JP6685896B2 - 太陽電池及びその製造方法 - Google Patents
太陽電池及びその製造方法 Download PDFInfo
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- H01L31/00—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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
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- H01L31/00—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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/075—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
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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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- H01L31/0256—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
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- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/541—CuInSe2 material PV cells
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Description
このようなCIGS太陽電池は、一般的には、ガラスを基板として用いるが、ガラス基板の他にも、高分子(例:ポリイミド)または金属薄膜(例:ステンレス鋼、Ti)基板の上に蒸着して、フレキシブル太陽電池の形態に製造することもでき、特に、最近、薄膜太陽電池の中で最も高い、19.5%のエネルギー変換効率が具現されるようになったことで、シリコン結晶質太陽電池を代替し得る低価型の高効率薄膜型太陽電池であって、商業化可能性が非常に高い太陽電池として知られている。
また、前記内蔵電界を増加させるための電場は、太陽電池の逆方向破壊電圧以内で印加されてもよい。
本発明の実施例1では、CIGS薄膜太陽電池を次のような過程を通じて製造した。
一例として、原子層蒸着法を用い、Ti化合物が混合された前駆体を光吸収層に吸着させるステップと、前記Ti化合物が混合さえた前駆体の吸着層を酸化させて酸化物に形成するステップとを通じて電気分極層を形成することができる。
本発明の比較例では、実施例1と同一の構造を有するCIGS薄膜太陽電池を形成したが、電気分極層を除いた他は、実施例1と同一に製造した。
本発明の実施例1においては、真空蒸着方法を適用して太陽電池を製造したが、非真空蒸着方法である、化学的液相成長(chemical bath deposition;CBD)、スピンコーティング(spin coating)、ドクターブレードコーティング(doctor−blade coating)、ドロップキャスティング(drop−casting)、スクリーンプリンティング(screen printing)及びインクジェットプリンティング(inkjet printing)などのウェットコーティング方法を用いて形成することができ、本発明の実施例2にかかる太陽電池は、ウェットコーティング方法を適用して電気分極層を形成したものを含む。
本発明の実施例1及び実施例2においては、太陽電池内に電気分極層を形成する場合の例を記述したが、太陽電池の外部において電気分極層を直列に連結して適用することもできる。すなわち、基板−下部電極−光吸収層(またはp−n接合半導体層)−上部電極からなる一般的な太陽電池構造において、基板と下部電極との間または上部電極の上側、或いはこれらを含めて両方に電気分極層が電極に直列に連結されるように形成すると、電気分極層の自発分極を用いるか、電気分極層に電場を印加して形成される残留分極を用いて、太陽電池で収集される電子と正孔に対して順方向の電界を印加する効果が得られるようになる。
110、210、310:基板
120、220、320:下部電極
130、230、330:光吸収層
140、240、340:電気分極層
150、250、350:上部電極
Claims (28)
- 相互対向するように配置される2つの電極の間に光吸収層が形成される太陽電池において、前記電極と光吸収層との間に、内蔵電界を形成する電気分極物質を含む電気分極層が形成されており、
前記電気分極層の層厚は、10nm〜100nmであり、
前記電気分極層はバッファ層の役割も遂行し、
前記2つの電極に隣接して2つ以上の電気分極層が形成される太陽電池。 - 前記電気分極物質は、自発分極特性を有する請求項1に記載の太陽電池。
- 前記電気分極物質は、残留分極特性を有する請求項1に記載の太陽電池。
- 前記電気分極物質は、強誘電体またはこれを含む複合物質である請求項1に記載の太陽電池。
- 前記電気分極物質は、反強誘電体またはこれを含む複合物質である請求項1に記載の太陽電池。
- 前記電気分極物質は、ペロブスカイト結晶構造を有する物質である請求項1に記載の太陽電池。
- 前記電気分極物質は、トンネリング誘電体またはキャパシタの特性を有する請求項1に記載の太陽電池。
- 前記電気分極物質は、2.54eV以下のバンドギャップエネルギーを有する物質を含む請求項1に記載の太陽電池。
- 前記光吸収層は、M1、M2、X(ここで、M1は、Cu、Ag、またはこれらの組み合わせ、M2は、In、Ga、Al、Zn、Ge、Sn、またはこれらの組み合わせ、Xは、Se、S、またはこれらの組み合わせである)、及びこれらの組み合わせからなる化合物を含む請求項1に記載の太陽電池。
- 前記強誘電体は、BaTiO3(BTO)、PbZrTiO3(PZT)、SrTiO3、CaTiO3、CuTiO3、KTaO3、KNbO3、NaNbO3、LiNbO3、ZrHfO2、BiFeO3、及びトルマリンの中から選択された1種以上を含む請求項4に記載の太陽電池。
- 前記反強誘電体は、ZrPbO3、NH4H2PO4、(NH4)2H3IO6、Cu(HCOO)2・4H2Oの中から選択された1種以上を含む請求項5に記載の太陽電池。
- 前記ペロブスカイト結晶構造を有する物質は、CCTO(CaCu3Ti4O12)、(Mg,Fe)SiO3、CaSiO3の中から選択された1種以上を含む請求項6に記載の太陽電池。
- 前記光吸収層は、p型半導体、n型半導体、i型(真性)半導体のいずれか1つ以上を含む請求項1に記載の太陽電池。
- 相互対向するように配置される2つの電極の間に光吸収層が形成される太陽電池の製造方法であって、前記電極と光吸収層の間または前記光吸収層に、内蔵電界を形成する電気分極物質からなる電気分極層を10nm〜100nmの層厚で形成し、
前記電気分極層は、
前記光吸収層の一面に金属酸化物層を形成するステップと、
前記光吸収層と金属酸化物層の間で化学反応を起こすステップとを含む工程を通じて形成され、
前記金属酸化物層は、Tiを含む化合物またはTiとCuを含む化合物であり、
前記電気分極層はバッファ層の役割も遂行する太陽電池の製造方法。 - 前記電気分極層の両端に電場を印加して内蔵電界を増加させる請求項14に記載の太陽電池の製造方法。
- 前記内蔵電界を増加させるための電場は、太陽電池の逆方向破壊電圧以内で印加する請求項15に記載の太陽電池の製造方法。
- 前記電気分極層を、物理気相蒸着(PVD)、化学気相蒸着(CVD)、原子層蒸着(ALD)、またはウェットコーティング方法により形成する請求項14に記載の太陽電池の製造方法。
- 前記電気分極層を原子層蒸着で形成する場合、Ca化合物前駆物質とCu化合物前駆物質のいずれか一方または両方と、Ti化合物前駆物質とを前記光吸収層に吸着させるステップと、前記前駆物質の吸着層を酸化反応によって酸化物に形成するステップとを含む過程を通じて形成される請求項17に記載の太陽電池の製造方法。
- 前記Ca化合物前駆物質は、Ca(Thd)2(Tetraen)及びCa3(thd)6の中から選択された1つ以上である請求項18に記載の太陽電池の製造方法。
- 前記Cu化合物前駆物質は、Cu(hfac)(tmvs)[=C10H13CuF6O2Si]、Cu(hfac)2[=Cu(CF3COCHCOCF3)2]、(hfac)Cu(DMB)[=Cu(CF3COCHCOCF3)[CH2CHC(CH3)3]]、Cu(ethylketoiminate)2[=Cu[(CH3COCHCN(CH2CH3)CH3)]2]の中から選択された1つ以上である請求項18に記載の太陽電池の製造方法。
- 前記Ti化合物前駆物質は、Ti(O-iPr)2(DPM)2[=Ti(C3H7O)2(C11H19O2)2]、TiO(thd)2[=TiO(C11H20O2)2]の中から選択された1つ以上である請求項18に記載の太陽電池の製造方法。
- 前記金属酸化物層は、物理気相蒸着(PVD)、化学気相蒸着(CVD)、または原子層蒸着(ALD)により形成する請求項14に記載の太陽電池の製造方法。
- 前記金属酸化物層は、Tiを含む前駆物質を用いて、原子層蒸着により形成することを特徴とする請求項14に記載の太陽電池の製造方法。
- 前記Tiを含む前駆物質は、テトラキス(ジメチルアミノ)チタン、テトラキス(ジエチルアミド)チタン、テトラキス(エチルメチルアミド)チタン、テトライソプロポキシド、またはこれらの組み合わせである請求項23に記載の太陽電池の製造方法。
- 前記ウェットコーティング方法は、化学的液相成長、スピンコーティング、ドクターブレードコーティング、ドロップキャスティング、スクリーンプリンティング及びインクジェットプリンティングの中から選択された1つ以上である請求項17に記載の太陽電池の製造方法。
- 前記ウェットコーティング方法は、
金属酸化物が溶解された溶液を準備するステップと、
前記溶液をコーティングするステップと、
熱処理を行うステップと
を含む請求項17に記載の太陽電池の製造方法。 - 前記金属酸化物は、Tiを含む化合物である請求項26に記載の太陽電池の製造方法。
- 前記金属酸化物は、TiとCuを含む化合物である請求項26に記載の太陽電池の製造方法。
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