JP5762552B2 - 光電変換装置とその製造方法 - Google Patents
光電変換装置とその製造方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 188
- 239000001257 hydrogen Substances 0.000 claims description 188
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 144
- 239000004065 semiconductor Substances 0.000 claims description 106
- 239000000758 substrate Substances 0.000 claims description 79
- 150000002431 hydrogen Chemical class 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 42
- 238000009792 diffusion process Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- 230000001629 suppression Effects 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 238000004544 sputter deposition Methods 0.000 claims description 19
- 239000004020 conductor Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910003437 indium oxide Inorganic materials 0.000 claims description 9
- 239000000969 carrier Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000010408 film Substances 0.000 description 157
- 229910021417 amorphous silicon Inorganic materials 0.000 description 73
- 229910021419 crystalline silicon Inorganic materials 0.000 description 29
- 239000013078 crystal Substances 0.000 description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 25
- 230000003287 optical effect Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011787 zinc oxide Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229910006404 SnO 2 Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 7
- 229910010271 silicon carbide Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910017875 a-SiN Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000313 electron-beam-induced deposition Methods 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000009751 slip forming Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- -1 ITO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
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- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
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Description
実施例1では、実質的に水素を含有しない透明導電膜から成る水素拡散抑制領域141が存在する場合の光電変換セルについて述べる。
第1導電型単結晶半導体基板11として、約1Ω・cmの抵抗率と約200μmの厚みとを有するとともに、(100)面を有するn型c−Si基板を使用する。n型c−Si基板を洗浄した後、アルカリ溶液を用いるエッチングによって、n型c−Si基板の表面に数μmから数十μmの高さを有するピラミッド状凹凸を形成する。ついで、このn型c−Si基板11a上を真空チャンバへ導入し、200℃で加熱を行って基板表面に付着した水分を除去した後、真空チャンバ内に水素ガスを導入し、プラズマ放電を行って基板表面のクリーニングを行う。その後、基板温度を約150℃とし、SiH4ガスおよびH2ガスを真空チャンバ内に導入して、RFプラズマCVD法によって、約5nmの厚みを有するi型a−Si:H層を形成する。続いて、SiH4ガス、H2ガスおよびB2H6ガスを導入して、約5nmの厚みを有する第2導電型非晶質水素含有半導体層13としてのp型a−Si:H層を形成する。
作製された光電変換セルについて、第1集電極15側から擬似太陽光をソーラシュミレータで照射し電流−電圧特性を測定し、変換効率(η)、短絡電流密度(Jsc)、開放端電圧(Voc)およびフィルファクタ(曲線因子、FF)を求める。
実施例1で作製した光電変換セルのセル特性を評価した結果、図3に示されるように、変換効率は21.5%、短絡電流密度は38.3mA/cm2、開放端電圧は0.71V、フィルファクタは0.79である。
比較例1では、水素拡散抑制領域141が存在しない場合の光電変換セルについて述べる。
比較例1の光電変換セルは、実施例1の光電変換セルと比較して、水素拡散抑制領域141が存在しないという点のみが異なる。つまり、比較例1の光電変換セルでは、p型a−Si:H層上には、水素拡散抑制領域を形成することなく、水素含有領域142として、約80nmの膜厚と約2.5at%の水素を有するIn2O3:H膜を形成する。なお、実施例1の光電変換セルの作製条件におけるIn2O3膜とIn2O3:H膜の作製条件以外は全て同一の条件を用いて作製される。また、評価方法についても実施例1と同一の条件で行われる。
比較例1で作製した光電変換セルのセル特性を評価した結果、図3に示されるように、変換効率(η)は18.9%、短絡電流密度(Jsc)は37.5mA/cm2、開放端電圧(Voc)は0.68V、フィルファクタ(FF)は0.74である。
比較例2では、n型c−Si基板11aの第1の面側の透明導電膜層としてITO膜を用いた従来型の光電変換セルについて述べる。
比較例2の光電変換セルは、比較例1の光電変換セルで作製したIn2O3:H膜の代わりにITO膜を形成する点だけが異なる。つまり、比較例2の光電変換セルでは、p型a−Si:H層上に、約200℃の基板温度で、In2O3に10wt%のSnO2を添加したターゲットを用いたスパッタ法によって約80nmの膜厚を有する水素含有領域142としてのITO膜を形成する。なお、比較例1の光電変換セルの作製条件におけるIn2O3:H膜の作製条件以外は全て同一の条件を用いて作製される。また、評価方法についても実施例1と同一の条件で行われる。
比較例2で作製した光電変換セルのセル特性を評価した結果、図3に示されるように、変換効率(η)は20.6%、短絡電流密度(Jsc)は36.8mA/cm2、開放端電圧(Voc)は0.70V、フィルファクタ(FF)は0.80である。
11 第1導電型単結晶半導体基板
11a n型c−Si基板
12 i型非晶質水素含有半導体層
12a,161a i型a−Si:H層
13 第2導電型非晶質水素含有半導体層
13a p型a−Si:H層
14 第1透明導電層
15,18 集電極
16 BSF層
17 第2透明導電層
17a ZnO膜
141 水素拡散抑制領域
141a In2O3膜
142 水素含有領域
142a In2O3:H膜
161 i型非晶質半導体層
162 第1導電型非晶質半導体層
162a n型a−Si:H層
Claims (3)
- 受光により光生成キャリアを生成するn型半導体基板の第一の面に、実質的に真性な半導体層と、p型半導体層と、透明導電層と、が順に積層される光電変換装置において、
前記透明導電層は、水素を含有する透明導電性材料からなる水素含有領域と、前記水素含有領域よりも前記p型半導体層側に存在し、実質的に水素を含有しない透明導電性材料からなる水素拡散抑制領域とを有し、
前記水素拡散抑制領域は、前記p型半導体層側での水素含有量が前記水素含有領域側での水素含有量に比して少なくなるような水素濃度分布を有し、
前記水素含有領域と前記水素拡散抑制領域は、酸化インジウム、または0.1wt%以上1wt%以下の酸化錫を含有する酸化インジウムを主体とする膜によって構成されることを特徴とする光電変換装置。 - 受光により光生成キャリアを生成するn型半導体基板上に、実質的に真性な半導体層と、p型半導体層と、透明導電層と、を順に積層させて光電変換装置を製造する光電変換装置の製造方法において、
前記透明導電層の製造工程では、前記p型半導体層上に、水素ガスを添加することなく第1透明導電性材料層を形成した後、前記第1透明導電性材料層上に、水素ガスを添加しながら第2透明導電性材料層を形成し、
前記第1透明導電性材料層と前記第2透明導電性材料層は、酸化インジウムを主成分とする膜であることを特徴とする光電変換装置の製造方法。 - 前記透明導電層の製造工程では、同一のターゲットを用いるスパッタ法を用い、成膜時の導入ガスの種類と流量比とを変更することによって、実質的に水素を含有しない前記第1透明導電性材料層と、水素を含有する前記第2透明導電性材料層と、を連続的に堆積して形成することを特徴とする請求項2に記載の光電変換装置の製造方法。
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WO2014033908A1 (ja) * | 2012-08-31 | 2014-03-06 | 三洋電機株式会社 | 太陽電池の製造方法 |
WO2015159805A1 (ja) * | 2014-04-15 | 2015-10-22 | 旭硝子株式会社 | 積層体、導電性積層体、および電子機器 |
US11942561B2 (en) * | 2014-05-27 | 2024-03-26 | Maxeon Solar Pte. Ltd. | Shingled solar cell module |
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CN107681020A (zh) * | 2017-09-26 | 2018-02-09 | 南开大学 | 一种提高平面硅异质结太阳电池长波长光响应的方法 |
CN108321240A (zh) * | 2017-12-21 | 2018-07-24 | 君泰创新(北京)科技有限公司 | 一种太阳能异质结电池及其制备方法 |
CN109075218A (zh) * | 2017-12-21 | 2018-12-21 | 君泰创新(北京)科技有限公司 | 一种太阳能异质结电池及其制备方法 |
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CN114342090A (zh) | 2019-08-30 | 2022-04-12 | 京浜乐梦金属科技株式会社 | 积层结构体及积层结构体的制造方法 |
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