CN107871795A - A kind of regulation and control 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 and control 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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- CN107871795A CN107871795A CN201711143306.2A CN201711143306A CN107871795A CN 107871795 A CN107871795 A CN 107871795A CN 201711143306 A CN201711143306 A CN 201711143306A CN 107871795 A CN107871795 A CN 107871795A
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- cadmium
- band gap
- film
- 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 67
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 61
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 43
- 239000011733 molybdenum Substances 0.000 title claims abstract description 43
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 38
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 230000008859 change Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 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
- 239000003381 stabilizer Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- 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
- 238000004140 cleaning Methods 0.000 claims description 7
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 238000011049 filling Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000004151 rapid thermal annealing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 53
- 239000010409 thin film Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 238000004544 sputter deposition Methods 0.000 abstract description 6
- 238000003475 lamination Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 8
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 7
- 235000014692 zinc oxide Nutrition 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver 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
- 238000000151 deposition Methods 0.000 description 5
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 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
- 229960001296 zinc oxide Drugs 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000001237 Raman spectrum Methods 0.000 description 2
- NKSXAYFZXLTLDA-UHFFFAOYSA-N [S].[Se].[Sn].[Zn] Chemical compound [S].[Se].[Sn].[Zn] NKSXAYFZXLTLDA-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid 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
- 230000005693 optoelectronics Effects 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
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 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 present invention relates to a kind of regulation and control method of the cadmium doping copper zinc tin sulfur selenium film band gap gradient based on flexible molybdenum substrate.Flexible molybdenum foil is cleaned with electrodeposition process first, then realizes the change of CZCTSSe film band gap gradients by lamination with the mode of solwution method dissolving simple substance and rear selenization, available for thin film solar cell of the preparation with the change of CZCTSSe band gap gradients.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, so as to reduce manufacturing cost；Precursor solution is prepared using solwution method dissolving simple substance, the shortcomings that foreign ion can be introduced when avoiding dissolved metal salt, and solwution method cost is cheap, technique is simple, is easy to large area production, it is green, large-scale mass production and commercialized demand are met, it is practical.
Description
Technical field
The invention belongs to thin film solar cell Material Field, and in particular to a kind of CZCTSSe based on flexible molybdenum substrate is thin
The regulation and control method of film band gap gradient.
Background technology
Photovoltaic industry is there is an urgent need to flexible solar cell at present, because compared to conventional rigid battery, it has material soft
Soft, thickness of thin, light weight, power-mass ratio are high, production process energy consumption is small, is easily achieved volume to volume large area continuous production, just
In carry the advantages that, and can be arranged on on-plane surface platform on, it is expected to extend the application field of solar cell, make its space should
With, military field, architecture-integral, the field such as outdoor sports have broad application prospects.With organic film and other metals
Paper tinsel（Such as stainless steel, aluminium, chromium steel, titanium）Compare, molybdenum foil has high temperature resistant（> 600℃）, mechanical strength is good, lightweight and compatible
The advantages that thermal linear expansion coefficient.In addition, the utilization of some metal foils, as stainless steel in battery structure, it is necessary to extra resistance
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, so as 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.Flexible copper-zinc-tin-selenium solar cell prepared by sputtering method obtains 6.1% highest conversion efficiency, but sputters
The problem of being difficult to effectively control film composition be present in method.And compared to other method, solwution method has that cost is cheap, thin film composition
The advantage 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 it is significant to prepare development of the flexible battery for this area with solwution method.
Absorbed layer of the copper zinc tin sulfur selenium as solar cell, its optical band gap are regulation and control thin film solar cell opto-electronic conversion effects
The important parameter of rate, the especially stacked solar cell, cascade solar cell with different band gap.At present, copper zinc tin sulfur selenium band gap adjusting method be
Metal chloride, doped metallic oxide are introduced in copper zinc tin sulfur selenium, its shortcoming is：Chlorine, oxygen heteroatom can be introduced in system.
And though hydrazine solution can dissolve metal simple-substance, metal sulfide and metal selenide, have in itself it is hypertoxic, inflammable and explosive,
It is unfavorable for industrial production.Therefore, it is of great significance using green safe dicyandiamide solution to adjust band gap tool.
The content of the invention
It is an object of the invention to provide a kind of cadmium doping copper zinc tin sulfur selenium adjusted based on flexible molybdenum substrate（CZCTSSe）It is thin
The method of film strips gap.
To achieve the above object, the present invention adopts the following technical scheme that：
（1）Cleaning treatment is carried out to substrate molybdenum foil：Molybdenum foil is entered in the mixed solution of the concentrated sulfuric acid and methanol using electrodeposition process
Row cleaning, is then rinsed well with deionized water and is dried up with nitrogen；
（2）After copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder are mixed, it is added in ethylenediamine and dithioglycol,
Heating stirring 1.5 hours, the addition of cadmium powder is adjusted, prepare the solution of different cadmium concentrations, wherein Cd/（Cd + Zn）Mole
Percentage is 0-10%；
（3）Again in step（2）Add a certain proportion of stabilizer in the solution of the different cadmium concentrations of preparation, heating stirring 1 hour,
Be made different cadmium concentrations precursor solution, the stabilizer be monoethanolamine, TGA, ethylene glycol monomethyl ether according to material amount
Than being made into for 1: 1: 2；
（4）Using spin-coating method by step（3）The precursor solution of the different cadmium concentrations of preparation coated on same molybdenum foil, moves back in batches
Fiery temperature is 250 ~ 350 DEG C, and prefabricated layer film is made；The thickness of the CZCTSSe films is controlled by the spin coating number of plies；
（5）Prefabricated layer film is positioned 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）In selenizing stove；Selenizing stove is allowed to be warming up to 500 ~ 600 DEG C,
Its heating rate is 9 DEG C/S；Room temperature is naturally cooled to after keeping 8 ~ 20min；Cadmium doping copper zinc tin sulfur selenium film is made.
Cadmium doping copper zinc tin sulfur selenium film is custerite（Kesterite）Structure.
The optical band gap of cadmium doping copper zinc tin sulfur selenium film changes between 0.9 eV to 1.2 eV.
The regulation and control method of the band gap gradient of CZCTSSe films：The solution by portions spin coating of different levels of doping is respectively adopted, leads to
Cross the change that lamination realizes band gap gradient.
A kind of method tool of cadmium doping copper zinc tin sulfur selenium film band gap adjusted based on flexible molybdenum substrate provided by the invention
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 adhesion issues between film and substrate,
And the splash-proofing sputtering metal conductive back contact layer in battery structure is instead of, so as to reduce manufacturing cost；
（2）The present invention prepares meeting introducing hetero-atoms when precursor solution avoids dissolved metal salt using solwution method dissolving simple substance
Shortcoming, and solwution method cost is cheap, technique is simple, is easy to large area production, it is green, meet large-scale mass production with
Commercialized demand, it is practical；
（3）The present invention adjusts band gap using green safe dicyandiamide solution, and optical band gap reduces with the increase of cadmium component；When
The solution by portions spin coating of different levels of doping is respectively adopted, the change of absorbed layer band gap gradient can be realized by lamination, can be used for
The thin film solar cell with CZCTSSe band gap gradients is prepared, is had very to regulation and control thin film solar cell photoelectric transformation efficiency
Important meaning；
Advantage in the thin film solar cell performance of CZCTSSe band gap gradients：
（a）Absorbed layer close to molybdenum back contacts uses high cadmium content, because optical band gap is reduced with the increase of cadmium content, because
This high cadmium content is advantageous to improve the utilization of long wave incident light.
（b）Absorbed layer in interlayer uses low cadmium content, its optical band gap highest in stacked, due to open-circuit voltage with
The increase of optical band gap and increase, therefore low cadmium is advantageous to keep optimal open-circuit voltage and electric conductivity.
（c）In cadmium sulfide and absorbed layer near interface, absorbed layer uses high cadmium content, will produce weak n-type Shi zhiming, energy
The fermi level pinning effect of near interface is effectively reduced, so as to reduce the loss of open-circuit voltage.
（4）The present invention can be used for preparing the flexible thin-film solar cell with CZCTSSe band gap gradients, can be arranged on non-flat
On the platform of face, it is expected to extend the application field of solar cell, it is lived in space application, military field, architecture-integral, field
The field such as dynamic has broad application prospects.
Brief description of the drawings
Fig. 1 is that the cadmium based on flexible molybdenum substrate of the embodiment of the present invention 1 adulterates the X optical diffraction figures of copper zinc tin sulfur selenium film
And partial enlarged drawing (a)（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 songs
Line.
Fig. 4 is the fexible film sun with CZCTSSe band gap gradients based on flexible molybdenum substrate of the embodiment of the present invention 3
Battery structure schematic diagram；Wherein 1 ~ 5 represents respectively：1- silver electrodes, 2- tin indium oxides（ITO）Window layer, 3- intrinsic zinc oxides（i-
ZnO）Film, 4- cadmium sulfides（CdS）Film, 5-Cd/（Cd + Zn）The cadmium that atomic ratio is 10% adulterates copper zinc tin sulfur selenium film,
6- Cd /（Cd + Zn）The cadmium doping copper zinc tin sulfur selenium film that atomic ratio is 3%, 7- Cd/（Cd + Zn）Atomic ratio is 10%
Cadmium doping copper zinc tin sulfur selenium film, 8- molybdenum foils.
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., in the concentrated sulfuric acid and methanol volume ratio is 1 by molybdenum foil:Using electricity in 7 mixed solution
Sedimentation is cleaned, and the molybdenum oxide on molybdenum foil surface is etched away, and is finally rinsed with deionized water and is dried up with nitrogen；It is used
The purity of molybdenum foil is 99 .99%, thickness is 0 .02mm, area is 2cm × 2cm；
（2）The mode that simple substance and rear selenization are dissolved using solwution method prepares the different copper of cadmium content on flexible molybdenum substrate
Zinc tin sulfur selenium film；
Its step（2）Described in solwution method comprise the following steps that：
A, after mixing copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder in proportion, ethylenediamine and ethylene dithiol are added to
In alcohol, heating stirring 1.5 hours；The amount of the cadmium powder wherein added according to Cd/（Cd + Zn）Molar percentage be respectively 0,
3%th, 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., monoethanolamine, TGA, ethylene glycol monomethyl ether are according to thing
The amount ratio of matter is to be made into stabilizer at 1: 1: 2, adds heating stirring 1 hour after stabilizer, 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, and it is thin that preformed layer is made
Film.The thickness of the cadmium doping copper zinc tin sulfur selenium film is controlled by the spin coating number of plies.
Its step（2）Described in selenizing comprise the following steps that：
A, prefabricated layer film is positioned 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）In selenizing stove；Selenizing stove is allowed to be warming up to 550 DEG C, it rises
Warm speed is 9 DEG C/S；Room temperature is naturally cooled to after keeping 12min；The CZCTSSe films with different cadmium doping concentrations are made.
Characterize：
Fig. 1 be the embodiment of the present invention 1 cadmium based on flexible molybdenum substrate adulterate copper zinc tin sulfur selenium film X optical diffraction figures (a) and
Partial enlarged drawing（b）.As can be observed from Figure（112）、（200）、（220）、（312）The diffraction maximum of crystal face, it is copper zinc-tin
Sulphur selenium phase, second phase related to impurity is not found, illustrate that it is single phase structure to obtain CZCTSSe films.Fig. 1（b）It can see
To with the increase of cadmium content（0%~10%）, for diffraction maximum gradually to low-angle skew, this is due to original of the cadmium atomic radius than zinc
Sub- radius is big, can cause the change of lattice lattice constant, causes lattice dilatation that XRD diffraction maximums are offset to low-angle, this
Illustrate that cadmium atom is doped in CZTSSe lattice.
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, belong to CZTSSe characteristic peak.Illustrate the crystal formation of film without because
The doping of cadmium and produce change, 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 films 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.Specifically corresponding relation is：Cd /（Cd + Zn）When 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）Clean molybdenum foil：With embodiment 1；
（2）The mode that simple substance and rear selenization are dissolved using solwution method prepares the different copper of cadmium content on flexible molybdenum substrate
Zinc tin sulfur selenium film：With embodiment 1；
（3）Existed using chemical bath method（2）Gained cadmium doping copper zinc tin sulfur selenium film surface deposition cadmium sulphide membrane, as buffering
Layer, wherein cadmium sulphide membrane thickness is 50nm；
（4）Existed using sputtering method（3）Deposition intrinsic zinc oxide on the cushion of gained（i-ZnO）Film；Wherein sputter gas is
Ar, air pressure 5mTorr, power 80W, time 25min, the i-ZnO film thicknesses of gained are 50nm；
（5）Existed using sputtering method（4）Depositing indium tin oxide on the i-ZnO films of gained（ITO）Window layer；Wherein sputter gas is
Ar gas, air pressure 1mTorr, power 75W, time 15min, the ito thin film thickness of gained is 200nm；
（6）（5）Cover mask plate on the ITO of gained, using Vacuum sublimation deposited metal silver electrode, filamentary silver used it is straight
Footpath is 1mm, length 10cm, heats filamentary silver with helical form tungsten boat, argent thickness of electrode is 300nm.
Characterize：
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 curves.
Embodiment 3
（1）Clean molybdenum foil：With embodiment 1；
（2）The cadmium for being prepared band gap gradient on flexible molybdenum substrate using the mode of solwution method dissolving simple substance and rear selenization is mixed
Miscellaneous copper zinc tin sulfur selenium film；
Its step（2）Described in solwution method comprise the following steps that：
A, after mixing copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder in proportion, ethylenediamine and ethylene dithiol are added to
In alcohol, heating stirring 1.5 hours；The amount of the cadmium powder wherein added according to Cd/（Cd + Zn）Molar percentage is respectively 3%,
10% 2 kinds of solution of configuration；
B, a certain proportion of stabilizer is added in 2 kinds of solution respectively, i.e., monoethanolamine, TGA, ethylene glycol monomethyl ether are according to thing
The amount ratio of matter is to be made into stabilizer at 1: 1: 2, adds heating stirring 1 hour after stabilizer, the presoma that different cadmium concentrations are made is molten
Liquid；
C, the precursor solution that the cadmium doping concentration of preparation is 10%, 3%, 10% is coated after the cleaning successively using spin-coating method
On molybdenum foil, annealing temperature is 280 DEG C, and every kind of solution repeats spin coating 3 times respectively, and prefabricated layer film is made；
Its step（2）Described in selenizing comprise the following steps that：
A, prefabricated layer film is positioned 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）In selenizing stove；Selenizing stove is allowed to be warming up to 550 DEG C, it rises
Warm speed 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）Deposit cadmium sulphide membrane：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.
Characterize：
Fig. 4 is the flexible thin-film solar cell with CZCTSSe band gap gradients based on flexible molybdenum substrate of the embodiment of the present invention 3
Structural representation；Wherein 1 ~ 5 represents respectively：1- silver electrodes, the indium-doped zinc oxide of 2-（ITO）Window layer, 3- intrinsic zinc oxides（i-
ZnO）Film, 4- cadmium sulfides（CdS）Film, 5-Cd/（Cd + Zn）The cadmium that molar percentage is 10% adulterates copper zinc tin sulfur selenium
Film, 6- Cd/（Cd + Zn）The cadmium doping copper zinc tin sulfur selenium film that molar percentage is 3%, 7- Cd/（Cd + Zn）Rub
The cadmium that your percentage is 10% adulterates copper zinc tin sulfur selenium film, 8- molybdenum foils.
The absorption layer film of preparation has band gap gradient：
（1）Absorbed layer close to molybdenum back contacts has high cadmium content（10%）, because optical band gap subtracts with the increase of cadmium content
It is few, therefore high cadmium content is advantageous to improve the utilization of long wave incident light.
（2）Absorbed layer in interlayer has low cadmium content（3%）, its optical band gap highest in stacked, due to open-circuit voltage
Increase with the increase of optical band gap, therefore low cadmium is advantageous to keep optimal open-circuit voltage and electric conductivity.
（3）In cadmium sulfide and absorbed layer near interface, absorbed layer has high cadmium content（10%）, weak n-type alms giver will be produced and lacked
Fall into, the fermi level pinning effect of near interface can be effectively reduced, so as to reduce the loss of open-circuit voltage.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (3)
1. a kind of regulation and control method of the band gap gradient of the cadmium doping copper zinc tin sulfur selenium film based on flexible molybdenum substrate, its feature exist
In：Comprise the following steps：
（1）Cleaning treatment is carried out to substrate molybdenum foil：Molybdenum foil is entered in the mixed solution of the concentrated sulfuric acid and methanol using electrodeposition process
Row cleaning, is then rinsed well with deionized water and is dried up with nitrogen；
（2）After copper, zinc powder, cadmium powder, glass putty, sulphur powder and selenium powder are mixed, ethylenediamine and dithioglycol are added to
In mixed liquor, heating stirring 1.5 hours, the addition of cadmium powder is adjusted, prepare the solution of different cadmium concentrations, wherein Cd/（Cd +
Zn）Molar percentage be 0-10%；
（3）Again in step（2）Add a certain proportion of stabilizer in the solution of the different cadmium concentrations of preparation, heating stirring 1 hour,
Be made different cadmium concentrations precursor solution, the stabilizer be monoethanolamine, TGA, ethylene glycol monomethyl ether according to material amount
Than being made into for 1: 1: 2；
（4）Using spin-coating method by step（3）The precursor solution of the different cadmium concentrations of preparation coated on same molybdenum foil, moves back in batches
Fiery temperature is 250 ~ 350 DEG C, and prefabricated layer film is made；
（5）Prefabricated layer film is positioned in the cylindrical graphite box for filling selenium powder 0.5g；
（6）Graphite is put into the rapid thermal annealing selenizing stove full of argon gas；Selenizing stove is allowed to be warming up to 500 ~ 600 DEG C, it rises
Warm speed is 9 DEG C/S；Room temperature is naturally cooled to after keeping 8 ~ 20min；Cadmium doping copper zinc tin sulfur selenium film is made.
2. regulation and control method according to claim 1, it is characterised in that：Cadmium doping copper zinc tin sulfur selenium film is custerite knot
Structure.
3. regulation and control 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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