CN104377271A - Method for producing two-sided light absorption type chalcogenide thin-film solar module - Google Patents
Method for producing two-sided light absorption type chalcogenide thin-film solar module Download PDFInfo
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- CN104377271A CN104377271A CN201410568172.9A CN201410568172A CN104377271A CN 104377271 A CN104377271 A CN 104377271A CN 201410568172 A CN201410568172 A CN 201410568172A CN 104377271 A CN104377271 A CN 104377271A
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- 239000010409 thin film Substances 0.000 title claims abstract description 33
- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 230000031700 light absorption Effects 0.000 title abstract 5
- 239000010408 film Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 35
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 230000008033 biological extinction Effects 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 13
- 238000002207 thermal evaporation Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- 238000000224 chemical solution deposition Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 238000007641 inkjet printing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 239000012780 transparent material Substances 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000429 assembly Methods 0.000 claims 1
- 230000000712 assembly Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000007756 gravure coating Methods 0.000 claims 1
- 238000004528 spin coating Methods 0.000 claims 1
- 238000009718 spray deposition Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 2
- 230000003139 buffering effect Effects 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- 229910018038 Cu2ZnSnSe4 Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000700 radioactive tracer Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 101000958041 Homo sapiens Musculin Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 102000046949 human MSC Human genes 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a method for producing a two-sided light absorption type chalcogenide thin-film solar module. The method for producing the two-sided light absorption type chalcogenide thin-film solar module is used for increasing the efficacy of an existing chalcogenide thin-film solar module. The method comprises the following steps that a rigid or flexible transparent substrate is plated with a bottom electrode, a first window layer and a first buffer layer with a vacuum magnetron sputtering method by adopting the prior art, a metal or chalcogenide metal reaction layer is deposited, a chalcogen layer is deposited on the metal reaction layer with a prepared high-purity chalcogen solution by adopting a conventional technology in a normal temperature environment, low-temperature baking is conducted, and then a cured chalcogen film is formed; after plating of a middle electrode is completed, the metal or chalcogenide metal reaction layer and the chalcogen layer are deposited again; then, the two reaction layers are made to be completely converted into a polycrystalline chalcogenide semiconductor thin film through high-temperature annealing treatment; finally, platting of a second buffering layer, a second window layer and an upper electrode is conducted, and then the two-sided light absorption type chalcogenide thin-film solar module is manufactured. According to the method for producing the two-sided light absorption type chalcogenide thin-film solar module, cost is low, production is simple, the preparation process is environmentally friendly, photoelectric converting efficiency is high, and the method is suitable for industrialization.
Description
Technical field
The invention belongs to technical field of solar batteries, particularly relate to a kind of production method of two-sided extinction chalkogenide thin film solar assembly.
Background technology
The fossil energy that current mankind's everyday life relies on; Comprising coal, oil, natural gas etc., is all formed through very long geological epoch by the animals and plants being embedded in underground, relative mankind's operating speed, and remaining unquarried fossil energy can say it is very limited.And also can pollute air, soil, water source while use fossil energy.In the face of above-mentioned two large problems, mankind's devote substantial resources between this many decades researches and develops clean regenerative resource.Wherein solar cell is the important a member in regenerative resource industry, is also be described as the most desirable energy.Mainly because of its very huge reserves, within about 40 minutes, be radiated at tellurian solar energy, be enough to the consumption for global human 1 year energy.Can say, solar energy is really inexhaustible, the nexhaustible energy.And have more absolute cleanliness (nuisanceless), widely distributed, limit by region, can generate electricity nearby, obtain the energy particular advantages such as source time is short.
And in the industry of solar cell, realize volume production mainly silicon series solar cell at present, but silicon machine battery has, and heaviness, extinction wave band are narrow, weak revolves the shortcomings such as optical activity difference.These shortcomings can make the generating efficiency pole of silicon thermomechanical components by the impact (four seasons, round the clock) shining upon position.And system installation business need utilize daylight tracer technique and movable supporting frame to increase generating efficiency, make installation cost high, so that the cost of current solar power generation is still far away higher than fossil energy cost of electricity-generating.For solving the restriction of silicon machine battery, development chalkogenide thin-film solar cells just becomes the new direction of industry; Chalkogenide hull cell with efficient, lightweight, high stability, tool is weak revolves the advantage such as optical activity and radiation resistance and favored, wherein with Copper Indium Gallium Selenide (CIGS) for representative, conversion efficiency reaches on 20%, makes an appointment with conventional crystalline silicon battery.Because tool is lightweight and weakly revolve the strong advantage of optical activity, chalkogenide film assembly does not need daylight tracer technique and movable supporting frame, so that installation cost significantly reduces.
Although chalkogenide hull cell can improve shine upon position to the impact of assembly generating efficiency (four seasons, round the clock), make it can be arranged on fixed support, still have many sunlight not to be converted to electric energy because of surface reflection.For increasing the extinction usefulness of assembly, some research groups can use optics anti-reflection film to optimize chalkogenide film assembly, its principle is by physioptial correlation theory, and the optical waveguide structure of optics anti-reflection film established by meter, and its transmission peak wavelength is mated with chalkogenide absorption spectra.Meter is set as fruit can be applied in encapsulating material surface, improving the efficiency of transmission of encapsulating material, realizing the hypersorption of chalkogenide film assembly to incident light wave by preparing optics anti-reflection film.In addition, Yi You research group can by unique product design, and as tubular type Copper Indium Gallium Selenide film assembly product, its principle is the extinction face by tubular type 360 degree, increases the probability that sorbent surface flashes back the sunlight, thus improves components performance.
Summary of the invention
The present invention is the usefulness increasing existing chalkogenide thin film solar assembly, provide a kind of unique, with low cost, produce simply, preparation process environmental friendliness, electricity conversion be high, and is suitable for the production method of industrialized two-sided extinction chalkogenide thin film solar assembly.
The present invention for the technical scheme solving in known technology the technical problem institute Bian existed is: chalkogenide thin-film solar cells/assembly, for sandwich construction, comprise transparent substrates, hearth electrode, Window layer (), resilient coating (), absorbed layer (), middle electrode, absorbed layer (two), resilient coating (two), Window layer (two), top electrode, encapsulating film and transparent panel.
Chalkogenide absorbing layer of thin film solar cell preparation method, its preparation technology's flow process comprises following step:
(1) preparation of chalcogen solution;
Solute is: high-purity chalcogen powder (purity >99.99%), chalcogen can be but be not limited to sulphur and selenium.
Solvent is: the organic solvents such as ketone, alcohols, amine, also can be used in combination
The mass ratio of viscosity modifier and solvent is 1:5 ~ 30;
Said viscosity modifier is: cellulose or ethyl cellulose
High-purity chalcogen powder is dissolved in solvent by the concentration of 0.01 ~ 5M, and also can adopt mixing chalcogen or mixed solvent, and add viscosity modifier, room temperature fully stirs >12 hour, forms stable precursor solution.By adding or reduce the consumption of solvent, chalcogen concentration in solution is controlled at 0.01 ~ 5M.
(2) preparation of substrate and hearth electrode;
Substrate can be transparent material or the polymeric membrane of glass, rigidity and flexibility
Hearth electrode material can be transparent conductive oxide etc.
Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. are prepared on substrate
Hearth electrode film, film thickness is determined by component calls.
(3) preparation of Window layer ();
Window layer chalcogen metal, metal can be able to be but be not limited to zinc.
Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. are prepared on substrate
Window layer film, film thickness is determined by component calls.
(4) preparation of resilient coating ();
Resilient coating chalcogenide metal, metal can be able to be but be not limited to cadmium and zinc.
Adopt chemical bath deposition method to be prepared on chalkogenide thin film semiconductor film and prepare resilient coating, film thickness is determined by component calls.
(5) preparation of metal or chalcogenide metal reaction substrate ()
Metal can be but be not limited to copper, zinc, tin, indium, gallium.
Adopt conventional high vacuum vapor method technique, if thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. are at hearth electrode film
Upper plated metal or chalcogenide metal reaction layer.Reaction layer thickness is 0.6-2um.
(6) preparation of chalcogen film ()
In the environment of normal temperature, high-purity sulfur family Element Solution of preparation is utilized conventional film-forming process, as sprayed deposit, inkjet printing, die slot coating or knife coating deposit chalcogen layer on metal reaction layer, after with low-temperature bake, form the chalcogen film of solidification, film thickness is determined by component calls.
(7) preparation of electrode in;
Middle electrode material can be molybdenum, titanium and transparent conductive oxide etc.
Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. are prepared on substrate
Window layer and upper electrode film, film thickness is determined by component calls.
(8) preparation of metal or chalcogenide metal reaction substrate (two)
Metal can be but be not limited to copper, zinc, tin, indium, gallium.
Adopt conventional high vacuum vapor method technique, if thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. are at hearth electrode film
Upper plated metal or chalcogenide metal reaction layer.Reaction layer thickness is 0.6-2um.
(9) preparation of chalcogen film (two)
In the environment of normal temperature, high-purity sulfur family Element Solution of preparation is utilized conventional film-forming process, as sprayed deposit, inkjet printing, die slot coating or knife coating deposit chalcogen layer on metal reaction layer, after with low-temperature bake, form the chalcogen film of solidification, film thickness is determined by component calls.
(10) the high temperature anneal
By the high temperature furnace depositing hearth electrode, the substrate of metal or chalcogenide metal and chalcogen film is placed in sectional temperature programmed control, vacuum seal, then heat up fast, uniformly, substrate region temperature is made to control at 200-1000 DEG C, according to the thickness of prefabricated conversion zone, carry out the process of 5-60min, make conversion zone change the chalcogenide semiconductor film of polycrystalline completely into.
(11) preparation of resilient coating (two);
Resilient coating chalcogenide metal, metal can be able to be but be not limited to cadmium and zinc.
Adopt chemical bath deposition method to be prepared on chalkogenide thin film semiconductor film and prepare resilient coating, film thickness is determined by component calls.
(12) preparation of Window layer (two) and top electrode;
Window layer chalcogen metal, metal can be able to be but be not limited to zinc.
Upper electrode material can transparent conductive oxide etc.
Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. are prepared on substrate
Window layer and upper electrode film, film thickness is determined by component calls.
(13) preparation of encapsulating film and transparent panel
Encapsulating film can be transparent waterproof materials or the polymeric membrane of rigidity and flexibility, can be but be not limited to EVA, ETFE.
Transparent panel material can be transparent material or the polymeric membrane of glass, rigidity and flexibility.
Adopt conventional high-temperature lamination process to encapsulate, the thickness of encapsulating film is determined by component calls.
(14) assembly delineation preparation technology
In response to the design of different assembly, above-mentioned battery component production process comprises delineation preparation technology.
Adopt conventional machinery/laser grooving and scribing preparation technology, the depth width of scribing process parameter, step, line is determined by component calls
Beneficial effect of the present invention is embodied in:
(1) unique two-sided extinction chalkogenide thin film solar component design, makes assembly have the extinction face on both sides, increases the probability that sorbent surface flashes back the sunlight, thus improves components performance.Another in response to different geographical conditions, coordinate different setting angles, the generating efficiency of whole solar components system can be increased.
(2) chalcogen solution preparation and membrane-film preparation process are all carry out in normal temperature environment, and equipment is simple, and quality control is simple and easy, with low cost;
(3) have employed antivacuum liquid phase method technique, relatively existing chalkogenide thin film solar assembly production technology, raw material availability is high, and prepared thin film composition uniformity is good, surface smoothness is high, is conducive to the chalkogenide film assembly producing large-area high-quality.
Accompanying drawing explanation
Fig. 1 is the structural representation of two-sided light absorbing element provided by the invention.
Fig. 2 is the current-voltage characteristic curve of front (A) and reverse side (B) Cu2ZnSnSe4 solar cell device.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail:
(1) adopt high-purity selenium powder, choosing ethylenediamine is solvent, and is that 1:10 adds cellulose by the mass ratio of viscosity modifier and solvent, and magnetic agitation 12 hours, forms stable solution.In solution, the concentration of Se atom controls at 2M.
(2) depositing indium tin oxide hearth electrode and ZnO Window layer (one) film thickness are respectively 1200nm and 500nm respectively on a glass substrate to utilize the method for sputtering.
(3) utilize chemical bath deposition method to prepare cadmium sulfide resilient coating (), film thickness is 50nm.
(4) utilize the method for sputtering in molybdenum electrode, plate zinc/tin/copper metal film () in order, film thickness is respectively 200/200/350nm.
(5) adopt die slot rubbing method to coat the high-purity selenium solution of preparation at zinc/tin/copper metal reaction substrate, then toast 10 minutes at 150 DEG C.
(6) utilize electrode molybdenum in the method deposition of sputtering, molybdenum thickness is 0.5um.
(7) utilize the method for sputtering in molybdenum electrode, plate zinc/tin/copper metal film (two) in order, film thickness is respectively 200/200/350nm.
(8) adopt die slot rubbing method to coat the high-purity selenium solution of preparation at zinc/tin/copper metal reaction substrate, then toast 10 minutes at 150 DEG C.
(9) substrate depositing molybdenum/zinc/tin/copper/selenium film is placed in the high temperature furnace of sectional temperature programmed control, vacuum seal, at 500 DEG C, annealing in process selenizing obtains Cu2ZnSnSe4 compound semiconductor film two-layer altogether for 30 minutes.
(10) utilize chemical bath deposition method to prepare cadmium sulfide resilient coating (two), film thickness is 50nm.
(11) method sputtered on cadmium sulfide, deposit ZnO Window layer respectively and tin indium oxide upper electrode film thickness is respectively 50nm and 1200nm.
Fig. 1 is the structural representation of two-sided light absorbing element provided by the invention.This substrate comprises-(1) transparent substrates, (2) hearth electrode, (3) Window layer/resilient coating/absorbed layer (), (4) electrode in, (5) absorbed layer/resilient coating/Window layer (two), (6) top electrode.The open circuit voltage of the two-sided Cu2ZnSnSe4 solar cell prepared on this basis is 540mV, 550mV, and short-circuit current density is 15.36mA/cm2,15.71mA/cm2, and fill factor, curve factor is 71%, 72%, and electricity conversion is 5.93%, 6.31%.The current-voltage characteristic curve of Fig. 2 front (A) and reverse side (B) Cu2ZnSnSe4 solar cell device.
Above-describedly specifically execute example; object of the present invention, technical scheme and positive effect are further described; be understood that; the foregoing is only of the present invention and specifically execute example; be not limited to the present invention; all do within principle of the present invention anyly to repair and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. the production method of a two-sided extinction chalkogenide thin film solar assembly, it is characterized in that step is as follows: the preparation solute of § A chalcogen solution is: high-purity sulfur family element powders (purity >99.99%), chalcogen can be but be not limited to sulphur and selenium; Solvent is: the organic solvents such as ketone, alcohols, amine, also can be used in combination, and adds viscosity modifier; Room temperature fully stirs >12 hour, forms stable precursor solution.By adding or reduce the consumption of solvent, chalcogen concentration in solution is controlled at 0.01 ~ 5M; § B prepares hearth electrode on substrate, and substrate can be transparent material or the polymeric membrane of glass, rigidity and flexibility; Hearth electrode material can transparent conductive oxide etc.; Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. prepare hearth electrode film on substrate; § C prepares Window layer () on hearth electrode; Window layer (one) chalcogen metal, metal can be able to be but be not limited to zinc; Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. prepare Window layer and upper electrode film on substrate.§ D prepares resilient coating () in Window layer (); Resilient coating (one) chalcogenide metal, metal can be able to be but be not limited to cadmium and zinc; Adopt chemical bath deposition method to be prepared on chalkogenide thin film semiconductor film and prepare resilient coating.§ E is at the upper metal processed of resilient coating () or chalcogenide metal reaction film (); Metal can be but be not limited to copper, zinc, tin, indium, gallium; Adopt conventional high vacuum vapor method technique, as plated metal or the chalcogenide metal reaction layer on hearth electrode film such as thermal evaporation, magnetron sputtering and molecular beam epitaxy.Reaction layer thickness is 0.6-2um.§ F prepares chalcogen film at metal reaction layer (); In the environment of normal temperature, high-purity sulfur family Element Solution of preparation is utilized conventional film-forming process, as sprayed deposit, inkjet printing, die slot coating or knife coating on metal reaction layer, deposit chalcogen layer, after with low-temperature bake, formed solidification chalcogen film.§ G is electrode in the upper preparation of chalcogen film (), and middle electrode material can be molybdenum, titanium and transparent conductive oxide etc.; Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. prepare hearth electrode film on substrate; § H is metal processed or chalcogenide metal reaction film (two) on middle electrode; Metal can be but be not limited to copper, zinc, tin, indium, gallium; Adopt conventional high vacuum vapor method technique, as plated metal or the chalcogenide metal reaction layer on hearth electrode film such as thermal evaporation, magnetron sputtering and molecular beam epitaxy.Reaction layer thickness is 0.6-2um.§ I prepares chalcogen film (two) at metal reaction layer (two); In the environment of normal temperature, high-purity sulfur family Element Solution of preparation is utilized conventional film-forming process, as sprayed deposit, inkjet printing, die slot coating or knife coating on metal reaction layer, deposit chalcogen layer, after with low-temperature bake, formed solidification chalcogen film (two).The substrate of plated metal or chalcogenide metal and chalcogen film is placed in the high temperature furnace of sectional temperature programmed control by § J, vacuum seal, then heat up fast, uniformly, substrate region temperature is made to control at 200-1000 DEG C, according to the thickness of prefabricated conversion zone, carry out the process of 5-60min, make conversion zone change the chalcogenide semiconductor film of polycrystalline completely into.§ K is at chalcogenide semiconductor film preparation resilient coating (two); Resilient coating (two) chalcogenide metal, metal can be able to be but be not limited to cadmium and zinc; Adopt chemical bath deposition method to be prepared on chalkogenide thin film semiconductor film and prepare resilient coating.§ L prepares Window layer (two) and top electrode on resilient coating (two); Window layer (two) chalcogen metal, metal can be able to be but be not limited to zinc; Upper electrode material can be transparent conductive oxide etc.; Adopt conventional high vacuum vapor method technique, as thermal evaporation, magnetron sputtering and molecular beam epitaxy etc. prepare Window layer and upper electrode film on substrate.
2. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: said chalcogen can be but be not limited to sulphur and selenium.
3. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: said solvent can be the organic solvents such as ketone, alcohols, amine, also can be used in combination.
4. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: said substrate can be the transparent material of glass, rigidity and flexibility or polymeric membrane.
5. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: said hearth electrode material can transparent conductive oxide etc.
6. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: said middle electrode material can be molybdenum, titanium and transparent conductive oxide etc.
7. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: said reactive group sheet material can be metal or chalcogenide metal; Metal can be but be not limited to copper, zinc, tin, indium, gallium.
8. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: step § B, § C, § E, § G, § H and § L prepare hearth electrode, metal or chalcogenide metallic film (/ bis-), middle electrode, Window layer (/ bis-) and top electrode high vacuum vapor method technique be thermal evaporation, magnetron sputtering and molecular beam epitaxy.
9. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: the antivacuum liquid phase process that step § E, § F, § H and § I prepare metal or chalcogenide metal reaction film and chalcogen film is spin-coating method, the tape casting, spray deposition, czochralski method, silk screen print method, ink-jet printing process, instillation membrane formation process, roll coating process, die slot rubbing method, flat excellent rubbing method, capillary rubbing method, comma rubbing method or gravure coating process.
10. the production method of a kind of two-sided extinction chalkogenide thin film solar assembly according to claim 1, is characterized in that: the high temperature anneal temperature described in step § J is 200-1000 DEG C.
The production method of 11. a kind of two-sided extinction chalkogenide thin film solar assemblies according to claim 1, is characterized in that: the thickness of said target polycrystalline area semiconductive thin film is 0.5 ~ 3um.
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