CN108807572B - Silver indium gallium selenide thin film and preparation method and application thereof - Google Patents
Silver indium gallium selenide thin film and preparation method and application thereof Download PDFInfo
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- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010409 thin film Substances 0.000 title abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 170
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 239000002002 slurry Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000004513 sizing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 3
- 238000010549 co-Evaporation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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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
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- 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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Abstract
The invention discloses a silver indium gallium selenide film, which comprises a substrate, wherein the surface of the substrate is coated with Ag in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer. The silver indium gallium selenide thin film has the characteristics of high electron drift saturation velocity, small dielectric constant and good conductivity, and meanwhile, a photovoltaic cell manufactured by the silver indium gallium selenide thin film has the characteristics of high photoelectric conversion efficiency and large open-circuit voltage. The invention also discloses a preparation method and application of the silver indium gallium selenide thin film. The preparation method of the silver indium gallium selenide thin film is obtained by grinding, preparing slurry, coating, heating and annealing, and the silver indium gallium selenide thin film is prepared by a non-vacuum method for the first time.
Description
Technical Field
The invention relates to a semiconductor material, in particular to a silver indium gallium selenide film and a preparation method and application thereof.
Background
Wide bandgap semiconductor materials, also known as third generation semiconductor materials (first and second generation silicon, germanium respectively), have a bandgap greater than or equal to 2.3 eV. The wide bandgap semiconductor material generally has the characteristics of high electron drift saturation velocity, small dielectric constant, good conductivity and the like, and is widely researched by researchers. The traditional wide bandgap semiconductor comprises SiC, GaN, ZnO and Ga2O3Etc., as well as other group II-VI compound materials. The wide bandgap material has the characteristics of short-wave absorption, high breakdown voltage and the like, and therefore has great application prospect in the fields of Light Emitting Diodes (LEDs) and Laser Diodes (LDs). In addition, with the rapid development of Solar Cells (SCs) in recent years, wide bandgap semiconductor materials are beginning to play an important role in the field of solar cells. For example, researchers developed many wide bandgap organic polymer semiconductor materials widely used in polymer solar cells, and also developed many wide bandgap materials (such as ZnO, NiO and MoO)3Etc.) thin films are applied to perovskite solar cells to serve as electron/hole transport layers.
The silver indium gallium selenide thin film is a wide-bandgap semiconductor material and is very suitable for being used as the top layer of a chalcopyrite-based laminated thin film solar cell, but the preparation method in the prior art mainly comprises a vacuum method and a non-vacuum method. The vacuum method is mainly classified into a co-evaporation method and a two-step method. The co-evaporation method needs to accurately control the evaporation rate and the deposition amount of each element, and requires high control precision of equipment, and high technical difficulty and manufacturing cost of the equipment. The sputtering metal preset film and the selenizing two-step method has the advantages of low target utilization rate, long film forming time, difficulty in controlling the selenizing process, and high investment cost and battery cost.
Disclosure of Invention
Aiming at the defects of the prior art, the first purpose of the invention is to provide the silver indium gallium selenide thin film which has the characteristics of high electron drift saturation velocity, small dielectric constant and good conductivity, and simultaneously, the photovoltaic cell manufactured by the silver indium gallium selenide thin film has the characteristics of high photoelectric conversion efficiency and large open-circuit voltage.
The second purpose of the invention is to provide a preparation method of the silver indium gallium selenide thin film, the silver indium gallium selenide thin film (AIGS thin film for short) is prepared by a non-vacuum method for the first time, and compared with the traditional vacuum method, the method has the advantages of simple preparation process, high preparation efficiency, low price and the like, and is suitable for preparing the AIGS thin film in a large area.
The third purpose of the invention is to provide an application of the silver indium gallium selenide thin film in a photovoltaic cell, and the photovoltaic cell has the characteristics of high photoelectric conversion efficiency and large open-circuit voltage.
The first purpose of the invention can be achieved by adopting the following technical scheme:
the silver indium gallium selenide film comprises a substrate and is characterized in that the surface of the substrate is coated with Ag in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer.
Preferably, Ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The total thickness of the nanoparticle layer is 1.6-2.2 microns.
Preferably, Ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer is 0.6-0.8 μm0.8-1.0 micron, 0.2-0.4 micron.
Preferably, Ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer was 0.7 microns, 0.9 microns, 0.3 microns, respectively.
Preferably, the substrate is a glass substrate plated with Mo.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of a silver indium gallium selenide film is characterized by comprising the following steps:
grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent;
coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in an inert gas environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
Preferably, in the grinding step, Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Average particle diameter of nanoparticlesLess than 2 microns.
Preferably, in the step of preparing the paste, Ag2The concentration of the Se sizing agent is that each gram of alcohol contains 3-5mgAg2Nanoparticles of Se, Ga2Se3The concentration of the slurry is 3-5mgAg per gram of alcohol2Se nanoparticles, In2Se3The concentration of the slurry is 3-5mgAg per gram of alcohol2Se nanoparticles.
The third purpose of the invention can be achieved by adopting the following technical scheme:
the application of the silver indium gallium selenide thin film is characterized in that the silver indium gallium selenide thin film is applied to a photovoltaic cell.
Preferably, the preparation method of the photovoltaic cell comprises the following steps:
grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent;
coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in an inert gas environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; cooling to 200 ℃ for 140min at 120 ℃ to obtain the silver indium gallium selenide film;
CdS manufacturing: preparing a CdS layer on the silver indium gallium selenide film in a CBD mode;
the window layer manufacturing step: manufacturing a window layer on the CdS by adopting an MOCVD (metal organic chemical vapor deposition) mode; the specific process is as follows: firstly, introducing Zn metal organic matter and water into a cavity of MOCVD equipment, reacting the metal organic matter and the water to generate i-ZnO, adding a compound of B after the thickness reaches 50nm, and reacting the three to generate ZnO: b; wherein, the meaning of i in i-ZnO refers to ZnO obtained under the condition of no doping; ZnO: b is ZnO doped with B;
manufacturing an Al grid: depositing an Al grid electrode on the window layer in an evaporation mode to obtain a photovoltaic cell;
CdS manufacturing: preparing a CdS layer on the silver indium gallium selenide film by adopting a CBD (chemical water bath deposition) mode;
the window layer manufacturing step: manufacturing a window layer on the CdS by adopting an MOCVD (metal organic chemical vapor deposition) mode; the specific process is as follows: firstly, introducing Zn metal organic matter and water into a cavity of MOCVD equipment, reacting the metal organic matter and the water to generate i-ZnO, adding a compound of B after the thickness reaches 50nm, and reacting the three to generate ZnO: b; wherein, the meaning of i in i-ZnO refers to ZnO obtained under the condition of no doping; ZnO: b is ZnO doped with B;
manufacturing an Al grid: and depositing an Al grid electrode on the window layer in an evaporation mode to obtain the photovoltaic cell.
The invention has the beneficial effects that:
1. the invention is characterized in that the surface of the substrate is coated with Ag in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of each nanoparticle layer is optimized simultaneously by the nanoparticle layers, so that the silver indium gallium selenide thin film has the characteristics of high electron drift saturation velocity, small dielectric constant and good conductivity, and meanwhile, a photovoltaic cell manufactured by the silver indium gallium selenide thin film has the characteristics of high photoelectric conversion efficiency and large open-circuit voltage.
2. According to the method, the AgInGaSe film is prepared through the steps of grinding, slurry preparation, coating and heating and annealing, parameters of the steps are optimized, the AgInGaSe film is prepared by a non-vacuum method for the first time, and compared with a traditional vacuum method, the method has the advantages of simple preparation process, high preparation efficiency, low price and the like, and is suitable for large-area preparation of the AIGS film.
3. The invention provides an application of a silver indium gallium selenide film in a photovoltaic cell, the photovoltaic cell has the characteristics of high photoelectric conversion efficiency and large open-circuit voltage, the photoelectric conversion efficiency of the photovoltaic cell is 6%, and the open-circuit voltage can reach 0.9V.
Detailed Description
The present invention will be further described with reference to specific embodiments, and the raw materials used in the following examples are commercially available unless otherwise specified.
The grinding step was carried out by using a B015-05 type ball mill from the Japan Long-tailed systems.
Example 1:
the silver indium gallium selenide film comprises a substrate, wherein Ag is sequentially coated on the surface of the substrate2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer; ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer was 0.7 microns, 0.9 microns, 0.3 microns, respectively. The substrate is a glass substrate plated with Mo.
A preparation method of a silver indium gallium selenide film comprises the following steps:
grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle; ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3The average particle size of the nanoparticles is less than 2 microns;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3The nanoparticles are dissolved inRespectively obtaining Ag in alcohol2Se paste, Ga2Se3Slurry and In2Se3Sizing agent; ag2The concentration of the Se sizing agent is that each gram of alcohol contains 4mgAg2Nanoparticles of Se, Ga2Se3The concentration of the slurry is 4mgAg per gram of alcohol2Se nanoparticles, In2Se3The concentration of the slurry is 4mgAg per gram of alcohol2Se nanoparticles.
Coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: and heating and annealing the coated substrate in a nitrogen environment, wherein the nitrogen concentration is 99.9%. The specific process is as follows: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
Example 2:
the silver indium gallium selenide film comprises a substrate, wherein Ag is sequentially coated on the surface of the substrate2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer; ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer was 0.6 microns, 0.8 microns, 0.2 microns, respectively. The substrate is a glass substrate plated with Mo.
A preparation method of a silver indium gallium selenide film comprises the following steps:
grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle; ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3The average particle size of the nanoparticles is less than 1 micron;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent; ag2The concentration of the Se sizing agent is that each gram of alcohol contains 3mgAg2Nanoparticles of Se, Ga2Se3The concentration of the slurry is 3mgAg per gram of alcohol2Se nanoparticles, In2Se3The concentration of the slurry is 3mgAg per gram of alcohol2Se nanoparticles.
Coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in a nitrogen environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
Example 3:
the silver indium gallium selenide film comprises a substrate, wherein Ag is sequentially coated on the surface of the substrate2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer; ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer was 0.8 microns, 1.0 microns, 0.4 microns, respectively. The substrate is a glass substrate plated with Mo.
A preparation method of a silver indium gallium selenide film comprises the following steps:
grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle; ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3The average particle size of the nanoparticles is less than 2 microns;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent; ag2The concentration of the Se sizing agent is that each gram of alcohol contains 5mgAg2Nanoparticles of Se, Ga2Se3The concentration of the slurry is 5mgAg per gram of alcohol2Se nanoparticles, In2Se3The concentration of the slurry is 5mgAg per gram of alcohol2Se nanoparticles.
Coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in a nitrogen environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
Example 4:
the silver indium gallium selenide film comprises a substrate, wherein Ag is sequentially coated on the surface of the substrate2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer; ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3Nano meterThe particle layer had a thickness of 0.7 microns, 0.9 microns, 0.4 microns, respectively. The substrate is a glass substrate plated with Mo.
A preparation method of a silver indium gallium selenide film comprises the following steps:
grinding: respectively grinding the Ag2Se bulk, the Ga2Se3 bulk and the In2Se3 bulk to respectively obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle; ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3The average particle size of the nanoparticles is less than 1 micron;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent; ag2The concentration of the Se sizing agent is that each gram of alcohol contains 3mgAg2Nanoparticles of Se, Ga2Se3The concentration of the slurry is 4mgAg per gram of alcohol2Se nanoparticles, In2Se3The concentration of the slurry is 5mgAg per gram of alcohol2Se nanoparticles.
Coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in a nitrogen environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
Example 5
An application of a silver indium gallium selenide thin film in a photovoltaic cell.
The preparation method of the photovoltaic cell comprises the following steps:
the preparation method of the silver indium gallium selenide thin film comprises the following steps: obtaining the silver indium gallium selenide thin film by adopting the preparation method of the silver indium gallium selenide thin film in the embodiment 1;
CdS manufacturing: preparing a CdS layer on the silver indium gallium selenide film by adopting a CBD (chemical water bath deposition) mode;
the window layer manufacturing step: manufacturing a window layer on the CdS by adopting an MOCVD (metal organic chemical vapor deposition) mode; the specific process is as follows: firstly, introducing Zn metal organic matter and water into a cavity of MOCVD equipment, reacting the metal organic matter and the water to generate i-ZnO, adding a compound of B after the thickness reaches 50nm, and reacting the three to generate ZnO: b; wherein, the meaning of i in i-ZnO refers to ZnO obtained under the condition of no doping; ZnO: b is ZnO doped with B;
manufacturing an Al grid: and depositing an Al grid electrode on the window layer in an evaporation mode to obtain the photovoltaic cell.
The photovoltaic cell prepared by the embodiment 5 has the photoelectric conversion efficiency of 6% and the open-circuit voltage of 0.9V.
Various other changes and modifications to the above-described embodiments and concepts will become apparent to those skilled in the art from the above description, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (9)
1. The silver indium gallium selenide film comprises a substrate and is characterized in that the surface of the substrate is coated with Ag in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
Ag2se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer is 0.6-0.8 micrometer, 0.8-1.0 micrometer, and 0.2-0.4 micrometer respectively;
the preparation method of the silver indium gallium selenide film comprises the following steps:
grinding: respectively mixing Ag2Se blockBody, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent;
coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in an inert gas environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
2. The film of claim 1, wherein the Ag2Se nanoparticle layer is Ga2Se3Nanoparticle layer and In2Se3The total thickness of the nanoparticle layer is 1.6-2.2 microns.
3. The film of claim 1, wherein Ag is Ag2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3The thickness of the nanoparticle layer was 0.7 microns, 0.9 microns, 0.3 microns, respectively.
4. The film of claim 1, wherein the substrate is a Mo-plated glass substrate.
5. The method for preparing the film of silver indium gallium selenide according to any one of claims 1 to 4, wherein the method comprises the following steps:
grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle;
preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent;
coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer;
heating and annealing treatment steps: heating and annealing the coated substrate in an inert gas environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; and (4) performing temperature reduction for 140min to 200 ℃ to obtain the silver indium gallium selenide film.
6. The method of claim 5, wherein Ag is Ag-in-Ga-Se2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3The nanoparticles have an average particle size of less than 2 microns.
7. The method of claim 5, wherein the step of preparing the paste comprises Ag2The concentration of the Se sizing agent is that each gram of alcohol contains 3-5mgAg2Se nanoparticles, Ga2Se3The concentration of the slurry is 3-5mgAg per gram of alcohol2Se nanoparticles, In2Se3The concentration of the slurry is 3-5mgAg per gram of alcohol2Se nanoparticles.
8. Use of the AgInGaSe film according to any one of claims 1 to 4 in a photovoltaic cell.
9. The use of the film of silver indium gallium selenide of claim 8, wherein the method for preparing the photovoltaic cell comprises: grinding: respectively mixing Ag2Bulk of Se, Ga2Se3Bulk and In2Se3Grinding the block to obtain Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3A nanoparticle; preparing slurry: respectively mixing Ag2Se nanoparticles, Ga2Se3Nanoparticles and In2Se3Dissolving the nanoparticles in alcohol to obtain Ag2Se paste, Ga2Se3Slurry and In2Se3Sizing agent; coating: coating Ag on the surface of the substrate in sequence by adopting a spin coating mode2Se paste, Ga2Se3Slurry and In2Se3Slurry, so that Ag is formed on the surface of the substrate in sequence2Se nanoparticle layer, Ga2Se3Nanoparticle layer and In2Se3A nanoparticle layer; heating and annealing treatment steps: heating and annealing the coated substrate in an inert gas environment, and the specific process comprises the following steps: heating for 0-15min from room temperature to 580 deg.C; 15-120min, keeping 580 deg.C; cooling to 200 ℃ for 140min at 120 ℃ to obtain the silver indium gallium selenide film; CdS manufacturing: preparing a CdS layer on the silver indium gallium selenide film in a CBD mode; the window layer manufacturing step: manufacturing a window layer on the CdS by adopting an MOCVD (metal organic chemical vapor deposition) mode; the specific process is as follows: firstly, introducing Zn metal organic matter and water into a cavity of MOCVD equipment, reacting the metal organic matter and the water to generate i-ZnO, and waiting to be thickAfter the temperature reaches 50nm, a compound of B is added, and the three react to generate ZnO: b; wherein, the meaning of i in i-ZnO refers to ZnO obtained under the condition of no doping; ZnO: b is ZnO doped with B; manufacturing an Al grid: and depositing an Al grid electrode on the window layer in an evaporation mode to obtain the photovoltaic cell.
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