CN107394007A - A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing - Google Patents
A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing Download PDFInfo
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- CN107394007A CN107394007A CN201710640438.XA CN201710640438A CN107394007A CN 107394007 A CN107394007 A CN 107394007A CN 201710640438 A CN201710640438 A CN 201710640438A CN 107394007 A CN107394007 A CN 107394007A
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- Prior art keywords
- selenizing
- solar cell
- vulcanization
- superstrate
- layer
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000004073 vulcanization Methods 0.000 title claims abstract description 34
- 239000012528 membrane Substances 0.000 title claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010408 film Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 22
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical group [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910003107 Zn2SnO4 Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- CHRUUJJXTYHZCK-UHFFFAOYSA-N antimony;sulfanylidenecopper Chemical compound [Sb].[Cu]=S CHRUUJJXTYHZCK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 230000004224 protection Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002207 thermal evaporation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 238000000889 atomisation Methods 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- 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 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical compound [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 thickness 80nm Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
Abstract
A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, belong to solar cell preparation field, it is comprised the concrete steps that：The cushion use of solar cell is not easy to cure or the oxide material of selenizing, after preparing absorption layer of thin film solar cell, transparency conducting layer is further processed, using method (a) or method (b)：(a) one layer of metallic film for preventing vulcanization and/or selenizing is plated over transparent conductive layer；(b) Zinc oxide film or the metallic film that can be cured with selenizing with vacuum method evaporation are prepared with spray pyrolysis over transparent conductive layer, washes appropriate section off with inorganic acid after vulcanization or selenizing, transparency conducting layer is exposed.The inventive method is ingenious, and technique is simple, and vulcanization or selenizing, transparency conducting layer square resistance are kept approximately constant, and has the advantages of good with existing thin film solar cell preparation technology compatibility, cost is low, safety and environmental protection, thus has extraordinary application value.
Description
Technical field
The invention belongs to solar cell preparation field, is applied to superstrate structural membranes more particularly to one kind
Solar cell vulcanizes or the method for selenizing.
Background technology
The solar cell of research and development low-cost high-efficiency is the core content of theCourse of PV Industry, and finds cheap, environmental protection, light
The semi-conducting material of volt high conversion efficiency is one of key for developing solar cell technology.It is thin for thin film solar cell
Film preparation is prepared with device and completed simultaneously, and membrane-film preparation process and solar battery structure are closely related, current film
Solar cell mainly has two kinds of structures：Substrate structures and superstrate structures, wherein copper indium gallium selenide cell are
Representative in substrate structures, cadmium telluride cells are the representatives in superstrate structures.Superstrate structures are relative
Simply, easily encapsulation, this be cadmium telluride cells can extensive industrialization the reason for one of, in addition, being also beneficial in laminated cell
Upper use.And substrate structures are relative complex, it is more to be related to the number of plies and the element species of battery, technological process length, therefore
Cost is of a relatively high.The sun of the new compound efficiency of solar cell of current superstrate structures than substrate structure
Battery efficiency is low, main cause be absorbed layer not through over cure or selenizing, crystallite dimension is too small, and defect is too many, film resistor
It is too big, cause the less efficient of battery.
It is sulphur that the thin film solar cell of current superstrate structures, which can not use vulcanization or selenizing method, main cause,
Change or when selenizing temperature is higher (more than 400 DEG C), vulcanization or selenizing can destroy the interface of transparency conducting layer and cushion, so as to lead
Cause component failure.At present, for problems, there is not yet document and the corresponding solution of patent report.
The content of the invention
The technology of the present invention is to be directed to above-mentioned deficiency of the prior art, there is provided one kind is applied to superstrate structures
Thin film solar cell vulcanize or selenizing method, this method is ingenious in design, cost is cheap and compatible superstrate structures too
The industrialization production in positive electricity pond.
Scheme is used by the present invention solves its technical problem：
A kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, it is comprised the concrete steps that：
(1) when preparing the solar cell of superstrate structures, the cushion of solar cell uses oxide material, the oxygen
Compound material is TiO2、ZnO、Zn1-xMgxO、Zn2SnO4In one kind, wherein Zn1-xMgxX≤0.4 in O；
(2) after preparing absorption layer of thin film solar cell, transparency conducting layer (TCO) is further processed, using method
(a), one kind in method (b)：(a) one layer of metallic film for preventing vulcanization and/or selenizing is plated over transparent conductive layer；(b) exist
Zinc oxide film or the metallic film that can be cured with selenizing with vacuum method evaporation are prepared with spray pyrolysis on transparency conducting layer,
Appropriate section is washed off with inorganic acid, transparency conducting layer is exposed after vulcanization or selenizing；
(3) corresponding device is vulcanized or selenizing after.
Further, vulcanization or during selenizing, temperature is 540 DEG C, time 15min.
Further, in step (2), the thickness of the cushion is 50nm-200nm.
Further, when preparing the solar cell of superstrate structures, prepare on the glass substrate successively conductive layer,
Cushion and absorbed layer, after vulcanization or selenizing, back electrode is prepared on absorbed layer.
Further, in step (2) method (a), the metallic film is gold thin film, thickness 50nm-300nm.
Further, in step (2) method (b), the metallic film is one kind in Ag films, zinc film, and thickness is
20nm-200nm, the Zinc oxide film thickness are 50nm-100nm.
Further, the conductive layer is fluorine-doped tin dioxide (FTO) conductive layer or indium tin oxide (ITO) conductive layer.
Further, the absorbed layer is copper zinc tin sulfur absorption layer, copper and tin sulphur absorbed layer or copper antimony sulphur absorbed layer, using spray
Prepared by mist pyrolysismethod or sol-gal process, thickness is 1 μm -5 μm.
Further, the inorganic acid is hydrochloric acid, nitric acid or sulfuric acid, volumetric concentration >=10% of the inorganic acid.
The present invention has beneficial effect following prominent：
It is right because the preparation method of the present invention is adapted to the vulcanization of superstrate structural membranes solar cell or selenizing
The thin film solar cell preparation process of superstrate structures does not carry out big change, and technique is simple, so having work
The advantages of skill compatibility is good, cost is low, safety and environmental protection, thus there is extraordinary application value.
Brief description of the drawings
Fig. 1 is the thin film solar cell preparation flow schematic diagram of the superstrate structures of the present invention；
Fig. 2 is the thin-film solar cell structure schematic diagram of the superstrate structures of the present invention；
In figure：1- substrate of glass, 2- transparency conducting layers, 3- cushions, 4- absorbed layers, 5- back electrodes, 6-TCO protective layers.
Embodiment
Embodiment 1
Such as Fig. 1 and Fig. 2, copper-zinc-tin-sulfur solar cell preparation flow schematic diagram and structural representation, the copper-zinc-tin-sulfur sun electricity
Pond includes substrate of glass, has protective effect provided with conductive layer and to the transparency conducting layer of conductive layer side on the glass substrate
TCO protective layers, cushion, absorbed layer and back electrode are sequentially provided with conductive layer.Preparation process is：
Step S1, there is provided conductive substrates
Conductive layer uses fluorine-doped tin dioxide (FTO), and substrate is put into beaker, pours into acetone, is cleaned by ultrasonic 8min, then use wine
Essence is cleaned by ultrasonic 8min, is then cleaned by ultrasonic 25min with saturation sodium hydroxide alcohol solution dipping, is finally rushed with deionized water
Wash, spontaneously dry；
It is prepared by step S2, cushion
ZnO buffer is prepared using atomization method for pyrolysis, detailed process is：
Conductive substrates (FTO) prepared by step S1 are placed on hot plate, set suitable temperature (300 DEG C -500 DEG C), are sprayed
Applying solution is：Zinc nitrate is dissolved in ionized water, solution concentration is 0.1mol/L zinc nitrate, and gas flow is protected during pyrolytic deposition
Hold in 5mL/min, sedimentation time 1min, spout to thermal station distance is 5cm, obtains ZnO buffer, thickness 50nm；Step
It is prepared by S3, absorbed layer
Copper zinc tin sulfur absorption layer is prepared using atomization method for pyrolysis, detailed process is：
Film prepared by step S2 is placed on hot plate, sets suitable temperature (300 DEG C -500 DEG C), spray solution is：
By copper chloride, zinc chloride, stannous chloride and thiocarbamide are added in methanol, are configured to copper chloride concentration as 0.1mol/L, zinc chloride
Concentration is 0.05mol/L, stannous chloride concentration is 0.05mol/L and thiourea concentration is 0.5mol/L, gas stream during pyrolytic deposition
Amount is maintained at 5mL/min, and sedimentation time 1min, spout to thermal station distance is 5cm, obtains copper zinc tin sulfur absorption layer, thickness 1
μm；
In TCO protections part using thermal evaporation methods evaporation layer of Au, thickness 80nm, sulphur is carried out to corresponding device afterwards
Change, curing temperature is 540 DEG C, time 15min；
It is prepared by step S4, back electrode
Layer surface evaporation layer of Au is being absorbed using thermal evaporation methods, the electric current of vacuum thermal evaporation is 80A, thickness 80nm.
Embodiment 2
As depicted in figs. 1 and 2, copper-zinc-tin-sulfur (selenium) solar cell preparation flow schematic diagram and structural representation, including following step
Suddenly：Step S1, there is provided conductive substrates
Conductive layer uses fluorine-doped tin dioxide (FTO), and substrate is put into beaker, pours into acetone, is cleaned by ultrasonic 8min, then use wine
Essence is cleaned by ultrasonic 8min, is then cleaned by ultrasonic 25min with saturation sodium hydroxide alcohol solution dipping, is finally rushed with deionized water
Wash, spontaneously dry；
It is prepared by step S2, cushion
Zn is prepared using atomization method for pyrolysis0.8Mg0.2O cushions, detailed process are：
On hot plate, temperature is 500 DEG C to conductive substrates (FTO) prepared by S1.Spray solution is：By zinc nitrate and magnesium nitrate
Be dissolved in ionized water, nitric acid zinc concentration be 0.08mol/L's and nitric acid magnesium density be 0.02mol/L, gas during pyrolytic deposition
Flow is maintained at 5mL/min, and sedimentation time 1min, spout to thermal station distance is 5cm, obtains Zn0.8Mg0.2O cushions, thickness
For 50nm；
It is prepared by step S3, absorbed layer
Copper zinc tin sulfur absorption layer is prepared using atomization method for pyrolysis, detailed process is：
Film prepared by step S2 is placed on hot plate, sets suitable temperature (300-500 DEG C)；Spray solution is：Will
Copper chloride, zinc chloride, stannous chloride and thiocarbamide are added in methanol, and it is dense for 0.1mol/L, zinc chloride to be configured to copper chloride concentration
Spend for 0.05mol/L, stannous chloride concentration is 0.05mol/L and thiourea concentration is 0.5mol/L, gas flow during pyrolytic deposition
5mL/min is maintained at, sedimentation time 1min, spout to thermal station distance is 5cm, obtains copper zinc tin sulfur absorption layer, thickness is 1 μ
m；One layer of zinc oxide, thickness 100nm are prepared using spray pyrolysis method in TCO protections part.Corresponding device is carried out afterwards
Vulcanization, conditions of vulcanization are 540 DEG C, time 15min.Vulcanized zinc oxide TCO is washed off with watery hydrochloric acid protect part afterwards；Step
It is prepared by rapid S4, back electrode
Layer of Au is deposited using thermal evaporation methods, the electric current of vacuum thermal evaporation is 80A, thickness 80nm.
Embodiment 3
As depicted in figs. 1 and 2, copper and tin sulfur solar energy preparation flow schematic diagram and structural representation, comprise the following steps：
Step S1, there is provided conductive substrates
Conductive layer uses indium tin oxide (ITO), and substrate is put into beaker, pours into acetone, is cleaned by ultrasonic 8min, then use alcohol
It is cleaned by ultrasonic 8min, is then cleaned by ultrasonic 25min with saturation sodium hydroxide alcohol solution dipping, finally with deionized water rinsing,
Spontaneously dry；
It is prepared by step S2, cushion
Zn is prepared using atomization method for pyrolysis2SnO4Cushion, detailed process are：
Conductive substrates (ITO) are placed on hot plate, temperature is 500 DEG C, and spray solution is：Zinc nitrate and butter of tin are added
Enter into methanol, be configured to zinc concentration containing nitric acid be 0.1mol/L's and butter of tin concentration be 0.05mol/L solution pyrolysis
Gas flow is maintained at 5mL/min during deposition, and sedimentation time 1min, spout to thermal station distance is 5cm, obtains Zn2SnO4Buffering
Layer by layer, thickness 50nm；
It is prepared by step S3, absorbed layer
Copper zinc tin sulfur absorption layer is prepared using atomization method for pyrolysis, detailed process is：
Film prepared by step S2 is placed on hot plate, sets suitable temperature (300-500 DEG C), and spray solution is by chlorine
Change copper, zinc chloride, stannous chloride and thiocarbamide are added in methanol, are configured to copper chloride concentration as 0.1mol/L, zinc oxide concentration
For 0.05mol/L, stannous chloride concentration is 0.05mol/L and thiourea concentration is 0.5mol/L, and gas flow is protected during pyrolytic deposition
Hold in 5mL/min, sedimentation time 1min, spout to thermal station distance is 5cm, obtains copper and tin sulphur film absorbed layer, and thickness is 1 μm；
In TCO protections part using thermal evaporation methods evaporation one layer of Ag, thickness 100nm.Corresponding device is vulcanized afterwards, sulphur
Change condition is 540 DEG C, time 15min；Wash silver sulfide off with dust technology afterwards (TCO protects part)；
It is prepared by step S4, back electrode
Layer of Au is deposited using thermal evaporation methods, the electric current of vacuum thermal evaporation is 80A, thickness 80nm.
Embodiment 4
It is as illustrated in figs. 1 and 2, copper-zinc-tin-sulfur solar cell preparation flow schematic diagram and structural representation, comprise the following steps：
Step S1, there is provided conductive substrates
Conductive layer uses indium tin oxide (ITO), and substrate is put into beaker, pours into acetone, is cleaned by ultrasonic 8min, then use alcohol
It is cleaned by ultrasonic 8min, is then cleaned by ultrasonic 25min with saturation sodium hydroxide alcohol solution dipping, finally with deionized water rinsing,
Spontaneously dry；
It is prepared by step S2, cushion
TiO is prepared using atomization method for pyrolysis2Cushion, detailed process are：
Conductive substrates indium tin oxide (ITO) is placed on hot plate, suitable temperature (300-500 DEG C) is set；Spray molten
Liquid is：0.1mol/L two (levulinic ketone group) metatitanic acid diisopropyl esters (solvent is ethanol), are sprayed, and obtain TiO2Buffering
Layer；
It is prepared by step S3, absorbed layer
Copper zinc tin sulfur absorption layer is prepared using sol-gel process, detailed process is：
The step S2 films prepared are placed on spin coating instrument, the solution of spin coating is：By dichloride copper, zinc dichloride, dichloride
Stannous and thiocarbamide are dissolved in glycol dimethyl ether and triethanolamine mixed solvent (volume ratio 1:5) in, it is dense to be configured to dichloride copper
Spend for 1mol/L, zinc dichloride concentration is 1mol/L, dichloride stannous concentration is 1mol/L, thiourea concentration 5mol/L；Will system
The substrate for getting cushion ready is placed on spin coating instrument, and absorbed layer precursor aqueous solution is added dropwise, first with 2000 revolutions per seconds of low speed spin coating 120s,
Then with 3000 revolutions per seconds of spin coating 500s；It is pyrolyzed to form the copper zinc tin sulfur absorption layer that thickness is 2 μm in buffer-layer surface；Protected in TCO
Shield part prepares one layer of zinc oxide, thickness 100nm using spray pyrolysis method；Selenizing, vulcanization are carried out to corresponding device afterwards
Condition is 540 DEG C, time 15min.Wash the zinc oxide of preparation off with watery hydrochloric acid afterwards；
It is prepared by step S4, back electrode
Layer of Au is deposited using thermal evaporation methods, the electric current of vacuum thermal evaporation is 80A, thickness 80nm.
Square resistance test value (the test equipment of transparency conducting layer before and after the processing：Dutch Sherescan cell pieces surface resistance
Test system)
Test the transparency conducting layer FTO of the embodiment of the present invention 1, square resistanceAfter TCO protects part gold evaporation, square electricity
Hinder and beSheet resistance is after vulcanizationAfter selenizing being carried out using the step identical with the method for embodiment 1, after testing, side
Block resistance is
Test the transparency conducting layer FTO of the embodiment of the present invention 2, square resistanceSunk in TCO protection part spray pyrolysis
After product ZnO, vulcanization, square resistance exceedes apparatus measures scope, at least aboveAfter being cleaned with watery hydrochloric acid, sheet resistance isAfter carrying out selenizing pickling using the step identical with the method for embodiment 2, after testing, square resistance is
According to embodiment 2 method prepare superstrate structure solar energy electrodes, TCO protect part evaporation Zn or
Person Ag, after cure, square resistance exceedes apparatus measures scope, at least aboveAfter being cleaned with diluted acid, square resistance is equal
For
Test the transparency conducting layer ITO of the embodiment of the present invention 3, square resistanceAfter TCO protects part gold evaporation, side
Block resistance isSheet resistance is after vulcanization
Superstrate structure solar energy electrodes are prepared according to the method for embodiment 3, part spray pyrolysis is protected in TCO
Deposit ZnO, after cure, square resistance exceedes apparatus measures scope, at least aboveAfter being cleaned with diluted acid, sheet resistance is equal
For
According to embodiment 3 method prepare superstrate structure solar energy electrodes, TCO protect part evaporation Zn or
Person Ag, after cure, square resistance exceedes apparatus measures scope, at least aboveAfter being cleaned with diluted acid, sheet resistance is
It was found from above-mentioned data, transparency conducting layer is by the vulcanization of this method method therefor or selenizing, and square resistance is almost
Constant (ITO effects are relatively weaker, and reason is sheet resistance rise after ITO heated) is kept, transparency conducting layer is not destroyed, full
Sufficient battery testing requirement.
It is described above, it is only the preferable case study on implementation of the present invention, any formal limitation not is done to the present invention.It is any
Those skilled in the art, without departing from the scope of the technical proposal of the invention, it may be by technology described above
Content makes many possible changes and modifications to technical solution of the present invention, or is revised as the equivalence enforcement case of equivalent variations.
Therefore, every content without departing from technical solution of the present invention, the technology according to the present invention are done any to above case study on implementation
Change modification, equivalent variations and modification, belong to the protection domain of the technical program.
Claims (9)
1. a kind of method suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, it is characterized in that：
Comprise the concrete steps that：
(1) when preparing the solar cell of superstrate structures, the cushion of solar cell uses oxide material, the oxygen
Compound material is TiO2、ZnO、Zn1-xMgxO、Zn2SnO4In one kind, wherein Zn1-xMgxX≤0.4 in O；
(2) after preparing absorption layer of thin film solar cell, transparency conducting layer (TCO) is further processed, using method
(a), one kind in method (b)：(a) one layer of metallic film for preventing vulcanization and/or selenizing is plated over transparent conductive layer；(b) exist
Zinc oxide film or the metallic film that can be cured with selenizing with vacuum method evaporation are prepared with spray pyrolysis on transparency conducting layer,
Appropriate section is washed off with inorganic acid, transparency conducting layer is exposed after vulcanization or selenizing；
(3) corresponding device is vulcanized or selenizing after.
2. the method according to claim 1 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：When vulcanization or selenizing, temperature is 540 DEG C, time 15min.
3. the method according to claim 1 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：In step (2), the thickness of the cushion is 50nm-200nm.
4. the method according to claim 1 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：When preparing the solar cell of superstrate structures, conductive layer, cushion and suction are prepared on the glass substrate successively
Layer is received, after vulcanization or selenizing, back electrode is prepared on absorbed layer.
5. the method according to claim 1 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：In step (2) method (a), the metallic film is gold thin film, thickness 50nm-300nm.
6. the method according to claim 1 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：In step (2) method (b), the metallic film is Ag films, one kind in zinc film, thickness 20nm-200nm,
The Zinc oxide film thickness is 50nm-100nm.
7. the method according to claim 6 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：The conductive layer is fluorine-doped tin dioxide (FTO) conductive layer or indium tin oxide (ITO) conductive layer.
8. the method according to claim 6 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：The absorbed layer is copper zinc tin sulfur absorption layer, copper and tin sulphur absorbed layer or copper antimony sulphur absorbed layer, using spray pyrolysis or
Prepared by sol-gal process, thickness is 1 μm -5 μm.
9. the method according to claim 1 suitable for the vulcanization of superstrate structural membranes solar cell or selenizing, its
It is characterized in：The inorganic acid is hydrochloric acid, nitric acid or sulfuric acid, volumetric concentration >=10% of the inorganic acid.
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| CN111762808A (en) * | 2019-03-28 | 2020-10-13 | 东泰高科装备科技有限公司 | Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell |
| CN112563343A (en) * | 2020-12-09 | 2021-03-26 | 电子科技大学 | Based on Zn1-xMgxInorganic solar cell with O buffer layer and preparation method thereof |
| CN114534990A (en) * | 2022-01-11 | 2022-05-27 | 西安理工大学 | ITO thin film suitable for flexible device and preparation method thereof |
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| CN114534990A (en) * | 2022-01-11 | 2022-05-27 | 西安理工大学 | ITO thin film suitable for flexible device and preparation method thereof |
| CN114534990B (en) * | 2022-01-11 | 2023-03-14 | 西安理工大学 | ITO thin film suitable for flexible device and preparation method thereof |
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