CN105977318A - Sodium-doped CIGS (copper indium gallium selenide) film based on composite substrate and preparation method thereof - Google Patents
Sodium-doped CIGS (copper indium gallium selenide) film based on composite substrate and preparation method thereof Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 92
- 229920001721 polyimide Polymers 0.000 claims abstract description 57
- 239000004642 Polyimide Substances 0.000 claims abstract description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 47
- 239000010408 film Substances 0.000 claims abstract description 16
- 238000000427 thin-film deposition Methods 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000001704 evaporation Methods 0.000 claims description 33
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 30
- 230000008020 evaporation Effects 0.000 claims description 29
- 229910052711 selenium Inorganic materials 0.000 claims description 28
- 229910052733 gallium Inorganic materials 0.000 claims description 24
- 229910052738 indium Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 235000013024 sodium fluoride Nutrition 0.000 claims description 15
- 239000011775 sodium fluoride Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 230000002000 scavenging effect Effects 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 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 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000928 Yellow copper Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical class [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000004080 punching Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 34
- 238000004528 spin coating Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 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
- 229920002647 polyamide Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- ZIALXKMBHWELGF-UHFFFAOYSA-N [Na].[Cu] Chemical compound [Na].[Cu] ZIALXKMBHWELGF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
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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
- H01L31/02—Details
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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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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a sodium-doped CIGS (copper indium gallium selenide) film based on a composite substrate and a preparation method thereof. The substrate is composed of soda glass and a polyimide film grown on the surface of the soda glass, the thickness of the soda glass is in the range of 1.5-2mm, the thickness of the polyimide film is in the range of 25-30[mu]m, the chemical formula of a CIGS film grown on the surface of the composite substrate is CuIn<1-x>Ga<x>Se<2>, x represents 0.25-0.35, and the conduction is in a p type, the CIGS film CuIn<1-x>Ga<x>Se<2> is arranged on the surface of the polyimide film-soda glass composite substrate by means of thin-film deposition, and the thickness is in the range of 1.5-2[mu]m. The CIGS film based on the polyimide film-soda glass composite substrate is good in quality, large in crystal grain, and has fewer defects, a flexible solar cell is made by a rigid substrate, and the preparation method is simple and easy to implement, and is favorable for large-scale popularization and application.
Description
Technical field
The present invention relates to thin film solar cell technical field, particularly a kind of based on polyimide film-soda glass
The CIGS thin-film of compound substrate.
Background technology
CIGS material belongs to I-III-VI race quaternary compound semiconductor, has the crystal structure of Chalkopyrite.
CIGS thin-film too can battery since 20 century 70s occur, obtain very fast development, and will be by
Step realizes industrialization.This battery has following characteristics: 1) energy gap of CIGS can be at 1.04ev-1.67ev
In the range of adjust；2) CIGS is a kind of direct band-gap semicondictor, is up to the absorptance of visible ray
105cm-1, CuInGaSe absorbed layer thickness only needs 1.52.5 μm, the thickness of whole battery to be 3-4 μm；3) anti-
Irradiation ability is strong, compares and is suitable as space power system；4) conversion efficiency is high, German solar energys in 2014 and hydrogen
The little area CIGS solar cell conversion efficiency that energy research center (ZSW) is developed up to 21.7%；5)
Low light level characteristic is good.Therefore CIGS polycrystalline thin-film solar cell is expected to become the main flow product of solar cell of future generation
One of product.
The Na mixing 0.1% in CIGS thin film can make CIGS solar cell performance improve 30～50%,
In tradition Na-Ca glass (SLG) substrate CIGS solar cell preparation, Na can be absorbed to CIGS by substrate
Layer spontaneous diffusion and realize the incorporation of Na.But, owing to PI substrate is without Na, therefore must add in preparation
Enter Na and mix technique, improve the performance of CIGS thin film, improve flexible Pl substrate CIGS thin film further
The photoelectric transformation efficiency of solar cell.Therefore, to copper and indium based on polyimide film-soda glass compound substrate
Gallium selenium absorbed layer thin film mixes sodium and just becomes particularly important.
At present, during preparing CIGS thin-film solar cell, the method mixing Na has a variety of, including:
On substrate, the initialization layer of one layer of NaF was first deposited before preparing Mo back electrode；On Mo back electrode surface
Deposition initialization layer Han Na；Na element is co-deposited (for the most general during preparing CuInGaSe absorbed layer
All over use three-step approach prepare CIGS, the first step can be divided into again to mix, second be co-doped with, the 3rd step is co-doped with)
Etc. method.Although using these methods doping Na element can improve the electric property of thin film solar cell,
But finding by observing its absorbed layer crystal structure, absorbed layer thin film crystallite dimension compares the sample not mixing Na
Having reduced, crystal boundary increases, and this most again can be to the performance band of CIGS thin-film solar cell
Carry out negative impact.
Summary of the invention
It is an object of the invention to for above-mentioned existing problems, it is provided that a kind of based on compound substrate mix sodium copper and indium
Gallium selenium thin film and preparation method thereof, this mixes sodium CIGS thin-film for being combined based on polyimide film-soda glass
Substrate mix sodium CIGS thin-film, it prepares flexible battery with rigidity substrate, and the CIGS thin-film of preparation is attached
The property is outstanding, crystalline quality good, crystal grain is big, defect is few；And after mixing sodium element, can be greatly
Improve the electrology characteristic of CIGS thin-film, improve open-circuit voltage and the fill factor, curve factor of battery, and then promote assembly
The performance of battery.
Technical scheme:
A kind of CIGS thin-film based on polyimide film-soda glass compound substrate, chemical molecular formula is
Culn1-xGaxSe2, in formula, x is 0.25-0.35, and conduction type is p-type；This CIGS thin-film Culn1-xGaxSe2
Thin film deposition is 1.5-2 μm in polyimide film-soda glass compound substrate surface, thickness.
A kind of described preparation method mixing sodium CIGS thin-film based on compound substrate, first by polyimides
Glue is coated on soda glass surface, is solidified into polyimide film-soda glass compound substrate, then on its surface
Make one layer of very thin sodium fluoride initialization layer thin film, prepare CIGS thin-film the most thereon.
Described acid imide film-soda glass compound substrate, by soda glass and the polyimides that is grown on its surface
Film is constituted, and wherein the thickness of soda glass is 1.5-2mm, and polyimides film thickness is 25-30 μm；Use even
Prepared by glue, solidification preparation technology, step is as follows:
1) by clean for soda glass removing surface；
2) preparation of polyimides prefabricated membrane: polyimides glue is coated on soda glass surface, uses spin coating
Technique carries out spin coating, and the technological parameter of spin processes is: rotating speed is 1300-1500r/min, and the time is 35-45s；
3) solidification of polyimides prefabricated membrane: the soda glass after spin coating is put into baking oven and controls ginseng by temperature
Number solidifies, and i.e. can get polyimide film-soda glass compound substrate.
The cleaning method on described soda glass surface is: the soda glass of 10cm × 10cm 1) is put into weight chromium
Acid potassium-concentrated sulfuric acid solution, it is by 300 grammes per square metre Neutral potassium chromates, 3 liters of concentrated sulphuric acids and the configuration of 300 ml deionized water
Become, soak 2h；2) by soda glass taking-up deionized water rinsing 2-3 time；3) clean soda will be rinsed
Glass is placed in the acetone soln that mass percent concentration is 99.5%, puts in ultrasonic washing unit and cleans, super
Frequency of sound wave is 20-30kHz, and scavenging period is 20-25min；4) soda glass is taken out from acetone soln,
With deionized water rinsing 2-3 time；5) then soda glass is placed in the second that mass percent concentration is 99.7%
In alcohol, putting in ultrasonic washing unit and clean, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min；
6) finally soda glass is taken out from ethanol, put in the beaker filling deionized water, be placed in ultrasound wave clear
Cleaning in washing machine, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min.
The temperature control parameter of described solidification is: 1) oven temperature is warming up to 125-135 DEG C in 25 DEG C, heats up
Time is 10-15min；2) oven temperature maintains 25-30min in 125-135 DEG C, then heats to
150-160 DEG C, the heating-up time is 5-10min；3) oven temperature maintains 10-15min in 150-160 DEG C, so
After be warming up to 200-210 DEG C, the heating-up time is 5-10min；4) oven temperature is in 200-210 DEG C of maintenance
15-20min, then heats to 250-260 DEG C, and the heating-up time is 5-10min；5) oven temperature is in 250-260 DEG C
Maintaining 15-20min, then heat to 340-350 DEG C, the heating-up time is 5-10min；6) oven temperature in
340-350 DEG C maintains 10-15min, is finally naturally cooling to 25 DEG C.
The preparation method of described sodium fluoride initialization layer thin film, sodium fluoride initialization layer thin film deposition in polyimide film-
Soda glass compound substrate surface, thickness is 20-30nm, uses selenizing stove film preparing system and coevaporation system
Standby technique, preparation method is: base vacuum be 3.0 × 10-4Pa, at underlayer temperature is 200-300 DEG C, altogether
Evaporation NaF initialization layer, wherein the temperature of NaF evaporation source is 770-820 DEG C, and evaporation time is 3-7min.
A kind of preparation method of described CIGS thin-film based on polyimide film-soda glass compound substrate,
Using selenizing stove film preparing system, apply coevaporation three-step approach preparation technology, preparation process is as follows:
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are
At 350-400 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is
820-850 DEG C, Ga source temperature is 920-950 DEG C, and Se source temperature is 240-280 DEG C, during evaporation
Between be 2-3min, control In/Ga atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se initialization layer, wherein In evaporation source
Temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is 240-280 DEG C,
Evaporation time is 15-20min, controls atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se2: 3:
3) at underlayer temperature is 550-580 DEG C, coevaporation Cu, Se, wherein Cu source temperature is
1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein
In source temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is
240-280 DEG C, evaporation time is 2-4min, obtains the CIGS p-type yellow copper structure of the leanest Cu,
The atomic ratio controlling Cu/ (In+Ga) is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step, close
Close Se evaporation source, then substrate is cooled to 18-25 DEG C.
The principle analysis of the present invention:
Preparing crystalline quality preferably to meet, crystal grain is relatively big, the defect less CIGS fexible film sun
The requirement of battery, it is necessary to selecting substrate soft, light, thermal coefficient of expansion more mates with CIGS thin-film
Substrate.Polyimide film-soda glass compound substrate can rely on soda glass and CuInGaSe absorbed layer thin film
The feature that thermal coefficient of expansion is closer to, prepares CIGS thin-film solar cell in compound substrate.The most again
Thin film solar cell is separated from soda glass surface for substrate with polyimides, obtains flexible copper indium gallium selenide thin-film
Solar cell, to realize preparing flexible solar cell with rigidity substrate.Wherein CIGS thin-film uses coevaporation
Prepared by one-step technology, obtain crystalline quality preferable, and crystal grain is relatively big, the less CIGS thin-film of defect, this
Preparation method is convenient, fast, energy-conservation, is suitable for large-scale industrialization and produces.
The benefit analysis of CIGS thin-film based on polyimide film-soda glass compound substrate:
1) polyimides glue is applied to glass surface, can preferably improve the roughness of substrate.
2) thermal coefficient of expansion of polyimides itself is bigger, it is impossible to well carry out with CIGS material itself
Coupling.It is easily deformed at relatively high temperatures, causes thin film to loosen, easily come off.And it is grown on glass surface
Polyimides, relies on the adhesive force between glass so that it is be not susceptible to relatively large deformation, with CIGS material
More mate.
3) due to glass contact, be not susceptible to deformation, polyimides can be given and be closer in its heatproof
The temperature of limit, contributes to CIGS thin-film and preferably grows.
4) its epontic CIGS thin-film crystalline quality is preferable, and crystal grain is relatively big, and defect is less, afterwards
Again it is separated from glass, it is possible to prepare the flexible copper indium gallium selenide sun electricity with bigger columnar grain
Pond, and convenient, fast, energy-conservation, it is suitable for large-scale industrialization and produces.
The invention have the advantage that this kind CIGS thin-film based on polyimide film-soda glass compound substrate
Crystalline quality is good, crystal grain is big, defect is few, utilizes rigidity substrate to prepare flexible solar cell；Its preparation method letter
Single, easy to implement, the most large-scale popularization and application, especially have the heaviest in space and special occasions
The application prospect wanted.
Accompanying drawing explanation
Figure is polyimide film-soda glass composite substrate structure schematic diagram.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that the present invention program, below in conjunction with the accompanying drawings and embodiment
The present invention is described in further detail.
Embodiment 1:
A kind of CIGS thin-film based on polyimide film-soda glass compound substrate, as it is shown in figure 1, change
Credit minor is Culn1-xGaxSe2, in formula, x is 0.25, and conduction type is p-type, this CIGS thin-film
Culn1-xGaxSe2Thin film deposition is 1.5 μm in polyimide film-soda glass compound substrate surface, thickness；Its
Preparation method, uses spin coating, curing process to prepare polyimide film-soda glass substrate, and use selenizing stove
Film preparing system, application coevaporation one-step preparation process is prepared the CIGS thin-film in compound substrate, is made
Standby step is as follows:
(1) cleaning of soda glass
1) soda glass of 10cm × 10cm being put into potassium dichromate-concentrated sulfuric acid solution, it is by 300 grams
Potassium dichromate, 3 liters of concentrated sulphuric acids and the configuration of 300 ml deionized water form, and soak 2h；2) by soda glass
Take out and use deionized water rinsing 2 times；3) soda glass rinsing cleaning being placed in mass percent concentration is
In the acetone soln of 99.5%, putting in ultrasonic washing unit and clean, ultrasonic frequency is 20kHz, during cleaning
Between be 25min；4) soda glass is taken out from acetone soln, with deionized water rinsing 2 times；5) then
Soda glass is placed in the ethanol that mass percent concentration is 99.7%, puts in ultrasonic washing unit and clean,
Ultrasonic frequency is 20kHz, and scavenging period is 25min；6) finally soda glass is taken out from ethanol,
Putting in the beaker filling deionized water, be placed in ultrasonic washing unit cleaning, ultrasonic frequency is 20kHz,
Scavenging period 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 with
It is overlying on soda glass surface, with the rotating speed at the uniform velocity spin coating 45s of 1300r/min, i.e. can get polyimides prefabricated
Film.
(3) solidification of polyimides prefabricated membrane
Soda glass after spin coating being put into baking oven solidify, temperature control parameter is: 1) oven temperature
Being warming up to 125 DEG C in 25 DEG C, the heating-up time is 15min；2) oven temperature maintains 30min in 125 DEG C, so
After be warming up to 150 DEG C, the heating-up time is 5min；3) oven temperature maintains 15min in 150 DEG C, then heats up
To 200 DEG C, the heating-up time is 5min；4) oven temperature maintains 20min in 200 DEG C, then heats to 250 DEG C,
Heating-up time is 5min；5) oven temperature maintains 20min in 250 DEG C, then heats to 350 DEG C, during intensification
Between be 10min；6) oven temperature maintains 10min in 350 DEG C, is finally naturally cooling to 25 DEG C, the most available
Polyimide film-soda glass compound substrate.
(4) preparation method of described sodium fluoride initialization layer thin film, sodium fluoride initialization layer thin film deposition is sub-in polyamides
Amine film-soda glass compound substrate surface, uses selenizing stove film preparing system and coevaporation preparation technology, system
Preparation Method is: base vacuum be 3.0 × 10-4Pa, underlayer temperature be at 200 DEG C, coevaporation NaF is preset
Layer, wherein the temperature of NaF evaporation source is 770 DEG C, and evaporation time is 7min.
(5) preparation of CIGS thin-film based on polyimide film-soda glass compound substrate
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are
At 350 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is 820 DEG C,
Ga source temperature is 920 DEG C, and Se source temperature is 240 DEG C, and evaporation time is 3min, controls In/Ga
Atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 350 DEG C, coevaporation In, Ga, Se initialization layer, wherein In source temperature
Being 850 DEG C, Ga source temperature is 880 DEG C, and Se source temperature is 240 DEG C, and evaporation time is 15min,
Control atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se=2: 3；
3) at underlayer temperature is 550 DEG C, coevaporation Cu, Se, wherein Cu source temperature is 1160 DEG C,
Se source temperature is 240 DEG C, and evaporation time is 15min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein
In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 240 DEG C, evaporation
Time is 4min, obtains the CIGS p-type yellow copper structure of the leanest Cu, controls the former of Cu/ (In+Ga)
Sub-ratio is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step,
Close Se evaporation source, then substrate is cooled to 25 DEG C.
Embodiment 2:
A kind of CIGS thin-film based on polyimide film-soda glass compound substrate, as it is shown in figure 1, change
Credit minor is Culn1-xGaxSe2, in formula, x is 0.35, and conduction type is p-type；This CIGS thin-film
CuIn1-xGaxSe2Thin film deposition is 2 μm in polyimide film-soda glass compound substrate surface, thickness；Its
Preparation method uses spin coating, curing process to prepare polyimide film-soda glass substrate, and use selenizing stove thin
Film preparation system, application coevaporation one-step preparation process is prepared the CIGS thin-film in compound substrate, is prepared
Step is as follows:
(1) cleaning of soda glass
1) soda glass of 10cm × 10cm being put into potassium dichromate-concentrated sulfuric acid solution, it is by 300
Grammes per square metre Neutral potassium chromate, 3 liters of concentrated sulphuric acids and the configuration of 300 ml deionized water form, and soak 2h；2) by soda glass
Glass takes out uses deionized water rinsing 3 times；3) soda glass rinsing cleaning being placed in mass percent concentration is
In the acetone soln of 99.5%, putting in ultrasonic washing unit and clean, ultrasonic frequency is 30kHz, during cleaning
Between be 20min；4) soda glass is taken out from acetone soln, with deionized water rinsing 3 times；5) then
Soda glass is placed in the ethanol that mass percent concentration is 99.7%, puts in ultrasonic washing unit and clean,
Ultrasonic frequency is 30kHz, and scavenging period is 20min；6) finally soda glass is taken out from ethanol,
Putting in the beaker filling deionized water, be placed in ultrasonic washing unit cleaning, ultrasonic frequency is 30kHz,
Scavenging period 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 with
It is overlying on soda glass surface, with the rotating speed at the uniform velocity spin coating 40s of 1400r/min, i.e. can get polyimides prefabricated
Film.
(3) solidification of polyimides prefabricated membrane
Soda glass after spin coating being put into baking oven solidify, temperature control parameter is: 1) oven temperature
Being warming up to 130 DEG C in 25 DEG C, the heating-up time is 20min；2) oven temperature maintains 25min in 130 DEG C, so
After be warming up to 160 DEG C, the heating-up time is 10min；3) oven temperature maintains 10min in 160 DEG C, then rises
Temperature is to 210 DEG C, and the heating-up time is 10min；1) oven temperature maintains 20min in 210 DEG C, then heats to
260 DEG C, the heating-up time is 10min；5) oven temperature maintains 20min in 260 DEG C, then heats to 345 DEG C,
Heating-up time is 10min；6) oven temperature maintains 15min in 345 DEG C, is finally naturally cooling to 25 DEG C, i.e.
Available polyimide film-soda glass compound substrate.
(4) preparation method of described sodium fluoride initialization layer thin film, sodium fluoride initialization layer thin film deposition is sub-in polyamides
Amine film-soda glass compound substrate surface, uses selenizing stove film preparing system and coevaporation preparation technology, system
Preparation Method is: base vacuum be 3.0 × 10-4Pa, underlayer temperature be at 300 DEG C, coevaporation NaF is preset
Layer, wherein the temperature of NaF evaporation source is 820 DEG C, and evaporation time is 3min.
(5) preparation of CIGS thin-film based on polyimide film-soda glass compound substrate
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are
At 400 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is 850 DEG C,
Ga source temperature is 950 DEG C, and Se source temperature is 280 DEG C, and evaporation time is 2min, controls In/Ga
Atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 400 DEG C, coevaporation In, Ga, Se initialization layer, wherein In source temperature
Being 900 DEG C, Ga source temperature is 920 DEG C, and Se source temperature is 280 DEG C, and evaporation time is 18min,
Control atomic ratio In: Ga=0.7: 0.3, (In+Ga)/Se=2: 3；
3) at underlayer temperature is 580 DEG C, coevaporation Cu, Se, wherein Cu source temperature is 1160 DEG C,
Se source temperature is 280 DEG C, and evaporation time is 18min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein
In source temperature is 900 DEG C, and Ga source temperature is 920 DEG C, and Se source temperature is 280 DEG C, evaporation
Time is 4min, obtains the CIGS p-type yellow copper structure of the leanest Cu, controls the former of Cu/ (In+Ga)
Sub-ratio is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step, close
Close Se evaporation source, then substrate is cooled to 25 DEG C.
In sum, for preparing the flexible copper indium gallium selenide battery of high conversion efficiency, the invention provides a kind of base
In the preparation scheme of the CIGS thin-film of polyimide film-soda glass compound substrate, polyimides glue is coated with
In soda glass surface, it is solidified into polyimide film-soda glass compound substrate, and steams altogether in its surface applications
Send out three-steps process and prepare CIGS thin-film, prepare flexible battery with rigidity substrate.This kind is based on polyimides
The CIGS thin-film crystalline quality of film-soda glass compound substrate is preferable, and crystal grain is relatively big, and defect is less.Should
Preparation method process conditions are convenient and easy, the most large-scale popularization and application, especially at space and special occasions
In there is extremely important application prospect.
The above is only the preferred embodiment of the present invention, it is noted that common for the art
For technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, this
A little improvements and modifications also should be regarded as protection scope of the present invention.
Claims (5)
1. a CIGS thin-film based on polyimide film-soda glass compound substrate, it is characterised in that: change
Credit minor is CuIn1-xGaxSe2, in formula, x is 0.25-0.35, and conduction type is p-type；This CIGS is thin
Film CuIn1-xGaxSe2Thin film deposition is in polyimide film-soda glass compound substrate surface, and thickness is
1.5-2μm。
2. the preparation method mixing sodium CIGS thin-film based on compound substrate as claimed in claim 1, its
It is characterised by: first polyimides glue is coated on soda glass surface, is solidified into polyimide film-soda glass
Glass compound substrate, then prepares one layer of very thin sodium fluoride initialization layer thin film, prepares the most thereon on its surface
CIGS thin-film.
CIGS thin-film based on polyimide film-soda glass compound substrate the most according to claim 2,
It is characterized in that: the cleaning method on described soda glass surface is: 1) by the soda glass of 10cm × 10cm
Putting into potassium dichromate-concentrated sulfuric acid solution, it is gone by 300 grammes per square metre Neutral potassium chromates, 3 liters of concentrated sulphuric acids and 300 milliliters
Ionized water configuration forms, and soaks 2h；2) by soda glass taking-up deionized water rinsing 2-3 time；3) will punching
The soda glass of detergent is placed in the acetone soln that mass percent concentration is 99.5%, puts into ultrasonic waves for cleaning
Cleaning in machine, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min；4) by soda glass from third
Ketone solution takes out, with deionized water rinsing 2-3 time；5) then soda glass is placed in mass percent dense
Degree is in the ethanol of 99.7%, puts in ultrasonic washing unit and cleans, and ultrasonic frequency is 20-30kHz, cleans
Time is 20-25min；6) finally soda glass is taken out from ethanol, put into the beaker filling deionized water
In, it being placed in ultrasonic washing unit cleaning, ultrasonic frequency is 20-30kHz, and scavenging period is 20-25min.
CIGS thin-film based on polyimide film-soda glass compound substrate the most according to claim 2,
It is characterized in that: the temperature control parameter of described solidification is: 1) oven temperature is warming up to 125-135 DEG C in 25 DEG C,
Heating-up time is 10-15min；2) oven temperature maintains 25-30min in 125-135 DEG C, then heats to
150-160 DEG C, the heating-up time is 5-10min；3) oven temperature maintains 10-15min in 150-160 DEG C, so
After be warming up to 200-210 DEG C, the heating-up time is 5-10min；4) oven temperature is in 200-210 DEG C of maintenance
15-20min, then heats to 250-260 DEG C, and the heating-up time is 5-10min；5) oven temperature is in 250-260 DEG C
Maintaining 15-20min, then heat to 340-350 DEG C, the heating-up time is 5-10min；6) oven temperature in
340-350 DEG C maintains 10-15min, is finally naturally cooling to 25 DEG C.
5. a CIGS based on polyimide film-soda glass compound substrate as claimed in claim 1 is thin
The preparation method of film, it is characterised in that: use selenizing stove film preparing system, application coevaporation three-step approach to prepare
Technique, preparation process is as follows:
1) sample to be prepared is placed in coevaporation system, is 3.0 × 10 at base vacuum-4Pa, underlayer temperature are
At 350-400 DEG C, coevaporation In, Ga, Se height Ga content initialization layer, wherein In source temperature is
820-850 DEG C, Ga source temperature is 920-950 DEG C, and Se source temperature is 240-280 DEG C, during evaporation
Between be 2-3min, control In/Ga atomic ratio be 0.3: 0.7, the atomic ratio of (In+Ga)/Se is 2: 3；
2) at underlayer temperature is 350-400 DEG C, coevaporation In, Ga, Se initialization layer, wherein In evaporation source
Temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and 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) at underlayer temperature is 550-580 DEG C, coevaporation Cu, Se, wherein Cu source temperature is
1120-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 15-20min；
4) underlayer temperature keep step 2) temperature-resistant under the conditions of, coevaporation In, Ga, Se, wherein
In source temperature is 850-900 DEG C, and Ga source temperature is 880-920 DEG C, and Se source temperature is
240-280 DEG C, evaporation time is 2-4min, obtains the CIGS p-type yellow copper structure of the leanest Cu,
The atomic ratio controlling Cu/ (In+Ga) is 0.88-0.92；
5) substrate is cooled down, when evaporating underlayer temperature when substrate is cooled to while Se the first step,
Close Se evaporation source, then substrate is cooled to 18-25 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109841702A (en) * | 2017-11-27 | 2019-06-04 | 中国电子科技集团公司第十八研究所 | Preparation method of alkali metal doped copper indium gallium selenide thin film solar cell absorption layer |
| CN110061075A (en) * | 2019-04-26 | 2019-07-26 | 圣晖莱南京能源科技有限公司 | A kind of CIGS solar battery and preparation method thereof of metal Na doping |
| CN113314629A (en) * | 2021-05-26 | 2021-08-27 | 深圳市泰晶太阳能科技有限公司 | CIGS flexible amorphous silicon solar module |
-
2016
- 2016-07-07 CN CN201610333959.6A patent/CN105977318A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109841702A (en) * | 2017-11-27 | 2019-06-04 | 中国电子科技集团公司第十八研究所 | Preparation method of alkali metal doped copper indium gallium selenide thin film solar cell absorption layer |
| CN110061075A (en) * | 2019-04-26 | 2019-07-26 | 圣晖莱南京能源科技有限公司 | A kind of CIGS solar battery and preparation method thereof of metal Na doping |
| CN110061075B (en) * | 2019-04-26 | 2020-06-26 | 圣晖莱南京能源科技有限公司 | CIGS solar cell doped with metal Na and preparation method thereof |
| CN113314629A (en) * | 2021-05-26 | 2021-08-27 | 深圳市泰晶太阳能科技有限公司 | CIGS flexible amorphous silicon solar module |
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