CN107871795B - A kind of regulation method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate - Google Patents
A kind of regulation method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate Download PDFInfo
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- CN107871795B CN107871795B CN201711143306.2A CN201711143306A CN107871795B CN 107871795 B CN107871795 B CN 107871795B CN 201711143306 A CN201711143306 A CN 201711143306A CN 107871795 B CN107871795 B CN 107871795B
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- band gap
- zinc tin
- copper zinc
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 63
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 44
- 239000011733 molybdenum Substances 0.000 title claims abstract description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229940031098 ethanolamine Drugs 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004151 rapid thermal annealing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 55
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000010409 thin film Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000004544 sputter deposition Methods 0.000 abstract description 6
- 238000003475 lamination Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229960001296 zinc oxide Drugs 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
- H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The regulation method for the cadmium doping copper zinc tin sulfur selenium film band gap gradient based on flexible molybdenum substrate that the present invention relates to a kind of.Flexible molybdenum foil is cleaned with electrodeposition process first, then can be used for preparing the thin film solar cell with the variation of CZCTSSe band gap gradient by the variation of lamination realization CZCTSSe film band gap gradient with the mode that solwution method dissolves simple substance and rear selenization.The present invention is using flexible molybdenum as substrate, and the utilization of high-purity molybdenum foil solves the adhesion issues between film and substrate, and instead of the splash-proofing sputtering metal conductive back contact layer in battery structure, to reduce manufacturing cost；Precursor solution is prepared using solwution method dissolution simple substance, the shortcomings that foreign ion can be introduced when avoiding dissolved metal salt, and solwution method is low in cost, simple process, is easy to large area production, it is environmentally protective, large-scale serial production and commercialized demand are met, it is practical.
Description
Technical field
The invention belongs to thin film solar cell Material Fields, and in particular to a kind of CZCTSSe based on flexible molybdenum substrate is thin
The regulation method of film band gap gradient.
Background technique
There is an urgent need to flexible solar cells for photovoltaic industry at present, because it has material soft compared to conventional rigid battery
It is soft, thickness is thin, light weight, power-mass ratio are high, production process energy consumption is small, is easily achieved roll-to-roll large area continuous production, just
It is and mountable on non-planar platform, it is expected to which that the application field for extending solar cell answers it in space in carry the advantages that
With, military field, architecture-integral, the fields such as outdoor sports have broad application prospects.With organic film and other metals
Foil (such as stainless steel, aluminium, chromium steel, titanium) is compared, and molybdenum foil has high temperature resistant (> 600 DEG C), and mechanical strength is good, lightweight and compatible
The advantages that thermal linear expansion coefficient.In addition, the utilization of some metal foils needs additional resistance if stainless steel is in battery structure
Barrier, to avoid the deep-level impurities such as iron, and the utilization of high-purity molybdenum foil solves adhesion issues, and instead of in battery structure
Splash-proofing sputtering metal conductive back contact layer, to reduce manufacturing cost.
Flexible copper zinc-tin sulfur system solar cell preparation method has continuous ionic layer, electrodeposition process, reel-to-reel printing at present
Technology, magnetron sputtering method.The flexible copper-zinc-tin-selenium solar cell of sputtering method preparation obtains 6.1% highest transfer efficiency, but sputters
Method there are problems that being difficult to effectively controlling film composition.And compared to other methods, solwution method has low in cost, thin film composition
The advantages such as be evenly distributed, and the rigid copper-zinc-tin-sulfur selenium film solar battery of peak efficiency 12.7% is also based on solwution method at present
's.Therefore flexible battery is prepared with solwution method to be of great significance for the development of this field.
Absorbed layer of the copper zinc tin sulfur selenium as solar cell, optical band gap are regulation thin film solar cell photoelectric conversion effects
The important parameter of rate, especially with the stacked solar cell, cascade solar cell of different band gap.Currently, copper zinc tin sulfur selenium band gap adjusting method be
Metal chloride, doped metallic oxide are introduced in copper zinc tin sulfur selenium, the disadvantage is that: chlorine, oxygen heteroatom can be introduced in system.
And although hydrazine solution can dissolve metal simple-substance, metal sulfide and metal selenide, but have in itself severe toxicity, it is inflammable and explosive,
It is unfavorable for industrial production.Therefore, it is had a very important significance using green safe dicyandiamide solution to adjust band gap.
Summary of the invention
A kind of cadmium doping copper zinc tin sulfur selenium (CZCTSSe) the object of the present invention is to provide adjusting based on flexible molybdenum substrate is thin
The method of film strips gap.
To achieve the above object, the present invention adopts the following technical scheme:
(1) cleaning treatment is carried out to substrate molybdenum foil: molybdenum foil is used into electro-deposition in the mixed solution of the concentrated sulfuric acid and methanol
Method is cleaned, and is then rinsed well and is used with deionized water and is dried with nitrogen；
(2) after mixing copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder, ethylenediamine and ethylene dithiol are added to
In alcohol, heating stirring 1.5 hours, the additional amount of cadmium powder is adjusted, prepares the solution of different cadmium concentrations, wherein Cd/(Cd+Zn)
Molar percentage be 0-10%；
(3) a certain proportion of stabilizer, heating stirring 1 is added in the solution of the different cadmium concentrations of step (2) preparation again
Hour, the precursor solution of different cadmium concentrations is made, the stabilizer is ethanol amine, thioacetic acid, ethylene glycol monomethyl ether according to object
The amount ratio of matter is made into for 1: 1: 2；
(4) precursor solution of different cadmium concentrations prepared by step (3) is coated in same molybdenum foil in batches using spin-coating method
On, annealing temperature is 250 ~ 350 DEG C, and prefabricated layer film is made；The thickness of the CZCTSSe film is controlled by the spin coating number of plies
System；
(5) prefabricated layer film is placed in the cylindrical graphite box for filling selenium powder 0.5g；
(6) graphite is put into the rapid thermal annealing full of argon gas (RTP) selenizing furnace；Allow selenizing furnace be warming up to 500 ~
600 DEG C, heating rate is 9 DEG C/S；Room temperature is naturally cooled to after keeping 8 ~ 20min；Cadmium is made and adulterates copper zinc tin sulfur selenium film.
It is custerite (Kesterite) structure that cadmium, which adulterates copper zinc tin sulfur selenium film,.
The optical band gap of cadmium doping copper zinc tin sulfur selenium film changes between 0.9 eV to 1.2 eV.
The regulation method of the band gap gradient of CZCTSSe film: being respectively adopted the solution by portions spin coating of different levels of doping, leads to
Cross the variation that lamination realizes band gap gradient.
A kind of method tool of cadmium doping copper zinc tin sulfur selenium film band gap of the adjusting provided by the invention based on flexible molybdenum substrate
There are following characteristics and advantage:
(1) for the present invention using flexible molybdenum as substrate, the utilization of high-purity molybdenum foil solves the adhesiveness between film and substrate
Problem, and instead of the splash-proofing sputtering metal conductive back contact layer in battery structure, to reduce manufacturing cost；
(2) present invention is prepared when precursor solution avoids dissolved metal salt using solwution method dissolution simple substance can introduce miscellaneous original
The disadvantage of son, and solwution method is low in cost, simple process, is easy to large area production, it is environmentally protective, it is raw to meet extensive batch
Production and commercialized demand, it is practical；
(3) present invention adjusts band gap using green safe dicyandiamide solution, and optical band gap is dropped with the increase of cadmium component
It is low；When the solution by portions spin coating that different levels of doping is respectively adopted, the variation of absorbed layer band gap gradient can be realized by lamination, it can
It is used to prepare the thin film solar cell with CZCTSSe band gap gradient, is had to regulation thin film solar cell photoelectric conversion efficiency
Highly important meaning；
Advantage in the thin film solar cell performance of CZCTSSe band gap gradient:
(a) high cadmium content is used close to the absorbed layer of molybdenum back contacts, since optical band gap subtracts with the increase of cadmium content
It is few, therefore high cadmium content is conducive to improve the utilization of long wave incident light.
(b) absorbed layer in interlayer uses low cadmium content, optical band gap highest in stacked, due to open-circuit voltage with
The increase of optical band gap and increase, therefore low cadmium is conducive to keep optimal open-circuit voltage and electric conductivity.
(c) near cadmium sulfide and absorption bed boundary, absorbed layer uses high cadmium content, will generate weak N-shaped Shi zhiming, energy
The fermi level pinning effect near interface is effectively reduced, to reduce the loss of open-circuit voltage.
(4) present invention can be used for preparing the flexible thin-film solar cell with CZCTSSe band gap gradient, mountable non-flat
On the platform of face, it is expected to which the application field for extending solar cell keeps it living in space application, military field, architecture-integral, field
It is dynamic that fields is waited to have broad application prospects.
Detailed description of the invention
Fig. 1 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 1 adulterates the X optical diffraction figure of copper zinc tin sulfur selenium film
(a) and partial enlarged view (b).
Fig. 2 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 1 adulterates the Raman spectrum of copper zinc tin sulfur selenium film.
Fig. 3 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 2 adulterates copper zinc tin sulfur selenium thin film solar cell J-V song
Line.
Fig. 4 is the fexible film sun with CZCTSSe band gap gradient based on flexible molybdenum substrate of the embodiment of the present invention 3
Battery structure schematic diagram；It wherein 1 ~ 5 respectively represents: 1- silver electrode, 2- tin indium oxide (ITO) Window layer, 3- intrinsic zinc oxide (i-
ZnO) film, 4- cadmium sulfide (CdS) film, the cadmium that 5-Cd/(Cd+Zn) atomic ratio is 10% adulterate copper zinc tin sulfur selenium film,
The cadmium that 6- Cd/(Cd+Zn) atomic ratio is 3% adulterates copper zinc tin sulfur selenium film, and 7- Cd/(Cd+Zn) atomic ratio is 10%
Cadmium adulterate copper zinc tin sulfur selenium film, 8- molybdenum foil.
Specific embodiment
Technical solutions according to the invention are described further With reference to embodiment, but the present invention is not
It is only limitted to this.
Embodiment 1
(1) cleaning treatment is carried out to molybdenum foil, i.e., adopted molybdenum foil in the mixed solution that the concentrated sulfuric acid and methanol volume ratio are 1:7
It is cleaned with electrodeposition process, the molybdenum oxide on molybdenum foil surface is etched away, finally rinsed and used with deionized water and be dried with nitrogen；
The purity of molybdenum foil used is 99 .99%, is 2cm × 2cm with a thickness of 0 .02mm, area；
(2) by solwution method dissolve simple substance and rear selenization in the way of cadmium content difference is prepared on flexible molybdenum substrate
Copper zinc tin sulfur selenium film；
Specific step is as follows for solwution method described in its step (2):
A, after mixing copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder in proportion, ethylenediamine and second are added to
In two mercaptan, heating stirring 1.5 hours；The amount for the cadmium powder being wherein added is distinguished according to Cd/(Cd+Zn) molar percentage
For 0,3%, 5%, 7%, 10% 5 kinds of solution of configuration；
B, a certain proportion of stabilizer is added in 5 kinds of solution respectively, i.e. ethanol amine, thioacetic acid, ethylene glycol monomethyl ether is pressed
It is made into stabilizer for 1: 1: 2 according to the mass ratio of the material, is added after stabilizer heating stirring 1 hour, precursor solution is made；
C, precursor solution is coated using spin-coating method on molybdenum foil after the cleaning, annealing temperature is 280 DEG C, is made prefabricated
Layer film.The thickness of the cadmium doping copper zinc tin sulfur selenium film is controlled by the spin coating number of plies.
Specific step is as follows for selenizing described in its step (2):
A, prefabricated layer film is placed in the open-topped cylindrical graphite box for filling selenium powder 0.5g；
B, graphite is put into the rapid thermal annealing full of argon gas (RTP) selenizing furnace；Selenizing furnace is allowed to be warming up to 550 DEG C,
Its heating rate is 9 DEG C/S；Room temperature is naturally cooled to after keeping 12min；It is thin that the CZCTSSe with different cadmium doping concentrations is made
Film.
Characterization:
Fig. 1 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 1 adulterates the X optical diffraction figure of copper zinc tin sulfur selenium film
(a) and partial enlarged view (b).As can be observed from Figure (112), (200), (220), (312) crystal face diffraction maximum, be copper
Zinc tin sulfur selenium phase does not find the second phase relevant to impurity, illustrates that obtaining CZCTSSe film is single phase structure.Fig. 1 (b) can
To see the increase (0% ~ 10%) with cadmium content, diffraction maximum is gradually deviated to low-angle, this is because cadmium atomic radius compares zinc
Atomic radius it is big, the variation of lattice lattice constant can be caused, cause lattice dilatation make XRD diffraction maximum to low-angle deviate,
This also illustrates that cadmium atom is doped in the lattice of CZTSSe.
Fig. 2 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 1 adulterates the Raman spectrum of copper zinc tin sulfur selenium film.Raman
Peak mainly appears on 174,196,236,336cm-1Place, belongs to the characteristic peak of CZTSSe.Illustrate the crystal form of film without because
The doping of cadmium and generate variation, be still custerite structure.
Using VarianCary5000UV-vis/NIR there is the spectrometer of integrating sphere to test different cadmiums at room temperature to mix
The CZCTSSe film of miscellaneous concentration, wave-length coverage are 400 to 1200nm.By (αhν)n=A(hν-Eg) be calculated, Cd/(Cd
+ Zn) molar percentage between 0-10% when, cadmium doping copper zinc tin sulfur selenium film optical band gap in 0.9 eV to 1.2
Change between eV.Specific corresponding relationship are as follows: when Cd/(Cd+Zn) atomic ratio is respectively 0,3%, 5%, 7%, 10%, band gap difference
For 1.2 eV, 1.1eV, 1.0eV, 1.05eV, 0.9eV.
Embodiment 2
(1) molybdenum foil is cleaned: with embodiment 1；
(2) by solwution method dissolve simple substance and rear selenization in the way of cadmium content difference is prepared on flexible molybdenum substrate
Copper zinc tin sulfur selenium film: with embodiment 1；
(3) cadmium sulphide membrane is deposited using the chemical water bath doping copper zinc tin sulfur selenium film surface of the cadmium obtained by (2), as
Buffer layer, wherein cadmium sulphide membrane is with a thickness of 50nm；
(4) sputtering method deposition intrinsic zinc oxide (i-ZnO) film on (3) resulting buffer layer is used；Wherein sputter gas
Body is Ar, air pressure 5mTorr, power 80W, time 25min, and resulting i-ZnO film thickness is 50nm；
(5) sputtering method depositing indium tin oxide (ITO) Window layer on (4) resulting i-ZnO film is used；Wherein sputter gas
Body is Ar gas, and air pressure 1mTorr, power 75W, time 15min, resulting ito thin film is with a thickness of 200nm；
(6) the mask film covering version on (5) resulting ITO, using Vacuum sublimation deposited metal silver electrode, filamentary silver used
Diameter be 1mm, length 10cm, with helical form tungsten boat heat filamentary silver, metallic silver thickness of electrode be 300nm.
Characterization:
Fig. 3 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 2 adulterates copper zinc tin sulfur selenium thin film solar cell J-V song
Line.
Embodiment 3
(1) molybdenum foil is cleaned: with embodiment 1；
(2) by solwution method dissolve simple substance and rear selenization in the way of on flexible molybdenum substrate prepare band gap gradient
The copper zinc tin sulfur selenium film of cadmium doping；
Specific step is as follows for solwution method described in its step (2):
A, after mixing copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder in proportion, ethylenediamine and second are added to
In two mercaptan, heating stirring 1.5 hours；The amount for the cadmium powder being wherein added is respectively according to Cd/(Cd+Zn) molar percentage
3%, 10% 2 kinds of solution of configuration；
B, a certain proportion of stabilizer is added in 2 kinds of solution respectively, i.e. ethanol amine, thioacetic acid, ethylene glycol monomethyl ether is pressed
It is made into stabilizer for 1: 1: 2 according to the mass ratio of the material, is added after stabilizer heating stirring 1 hour, the forerunner of different cadmium concentrations is made
Liquid solution；
C, the precursor solution that the cadmium doping concentration of preparation is 10%, 3%, 10% is successively coated in cleaning using spin-coating method
On molybdenum foil afterwards, annealing temperature is 280 DEG C, and every kind of solution repeats spin coating 3 times respectively, and prefabricated layer film is made；
Specific step is as follows for selenizing described in its step (2):
A, prefabricated layer film is placed in the cylindrical graphite box for filling selenium powder 0.5g；
B, graphite is put into the rapid thermal annealing full of argon gas (RTP) selenizing furnace；Selenizing furnace is allowed to be warming up to 550 DEG C,
Its heating rate is 9 DEG C/S；Room temperature is naturally cooled to after keeping 12min；The copper zinc tin sulfur selenium film of cadmium doping is made.
(3) cadmium sulphide membrane is deposited: with embodiment 2；
(4) deposition intrinsic zinc-oxide film: with embodiment 2；
(5) depositing indium tin oxide (ITO) Window layer: with embodiment 2；
(6) deposited metal silver electrode: with embodiment 2.
Characterization:
Fig. 4 is the fexible film sun with CZCTSSe band gap gradient based on flexible molybdenum substrate of the embodiment of the present invention 3
Battery structure schematic diagram；It wherein 1 ~ 5 respectively represents: 1- silver electrode, the indium-doped zinc oxide of 2- (ITO) Window layer, 3- intrinsic zinc oxide
(i-ZnO) film, 4- cadmium sulfide (CdS) film, the cadmium that 5-Cd/(Cd+Zn) molar percentage is 10% adulterate copper-zinc-tin-sulfur
Selenium film, the cadmium that 6- Cd/(Cd+Zn) molar percentage is 3% adulterate copper zinc tin sulfur selenium film, 7- Cd/(Cd+Zn)
The cadmium that molar percentage is 10% adulterates copper zinc tin sulfur selenium film, 8- molybdenum foil.
The absorption layer film of preparation has band gap gradient:
(1) there is high cadmium content (10%) close to the absorbed layer of molybdenum back contacts, since optical band gap is with the increase of cadmium content
And it reduces, therefore high cadmium content is conducive to improve the utilization of long wave incident light.
(2) absorbed layer in interlayer has low cadmium content (3%), optical band gap highest in stacked, due to open-circuit voltage
Increase with the increase of optical band gap, therefore low cadmium is conducive to keep optimal open-circuit voltage and electric conductivity.
(3) near cadmium sulfide and absorption bed boundary, absorbed layer has high cadmium content (10%), will generate weak N-shaped alms giver and lack
It falls into, the fermi level pinning effect near interface can be effectively reduced, to reduce the loss of open-circuit voltage.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (3)
1. a kind of regulation method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate, feature exist
In: the following steps are included:
(1) to substrate molybdenum foil carry out cleaning treatment: by molybdenum foil in the mixed solution of the concentrated sulfuric acid and methanol using electrodeposition process into
Row cleaning, is then rinsed well and is used with deionized water and be dried with nitrogen；
(2) after mixing copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder, ethylenediamine and dithioglycol are added to
In mixed liquor, heating stirring 1.5 hours, adjust cadmium powder additional amount, prepare the solution of different cadmium concentrations, wherein Cd/(Cd+
Zn molar percentage) is 0-10%；
(3) a certain proportion of stabilizer is added in the solution of the different cadmium concentrations of step (2) preparation again, heating stirring 1 hour,
Be made the precursor solution of different cadmium concentrations, the stabilizer be ethanol amine, thioacetic acid, ethylene glycol monomethyl ether according to substance amount
Than being made into for 1: 1: 2；
(4) precursor solution of different cadmium concentrations prepared by step (3) is coated in batches on same molybdenum foil using spin-coating method, is moved back
Fiery temperature is 250 ~ 350 DEG C, and prefabricated layer film is made；
(5) prefabricated layer film is placed in the cylindrical graphite box for filling selenium powder 0.5g；
(6) graphite is put into the rapid thermal annealing selenizing furnace full of argon gas；It allows selenizing furnace to be warming up to 500 ~ 600 DEG C, rises
Warm rate is 9 DEG C/S；Room temperature is naturally cooled to after keeping 8 ~ 20min；Cadmium is made and adulterates copper zinc tin sulfur selenium film；
Wherein, in cadmium obtained doping copper zinc tin sulfur selenium film, high cadmium content is used close to the absorbed layer of molybdenum back contacts, in interlayer
Absorbed layer use low cadmium content, cadmium sulfide and absorb bed boundary near absorbed layer use high cadmium content.
2. regulation method according to claim 1, it is characterised in that: it is custerite knot that cadmium, which adulterates copper zinc tin sulfur selenium film,
Structure.
3. regulation method according to claim 1, it is characterised in that: the optical band gap of cadmium doping copper zinc tin sulfur selenium film exists
Change between 0.9 eV to 1.2 eV.
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| CN109395748B (en) * | 2018-11-29 | 2020-09-08 | 山东大学 | Ag with visible light response2ZnSnS4Optical anode with/Mo structure and preparation method and application thereof |
| CN111416007B (en) * | 2020-04-01 | 2022-04-29 | 中国科学院物理研究所 | Copper-based light absorption layer film, preparation method thereof and copper-based film solar cell |
| CN111640820B (en) * | 2020-06-02 | 2023-06-13 | 东北师范大学 | Simple method for improving back contact of copper-zinc-tin-sulfur-selenium thin film photovoltaic device |
| CN111969081A (en) * | 2020-08-28 | 2020-11-20 | 深圳先进电子材料国际创新研究院 | Preparation method of near-infrared detector |
| CN112531075B (en) * | 2020-11-24 | 2022-09-16 | 中山大学 | Method for preparing flexible copper-zinc-tin-sulfur-selenium film and device thereof based on molecular formula ink blade coating |
| CN112563117B (en) * | 2020-12-09 | 2023-06-06 | 云南师范大学 | Preparation method of copper zinc tin sulfur selenium film with sulfur component gradient |
| CN112531036B (en) * | 2020-12-15 | 2022-06-10 | 福州大学 | Flexible silver-indium double gradient doped CZTSSe film and preparation method and application thereof |
| CN112490332B (en) * | 2020-12-17 | 2022-07-22 | 福州大学 | Flexible double-cation doped CZTSSe solar cell interface passivation method |
| CN112786716A (en) * | 2021-02-05 | 2021-05-11 | 深圳先进技术研究院 | CCZTSE short-wave infrared detector and preparation method thereof |
| CN113097314B (en) * | 2021-03-31 | 2022-06-03 | 福州大学 | Flexible antimony sulfide thin-film solar cell and preparation method thereof |
| CN114388660A (en) * | 2022-01-13 | 2022-04-22 | 黑龙江工业学院 | Method for reducing small crystal grain layer in CZTSSe film |
| CN114899280A (en) * | 2022-05-11 | 2022-08-12 | 中南大学 | Preparation method of cadmium-doped copper-zinc-tin-sulfur-selenium film and application of cadmium-doped copper-zinc-tin-sulfur-selenium film in solar cell |
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