JP2013531366A - カルコゲン化物系光起電力電池の製造方法 - Google Patents
カルコゲン化物系光起電力電池の製造方法 Download PDFInfo
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- JP2013531366A JP2013531366A JP2013508239A JP2013508239A JP2013531366A JP 2013531366 A JP2013531366 A JP 2013531366A JP 2013508239 A JP2013508239 A JP 2013508239A JP 2013508239 A JP2013508239 A JP 2013508239A JP 2013531366 A JP2013531366 A JP 2013531366A
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- Prior art keywords
- absorber
- layer
- cadmium
- less
- transparent conductive
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- 150000004770 chalcogenides Chemical class 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000006096 absorbing agent Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 28
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 238000004544 sputter deposition Methods 0.000 claims description 18
- 229910052738 indium Inorganic materials 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011669 selenium Substances 0.000 claims description 13
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 9
- 229910052711 selenium Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims 2
- 210000000416 exudates and transudate Anatomy 0.000 claims 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract description 28
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 20
- -1 copper chalcogenide Chemical class 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 53
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- 238000000151 deposition Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 150000004763 sulfides Chemical class 0.000 description 6
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000004771 selenides Chemical class 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WGMIDHKXVYYZKG-UHFFFAOYSA-N aluminum copper indium(3+) selenium(2-) Chemical compound [Al+3].[Cu++].[Se--].[Se--].[Se--].[Se--].[In+3] WGMIDHKXVYYZKG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- YNLHHZNOLUDEKQ-UHFFFAOYSA-N copper;selanylidenegallium Chemical compound [Cu].[Se]=[Ga] YNLHHZNOLUDEKQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRQCEIJCBUOBRF-UHFFFAOYSA-N [Al+3].[S--].[S--].[S--].[S--].[Cu++].[In+3] Chemical compound [Al+3].[S--].[S--].[S--].[S--].[Cu++].[In+3] NRQCEIJCBUOBRF-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000750 constant-initial-state spectroscopy Methods 0.000 description 1
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- FFWOKTFYGVYKIR-UHFFFAOYSA-N physcion Chemical compound C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1O FFWOKTFYGVYKIR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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 potential barriers 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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- 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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- 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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Abstract
【選択図】なし
Description
基板の上にカルコゲン化物系吸収体層を形成する工程、
0.08〜0.12mbar(0.06〜0.09トールまたは8〜12Pa)の作動圧力で不活性雰囲気でスパッタすることによって、吸収体の上にカドミウムおよび硫黄を含むバッファー層を形成する工程
を含む方法である。
CuaInbGacAldSewSxTeyNaz (A)
式中、「a」が1と定義されるならば、
「(b+c+d)/a」=1.0〜2.5、好ましくは1.0〜1.65であり、
「b」は0〜2、好ましくは0.8〜1.3であり、
「c」は0〜0.5、好ましくは0.05〜0.35であり、
「d」は0〜0.5、好ましくは0.05〜0.35であり、好ましくはd=0であり、
「(w+x+y)」は2〜3、好ましくは2〜2.8であり、
「w」は0以上、好ましくは少なくとも1、そしてより好ましくは少なくとも2〜3であり、
「x」は0〜3、好ましくは0〜0.5であり、
「y」は0〜3、好ましくは0〜0.5であり、
「z」は0〜0.5、好ましくは0.005〜0.02である。
光起電力電池を以下のように作製する。ステンレス鋼基板を用意する。基板の上にスパッタによってニオブおよびモリブデンの裏面電気接点を形成する。約550℃に保持されたステンレス鋼基板の上にエフュージョン源から銅、インジウム、ガリウムおよびセレンを同時に80分間蒸発させる1段蒸発法によってセレン化銅インジウムガリウム吸収体を形成する。この方法は、ほぼCu(In0.8Ga0.2)Se2の化学量論の吸収体を生じる。
硫化カドミウム層は、表1に示されるように圧力を変えて、アルゴンの存在下、160ワットでCdSターゲット(純度99.9%以上)から高周波(rf)スパッタされる。基板の温度は35℃以下に維持され、ターゲットから基板までの距離は約90mmである。この層のおよその厚さは、表1に記載したとおりである。
硫化カドミウム層の上に、i−ZnOおよびAlドープZnOを高周波スパッタによって析出させた。AlドープZnOの上に集電グリッドを析出させる。
本質的に上記の手順によって作られた電池を、照明下で電流電圧特性の測定によって効率について試験する。表に示されるように、効率は約0.1ミリバール(10Pa)でピークに達した。
本質的に実施例1の方法によって作製された光起電力電池の断面は、上記の明細書の中に記述されるような集束イオンビームによって調製される。上記参照。
図2は、セレン化銅インジウムガリウム系吸収体の上に、上記のようにアルゴン雰囲気中で99.9%の純度の硫化カドミウムターゲットから硫化カドミウムをスパッタして作られた電池のEDSによる原子分率を示す。図2a)は、0.1ミリバールでスパッタすることによって本発明の方法で作られた電池の原子分率を示す。図2b)は、0.002ミリバールでスパッタすることによって作られた比較の電池の原子分率を示す。これは、より高い圧力で形成された試料においては相互拡散が約10nmの範囲に限定されることを示す。
銅、インジウムおよびガリウム元素を含むスパッタされた層の(セレン元素を使用した)セレン化によって、そして表2に示されるようにCdSスパッタリング中に圧力を変えて作られた吸収体を使用して、実施例1を繰り返す。吸収体形成プロセスは以下のように進行する。ニオブおよびモリブデンをあらかじめ析出させたステンレス鋼基板の上に、銅、インジウムおよびガリウムを、各元素のターゲットまたは銅、インジウムおよびガリウムの合金から作られたターゲットのいずれかからスパッタすることによって析出させる。100℃以下に基板温度を維持しながら、被覆された基板の上にセレン元素を蒸着させる。その後、この被覆された基板を加熱し、銅、インジウム、ガリウム前駆体をセレン化させる。
Claims (16)
- 基板の上にカルコゲン化物系吸収体層を形成する工程、
0.08〜0.12mbarの作動圧力でスパッタすることによって、吸収体の上にカドミウムおよび硫黄を含むバッファー層を形成する工程
を含む方法。 - 雰囲気が不活性である、請求項1に記載の方法。
- スパッタがカドミウムおよび硫黄のターゲットからである、請求項1または2に記載の方法。
- 吸収体層とバッファー層の間に厚さ10nm未満の界面が形成され、前記界面は、一方の側では、電池の断面をエネルギー分散型X線分光法走査においてカドミウムの原子分率が0.05を超える点によって境界が定められ、第二の側では、インジウムおよびセレンの原子分率が0.05未満になる点によって境界が定められる、請求項1〜3のいずれか1項に記載の方法。
- 界面がさらに第二の側で0.10未満の銅の原子分率によって境界が定められる、請求項4に記載の方法。
- バッファー層の上に透明伝導層を形成する工程、所望により透明伝導層とバッファー層の間に窓層を形成する工程、および透明伝導層の上に電気的接続グリッドを形成する工程をさらに含み、透明伝導層の上にバリヤー層を設ける工程を含む請求項1〜5のいずれか1項に記載の方法。
- 透明伝導層および/またはグリッドの上にバリヤー層を設ける工程を含む請求項6に記載の方法。
- 請求項1〜7の方法によって形成された光起電力電池。
- 裏面電極、裏面電極に接するカルコゲン化物系吸収体、吸収体の上にカドミウムおよび硫黄を含むバッファー層、吸収体層と反対側のバッファー層の面に位置する透明伝導層、透明伝導層の上の集電体を含む光起電力電池であって、該電池が吸収体とバッファー層の間に界面を有し、該界面は、一方の側では、電池の断面をエネルギー分散型分光法走査においてカドミウムの原子分率が0.05を超える点によって境界が定められ、第二の側では、インジウムとセレンの原子分率が0.05未満になる点によって境界が定められ、そして該界面は10nm未満の厚さを有する、電池。
- 平均粒径が20nm未満である、請求項9に記載の電池。
- バッファーが本質的にカドミウム硫黄、銅および酸素からなり、カドミウムおよび硫黄の原子分率が少なくとも0.30である、請求項9〜10のいずれか1項に記載の電池。
- 裏面電極、裏面電極に接するカルコゲン化物系吸収体、吸収体の上にカドミウムおよび硫黄を含むバッファー層、吸収体層と反対側のバッファー層の面に位置する透明伝導層、透明伝導層の上の集電体を含む光起電力電池であって、バッファーは本質的にカドミウム硫黄、酸素、および所望により銅からなり、カドミウムおよび硫黄の原子分率は少なくとも0.30であり、酸素の原子分率は少なくとも0.20であり、そして銅の原子分率は0.10未満である、電池。
- バッファー層の厚さが30nm未満である、請求項9〜12のいずれか1項に記載の電池。
- 電池からのカドミウム浸出物が1mg/L未満である、請求項9〜13のいずれか1項に記載の電池。
- 裏面電極、裏面電極に接するカルコゲン化物系吸収体、吸収体の上のカドミウムおよび硫黄を含むバッファー層、吸収体層と反対側のバッファー層の面に位置する透明伝導層、透明伝導層の上の集電体を含む光起電力電池であって、バッファーがカドミウムを含み、そしてバッファー層の厚さが30nm未満である、電池。
- 電池からのカドミウム浸出物が1mg/L未満である、請求項15に記載の電池。
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US9159850B2 (en) * | 2012-04-25 | 2015-10-13 | Guardian Industries Corp. | Back contact having selenium blocking layer for photovoltaic devices such as copper—indium-diselenide solar cells |
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US11131018B2 (en) * | 2018-08-14 | 2021-09-28 | Viavi Solutions Inc. | Coating material sputtered in presence of argon-helium based coating |
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