CN101809756B - 包含镁掺杂半导体薄膜的光伏器件 - Google Patents
包含镁掺杂半导体薄膜的光伏器件 Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 132
- 239000011777 magnesium Substances 0.000 claims description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 30
- 229910052749 magnesium Inorganic materials 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910004613 CdTe Inorganic materials 0.000 claims 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 33
- 238000000151 deposition Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910017115 AlSb Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910005542 GaSb Inorganic materials 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- 229910004262 HgTe Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910000673 Indium arsenide Inorganic materials 0.000 description 3
- 229910017680 MgTe Inorganic materials 0.000 description 3
- 229910017231 MnTe Inorganic materials 0.000 description 3
- 229910007709 ZnTe Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 3
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- RNTJDJDUXWVMJY-UHFFFAOYSA-N CC(C)(OC(=O)C(=O)c1ccc(O)cc1)C1Cc2cc3ccc(=O)oc3cc2O1 Chemical compound CC(C)(OC(=O)C(=O)c1ccc(O)cc1)C1Cc2cc3ccc(=O)oc3cc2O1 RNTJDJDUXWVMJY-UHFFFAOYSA-N 0.000 description 1
- -1 CdTe Chemical compound 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
- 229910005540 GaP Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/0248—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
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
-
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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
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/0248—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
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
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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
- 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
- H01L31/073—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 comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
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Abstract
本发明公开了一种可以包含与半导体层接触的掺杂剂的光伏电池。
Description
本申请要求2008年7月24日提交的第61/083,325号美国临时专利申请的优先权,该申请通过引用包含于此。
技术领域
本发明涉及一种光伏电池。
背景技术
在光伏器件的制造过程中,将一层用为窗口层并且第二层用为吸收层而将半导体材料层应用到基板。窗口层可以允许太阳能穿透至吸收层,在吸收层光能转化为电能。一些光伏器件可以使用同样是电荷导体的透明薄膜。导电薄膜可以是诸如掺氟氧化锡、掺铝氧化锌或氧化铟锡的透明导电氧化物(TCO)。TCO可以允许光穿过基板窗口至有源光吸收材料,并且还起到欧姆接触的作用来传送光生载流子离开光吸收材料。可以在半导体层的背表面上形成背电极。背电极可以包括诸如金属银、镍、铜、铝、钛、钯或任何它们实际的组合的导电材料,以提供与半导体层的电连接。背电极可以是半导体材料。掺杂半导体层可以提高光伏器件的效率。
发明内容
通常,光伏电池可以包括透明导电层和与透明导电层接触的第一半导体层,其中,第一半导体层包含镁。在特定的情况下,基板可以是玻璃基板。在其他情况下,基板可以是金属层。
第一半导体层可以包含CdS。第一半导体层的厚度可以在大约200埃-3000埃之间。第一半导体层可以包含1%-20%的镁。在某些情况下,透明导电层可以设置在基板上方。在某些情况下,透明导电层可以设置在第一半导体层上方。在某些情况下,光伏电池还可以包括与第一半导体层接触的第二半导体层。该第二半导体层可以包含CdTe。该第二半导体层可以包含氯化镉处理的CdTe。
制造光伏电池的方法可以包括提供透明导电层以及沉积与透明导电层接触的第一半导体层的步骤,其中,第一半导体层用镁处理。可以用氯化镉来处理第二半导体层。可以在大约380℃-450℃用热来处理第二半导体层。
用于产生电能的系统可以包括:透明导电层;与透明导电层接触的第一半导体层,用镁处理;第一电连接,连接到透明导电层;第二电连接,连接到与第二半导体层相邻的背金属电极。第一半导体层可以包含CdS。第一半导体层可以包含1%-20%的镁。在某些情况下,可以将透明导电层设置在基板上方。在某些情况下,可以将透明导电层设置在第一半导体层上方。在某些情况下,光伏电池还可以包括与第一半导体层接触的第二半导体层。该第二半导体层可以包含CdTe。该第二半导体层可以包含氯化镉处理的CdTe。
附图说明
图1是具有多层的基板的示意图。
图2是具有多层的基板的示意图。
图3是具有多层的基板的示意图。
图4是示出Mg浓度增加的效果的图表。
图5是示出CdCl2处理温度的效果的图表。
具体实施方式
光伏电池可以包括在基板的表面上的透明导电层以及包含镁的第一半导体层。通常,用镁处理使得更薄的半导体层得以使用,热处理条件越强,器件的性能改善得越多。
参照图1,光伏电池可以包括第一半导体层100,第一半导体层100可以包含例如CdS。可以用镁101来处理第一半导体层(例如CdS层)。CdS层可以包括例如1%-20%的镁。可选择地,还可以加入另一掺杂剂102来处理第一半导体层。透明导电层可以包含透明导电氧化物(TCO)。镁或其他掺杂剂可以由诸如载气的气源或者通过从基板130、TCO120本身或者TCO上的表面层140扩散来供应。第二半导体层150可以沉积在第一半导体层上方。第二半导体层可以包含例如CdTe。
参照图2,可以用镁201或者其他掺杂剂来处理第一半导体层(例如CdS层)。镁或其他掺杂剂可以由诸如载气的气源或者通过从基板130、TCO120本身或者TCO上的表面层140扩散来供应。掺杂剂可以在第一半导体层200a和附加的第一半导体层200b之间形成层202。含有掺杂剂的层可以包含例如1%-20%的镁。第一半导体层200a的厚度可以大于另一第一半导体层200b的厚度。例如,第一半导体层的厚度可以大于200埃、大于400埃以及大于800埃,或者大约900埃。另一第一半导体层的厚度可以大于50埃、大于75埃,或者大约100埃。第二半导体层250可以沉积在第一半导体层上方。可以用镁或者可选择地用另一掺杂剂来处理第二半导体层。第二半导体层可以包含例如CdTe。掺杂剂层的厚度可以例如大于4埃、大于8埃、大于12埃,或者大约15埃。
参照图3,光伏器件可以包括第二半导体层350和用镁301处理的第一半导体层300。第一半导体层可以由基板330支撑。可选择地,可以用另一掺杂剂302来处理第二半导体层。可以有意地加入第一掺杂剂和第二掺杂剂作为非本征掺杂剂(extrinsicdopant)。
通常,光伏电池效率取决于至少三个参数:开路电压、短路电流密度和填充因数。开路电压(Voc)是外部电路的电流为零时的电压。短路电流密度(Jsc)是电流在零偏压下流出太阳能电池的电流密度。填充因数(FF)是最大功率点与开路电压(Voc)和短路电流(Jsc)的比值。
增加的Jsc导致光伏电池效率增加。可以通过降低半导体层(例如Cds层)的厚度来增加Jsc。然而,如果CdS层的厚度被降低至一定限度以下,则会对Voc产生不利的影响,导致电池效率降低。传统地,已使用在TCO层和CdS层之间的高阻抗氧化物层来克服这样的问题。然而,尽管使用高阻抗氧化物,但是为获得高效率电池通常仍需要大约1000埃的CdS厚度来制造有效的CdS/CdTe结。
光伏电池的加工通常涉及对用氯化镉涂覆的CdTe板的热处理步骤。可以通过诸如溶液喷射、蒸气或喷雾的多种技术来涂覆氯化镉。也可以通过诸如电沉积、溅射、近距离升华、丝网印刷、蒸发和气相传输沉积的多种技术来涂覆CdTe。无论哪种CdTe沉积技术,380℃-450℃的热处理温度通常都是最有效的。通常,低于380℃的温度会导致光伏电池的初始Voc和FF降低。高于450℃的温度也会导致光伏电池的初始Voc和FF降低,但是Jsc较高。Jsc的增加通常是由于CdS层扩散至CdTe层,这会降低有效的CdS厚度,进而降低Voc。
本发明的发明人已经发现对CdS的改性掺杂(例如通过掺杂镁)可以克服由于较薄的CdS层引起的Voc损失。CdS的镁掺杂也可以降低装置对CdCl2处理温度变化的敏感度,并且降低在较高CdCl2处理温度的装置性能损失。
如表1所示,实验显示当用镁处理的硫化镉(CdS:Mg)用在CdTe光伏电池中时,显示出下面的结果,表明CdS厚度可以被降低,从而允许在不损失Voc的情况下增加Jsc。还可以在不降低Voc的情况下应用更高温度的热处理。
表1
控制 | 镁处理 | |
不丢失Voc情况下所需的CdS厚度 | ~1000埃 | 500埃-700埃 |
不降低Voc情况下的允许热度 | 395℃-410℃ | 430℃-450℃ |
参照图4和图5,当与具有未掺杂CdS的层的电池相比时,经处理而具有镁处理的CdS层的光伏电池被证明比氯化镉处理的不同温度下的电池电量更充沛。此外,具有镁处理的CdS层的光伏电池相比于具有未掺杂CdS的层的电池达到更高的平均Voc。此外,在具有镁处理的CdS层的光伏电池中,镁浓度的增加与Voc的增加直接相关。
通常,在第一半导体层(例如含有CdS的层)中不含任何杂质掺杂剂或者在第二半导体层(例如CdTe层)中不含任何杂质掺杂剂,或者这两种层中均不含杂质掺杂剂的情况下来加工光伏电池。用镁掺杂第一半导体层可以降低光伏电池的不稳定性并提高效率。
可以以多种方式来执行半导体层的掺杂。例如,掺杂剂可以由引入的粉末(例如混合粉末)、载气或者直接掺杂的粉末(例如CdS粉末)来供应。粉末可以是单相材料或者多相材料。在其他情况下,掺杂剂可以通过从层(例如,基板层、透明导电层或者半导体层)扩散来供应。可以加入掺杂剂通过整个半导体层,或者通过层的一部分。
可以通过从透明半导体层扩散或者从在透明导电层上的表面层扩散加入用于第一半导体层的掺杂剂(例如CdS)。可选择地,可以通过引入的粉末或供给到气相传输沉积系统的载气加入用于第一半导体层的掺杂剂。用于第一半导体层的掺杂剂可以在例如低于1500℃、低于1400℃、低于1200℃、低于1000℃或低于800℃的温度与第一半导体一起挥发。挥发性物质可以是原子或者硫化物分子(例如In2S)。由于铟在典型的CdS分布器温度(大约1100℃)下具有合理的蒸气压,所以铟可以作为有效的掺杂剂。
可以以多种方式对第二半导体层(CdTe)进行掺杂。例如,可以将掺杂剂与CdTe源粉末一起供应到气相传输沉积(VTD)分布器系统中。用于第二半导体层的掺杂剂可以作为粉末(即,单相材料或多相材料)被引入,或者在载气中被引入。可选择地,用于第二半导体层的掺杂剂可以通过将外层沉积到第二半导体层上而被引入。例如,外层可以包含掺杂剂,所述掺杂剂可以扩散到CdTe表面上。
P型掺杂对于第二半导体层(例如CdTe)可以是有效的。V族元素(例如N、P、As、Sb或Bi)以及I族元素(例如Li、Na、K、Rb、Cs、Cu、Ag或Au)是可以用于第二半导体层的有效的掺杂剂。当将磷(P)、砷(As)、锑(Sb)、钠(Na)、钾(K)、铷(Rb)引入在典型的CdTe分布器温度(大约900℃-1100℃)下运行的VTD系统中时,它们不存在挥发问题。
可以在热处理过程中引入用于第二半导体层的掺杂剂。可以用CdCl2助熔剂执行热处理。可以将I族和V族物质(例如氯化物)加入到助熔剂溶液中,在热处理之前将所述助熔剂溶液涂覆到第二半导体层的外表面。在热处理过程中会发生重结晶,从而使得膜内的掺杂分布成为可能。
掺杂剂的掺杂可能受到空位缺陷的浓度的影响。可以通过气相超压来控制空位浓度。例如,可以施加过量的Cd或Te来改变最终器件的电子缺陷。可以通过在CdTe源粉末中引入过量的Cd或Te来实现Cd或Te超压。这可以通过两相粉末混合或通过偏离化学计量源材料来实现。材料可以偏离化学计量大于5%、大于10%或大于15%(例如大约20%)。
可以以任何浓度(例如大于0.5ppma、大于50ppma、大于500ppma,或者例如在1ppma-1000ppma之间)施加掺杂剂。特定的气源掺杂剂(例如那些含有氮的气源掺杂剂)可能太易在加热的CdTe分布器中分解,因而可以被引入第二较低温分布系统中。掺杂剂例如可以加入整个第二半导体层,或者通过使用多层VTD结构仅加入到层的一部分中。
第一半导体层(例如CdS层)可以用掺杂剂(例如镁)以多种方式处理,例如通过从透明导电层扩散或者从透明导电层上的表面层扩散。可选择地,可以通过引入的粉末或者供应到气相传输沉积系统中的载气加入用于第一半导体层的镁。
第二半导体层(例如CdTe层)也可以用掺杂剂(例如钠)以多种方式处理。在一个实施例中,使用Na2S粉末和Rb将CdTe层用钠掺杂。表明Na的加入引起接下来的氯化物热处理过程中重结晶的改变,这显示Na掺杂使得CdCl2重结晶助熔剂更有活性。
CdTe层还可以与P、As、Sb、Na、Rb或者Cu掺杂。在另一实施例中,示出以Cu掺杂的CdTe层,以展示改善的电信号。向CdTe粉末加入额外的Te致使对膜进行掺杂的能力提高。此外,富含Cd的条件致使膜晶粒结构的改变,这显示对膜进行掺杂的能力提高。
常见的光伏电池可以具有多层。所述多层可以包括底层(即透明导电层)、覆盖层、窗口层、吸收层和顶层。可以使用在所期望的每个位置的单独的沉积气源和真空密封的沉积室在生产线的不同沉积位置来沉积每一层。通过滚动传送带可以将基板从一个沉积位置传递到另一沉积位置直到所有期望的层都被沉积。可以使用其他技术(例如溅镀)加入另外的层。可以将导电体分别连接到顶层和底层,以收集当太阳能入射到吸收层时产生的电能。可以将顶基板层放置在顶层的顶部,以形成三明治结构并且完成光伏电池。
底层可以是透明导电层,并且可以是例如透明导电氧化物(例如氧化锡或者掺氟氧化锡)。在高温下直接在透明导电氧化物层上沉积半导体层可以导致对光伏电池性能和稳定性有消极影响的反应。具有高化学稳定性的覆盖层材料(例如二氧化硅、三氧化二铝、二氧化钛、三氧化二硼和其他类似物质)可以显著减小这些反应对器件性能和稳定性的影响。由于所使用的材料的高电阻率,因此应该使覆盖层的厚度最小化。否则可能出现与期望的电流反向的电阻块(resistiveblock)。通过填充透明导电氧化物层的表面的不规则性,覆盖层可以降低透明导电氧化物层的表面粗糙程度,这有助于窗口层的沉积并且可以允许窗口层具有更薄的横截面。降低的表面粗糙程度可以有助于改善窗口层的均匀性。在光伏电池中包括覆盖层的其他优点可以包括改善光学清晰度、改善带隙连续性、在结点提供更好的场强以及提供更好的由开路电压损失测定的器件效率。例如在第20050257824号美国专利公开中描述的覆盖层通过引用而全部包含于此。
窗口层和吸收层可以例如包含诸如II-VI族、III-V族或IV族半导体的二元半导体,例如ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgO、MgS、MgSe、MgTe、HgO、HgS、HgSe、HgTe、MnO、MnS、MnTe、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、TlN、TlP、TlAs、TlSb或它们的混合物。窗口层和吸收层的示例是由CdTe层涂覆的CdS层。顶层可以覆盖半导体层。顶层可以包含诸如铝、钼、铬、钴、镍、钛、钨或它们的合金的金属。顶层也可以包含金属氧化物或金属氮化物或它们的合金。
例如在第5,248,349、5,372,646、5,470,397、5,536,333、5,945,163、6,037,241和6,444,043号美国专利中描述了光伏器件制造中的半导体层的沉积,所述美国专利均通过引用而全部结合于此。沉积可以涉及从源到基板的蒸气的传输,或者在密闭的系统中的固体的升华。用于制造光伏电池的装置可以包括传送带(例如具有辊子的滚动传送带)。其他类型的传送带是可以的。传送带传送基板到一系列的一个或多个沉积位置,所述沉积位置用以在基板的暴露的表面上沉积材料层。在第11/692,667号美国临时申请中描述的传送带通过引用而包含于此。
可以将沉积室加热到达不低于大约450℃且不高于大约700℃的处理温度,例如温度范围在450℃-550℃、550℃-650℃、570℃-600℃、600℃-640℃之间或在其他任何高于约450℃且低于约700℃范围之间。沉积室包括连接到沉积蒸气供应器的沉积分布器。可以将分布器连接到用于不同层的沉积的多个蒸气供应器,或者可以将具有其自身的蒸气分布器和供应器的基板移动通过多个不同沉积位置。分布器可以是具有不同喷嘴尺寸的喷雾嘴形式,以有助于蒸气供应的均匀分布。
光伏电池的底层可以是透明导电层。薄的覆盖层可以在透明导电层上方,并且至少部分地覆盖透明导电层。接下来沉积的层是第一半导体层,其作为窗口层并且根据透明导电层和覆盖层的用途可以更薄。接下来沉积的层是第二半导体层,其作为吸收层。其他层,例如包含掺杂剂的层,可以在整个制造过程中根据需要而沉积或者放置在基板上。
透明导电层可以是透明导电氧化物(例如像氧化锡这样的金属氧化物),其可以被例如氟掺杂。可以在前接触和第一半导体层之间沉积该层,并且该层可以具有足够高的电阻率以降低第一半导体层中的针孔效应。第一半导体层中的针孔会导致第二半导体层和第一电极之间的形成分流(shuntformation),导致围绕针孔的局部场上形成漏端(drain)。该通道的电阻的微小增加可以显著地减少受到分流影响的区域。
可以提供覆盖层以供应电阻的增加。覆盖层可以是具有高化学稳定性的材料的非常薄的层。覆盖层与厚度可与之比较的具有相同厚度的半导体材料相比,可以具有更高的透明度。适合用作覆盖层的材料的示例包括二氧化硅、三氧化二铝、二氧化钛、三氧化二硼和其他类似物质。覆盖层还起到将透明导电层与第一半导体层电学且化学地隔离的作用,从而防止在高温下出现的会对性能和稳定性产生消极影响的反应。覆盖层还可以提供可以更适合支持第一半导体层的沉积的导电表面。例如,覆盖层可以提供表面粗糙程度降低的表面。
第一半导体层可以用作第二半导体层的窗口层。第一半导体层可以比第二半导体层薄。通过变得更薄,第一半导体层可以允许短波长的入射光更大程度地穿透至第二半导体层。
第一半导体层可以包括II-VI族、III-V族或IV族半导体,例如ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgO、MgS、MgSe、MgTe、HgO、HgS、HgSe、HgTe、MnO、MnS、MnTe、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、TlN、TlP、TlAs、TlSb或它们的混合物或它们的合金。第一半导体层可以包括二元半导体,例如其可以是CdS。第二半导体层可以沉积到第一半导体层上。当第一半导体层用作窗口层时,第二半导体层可以作为对入射光的吸收层。与第一半导体层相似,第二半导体层也可以包括II-VI族、III-V族或IV族半导体,例如ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgO、MgS、MgSe、MgTe、HgO、HgS、HgSe、HgTe、MnO、MnS、MnTe、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、TlN、TlP、TlAs、TlSb或它们的混合物。
第二半导体层可以沉积到第一半导体层上。覆盖层可以用以将透明导电层与第一半导体层电学地且化学地隔离,从而防止在高温下出现的会对性能和稳定性产生消极影响的反应。可以将透明导电层沉积在基板上方。
已经描述了多个实施例。但是,应该理解的是,在不脱离本发明的精神和范围的情况下可以做出各种改变。例如,半导体层可以包括多种可以用作缓冲层和覆盖层材料的其他材料。因此,其他实施例在权利要求的范围之内。
Claims (16)
1.一种光伏电池,所述光伏电池包括:
透明导电层;
与透明导电层直接物理接触的第一半导体层,其中,第一半导体层掺杂有镁,第一半导体层包含CdS,第一半导体层的厚度为500埃-700埃;
与所述第一半导体层接触的第二半导体层,其中,第二半导体层掺杂有V族元素和I族元素中的至少一种,第二半导体层包含CdTe。
2.如权利要求1所述的光伏电池,其中,所述第一半导体层掺杂有1%-20%的镁。
3.如权利要求1所述的光伏电池,其中,所述透明导电层设置在基板上方。
4.如权利要求1所述的光伏电池,其中,所述透明导电层设置在第一半导体层的上方。
5.如权利要求1所述的光伏电池,其中,所述第二半导体层是氯化镉处理的CdTe。
6.一种制造光伏电池的方法,所述方法包括以下步骤:
提供透明导电层;
沉积与透明导电层直接物理接触的第一半导体层的步骤,其中,第一半导体层掺杂有镁,第一半导体层包含CdS,第一半导体层的厚度为500埃-700埃;
沉积与所述第一半导体层接触的第二半导体层的步骤,其中,第二半导体层掺杂有V族元素和I族元素中的至少一种,第二半导体层包含CdTe。
7.如权利要求6所述的方法,其中,所述第一半导体层掺杂有1%-20%的镁。
8.如权利要求6所述的方法,其中,所述透明导电层设置在基板上方。
9.如权利要求6所述的方法,其中,所述透明导电层设置在第一半导体层上方。
10.如权利要求6所述的方法,其中,用氯化镉处理所述第二半导体层。
11.如权利要求10所述的方法,其中,在380℃-450℃用热来处理所述第二半导体层。
12.一种产生电能的系统,所述系统包括:
透明导电层;
与透明导电层直接物理接触的第一半导体层,第一半导体层掺杂有镁,第一半导体层包含CdS,第一半导体层的厚度为500埃-700埃;
与所述第一半导体层接触的第二半导体层,其中,第二半导体层掺杂有V族元素和I族元素中的至少一种,第二半导体层包含CdTe;
第一电连接,连接到透明导电层;
第二电连接,连接到与第二半导体层相邻的背金属电极。
13.如权利要求12所述的系统,其中,所述第一半导体层掺杂有1%-20%的镁。
14.如权利要求12所述的系统,其中,所述透明导电层设置在基板上方。
15.如权利要求12所述的系统,其中,所述透明导电层设置在第一半导体层上方。
16.如权利要求12所述的系统,其中,所述第二半导体层用氯化镉处理。
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CN103303970B (zh) * | 2013-06-26 | 2015-03-11 | 吉林大学 | 一种带隙可调的镁掺杂铜锌锡硫薄膜的制备方法 |
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US20100059112A1 (en) | 2010-03-11 |
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