JP2011149082A - 酸化物蒸着材と蒸着薄膜並びに太陽電池 - Google Patents
酸化物蒸着材と蒸着薄膜並びに太陽電池 Download PDFInfo
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- JP2011149082A JP2011149082A JP2010013313A JP2010013313A JP2011149082A JP 2011149082 A JP2011149082 A JP 2011149082A JP 2010013313 A JP2010013313 A JP 2010013313A JP 2010013313 A JP2010013313 A JP 2010013313A JP 2011149082 A JP2011149082 A JP 2011149082A
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- sintered body
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
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- 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
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- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- H—ELECTRICITY
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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Abstract
【解決手段】この蒸着用酸化物タブレットは、酸化インジウムを主成分としセリウムを含み焼結後の表面研削加工がされていない焼結体により構成されており、焼結体表面から5μmの深さまでの表面層におけるセリウム含有量をCe/In原子数比(CompS)とし、焼結体全体におけるセリウム含有量の平均値をCe/In原子数比(CompA)とした場合、CompS/CompA=0.9〜1.1であることを特徴とする。また、蒸着薄膜は本発明の蒸着用酸化物タブレットを用いて成膜されていることを特徴とし、太陽電池は上記蒸着薄膜を電極に用いたことを特徴とする。
【選択図】 図1
Description
酸化インジウムを主成分とし、かつ、セリウムを含むと共に、焼結後の表面研削加工がされていない焼結体により構成された酸化物蒸着材において、
焼結体表面から5μmの深さまでの表面層におけるセリウム含有量をCe/In原子数比(CompS)とし、焼結体全体におけるセリウム含有量の平均値をCe/In原子数比(CompA)とした場合、
CompS/CompA=0.9〜1.1であることを特徴とする。
請求項1に記載の発明に係る酸化物蒸着材において、
上記焼結体全体におけるセリウム含有量の平均値Ce/In原子数比(CompA)が0.001〜0.538であることを特徴とし、
請求項3に係る発明は、
請求項1または2に記載の発明に係る酸化物蒸着材において、
上記焼結体が円柱形状を有することを特徴とするものである。
酸化インジウムを主成分とし、かつ、セリウムを含む蒸着薄膜において、
請求項1〜3のいずれか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、かつ、成膜された薄膜中におけるセリウム含有量の平均値がCe/In原子数比で0.001〜0.538であることを特徴とし、
請求項5に係る発明は、
請求項4に記載の発明に係る蒸着薄膜において、
成膜された薄膜中におけるセリウム含有量の平均値がCe/In原子数比で0.004〜0.056であり、かつ、比抵抗が3.5×10-4Ωcm以下である導電性の透明結晶膜により構成されることを特徴とし、
請求項6に係る発明は、
請求項5に記載の発明に係る蒸着薄膜において、
ホール移動度が80cm2/V・s以上、キャリア濃度が3.3×1020cm-3以下である導電性の透明結晶膜により構成されることを特徴とし、
請求項7に係る発明は、
請求項4〜6のいずれかに記載の発明に係る蒸着薄膜において、
波長800〜1200nmにおける薄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4〜7のいずれかに記載の蒸着薄膜を電極として用いていることを特徴とし、
請求項9に係る発明は、
請求項4に記載の発明に係る蒸着薄膜において、
成膜された薄膜中におけるセリウム含有量の平均値がCe/In原子数比で0.090〜0.538であり、かつ、波長550nmにおける屈折率が2.15以上である高屈折率性の透明膜により構成されることを特徴とするものである。
焼結体表面から5μmの深さまでの表面層におけるセリウム含有量をCe/In原子数比(CompS)とし、焼結体全体におけるセリウム含有量の平均値をCe/In原子数比(CompA)とした場合、CompS/CompA=0.9〜1.1であることから、焼結体表面の組成が内部と略同一であるため、焼成後に研削加工を行わなくとも蒸着材としてそのまま使用することができる。
本発明の酸化物蒸着材(蒸着用酸化物タブレット)は、酸化インジウムを主成分としかつセリウムを含むと共に焼結後の表面研削加工がされていない焼結体により構成されており、焼結体表面から5μmの深さまでの表面層におけるセリウム含有量をCe/In原子数比(CompS)とし、焼結体全体におけるセリウム含有量の平均値をCe/In原子数比(CompA)とした場合、CompS/CompA=0.9〜1.1であることを特徴とし、かつ、上述したように焼成後に焼結体表面を研削加工せずに製造されることを最大の特徴としている。
次に、本発明に係る蒸着薄膜は、上述した本発明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酸化インジウムを主成分としかつセリウムを含む薄膜で構成される。
本発明に係る太陽電池は、上述した蒸着薄膜(以下、透明導電膜と称する)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て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)蒸着薄膜(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の「雰囲気調整用パウダー」を使用しなかった以外は実施例1と同じ条件で比較例1に係る酸化物蒸着材(蒸着用酸化物タブレット)を製造し、かつ、実施例1と同様の評価を行なうと共に、比較例1に係る酸化物蒸着材(蒸着用酸化物タブレット)を用いて実施例1と同様の蒸着薄膜(透明導電膜)を成膜しかつ同様の評価を行なった。
成形体の焼成中に酸素を導入しなかった以外は実施例1と同じ条件で比較例2に係る酸化物蒸着材(蒸着用酸化物タブレット)を製造し、かつ、実施例1と同様の評価をすると共に、比較例2に係る酸化物蒸着材(蒸着用酸化物タブレット)を用いて実施例1と同様の蒸着薄膜(透明導電膜)を成膜しかつ同様の評価を行なった。
次に、特開2005−290458号公報(特許文献4)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。
原料であるIn2O3粉末とCeO2粉末を調合する際、Ce/Inの原子数比を0.001(実施例2)、0.002(実施例3)、0.004(実施例4)、0.051(実施例5)、0.061(実施例6)、0.110(実施例7)となるような割合で調合した以外は、実施例1と同じ条件で焼結体(蒸着用酸化物タブレット)を作製した。
In2O3粉末とCeO2粉末を調合する際にCe/Inの原子数比を0.346となるような割合で調合し、焼結温度を1350℃で2時間とした以外は、実施例1と同一条件で焼結体(蒸着用酸化物タブレット)を作製した。得られた焼結体(酸化物蒸着材)の体積と重量を測定して密度を算出したところ5.2〜5.4g/cm3であった。
実施例8の「雰囲気調整用パウダー」を使用しなかった以外は実施例8と同じ条件で比較例4に係る酸化物蒸着材(蒸着用酸化物タブレット)を製造し、かつ、実施例8と同様の評価を行なうと共に、比較例4に係る酸化物蒸着材(蒸着用酸化物タブレット)を用いて実施例8と同様の蒸着薄膜を成膜しかつ同様の評価を行なった。
成形体の焼成中に酸素を導入しなかった以外は実施例8と同じ条件で比較例5に係る酸化物蒸着材(蒸着用酸化物タブレット)を製造し、かつ、実施例8と同様の評価をすると共に、比較例5に係る酸化物蒸着材(蒸着用酸化物タブレット)を用いて実施例8と同様の蒸着薄膜を成膜しかつ同様の評価を行なった。
次に、比較例3と同様、特開2005−290458号公報(特許文献4)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。
原料であるIn2O3粉末とCeO2粉末を調合する際、Ce/Inの原子数比を0.090(実施例9)、0.142(実施例10)、0.538(実施例11)となるような割合で調合した以外は、実施例8と同じ条件で焼結体(蒸着用酸化物タブレット)を作製した。
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 (9)
- 酸化インジウムを主成分とし、かつ、セリウムを含むと共に、焼結後の表面研削加工がされていない焼結体により構成された酸化物蒸着材において、
焼結体表面から5μmの深さまでの表面層におけるセリウム含有量をCe/In原子数比(CompS)とし、焼結体全体におけるセリウム含有量の平均値をCe/In原子数比(CompA)とした場合、
CompS/CompA=0.9〜1.1であることを特徴とする酸化物蒸着材。 - 上記焼結体全体におけるセリウム含有量の平均値Ce/In原子数比(CompA)が0.001〜0.538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。
- 上記焼結体が円柱形状を有することを特徴とする請求項1または2に記載の酸化物蒸着材。
- 酸化インジウムを主成分とし、かつ、セリウムを含む蒸着薄膜において、
請求項1〜3のいずれか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、かつ、成膜された薄膜中におけるセリウム含有量の平均値がCe/In原子数比で0.001〜0.538であることを特徴とする蒸着薄膜。 - 成膜された薄膜中におけるセリウム含有量の平均値がCe/In原子数比で0.004〜0.056であり、かつ、比抵抗が3.5×10-4Ωcm以下である導電性の透明結晶膜により構成されることを特徴とする請求項4に記載の蒸着薄膜。
- ホール移動度が80cm2/V・s以上、キャリア濃度が3.3×1020cm-3以下である導電性の透明結晶膜により構成されることを特徴とする請求項5に記載の蒸着薄膜。
- 波長800〜1200nmにおける薄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4〜6のいずれかに記載の蒸着薄膜。
- 請求項4〜7のいずれかに記載の蒸着薄膜を電極として用いていることを特徴とする太陽電池。
- 成膜された薄膜中におけるセリウム含有量の平均値がCe/In原子数比で0.090〜0.538であり、かつ、波長550nmにおける屈折率が2.15以上である高屈折率性の透明膜により構成されることを特徴とする請求項4に記載の蒸着薄膜。
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WO2014150235A1 (en) * | 2013-03-15 | 2014-09-25 | The Trustees Of Dartmouth College | Multifunctional nanostructured metal-rich metal oxides |
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