CN104393089A - Na-doped CIGS solar battery device and preparation method thereof - Google Patents
Na-doped CIGS solar battery device and preparation method thereof Download PDFInfo
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- CN104393089A CN104393089A CN201410532539.1A CN201410532539A CN104393089A CN 104393089 A CN104393089 A CN 104393089A CN 201410532539 A CN201410532539 A CN 201410532539A CN 104393089 A CN104393089 A CN 104393089A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 77
- 239000011521 glass Substances 0.000 claims abstract description 87
- 239000000758 substrate Substances 0.000 claims abstract description 76
- 229920001721 polyimide Polymers 0.000 claims abstract description 60
- 239000004642 Polyimide Substances 0.000 claims abstract description 51
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 50
- 239000010408 film Substances 0.000 claims description 64
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 40
- 238000001704 evaporation Methods 0.000 claims description 34
- 230000008020 evaporation Effects 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000004140 cleaning Methods 0.000 claims description 28
- 229910052711 selenium Inorganic materials 0.000 claims description 28
- 229910052733 gallium Inorganic materials 0.000 claims description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 235000013024 sodium fluoride Nutrition 0.000 claims description 20
- 239000011775 sodium fluoride Substances 0.000 claims description 20
- 239000010409 thin film Substances 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000004062 sedimentation Methods 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 15
- 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 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 12
- 239000005695 Ammonium acetate Substances 0.000 claims description 12
- 229940043376 ammonium acetate Drugs 0.000 claims description 12
- 235000019257 ammonium acetate Nutrition 0.000 claims description 12
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical class [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010583 slow cooling Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000928 Yellow copper Inorganic materials 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 3
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 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
- H01L31/04—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
-
- 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
-
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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
- H01L31/18—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
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- 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
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- 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 discloses a Na-doped CIGS solar battery device based on a polyimide film-soda glass composite substrate. The Na-doped CIGS solar battery device is characterized in that the substrate is composed of soda glass and a polyimide film growing on the surface of the soda glass. A CIGS solar battery is prepared on the surface of the composite substrate. The advantages are as follows: the CIGS film based on the polyimide film-soda glass composite substrate is excellent in adhesiveness, good in crystallization quality and coarse in crystal grains and has fewer defects; after the complete CIGS solar battery is prepared, the battery is separated from the soda glass to form the flexible CIGS solar battery with the polyimide film as the substrate, such that the flexible battery is prepared through the rigid substrate; and the preparation method is simple and easily implemented, facilitates large-scale popularization and application, and has extremely important application prospect especially on space and special occasions.
Description
Technical field
The present invention relates to thin film solar cell technical field, particularly a kind ofly mix sodium CIGS solar cell device and preparation thereof based on polyimide film-soda glass compound substrate.
Background technology
Copper Indium Gallium Selenide material (CIGS) belongs to I-III-VI race 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 10
5cm
-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 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.
Aerospace field needs solar cell to have higher quality than power, namely wishes that the solar cell of unit mass can send more electricity.The surface modeling of ground photovoltaic building and the photovoltaic plant etc. of movable type are required that solar cell has flexibility, foldability and is not afraid of to fall touch, this promotes the development of flexible solar cell.Due to relatively strong heat-resisting ability and the comparatively applicable coefficient of expansion, polyimides (PI) is shown one's talent wherein.
But the thermal coefficient of expansion of polyimides still well cannot mate with Copper Indium Gallium Selenide material itself.When temperature is higher, polyimides can produce larger deformation, causes CIGS thin-film comparatively loose, easily comes off.So underlayer temperature is lower when preparing based on the Copper Indium Gallium Selenide of polyimide substrate at present.Thus causing the film tack that grows poor, crystalline quality is poor, and crystal grain is tiny, and defect is more, adds the compound of charge carrier, shortens the life-span of few son, and then have impact on battery performance.
Mixing appropriate sodium (Na) in CIGS thin-film can make the performance of CIGS solar cell improve 30-50%.In the preparation of the CIGS solar cell of traditional soda glass substrate, sodium can be realized the doping of Na to the spontaneous diffusion of CuInGaSe absorbed layer by substrate.But owing to not containing sodium element in polyimide film, and its high molecular structure stops sodium in compound substrate to enter CuInGaSe absorbed layer.Therefore, in the CuInGaSe absorbed layer film based on polyimide film-soda glass compound substrate, mix sodium and just become very important.
Summary of the invention
In view of this, for overcoming the deficiencies in the prior art, the invention provides and a kind ofly mix sodium CIGS solar cell device and preparation scheme thereof based on polyimide film-soda glass compound substrate, first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly back contact is prepared successively on its surface, CuInGaSe absorbed layer, sodium fluoride preformed layer, cadmium sulfide resilient coating, transparent window layer and top electrode, after prepared by complete CIGS solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as the flexible copper indium gallium selenide solar cell of substrate.Its central characteristics is: prepare flexible battery with rigidity substrate.This kind is outstanding based on the CIGS thin-film tack of polyimide film-soda glass compound substrate, and crystalline quality is good, coarse grains, and defect is few.
Technical scheme of the present invention:
A kind of CIGS solar cell device based on polyimide film-soda glass compound substrate, it is characterized in that: its substrate is made up of soda glass and the polyimide film that is grown on its surface, wherein the thickness of soda glass is 1.5-2mm, polyimides film thickness is 25-30 μm, adopts even glue, solidification preparation technology; Molybdenum back contact is grown on polyimide film-soda glass compound substrate, is divided into resistive formation and low resistivity layer, and wherein the thickness of resistive formation is 80-120nm, and the thickness of low resistivity layer is 600-700nm, adopts DC magnetron sputtering system preparation; CuInGaSe absorbed layer is grown on sodium fluoride preformed layer film, and chemical molecular formula is CuIn
1-xga
xse
2, in formula, x is 0.25-0.35, and conduction type is p-type, and thickness is 1.5-2 μm, adopts selenizing stove film preparing system, application coevaporation modified model three-step approach preparation technology; The film growth of sodium fluoride preformed layer is on CuInGaSe absorbed layer, and chemical molecular formula is NaF, and thickness is 20-30nm, adopts selenizing stove film preparing system, application coevaporation preparation technology; Cadmium sulfide buffer growth is in CuInGaSe absorbed layer surface, and chemical molecular formula is CdS, and conduction type is N-shaped, and thickness is 45-50nm, adopts chemical bath method preparation technology; Transparent window layer is grown on cadmium sulfide resilient coating, be divided into high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, conduction type is N-shaped, wherein the thickness of native oxide zinc film is 50-100nm, the thickness of zinc oxide aluminum film is 0.4-0.6 μm, adopts rf magnetron sputtering preparation system and the preparation of magnetically controlled DC sputtering preparation system respectively; Aluminium upper electrode film is grown on transparent window layer, thereafter for being 0.8-1.5 μm, adopts the preparation of coevaporation preparation system.
The preparation process of polyimide film-soda glass compound substrate is as follows:
1) removing surface is carried out to soda glass;
2) polyimides glue is coated on soda glass surface, adopts spin processes to carry out even glue;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained.
Describedly to soda glass method for cleaning surface be: 1. the soda glass of 10cm × 10cm is put into potassium bichromate solution (solution configured by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and 300 ml deionized water) immersion 2h; 2. by soda glass taking-up deionized water rinsing after; 3. be placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, (ultrasonic frequency is 20-30kHz to put into supersonic wave cleaning machine cleaning, time is 20-25min) 4. soda glass is taken out from acetone soln, with deionized water rinsing; 5. soda glass is placed in the alcohol that concentration is 99.7%, puts into supersonic wave cleaning machine cleaning (ultrasonic frequency is 20-30kHz, and the time is 20-25min); 6. last soda glass to be taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times (ultrasonic frequency is 20-30kHz, and the time is 20-25min).
The technological parameter of described spin processes is: rotating speed is 1300-1500r/min, and the time is 35-45s.
Described parameters of curing is: 1. oven temperature is warming up to 125-135 DEG C in room temperature 25 DEG C, and the heating-up time is 10-15min; 2. oven temperature maintains 25-30min in 125-135 DEG C; 3. oven temperature is warming up to 150-160 DEG C in 125-135 DEG C, and the heating-up time is 5-10min; 4. oven temperature maintains 10-15min in 150-160 DEG C; 5. oven temperature is warming up to 200-210 DEG C in 150-160 DEG C, and the heating-up time is 5-10min; 6. oven temperature maintains 15-20min in 200-210 DEG C; 7. oven temperature is warming up to 250-260 DEG C in 200-210 DEG C, and the heating-up time is 5-10min; 8. oven temperature maintains 15-20min in 250-260 DEG C; 9. oven temperature is warming up to 340-350 DEG C in 250-260 DEG C, and the heating-up time is 5-10min; 10. oven temperature maintains 10-15min in 340-350 DEG C, and slow cooling is to room temperature afterwards.
The preparation process of molybdenum back contact is as follows:
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.
The described technological parameter depositing one deck high resistance film at substrate surface is: base vacuum: 3.0 × 10
-4pa, operating air pressure is 1-2Pa, and underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 500-700W, Ar throughput is 30-50sccm, and the base target speed of travel is 4-6mm/s, and sedimentation time (reciprocal time of base target) is for 2-4 time.
The described technological parameter depositing one deck low-resistance film at substrate surface is: operating air pressure is 0-0.5Pa, underlayer temperature is room temperature 25-50 DEG C, radio-frequency power is 1500-2000W, Ar throughput is 15-20sccm, the base target speed of travel is 4-6mm/s, and sedimentation time (reciprocal time of base target) is for 4-6 time.
The preparation process of CuInGaSe absorbed layer film is as follows:
1) base vacuum is 3.0 × 10
-4pa, underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se height Ga content preformed layer, wherein In source temperature is 820-850 DEG C, Ga source temperature is 920-950 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 2-3min, control atomic ratio In:Ga=0.3: 0.7, (In+Ga)/Se=2: 3;
2) underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se initialization layer, 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, evaporation time is 15-20min, controls atomic ratio In:Ga=0.7: 0.3, (In+Ga)/Se=2: 3;
3) underlayer temperature is 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;
4) what underlayer temperature kept in second step is temperature-resistant, 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, evaporation time is 2-4min, and obtain the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, control Cu/ (In+Ga) ratio is at 0.88-0.92.
5) substrate being cooled, when evaporating underlayer temperature when substrate to be cooled to while Se the first step, closing Se evaporation source, then by substrate cool to room temperature.
The preparation process of sodium fluoride initialization layer film is as follows:
1) base vacuum is 8.0 × 10
-4pa, underlayer temperature is 200-300 DEG C, coevaporation NaF initialization layer, and wherein the temperature of NaF evaporation source is 800-850 DEG C, and evaporation time is 1-2min.
2) underlayer temperature is 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.
The preparation process of cadmium sulfide resilient coating is as follows:
1) configure solution, prepare thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.
2) configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.
3) sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 78-80 DEG C, and preparation time is 50-60min.
4) after having prepared, by clean for sample deionized water rinsing.
The preparation process of native oxide zinc film is as follows:
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the i-ZnO of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit one deck native oxide zinc film at substrate surface.
The described technological parameter depositing one deck zinc oxide aluminum film at substrate surface is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 800-1000W, Ar throughput is 10-20sccm, O
2throughput is 2-6sccm, and the base target speed of travel is 2-6mm/s, and sedimentation time (reciprocal time of base target) is for 6-10 time.
The preparation process of zinc oxide aluminum film is as follows:
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% be target, adopt DC magnetron sputtering process to deposit layer of ZnO at substrate surface: Al film.
The described technological parameter depositing one deck zinc oxide aluminum film at substrate surface is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is 25-50 DEG C, and direct current power is 1000-1200W, Ar throughput is 12-18sccm, and the base target speed of travel is 2-6mm/s, and sedimentation time (reciprocal time of base target) is for 10-15 time.
The preparation process of aluminium top electrode is as follows:
1) base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 1-2min; Give heater strip 50A electric current, continue 1-2min; Give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min.
2) after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Principle analysis of the present invention:
In order to satisfied preparation tack is outstanding, crystalline quality is better, coarse grains, the requirement of the Copper Indium Gallium Selenide flexible thin-film solar cell that defect is less, substrate must be selected soft, light, the substrate that thermal coefficient of expansion and CIGS thin-film are comparatively mated.Polyimide film-soda glass compound substrate can rely on soda glass and the comparatively close feature of the CuInGaSe absorbed layer film thermal coefficient of expansion, and compound substrate prepares CIGS thin-film solar cell.Be that substrate is separated from soda glass surface afterwards again with polyimides by thin film solar cell, obtain flexible CIGS thin-film solar cell, realize preparing flexible solar cell with rigidity substrate.
Benefit analysis based on the CIGS solar cell of polyimide film-soda glass compound substrate:
1) polyimides glue is applied to glass surface, better can improves the roughness of substrate.
2) thermal coefficient of expansion of polyimides itself is comparatively large, can not itself mate with Copper Indium Gallium Selenide material well.Easily be out of shape at relatively high temperatures, cause film to loosen, very easily come off.And be grown on the polyimides of glass surface, rely on the adhesive force between glass, make it that comparatively large deformation not easily occur, more mate with Copper Indium Gallium Selenide material.
3) due to the improvement to three-steps process, prepare the preformed layer of a floor height Ga content, greatly improve the tack of CIGS thin film on polyimide film.
4) due to glass contact, not easily there is deformation, polyimides can be given comparatively close to the temperature of its heatproof upper limit, contribute to CIGS thin-film and better grow.
5) its epontic CIGS thin-film crystalline quality is good, and crystal grain is large, and defect is few.
6) the mixing of sodium element, can promote the electrology characteristic of CuInGaSe absorbed layer film effectively.
7) after prepared by complete CIGS solar cell, it is separated from glass, just can prepares the flexible copper indium gallium selenide solar cell with larger columnar grain.
Advantage of the present invention is: this kind is outstanding based on the CIGS solar cell absorbed layer film tack of polyimide film-soda glass compound substrate, and crystalline quality is good, coarse grains, and defect is few, utilizes rigidity substrate to prepare flexible solar cell; Its preparation method is simple, easy to implement, is conducive to applying on a large scale, especially in space and special occasions, has extremely important application prospect.
Accompanying drawing explanation
Accompanying drawing 1 is the CIGS solar cell device architecture schematic diagram based on polyimide film-soda glass compound substrate.
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
Embodiment 1:
Based on the preparation of mixing sodium CIGS solar cell of polyimide film-soda glass compound substrate, its preparation process is as follows:
1) cleaning of soda glass
1. the soda glass of 10cm × 10cm is put into potassium bichromate solution (solution configured by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and 300 ml deionized water) and soak 2h; 2. by soda glass taking-up deionized water rinsing after; 3. being placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, putting into supersonic wave cleaning machine cleaning (ultrasonic frequency is 20kHz, and the time is 25min) and 4. soda glass being taken out from acetone soln, with deionized water rinsing; 5. soda glass is placed in the alcohol that concentration is 99.7%, puts into supersonic wave cleaning machine cleaning (ultrasonic frequency is 20kHz, and the time is 25min); 6. last soda glass to be taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times (ultrasonic frequency is 20kHz, and the time is 25min).
2) preparation of polyimides prefabricated membrane
Soda glass nitrogen after cleaned is dried up, is placed on the rotating disk of sol evenning machine, polyimides glue is coated on soda glass surface.With the at the uniform velocity even glue 45s of the rotating speed of 1300r/min, polyimides prefabricated membrane can be obtained.
3) solidification of polyimides prefabricated membrane
1. oven temperature is warming up to 125 DEG C in room temperature 25 DEG C, and the heating-up time is 15min; 2. oven temperature maintains 30min in 125 DEG C; 3. oven temperature is warming up to 150 DEG C in 125 DEG C, and the heating-up time is 5min; 4. oven temperature maintains 15min in 150 DEG C; 5. oven temperature is warming up to 200 DEG C in 150 DEG C, and the heating-up time is 5min; 6. oven temperature maintains 20min in 200 DEG C; 7. oven temperature is warming up to 250 DEG C in 200 DEG C, and the heating-up time is 5min; 8. oven temperature maintains 20min in 250 DEG C; 9. oven temperature is warming up to 350 DEG C in 250 DEG C, and the heating-up time is 10min; 10. oven temperature maintains 10min in 350 DEG C, and slow cooling to room temperature can obtain polyimide film-soda glass compound substrate afterwards.
4) preparation of molybdenum back contact
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0 × 10
-4pa, operating air pressure is 1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 600W, Ar throughput is 40sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 2 times.2. operating air pressure is 0.1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
5) preparation of CuInGaSe absorbed layer film
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 380 DEG C, coevaporation In, Ga, Se height Ga content preformed layer, wherein In source temperature is 840 DEG C, Ga source temperature is 930 DEG C, and Se source temperature is 260 DEG C, and evaporation time is 2min, control atomic ratio In:Ga=0.3: 0.7, (In+Ga)/Se=2: 3; 2. underlayer temperature is 380 DEG C, coevaporation In, Ga, Se initialization layer, and wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 17min; 3. underlayer temperature is 550 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1140 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 15min; What 4. underlayer temperature kept in second step is temperature-resistant, coevaporation In, Ga, Se, and wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 3min; 5. substrate is cooled, when evaporate substrate to be cooled to while Se 380 DEG C time, close Se evaporation source, then substrate cool to room temperature can be obtained the CIGS thin-film based on polyimide film-soda glass compound substrate.
6) preparation of sodium fluoride initialization layer
1. base vacuum is 8.0 × 10
-4pa, underlayer temperature is 200 DEG C, coevaporation NaF initialization layer, and wherein the temperature of NaF evaporation source is 810 DEG C, and evaporation time is 2min.2. underlayer temperature is 400 DEG C, anneals under Se atmosphere, and wherein the temperature of Se evaporation source is 250 DEG C, and annealing time is 30min.
7) preparation of cadmium sulfide buffer layer thin film
1. configure solution, prepare thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.
2. configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.3. sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 78 DEG C, and preparation time is 60min.4. after having prepared, by clean for sample deionized water rinsing.
8) preparation of native oxide zinc film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the i-ZnO of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit one deck native oxide zinc film at substrate surface.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 35 DEG C, and radio-frequency power is 800W, Ar throughput is 10sccm, O
2throughput is 3sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 8 times.
9) preparation of zinc oxide aluminum film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% be target, adopt DC magnetron sputtering process to deposit layer of ZnO at substrate surface: Al film.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25 DEG C, and direct current power is 1000W, Ar throughput is 15sccm, and the base target speed of travel is 6mm/s, and sedimentation time (reciprocal time of base target) is 10 times.
10) preparation of aluminium top electrode
1. base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 2min; Give heater strip 50A electric current, continue 2min; Give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 6min.2. after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Accompanying drawing 1 is for mixing sodium CIGS solar cell device architecture schematic diagram based on polyimide film-soda glass compound substrate.
Embodiment 2:
Based on the preparation of the CIGS solar cell of polyimide film-soda glass compound substrate, its preparation process is as follows:
1) cleaning of soda glass
1. the soda glass of 10cm × 10cm is put into potassium bichromate solution (solution configured by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and 300 ml deionized water) and soak 2h; 2. by soda glass taking-up deionized water rinsing after; 3. being placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, putting into supersonic wave cleaning machine cleaning (ultrasonic frequency is 30kHz, and the time is 20min) and 4. soda glass being taken out from acetone soln, with deionized water rinsing; 5. soda glass is placed in the alcohol that concentration is 99.7%, puts into supersonic wave cleaning machine cleaning (ultrasonic frequency is 30kHz, and the time is 20min); 6. last soda glass to be taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times (ultrasonic frequency is 30kHz, and the time is 20min).
2) preparation of polyimides prefabricated membrane
Soda glass nitrogen after cleaned is dried up, is placed on the rotating disk of sol evenning machine, polyimides glue is coated on soda glass surface.With the at the uniform velocity even glue 40s of the rotating speed of 1400r/min, polyimides prefabricated membrane can be obtained.
3) solidification of polyimides prefabricated membrane
1. oven temperature is warming up to 130 DEG C in room temperature 25 DEG C, and the heating-up time is 20min; 2. oven temperature maintains 25min in 130 DEG C; 3. oven temperature is warming up to 160 DEG C in 130 DEG C, and the heating-up time is 10min; 4. oven temperature maintains 10min in 160 DEG C; 5. oven temperature is warming up to 210 DEG C in 160 DEG C, and the heating-up time is 10min; 6. oven temperature maintains 20min in 210 DEG C; 7. oven temperature is warming up to 260 DEG C in 210 DEG C, and the heating-up time is 10min; 8. oven temperature maintains 20min in 260 DEG C; 9. oven temperature is warming up to 345 DEG C in 260 DEG C, and the heating-up time is 10min; 10. oven temperature maintains 15min in 345 DEG C, and slow cooling to room temperature can obtain polyimide film-soda glass compound substrate afterwards.
4) preparation of molybdenum back contact film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0 × 10
-4pa, operating air pressure is 1.5Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 700W, Ar throughput is 50sccm, and the base target speed of travel is 5mm/s, and sedimentation time (reciprocal time of base target) is 4 times.2. operating air pressure is 0.5Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1800W, Ar throughput is 20sccm, and the base target speed of travel is 6mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
5) preparation of CuInGaSe absorbed layer film
1. base vacuum is 3.0 × 10
-4pa, underlayer temperature is 360 DEG C, coevaporation In, Ga, Se height Ga content preformed layer, wherein In source temperature is 820 DEG C, Ga source temperature is 930 DEG C, and Se source temperature is 260 DEG C, and evaporation time is 3min, control atomic ratio In:Ga=0.3: 0.7, (In+Ga)/Se=2: 3; 2. underlayer temperature is 380 DEG C, coevaporation In, Ga, Se initialization layer, and wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 17min; 3. underlayer temperature is 550 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1140 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 15min; What 4. underlayer temperature kept in second step is temperature-resistant, coevaporation In, Ga, Se, and wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 3min; 5. substrate is cooled, when evaporate substrate to be cooled to while Se 380 DEG C time, close Se evaporation source, then substrate cool to room temperature can be obtained the CIGS thin-film based on polyimide film-soda glass compound substrate.
6) preparation of sodium fluoride initialization layer
1. base vacuum is 8.0 × 10
-4pa, underlayer temperature is 250 DEG C, coevaporation NaF initialization layer, and wherein the temperature of NaF evaporation source is 840 DEG C, and evaporation time is 1min.2. underlayer temperature is 450 DEG C, anneals under Se atmosphere, and wherein the temperature of Se evaporation source is 260 DEG C, and annealing time is 25min.
7) preparation of cadmium sulfide buffer layer thin film
1. configure solution, prepare thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.
2. configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.3. sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 80 DEG C, and preparation time is 50min.4. after having prepared, by clean for sample deionized water rinsing.
8) preparation of native oxide zinc film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the i-ZnO of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit one deck native oxide zinc film at substrate surface.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 50 DEG C, and radio-frequency power is 1000W, Ar throughput is 15sccm, O
2throughput is 4sccm, and the base target speed of travel is 6mm/s, and sedimentation time (reciprocal time of base target) is 8 times.
9) preparation of zinc oxide aluminum film
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% be target, adopt DC magnetron sputtering process to deposit layer of ZnO at substrate surface: Al film.Technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25 DEG C, and direct current power is 1200W, Ar throughput is 17sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 12 times.
10) preparation of aluminium top electrode
1. base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 1min; Give heater strip 50A electric current, continue 1min; Give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 5min.2. after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Test result is identical with embodiment 1.
In sum, for preparing the flexible copper indium gallium selenide battery of high conversion efficiency, the invention provides a kind of preparation scheme of mixing sodium CIGS solar cell device based on polyimide film-soda glass compound substrate, polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, and prepare CIGS solar cell on its surface, after prepared by complete CIGS solar cell, it is separated with soda glass, formation take polyimide film as the flexible copper indium gallium selenide solar cell of substrate, realize preparing flexible battery with rigidity substrate.These preparation method's process conditions are convenient and easy, are conducive to applying on a large scale, especially in space and special occasions, have extremely important application prospect.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. mix sodium CIGS solar cell based on polyimide film-soda glass compound substrate for one kind, it is characterized in that: substrate is made up of soda glass and the polyimide film that is grown on its surface, wherein the thickness of soda glass is 1.5-2mm, and polyimides film thickness is 25-30 μm; Molybdenum back contact is grown on polyimide film-soda glass compound substrate, is divided into resistive formation and low resistivity layer, and wherein the thickness of resistive formation is 80-120nm, and the thickness of low resistivity layer is 600-700nm; CuInGaSe absorbed layer is grown on molybdenum film, and chemical molecular formula is CuIn
1-xga
xse
2, in formula, x is 0.25-0.35, and conduction type is p-type, and thickness is 1.5-2 μm; The film growth of sodium fluoride preformed layer is on CuInGaSe absorbed layer, and chemical molecular formula is NaF, and thickness is 20-30nm; Cadmium sulfide buffer growth is in CuInGaSe absorbed layer surface, and chemical molecular formula is CdS, and conduction type is N-shaped, and thickness is 45-50nm; Transparent window layer is grown on cadmium sulfide resilient coating, and be divided into high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, conduction type is N-shaped, and wherein the thickness of native oxide zinc film is 50-100nm, and the thickness of zinc oxide aluminum film is 0.4-0.6 μm; Aluminium upper electrode film is grown on transparent window layer, thereafter for being 0.8-1.5 μm.
2. a preparation method for polyimide film as claimed in claim 1-soda glass compound substrate, is characterized in that: adopt even glue, solidification preparation technology, preparation process is as follows:
1) removing surface is carried out to soda glass;
2) polyimides glue is coated on soda glass surface, adopts spin processes to carry out even glue;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained.
The described cleaning method to soda glass is: 1. the soda glass of 10cm × 10cm is put into potassium bichromate solution (solution configured by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and 300 ml deionized water) and soak 2h; 2. by soda glass taking-up deionized water rinsing after; 3. be placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, (ultrasonic frequency is 20-30kHz to put into supersonic wave cleaning machine cleaning, time is 20-25min) 4. soda glass is taken out from acetone soln, with deionized water rinsing; 5. soda glass is placed in the alcohol that concentration is 99.7%, puts into supersonic wave cleaning machine cleaning (ultrasonic frequency is 20-30kHz, and the time is 20-25min); 6. last soda glass to be taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times (ultrasonic frequency is 20-30kHz, and the time is 20-25min).
Described spin processes parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s.
Described parameters of curing is: 1. oven temperature is warming up to 125-135 DEG C in room temperature 25 DEG C, and the heating-up time is 10-15min; 2. oven temperature maintains 25-30min in 125-135 DEG C; 3. oven temperature is warming up to 150-160 DEG C in 125-135 DEG C, and the heating-up time is 5-10min; 4. oven temperature maintains 10-15min in 150-160 DEG C; 5. oven temperature is warming up to 200-210 DEG C in 150-160 DEG C, and the heating-up time is 5-10min; 6. oven temperature maintains 15-20min in 200-210 DEG C; 7. oven temperature is warming up to 250-260 DEG C in 200-210 DEG C, and the heating-up time is 5-10min; 8. oven temperature maintains 15-20min in 250-260 DEG C; 9. oven temperature is warming up to 340-350 DEG C in 250-260 DEG C, and the heating-up time is 5-10min; 10. oven temperature maintains 10-15min in 340-350 DEG C, and slow cooling is to room temperature afterwards.
3. the preparation method of a molybdenum back contact film as claimed in claim 1, it is characterized in that: adopt magnetically controlled DC sputtering preparation system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.
The preparation technology parameter of resistive formation film is: base vacuum: 3.0 × 10
-4pa, operating air pressure is 1-2Pa, and underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 500-700W, Ar throughput is 30-50sccm, and the base target speed of travel is 4-6mm/s, and sedimentation time (reciprocal time of base target) is for 2-4 time; The preparation technology parameter of low resistivity layer film is: operating air pressure is 0-0.5Pa, underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 1500-2000W, Ar throughput is 15-20sccm, the base target speed of travel is 4-6mm/s, and sedimentation time (reciprocal time of base target) is for 4-6 time.
4. a preparation method for the CuInGaSe absorbed layer film as described in right 1, is characterized in that: adopt selenizing stove film preparing system, application coevaporation modified model three-step approach preparation technology, and preparation process is as follows:
1) base vacuum is 3.0 × 10
-4pa, underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se height Ga content preformed layer, wherein In source temperature is 820-850 DEG C, Ga source temperature is 920-950 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 2-3min, control atomic ratio In: Ga=0.3: 0.7, (In+Ga)/Se=2: 3;
2) underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se initialization layer, 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, evaporation time is 15-20min, controls atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se=2: 3;
3) underlayer temperature is 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;
4) what underlayer temperature kept in second step is temperature-resistant, 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, evaporation time is 2-4min, and obtain the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, control Cu/ (In+Ga) ratio is at 0.88-0.92.
5) substrate being cooled, when evaporating underlayer temperature when substrate to be cooled to while Se the first step, closing Se evaporation source, then by substrate cool to room temperature.
5. the preparation method of sodium fluoride initialization layer film according to claim 1, it is characterized in that: the film growth of sodium fluoride preformed layer is on CuInGaSe absorbed layer, achieve the rear doping that three-step approach prepares the sodium element of CIGS thin-film solar cell like this, sodium fluoride preformed layer adopts selenizing stove film preparing system, application coevaporation preparation technology, preparation process is as follows:
1) base vacuum is 8.0 × 10
-4pa, underlayer temperature is 200-300 DEG C, coevaporation NaF initialization layer, and wherein the temperature of NaF evaporation source is 800-850 DEG C, and evaporation time is 1-2min.
2) underlayer temperature is 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.
6. a preparation method for cadmium sulfide buffer layer thin film as claimed in claim 1, is characterized in that: described preparation technology parameter is: 1. configure solution, prepares thiocarbamide SC (NH
2)
2solution 1L, concentration is 0.01mol/L; Cadmium acetate (CH
3cOO)
2cd and Ammonium Acetate CH
3cOONH
4mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and Ammonium Acetate solubility is 0.003mol/L; Ammoniacal liquor NH
3h
2o solubility is 1.3 × 10
-3mol/L.2. configure reaction solution 1L, get the various solution configured in the first step; Wherein thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL, ammonia spirit 4.Stir.3. sample is put into beaker, and beaker is put into water-bath.Bath temperature is set to 78-80 DEG C, and preparation time is 50-60min.4. after having prepared, by clean for sample deionized water rinsing.
7. a preparation method for native oxide zinc film as claimed in claim 1, is characterized in that: described technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 800-1000W, Ar throughput is 10-20sccm, O
2throughput is 2-6sccm, and the base target speed of travel is 2-6mm/s, and sedimentation time (reciprocal time of base target) is for 6-10 time.
8. a preparation method for zinc oxide aluminum film as claimed in claim 1, is characterized in that: described technological parameter is: base vacuum: 3.0 × 10
-4pa, underlayer temperature is room temperature 25 DEG C, and direct current power is 1000-1200W, Ar throughput is 12-18sccm, and the base target speed of travel is 2-6mm/s, and sedimentation time (reciprocal time of base target) is for 10-15 time.
9. a preparation method for aluminium upper electrode film as claimed in claim 1, is characterized in that: described technological parameter is: 1. base vacuum: 3.0 × 10
-4pa, gives heater strip 20A electric current, continues 1-2min; Give heater strip 50A electric current, continue 1-2min; Give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min.2. after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, cool afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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