JP7485991B2 - 半導体光電極および半導体光電極の製造方法 - Google Patents
半導体光電極および半導体光電極の製造方法 Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims description 153
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010409 thin film Substances 0.000 claims description 76
- 239000000758 substrate Substances 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 26
- 238000006479 redox reaction Methods 0.000 claims description 15
- 239000011241 protective layer Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 description 31
- 238000006722 reduction reaction Methods 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 21
- 229910002601 GaN Inorganic materials 0.000 description 19
- 239000000463 material Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910052594 sapphire Inorganic materials 0.000 description 10
- 239000010980 sapphire Substances 0.000 description 10
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001312 dry etching Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 perfluoro side chains Chemical group 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
還元反応:4H++4e-→2H2
図1は、本実施形態の半導体光電極の構成の一例を示す断面図である。半導体光電極1は、水溶液中にて、光照射することにより触媒機能を発揮して酸化還元反応を生じる。同図に示す半導体光電極1は、絶縁性または導電性の基板11、基板11の表面上に配置され、基板11の反対側の面に凹凸構造が設けられた半導体薄膜12、半導体薄膜12の凹凸構造に沿って配置された触媒層13、および基板11の裏面並びに基板11と半導体薄膜12の側面を覆うように形成された保護層14を備える。
図2を参照し、半導体光電極の製造方法について説明する。
基板の材料および凹凸構造のサイズを変えた実施例1-4の半導体光電極を作製し、後述の酸化還元反応試験を行った。以下、実施例1-4の半導体光電極について説明する。
実施例1の半導体光電極は、半導体光電極の表面積が試料面積の約1.5倍となるように半導体薄膜を凹凸加工したものである。サファイア基板を用いた。
実施例2の半導体光電極は、半導体光電極の表面積が試料面積の約1.5倍となるように半導体薄膜を凹凸加工したものである。実施例1とはn-GaN基板を用いた点で異なる。
実施例3の半導体光電極は、半導体光電極の表面積が試料面積の約2倍となるように半導体薄膜を凹凸加工したものである。
実施例4の半導体光電極は、半導体光電極の表面積が試料面積の約2.5倍となるように半導体薄膜を凹凸加工したものである。
比較対象例1の半導体光電極は、半導体薄膜を凹凸加工せずに、半導体光電極の表面が平坦である。試料面積と表面積はいずれも1cm2である。サファイア基板を用いた。
比較対象例2の半導体光電極は、半導体薄膜を凹凸加工せずに、半導体光電極の表面が平坦である。試料面積と表面積はいずれも1cm2である。n-GaN基板を用いた。
比較対象例3の半導体光電極は、半導体薄膜を凹凸加工せずに、半導体光電極の表面が平坦である。試料面積と表面積はいずれも1.5cm2である。表面積を実施例1と同じにした。サファイア基板を用いた。
比較対象例4の半導体光電極は、半導体薄膜を凹凸加工せずに、半導体光電極の表面が平坦である。試料面積と表面積はいずれも2cm2である。表面積を実施例3と同じにした。サファイア基板を用いた。
比較対象例5の半導体光電極は、半導体薄膜を凹凸加工せずに、半導体光電極の表面が平坦である。試料面積と表面積はいずれも2.5cm2である。表面積を実施例4と同じにした。サファイア基板を用いた。
実施例1-4と比較対象例1-5について図5の装置を用いて酸化還元反応試験を行った。
実施例1-4および比較対象例1-5における、光照射時間に対する酸素・水素ガスの生成量を表1に示す。各ガスの生成量は、半導体光電極の表面積で規格化して示した。
11…基板
12…半導体薄膜
13…触媒層
14…保護層
Claims (7)
- 光照射により触媒機能を発揮して酸化還元反応を生じる半導体光電極であって、
導電性または絶縁性の基板と、
前記基板の表面上に配置され、凹凸構造を備える半導体薄膜と、
前記半導体薄膜の凹凸構造に沿って配置された触媒層と、
前記基板の裏面および前記基板と前記半導体薄膜の側面を完全に覆うように配置された絶縁性の保護層を有する
半導体光電極。 - 請求項1に記載の半導体光電極であって、
前記触媒層は前記半導体薄膜の表面の全体を覆って配置された
半導体光電極。 - 請求項1に記載の半導体光電極であって、
前記触媒層は前記半導体薄膜の表面の一部を覆って配置された
半導体光電極。 - 請求項1ないし3のいずれかに記載の半導体光電極であって、
前記半導体薄膜はn型半導体である
半導体光電極。 - 請求項1ないし4のいずれかに記載の半導体光電極であって、
凹凸構造は格子状である
半導体光電極。 - 光照射により触媒機能を発揮して酸化還元反応を生じる半導体光電極の製造方法であって、
導電性または絶縁性の基板の表面上に半導体薄膜を形成する工程と、
エッチング加工により前記半導体薄膜の表面に凹凸構造を形成する工程と、
前記半導体薄膜の表面の凹凸構造に沿って触媒層を形成する工程と、
前記半導体薄膜と前記触媒層を熱処理する工程と、
前記基板の裏面および前記基板と前記半導体薄膜の側面を完全に覆うように絶縁性の保護層を形成する工程を有する
半導体光電極の製造方法。 - 請求項6に記載の半導体光電極の製造方法であって、
凹凸構造は格子状である
半導体光電極の製造方法。
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