の形成方法、エッチング方法、物品の製造方法、半導体装置の製造方法、及びめっき液 |
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CN114250501A (zh) * | 2021-12-24 | 2022-03-29 | 新阳硅密(上海)半导体技术有限公司 | 一种可连续进行电镀和化镀的设备和方法 |
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