JP5257372B2 - 酸化物蒸着材と透明導電膜および太陽電池 - Google Patents
酸化物蒸着材と透明導電膜および太陽電池 Download PDFInfo
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- JP5257372B2 JP5257372B2 JP2010016289A JP2010016289A JP5257372B2 JP 5257372 B2 JP5257372 B2 JP 5257372B2 JP 2010016289 A JP2010016289 A JP 2010016289A JP 2010016289 A JP2010016289 A JP 2010016289A JP 5257372 B2 JP5257372 B2 JP 5257372B2
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- oxide
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Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Description
酸化物蒸着材において、
酸化インジウムを主成分とし、セリウムを含む焼結体により構成され、かつ、セリウムの含有量がCe/In原子数比で0.001〜0.110で、CIE1976表色系におけるL*値が62〜95であることを特徴とし、
請求項2に係る発明は、
請求項1に記載の発明に係る酸化物蒸着材において、
上記セリウムの含有量がCe/In原子数比で0.004〜0.051であることを特徴とする。
請求項2に記載の発明に係る酸化物蒸着材において、
W/In原子数比でタングステンが0.001〜0.020の割合で含まれることを特徴とし、
請求項4に係る発明は、
請求項2に記載の発明に係る酸化物蒸着材において、
Mo/In原子数比でモリブデンが0.001〜0.050の割合で含まれることを特徴とする。
酸化インジウムを主成分とし、セリウムを含む透明導電膜において、
請求項1に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.001〜0.110であることを特徴とし、
請求項6に係る発明は、
請求項5に記載の発明に係る透明導電膜において、
請求項2に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.004〜0.051、比抵抗が3.5×10-4Ωcm以下であることを特徴し、
請求項7に係る発明は、
酸化インジウムを主成分とし、セリウムとタングステンを含む透明導電膜において、
請求項3に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.004〜0.051、タングステンの含有量がW/In原子数比で0.001〜0.020であり、比抵抗が3.5×10-4Ωcm以下であることを特徴とし、
請求項8に係る発明は、
酸化インジウムを主成分とし、セリウムとモリブデンを含む透明導電膜において、
請求項4に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.004〜0.051、モリブデンの含有量がMo/In原子数比で0.001〜0.050であり、比抵抗が3.5×10-4Ωcm以下であることを特徴とする。
請求項5〜8のいずれかに記載の発明に係る透明導電膜において、
キャリア濃度が3.5×1020cm-3以下、ホール移動度が80cm2/V・s以上であることを特徴とし、
請求項10に係る発明は、
請求項5〜9のいずれかに記載の発明に係る透明導電膜において、
波長800〜1200nmにおける膜自体の平均透過率が80%以上であることを特徴とする。
太陽電池において、
請求項5〜10のいずれかに記載の透明導電膜を電極として用いていることを特徴とし、
請求項12に係る発明は、
請求項11に記載の発明に係る太陽電池において、
光電変換素子として、シリコン系半導体若しくは化合物半導体を用いた薄膜系太陽電池であることを特徴とし、
請求項13に係る発明は、
請求項11に記載の発明に係る太陽電池において、
電極層を設けた非金属基板若しくは電極性を備えた金属基板上に、p型半導体の光吸収層と、n型半導体の中間層と、半導体の窓層と、透明導電膜から成る電極層が順次積層された構造を含むことを特徴とし、
請求項14に係る発明は、
請求項11に記載の発明に係る太陽電池において、
透明基板上に設けた透明導電膜から成る電極層の上に、半導体の窓層と、n型の半導体の中間層と、p型の半導体の光吸収層が順次積層された構造を含むことを特徴とし、
請求項15に係る発明は、
請求項13または14に記載の発明に係る太陽電池において、
上記光吸収層が、CuInSe2、CuInS2、CuGaSe2、CuGaS2、これらの固溶体またはCdTeから選ばれる少なくとも一つで構成されることを特徴とし、
請求項16に係る発明は、
請求項13〜15のいずれかに記載の発明に係る太陽電池において、
上記中間層が、溶液析出のCdS層または(Cd,Zn)S層で構成されることを特徴とし、
また、請求項17に係る発明は、
請求項13〜16のいずれかに記載の発明に係る太陽電池において、
上記窓層が、ZnOまたは(Zn,Mg)Oで構成されることを特徴とする。
本発明の酸化物蒸着材は、酸化インジウムを主成分とし、かつ、セリウムがCe/In原子数比で0.001〜0.110の割合で含有された組成を有する。そして、本発明の酸化物蒸着材を用いて真空蒸着法により製造された透明導電膜の組成は、酸化物蒸着材の組成に極めて近いため、製造される膜組成も、酸化インジウムを主成分としかつセリウムが0.001〜0.110の割合だけ含有する組成となる。セリウムを上記割合だけ含有させる理由としては、酸化インジウム膜の移動度を増加させることができるからである。膜組成、すなわち酸化物蒸着材組成のセリウム含有量(Ce/In原子数比)が0.001未満では、移動度増加の効果が小さくて低抵抗の膜を得ることができない。また、0.110を超えると、膜中のセリウム量が多過ぎて、電子移動の際の中性不純物散乱が大きくなってしまい、移動度が低下して低抵抗の膜が得られない。更に、より高い移動度を発揮して低抵抗の膜を得るためのより好ましいセリウムの含有量は、Ce/In原子数比で0.004〜0.051である。
酸化インジウムを主成分としかつセリウムを含む焼結体により構成され、セリウムの含有量がCe/In原子数比で0.001〜0.110で、CIE1976表色系におけるL*値が62〜95である本発明に係る酸化物蒸着材を適用し、電子ビーム蒸着法、イオンプレーティング法や高密度プラズマアシスト蒸着法等の各種真空蒸着法により、セリウムを含有する酸化インジウムの結晶膜(透明導電膜)を製造することができる。
本発明に係る太陽電池は、上述した透明導電膜を電極として用いていることを特徴とする光電変換素子である。太陽電池素子の構造は特に限定されず、p型半導体とn型半導体を積層したPN接合型、p型半導体とn型半導体の間に絶縁層(I層)を介在させたPIN接合型等が挙げられる。
酸化物蒸着材の作製
平均粒径が0.8μmのIn2O3粉末、および、平均粒径が1μmのCeO2粉末を原料粉末とし、これ等のIn2O3粉末とCeO2粉末を、Ce/Inの原子数比が0.008となるような割合で調合し、かつ、樹脂製ポットに入れ、湿式ボールミルで混合した。この際、硬質ZrO2ボールを用い、混合時間を20時間とした。
(1)透明導電膜の作製には磁場偏向型電子ビーム蒸着装置を用いた。
実施例1〜4において、焼結体酸素量調整工程における導入ガスの混合比のみを変えて酸化物焼結体を製造した。すなわち、比較例1では、O2/Ar流量比で30/70とし、比較例2では100/0とした。得られた焼結体について、密度、比抵抗、結晶粒経、組成を同様に評価したが実施例1〜4と同等であった。得られた酸化物焼結体の表面と内部の色身は同等であり、そのL*値を測定したところ表1のような値を示した。
次に、特開2005−290458号公報(特許文献3)に紹介されたスパッタターゲットの焼結体作製技術に従ってセリウムを含有する酸化インジウム焼結体を製造した。
In2O3粉末とCeO2粉末を調合する際、Ce/Inの原子数比が0.051となるような割合で調合した以外は、焼結体酸素量調整の条件も含めて実施例1〜4と全く同様の条件で実施例5〜8の酸化物焼結体(酸化物蒸着材)を作製した。
比較例1〜2において、In2O3粉末とCeO2粉末を調合する際のCe/Inの原子数比を0.051とした以外は、比較例1〜2と同様の条件で酸化物蒸着材を作製した。すなわち、焼結体酸素量調整の条件が、比較例4では、O2/Ar流量比で30/70とし、比較例5では100/0とした。得られた焼結体について、密度、比抵抗、結晶粒経、組成を同様に評価したが、実施例5〜8と同等であった。また、得られた焼結体の表面と内部の色身は同等であり、そのL*値を測定したところ、表1のような値を示した。
比較例3において、In2O3粉末とCeO2粉末を調合する際のCe/Inの原子数比を0.051とした以外は、比較例3と同様の条件で酸化物蒸着材を作製した。得られた焼結体について、密度、比抵抗、結晶粒経、組成を同様に評価したが、比較例3と同等であった。また、得られた焼結体の表面と内部の色身は同等であり、そのL*値を測定したところ表1のような値を示した。
In2O3粉末とCeO2粉末を調合する際の配合割合が、Ce/In原子数比で0.001(実施例9)、0.002(実施例10)、0.004(実施例11)、0.061(実施例12)、0.070(実施例13)、0.090(実施例14)、0.110(実施例15)となるように変化させた以外は、実施例2と同じ条件(すなわち、酸素ガス/アルゴンガス流量比が「60/40」の条件)で実施例9〜15の酸化物焼結体(酸化物蒸着材)を作製した。
In2O3粉末とCeO2粉末の他に、WO3粉末(平均粒径が1μm)を原料粉末として用いてセリウムとタングステンを含有する酸化インジウムの酸化物焼結体(酸化物蒸着材)を作製した。
In2O3粉末とCeO2粉末の他に、MoO3粉末(平均粒径が1μm)を原料粉末として用いてセリウムとモリブデンを含有する酸化インジウムの酸化物焼結体(酸化物蒸着材)を作製した。
次に、特許第3445891公報(特許文献2)に紹介されたスパッタターゲットの焼結体作製技術に従ってセリウムを含有する酸化インジウム焼結体を製造した。
次に、特開平08−104978号公報(特許文献1)に紹介されたITO酸化物蒸着材を製造して同様の評価を行った。
2 表側(受光部側)透明電極膜
3 p型アモルファスシリコン膜または水素化アモルファスシリコンカーバイド膜
4 不純物を含まないアモルファスシリコン膜
5 n型アモルファスシリコン膜
6 裏側透明電極膜(接触改善層)
7 裏側金属電極(裏面電極)
8 光吸収層
9 半導体の中間層
10 窓層
11 透明電極膜
12 ガラス基板
13 下部電極
Claims (17)
- 酸化インジウムを主成分とし、セリウムを含む焼結体により構成され、かつ、セリウムの含有量がCe/In原子数比で0.001〜0.110で、CIE1976表色系におけるL*値が62〜95であることを特徴とする酸化物蒸着材。
- 上記セリウムの含有量がCe/In原子数比で0.004〜0.051であることを特徴とする請求項1に記載の酸化物蒸着材。
- W/In原子数比でタングステンが0.001〜0.020の割合で含まれることを特徴とする請求項2に記載の酸化物蒸着材。
- Mo/In原子数比でモリブデンが0.001〜0.050の割合で含まれることを特徴とする請求項2に記載の酸化物蒸着材。
- 酸化インジウムを主成分とし、セリウムを含む透明導電膜において、
請求項1に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.001〜0.110であることを特徴とする透明導電膜。 - 請求項2に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.004〜0.051、比抵抗が3.5×10-4Ωcm以下であることを特徴とする請求項5に記載の透明導電膜。
- 酸化インジウムを主成分とし、セリウムとタングステンを含む透明導電膜において、
請求項3に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.004〜0.051、タングステンの含有量がW/In原子数比で0.001〜0.020であり、比抵抗が3.5×10-4Ωcm以下であることを特徴とする透明導電膜。 - 酸化インジウムを主成分とし、セリウムとモリブデンを含む透明導電膜において、
請求項4に記載の酸化物蒸着材を原料として用い、電子ビーム蒸着法、イオンプレーティング法若しくは高密度プラズマアシスト蒸着法により成膜された結晶性の透明導電膜で構成され、かつ、セリウムの含有量がCe/In原子数比で0.004〜0.051、モリブデンの含有量がMo/In原子数比で0.001〜0.050であり、比抵抗が3.5×10-4Ωcm以下であることを特徴とする透明導電膜。 - キャリア濃度が3.5×1020cm-3以下、ホール移動度が80cm2/V・s以上であることを特徴とする請求項5〜8のいずれかに記載の透明導電膜。
- 波長800〜1200nmにおける膜自体の平均透過率が80%以上であることを特徴とする請求項5〜9のいずれかに記載の透明導電膜。
- 請求項5〜10のいずれかに記載の透明導電膜を電極として用いていることを特徴とする太陽電池。
- 光電変換素子としてシリコン系半導体若しくは化合物半導体を用いた薄膜系太陽電池であることを特徴とする請求項11に記載の太陽電池。
- 電極層を設けた非金属基板若しくは電極性を備えた金属基板上に、p型半導体の光吸収層と、n型半導体の中間層と、半導体の窓層と、透明導電膜から成る電極層が順次積層された構造を含むことを特徴とする請求項11に記載の太陽電池。
- 透明基板上に設けた透明導電膜から成る電極層の上に、半導体の窓層と、n型の半導体の中間層と、p型の半導体の光吸収層が順次積層された構造を含むことを特徴とする請求項11に記載の太陽電池。
- 上記光吸収層が、CuInSe2、CuInS2、CuGaSe2、CuGaS2、これらの固溶体またはCdTeから選ばれる少なくとも一つで構成されることを特徴とする請求項13または14に記載の太陽電池。
- 上記中間層が、溶液析出のCdS層または(Cd,Zn)S層で構成されることを特徴とする請求項13〜15のいずれかに記載の太陽電池。
- 上記窓層が、ZnOまたは(Zn,Mg)Oで構成されることを特徴とする請求項13〜16のいずれかに記載の太陽電池。
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JP2009231549A (ja) * | 2008-03-24 | 2009-10-08 | Toyoda Gosei Co Ltd | 窒化物系半導体発光素子 |
WO2011016387A1 (ja) * | 2009-08-05 | 2011-02-10 | 住友金属鉱山株式会社 | イオンプレーティング用タブレットとその製造方法、および透明導電膜 |
JP5895144B2 (ja) * | 2009-09-17 | 2016-03-30 | パナソニックIpマネジメント株式会社 | 透明導電膜及びこれを備えた装置 |
JP5257372B2 (ja) * | 2009-11-30 | 2013-08-07 | 住友金属鉱山株式会社 | 酸化物蒸着材と透明導電膜および太陽電池 |
JP5381744B2 (ja) * | 2010-01-25 | 2014-01-08 | 住友金属鉱山株式会社 | 酸化物蒸着材と蒸着薄膜並びに太陽電池 |
KR101789347B1 (ko) * | 2010-03-19 | 2017-10-23 | 스미토모 긴조쿠 고잔 가부시키가이샤 | 투명 도전막 |
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KR20170040792A (ko) | 2017-04-13 |
KR101759700B1 (ko) | 2017-07-20 |
KR20110060828A (ko) | 2011-06-08 |
TW201129704A (en) | 2011-09-01 |
CN102102173A (zh) | 2011-06-22 |
US9099219B2 (en) | 2015-08-04 |
EP2336386A1 (en) | 2011-06-22 |
CN102102173B (zh) | 2014-11-05 |
TWI523960B (zh) | 2016-03-01 |
EP2336386B1 (en) | 2017-04-12 |
US8574464B2 (en) | 2013-11-05 |
US20110126899A1 (en) | 2011-06-02 |
US20130327395A1 (en) | 2013-12-12 |
JP2011132593A (ja) | 2011-07-07 |
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