CN111630669B - 光伏器件中吸收层的v族掺杂方法 - Google Patents
光伏器件中吸收层的v族掺杂方法 Download PDFInfo
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- CN111630669B CN111630669B CN201980010956.0A CN201980010956A CN111630669B CN 111630669 B CN111630669 B CN 111630669B CN 201980010956 A CN201980010956 A CN 201980010956A CN 111630669 B CN111630669 B CN 111630669B
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000010521 absorption reaction Methods 0.000 title claims description 3
- 239000006096 absorbing agent Substances 0.000 claims abstract description 97
- 238000000137 annealing Methods 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 229910021478 group 5 element Inorganic materials 0.000 claims abstract description 17
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 239000002019 doping agent Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 15
- 229910052793 cadmium Inorganic materials 0.000 claims description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052714 tellurium Inorganic materials 0.000 claims description 10
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- XPVHUBFHKQQSDA-UHFFFAOYSA-N ammonium arsenate Chemical group [NH4+].[NH4+].O[As]([O-])([O-])=O XPVHUBFHKQQSDA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000010410 layer Substances 0.000 description 184
- 239000000463 material Substances 0.000 description 25
- 239000004065 semiconductor Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- -1 F-SnO 2) Chemical compound 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 239000002800 charge carrier Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910017251 AsO4 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- SKJCKYVIQGBWTN-UHFFFAOYSA-N (4-hydroxyphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(O)C=C1 SKJCKYVIQGBWTN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 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
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- KEFYKDIPBYQPHW-UHFFFAOYSA-N 2,4,6,8-tetraselena-1,3,5,7-tetrazatricyclo[3.3.0.03,7]octane Chemical compound [Se]1N2[Se]N3[Se]N2[Se]N13 KEFYKDIPBYQPHW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- XDYMOMWDVWJACM-UHFFFAOYSA-H cadmium(2+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Cd+2].[Cd+2].[Cd+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O XDYMOMWDVWJACM-UHFFFAOYSA-H 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DOVLZBWRSUUIJA-UHFFFAOYSA-N oxotin;silicon Chemical compound [Si].[Sn]=O DOVLZBWRSUUIJA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1832—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising ternary compounds, e.g. Hg Cd Te
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1872—Recrystallisation
-
- 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
-
- 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
- H01L31/02966—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe including ternary compounds, e.g. HgCdTe
-
- 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
- H01L31/04—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
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Abstract
根据本文提供的实施方案,用于掺杂吸收层的方法可包括使吸收层与退火化合物接触。退火化合物可包含氯化镉和包含阴离子和阳离子的V族盐。阴离子、阳离子或二者可包含V族元素。方法可包括使吸收层退火,由此用退火化合物的V族元素的至少一部分掺杂吸收层。
Description
背景
本说明书主要涉及用V族掺杂剂掺杂光伏器件的方法,更具体地讲,涉及使用退火化合物用V族掺杂剂掺杂光伏器件的方法。
光伏器件通过用显示光伏效应的半导体材料将光转换成电来产生电力。半导体材料可掺杂有掺杂剂,掺杂剂可活化以增加半导体层的电荷载流子浓度。向半导体材料层加入掺杂剂可产生主要具有负、n-型或正、p-型电荷载流子的材料层。然而,使用现有方法可能难以将V族掺杂剂掺入半导体层。例如,已知的掺杂方法可导致半导体层内的V族掺杂剂的体积不足。
因此,需要用V族掺杂剂掺杂光伏器件的替代方法。
概述
本文提供的实施方案涉及用V族掺杂剂掺杂光伏器件的方法。鉴于以下详述,结合附图,将更充分地理解本文所述实施方案提供的这些和另外的特征。
附图简述
在附图中阐明的实施方案在本质上为说明性和示例性,并且不旨在限制由权利要求限定的主题。在结合以下附图阅读时,可理解以下说明性实施方案的详述,其中相似的结构用相似的参考数字表示,其中:
图1示意性描绘根据本文所示和所述的一个或多个实施方案的光伏器件;
图2示意性描绘根据本文所示和所述的一个或多个实施方案的衬底;
图3示意性描绘根据本文所示和所述的一个或多个实施方案的光伏器件;
图4和5示意性描绘根据本文所示和所述的一个或多个实施方案的部分形成的光伏器件;并且
图6示意性描绘根据本文所示和所述一个或多个实施方案用于用V族掺杂剂掺杂吸收层的进行溶液基方法的方法。
详述
本文描述了用于从光产生电力的光伏器件的实施方案。光伏器件通常包括由半导体材料形成的吸收层。吸收层可经过一个或多个构造成用V族掺杂剂(例如砷或磷)掺杂吸收层的处理步骤。将在本文中更详细地描述用V族掺杂剂掺杂吸收层的方法的各种实施方案。
现在参照图1,示意性描绘了光伏器件100的实施方案。光伏器件100可构造成接收光并将光转换成电信号,例如,可从光吸收光子,并且通过光伏效应转换成电信号。因此,光伏器件100可限定能量侧102,能量侧102构造成曝露于诸如太阳之类的光源。光伏器件102还可限定偏离能量侧102的相反侧104。应注意,术语“光”可以指电磁谱的各种波长,例如但不限于在电磁谱的紫外(UV)、红外(IR)和可见部分中的波长。光伏器件100可包括在能量侧102和相反侧104之间布置的多个层。本文所用术语“层”指在表面上提供的一定厚度的材料。各层可覆盖表面的全部或任何部分。
光伏器件100可包括衬底110,衬底110构造成有利于将光传输入光伏器件100。衬底110可布置在光伏器件100的能量侧102。共同参照图1和2,衬底110可具有基本面向光伏器件100的能量侧102的第一表面112和基本面向光伏器件100的相反侧104的第二表面114。可在衬底110的第一表面112和第二表面114之间布置一个或多个材料层。
衬底110可包括透明层120,透明层120具有基本面向光伏器件100的能量侧102的第一表面122和基本面向光伏器件100的相反侧104的第二表面124。在一些实施方案中,透明层120的第二表面124可形成衬底110的第二表面114。透明层120可由基本透明的材料例如玻璃形成。适合的玻璃可包括钠钙玻璃,或任何具有减小的铁含量的玻璃。透明层120可具有任何适合的透射性,在一些实施方案中包括约250nm至约950nm。透明层120还可具有任何适合的透射百分率,包括,例如在一个实施方案中大于约50%,在另一个实施方案中大于约60%,在另一个实施方案中大于约70%,在另一个实施方案中大于约80%,或在另一个实施方案中大于约85%。在一个实施方案中,透明层120可由具有约90%透射率的玻璃形成。衬底110可任选包括施加到透明层120的第一表面122的涂层126。涂层126可构造成与光相互作用,或改善衬底110的耐久性,例如但不限于抗反射涂层、防污涂层或其组合。
再次参照图1,光伏器件100可包括阻挡层130,阻挡层130构造成减轻污染物(例如钠)从衬底110扩散,污染物扩散可导致降解或分层。阻挡层130可具有基本面向光伏器件100的能量侧102的第一表面132和基本面向光伏器件100的相反侧104的第二表面134。在一些实施方案中,可邻近衬底110提供阻挡层130。例如,可在衬底100的第二表面114上提供阻挡层130的第一表面132。本文所用词语“邻近”指两个层毗邻地布置,并且在至少一部分层之间没有任何中间材料。
通常,阻挡层130可基本透明,热稳定,具有减少的针孔数,并且具有高阻钠能力以及良好的粘着性能。作为替代或补充,阻挡层130可构造成对光施加颜色抑制。阻挡层130可包括一个或多个适合材料的层,包括但不限于氧化锡、二氧化硅、铝掺杂的氧化硅、氧化硅、氮化硅或氧化铝。阻挡层130可具有由第一表面132和第二表面134界定的任何适合厚度,包括例如在一个实施方案中大于约500Å,在另一个实施方案中大于约750Å,或在另一个实施方案中小于约1200Å。
仍参照图1,光伏器件100可包括透明导电氧化物(TCO)层140,其构造成提供电接触,以传输由光伏器件100产生的电荷载流子。TCO层140可具有基本面向光伏器件100的能量侧102的第一表面142和基本面向光伏器件100的相反侧104的第二表面144。在一些实施方案中,可邻近阻挡层130提供TCO层140。例如,可在阻挡层130的第二表面134上提供TCO层140的第一表面142。通常,TCO层140可由基本透明且具有宽带隙的一个或多个n型半导体材料层形成。具体地讲,与光的光子能量相比,宽带隙可具有更大的能量值,这可减轻不希望的光吸收。TCO层140可包括一个或多个适合材料的层,包括但不限于二氧化锡、经掺杂的二氧化锡(例如,F-SnO2)、氧化锡铟或锡酸镉。
光伏器件100可包括缓冲层150,缓冲层150构造成在TCO层140和任何相邻半导体层之间提供绝缘层。缓冲层150可具有基本面向光伏器件100的能量侧102的第一表面152和基本面向光伏器件100的相反侧104的第二表面154。在一些实施方案中,可邻近 TCO层140提供缓冲层150。例如,可在TCO层140的第二表面144上提供缓冲层150的第一表面152。缓冲层140可包括具有比TCO层140 更高的电阻率的材料,包括但不限于本征二氧化锡、氧化镁锌(例如Zn1-xMgxO)、二氧化硅(SnO2)、氧化铝(Al2O3)、氮化铝(AlN)、氧化锡锌、氧化锌、氧化硅锡或其任何组合。在一些实施方案中,缓冲层140的材料可构造成基本匹配相邻半导体层(例如,吸收层)的带隙。缓冲层150可具有在第一表面152和第二表面154之间的任何适合厚度,包括例如在一个实施方案中大于约100Å,在另一个实施方案中在约100Å和约800Å之间,或在另一个实施方案中在约150Å和约600Å之间。
再次参照图1,光伏器件100可包括吸收层160,吸收层160构造成在光伏器件100内与另一层协作并形成p-n结。因此,光的被吸收光子可释放电子-空穴对并产生载流子流,载流子流可产生电力。吸收层160可具有基本面向光伏器件100的能量侧102的第一表面162和基本面向光伏器件100的相反侧104的第二表面164。吸收层160的厚度可在第一表面162和第二表面164之间限定。吸收层160的厚度可在约0.5μm至约10μm之间,例如在一个实施方案中在约1μm至约7μm之间,或者在另一个实施方案中在约2μm至约5μm之间。
根据本文所述的实施方案,吸收层160可由具有过量正电荷载流子(即,空穴或受主)的p-型半导体材料形成。吸收层160可包括任何适合的p-型半导体材料,例如II-VI族半导体。具体实例包括但不限于包含镉、碲、硒或其任何组合的半导体材料。适合的实例包括但不限于碲化镉,镉、硒和碲的三元化合物(例如CdSexTe1-x),或包含镉、硒和碲的四元化合物。在吸收层160包含硒和镉的实施方案中,硒的原子%可大于约0原子%且小于约20原子%。在吸收层160包含碲和镉的实施方案中,碲的原子%可大于约30原子%且小于约50原子%。应注意,本文所述的原子%代表吸收层160的整体,与吸收层160的整体组成相比,在吸收层160内特定位置的材料的原子%可随着厚度而改变。应注意,碲、硒或二者的浓度可在吸收层160的厚度上变化。例如,当吸收层160包括镉、硒和碲的三元化合物(CdSexTe1-x)时,x可在吸收层160中随着距吸收层160的第一表面162的距离而改变。在一些实施方案中,x的值可在吸收层160中随着距吸收层160的第一表面162的距离而减小。
根据本文提供的实施方案,可使吸收层160内的掺杂剂活化到希望的电荷载流子浓度。在一些实施方案中,吸收层160可掺杂有V族掺杂剂,例如,氮(N)、磷(P)、砷(As)、锑(Sb)、铋(Bi)、第115号元素(ununpentium,Uup)或其组合。可控制吸收层160内掺杂剂的总剂量。在一些实施方案中,吸收层160的中心区域166中的V族掺杂剂的原子浓度可大于约1x1016cm-3,例如,在一个实施方案中在约1x1017cm-3和约5x1020cm-3之间,在另一个实施方案中在约3x1017cm-3和约1x1019cm-3之间,或在另一个实施方案中在约5x1017cm-3和约5x1018cm-3之间。中心区域166为吸收层160的中间50%,它从吸收层160的第一表面162和第二表面164各自偏离吸收层160的厚度的25%。作为替代或补充,V族掺杂剂的浓度分布可在吸收层160的厚度上变化。具体地讲,V族掺杂剂的量可随着距吸收层160的第二表面164的距离而改变。
仍参照图1,通过提供吸收层160,该吸收层160足够接近光伏器件100具有过量负电荷载流子(即,电子或施主)的部分,则可形成p-n结。在一些实施方案中,可邻近n-型半导体材料提供吸收层160。或者,可在吸收层160和n-型半导体材料之间提供一个或多个中间层。在一些实施方案中,可邻近缓冲层150提供吸收层160。例如,可在缓冲层150的第二表面154上提供吸收层160的第一表面162。
现在参照图3,在一些实施方案中,光伏器件200可包括包含n-型半导体材料的窗层170。除窗层170外,光伏器件200可具有与光伏器件100(图1)基本相似的层结构。可邻近窗层170形成吸收层160。窗层170可具有基本面向光伏器件200的能量侧102的第一表面172和基本面向光伏器件200的相反侧104的第二表面174。在一些实施方案中,可在吸收层160和TCO层140之间安置窗层170。在一个实施方案中,可在吸收层160和缓冲层150之间安置窗层170。窗层170可包括任何适合的材料,包括例如硫化镉、硫化锌、硫化锌镉、氧化镁锌或其任何组合。
再次参照图1,光伏器件100可包括背接触层180,背接触层180构造成减轻掺杂剂的不希望的改变,并且提供与吸收层160的电接触。背接触层180可具有基本面向光伏器件100的能量侧102的第一表面182和基本面向光伏器件100的相反侧104的第二表面184。背接触层180的厚度可在第一表面182和第二表面184之间限定。背接触层180的厚度可在约5nm至约200nm之间,例如在一个实施方案中在约10nm至约50nm之间。
在一些实施方案中,可邻近吸收层160提供背接触层180。例如,可在吸收层160的第二表面164上提供背接触层180的第一表面182。在一些实施方案中,背接触层180可包括来自I、II、VI族的材料的二元或三元组合,例如,包含为各种组成的锌、铜、镉和碲的一层或多层。其它示例性材料包括但不限于掺杂有掺杂剂(例如,碲化铜)的碲化锌或与碲化铜成合金的碲化锌。
光伏器件100可包括导电层190,导电层190构造成提供与吸收层160的电接触。导电层190可具有基本面向光伏器件100的能量侧102的第一表面192和基本面向光伏器件100的相反侧104的第二表面194。在一些实施方案中,可邻近背接触层180提供导电层190。例如,可在背接触层180的第二表面184上提供导电层190的第一表面192。导电层190可包括任何适合的导电材料,例如,含氮金属、银、镍、铜、铝、钛、钯、铬、钼、金等的一层或多层。含氮金属层的适合实例可包括氮化铝、氮化镍、氮化钛、氮化钨、氮化硒、氮化钽或氮化钒。
光伏器件100可包括背支持体196,背支持体196构造成与衬底110协作以形成用于光伏器件100的壳。背支持体196可布置在光伏器件100的相反侧102。例如,可邻近导电层190形成背支持体196。背支持体196可包括任何适合的材料,包括例如玻璃(例如钠钙玻璃)。
共同参照图1和3,光伏器件100, 200的制造一般包括通过一个或多个过程以层的“堆叠体”来顺序布置功能层或层前体,这些过程包括但不限于溅射、喷洒、蒸发、分子束沉积、热解、封闭空间升华(CSS)、脉冲激光沉积(PLD)、化学气相沉积(CVD)、电化学沉积(ECD)、原子层沉积(ALD)或气相传输沉积(VTD)。一旦形成层,就可能合乎需要通过随后的处理过程改变层的物理特性。
共同参照图4和5,部分形成的器件的层可被处理。在一些实施方案中,部分形成的光伏器件202可包括邻近于层堆叠体204的吸收层160。层堆叠体204可包括在吸收层160和能量侧102之间布置的光伏器件100, 200(图1和3)的一层或多层。或者,部分形成的光伏器件206可包括邻近于层堆叠体208的吸收层160。层堆叠体208可包括在吸收层160和相反侧104之间的光伏器件100, 200(图1和3)的一层或多层。
现在参照图6,描绘了用于进行V族掺杂的方法210。V族掺杂包括采用化合物和任选还原气氛的退火过程。共同参照图4、5和6,方法210可包括用于使吸收层160暴露于还原环境220的过程212。吸收层160的第一表面162或第二表面164可经过还原环境220。还原环境220为其中通过去除氧气和其它氧化性气体或蒸气来减轻氧化的气氛条件,即,还原环境可基本不含倾向于氧化V族掺杂剂的物质。另外,还原环境220可包括构造成减轻V族氧化物生成的形成气体。与V族掺杂剂相比,形成气体可在能量上更有利于氧化,即,在ARHT期间,形成气体的氧化反应可具有比V族掺杂剂更负的吉布斯自由能变化(ΔG)。
在一些实施方案中,形成气体可包括氢、氮、碳或其组合。在一个实施方案中,形成气体基本由H2和N2的混合物组成。例如,形成气体可包括约50.0至99.4%N2和约0.6至3.0%H2的混合物。或者,形成气体可包含原子分数范围为0.5-100%的H2。因此,还原环境220可包括基本由100%H2组成的形成气体。其它适合的还原剂可包括甲烷(CH4)、一氧化碳(CO)、硫化氢(H2S)和氨化合物(NH3)。在一些实施方案中,还原环境220可在处理室222内提供,处理室222构造成基本防止在还原环境220内包含倾向于氧化V族掺杂剂的物质。因此,在一些实施方案中,还原环境220可基本由形成气体组成。作为替代或补充,处理室222可构造成保持局部真空压力。因此,可在约200Torr至约800Torr的真空压力下提供还原环境220,例如在约3Torr至约50Torr的范围内。
用于V族掺杂的方法210可包括用于使吸收层160与退火化合物224接触的过程214。在一些实施方案中,可将退火化合物224作为溶液施加到吸收层160的第一表面162或第二表面164。例如,可在吸收层160上喷洒、旋涂或辊涂退火化合物224。退火化合物224包括氯化镉(CdCl2)和V族盐的组合。本文所用术语“盐”可以指具有两个部分(阳离子和阴离子)的离子化合物。阳离子、阴离子或二者可由元素或化合物形成。V族盐为其中阳离子、阴离子或二者包含V族元素的盐,所述V族元素例如氮(N)、磷(P)、砷(As)、锑(Sb)、铋(Bi)、第115号元素(Uup)或其组合。V族盐的适合实例包括但不限于砷酸二氢铵(NH4H2AsO4)、磷酸氢二铵((NH4)2HPO4)、砷酸铵((NH4)3AsO4)、砷酸镉(Cd3(AsO4)2)、(偏)亚砷酸钠(NaAsO2)、三氯化铋(BiCl3)或其组合。在一些实施方案中,V族盐可由溶剂例如水、醇等溶解。
控制退火化合物224的组成,使得希望比例的退火化合物224作为V族盐提供。例如,V族盐与退火化合物224总量的希望比例可小于约100克/升(g/L),例如在一个实施方案中小于约25g/L,在另一个实施方案中在约1/25g/L和约20g/L之间,在另一个实施方案中在约1/10g/L和约10g/L之间,或在另一个实施方案中在约1/2g/L和约2g/L之间。通常,按重量/体积计,例如按克/升测量,退火化合物224包含比V族盐更多的氯化镉。具体地讲,按重量/体积计,退火化合物224内氯化镉与V族盐之比可以为至少30:1,例如在一个实施方案中在约35:1和约8,000:1之间,在另一个实施方案中在约150:1和约6,500:1之间,在另一个实施方案中在约300:1和约2,000:1之间。
在一些实施方案中,退火化合物224可作为单独的组分提供。例如,V族盐、氯化镉或二者可蒸发到吸收层160上,并冷凝成膜。例如,V族盐和氯化镉可顺序相互叠加地蒸发。或者,可使V族盐和氯化镉共蒸发到吸收层160上。在另外的实施方案中,可以气相提供退火化合物224的一种或多种组分。例如,V族盐、氯化镉或二者可以气相接触吸收层160。
用于V族掺杂的方法210可包括用于使吸收层160在还原环境220中退火的过程216。通常,退火包括加热吸收层160(例如,多晶半导体材料)足够的时间和温度,以促进吸收层160重结晶。例如,吸收层160可在约350℃和约500℃之间的温度下处理约5分钟至约60分钟,例如,在一个实施方案中在约400℃至约500℃范围的温度下处理约10分钟至约55分钟的持续时间,或在另一个实施方案中在约400℃至约450℃的温度下处理约15分钟至约50分钟的持续时间。在替代实施方案中,可在形成气体的存在下进行退火,可进行多次退火,或者二者均可进行。例如,在一些实施方案中,可使吸收层160暴露于氯化镉,并在非还原气氛中退火,并在V族盐存在下进行随后的退火。
应注意,虽然可在图6中以顺序方式描绘过程212、过程214和过程216,但本文提供的实施方案不限于过程212、过程214和过程216的任何特定次序。在一些实施方案中,吸收层160的表面可初始与退火化合物224在还原环境220中时和在退火过程中接触。在其它实施方案中,吸收层160的表面可与退火化合物224接触,随后放入还原环境220并退火。在一些实施方案中,过程212、过程214和过程216各自可同时进行,即,在还原环境220中,退火化合物224可保持与吸收层160接触,用于至少部分退火。例如,可在气相中围绕涂覆有氯化镉的吸收层160提供V族盐。
除了吸收层160的重结晶外,氯化镉的存在还可引起吸收层160中的晶粒生长,即,吸收层160的晶粒粒度增大。另外,在退火化合物224中作为V族盐存在的V族掺杂剂可扩散进入吸收层160,并掺杂吸收层160。因此,吸收层160的晶粒生长和吸收层160的掺杂可同时进行。
在一些实施方案中,吸收层160的晶粒生长、吸收层160的掺杂以及V族掺杂剂的活化可同时进行。例如,在一些实施方案中,退火化合物224可包括一种或多种碱金属氯化物。碱金属氯化物可由碱金属例如锂(Li)、钠(Na)、钾(K)、铷(Rb)、铯(Cs)和钫(Fr)形成。适合的碱金属氯化物包括但不限于LiCl、NaCl、KCl、RbCl或其组合。控制退火化合物224的组成,以便保持期望的镉与碱金属之比。通常,按原子比测量,退火化合物224包含比碱金属更多的镉。例如,期望的碱金属与镉之比可小于约10,000ppm。
现在应理解,本文提供的实施方案涉及使用包含V族盐的退火化合物的用V族掺杂剂掺杂吸收层的方法。试验表明,与已知方法相比,使用V族盐可改善V族掺杂剂进入吸收层的转移效率。例如,当以每单位面积掺入的掺杂剂的重量:每单位面积施加的掺杂剂的重量来测定转移效率时,与在吸收层的气相传输沉积期间掺杂相比,转移效率改善。具体地讲,砷掺杂显示改善约300%至600%。
根据本公开的实施方案,用于掺杂吸收层的方法可包括使吸收层暴露于还原环境。吸收层可包含镉和碲。方法可包括使吸收层与退火化合物接触。退火化合物可包含氯化镉和包含阴离子和阳离子的V族盐。阴离子、阳离子或二者可包含V族元素。按重量/体积计,退火化合物内氯化镉与V族盐之比可以为至少30:1。方法可包括使吸收层退火,由此用退火化合物的V族元素的至少一部分掺杂吸收层。
应注意,术语“基本”和“约”在本文中可用来表示固有的不确定性程度,这可归因于任何定量比较、值、测定或其它表达。这些术语在本文中也用来表示定量表达可从所述提及物改变、而不引起所讨论主题的基本功能变化的程度。
虽然在本文中已说明和描述了具体实施方案,但应理解,可在不脱离要求保护的主题的精神和范围的情况下,做出各种其它变化和更改。另外,虽然在本文中已描述了所要求保护主题的各个方面,但这些方面不必结合使用。因此,本发明旨在由附加权利要求覆盖所要求保护主题的范围内的所有这些变化和更改。
Claims (27)
1.一种掺杂吸收层的方法,所述方法包括:
使吸收层与退火化合物接触,其中:
吸收层包含镉和碲;
退火化合物包含氯化镉和包含阴离子和阳离子的V族盐;
阴离子、阳离子或二者包含V族元素;
按重量/体积计,退火化合物内氯化镉与V族盐之比为至少30:1;和
使吸收层退火,由此用退火化合物的V族元素的至少一部分掺杂吸收层。
2.权利要求1的方法,其中退火化合物为溶液,并且V族盐与退火化合物总量的比例小于100克/升。
3.权利要求2的方法,其中V族盐与退火化合物总量的比例在1/25克/升和20克/升之间。
4.权利要求1的方法,其中吸收层的晶粒粒度在吸收层退火期间增大。
5.权利要求1的方法,其中V族盐为砷酸二氢铵。
6.权利要求1的方法,其中V族盐为磷酸氢二铵。
7.权利要求1的方法,其中V族元素为氮。
8.权利要求1的方法,其中V族元素为磷。
9.权利要求1的方法,其中V族元素为砷。
10.权利要求1的方法,其中V族元素为锑。
11.权利要求1的方法,其中V族元素为铋。
12.权利要求1的方法,所述方法包括在使吸收层退火的同时使吸收层暴露于还原环境。
13.权利要求12的方法,其中还原环境包括构造成减轻V族氧化物生成的形成气体,所述形成气体包括氢、氮、碳或其组合。
14.权利要求1的方法,其中吸收层在350℃和500℃之间的温度下退火5分钟至60分钟。
15.权利要求1的方法,其中:
退火化合物包括碱金属氯化物;并且
至少部分V族掺杂剂在吸收层退火期间活化。
16.权利要求1的方法,其中在使吸收层退火后,在吸收层中心区域中的V族掺杂剂的原子浓度大于1x1016cm-3。
17.权利要求1的方法,其中吸收层包含硒。
18.权利要求1至3中任一项的方法,其中吸收层的晶粒粒度在吸收层退火期间增大。
19.权利要求1至3中任一项的方法,其中V族盐为砷酸二氢铵。
20.权利要求1至3中任一项的方法,其中V族盐为磷酸氢二铵。
21.权利要求1至3中任一项的方法,其中V族元素为氮。
22.权利要求1至3中任一项的方法,其中V族元素为磷。
23.权利要求1至3中任一项的方法,其中V族元素为砷。
24.权利要求1至3中任一项的方法,其中V族元素为锑。
25.权利要求1至3中任一项的方法,其中V族元素为铋。
26.权利要求1至3中任一项的方法,所述方法包括在使吸收层退火的同时使吸收层暴露于还原环境。
27.权利要求26的方法,其中还原环境包括构造成减轻V族氧化物生成的形成气体,所述形成气体包括氢、氮、碳或其组合。
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