JP6927646B2 - 半導体反応器及び半導体反応器用金属母材のコーティング層形成方法 - Google Patents
半導体反応器及び半導体反応器用金属母材のコーティング層形成方法 Download PDFInfo
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- 239000011247 coating layer Substances 0.000 title claims description 119
- 229910052751 metal Inorganic materials 0.000 title claims description 75
- 239000002184 metal Substances 0.000 title claims description 75
- 239000000463 material Substances 0.000 title claims description 73
- 239000004065 semiconductor Substances 0.000 title claims description 69
- 238000000034 method Methods 0.000 title claims description 50
- 239000010949 copper Substances 0.000 claims description 70
- 229910000838 Al alloy Inorganic materials 0.000 claims description 56
- 229910052710 silicon Inorganic materials 0.000 claims description 54
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000010703 silicon Substances 0.000 claims description 51
- 229910052802 copper Inorganic materials 0.000 claims description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000011777 magnesium Substances 0.000 claims description 39
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 229910052700 potassium Inorganic materials 0.000 claims description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 21
- 239000011591 potassium Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 10
- 150000003746 yttrium Chemical class 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 6
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000003628 erosive effect Effects 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000009931 harmful effect Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910016569 AlF 3 Inorganic materials 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- -1 2 g / l NaAlO 2 Substances 0.000 description 1
- 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 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- YNAAFGQNGMFIHH-UHFFFAOYSA-N ctk8g8788 Chemical compound [S]F YNAAFGQNGMFIHH-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
(付記)
本開示は、以下の態様を含む。
<1>
半導体反応器用金属母材をNaOH及びNaAlO 2 を含むアルカリ水溶液性電解液に担持する段階と、
前記金属母材に電極を連結し、前記電極に電源を供給して、プラズマ電解酸化(PEO)法で前記金属母材上にコーティング層を形成する段階と、
を含む 半導体反応器用金属母材上のコーティング層形成方法。
<2>
前記金属母材は、アルミニウム合金を含み、
前記電解液は、イットリウム塩をさらに含み、
前記コーティング層は、内部にアルミニウム酸化膜を含み、表面部にアルミニウム酸化物及びイットリウム酸化物の複合酸化膜を含む<1>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<3>
前記複合酸化膜は、アルミニウム−イットリウム酸化物をさらに含む<2>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<4>
前記電解液は、イットリウム塩としてY(NO 3 ) 3 を含む<2>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<5>
前記コーティング層を形成する段階で、プラズマ電解酸化のために、負電圧印加時間が正電圧印加時間よりも大きな双極パルス電流を印加する<1>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<6>
前記コーティング層を形成する段階で、前記双極パルス電流の負電流密度が正電流密度よりも大きい<5>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<7>
前記コーティング層内の銅(Cu)及びケイ素(Si)の含量を低めるために、前記金属母材は、0.5重量%以下(0重量%超過)の銅(Cu)及び0.5重量%以下(0重量%超過)のケイ素(Si)を含有するアルミニウム合金を含む<1>から<6>のうち何れか一項に記載の半導体反応器用金属母材上のコーティング層形成方法。
<8>
前記コーティング層内のマグネシウム(Mg)の含量を高めるために、前記アルミニウム合金は、0.5重量%以下(0重量%超過)の銅(Cu)、0.5重量%以下(0重量%超過)のケイ素(Si)及び1.0〜50重量%のマグネシウム(Mg)を含有する<7>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<9>
前記アルミニウム合金は、0.2重量%以下(0重量%超過)の銅(Cu)、0.4重量%以下(0重量%超過)のケイ素(Si)及び2.0〜50重量%のマグネシウム(Mg)を含有し、
前記コーティング層でカリウム濃度が0.1重量%以下であり、銅濃度が0.1重量%以下であり、シリコン濃度が0.5重量%以下である<8>に記載の半導体反応器用金属母材上のコーティング層形成方法。
<10>
金属母材と、
前記金属母材上にプラズマ電解酸化(PEO)法で形成されたコーティング層と、を含み、
前記コーティング層は、前記金属母材をNaOH及びNaAlO 2 を含むアルカリ水溶液性電解液に担持した状態で前記金属母材に電極を連結し、前記電極に電源を供給して、プラズマ電解酸化(PEO)法で形成された半導体反応器。
<11>
前記金属母材は、アルミニウム合金を含み、
前記電解液は、イットリウム塩をさらに含み、
前記コーティング層は、内部にアルミニウム酸化膜を含み、表面部にアルミニウム酸化物及びイットリウム酸化物の複合酸化膜を含む<10>に記載の半導体反応器。
<12>
前記複合酸化膜は、アルミニウム−イットリウム酸化物をさらに含む<11>に記載の半導体反応器。
<13>
前記アルミニウム合金は、0.5重量%以下(0重量%超過)の銅(Cu)、0.5重量%以下(0重量%超過)のケイ素(Si)を含有し、
前記コーティング層のカリウム濃度が0.1重量%以下であり、銅濃度が0.1重量%以下であり、シリコン濃度が0.5重量%以下である結晶質α−Al 2 O 3 とγ−Al 2 O 3 とを含む<11>に記載の半導体反応器。
<14>
前記アルミニウム合金は、0.5重量%以下(0重量%超過)の銅(Cu)、0.5重量%以下(0重量%超過)のケイ素(Si)を含有し、
前記コーティング層の表面部でカリウム濃度は、0.1重量%以下であり、イットリウム酸化物の濃度は、10.0重量%以上であるAl−Y−O−rich複合酸化膜を含む<11>に記載の半導体反応器。
<15>
前記コーティング層の厚さは、20〜100μmの範囲である<11>に記載の半導体反応器。
Claims (8)
- 半導体反応器用金属母材をNaOH及びNaAlO2を含むアルカリ水溶液性電解液に担持する段階と、
前記金属母材に電極を連結し、前記電極に電源を供給して、プラズマ電解酸化(PEO)法で前記金属母材上にコーティング層を形成する段階と、
を含み、
前記アルカリ水溶液性電解液には、カリウム(K)が含まれず、
前記金属母材は、アルミニウム合金を含み、
前記電解液は、イットリウム塩をさらに含み、
前記コーティング層は、内部にアルミニウム酸化膜を含み、表面部にアルミニウム酸化物及びイットリウム酸化物の複合酸化膜を含む、
半導体反応器用金属母材上のコーティング層形成方法。 - 前記複合酸化膜は、アルミニウム−イットリウム酸化物をさらに含む請求項1に記載の半導体反応器用金属母材上のコーティング層形成方法。
- 前記電解液は、イットリウム塩としてY(NO3)3を含む請求項1に記載の半導体反応器用金属母材上のコーティング層形成方法。
- 前記コーティング層を形成する段階で、プラズマ電解酸化のために、負電圧印加時間が正電圧印加時間よりも大きな双極パルス電流を印加する請求項1に記載の半導体反応器用金属母材上のコーティング層形成方法。
- 前記コーティング層を形成する段階で、前記双極パルス電流の負電流密度が正電流密度よりも大きい請求項4に記載の半導体反応器用金属母材上のコーティング層形成方法。
- 前記コーティング層内の銅(Cu)及びケイ素(Si)の含量を低めるために、前記金属母材は、0.5重量%以下(0重量%超過)の銅(Cu)及び0.5重量%以下(0重量%超過)のケイ素(Si)を含有するアルミニウム合金を含む請求項1から請求項5のうち何れか一項に記載の半導体反応器用金属母材上のコーティング層形成方法。
- 前記コーティング層内のマグネシウム(Mg)の含量を高めるために、前記アルミニウム合金は、0.5重量%以下(0重量%超過)の銅(Cu)、0.5重量%以下(0重量%超過)のケイ素(Si)及び1.0〜50重量%のマグネシウム(Mg)を含有する請求項6に記載の半導体反応器用金属母材上のコーティング層形成方法。
- 前記アルミニウム合金は、0.2重量%以下(0重量%超過)の銅(Cu)、0.4重量%以下(0重量%超過)のケイ素(Si)及び2.0〜50重量%のマグネシウム(Mg)を含有し、
前記コーティング層でカリウム濃度が0.1重量%以下であり、銅濃度が0.1重量%以下であり、シリコン濃度が0.5重量%以下である請求項7に記載の半導体反応器用金属母材上のコーティング層形成方法。
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