CN111312833B - Photovoltaic thin film material for solar cell - Google Patents
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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
- H01L31/0248—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
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
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- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of solar cells, and particularly relates to a photovoltaic thin film material for a solar cell; the preparation raw materials of the photovoltaic thin film material comprise: nano spinel type powder, nano copper indium gallium powder; the preparation method is simple, and overcomes the defects of multiple steps, difficult post-treatment, low yield and the like of the conventional methods. Meanwhile, the method has the advantages of high photoelectric conversion efficiency and low cost of raw materials and production equipment, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a photovoltaic thin film material for a solar cell.
Background
Solar cells are devices that directly convert light energy into electrical energy by the photoelectric or photochemical effect. In recent years, solar cells have become a global subject of intense research, and it is widely believed that the development of solar cells has entered the third generation, thin-film solar cells. (the first generation is a monocrystalline silicon solar cell, the second generation is a solar cell of polycrystalline silicon, amorphous silicon and the like, and the third generation is a compound thin film solar cell of copper indium gallium selenide CIGS (Ga doped in CIS) and a thin film Si series solar cell.)
CIS was first synthesized by Hahn in 1953. In 1974, Wagner et al prepared a p-type CIS single crystal, and evaporated a n-type CdS layer on the CIS single crystal to prepare a first CIS solar cell with a photoelectric conversion efficiency of 12%. In 1981, the efficiency of a polycrystalline CIS thin film solar cell prepared by Boeing company by using a multiple co-evaporation deposition technology was 9.4%. Acrosollar proposed a new technique for preparing a polycrystalline CIS thin film by a selenization method in 1987, and compared with a multiple coevaporation method, the technique is simpler and lower in cost. From the 80 s in the 20 th century, people find that the gap width can be improved by adding the Ga element into the CIS, solar energy can be absorbed more effectively, and higher conversion efficiency can be obtained. The three-step co-evaporation invented by the united states renewable energy laboratory (NREL) can produce a CIGS thin film with large grain size, the improvement of the CIGS crystallization quality and the specific gradient distribution of the Ga element in the thin film obviously improve the open-circuit voltage and the short-circuit current of the cell, and the conversion efficiency of the produced cell is from 16.4% in 1994, 18.8% in 1999 and 19.9% in 2008.
The quality of the CIGS thin film of the absorption layer is related to the conversion efficiency of the cell, various properties of the absorption layer are often determined by different preparation processes, and the requirements of production cost, large-scale production application and the like are also related. The CIGS layer may be prepared through several processes, such as multiple co-evaporation, selenization after magnetron sputtering, electrodeposition, spraying conversion, etc. The spray conversion method is easy to control the dosage of raw materials and additives, can conveniently control the components, thickness and uniformity of the film, fully utilizes materials, has high stacking density, can reduce the dosage of noble metals Ga and In, and greatly reduces the cost.
Currently, CIGS solar cells have been the research hot spot in the photovoltaic field due to their excellent photovoltaic performance, but there are many problems to be solved in the CIGS solar cells from the laboratory to the real commercial application.
Researchers have improved the photovoltaic thin film material, but the improvement effect is not good, for example, chinese patent CN 103137720 a discloses a photovoltaic thin film material doped with rare earth element, which is obtained by doping rare earth element and photovoltaic thin film material, wherein the photovoltaic material is one of monocrystalline silicon, polycrystalline silicon, amorphous silicon, polynary compound and organic polymer; the photovoltaic thin film material prepared in the patent application technology has the defects of low target material deposition rate, uneven erosion and low target material utilization rate due to the defects of the preparation method and the material; meanwhile, the photovoltaic film is inhomogeneous, the resistance is high, and the photoelectric conversion efficiency is low. Therefore, in order to generate electricity by using solar energy more effectively, it is necessary to provide a technology that can improve photoelectric conversion efficiency well, reduce cost, and facilitate industrial production.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a photovoltaic thin film material for a solar cell, which overcomes the defects of more steps, difficult post-treatment, low yield and the like of the conventional methods. Meanwhile, the method has the advantage of low cost of raw materials, and is suitable for industrial production.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a photovoltaic thin film material for a solar cell is prepared from the following raw materials: nano spinel type powder, nano copper indium gallium powder;
preferably, the raw materials for preparing the photovoltaic film material comprise, by weight: 2-10 parts of nano spinel type powder and 90-120 parts of nano copper indium gallium powder;
preferably, the raw materials for preparing the photovoltaic film material comprise, by weight: 2-5 parts of nano spinel type powder and 110 parts of nano copper indium gallium powder;
preferably, the nano spinel type powder consists of MCl2And NCl3The preparation is carried out;
wherein M ═ any of Mg, Cu, Ni, Zn, or Cd;
n ═ any of Al, Co, Cr, and Ga;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) mixing MCl2And NCl3Mixing, dissolving in alcohol-water solution, and adjusting pH to 8-9 to obtain composite hydroxide precursor; washing the composite hydroxide precursor with water, adding PEG, refluxing in ethanol, drying, grinding and roasting to obtain nano spinel powder A;
(2) preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Mixing the solution and adding an auxiliary agent; heating and adjusting the pH value to 7.5-10.5; filtering, and washing with ethanol solution; drying, calcining and cooling to obtain nano metal oxide powder B;
(3) mixing A and B, adding a dispersant, performing ball milling, adding an auxiliary agent, and performing ultrasonic treatment to obtain nano composite ink;
taking a substrate, carrying out oil stain treatment, and then carrying out ultrasonic treatment and drying; spraying the nano composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) treating the nano composite film at high temperature, and reducing to obtain an alloy film;
(5) selenizing the alloy film to obtain the CIGS film doped with spinel phase.
Preferably, the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing MCl2And NCl3According to n (M)2+)：n(N3+) 1: 2 (molar ratio), dissolving in an alcohol-water solution, stirring, adding ammonia water, and adjusting the pH value to 8-9 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 1-3 wt% of PEG, refluxing in ethanol, drying, grinding, and roasting to obtain nano spinel type powder A;
(2) preparing nano copper indium gallium (CuInGa) powder:
preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Mixing the solution and adding an auxiliary agent; heating, stirring, and adjusting pH to 7.5-10.5; filtering, and washing with ethanol solution; drying, calcining and cooling to obtain nano metal oxide powder B;
(3) preparation and film formation of nano composite ink
Mixing the A and the B, adding a dispersing agent, carrying out ball milling for 5-10 h, adding water for dilution, adding an auxiliary agent, and carrying out ultrasonic treatment to obtain nano composite ink;
carrying out oil stain treatment on a substrate, placing the substrate in deionized water and acetone for ultrasonic treatment, and drying; spraying the composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) alloy film prepared by reduction of nano composite film
Treating the nano composite film at high temperature, and reducing by using hydrogen or hydrogen/argon mixed gas to obtain an alloy film;
(5) method for preparing spinel phase-doped photovoltaic film by solid-state source selenization method
Placing the alloy film in a tube furnace, placing Se powder beside the alloy film, sealing the tube furnace, and vacuumizing for 30-60 min; and (4) heating, and carrying out a selenization process on the alloy film to obtain the CIGS film doped with the spinel phase.
Preferably, in the step (1), the alcohol-water solution is ethanol water solution with a volume concentration of 50-75%;
preferably, in the step (1), the adding of the ammonia water is carried out in a water bath at the temperature of 40-50 ℃;
preferably, in step (1), the molecular weight of PEG is 3000-8000, preferably M4000;
preferably, in the step (1), the refluxing time in the ethanol is 1-3 h;
preferably, in the step (1), the roasting is carried out in a muffle furnace, and the roasting temperature is 800-1200 ℃; the roasting time is 1-4 h;
preferably, in the step (1), the particle size of the nano spinel type powder A is intensively distributed (the volume fraction is more than or equal to 70%) within 22-41 nm;
preferably, in step (2), the pH is 8;
preferably, in the step (2), the heating temperature is 50-60 ℃;
preferably, in the step (2), the Cu (NO) is3)2、In(NO3)3And Ga (NO)3)3The molar ratio of Cu, In and Ga In the solution is 1: (0.4-0.9): (0.2-0.6); preferably, Cu/(In + Ga) ═ 1: 1; preferably, the molar ratio of Cu, In and Ga is 1: 0.7: 0.3;
preferably, in the step (2), the auxiliary agent is a mixture of polyvinylpyrrolidone and ethanol; the adjuvant is Cu (NO)3)2、In(NO3)3And Ga (NO)3)31-3% of the total mass; wherein the mass ratio of the polyvinylpyrrolidone to the ethanol is 1-3: 1;
preferably, in the step (2), the temperature of the calcination is 300-;
preferably, in step (3), the dispersant is Orotan 1124 or LM-5020; the dosage is 1-3% of the mixed mass of A and B; the auxiliary agent is OP or Tween emulsifier; the dosage is 0.5-2% of the mixed mass of A and B;
preferably, in the step (4), the high temperature is 400-800 ℃, preferably 500 ℃.
Compared with the prior art, the invention has the technical advantages that:
(1) the invention prepares the composite oxide nanometer material by different metal simple substances, and overcomes the defects of more steps, difficult post-treatment, low yield and the like of the prior methods; meanwhile, the method has the advantage of low cost of raw materials, and is suitable for industrial production.
(2) The CIGS thin film doped with the spinel phase has strong homogeneity and good proportion of metal elements, and can effectively improve the photoelectric conversion rate; the use amount of the nano spinel type powder has great influence on the performance of the modified CIGS thin film, and too much or too little is not beneficial to exerting the good photoelectric conversion performance of the CIGS thin film.
(3) The CIGS thin film doped with the spinel phase effectively improves the spectrum utilization range, well utilizes solar energy under the limited illumination condition, enhances the utilization rate of the solar energy and improves the power generation efficiency of a solar cell.
(4) In the preparation process of the nano spinel type powder, the concentration of the ethanol water solution, the molecular weight and the dosage of the PEG have great influence on the particle size distribution of the nano spinel type powder, and the modified CIGS film has good homogeneity only if the concentration of the ethanol water solution, the molecular weight and the dosage of the PEG are in a limited application range, so that the photoelectric property is further changed.
(5) In the preparation process of the nano spinel type powder, the formed nano spinel type powder is easy to agglomerate due to overhigh roasting temperature, the quality of the formed nano spinel type powder is poor due to overlow temperature, and the photoelectric property of the modified CIGS film is not favorably improved.
Detailed Description
Example 1
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 5 parts of nano spinel type powder and 100 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing MgCl2And AlCl3According to the following steps: mixing at 2 mol ratio, dissolving in 50% ethanol water solution, stirring, and water bath at 50 deg.CAdding ammonia water, and adjusting the pH value to 8 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 2 wt% of PEG (M ═ 4000), refluxing in ethanol for 2h, drying, grinding, and roasting in a muffle furnace at 1000 ℃; the roasting time is 2 hours; preparing nano spinel type powder A;
the particle size of the nano spinel type powder A is intensively distributed (the volume fraction is more than or equal to 70 percent, the same below) at 24-37 nm;
(2) preparing nano copper indium gallium (CuInGa) powder:
preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Solution, according to a molar ratio of Cu, In and Ga of 1: 0.7: 0.3 mixing, adding 2% (by Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Total mass) of polyvinylpyrrolidone and ethanol (mass ratio of polyvinylpyrrolidone to ethanol is 2: 1; ) (ii) a Heating to 50 deg.C, stirring, and adjusting pH to 8; filtering, and washing with ethanol solution; drying, calcining at 550 ℃, and cooling to obtain nano metal oxide powder B;
(3) preparation and film formation of nano composite ink
Mixing A and B, adding 2% of Orotan 1124 serving as a dispersing agent, performing ball milling for 6 hours, adding water for dilution, adding 1% (based on the mixed mass of A and B) of OP-10 serving as an auxiliary agent, and performing ultrasonic treatment to obtain nano composite ink;
carrying out oil stain treatment on a substrate, placing the substrate in deionized water and acetone for ultrasonic treatment, and drying; spraying the composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) alloy film prepared by reduction of nano composite film
Treating the nano composite film at a high temperature of 500 ℃ to remove the organic dispersant and other additives, then placing the nano composite film in a tubular furnace, and reducing the nano composite film by using hydrogen to obtain an alloy film;
(5) method for preparing spinel phase-doped photovoltaic film by solid-state source selenization method
Placing the alloy film in a tube furnace, and placing a corundum boat filled with excessive solid Se powder near the alloy film; sealing the tube furnace, and vacuumizing for 30 min; and carrying out a selenization process on the alloy film to obtain the CIGS film doped with the spinel phase.
Example 2
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 2 parts of nano spinel type powder and 110 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
adding CuCl2And CrCl3According to the following steps: mixing the components according to a molar ratio of 2, dissolving the mixture in 75% ethanol aqueous solution, stirring, adding ammonia water under the condition of water bath at 40 ℃, and adjusting the pH value to 9 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 1 wt% of PEG (M is 3000), refluxing in ethanol for 1h, drying, grinding, and roasting in a muffle furnace at 800 ℃; the roasting time is 4 hours; preparing nano spinel type powder A;
the particle size of the nano spinel type powder A is intensively distributed at 22-39 nm;
(2) preparing nano copper indium gallium (CuInGa) powder:
preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3A solution, wherein the molar ratio of Cu, In and Ga is 1: 0.4: 0.6; mixing, adding 1% (based on Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Total mass) of polyvinylpyrrolidone and ethanol (mass ratio of polyvinylpyrrolidone to ethanol is 1: 1); heating to 60 ℃, stirring, and adjusting the pH value to 7.5; filtering, and washing with ethanol solution; drying, calcining at 300 ℃, and cooling to obtain nano metal oxide powder B;
(3) preparation and film formation of nano composite ink
Mixing A and B, adding 1% (based on the mixing mass of A and B) of LM-5020 serving as a dispersing agent, performing ball milling for 5 hours, adding water for dilution, adding 2% (based on the mixing mass of A and B) of Tween-20 serving as an auxiliary agent, and performing ultrasonic treatment to obtain the nano composite ink;
carrying out oil stain treatment on a substrate, placing the substrate in deionized water and acetone for ultrasonic treatment, and drying; spraying the composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) alloy film prepared by reduction of nano composite film
Treating the nano composite film at a high temperature of 400 ℃ to remove the organic dispersant and other additives, then placing the nano composite film in a tubular furnace, and reducing the nano composite film by using hydrogen/argon mixed gas to obtain an alloy film;
(5) method for preparing spinel phase-doped photovoltaic film by solid-state source selenization method
Placing the alloy film in a tube furnace, and placing a corundum boat filled with excessive solid Se powder near the alloy film; sealing the tube furnace, and vacuumizing for 60 min; and carrying out a selenization process on the alloy film to obtain the CIGS film doped with the spinel phase.
Example 3
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 2 parts of nano spinel type powder and 90 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing NiCl2And CoCl3According to the following steps: mixing the components according to a molar ratio of 2, dissolving the mixture in an ethanol aqueous solution with a volume concentration of 60%, stirring, adding ammonia water under the condition of water bath at 45 ℃, and adjusting the pH value to 8 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 3 wt% of PEG (M is 8000), refluxing in ethanol for 3h, drying, grinding, and roasting in a muffle furnace at 1200 ℃; the roasting time is 1 h; preparing nano spinel type powder A; the particle size of the nano spinel type powder A is intensively distributed at 24-38 nm;
(2) preparing nano copper indium gallium (CuInGa) powder:
preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3A solution, wherein the molar ratio of Cu, In and Ga is 1: 0.8: 0.2; mixing, adding 3% (by Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Total mass) of polyvinylpyrrolidone and ethanol (mass ratio of polyvinylpyrrolidone to ethanol is 3: 1); heating to 50 deg.C, stirring, and adjusting pH to 10.5; filtering, and washing with ethanol solution; drying, calcining at 800 ℃, and cooling to obtain nano metal oxide powder B;
(3) preparation and film formation of nano composite ink
Mixing A and B, adding 3% (based on the mixed mass of A and B) of LM-5020 serving as a dispersing agent, performing ball milling for 10 hours, adding water for dilution, adding 0.5% (based on the mixed mass of A and B) of Tween-80, and performing ultrasonic treatment to obtain the nano composite ink;
carrying out oil stain treatment on a substrate, placing the substrate in deionized water and acetone for ultrasonic treatment, and drying; spraying the composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) alloy film prepared by reduction of nano composite film
Treating the nano composite film at a high temperature of 800 ℃ to remove the organic dispersant and other additives, then placing the nano composite film in a tubular furnace, and reducing the nano composite film by using hydrogen to obtain an alloy film;
(5) method for preparing spinel phase-doped photovoltaic film by solid-state source selenization method
Placing the alloy film in a tube furnace, and placing a corundum boat filled with excessive solid Se powder near the alloy film; sealing the tube furnace, and vacuumizing for 40 min; and carrying out a selenization process on the alloy film to obtain the CIGS film doped with the spinel phase.
Example 4
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 10 parts of nano spinel type powder and 120 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
reacting ZnCl2And GaCl3According to the following steps: mixing the components according to a molar ratio of 2, dissolving the mixture in an ethanol aqueous solution with a volume concentration of 50%, stirring, adding ammonia water under a water bath condition of 50 ℃, and adjusting the pH value to 9 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 3 wt% of PEG (M is 5000), refluxing in ethanol for 1h, drying, grinding, and roasting in a muffle furnace at 1200 ℃; the roasting time is 1 h; preparing nano spinel type powder A; the particle size of the nano spinel type powder A is intensively distributed at 22-41 nm;
(2) preparing nano copper indium gallium (CuInGa) powder:
preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3A solution, wherein the molar ratio of Cu, In and Ga is 1: 0.9: 0.2 mixing, adding 2% (with Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Total mass) mixture of polyvinylpyrrolidone and ethanol (mass ratio of polyvinylpyrrolidone to ethanol is 1: 1; ) (ii) a Heating to 60 deg.C, stirring, and adjusting pH to 9; filtering, and washing with ethanol solution; drying, calcining at 600 ℃, and cooling to obtain nano metal oxide powder B;
(3) preparation and film formation of nano composite ink
Mixing A and B, adding 1% (based on the mixing mass of A and B) of Orotan 1124 serving as a dispersing agent, performing ball milling for 5 hours, adding water for dilution, adding 2% (based on the mixing mass of A and B) of OP-10 serving as an auxiliary agent, and performing ultrasonic treatment to obtain nano composite ink;
carrying out oil stain treatment on a substrate, placing the substrate in deionized water and acetone for ultrasonic treatment, and drying; spraying the composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) alloy film prepared by reduction of nano composite film
Treating the nano composite film at a high temperature of 600 ℃ to remove the organic dispersant and other additives, then placing the nano composite film in a tubular furnace, and reducing the nano composite film by using hydrogen/argon mixed gas to obtain an alloy film;
(5) method for preparing spinel phase-doped photovoltaic film by solid-state source selenization method
Placing the alloy film in a tube furnace, and placing a corundum boat filled with excessive solid Se powder near the alloy film; sealing the tube furnace, and vacuumizing for 30 min; and carrying out a selenization process on the alloy film to obtain the CIGS film doped with the spinel phase.
Comparative example 1
Compared with the embodiment 1, the addition amount of the nano spinel type powder is different;
a photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 15 parts of nano spinel type powder and 90 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the same steps as example 1.
Comparative example 2
Compared with the embodiment 1, the concentration of the ethanol water solution is different in the preparation process of the nano spinel type powder.
A photovoltaic thin film material for a solar cell is prepared by the following steps of (1) preparing the same raw materials in parts by weight as those in example 1;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing MgCl2And AlCl3According to the following steps: mixing the components according to a molar ratio of 2, dissolving the mixture in an ethanol aqueous solution with a volume concentration of 30%, stirring, adding ammonia water under a water bath condition of 50 ℃, and adjusting the pH value to 8 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 2 wt% of PEG (M ═ 4000), refluxing in ethanol for 2h, drying, grinding, and roasting in a muffle furnace at 1000 ℃; the roasting time is 2 hours; preparing nano spinel type powder A; the particle size of the nano spinel type powder A is not uniform and is intensively distributed in the range of 19-327 nm;
(2) - (5) preparation Process the same as in example 1.
Comparative example 3
Compared with example 1, the calcination temperature in the preparation process of the nano spinel type powder is different.
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 5 parts of nano spinel type powder and 100 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing MgCl2And AlCl3According to the following steps: mixing the components according to a molar ratio of 2, dissolving the mixture in an ethanol aqueous solution with a volume concentration of 50%, stirring, adding ammonia water under a water bath condition of 50 ℃, and adjusting the pH value to 8 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 2 wt% of PEG (M ═ 4000), refluxing in ethanol for 2h, drying, grinding, and roasting in a muffle furnace at the roasting temperature of 500 ℃; the roasting time is 2 hours; preparing nano spinel type powder A; the particle size of the nano spinel type powder A is not uniform and is concentrated to 52-459 nm;
(2) the procedure for preparation of (5) is the same as in example 1.
Comparative example 4
Compared with example 1, the molecular weight of PEG in the preparation process of the nano spinel type powder is different.
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 5 parts of nano spinel type powder and 100 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing MgCl2And AlCl3According to the following steps: 2 mol ratio, dissolving in 50% ethanol water solution, stirring, adding ammonia water under water bath at 50 deg.C, adjusting pH to 8 to obtain composite oxyhydrogenA compound precursor;
washing the composite hydroxide precursor with water, adding 2 wt% of PEG (M ═ 4000), refluxing in ethanol for 2h, drying, grinding, and roasting in a muffle furnace at 1000 ℃; the roasting time is 2 hours; preparing nano spinel type powder A; the particle size of the nano spinel type powder A is not uniform, and more aggregates appear;
(2) - (5) preparation Process the same as in example 1.
Comparative example 5
Compared with the embodiment 1, the PEG dosage in the preparation process of the nano spinel type powder is different.
A photovoltaic thin film material for a solar cell is prepared from the following raw materials in parts by weight: 5 parts of nano spinel type powder and 100 parts of nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) preparing nano spinel type powder:
mixing MgCl2And AlCl3According to the following steps: mixing the components according to a molar ratio of 2, dissolving the mixture in an ethanol aqueous solution with a volume concentration of 50%, stirring, adding ammonia water under a water bath condition of 50 ℃, and adjusting the pH value to 8 to obtain a composite hydroxide precursor;
washing the composite hydroxide precursor with water, adding 5 wt% of PEG (M ═ 4000;), refluxing in ethanol for 2h, drying, grinding, roasting in a muffle furnace at 1000 ℃; the roasting time is 2 hours; preparing nano spinel type powder A; the particle size of the nano spinel type powder A is not uniform, and more aggregates appear;
(2) - (5) preparation Process the same as in example 1.
Effect example-performance testing of photovoltaic thin film materials:
(1) detection of photoelectric conversion efficiency: the photovoltaic conversion efficiency of the photovoltaic thin film materials prepared in examples 1 to 4 and comparative examples 1 to 5 is detected by adopting a GBT34160-2017 detection method for the photovoltaic conversion efficiency of the photovoltaic module for the ground; the results are shown in Table 1;
(2) detecting the effective spectral region of the photovoltaic film materials prepared in the examples 1-4 and the comparative examples 1-5 by using a Hitachi U-4100 type ultraviolet-visible/near infrared spectrophotometer; the results are shown in Table 1;
table 1 performance test results of photovoltaic thin film materials
Therefore, the photovoltaic thin film material provided by the invention has better photoelectric conversion efficiency, and the spectrum utilization range is effectively improved; meanwhile, the selection of parameters such as the dosage of the doped material nano spinel type powder, the concentration of the ethanol aqueous solution of the dispersion solvent, the roasting temperature and the like has great influence on the performance of the doped material nano spinel type powder.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. A photovoltaic thin film material for a solar cell is prepared from the following raw materials: nano spinel type powder, nano copper indium gallium powder;
the preparation method of the photovoltaic thin film material comprises the following steps:
(1) mixing MCl2And NCl3Mixing, dissolving in alcohol-water solution, and adjusting pH to 8-9 to obtain composite hydroxide precursor; washing the composite hydroxide precursor with water, adding PEG, refluxing in ethanol, drying, grinding and roasting to obtain nano spinel powder A;
(2) preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Mixing the solution and adding an auxiliary agent; heating and adjusting the pH value to 7.5-10.5;filtering, and washing with ethanol solution; drying, calcining and cooling to obtain nano metal oxide powder B;
(3) mixing A and B, adding a dispersant, performing ball milling, adding an auxiliary agent, and performing ultrasonic treatment to obtain nano composite ink;
taking a substrate, carrying out oil stain treatment, and then carrying out ultrasonic treatment and drying; spraying the nano composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) treating the nano composite film at high temperature, and reducing to obtain an alloy film;
(5) selenizing the alloy film to obtain a CIGS film doped with a spinel phase;
in the step (2), the auxiliary agent is a mixture of polyvinylpyrrolidone and ethanol;
in the step (3), the auxiliary agent is OP or Tween emulsifier;
wherein M ═ any of Mg, Cu, Ni, Zn, or Cd; n is any one of Al, Co, Cr, and Ga.
2. The photovoltaic thin film material according to claim 1, wherein the raw materials for preparing the photovoltaic thin film material comprise, in parts by weight: 2-10 parts of nano spinel type powder and 90-120 parts of nano copper indium gallium powder.
3. A method of preparing the photovoltaic thin film material for a solar cell according to claim 1, comprising the steps of:
(1) mixing MCl2And NCl3Mixing, dissolving in alcohol-water solution, and adjusting pH to 8-9 to obtain composite hydroxide precursor; washing the composite hydroxide precursor with water, adding PEG, refluxing in ethanol, drying, grinding and roasting to obtain nano spinel powder A;
(2) preparing Cu (NO)3)2、In(NO3)3And Ga (NO)3)3Mixing the solution and adding an auxiliary agent; heating and adjusting the pH value to 7.5-10.5; filtering, and washing with ethanol solution; drying, calcining and cooling to obtain the nano metal oxide powderAnd finally B;
(3) mixing A and B, adding a dispersant, performing ball milling, adding an auxiliary agent, and performing ultrasonic treatment to obtain nano composite ink;
taking a substrate, carrying out oil stain treatment, and then carrying out ultrasonic treatment and drying; spraying the nano composite ink on the surface of a substrate, and drying after the ink is leveled to prepare a nano composite film;
(4) treating the nano composite film at high temperature, and reducing to obtain an alloy film;
(5) selenizing the alloy film to obtain a CIGS film doped with a spinel phase;
in the step (2), the auxiliary agent is a mixture of polyvinylpyrrolidone and ethanol;
in the step (3), the auxiliary agent is OP or Tween emulsifier.
4. The method for preparing the photovoltaic thin film material according to claim 3, wherein in the step (1), the molecular weight of PEG is 3000-8000.
5. The method for preparing a photovoltaic thin film material according to claim 3, wherein in the step (1), the molecular weight of PEG is 4000.
6. The method for preparing the photovoltaic thin film material as claimed in claim 3, wherein in the step (1), the baking is performed in a muffle furnace, and the baking temperature is 800-1200 ℃; the roasting time is 1-4 h.
7. The method for preparing a photovoltaic thin film material according to claim 3, wherein in the step (1), the particle size of the nano spinel type powder A is intensively distributed in a range of 22-41 nm.
8. The method for preparing a photovoltaic thin film material according to claim 3, wherein in the step (2), the Cu (NO) is3)2、In(NO3)3And Ga (NO)3)3The molar ratio of Cu, In and Ga is 1: 0.4-0.9: 0.2-0.6.
9. The method for preparing a photovoltaic thin film material according to claim 3, wherein in the step (2), the amount of the auxiliary agent is Cu (NO)3)2、In(NO3)3And Ga (NO)3)31-3% of the total mass; wherein the mass ratio of the polyvinylpyrrolidone to the ethanol is 1-3: 1.
10. The method for preparing a photovoltaic thin film material according to claim 3, wherein in the step (3), the dispersing agent is Orotan 1124 or LM-5020; the dosage is 1-3% of the mixed mass of A and B; the dosage of the auxiliary agent is 0.5-2% of the mixed mass of the A and the B.
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| CN103137720A (en) * | 2013-02-06 | 2013-06-05 | 内蒙古大学 | Photovoltaic film material mixed with rare earth elements |
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| CN104781445A (en) * | 2012-11-07 | 2015-07-15 | 住友金属矿山株式会社 | Transparent-conductive-film laminate, manufacturing method therefor, thin-film solar cell, and manufacturing method therefor |
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| CN102484164A (en) * | 2010-03-05 | 2012-05-30 | 株式会社东芝 | Compound thin-film solar cell and method for producing same |
| CN104781445A (en) * | 2012-11-07 | 2015-07-15 | 住友金属矿山株式会社 | Transparent-conductive-film laminate, manufacturing method therefor, thin-film solar cell, and manufacturing method therefor |
| CN103137720A (en) * | 2013-02-06 | 2013-06-05 | 内蒙古大学 | Photovoltaic film material mixed with rare earth elements |
| CN103346201A (en) * | 2013-05-24 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Preparation method of germanium-doped CZTS thin film, thin film and solar cell |
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