CN106098844A - A kind of preparation method of copper-zinc-tin-sulfur solaode based on flexible molybdenum substrate - Google Patents
A kind of preparation method of copper-zinc-tin-sulfur solaode based on flexible molybdenum substrate Download PDFInfo
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- CN106098844A CN106098844A CN201610490142.XA CN201610490142A CN106098844A CN 106098844 A CN106098844 A CN 106098844A CN 201610490142 A CN201610490142 A CN 201610490142A CN 106098844 A CN106098844 A CN 106098844A
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- copper
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- sulfur
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011733 molybdenum Substances 0.000 title claims abstract description 51
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 51
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 title claims abstract description 16
- 239000010408 film Substances 0.000 claims abstract description 48
- 239000010409 thin film Substances 0.000 claims abstract description 44
- 239000011888 foil Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004544 sputter deposition Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 24
- 239000004411 aluminium Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 238000005987 sulfurization reaction Methods 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002061 vacuum sublimation Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 229910052802 copper Inorganic materials 0.000 claims 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 claims 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims 1
- 235000013904 zinc acetate Nutrition 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 235000011150 stannous chloride Nutrition 0.000 description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses the preparation method of the aluminum electrode of a kind of copper-zinc-tin-sulfur based on flexible molybdenum substrate.First clean flexible molybdenum foil with electrodeposition process, then prepare copper-zinc-tin-sulfur film with sol-gal process, use chemical bath method, sputtering method, evaporation to prepare cushion, Window layer, electrode the most successively.Use flexible molybdenum as the back electrode of battery, lower thin-film solar cells and the manufacturing cost of device thereof；Environmentally friendly CZTS is used to match with molybdenum foil substrate as the absorbed layer of battery, environmental protection, thermal coefficient of expansion；And CZTS preparation technology is simple, it is with a wide range of applications.
Description
Technical field
The invention belongs to area of solar cell, be specifically related to a kind of copper-zinc-tin-sulfur solar-electricity based on flexible molybdenum substrate
The preparation method in pond.
Background technology
Along with rapid development of economy, people are increasing to energy demand, but environmental problem is more and more prominent.The sun
Can battery be the product meeting clean energy resource demand.Wherein, second filial generation thin film solar cell, such as cadmium telluride, CIGS thin-film
Battery conversion efficiency has respectively reached 20% and 21%.Because of Cu2ZnSnS4(CZTS) there is environmental friendliness, obvious P-type semiconductor
Characteristic, applicable energy gap (1.5eV), higher absorption coefficient are (more than 104cm-1) etc. advantage, become more satisfactory thin film
Battery obsorbing layer material, was paid close attention to by everybody in recent years.
Compared to rigidity CZTS thin-film solar cells, flexible battery because thickness is thin, light weight, to be easily achieved volume to volume big
The advantages such as area production continuously and have broad application prospects.Flexible substrate includes organic film and metal forming (such as: rustless steel
Material, aluminium foil, molybdenum foil, titanium foil), organic film tolerable temperature (< 500 DEG C) the highest, it is impossible to meet the high temperature vulcanized requirement of CZTS；
Rustless steel contains ferrum because of it, and easy and CZTS forms the impurity such as iron sulfide, affects film quality；Though aluminium foil free from admixture spreads, but
It is that quality of forming film thereon is poor compared with molybdenum foil；Titanium foil various aspects of performance is better than molybdenum foil, but it is expensive.Comprehensively examine
Considering, molybdenum foil is one of optimum selection of flexible copper-zinc-tin-sulfur battery back electrode.
The preparation method being currently based on flexible molybdenum substrate CZTS hull cell has continuous ionic layer, electrodeposition process.Compared to this two
The method of kind, sol-gal process has the advantages such as with low cost, thin film composition is evenly distributed, and the most not yet sees and existing with sol-gal process
CZTS solar cell is prepared on flexible molybdenum substrate.So the present invention uses molybdenum foil as flexible substrate, its substrate use molten
Sol-gel prepares CZTS thin film, and can be used in solaode.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of copper-zinc-tin-sulfur solaode based on flexible molybdenum substrate
For achieving the above object, the present invention adopts the following technical scheme that
The preparation method of a kind of copper-zinc-tin-sulfur solaode based on flexible molybdenum substrate, comprises the following steps:
(1) it is cleaned molybdenum foil processing, electricity will be used in concentrated sulphuric acid and mixed solution that methanol volume ratio is 1:7 by molybdenum foil
Sedimentation is carried out, and is etched away by the molybdenum oxide on molybdenum foil surface, finally rinses with deionized water and dries up with nitrogen；Used
The purity of molybdenum foil is 99.99%, thickness is 0.02mm, area is 3cm × 3cm；
(2) utilize sol-gal process to prepare metal preformed layer thin film, followed by sulfuration on molybdenum foil thus obtain CZTS thin film:
(3) use chemical bath method in (2) gained copper-zinc-tin-sulfur film surface CdS thin films, as cushion, wherein CdS
Film thickness is 50 ~ 70nm；
(4) sputtering method is used to deposit i-ZnO thin film on the cushion of (3) gained；Wherein sputter gas is Ar, and air pressure is
2.0Pa, power is 80W, and the time is 20 ~ 30min, and the i-ZnO film thickness of gained is 60 ~ 90nm；
(5) sputtering method is used to deposit AZO Window layer on the i-ZnO thin film of (4) gained；Wherein sputter gas is Ar gas, air pressure
For 0.2Pa, power is 120W, and the time is 15 ~ 25min, and the AZO film thickness of gained is 200 ~ 300nm；
(6) on the AZO of (5) gained, cover mask plate, use Vacuum sublimation deposition metal aluminium electrode；Aluminium wire used straight
Footpath is 1mm, a length of 2cm, and quantity is 25, heats aluminium wire with helical form tungsten boat, and ' leading ' shape metal aluminium electrode thickness of gained is
200~300nm。
Sol-gal process described in its step (2), specifically comprises the following steps that
A, by copper acetate monohydrate (Cu (CH3COOH) 2 H2O), Zinc diacetate dihydrate (Zn (CH3COOH) 2 2H2O), two hydration
After stannous chloride (SnCl2 2H2O) and thiourea are mixed in the ratio of lean copper zinc-rich, join organic solvent ethylene glycol monomethyl ether
In, and add a certain proportion of stabilizer, and 50 DEG C of heating in water bath stirring 1h, obtain colloid；
B, utilize spin-coating method to be coated on the molybdenum foil of (1) gained by colloid prepared by step (A), make through 280 DEG C of high-temperature bakings
Copper-zinc-tin-sulfur preformed layer thin film；It is repeated several times to reach required film thickness, thickness about 1 ~ 1.5 m；
The wherein concrete steps of sulfuration in step (2):
Sample is put in vulcanizing oven, is evacuated down to below 5pa；Allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, be passed through in stove
N2And H2S gas, flow is respectively 180sccm, 20sccm；Make preformed layer at N2And H2The mixed gas of S keeps 1h；Finally
It is cooled to room temperature, followed by vulcanizes, obtain copper-zinc-tin-sulfur film.
The present invention have the characteristics that for the preparation method of copper-zinc-tin-sulfur solaode based on flexible molybdenum substrate and
Advantage:
(1) present invention uses flexible molybdenum as the back electrode of battery, reduces being manufactured into of thin-film solar cells and device thereof
This.
(2) present invention use environmentally friendly CZTS as the absorbed layer of battery, environmental protection, thermal coefficient of expansion with
Molybdenum foil substrate matches.
(3) absorbed layer CZTS of the present invention uses sol-gal process to prepare, inexpensive, and technique is simple, and equipment is cheap.
(4) present configuration is simple, and environmental protection is with low cost, it is easy to produce and manufacture, have wide application prospect,
It is suitable for popularization and application.
Accompanying drawing explanation
Fig. 1 is the copper-zinc-tin-sulfur film solar cell structure of embodiment of the present invention 1-3.
Fig. 2 is the XRD spectrum of the copper-zinc-tin-sulfur film of embodiment of the present invention 1-3.
Fig. 3 is the Raman spectrum of the copper-zinc-tin-sulfur film of embodiment of the present invention 1-3.
Fig. 4 is the copper-zinc-tin-sulfur film solar cell I-V curve of embodiment of the present invention 1-3.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention is not
It is only limitted to this.
Embodiment 1
(1) it is cleaned molybdenum foil processing, will use in concentrated sulphuric acid and mixed solution that methanol volume ratio is 1:7 by molybdenum foil
Electrodeposition process is carried out, and is etched away by the molybdenum oxide on molybdenum foil surface, finally rinses with deionized water and dries up with nitrogen；Institute
With the purity of molybdenum foil be 99.99%, thickness be 0.02mm, area be 3cm × 3cm；
(2) utilize sol-gal process to prepare metal preformed layer thin film, followed by sulfuration on molybdenum foil thus obtain CZTS thin film;
(3) use chemical bath method in (2) gained copper-zinc-tin-sulfur film surface CdS thin films, as cushion, wherein CdS
Film thickness is 70nm；
(4) sputtering method is used to deposit i-ZnO thin film on the cushion of (3) gained；Wherein sputter gas is Ar, and air pressure is
2.0Pa, power is 80W, and the time is 30min, and the i-ZnO film thickness of gained is 90nm；
(5) sputtering method is used to deposit AZO Window layer on the i-ZnO thin film of (4) gained；Wherein sputter gas is Ar gas, air pressure
For 0.2Pa, power is 120W, and the time is 25min, and the AZO film thickness of gained is 300nm；
(6) on the AZO of (5) gained, cover mask plate, use Vacuum sublimation deposition metal aluminium electrode；The diameter of aluminum used
For 1mm, a length of 2cm, quantity is 25, heats aluminium wire with helical form tungsten boat, and ' leading ' shape metal aluminium electrode thickness of gained is
300nm。
Sol-gal process described in its step (2), specifically comprises the following steps that
A, by copper acetate monohydrate (Cu (CH3COOH) 2 H2O), Zinc diacetate dihydrate (Zn (CH3COOH) 2 2H2O), two hydration
After stannous chloride (SnCl2 2H2O) and thiourea are mixed in the ratio of lean copper zinc-rich, join organic solvent ethylene glycol monomethyl ether
In, and add a certain proportion of stabilizer, and 50 DEG C of heating in water bath stirring 1h, obtain colloid；
B, utilize spin-coating method to be coated on the molybdenum foil of (1) gained by colloid prepared by step (A), make through 280 DEG C of high-temperature bakings
Copper-zinc-tin-sulfur preformed layer thin film；It is repeated 10 times to reach required film thickness, thickness about 1 m；
The wherein concrete steps of sulfuration in step (2):
Sample is put in vulcanizing oven, is evacuated down to below 5pa；Allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, be passed through in stove
N2And H2S gas, flow is respectively 180sccm, 20sccm；Make preformed layer at N2And H2The mixed gas of S keeps 1h；Finally
It is cooled to room temperature, followed by vulcanizes, obtain copper-zinc-tin-sulfur film.
Embodiment 2
(1) it is cleaned molybdenum foil processing, electricity will be used in concentrated sulphuric acid and mixed solution that methanol volume ratio is 1:7 by molybdenum foil
Sedimentation is carried out, and is etched away by the molybdenum oxide on molybdenum foil surface, finally rinses with deionized water and dries up with nitrogen；Used
The purity of molybdenum foil is 99.99%, thickness is 0.02mm, area is 3cm × 3cm；
(2) utilize sol-gal process to prepare metal preformed layer thin film, followed by sulfuration on molybdenum foil thus obtain CZTS thin film;
(3) use chemical bath method in (2) gained copper-zinc-tin-sulfur film surface CdS thin films, as cushion, wherein CdS
Film thickness is 50nm；
(4) sputtering method is used to deposit i-ZnO thin film on the cushion of (3) gained；Wherein sputter gas is Ar, and air pressure is
2.0Pa, power is 80W, and the time is 20min, and the i-ZnO film thickness of gained is 60nm；
(5) sputtering method is used to deposit AZO Window layer on the i-ZnO thin film of (4) gained；Wherein sputter gas is Ar gas, air pressure
For 0.2Pa, power is 120W, and the time is 15min, and the AZO film thickness of gained is 200nm；
(6) on the AZO of (5) gained, cover mask plate, use Vacuum sublimation deposition metal aluminium electrode；Aluminium wire used straight
Footpath is 1mm, a length of 2cm, and quantity is 25, heats aluminium wire with helical form tungsten boat, and ' leading ' shape metal aluminium electrode thickness of gained is
200nm。
Sol-gal process described in its step (2), specifically comprises the following steps that
A, by copper acetate monohydrate (Cu (CH3COOH) 2 H2O), Zinc diacetate dihydrate (Zn (CH3COOH) 2 2H2O), two hydration
After stannous chloride (SnCl2 2H2O) and thiourea are mixed in the ratio of lean copper zinc-rich, join organic solvent ethylene glycol monomethyl ether
In, and add a certain proportion of stabilizer, and 50 DEG C of heating in water bath stirring 1h, obtain colloid；
B, utilize spin-coating method to be coated on the molybdenum foil of (1) gained by colloid prepared by step (A), make through 280 DEG C of high-temperature bakings
Copper-zinc-tin-sulfur preformed layer thin film；It is repeated 12 times to reach required film thickness, thickness about 1.2 m；
The wherein concrete steps of sulfuration in step (2):
Sample is put in vulcanizing oven, is evacuated down to below 5pa；Allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, be passed through in stove
N2And H2S gas, flow is respectively 180sccm, 20sccm；Make preformed layer at N2And H2The mixed gas of S keeps 1h；Finally
It is cooled to room temperature, followed by vulcanizes, obtain copper-zinc-tin-sulfur film.
Embodiment 3
(1) it is cleaned molybdenum foil processing, electricity will be used in concentrated sulphuric acid and mixed solution that methanol volume ratio is 1:7 by molybdenum foil
Sedimentation is carried out, and is etched away by the molybdenum oxide on molybdenum foil surface, finally rinses with deionized water and dries up with nitrogen；Used
The purity of molybdenum foil is 99.99%, thickness is 0.02mm, area is 3cm × 3cm；
(2) utilize sol-gal process to prepare metal preformed layer thin film, followed by sulfuration on molybdenum foil thus obtain CZTS thin film；
(3) use chemical bath method in (2) gained copper-zinc-tin-sulfur film surface CdS thin films, as cushion, wherein CdS
Film thickness is 60nm；
(4) sputtering method is used to deposit i-ZnO thin film on the cushion of (3) gained；Wherein sputter gas is Ar, and air pressure is
2.0Pa, power is 80W, and the time is 25min, and the i-ZnO film thickness of gained is 70nm；
(5) sputtering method is used to deposit AZO Window layer on the i-ZnO thin film of (4) gained；Wherein sputter gas is Ar gas, air pressure
For 0.2Pa, power is 120W, and the time is 20min, and the AZO film thickness of gained is 250nm；
(6) on the AZO of (5) gained, cover mask plate, use Vacuum sublimation deposition metal aluminium electrode；Aluminium wire used straight
Footpath is 1mm, a length of 2cm, and quantity is 25, heats aluminium wire with helical form tungsten boat, and ' leading ' shape metal aluminium electrode thickness of gained is
220nm。
Sol-gal process described in its step (2), specifically comprises the following steps that
A, by copper acetate monohydrate (Cu (CH3COOH) 2 H2O), Zinc diacetate dihydrate (Zn (CH3COOH) 2 2H2O), two hydration
After stannous chloride (SnCl2 2H2O) and thiourea are mixed in the ratio of lean copper zinc-rich, join organic solvent ethylene glycol monomethyl ether
In, and add a certain proportion of stabilizer, and 50 DEG C of heating in water bath stirring 1h, obtain colloid；
B, utilize spin-coating method to be coated on the molybdenum foil of (1) gained by colloid prepared by step (A), make through 280 DEG C of high-temperature bakings
Copper-zinc-tin-sulfur preformed layer thin film；It is repeated 15 times to reach required film thickness, thickness about 1.5 m；
The wherein concrete steps of sulfuration in step (2):
Sample is put in vulcanizing oven, is evacuated down to below 5pa；Allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, be passed through in stove
N2And H2S gas, flow is respectively 180sccm, 20sccm；Make preformed layer at N2And H2The mixed gas of S keeps 1h；Finally
It is cooled to room temperature, followed by vulcanizes, obtain copper-zinc-tin-sulfur film.
Fig. 1 is the layer structure schematic diagram of the present invention.Sequentially consist of molybdenum foil, CZTS, CdS, i-ZnO, AZO, Al.
Fig. 2 is the XRD spectrum of the copper-zinc-tin-sulfur film of embodiment of the present invention 1-3.As can be seen from Figure 2 prepared based on
The CZTS thin film diffraction peak of molybdenum foil substrate corresponds very well to the standard card number 026-0575 of custerite structure C ZTS, it was demonstrated that
CZTS thin film has good crystallinity, and sample have also appeared (200) face from molybdenum foil simultaneously.Along with copper-zinc-tin-sulfur film is thick
The increase of degree, (112), (200), the diffraction maximum in (220) (312) face gradually strengthen, MoS2Peak gradually weakens, this explanation preparation
Copper-zinc-tin-sulfur film improves along with the increase of thickness, the crystallinity of thin film, miscellaneous MoS2Reduce.
Fig. 3 is the Raman spectrum of the copper-zinc-tin-sulfur film of embodiment of the present invention 1-3.Its excitation wavelength is 532nm, can from figure
To find out, it is positioned at 284,335,367 cm-1Raman peaks all can be clear from being observed, the Raman peaks of these peaks and CZTS
Match.Along with the increase of copper-zinc-tin-sulfur film thickness, CZTS main peak strengthens, and the copper-zinc-tin-sulfur film of this explanation preparation is along with thickness
The increase of degree, the crystallinity of thin film improves, and correlates mutually with the XRD figure of Fig. 2.
Fig. 4 is the copper-zinc-tin-sulfur film solar cell I-V curve of embodiment of the present invention 1-3.
When copper-zinc-tin-sulfur film thickness is 1.5 m, its open-circuit voltage is 370 mV, short-circuit current density 13.52 mA/
cm2, fill factor, curve factor 0.45, the transformation efficiency of battery is 2.25%.
When copper-zinc-tin-sulfur film thickness is 1.2 m, its open-circuit voltage is 360 mV, short-circuit current density 12.52mA/
cm2, fill factor, curve factor 0.4, the transformation efficiency of battery is 1.8%.
When copper-zinc-tin-sulfur film thickness is 1 m, its open-circuit voltage is 320 mV, short-circuit current density 9.00 mA/cm2,
Fill factor, curve factor 0.29, the transformation efficiency of battery is 0.84%.
This explanation is along with the increase of copper-zinc-tin-sulfur film thickness, and the transformation efficiency of battery is also increasing.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (6)
1. the preparation method of a copper-zinc-tin-sulfur solaode based on flexible molybdenum substrate, it is characterised in that: include following step
Rapid:
(1) it is cleaned molybdenum foil processing, electrodeposition process will be used in the mixed solution of concentrated sulphuric acid and methanol to carry out by molybdenum foil
Clean, then rinse with deionized water and dry up with nitrogen；
(2) utilize sol-gal process to prepare metal preformed layer thin film on molybdenum foil, followed by vulcanize, obtain copper-zinc-tin-sulfur thin
Film；
(3) use chemical bath method in (2) gained copper-zinc-tin-sulfur film surface CdS thin films, as cushion, wherein CdS
Film thickness is 50 ~ 70nm；
(4) sputtering method is used to deposit i-ZnO thin film on the cushion of (3) gained；
(5) sputtering method is used to deposit AZO Window layer on the i-ZnO thin film of (4) gained；
(6) on the AZO of (5) gained, cover mask plate, use Vacuum sublimation deposition metal aluminium electrode, obtain described copper zinc
Stannum sulfur solaode.
Preparation method the most according to claim 1, it is characterised in that: the sol-gal process described in step (2) concrete
Step is as follows:
(1), after a water acetic acid copper, two water zinc acetates, stannous chloride dihydrate and thiourea being mixed in proportion, ethylene glycol is joined
In methyl ether, and add a certain proportion of stabilizer, 50 DEG C of heating in water bath stirring 1h, obtain colloid；
(2) colloid utilizing spin-coating method step (1) to be prepared coats on molybdenum foil after the cleaning, and at 280 DEG C, copper is made in baking
Zinc-tin sulfur preformed layer thin film；Being repeated several times and obtain desired thickness thin film, thickness is 1 ~ 1.5 m.
Preparation method the most according to claim 1, it is characterised in that: the concrete steps of the sulfuration described in step (2) are such as
Under:
Preformed layer thin film is put in vulcanizing oven, is evacuated down to below 5pa；Allowing vulcanizing oven be warmed up to 580 DEG C, its heating rate is
10℃/min；It is passed through N in stove2And H2S gas；Make preformed layer at N2And H2The mixed gas of S keeps 1h；Finally it is cooled to
Room temperature；Prepare copper-zinc-tin-sulfur film.
Preparation method the most according to claim 1, it is characterised in that: described in step (4), the condition of sputtering method is: sputtering
Gas is Ar, and air pressure is 2.0Pa, and power is 80W, and the time is 20 ~ 30min, and gained i-ZnO film thickness is 60 ~ 90nm.
Preparation method the most according to claim 1, it is characterised in that: described in step (5), the condition of sputtering method is: sputtering
Gas is Ar, and air pressure is 0.2Pa, and power is 120W, and the time is 15 ~ 25min, and the AZO thickness of gained is 200 ~ 300nm.
Preparation method the most according to claim 1, it is characterised in that: used in Vacuum sublimation described in step (6)
A diameter of 1mm of aluminium wire, a length of 2cm, quantity is 25, and heats aluminium wire, gained metal aluminium electrode thickness with helical form tungsten boat
It is 200 ~ 300nm.
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