JP5785931B2 - 薄膜光起電力材料へ制御可能なナトリウムを配送する方法および装置 - Google Patents
薄膜光起電力材料へ制御可能なナトリウムを配送する方法および装置 Download PDFInfo
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- JP5785931B2 JP5785931B2 JP2012504879A JP2012504879A JP5785931B2 JP 5785931 B2 JP5785931 B2 JP 5785931B2 JP 2012504879 A JP2012504879 A JP 2012504879A JP 2012504879 A JP2012504879 A JP 2012504879A JP 5785931 B2 JP5785931 B2 JP 5785931B2
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- transition metal
- layer
- metal layer
- sputtering
- type semiconductor
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- 230000003667 anti-reflective effect Effects 0.000 description 3
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- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 2
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- 238000000137 annealing Methods 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
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- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
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- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01L31/0256—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 characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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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
- H01L31/036—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 characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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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
- H01L31/036—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 characterised by their crystalline structure or particular orientation of the crystalline planes
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Description
本願は、その全体が本願明細書において参照により援用されている、2009年4月13日に出願された米国特許出願第12/385,572号(特許文献1)の利益を主張する。
透明上部電極とも呼ばれる第2の電極400はn形半導体層302の上にさらに堆積される。透明上部電極400は複数の透明導電層、例えば、これらに限定されるわけではないが、随意の抵抗性酸化アルミニウム亜鉛(RAZO)層401の上に位置する、酸化インジウムスズ(ITO)、酸化亜鉛(ZnO)または酸化アルミニウム亜鉛(AZO)層402のうちの1種類以上を含むことができる。もちろん、透明上部電極400は任意の他の適切な材料、例えば、ドープZnOまたはSnOを含むことができる。
場合によっては、1つ以上の反射防止(AR)膜(図示せず)を透明上部電極400の上に堆積させて電池における光吸収を最適化し、ならびに/または電流収集グリッド線を上部導電性酸化物の上に堆積させることができる。
好ましくは、層202を少なくとも1つのアルカリ含有ターゲットからスパッタリングし、その一方で層203は実質的にアルカリを含まない1つ以上のターゲットからスパッタリングする。例えば、層203は1つ以上のモリブデンターゲットから酸素含有環境中で反応性スパッタリングすることができる。
最後に、ウェブ100を排出モジュール21bに送り、巻き取りスプール31bに巻き取るか、または切断装置29を用いて太陽電池へとスライスする。
実施例I
図5に示される構造を有する非限定的な実施例を以下のステップによって得る。第1に、モリブデン障壁層201を基板の上に堆積させる。第2に、第1の遷移金属層202をモリブデン障壁層201の上に複合モリブデンおよびモリブデン酸ナトリウムターゲットからのスパッタリングによって堆積させる。最後に、CIGS層301を第1の遷移金属層202の上に堆積させ、図5aに示される構造を得る。
図5bは膜スタックを通してのCu、In、Ga、Se、OおよびMoのAES深さプロファイルを示す。CIGS層301および第1の遷移金属層202(ナトリウム−酸素含有モリブデン層)の界面はCu/In/Ga/SeおよびMoスペクトルによって明瞭に決定することができる。同様に、第1の遷移金属層202およびMo層201の界面は酸素のAESスペクトルによって明瞭に決定することができる。この非限定的な例の第1の遷移層202は約20原子%の酸素を含み、図5bに示されるように、約500nm(1.9ミクロンから2.4ミクロンまでの深さ)の厚みを有する。もちろん、第1の遷移層202は、スパッタリングターゲットおよび/またはスパッタリングパラメータを変化させることにより、異なる組成および/または厚みを有することができる。
図6aに示される非限定的な実施例を以下のステップによって得る。第1に、モリブデン障壁層201を基板100の上にモリブデンターゲットからのDCスパッタリングによって約0.5〜1.5mTorrの低圧下で堆積させる。第2に、第1の遷移金属層202をモリブデン障壁層201の上に複合モリブデンおよびモリブデン酸ナトリウムターゲットのアレイからのDCスパッタリングによって約3〜6mTorrの中程度スパッタリング圧の下で堆積させる。最後に、別のモリブデン層211を第1の遷移金属層202の上に堆積させ、図6aに示される構造を得る。したがって、この非限定的な例において、第1の遷移金属層202はナトリウムおよび酸素が意図的にドープされているモリブデン層であり、その一方でモリブデン層201および211はそうではない。
図6bに示されるように、SIMS深さプロファイルは、第1の遷移金属層202内では、ナトリウム濃度プロファイルが酸素濃度プロファイルと明確に相関することを示す。特定の理論に結びつけられることを望むものではないが、酸化モリブデンによる格子歪みの程度がより高いとき、より多量のナトリウム不純物が組み込まれ得るものと信じられる。
障壁層201および211は、層201および211のより高密度のモリブデンが有効なナトリウム拡散障壁として機能するため、含まれるナトリウムが実質的により少ない。
この非限定的な実施例において、第1の遷移金属層202を鋼ウェブ基板100の上にスパッタ堆積させた後、CIGS層301を第1の遷移金属層202の上に堆積させ、CdS層302をCIGS層301の上に堆積させることにより、図7aに示される構造を有するサンプルa〜cを得る。サンプルa〜cの第1の遷移金属層202は、それぞれ、3つの複合モリブデンおよびモリブデン酸ナトリウムターゲットからの6kW、9.5kWおよび13kWのスパッタリング出力でのスパッタリングによって堆積させる。
図7bに示される、サンプルa〜cの膜スタックを通してのSIMS深さプロファイルは、得られるサンプルCのCIGS層中のナトリウム濃度(約9×1020原子/cm3 のピーク濃度を有する)がサンプルbのものよりも高く、ひいてはサンプルaのもの(約3×1020原子/cm3 のピーク濃度を有する)よりも高いことを示す。これは第1の遷移金属層202の厚みを増加させることで第1の遷移金属層202からのナトリウム拡散を強化できることを示す。
この実施例は、本発明の非限定的な例としての、ナトリウムドープCIGS層301を含む太陽電池Aの効率を実質的にナトリウムを含まないCIGS層301を含む従来の太陽電池Bのものと比較する。
図8は太陽電池AおよびBの電流−電圧プロットを示す。実線はナトリウムドープCIGS層301を含む太陽電池AのI−V曲線を指し、その一方で破線は実質的にナトリウムを含まないCIGS層301を含む太陽電池BのI−V曲線を指す。図8に示されるように、太陽電池Aは11.3%の効率(η)を有し、これは従来の太陽電池Bのもの(5.4%)より著しく高い。
この実施例において、太陽電池の第1の遷移金属層202を、様々なスパッタリング出力の下、2つのスパッタリングシステム、システムAおよびシステムBで堆積させる。図9のy軸は太陽電池の効率を指し、その一方でx軸は用いられるスパッタリング出力を指す。図9は、2つの異なるCIGS組成(線Aおよび線B)が、Na含有率を最適化して効率が最大化されるように異なるスパッタリング出力の下でスパッタ堆積された2つのナトリウム含有モリブデン層の上に形成されることを示す。この実験は、組成物AのCIGS吸収層を堆積させながら、ナトリウム含有モリブデンターゲットのスパッタリング出力を調整することによって行った(この場合、より高いCu含有率、より高いセレン対金属比およびこの組成物に対して独立して最適化された基板温度)。組成物Bの第2のCIGS吸収層は、異なるCIGターゲット、より低い全Cu含有率、より低いセレン対金属比およびこの組成物に対して独立して最適化された基板温度の組み合わせを用いて堆積させた。
一貫して、得られる太陽電池の効率はスパッタリング出力が増加するときに最初は増加し、最適スパッタリング出力に到達した後に低下する。特定の理論に結びつけられることを望むものではないが、最適スパッタリング出力を用いるときに最適ナトリウム濃度が得られるものと信じられる。
図9に示される結果は、最適スパッタリング出力がスパッタリングシステム特異的であり得ることも示す。所望であれば、特定のスパッタリングパラメータを変化させることができる。
Claims (12)
- 太陽電池であって、
基板と、
前記基板の上に位置する第1の電極であって、一方の側から他方の側へ、アルカリ拡散遮断層と、第1の遷移金属層と、第2の遷移金属層とを含むスタックである第1の電極と、を備え、
前記アルカリ拡散遮断層が、Mo、W、Ta、V、Ti、Nb、Zr、Cr、TiN、ZrN、TaN、VN、V2 Nまたはそれらの組み合わせからなる群より選択され、
前記第1の遷移金属層が、遷移金属と、アルカリ元素またはアルカリ化合物と、前記第1の遷移金属層の多結晶格子を歪ませ、かつ酸素、MoO 2 およびMoO 3 からなる群より選択される格子歪曲元素または格子歪曲化合物とを含み、
前記格子歪曲化合物または格子歪曲元素が、前記第1の遷移金属層の多結晶格子を歪ませるために前記第1の遷移金属層のものとは異なる結晶構造を有し、
前記第2の遷移金属層が、前記アルカリ拡散障壁層よりも大きい空隙率を有し、かつ前記第1の遷移金属層からp形半導体吸収層へのアルカリ拡散を許容し、
前記アルカリ拡散遮断層が、前記第2の遷移金属層よりも大きい密度およびより厚い厚みを有し、かつ前記第1の遷移金属層から前記基板へのアルカリ拡散を実質的に減少させるか、またはそれを妨げ、
前記第1の遷移金属層が、モリブデンを含み、
前記アルカリ元素またはアルカリ化合物が、ナトリウムを含み、
前記太陽電池が、
前記第1の電極の上に位置する少なくとも1つのp形半導体吸収層であって、セレン化銅インジウム(CIS)系合金材料を含むp形半導体吸収層と、
前記p形半導体吸収層の上に位置するn形半導体層と、
前記n形半導体層の上に位置する第2の電極と、をさらに備える太陽電池。 - 請求項1記載の太陽電池において、
前記p形半導体吸収層が、前記第1の遷移金属層から拡散した0.005〜1.5原子%のナトリウムを含み、
前記第1の遷移金属層が、少なくとも59原子%のモリブデン、5〜40原子%の酸素および0.01〜1.5原子%のナトリウムを含む太陽電池。 - 請求項1,2のいずれか記載の太陽電池において、
前記アルカリ拡散障壁層が、100〜400nmの厚みを有し、
前記第1の遷移金属層が、100〜500nmの厚みを有し、
前記第2の遷移金属層が、50〜200nmの厚みを有し、
前記アルカリ拡散障壁層が、実質的に酸素を含まないモリブデン層を含み、
前記第1の遷移金属層が、少なくとも59原子%のモリブデン、5〜40原子%の酸素および0.01〜1.5原子%のナトリウムを含み、
前記第2の遷移金属層が、少なくとも95原子%のモリブデンおよび1〜5原子%の酸素を含み、
前記アルカリ拡散障壁層、第1の遷移金属層および第2の遷移金属層が、各々1〜20の副層を含む太陽電池。 - 請求項1記載の太陽電池において、
前記アルカリ拡散障壁層が、実質的に酸素を含まず、
前記第1の遷移金属層および/または第2の遷移金属層が、酸素を含む太陽電池。 - 太陽電池を製造する方法であって、
基板を提供するステップと、
アルカリ拡散障壁層と、第1の遷移金属層と、第2の遷移金属層とを順次に堆積することによって前記基板上に第1の電極を形成するステップと、を含み、
前記アルカリ拡散遮断層が、Mo、W、Ta、V、Ti、Nb、Zr、Cr、TiN、ZrN、TaN、VN、V2 Nまたはそれらの組み合わせからなる群より選択され、
前記第1の遷移金属層が、遷移金属と、アルカリ元素またはアルカリ化合物と、前記第1の遷移金属層の多結晶格子を歪ませ、かつ酸素、MoO 2 およびMoO 3 からなる群より選択される格子歪曲元素または格子歪曲化合物とを含み、
前記格子歪曲化合物または格子歪曲元素が、前記第1の遷移金属層の多結晶格子を歪ませるために前記第1の遷移金属層のものとは異なる結晶構造を有し、
前記第2の遷移金属層が、前記アルカリ拡散障壁層よりも大きい空隙率を有し、かつ前記第1の遷移金属層からp形半導体吸収層へのアルカリ拡散を許容し、
前記アルカリ拡散遮断層が、前記第2の遷移金属層よりも大きい密度およびより厚い厚みを有し、かつ前記第1の遷移金属層から前記基板へのアルカリ拡散を実質的に減少させるか、またはそれを妨げ、
前記第1の遷移金属層が、モリブデンを含み、
前記アルカリ元素またはアルカリ化合物が、ナトリウムを含み、
前記方法が、
前記第1の電極の上に少なくとも1つのp形半導体吸収層を堆積させるステップであって、前記p形半導体吸収層がセレン化銅インジウム(CIS)系合金材料を含むステップと、
前記p形半導体吸収層の上にn形半導体層を堆積させるステップと、
前記n形半導体層の上に第2の電極を堆積させるステップと、をさらに含み、
前記p形半導体吸収層を堆積させるステップの間、アルカリ拡散が前記第2の遷移金属層を介して前記第1の遷移金属層から前記p形半導体吸収層に生じる方法。 - 請求項5記載の方法において、
前記p形半導体吸収層が、前記第1の遷移金属層から拡散する、0.005〜1.5原子%のナトリウムを含み、
前記第1の遷移金属層が、少なくとも59原子%のモリブデン、5〜40原子%の酸素および0.01〜1.5原子%のナトリウムを含む方法。 - 請求項5記載の方法において、
前記アルカリ拡散障壁層と、前記第1の遷移金属層と、前記第2の遷移金属層とを順次に堆積することが、同じスパッタリング装置内で前記アルカリ拡散障壁層、前記第1および第2の遷移金属層をスパッタリングすることを含む方法。 - 請求項7記載の方法において、
前記第1の遷移金属層をスパッタリングすることが、
モリブデン酸ナトリウムを含むターゲットから前記第1の遷移金属層をスパッタリングするか、または
互いに異なる組成を有する少なくとも1対のスパッタリングターゲットから前記第1の遷移金属層をスパッタリングするかのいずれかを含み、
前記少なくとも1対のスパッタリングターゲットが、(i)第1のモリブデンターゲットおよび第2のモリブデン酸ナトリウムもしくは酸化ナトリウムターゲット、(ii)第1の酸化モリブデンターゲットおよび第2のセレン化ナトリウム、フッ化ナトリウム、セレン化ナトリウムもしくは硫酸ナトリウムターゲット、または(iii)酸素含有反応性スパッタリングシステム内の第1のモリブデンターゲットおよび第2のナトリウムターゲットから選択され、
前記少なくとも1対のターゲットがマグネトロンスパッタリングシステムの同じ真空チャンバ内に位置する方法。 - 請求項7記載の方法において、
前記アルカリ拡散障壁層をスパッタリングすることが、マグネトロンスパッタリングシステムの第1の真空チャンバ内の第1のスパッタリング環境下で生じ、
前記第2の遷移金属層をスパッタリングすることが、前記第1の真空チャンバとは異なる、前記マグネトロンスパッタリングシステムの第2の真空チャンバ内の第2のスパッタリング環境下で生じ、
前記第2のスパッタリング環境が、アルゴン圧、酸素圧または窒素圧のうちの少なくとも1つで前記第1のスパッタリング環境とは異なり、
前記アルカリ拡散障壁層をスパッタリングすることが、前記アルカリ拡散障壁層が圧縮応力の状態にあるように、前記第2の遷移金属層をスパッタリングすることよりも低い圧力で生じ、
前記アルカリ拡散障壁層をスパッタリングすることが、酸素非含有雰囲気中で生じ、
前記第2の遷移金属層をスパッタリングすることが、酸素含有雰囲気中で生じる方法。 - 請求項5記載の方法において、
前記アルカリ拡散障壁層と、前記第1の遷移金属層と、前記第2の遷移金属層とを順次に堆積することを独立して制御して、
(i)前記少なくとも1つのp形半導体吸収層に拡散するナトリウムの量を制御することと、
(ii)可変ナトリウム含有率を前記第1の遷移金属層の厚みに応じて発生させることとのうちの少なくとも1つを行うステップをさらに含む方法。 - 請求項5記載の方法において、
前記基板が、金属性ウェブ基板を含み、
前記第1の電極を形成するステップ、前記少なくとも1つのp形半導体吸収層を堆積させるステップ、前記n形半導体層を堆積させるステップ、および前記第2の電極を堆積させるステップが、複数の独立して分離されて真空を破壊することなしに接続された処理モジュールの対応する処理モジュール内で、前記金属性ウェブ基板が複数の独立して分離されて接続された前記処理モジュールを通過する間に投入モジュールから排出モジュールまで連続的に伸長するように前記金属性ウェブ基板を前記投入モジュールから前記排出モジュールまで複数の独立して分離されて接続された前記処理モジュールを通過させながら、前記第1の電極の1つ以上の導電性層、前記p形半導体吸収層、前記n形半導体層および前記第2の電極の1つ以上の導電性層を前記基板の上にスパッタリングすることを含む方法。 - 請求項5記載の方法において、
前記アルカリ拡散障壁層が、実質的に酸素を含まず、
前記第1の遷移金属層および/または第2の遷移金属層が、酸素を含む方法。
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KR20120018136A (ko) | 2012-02-29 |
US8313976B2 (en) | 2012-11-20 |
US8134069B2 (en) | 2012-03-13 |
EP2419940A4 (en) | 2017-12-20 |
WO2010120631A2 (en) | 2010-10-21 |
JP2012523709A (ja) | 2012-10-04 |
US20120003785A1 (en) | 2012-01-05 |
WO2010120631A3 (en) | 2011-02-24 |
KR101670708B1 (ko) | 2016-11-10 |
US20100258191A1 (en) | 2010-10-14 |
EP2419940B1 (en) | 2019-06-19 |
EP2419940A2 (en) | 2012-02-22 |
MY149756A (en) | 2013-10-14 |
SG175978A1 (en) | 2011-12-29 |
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