CN104425655A - Preparation method of flexible solar battery doped with sodium after formation of three-step-method absorption layer - Google Patents
Preparation method of flexible solar battery doped with sodium after formation of three-step-method absorption layer Download PDFInfo
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- CN104425655A CN104425655A CN201310395080.0A CN201310395080A CN104425655A CN 104425655 A CN104425655 A CN 104425655A CN 201310395080 A CN201310395080 A CN 201310395080A CN 104425655 A CN104425655 A CN 104425655A
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- rigid composite
- sodium
- absorbed layer
- flexible solar
- temperature
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 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 title claims abstract description 29
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 29
- 239000011734 sodium Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 title abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 229920001721 polyimide Polymers 0.000 claims abstract description 56
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000011521 glass Substances 0.000 claims abstract description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 26
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims description 61
- 238000001704 evaporation Methods 0.000 claims description 28
- 230000008020 evaporation Effects 0.000 claims description 28
- 229910052733 gallium Inorganic materials 0.000 claims description 20
- 229910052711 selenium Inorganic materials 0.000 claims description 20
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 24
- 239000010409 thin film Substances 0.000 description 14
- 239000010949 copper Substances 0.000 description 7
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000013077 target material Substances 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
-
- 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
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a preparation method of a flexible solar battery doped with sodium after the formation of a three one-step-method absorption layer. The process comprises the following steps: 1, preparing a rigid compound substrate; 2, preparing a flexible solar battery on a polyimide film of the rigid compound substrate; preparing a copper-indium-gallium-selenium absorption layer in the solar battery by adopting a three-step method; preparing one sodium fluoride pre-configured layer on the copper-indium-gallium-selenium absorption layer; 3, separating the polyimide film from soda glass so as to finish a process of preparing the flexible solar battery doped with sodium after the formation of the three-step-method absorption layer. According to the preparation method, a polyimide substrate and the glass have an adhering force, so that the polyimide substrate is not deformed at a high temperature, and the grown flexible solar battery is not loosened and does not fall off; sodium element is doped before the absorption layer grows, so that the electric property of the absorption layer is further improved, and the flexible solar battery with the high conversion efficiency is obtained.
Description
Technical field
The invention belongs to solar cell manufacture technology field, after particularly relating to a kind of three-step approach absorbed layer, mix the preparation method of sodium flexible solar cell.
Background technology
Copper Indium Gallium Selenide material (CIGS) belongs to I-III-VI race's quaternary compound semiconductor, has the crystal structure of chalcopyrite.CIGS thin-film too can battery from 20 century 70s occur since, obtain very fast development, and progressively will realize industrialization.This battery has following characteristics: 1. the energy gap of Copper Indium Gallium Selenide can adjust within the scope of 1.04ev-1.67ev.2. Copper Indium Gallium Selenide is a kind of direct gap semiconductor, to the absorption coefficient of visible ray up to 105cm-1.CuInGaSe absorbed layer thickness only needs 1.5 ~ 2.5 μm, and the thickness of whole battery is 3 ~ 4 μm.3. Radiation hardness is strong, compares and is suitable as space power system.4. conversion efficiency is high.The small size CIGS thin-film solar cell conversion efficiency that German solar energy in 2010 and Hydrogen Energy research center (ZSW) develop is up to 20.3%.5. low light level characteristic is good.Therefore Copper Indium Gallium Selenide polycrystalline thin-film solar cell is expected to one of main product becoming solar cell of future generation.
Along with the development of science and technology, increasing field needs solar cell namely to have higher quality than power, normally can use again, this promotes the development of flexible solar cell technology in adverse circumstances.For realizing both having had higher quality than power, have again flexibility, foldability and be not afraid of the CIGS thin-film solar cell falling and touch, the CIGS thin-film solar cell that polyimides (PI) is substrate is shown one's talent.But itself cannot have good coupling with Copper Indium Gallium Selenide material due to the thermal coefficient of expansion of polyimides, and when temperature is higher, the polyimides as substrate can produce larger deformation, causes CIGS thin-film comparatively loose, easily come off, and temperature lower time, the CIGS thin-film crystalline quality grown is poor, and crystal grain is tiny, defect is more, add the compound of charge carrier, shorten the life-span of few son, and then have impact on battery performance.
Summary of the invention
The present invention for solve in known technology the technical problem that exists and a kind of high temperature is provided time substrate indeformable, the CIGS thin-film grown does not come off, and CIGS thin-film crystalline quality is good, crystal grain is large, defect is few, mixes the preparation method of sodium flexible solar cell after the three-step approach absorbed layer that electrology characteristic is good.
The present invention includes following technical scheme:
Mix the preparation method of sodium flexible solar cell after three-step approach absorbed layer, be characterized in: comprise following preparation process:
Step 1. prepares the rigid composite substrate that polyimide film-soda glass is formed;
Step 2. mixes sodium flexible solar cell after preparing on the polyimide film of rigid composite substrate; Preparation process comprises: on the polyimide film of step 1, prepare Mo back contact, CuInGaSe absorbed layer, sodium fluoride initialization layer, cadmium sulfide resilient coating, transparent window layer and top electrode successively; The preparation process of described CuInGaSe absorbed layer comprises: the rigid composite substrate being shaped with Mo back contact is placed in the selenizing stove of film preparing system; (1) by selenizing stove evacuation, rigid composite underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min, control atomic ratio In:Ga=0.7:0.3, (In+Ga): Se is 2:3; (2) rigid composite substrate is warming up to 550-580 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min; (3) rigid composite underlayer temperature keeps 550-580 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, the evaporation time of In and Ga is 2-4min, control Cu/ (In+Ga) is at 0.88-0.92, substrate is cooled to 350-400 DEG C, close Se evaporation source, when rigid composite substrate is cooled to 25 DEG C, back contact is formed 1.5-2 μm of thick p-CIGS film, be CuInGaSe absorbed layer; The preparation process of described sodium fluoride initialization layer comprises: the rigid composite substrate being shaped with CuInGaSe absorbed layer is placed in the selenizing stove of film preparing system, by selenizing stove evacuation, underlayer temperature is the temperature of 200-300 DEG C, NaF evaporation source when reaching 800-850 DEG C, evaporation 1-2min; Underlayer temperature reaches 400-450 DEG C, anneals under Se atmosphere, and wherein the temperature of Se evaporation source is 240-280 DEG C, and annealing time is 20-30min; CuInGaSe absorbed layer is formed the sodium fluoride initialization layer that chemical molecular formula is NaF, thickness is 20-30nm.
Polyimide film is separated with soda glass by step 3., completes the process of mixing sodium flexible solar cell after rigid substrate prepares three-step approach absorbed layer.
The present invention can also adopt following technical measures:
In step 1, the preparation process of rigid composite substrate comprises: (1) carry out surface clean to soda glass; (2) polyimides glue is evenly coated on soda glass surface, forms polyimides prefabricated membrane; (3) the soda glass scribbling polyimides prefabricated membrane is put into baking oven to be cured, namely obtain the rigid composite substrate that polyimide film-soda glass is formed.
In step 3, polyimide film and soda glass separation process comprise: (1) the rigid composite substrate mixing sodium flexible solar cell after being shaped with three-step approach absorbed layer is put into vacuum drying oven, be heated to 80-90 DEG C, continue 2-3min; (2) taken out by rigid composite substrate after being dipped into the liquid nitrogen of subzero 100 DEG C, naturally return back to room temperature, polyimide film comes off from soda glass automatically, completes the process of mixing sodium flexible solar cell after rigid substrate prepares three-step approach absorbed layer.
The advantage that the present invention has and good effect:
1, the present invention adopts three-step approach to prepare CuInGaSe absorbed layer, and preparing on absorbed layer one deck sodium fluoride initialization layer processed again, makes sodium element be incorporated in CuInGaSe absorbed layer, the electrology characteristic that can promote further; Adopt polyimide film-soda glass rigid composite substrate, take full advantage of soda glass and CuInGaSe absorbed layer thermal coefficient of expansion close to and resistant to elevated temperatures feature, polyimides relies on the adhesive force between glass, during high temperature, polyimide substrate is indeformable, the CIGS thin-film grown is not loosened, is not come off, and CIGS thin-film crystalline quality is good, crystal grain is large, defect is few, after separating the soda glass of rigidity, after achieving the three-step approach absorbed layer with larger columnar grain high conversion efficiency, mix sodium flexible solar cell.
2, polyimides glue is applied to glass surface by the present invention, better can improve the roughness of substrate; Have preparation technology simple, easy to implement, the product prepared can be adapted to various environment, has application prospect extremely widely.
Accompanying drawing explanation
Fig. 1 be mix after the three-step approach absorbed layer prepared on rigid composite substrate of the present invention sodium flexible solar cell be separated rigid substrate before schematic diagram.
In figure, 1-soda glass, 2-polyimide film, 3-back contact, 4-CuInGaSe absorbed layer, 5-sodium fluoride initialization layer, 6-cadmium sulfide resilient coating, 7-transparent window layer, 8-top electrode.
Embodiment
For summary of the invention of the present invention, Characteristic can be disclosed further, be also described in detail as follows by reference to the accompanying drawings especially exemplified by following instance:
Mix the preparation method of sodium flexible solar cell after three-step approach absorbed layer, comprise following preparation process:
Step 1. prepares the rigid composite substrate that polyimide film 2-soda glass 1 is formed;
Step 2. mixes sodium flexible solar cell after preparing on the polyimide film of rigid composite substrate; Preparation process comprises: on the polyimide film of step 1, prepare Mo back contact 3, CuInGaSe absorbed layer 4, sodium fluoride initialization layer 5, cadmium sulfide resilient coating 6, transparent window layer 7 and top electrode 8 successively; The preparation process of described CuInGaSe absorbed layer comprises: the rigid composite substrate being shaped with Mo back contact is placed in the selenizing stove of film preparing system; (1) by selenizing stove evacuation, rigid composite underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min, control atomic ratio In:Ga=0.7:0.3, (In+Ga): Se is 2:3; (2) rigid composite substrate is warming up to 550-580 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min; (3) rigid composite underlayer temperature keeps 550-580 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, the evaporation time of In and Ga is 2-4min, control Cu/ (In+Ga) is at 0.88-0.92, substrate is cooled to 350-400 DEG C, close Se evaporation source, when rigid composite substrate is cooled to 25 DEG C, back contact is formed 1.5-2 μm of thick p-CIGS film, be CuInGaSe absorbed layer; The preparation process of described sodium fluoride initialization layer comprises: the rigid composite substrate being shaped with CuInGaSe absorbed layer is placed in the selenizing stove of film preparing system, by selenizing stove evacuation, underlayer temperature is the temperature of 200-300 DEG C, NaF evaporation source when reaching 800-850 DEG C, evaporation 1-2min; Underlayer temperature reaches 400-450 DEG C, anneals under Se atmosphere, and wherein the temperature of Se evaporation source is 240-280 DEG C, and annealing time is 20-30min; CuInGaSe absorbed layer is formed the sodium fluoride initialization layer that chemical molecular formula is NaF, thickness is 20-30nm.
Polyimide film is separated with soda glass by step 3., completes the process of mixing sodium flexible solar cell after rigid substrate prepares three-step approach absorbed layer.
In described step 1, the preparation process of rigid composite substrate comprises: (1) carry out surface clean to soda glass; (2) polyimides glue is evenly coated on soda glass surface, forms polyimides prefabricated membrane; (3) the soda glass scribbling polyimides prefabricated membrane is put into baking oven to be cured, namely obtain the rigid composite substrate that polyimide film-soda glass is formed.
In described step 3, polyimide film and soda glass separation process comprise: (1) the rigid composite substrate mixing sodium flexible solar cell after being shaped with three-step approach absorbed layer is put into vacuum drying oven, be heated to 80-90 DEG C, continue 2-3min; (2) taken out by rigid composite substrate after being dipped into the liquid nitrogen of subzero 100 DEG C, naturally return back to room temperature, polyimide film comes off from soda glass automatically, completes the process of mixing sodium flexible solar cell after rigid substrate prepares three-step approach absorbed layer.
Embodiment:
1, polyimide film-soda glass rigid composite substrate is prepared
(1) clean soda glass: be that the soda glass of 1.5-2mm is put into potassium bichromate solution and soaked 2h, by soda glass taking-up deionized water rinsing by 10cm × 10cm, thickness; Be placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, put into supersonic wave cleaning machine, ultrasonic frequency is 20-30kHz, cleaning 20-25min; Soda glass taken out from acetone soln, after deionized water rinsing, then soda glass is placed in the alcohol that concentration is 99.7%, puts into supersonic wave cleaning machine, ultrasonic frequency is 20-30kHz, cleaning 20-25min; Finally soda glass taken out from alcohol, put into the beaker filling deionized water, in supersonic wave cleaning machine, ultrasonic frequency is 20-30kHz, and every 20-25min cleans one time, cleans three times altogether;
(2) prepare polyimides prefabricated membrane: the soda glass nitrogen after cleaned is dried up, be placed on the rotating disk of sol evenning machine, polyimides glue is coated on soda glass surface, and with the at the uniform velocity even glue 35-45s of the rotating speed of 1300-1500r/min, soda glass surface forms polyimides prefabricated membrane;
(3) cure polyimide prefabricated membrane: will the soda glass of polyimides prefabricated membrane be had to put into baking oven, 10-20min, oven temperature rises to 125-135 DEG C from 25 DEG C; 125-135 DEG C maintains 20-30min; 5-10min, oven temperature rises to 150-160 DEG C from 125-135 DEG C; 150-160 DEG C maintains 10-15min; 5-10min, oven temperature is warming up to 200-210 DEG C from 150-160 DEG C; 200-210 DEG C maintains 15-20min; 5-10min, oven temperature rises to 250-260 DEG C from 200-210 DEG C; 250-260 DEG C maintains 15-20min; 5-10min, rises to 340-350 DEG C by oven temperature from 250-260 DEG C; 340-350 DEG C maintains 10-15min, then 25 DEG C are naturally down to, polyimides prefabricated membrane is solidificated in soda glass, forms the polyimide film of one deck 25-30 μm above soda glass, completes the manufacturing process of the rigid composite substrate that polyimide film-soda glass is formed.
2, on rigid composite substrate, flexible solar cell is made
(1) make back contact: in the settling chamber of Deposited By Dc Magnetron Sputtering system, purity be 99.99% Mo be that target material deposition is on the polyimide film of rigid composite substrate; Manufacturing process is: in settling chamber, vacuum degree is 3.0 × 10
-4pa, operating air pressure 1-2Pa, rigid composite underlayer temperature 25-50 DEG C, radio-frequency power 500-700W, Ar throughput 30-50sccm, target is back and forth walked 2-4 time above the polyimide film of rigid composite substrate with the speed of 4-6mm/s, polyimide film deposits the resistive formation Mo film that one deck 80-120nm is thick; Again operating air pressure is modulated 0-0.5Pa, rigid composite underlayer temperature keeps 25-50 DEG C, radio-frequency power 1500-2000W, Ar throughput 15-50sccm, target is still back and forth walked 4-6 time at resistive formation Mo film surface with 4-6mm/s speed, resistive formation Mo film surface forms the thick low resistivity layer Mo film of 600-700nm, and resistive formation Mo film and low resistivity layer Mo film constitute Mo back contact;
(2) make CuInGaSe absorbed layer: the rigid composite substrate being shaped with Mo back contact is placed in the selenizing stove of film preparing system, adopt coevaporation three-step approach to make CuInGaSe absorbed layer on back contact; Manufacturing process comprises: 1. selenizing stove vacuum degree is 3.0 × 10
-4pa, rigid composite underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se on back contact, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min, control atomic ratio In:Ga=0.7:0.3, (In+Ga)/Se=2:3; 2. rigid composite substrate is warming up to 550-580 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min; 3. rigid composite underlayer temperature keeps 550-580 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, the evaporation time of In and Ga is 2-4min, when substrate is cooled to 350-400 DEG C, close Se evaporation source, again substrate is cooled to 25 DEG C, control Cu/ (In+Ga) ratio, at 0.88-0.92, back contact is formed 1.5-2 μm of thick p-CIGS film, is CuInGaSe absorbed layer; The chemical molecular formula of p-CIGS film is CuIn
1-xga
xse
2, in formula, x is 0.25-0.35, and conduction type is the Copper Indium Gallium Selenide yellow copper structure of the poor a little Cu of p-type;
(3) make sodium fluoride initialization layer: the rigid composite substrate being shaped with CuInGaSe absorbed layer is placed in the selenizing stove of film preparing system, adopt coevaporation method on CuInGaSe absorbed layer, make sodium fluoride initialization layer; Manufacturing process comprises: selenizing stove vacuum degree is 8.0 × 10
-4pa, rigid composite underlayer temperature is the temperature of 200-300 DEG C, NaF evaporation source when reaching 800-850 DEG C, evaporation 1-2min; Rigid composite underlayer temperature reaches 400-450 DEG C, anneals under Se atmosphere, and wherein the temperature of Se evaporation source is 240-280 DEG C, and annealing time is 20-30min; CuInGaSe absorbed layer is formed the sodium fluoride initialization layer that chemical molecular formula is NaF, thickness is 20-30nm;
(4) make cadmium sulfide resilient coating: adopt chemical bath method to make cadmium sulfide resilient coating on sodium fluoride initialization layer, manufacturing process comprises: 1. configuration concentration is the thiocarbamide SC (NH of 0.01mol/L
2)
2solution; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Concentration is 1.3 × 10
-3the ammoniacal liquor NH of mol/L
3h
2o solubility; 2. 25mL thiourea solution, 25mL cadmium acetate and Ammonium Acetate mixed solution, 4 ammonia spirits are stirred in beaker; 3. the rigid composite substrate being shaped with sodium fluoride initialization layer is put into beaker, and beaker is put into water-bath; Bath temperature is set to 78-80 DEG C, reaction 50-60min; 4. take out substrate, clean with deionized water rinsing, it is CdS that sodium fluoride initialization layer surface forms one deck chemical molecular formula, and conduction type is N-shaped, and thickness is that the n-CdS layer of 45-50nm is as cadmium sulfide resilient coating;
(5) making transparent window layer: the rigid composite substrate being shaped with cadmium sulfide resilient coating is placed in the settling chamber of rf magnetron sputtering preparation system, take purity as the i-ZnO of 99.99% is target, vacuum degree modulation 3.0 × 10 in settling chamber
-4pa, rigid composite underlayer temperature is 25-50 DEG C, and radio-frequency power is 800-1000W, Ar throughput is 10-20sccm, O
2throughput is 2-6sccm, and target is with the speed of 2-6mm/s walking 6-10 time on cadmium sulfide resilient coating, and cadmium sulfide buffer-layer surface deposits the thick i-ZnO high resistant native oxide zinc film of one deck 50-100nm; The rigid composite substrate being shaped with high resistant native oxide zinc film is placed in the settling chamber of magnetically controlled DC sputtering preparation system, take purity as the ZnO:Al of 99.99% is target, and in settling chamber, vacuum degree is adjusted to 3.0 × 10
-4pa, rigid composite underlayer temperature is 25 DEG C, direct current power is 1000-1200W, Ar throughput is 12-18sccm, target is with 2-6mm/s speed walking 10-15 time on high resistant native oxide zinc film, and high resistant native oxide zinc film surface deposits one deck 0.4-0.6 μm of thick n-ZnO:Al low-resistance zinc oxide aluminum film; High resistant native oxide zinc film and low-resistance zinc oxide aluminum film constitute the transparent window layer of N-shaped conduction type;
(6) make top electrode:
The transparent window layer be shaped with on the rigid composite substrate of transparent window layer is placed in the vaporization chamber of coevaporation preparation system down, and molybdenum (Mo) heater strip hanging with aluminum strip is positioned at immediately below transparent window layer, vacuum degree modulation 3.0 × 10 in vaporization chamber
-4pa, heater strip is logical 20A continuing current flow 1-2min, logical 50A continuing current flow 1-2min, logical 80A continuing current flow 1-2min, logical 120A continuing current flow 5-8min respectively, stop heating, heater strip naturally cools to room temperature, transparent window layer surface formed two be parallel to each other, 0.8-1.5 μm thick Al film as top electrode, formed to be separated as shown in Figure 1 after before rigid substrate and mix sodium flexible CIGS thin-film solar cell;
(7) be separated rigid composite substrate:
The rigid composite substrate being shaped with flexible CIGS thin-film solar cell is put into vacuum drying oven, be heated to 80-90 DEG C, after continuing 2-3min, rigid composite substrate is taken out after being dipped into the liquid nitrogen of subzero 100 DEG C, naturally room temperature is returned back in room temperature environment, polyimide film comes off from soda glass automatically, mixes the process of sodium flexible CIGS thin-film solar cell after completing the three-step approach absorbed layer that rigid substrate makes.
Although be described the preferred embodiments of the present invention by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.
Claims (3)
1. mix the preparation method of sodium flexible solar cell after three-step approach absorbed layer, it is characterized in that: comprise following preparation process:
Step 1. prepares the rigid composite substrate that polyimide film-soda glass is formed;
Step 2. mixes sodium flexible solar cell after preparing on the polyimide film of rigid composite substrate; Preparation process comprises: on the polyimide film of step 1, prepare Mo back contact, CuInGaSe absorbed layer, sodium fluoride initialization layer, cadmium sulfide resilient coating, transparent window layer and top electrode successively; The preparation process of described CuInGaSe absorbed layer comprises: the rigid composite substrate being shaped with Mo back contact is placed in the selenizing stove of film preparing system; (1) by selenizing stove evacuation, rigid composite underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min, control atomic ratio In:Ga=0.7:0.3, (In+Ga): Se is 2:3; (2) rigid composite substrate is warming up to 550-580 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min; (3) rigid composite underlayer temperature keeps 550-580 DEG C, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, the evaporation time of In and Ga is 2-4min, control Cu/ (In+Ga) is at 0.88-0.92, substrate is cooled to 350-400 DEG C, close Se evaporation source, when rigid composite substrate is cooled to 25 DEG C, back contact is formed 1.5-2 μm of thick p-CIGS film, be CuInGaSe absorbed layer; The preparation process of described sodium fluoride initialization layer comprises: the rigid composite substrate being shaped with CuInGaSe absorbed layer is placed in the selenizing stove of film preparing system, by selenizing stove evacuation, underlayer temperature is the temperature of 200-300 DEG C, NaF evaporation source when reaching 800-850 DEG C, evaporation 1-2min; Underlayer temperature reaches 400-450 DEG C, anneals under Se atmosphere, and wherein the temperature of Se evaporation source is 240-280 DEG C, and annealing time is 20-30min; CuInGaSe absorbed layer is formed the sodium fluoride initialization layer that chemical molecular formula is NaF, thickness is 20-30nm.
Polyimide film is separated with soda glass by step 3., completes the process of mixing sodium flexible solar cell after rigid substrate prepares three-step approach absorbed layer.
2. mix the preparation method of sodium flexible solar cell after three-step approach absorbed layer according to claim 1, it is characterized in that: in step 1, the preparation process of rigid composite substrate comprises: (1) surface clean is carried out to soda glass; (2) polyimides glue is evenly coated on soda glass surface, forms polyimides prefabricated membrane; (3) the soda glass scribbling polyimides prefabricated membrane is put into baking oven to be cured, namely obtain the rigid composite substrate that polyimide film-soda glass is formed.
3. after three-step approach absorbed layer according to claim 1, mix the preparation method of sodium flexible solar cell, it is characterized in that: in step 3, polyimide film and soda glass separation process comprise: (1) the rigid composite substrate mixing sodium flexible solar cell after being shaped with three-step approach absorbed layer is put into vacuum drying oven, be heated to 80-90 DEG C, continue 2-3min; (2) taken out by rigid composite substrate after being dipped into the liquid nitrogen of subzero 100 DEG C, naturally return back to room temperature, polyimide film comes off from soda glass automatically, completes the process of mixing sodium flexible solar cell after rigid substrate prepares three-step approach absorbed layer.
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Application publication date: 20150318 |