JP6743289B2 - 窒化ガリウム半導体の活性化されていない表面上へのパラジウムの直接的な堆積方法 - Google Patents
窒化ガリウム半導体の活性化されていない表面上へのパラジウムの直接的な堆積方法 Download PDFInfo
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- JP6743289B2 JP6743289B2 JP2019510919A JP2019510919A JP6743289B2 JP 6743289 B2 JP6743289 B2 JP 6743289B2 JP 2019510919 A JP2019510919 A JP 2019510919A JP 2019510919 A JP2019510919 A JP 2019510919A JP 6743289 B2 JP6743289 B2 JP 6743289B2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 384
- 229910052763 palladium Inorganic materials 0.000 title claims description 167
- 239000004065 semiconductor Substances 0.000 title claims description 112
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims description 71
- 229910002601 GaN Inorganic materials 0.000 title claims description 68
- 238000000151 deposition Methods 0.000 title claims description 50
- 238000000034 method Methods 0.000 claims description 98
- 238000007747 plating Methods 0.000 claims description 88
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- 239000003638 chemical reducing agent Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 43
- 230000008021 deposition Effects 0.000 claims description 39
- 150000002500 ions Chemical class 0.000 claims description 36
- -1 halogen ions Chemical class 0.000 claims description 32
- 230000002378 acidificating effect Effects 0.000 claims description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000001603 reducing effect Effects 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 229910001432 tin ion Inorganic materials 0.000 claims description 8
- 230000000536 complexating effect Effects 0.000 claims description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 description 47
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 26
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 20
- 125000004429 atom Chemical group 0.000 description 19
- 150000002148 esters Chemical class 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 14
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 13
- 230000004913 activation Effects 0.000 description 13
- 235000019253 formic acid Nutrition 0.000 description 13
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 239000010931 gold Substances 0.000 description 11
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 7
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 150000002739 metals Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 206010070834 Sensitisation Diseases 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229940081974 saccharin Drugs 0.000 description 3
- 235000019204 saccharin Nutrition 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229940085605 saccharin sodium Drugs 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
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- 238000005476 soldering Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SJBOEHIKNDEHHO-UHFFFAOYSA-N 2-[2-aminoethyl(carboxymethyl)amino]acetic acid Chemical compound NCCN(CC(O)=O)CC(O)=O SJBOEHIKNDEHHO-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- YHZQOKUDQQISEW-UHFFFAOYSA-N 4-Cumylphenol Natural products C1=CC(C(C)C)=CC=C1C1=CC=C(O)C=C1 YHZQOKUDQQISEW-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102100036449 Early lymphoid activation gene protein Human genes 0.000 description 1
- 101100118945 Homo sapiens DIAPH2-AS1 gene Proteins 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical class OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical compound OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 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 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 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
- 150000002823 nitrates Chemical class 0.000 description 1
- RGHXWDVNBYKJQH-UHFFFAOYSA-N nitroacetic acid Chemical compound OC(=O)C[N+]([O-])=O RGHXWDVNBYKJQH-UHFFFAOYSA-N 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HTIMQENIYIHRMC-UHFFFAOYSA-N propane-1,1,2-triamine Chemical compound CC(N)C(N)N HTIMQENIYIHRMC-UHFFFAOYSA-N 0.000 description 1
- XNYADZUHUHIGRZ-UHFFFAOYSA-N propane-1,1,3-triamine Chemical compound NCCC(N)N XNYADZUHUHIGRZ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1642—Substrates other than metallic, e.g. inorganic or organic or non-conductive semiconductor
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28035—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities
- H01L21/28044—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities the conductor comprising at least another non-silicon conductive layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/1026—Compound semiconductors
- H01L2924/1032—III-V
- H01L2924/1033—Gallium nitride [GaN]
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- Manufacturing & Machinery (AREA)
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- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Chemically Coating (AREA)
- Electrodes Of Semiconductors (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Vapour Deposition (AREA)
Description
a. 0.001〜1.0モルの範囲の濃度のパラジウム源
b. 前記浴のpHが2未満であるために十分な酸、および
c. ホルムアルデヒド、ギ酸、次リン酸およびトリメトキシホウ化水素からなる群から選択される少なくとも1つの化合物から本質的になる還元剤
を含み、前記還元剤が濃度範囲0.001〜2.0モルで存在することを特徴とする、前記方法」を開示している。好ましくは、有機添加剤が追加的にめっき浴中に含まれ、それは好ましくはサッカリンである。めっきは半導体表面、例えばヒ化ガリウム上でも得られる。
・ 前記半導体の活性化されていない表面上に直接的に、つまり無電解堆積前に活性化されていない表面の追加的な活性化を行わずに、パラジウムを堆積し、
・ 速く且つ信頼性があり、
・ 適切な表面粗さをもたらし、且つ
・ 同時に窒化ガリウム上のパラジウムの選択的堆積を可能にする、
前記方法を提供することであった。
(i) 活性化されていない表面を有する、ドープされたまたはノンドープの窒化ガリウムを準備する段階、
(ii) 以下:
(a) Pd2+イオン
(b) Pd2+イオンを金属Pd0に還元するために適した1つ以上の還元剤、
(c) 式(I)および(II)の化合物
R1、R2、R3、R4、R5、R6、R7およびR8は独立してH、アルキル、アリール、ヘテロアリール、NH2、SO3HまたはOHであり、且つ
R9は独立してH、アルキル、アリールまたはヘテロアリールである]
からなる群から選択される1つ以上の化合物
を含む、水性酸性パラジウムめっき浴を準備する段階、
(iii) 前記半導体と前記めっき浴とを接触させて、半導体の活性化されていない表面上に金属パラジウムまたはパラジウム合金を、めっき浴の温度範囲70℃〜99℃で、無電解で堆積させる段階
をこの順で含む、前記方法によって解決される。
且つ、
・ 半導体表面が、段階(iii)の前に、Pd2+イオンを金属Pd0に還元するために適した1つ以上の還元剤と接触せず、好ましくは、段階(iii)の前に、グリオキシル酸およびその塩、ヒドラジン、ヒドロキシルアミン、ギ酸およびその塩、ホルムアルデヒド、トリメチルアミンボラン、トリメトキシホウ化水素、次亜リン酸(ホスフィン酸とも称する)およびその塩(つまり、ハイポホスフィットまたはホスフィネート)、亜リン酸およびその塩(つまり、ホスフィット)および次リン酸およびその塩(つまり、ハイポホスフェート)からなる群から選択される1つ以上の還元剤と接触しない、本発明による(上記で記載された、好ましくは、好ましいとして記載された)方法がより好ましい。
且つ、
・ 半導体表面が、段階(iii)の前に、Pd2+イオンを金属Pd0に還元するために適した1つ以上の還元剤と接触しない、
本発明による(上記で記載された、好ましくは、好ましいとして記載された)方法が最も好ましい。
・ 活性化されていない表面を、好ましくは酸、塩基、酸化剤、ハロゲンイオンおよび有機溶剤からなる群から選択される1つ以上の成分を含む洗浄溶液で洗浄する段階
を含む、本発明による(上記で記載された、好ましくは、好ましいとして記載された)方法が好ましい。
(d) アミンからなる群から選択される、
好ましくは第一級アミンおよび第二級アミンからなる群から選択される、
より好ましくはエチレンジアミン、1,3−ジアミノプロパン、1,2−ビス(3−アミノプロピルアミノ)エタン、2−ジエチルアミノエチルアミン、ジエチレントリアミン、ジエチレントリアミン五酢酸、ニトロ酢酸、N−(2−ヒドロキシエチル)エチレンジアミン、エチレンジアミン−N,N−二酢酸、2−(ジメチルアミノ)エチルアミン、1,2−ジアミノプロピルアミン、1,3−ジアミノプロピルアミン、3−(メチルアミノ)プロピルアミン、3−(ジメチルアミノ)プロピルアミン、3−(ジエチルアミノ)プロピルアミン、ビス−(3−アミノプロピル)アミン、1,2−ビス−(3−アミノプロピル)アルキルアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミンおよびペンタエチレンヘキサミンからなる群から選択される、
1つ以上の錯化化合物を含有する、本発明の(上記で記載された、好ましくは、好ましいとして記載された)方法が好ましい。
(e) 1つ以上の脂肪族アルデヒド
および/または
(f) 1つ以上の置換されていない、また置換されたフェノール
を含む、本発明の(上記で記載された、好ましくは、好ましいとして記載された)方法が好ましい。
(iv) 段階(iii)の後に得られる無電解で堆積された金属パラジウム/パラジウム合金上に、追加的な金属層または金属合金層を、好ましくは無電解堆積によって堆積する段階
を含む、本発明の(上記で記載された、好ましくは、好ましいとして記載された)方法が好ましい。
(iv) 段階(iii)の後に得られる無電解で堆積された金属パラジウム/パラジウム合金(好ましくは金属パラジウム)上に、1つ以上の追加的な金属層または金属合金層(好ましくは金属層)を、無電解堆積する段階
を含む、本発明の(上記で記載された、好ましくは、好ましいとして記載された)方法が好ましい。
(a) Pd2+イオン、
(b) Pd2+イオンを金属Pd0に還元するために適した1つ以上の還元剤、
(c) 式(I)および(II)の化合物からなる群から選択される1つ以上の化合物
R1、R2、R3、R4、R5、R6、R7およびR8は独立してH、アルキル、アリール、ヘテロアリール、NH2、SO3HまたはOHであり、且つ
R9は独立してH、アルキル、アリールまたはヘテロアリールである]
を含む水性酸性パラジウムめっき浴(好ましくは本発明の方法について定義されためっき浴)を、ドープされたまたはノンドープの窒化ガリウム半導体の活性化されていない表面上に直接的且つ無電解で、金属パラジウムまたはパラジウム合金を、好ましくは本発明の(上記で記載された、好ましくは、好ましいとして記載された)方法において堆積するために用いる使用にも関する。本発明の方法に関する特徴(例えばアルキル、アリール等の意味)は、めっき浴の使用にも同様に適用される。
・ 前記パラジウムおよびパラジウム合金が湿式化学法により堆積され、好ましくは無電解で堆積され、且つ
・ 前記界面はスズイオン、スズ原子またはスズ含有化合物を含有せず、好ましくは活性化金属イオン、活性化金属原子または活性化金属含有化合物を含有しない、
前記半導体にも関する。
第1の段階において、活性化されていない表面を有する4つのノンドープの窒化ガリウム(GaN)半導体(Siウェハ上に施与)を準備した(基本試料1〜4)。その表面は、活性化金属イオン/原子、例えばスズイオンと接触されないか、またはそれを含まなかった。
各々の基本試料について、活性化されていない表面を、酸および湿潤剤(Xenolyte Cleaner D、Atotechの製品)を含み且つ約40℃の温度を有する洗浄溶液で洗浄した。各々の試料を前記洗浄溶液中に5分間浸漬することによって洗浄を行った。その後、各々の試料を脱イオン水で濯いだ。その結果、洗浄された試料1〜4が得られた。
各々、pH値5.8を有し、且つパラジウムイオン(0.6mmol/L〜20mmol/Lの範囲内の濃度)、パラジウムイオン用還元剤としてのギ酸ナトリウム(10mmol/L〜70mmol/Lの範囲内の濃度)、パラジウムイオンの錯化化合物としてのエチレンジアミン(15mmol/L〜85mmol/L)の範囲内の濃度、および(c)の化合物としてのサッカリンナトリウム水和物を含む、種々の水性酸性パラジウムめっき浴を調製して準備した。各々のめっき浴中でのサッカリンナトリウム水和物の総量に関するさらなる詳細は以下の表1を参照のこと。
次の段階において、4つ全ての洗浄された試料を、300秒間、それぞれの水性酸性パラジウムめっき浴と接触させた。めっき浴の条件に関するさらなる詳細は以下の表1を参照のこと。
段階(iii)の後、各々半導体表面上のパラジウムの存在、および堆積されたパラジウムの層厚を、光学顕微鏡および蛍光X線(XRF、Fischer、Fischerscope(登録商標)X−Ray XDV(登録商標)11)によって調査した。結果を以下の表1に示す。
** 半導体と水性酸性パラジウムめっき浴との接触時間[秒]
# 光学顕微鏡およびXRFによって測定された段階(iii)の後のパラジウムの層厚。
Claims (14)
- 窒化ガリウム半導体の活性化されていない表面上にパラジウムを直接的に堆積する方法であって、以下の段階:
(i) 活性化されていない表面を有する、ドープされたまたはノンドープの窒化ガリウム半導体を準備する段階、
(ii) 以下:
(a) Pd2+イオン
(b) Pd2+イオンを金属Pd0に還元するために適した1つ以上の還元剤、
(c) 式(I)および(II)の化合物
R1、R2、R3、R4、R5、R6、R7およびR8は独立してH、アルキル、アリール、ヘテロアリール、NH2、SO3HまたはOHであり、且つ
R9は独立してH、アルキル、アリールまたはヘテロアリールである]
からなる群から選択される1つ以上の化合物
を含む、水性酸性パラジウムめっき浴を準備する段階、
(iii) 前記半導体と前記めっき浴とを接触させて、半導体の活性化されていない表面上に金属パラジウムまたはパラジウム合金を、めっき浴の温度範囲70℃〜99℃で、無電解で堆積させる段階
をこの順で含む、前記方法。 - 前記半導体の表面が、段階(iii)の前または段階(iii)が行われる際に、Sn2+イオンと接触しないか、またはSn 2+ イオンを含まない、請求項1に記載の方法。
- 段階(iii)の前に追加的な段階:
・ 前記活性化されていない表面を、酸、塩基、酸化剤、ハロゲンイオンおよび有機溶剤からなる群から選択される1つ以上の成分を含む洗浄溶液で洗浄する段階
を含む、請求項1または2に記載の方法。 - 前記酸性パラジウムめっき浴のpHが、4.0〜6.5の範囲である、請求項1から3までのいずれか1項に記載の方法。
- (c)が、式(I)の1つ以上の化合物である、請求項1から4までのいずれか1項に記載の方法。
- 前記パラジウムめっき浴が追加的に、
(d) アミンからなる群から選択される、1つ以上の錯化化合物を含有する、請求項1から5までのいずれか1項に記載の方法。 - 段階(iii)において、前記半導体と前記めっき浴とを、10〜1200秒の間、接触させる、請求項1から6までのいずれか1項に記載の方法。
- 段階(iii)における前記めっき浴の温度が、70℃〜95℃の範囲である、請求項1から7までのいずれか1項に記載の方法。
- 堆積されたパラジウムおよびパラジウム合金が、10nm〜1000nmの範囲の合計の層厚を有する、請求項1から8までのいずれか1項に記載の方法。
- 前記金属パラジウムまたはパラジウム合金が前記活性化されていない表面上に選択的に堆積されて、パラジウムのパターンまたはパラジウム合金のパターンが半導体表面上に得られる、請求項1から9までのいずれか1項に記載の方法。
- 段階(iii)の後に、追加的な段階:
(iv) 段階(iii)の後に得られる無電解で堆積された金属パラジウム/パラジウム合金上に、追加的な金属層または金属合金層を堆積する段階
を含む、請求項1から10までのいずれか1項に記載の方法。 - パラジウムまたはパラジウム合金で被覆された、ドープされたまたはノンドープの窒化ガリウム半導体の製造方法であって、パラジウムまたはパラジウム合金被覆物と、前記ドープされたまたはノンドープの窒化ガリウム半導体との間に界面を有し、
・ 前記パラジウムおよびパラジウム合金が請求項1から11までのいずれか1項に定義された方法により堆積され、且つ、
・ 前記界面はスズイオン、スズ原子またはスズ含有化合物を含有しない、
前記半導体の製造方法。 - 前記堆積されたパラジウムおよびパラジウム合金が、10nm〜1000nmの範囲の合計の層厚を有する、請求項13に記載の方法。
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US4424241A (en) | 1982-09-27 | 1984-01-03 | Bell Telephone Laboratories, Incorporated | Electroless palladium process |
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