CN1174118C - Method for metal plating, pretreating agent, and semiconductor wafer and semiconductor device using same - Google Patents
Method for metal plating, pretreating agent, and semiconductor wafer and semiconductor device using same Download PDFInfo
- Publication number
- CN1174118C CN1174118C CNB008182019A CN00818201A CN1174118C CN 1174118 C CN1174118 C CN 1174118C CN B008182019 A CNB008182019 A CN B008182019A CN 00818201 A CN00818201 A CN 00818201A CN 1174118 C CN1174118 C CN 1174118C
- Authority
- CN
- China
- Prior art keywords
- plating
- metal
- copper
- coupling agent
- semiconductor wafer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000007747 plating Methods 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 61
- 239000000126 substance Substances 0.000 claims description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 48
- 239000010949 copper Substances 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- 238000002203 pretreatment Methods 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000002460 imidazoles Chemical class 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000001465 metallisation Methods 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 16
- 125000000524 functional group Chemical group 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000007772 electroless plating Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 150000002739 metals Chemical class 0.000 abstract 2
- 235000012431 wafers Nutrition 0.000 abstract 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 48
- 229910052710 silicon Inorganic materials 0.000 description 34
- 239000010703 silicon Substances 0.000 description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 239000004744 fabric Substances 0.000 description 16
- 239000010970 precious metal Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 15
- 229920002799 BoPET Polymers 0.000 description 13
- 239000005041 Mylar™ Substances 0.000 description 13
- -1 amino silicane Chemical compound 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 150000003851 azoles Chemical class 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 150000003376 silicon Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 229910000085 borane Inorganic materials 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- CQDAMYNQINDRQC-UHFFFAOYSA-N oxatriazole Chemical compound C1=NN=NO1 CQDAMYNQINDRQC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical compound C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
-
- 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
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
-
- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Resin cloths, powders, specular bodies and other objects resistant to conventional plating can be plated with metals by a simple method. According to the metal plating method of the present invention, electroless plating is performed after the surface of a object to be plated is treated with a pretreatment agent obtained by reacting or mixing in advance a noble metal compound (catalyst) with a silane-coupling agent having functional groups capable of capturing metals. According to this method, metal plating can be securely applied to powders, resin cloths, semiconductor wafers, and other specular bodies. Moreover, the problem of the insufficient coverage of the seed layer on the inside walls of vias and trenches during the formation of fine wiring can be addressed by applying this method to semiconductor wafers. The silane-coupling agent may be a compound containing azole groups, preferably an imidazole.
Description
Technical field
The present invention relates to a kind of chemical plating is used for that metal deposition is had method on the body surface of low electric conductivity to certain material, specular surface body, powder or other.The invention still further relates to a kind of chemical plating method that on semiconductor wafer, forms the copper wiring, more particularly, relate to a kind of like this chemical plating method that is applicable to semiconductor wafer, in this method, can under the condition that does not form cavity, crack or other defect, small path or groove be imbedded in the semiconductor wafer.
Background technology
Chemical plating is a kind of in the method that does not have to form on the base material of electroconductibility metallic membrane, uses this method when for example forming printed wiring on resin base material.Common method requires to carry out so-called activation, and it is a kind of like this technology, as the pretreated part of chemical plating, make in advance palladium or other precious metals as catalyst deposit on base material.The method of Shi Yonging comprises such certain methods traditionally, wherein at first uses SnCl
2Hydrochloric acid soln handle base material, and then it is immersed in PdCl
2In the aqueous solution, so that absorption Pd; And comprise such certain methods, wherein use the colloidal solution that contains Sn and Pd to make the Pd deposition from the teeth outwards.These methods have many shortcomings, for example the complicacy of the use of highly toxic Sn and treatment process.Given this, propose recently some and contain the method for silane coupling agent that can form the functional group of title complexs with Pd and other precious metals based on use, so as with these precious metals as chemical plating catalyzer covering surfaces (Japanese patent gazette No.S59-52701, S60-181294, S61-194183 and H3-44149).
But, just has some method of above-mentioned silane coupling agent characteristics, when plating catalyzer fixing agent and plating catalyzer separate treatment, want the feasible settling that be difficult to be adhered to by force and uniform of material of plating object, that is to say, after coupling agent is adsorbed on the object, just deposit as the precious metal ion of catalyzer.This is owing to such fact: object surfaces is changed coupling agent or precious metal ion can not enough deposit effectively.Owing to similar reason or because palladium does not have enough catalytic activitys, for some type want the object materials of plating or have amino silicane coupling agent and the method for Palladous chloride mixing solutions characteristics in the plating condition, can not reach uniform plating sometimes.Particularly, for for example forming the chemical plating settling on the semiconductor substrate on the semi-conductor specular surface, use traditional SnCl
2For the treatment process on basis is difficult to make precious metal ion (catalyzer) to be fixed on such surface.
Traditionally, in semiconductor wafer processing, aluminium is mainly as wiring material.Because the wiring integrated level improves, the copper of high conductivity has replaced aluminium at present, increases so that prevent the signal delay time.Method for embedding is used for forming the copper wiring, in this method, forms wiring pattern on silicon wafer usually, forms blocking layer and crystal seed layer by sputter or CVD, with electroplating wiring pattern is imbedded, and removes the copper of excess deposition then with CMP.
When LSI is routed in silicon or the formation of other semiconductor wafer surfaces, for the copper wiring of imbedding forms path or ditch mortise, the barrier metal that is selected from titanium, tantalum, tungsten, its nitride etc. deposits to about 0.01-0.1 micron thickness with methods such as sputter, CVD, is diffused in the silicon on the wafer surface so that prevent copper.Traditionally, this barrier metal layer covers with thin copper layer (crystal seed layer) by above-mentioned identical mode by methods such as sputter, CVD.Barrier metal has high resistance usually, and it has low-resistance copper (veneer) for what provide in advance, so that avoid in electro-coppering subsequently the sizable difference of current density that produces between the centre portions of each point of contact and periphery on the wafer perimeter.
Along with more and more narrow LSI wiring pattern is designed and path is corresponding with groove becomes narrower, above-mentionedly can not provide enough coverings to the crystal seed layer on path and the trench wall, thereby in electroplating process subsequently, produce defective in (cavity and crack) at the sputtering method that carries out traditionally.Though can improve covering with CVD, very high expense is a problem.
Summary of the invention
In view of the foregoing, an object of the present invention is and to provide a kind of method for metal plating that can produce enough electroless plating coating for being difficult to powder, specular surface body and resin fabric that traditional chemical plating method covers.Another object of the present invention provide a kind of can to specular surface body particularly semiconductor wafer for example silicon wafer form enough electroless plating coating and can solve crystal seed layer does not have enough to cover this difficult problem on trench wall at path method for metal plating, when thin being routed in formed on the semiconductor wafer, described problem existed.
Because fully the result of research can solve above-mentioned technical barrier according to discovery by the object that uses the prior solution-treated that silane coupling agent mixes or reaction obtains that can catch metal to want the body surface of plating to make, the inventor has finished the present invention.
Specifically, the invention provides following content.
(1) a kind of method of metal deposition, described method comprises: prepare pretreating agent by in advance precious metal chemical complex being caught the silane coupling agent reaction of metal or mixed with its functional group; Want the body surface of plating with described pre-treatment treatment; The described object of chemical plating then.
(2) according to the method for metal plating of above-mentioned (1), the functional group that wherein can catch metal is the azoles base.
(3) according to the method for metal plating of above-mentioned (2), wherein by making the silane coupling agent that contains the azoles base based on the compound of azoles with based on the compound reaction of epoxy silane.
(4) according to the method for metal plating of above-mentioned (2) or (3), wherein the azoles group is an imidazolyl.
(5) according to each method for metal plating in above-mentioned (1) to (4), wherein precious metal chemical complex is a palladium compound.
(6) according to each method for metal plating in above-mentioned (1) to (5), wherein object is a semiconductor wafer.
(7) according to the method for metal plating of above-mentioned (6), wherein chemical plating is the chemical plating of copper or nickel.
(8) according to the method for metal plating of above-mentioned (7), wherein the chemical plating by described copper or nickel forms conductive layer, and copper is plated on the conductive layer.
(9) a kind of metal deposition pretreating agent, described pre-treatment comprise by the silane coupling agent reaction that in advance precious metal chemical complex and its functional group can be caught metal or mixed must solution.
(10) according to the metal deposition pretreating agent of above-mentioned (9), the functional group that wherein can catch metal is the azoles group.
(11) a kind of semiconductor wafer forms the metal-plated coating with each method for metal plating in above-mentioned (6) to (8) on described semiconductor wafer.
(12) semiconducter device made of a kind of semiconductor wafer that uses above-mentioned (11).
The invention is characterized in, being used in the specific silane coupling agent that has following function in the same molecular handles and wants the body surface of plating to carry out chemical plating later on again: catch the function as the precious metal ion of chemical plating catalyzer, and these precious metal ions are fixed to function on the object.By using such silane coupling agent not only can shorten the plating process, but also catalyzer is fixed on the object reliably.In addition, past is difficult in order to be fixed on for example above-mentioned wafer of semi-conductor specular surface body as the precious metal ion of catalyzer, but the present invention is fixed on the semiconductor wafer catalyzer by using capture catalyst and it being fixed to the treatment agent that function on the semiconductor wafer is present in same molecular reliably.That is to say, be present in the molecular arrangement, so can obtain by required electronic state and the orientation of efficient manner activation plating catalyzer because can catch the functional group of metal.In addition, also can reach the well attached of metal pair semiconductor wafer and other reluctant objects with described silane coupling agent.
Imidazolyl preferably used according to the invention is as the functional group that can catch metal.
The example of the azoles group that is fit to comprises imidazoles, oxazole, thiazole, smile azoles, pyrazoles, isoxazole, isothiazole, triazole, oxadiazole, thiadiazoles, tetrazolium, oxatriazole, thiatriazole, indoles, indazole, benzoglyoxaline and benzotriazole.Wherein, imidazoles is particularly preferred.When using is not the imidazoles (though it is an azole compounds) of silane coupling agent when carrying out pre-treatment, extremely low to the plating tack of object, although enough uniform plating is arranged.
Silane coupling agent among the present invention is for containing-SiX
1X
2X
3The compound of group, wherein X
1, X
2And X
3Be alkyl, halogen, alkoxyl group or other any functional groups that can be attached on the object of wanting coated.X
1, X
2And X
3Can be identical or different.Can be used as an example with reference to (Japanese patent gazette No.H6-256358) by the silane coupling agent that makes based on the compound of azoles and compound reaction based on epoxy silane.The epoxy silane coupling agent that following formula is represented.
(R in the formula
1And R
2Be hydrogen or C
1-C
3Alkyl and n are 1-3) be preferably used as the silane compound that contains epoxy group(ing) with such compound reaction based on azoles.
Can in Japanese patent gazette No.H6-256358, carry out under the disclosed condition based on the reaction between the compound of azoles and the above-mentioned silane compound that contains epoxy group(ing).For example, the silane compound that the 0.1-10 mole is contained epoxy group(ing) under 80-200 ℃ is added drop-wise in 1 mole of compound based on azoles, reacts then 5 minutes to 2 hours.For this process, solvent is not to need especially, but can be with an organic solvent, for example chloroform, diox, methyl alcohol and ethanol.
The example of the precious metal chemical complex that is fit to comprises that palladium, silver, platinum, gold and other show muriate, oxyhydroxide, oxide compound, vitriol, ammonium salt and the amine complex of the metal of katalysis from chemical plating solution when copper, nickel etc. is deposited on the body surface of wanting plating.Palladous chloride is particularly preferred.Precious metal chemical complex is preferably the aqueous solution, and its concentration in treatment soln is preferably the 20-300 mg/litre.
According to method for metal plating of the present invention, the object of plating not to be subjected to the restriction of shape or character.For example, the present invention is applicable to insulating bodies, for example inorganic materials (comprising glass, pottery etc.), plastics (comprising polyester, polymeric amide, pi, fluorine resin etc.), film and the sheet material made by them; And the insulcrete of making by Resins, epoxy and fibre-reinforced other materials, or opticglass fabric substrate; And the object of wanting plating that low electric conductivity is arranged, for example silicon wafer and other semi-conductors.Method of the present invention can perform well in powder or specular surface body, for example transparency glass plate, silicon wafer and other semiconductor substrates.For example, such powder comprises little glass sphere, molybdenumdisulphide powder, magnesium oxide powder, powdered graphite, silicon carbide powder, Zirconium oxide powder, alumina powder, silicon oxide powder, sheet mica, glass fibre, silicon nitride and Teflon
Powder.
Term used herein " semiconductor wafer " also refers to the wafer of based compound semiconductor, for example gallium/arsenic, gallium/phosphorus and indium/phosphorus except that referring to silicon wafer.Method for metal plating of the present invention to the material of the coating surface material that constitutes semiconductor wafer without any restriction.For example, when forming the LSI wiring, the surface of plating is the low electric conductivity barrier metal that is selected from titanium, tantalum, tungsten and nitride thereof and uses sedimentary other materials such as vapor deposition, sputter, CVD usually.Method of the present invention can perform well in any situation in these situations.In addition, when the surface of plating was silicon or its oxide film, the present invention can use well.
When method for metal plating of the present invention, the silane coupling agent that precious metal ion and its functional group can be caught metal mixes or reaction in advance mutually, obtains being used to handle the pretreating agent of chemical plating base material.When wanting the plating object surfaces with this pre-treatment treatment, pretreating agent dissolves in the The suitable solvent.The example of suitable solvent comprises water, methyl alcohol, ethanol, 2-propyl alcohol, acetone, toluene, ethylene glycol, polyoxyethylene glycol, dimethyl formamide, dimethyl sulfoxide (DMSO), diox and composition thereof.When making water, the pH value of solution needs concrete according to wanting the object of plating and the condition optimizing of plating.
To the concentration of the pretreating agent that is used for the surface or the pretreating agent solution silane coupling agent that contains the functional group that to catch metal without limits, but preferred concentration is 0.001-10% (weight).When concentration during less than 0.001% (weight), the compound quantity that is deposited on the substrate surface is tending towards reducing, and desirable effect is more difficult to be reached thereby make.When concentration surpassed 10% (weight), too much compound was deposited, thereby hindered drying and make the easier cohesion of powder.
Usually the method for using dip-coating, brushing and other technologies to carry out evaporating solvent is subsequently handled cloth shape or plate-like substrate surface, but these are not unique selections, and any method all can adopt, as long as silane coupling agent combines equably with the surface.Being used for the method for powder, make solvent evaporates later in dip-coating, the silane coupling agent that is contained in the solvent is attached to substrate surface.Also may use a kind of like this method, in this method, after handling, solvent be told dry then wetting powder with filtering.Because the even film forming character of silane coupling agent can reach in submerged state in the absorption on the substrate surface.In some cases, decide on adsorption conditions, following drying process may be saved, and this process can only be finished by cleaning.In addition, for pre-treatment (surface treatment) temperature, room temperature is enough, but heating may be effectively in some cases, decides on the object of wanting plating.
Carrying out before the plating pre-treatment, the object of plating is wanted in washing earlier.If the special requirement adhesion strength can be carried out the etching method of traditional chromic acid etc.
For the solvent evaporates that made later in surface treatment, it is enough making surface drying by the vaporization temperature that this solvent is heated to solvent, but preferably further heats 3-60 minute down at 60-120 ℃.When water was used as solvent, drying process can be saved, and therefore only just can carry out plating with cleaning after handling.But, in this case, need in the coating solution fully to wash down in order to prevent that catalyzer from bringing into.
In solution and coating method of the present invention, after above-mentioned surface treatment, carry out chemical plating.In this stage, metal for example copper, nickel, cobalt, tin and Jin Ke is pressed plating of the present invention.Under these circumstances, it may be effective using the solvent treatment object that contains reductive agent before plating.Under the particular case of copper plating, available dimethyamine borane solution is handled as reductive agent.After the electroconductibility that provides by chemical plating formation metallic film and for nonconducting base material to a certain degree, might carry out electrolytic coating or relate to the displacement plating of using less noble metal.
When method for metal plating of the present invention is used for semiconductor wafer, traditional seed layer deposition method replaces with a kind of like this method, by by above-mentioned treat surface catalyzer being provided in the barrier metal, the chemical plating by copper or nickel forms crystal seed layer then in this method.According to this method, the path of available ratio lower expense solution thin wires when using CVD and the inadequate problem of covering of trench wall.When with the chemical plating deposited copper, available identical chemical plating process not only forms crystal seed layer continuously but also forms the wiring of imbedding continuously.When catalyzer is deposited on the coating surface equably, when forming forming fine wiring,, tend to generate the crack because grow equably at the surperficial upper film of plating.But when depositing according to the present invention, catalyzer tends to be attached to better the inwall of thin wires.Because having, metal deposits to the more trend in the sedimentary zone of multi-catalyst, the result is bottom-up (bottom-up) deposition process that is similar to the process that the situation at the cupric electrolysis coating solution that is used to imbed thin wires occurs, so thin wires can be imbedded not forming under the fissured condition.Certainly, might form crystal seed layer later on by cupric electrolysis plating buried wiring with the copper chemical plating.
When method for metal plating of the present invention was used for semiconductor wafer, common practice was to adopt a kind of like this method, and wafer surface is passed through dip-coating processing later on solvent evaporation in this method.But this is not unique selection, adopts in any method, as long as silane coupling agent can be attached on the surface equably.For treat surface, room temperature is enough, makes catalyzer with higher speed and bigger quantity deposition but add heat energy.30-80 ℃ Heating temperature is enough.By above-mentioned mode pretreating agent is dissolved in the solution that makes in the The suitable solvent and can be used for surface treatment.On deciding in conjunction with condition, drying step can save, and therefore can only clean.
Make the solvent slop volatilization for after handling in wafer surface, be enough to make surface drying more than the solvent vaporization temperature, system was kept under 60-120 ℃ 3-6 minute again by temperature is raised to.When water was used as solvent, drying process can be saved, and can only clean after handling and carry out plating.But, bring in the coating solution in order to prevent catalyzer, cleaning fully in this case needs.
Formalin is contained in the copper chemical plating solution as reductive agent usually.But in recent years, because the problems relevant with environmental protection, the use of formalin is abandoned gradually.The use of nickel chemical plating solution makes this problem more outstanding.For the nickel chemical plating, because the phosphorus or the boron of filming and containing percentum usually, so resistance increases.So when the nickel chemical plating forms crystal seed layer, must obtain still providing the minimum thickness of electroconductibility.
Alkaline components is contained in the solution of copper chemical plating and nickel plating as raw material usually.Because alkaline components is the most deleterious impurity in the wiring material, there is not alkali-metal raw material so must use.For example, can use Tetramethylammonium hydroxide to replace sodium hydroxide, be used for balance pH value.In addition, dimethyamine borane also can be used as the reductive agent of nickel chemical plating solution.
Brief description
Fig. 1 is the SEM photo of the copper plating film that forms among the embodiment 5 on silicon wafer; And
Fig. 2 is the SEM photo of the copper plating film that forms in the Comparative Examples 6 on silicon wafer.
DESCRIPTION OF THE PREFERRED
Describe embodiments of the invention below in detail.Embodiment 1-4 and Comparative Examples 1-5 describe with the plating of method for metal plating of the present invention on the object of similar cloth.Embodiment 5-8 and Comparative Examples 6-7 describe with the plating of method for metal plating of the present invention on semiconductor wafer.
Embodiment 1
At first between imidazoles and γ-glycidoxypropyltrimewasxysilane, carry out reaction with same mole, generate silane coupling agent as product.At room temperature palladium chloride aqueous solution is added in the aqueous solution that contains the described silane coupling agent of 0.2% (weight) subsequently, makes the concentration of Palladous chloride reach 150 mg/litre, thereby make the agent of pre-treatment plating.With the submergence 3 minutes in the agent of pre-treatment plating at room temperature of cloth shape vibrin, clear cleaning mylar in flowing water then.Then mylar is used nickel chemical plating solution (by the nickel coating solution FM-0 of Nikko Metal Plating manufacturing) plating 5 minutes down at 70 ℃.As a result, polyester is furnished with one deck enough adhesion strengths and inhomogeneity nickel plating on whole surface.
Embodiment 2
At room temperature, soaked fully cleaning in flowing water then 3 minutes in the pre-treatment plating agent that nylon cloth is prepared in embodiment 1.Use then nickel chemical plating solution (Nikko MetalPlating make nickel coating solution FM-0) with nylon cloth 70 ℃ of following plating 5 minutes.Nylon is furnished with one deck as a result enough adhesion strengths and inhomogeneity nickel coating layer on whole surface.
Embodiment 3
At room temperature, palladium chloride aqueous solution is added in the aqueous solution that contains the silane coupling agent of preparation among 0.05% (weight) embodiment 1, makes the concentration of Palladous chloride reach 80 mg/litre, thereby make the agent of pre-treatment plating.At room temperature, mylar was soaked 3 minutes at the pre-treatment plating, fully clean mylar with mobile water then.Use then nickel chemical plating solution (NikkoMetal Plating make nickel coating solution FM-0) with mylar 70 ℃ of following plating 5 minutes.As a result, polyester is furnished with one deck enough adhesion strengths and inhomogeneity nickel coating layer on whole surface.
Embodiment 4
At room temperature, soaked fully cleaning in mobile water then 3 minutes in the pre-treatment plating agent that cloth shape vibrin is prepared in embodiment 1.Then mylar was soaked 3 minutes in being heated to 60 ℃ dimethyamine borane (3.7 grams per liter) aqueous solution.Use then copper chemical plating solution (Nikko Metal Plating make copper coating solution PM-0) with mylar 70 ℃ of following plating 10 minutes.As a result, polyester is furnished with one deck enough adhesion strengths and inhomogeneity copper coating layer on whole surface.
Comparative Examples 1
Make silane coupling agent by mode identical among the embodiment 1.At room temperature, cloth shape vibrin was soaked 3 minutes in the aqueous solution that only contains 0.2% (weight) silane coupling agent.Subsequently vibrin was at room temperature soaked 3 minutes in the aqueous solution that contains 30 mg/litre Palladous chlorides, in flowing water, fully clean then.Use nickel chemical plating solution (the nickel coating solution FM-0 that Nikko MetalPlating makes) that mylar was soaked 5 minutes down at 70 ℃ then.As a result, mylar still major part do not have the nickel coating layer.
Comparative Examples 2
With the cloth shape vibrin in the nylon cloth replacement Comparative Examples 1, the plating of nickel is undertaken by Comparative Examples 1 identical mode.As a result, nylon cloth still major part do not have the nickel coating layer.
Comparative Examples 3
At room temperature, cloth shape vibrin was soaked 3 minutes in the aqueous solution that only contains 0.2% (weight) silane coupling agent that makes by embodiment 1 same way as.At room temperature vibrin was soaked 3 minutes in the aqueous solution that contains 30 mg/litre Palladous chlorides subsequently, in flowing water, fully clean then.Subsequently mylar was soaked 3 minutes in being heated to 60 ℃ dimethyamine borane (3.7 grams per liter) aqueous solution, use then copper chemical plating solution (the copper coating solution PM-0 that Nikko Metal Plating makes) with mylar 70 ℃ of following plating 10 minutes.As a result, vibrin cloth still major part do not have the copper coating layer.
Comparative Examples 4
Mylar is pressed the identical mode plating of embodiment 1, different is the silane coupling agent that replaces use among the embodiment 1 with γ-An Jibingjisanyiyangjiguiwan (being made by Kanto Kagaku), and this silane coupling agent is the reaction with same mole product of imidazoles and γ-glycidoxypropyltrimewasxysilane.As a result, vibrin cloth still major part do not have the nickel coating layer.
Comparative Examples 5
Use embodiment 1 identical operations, make the mylar plating with nickel chemical plating method, different is to replace the imidazoles of use among the embodiment 1 and the reaction with same mole product of γ-glycidoxypropyltrimewasxysilane with imidazoles, and the concentration of Palladous chloride is risen to 300 mg/litre.As a result, polyester is furnished with enough coverings, but adhesion strength is poor.
Embodiment 5
In following embodiment 5-8 and Comparative Examples 6-7, there are trickle via pattern and sputter the silicon wafer of 30 nanometer TaN to be arranged as the object of wanting plating.The degree of depth of the pattern of path is 1 micron, and bore dia is 0.18 micron.
At room temperature, palladium chloride aqueous solution is added in the aqueous solution that contains the silane coupling agent that 0.05% (weight) makes by embodiment 1 identical mode, makes the concentration of Palladous chloride reach 150 mg/litre, thereby make the agent of pre-treatment plating.Under 60 ℃, above-mentioned silicon wafer was soaked 10 minutes in this pre-treatment plating agent solution, in flowing water, fully clean then.This silicon wafer was soaked 15 minutes in being heated to 60 ℃ the 10 grams per liter dimethyamine borane aqueous solution, in flowing water, fully clean then.Use then copper chemical plating solution (Nikko Metal Plating make copper coating solution NKM 554) with this silicon wafer 60 ℃ of following plating 1 minute.As a result, at the whole coating surface of silicon wafer the copper of enough tacks arranged.The SEM observation of imbedding the character cross-sectioned for thin via pattern shows, as shown in Figure 1, does not form cavity or crack, and obtains the enough character of imbedding.
Embodiment 6
At room temperature, palladium chloride aqueous solution is added in the aqueous solution that contains the silane coupling agent that 0.05% (weight) makes by embodiment 1 identical mode, makes the concentration of Palladous chloride reach 200 mg/litre, thereby make the agent of pre-treatment plating.Above-mentioned silicon wafer was being soaked 5 minutes in this pre-treatment plating agent under 60 ℃, in flowing water, fully cleaning then.Use nickel chemical plating solution (Nikko Metal Plating make nickel coating solution Ni-B) to make this silicon wafer then, in flowing water, fully clean then 65 ℃ of following plating 4 seconds.Use copper chemical plating solution (Nikko Metal Plating make copper coating solution NKM-554) to make silicon wafer then 60 ℃ of following plating 1 minute.The copper that enough tacks are arranged at the whole coating surface of silicon wafer as a result.For the character of imbedding of thin via pattern, the SEM of cross-sectioned observation shows and does not form cavity or crack and obtain the enough character of imbedding.
Embodiment 7
At room temperature, palladium chloride aqueous solution is added in the aqueous solution that contains the silane coupling agent that 0.1% (weight) makes by embodiment 1 same way as, makes the concentration of Palladous chloride reach 150 mg/litre, thereby make the agent of pre-treatment plating.Above-mentioned silicon wafer was being soaked 10 minutes in this pre-treatment plating agent under 60 ℃, in flowing water, fully cleaning then.Subsequently silicon wafer was soaked 15 minutes in being heated to 60 ℃ the 10 grams per liter dimethyamine borane aqueous solution, in flowing water, fully clean then.Make this silicon wafer 60 ℃ of following plating 30 seconds with copper chemical plating solution (Nikko Metal Plating make copper coating solution NKM-554).As another step, at room temperature, use cupric electrolysis coating solution (copper 20 grams per liters, sulfuric acid 200 grams per liters, chlorine 70 mg/litre, polyoxyethylene glycol (molecular weight 15000) 13 micromoles per liter, two (3-sulfopropyl) disodium 20 micromoles per liter of curing) at cathode current density 1 peace/decimetre
2Under to make this silicon wafer be plated to equivalent thickness be 1 micron.As a result, at the copper of the enough tacks of whole coating surface of silicon wafer.For the character of imbedding of thin road, the SEM of cross-sectioned observation shows and does not form space or crack and reach the enough character of imbedding.
Embodiment 8
At room temperature, palladium chloride aqueous solution is added in the aqueous solution that contains 0.05% (weight) and embodiment 1 identical silane coupling agent, makes the concentration of Palladous chloride reach 100 mg/litre, thereby make the agent of pre-treatment plating.Above-mentioned silicon wafer was being soaked 5 minutes in this pre-treatment plating agent under 60 ℃, in flowing water, fully cleaning then.Use subsequently nickel chemical plating solution (NikkoMetal Plating make nickel coating solution Ni-B) with silicon wafer 65 ℃ of following plating 4 seconds, in flowing water, fully clean then.As another step, at room temperature use cupric electrolysis coating solution (copper 16 grams per liters, sulfuric acid 240 grams per liters, chlorine 50 mg/litre, polyoxyethylene glycol (molecular weight 3350) 90 micromoles per liter, 3-sulfydryl-1-propane sulfonic acid sodium 40 micromoles per liter) at cathode current density 1 peace/decimetre
2Down 1 micron coating layer is plated on this silicon wafer.The copper that enough tacks are arranged at the whole coating surface of silicon wafer as a result.For the character of imbedding of thin via pattern, the SEM of cross-sectioned observation shows that not forming cavity or crack produces and obtain the enough character of imbedding.
Comparative Examples 6
On above-mentioned silicon wafer, copper further is splashed to thickness 100 nanometers.At room temperature, use cupric electrolysis coating solution (copper 20 grams per liters, sulfuric acid 200 grams per liters, chlorine 70 mg/litre, polyoxyethylene glycol (molecular weight 15000) 13 micromoles per liter, two (3-sulfopropyl) disodium 20 micromoles per liter of curing) at cathode current density 1 peace/decimetre
2Down this silicon wafer is plated to 1 micron of thickness.As a result, plating has the copper of enough tacks on silicon wafer.For the character of imbedding of thin via pattern, the SEM of cross-sectioned observation shows there is not the cavity as shown in Figure 2.
Comparative Examples 7
Use SnCl
2Aqueous hydrochloric acid handle above-mentioned silicon wafer, be immersed in PdCl
2The aqueous solution in, in flowing water, fully clean then.Use copper chemical plating solution (the copper coating solution NKM-554 that Nikko MetalPlating makes) under 60 ℃, to make this silicon wafer plating 1 minute subsequently.As a result, silicon wafer still major part do not have the copper coating layer.
As mentioned above, method of the present invention simply process makes chemical plating be used for like this some materials, for example powder and resin cloth, and these materials can not be with traditional solution and coating method plating.Another characteristics of solution and coating method of the present invention are, can be fixed to the semi-conductor specular surface body for example on the semiconductor wafer as the precious metal ion of catalyzer, so chemical plating can be easy to carry out, in that they are difficult to combine with such catalyzer traditionally.Also may overcome in meticulous LSI wiring and carry out on path and trench wall, covering a not enough relevant difficult problem with crystal seed layer in the process.
Claims (7)
1. method for metal plating, described method comprises: in advance by in the muriate, vitriol, ammonium salt and the amine complex that are selected from palladium at least a with prepare pretreating agent by reacting or mix based on the compound of imidazoles with based on the silane coupling agent that the compound reaction of epoxy silane makes; Want the article surface of plating with described pre-treatment treatment; And the described object of chemical plating.
2. according to the method for metal plating of claim 1, wherein said object is a semiconductor wafer.
3. according to the method for metal plating of claim 1 or 2, wherein said chemical plating is the chemical plating of copper or nickel.
4. according to the method for metal plating of claim 3, wherein the chemical plating by described copper or nickel forms conductive layer, and on conductive layer the electrolysis plated copper.
5. metal deposition pretreating agent, described pretreating agent comprise in advance by in the muriate, vitriol, ammonium salt and the amine complex that are selected from palladium at least a with by silane coupling agent reaction that makes based on the compound of imidazoles with based on the compound reaction of epoxy silane or mixed solution.
6. semiconductor wafer, the metal-plated coating that each method for metal plating forms among useful claim 1-4 on it.
7. semiconducter device that uses the semiconductor wafer of claim 6.
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| JP001645/2000 | 2000-01-07 | ||
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| JP2000238047 | 2000-08-07 |
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|---|---|---|---|---|
| WO2003091476A1 (en) * | 2002-04-23 | 2003-11-06 | Nikko Materials Co., Ltd. | Method of electroless plating and semiconductor wafer having metal plating layer formed thereon |
| JP3849946B2 (en) | 2002-09-10 | 2006-11-22 | 日鉱金属株式会社 | Metal plating method and pretreatment agent |
| WO2004068576A2 (en) * | 2003-01-23 | 2004-08-12 | Advanced Micro Devices, Inc. | Method of forming a catalyst containing layer over a patterned dielectric |
| FR2851258B1 (en) * | 2003-02-17 | 2007-03-30 | Commissariat Energie Atomique | METHOD OF COATING A SURFACE, FABRICATION OF MICROELECTRONIC INTERCONNECTION USING THE SAME, AND INTEGRATED CIRCUITS |
| US8182873B2 (en) | 2003-06-09 | 2012-05-22 | Nippon Mining & Metals Co., Ltd. | Method for electroless plating and metal-plated article |
| JP4327163B2 (en) * | 2003-10-17 | 2009-09-09 | 日鉱金属株式会社 | Electroless copper plating solution and electroless copper plating method |
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| KR100717336B1 (en) * | 2005-11-30 | 2007-05-10 | 한국기계연구원 | A plating method of metal layer by a galvanic displacement |
| JP5514548B2 (en) * | 2007-09-18 | 2014-06-04 | Ｊｘ日鉱日石金属株式会社 | Nano metal particle supporting method and nano metal particle supporting substrate |
| WO2009110431A1 (en) * | 2008-03-07 | 2009-09-11 | 独立行政法人科学技術振興機構 | Compound material, method of producing the same and apparatus for producing the same |
| WO2010029635A1 (en) * | 2008-09-11 | 2010-03-18 | パイオニア株式会社 | Method for metallic wiring formation and electronic component comprising metallic wiring |
| JP5604787B2 (en) * | 2009-01-21 | 2014-10-15 | 富士通株式会社 | Method for producing electroless plating |
| DE102010036535A1 (en) * | 2010-07-21 | 2012-01-26 | Saint-Gobain Isover G+H Ag | Method for metallizing mineral fibers and use thereof |
| KR101483920B1 (en) * | 2011-12-15 | 2015-01-16 | 헨켈 아이피 앤드 홀딩 게엠베하 | Electroless plating of silver onto graphite |
| TWI573687B (en) * | 2013-12-31 | 2017-03-11 | 財團法人工業技術研究院 | Laminated substrate and manufacturing method thereof |
| TWI672175B (en) * | 2017-10-20 | 2019-09-21 | 國立清華大學 | Self-adsorbed catalyst composition, method for preparing the same and method for manufacturing electroless plating substrate |
| CN111826643B (en) * | 2020-07-14 | 2023-05-12 | 华东理工大学 | Method for improving binding force of plating layer by activating copper plating on surface of modified metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63270474A (en) * | 1986-12-10 | 1988-11-08 | Minoru Tsuda | Catalytic ink |
| JPS63227784A (en) * | 1987-03-16 | 1988-09-22 | Toyobo Co Ltd | Method for providing electroless plating catalyst |
| JPH01117089A (en) * | 1987-10-29 | 1989-05-09 | Mitsumi Electric Co Ltd | Manufacture of fpc substrate |
| US4986848A (en) * | 1988-01-28 | 1991-01-22 | Hitachi Chemical Company, Ltd. | Catalyst for electroless plating |
| JPH06256358A (en) * | 1993-03-01 | 1994-09-13 | Japan Energy Corp | New imidazolesilane compound and its production, and metal surface treating agent using the same |
| JP3371072B2 (en) * | 1997-04-25 | 2003-01-27 | 株式会社ジャパンエナジー | Copper or copper alloy discoloration prevention liquid and discoloration prevention method |
| JP3555825B2 (en) * | 1997-09-22 | 2004-08-18 | 株式会社日鉱マテリアルズ | Novel organosilicon compound, method for producing the same, surface treating agent and resin additive using the same |
| US6197688B1 (en) * | 1998-02-12 | 2001-03-06 | Motorola Inc. | Interconnect structure in a semiconductor device and method of formation |
-
2000
- 2000-11-20 JP JP2001550424A patent/JP3670238B2/en not_active Expired - Lifetime
- 2000-11-20 CN CNB008182019A patent/CN1174118C/en not_active Expired - Lifetime
- 2000-11-20 WO PCT/JP2000/008166 patent/WO2001049898A1/en active Application Filing
- 2000-11-27 TW TW89125101A patent/TW593743B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW593743B (en) | 2004-06-21 |
| WO2001049898A1 (en) | 2001-07-12 |
| JP3670238B2 (en) | 2005-07-13 |
| CN1420944A (en) | 2003-05-28 |
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