CN112736150B - Copper indium gallium selenide thin-film solar cell and preparation method thereof - Google Patents
Copper indium gallium selenide thin-film solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN112736150B CN112736150B CN202110017020.XA CN202110017020A CN112736150B CN 112736150 B CN112736150 B CN 112736150B CN 202110017020 A CN202110017020 A CN 202110017020A CN 112736150 B CN112736150 B CN 112736150B
- Authority
- CN
- China
- Prior art keywords
- layer
- solution
- substrate
- temperature
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000002161 passivation Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 45
- 239000010408 film Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- 229910052738 indium Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000004093 laser heating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 78
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
According to the preparation method of the CIGS thin-film solar cell and the CIGS thin-film solar cell, the thin-film absorption layer is prepared on the substrate, the thin-film absorption layer is subjected to local laser heating passivation, the CdS buffer layer grows on the passivated thin-film absorption layer, the window layer is formed on the surface of the CdS buffer layer, and the metal gate electrode is formed on the surface of the window layer.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a copper indium gallium selenide thin-film solar cell and a preparation method thereof.
Background
Solar energy is concerned about and popularized all over the world due to the advantages of being clean, environment-friendly, renewable and the like. Among various solar cells, the thin film solar cell has the advantages of low cost, large-scale production, capability of manufacturing a multijunction serial cell module and the like, and is concerned. Among all kinds of thin-film solar cells, the copper indium gallium selenide CIGS thin-film solar cell has the characteristics of small pollution, good weak light property, high efficiency and the like, and becomes a kind of thin-film solar cell with practical application prospect.
Although CIGS single layer cells have achieved higher cell efficiencies, the pace of pursuing more efficient devices has never stopped. The open-circuit voltage of the CIGS battery device is greatly improved by regulating the energy band structure through Ga gradient distribution and optimizing the process through an alkali metal post-treatment mode such as KF (KF). Interfacial recombination due to interfacial defects remains a significant cause of the increased efficiency of CIGS cells. At present, the problems of lattice mismatch and the like are also solved by optimizing a CdS buffer layer or adopting a composite buffer layer to regulate and control an interface, but the introduction of the CdS buffer layer has the defect that a certain amount of light in a short-wave spectrum section can be absorbed, the diffusion length of minority carriers is too short to generate photocurrent, and the absorbed photons are wasted to reduce short-circuit current.
Disclosure of Invention
In view of the above, it is desirable to provide a copper indium gallium selenide thin film solar cell and a method for manufacturing the same, which can improve the cell efficiency.
In order to solve the problems, the invention adopts the following technical scheme:
the application provides a preparation method of a copper indium gallium selenide thin-film solar cell, which comprises the following steps:
providing a substrate;
preparing a thin film absorption layer on the substrate;
carrying out laser local heating passivation on the thin film absorption layer;
growing a CdS buffer layer on the passivated film absorption layer;
forming a window layer on the surface of the CdS buffer layer; and
and forming a metal gate electrode on the surface of the window layer.
In some embodiments, in the step of providing a substrate, the substrate is a molybdenum substrate.
In some of these embodiments, in the step of preparing a thin film absorber layer on the substrate, the thin film absorber layer comprises CIGS or CZTS or CIS.
In some embodiments, the step of preparing the copper indium gallium selenide thin-film absorber layer on the substrate specifically includes the following steps:
the first step is as follows: the Se source heater is started, the temperature controller is manually set to raise the temperature, the In source temperature is set to be 840-plus-985 ℃, the Ga source temperature is set to be 880-plus-970 ℃, meanwhile, the substrate is set to be heated, and at the moment, the temperature controller controls all the sourcesUniformly heating, opening the In source baffle, the Ga source baffle and the sample rack baffle after the temperature of each source reaches a set value, simultaneously opening a needle valve of the Se furnace, and starting the first layer (In, Ga) 2 Se 3 The growth of the film, closing the In and Ga baffles after the reaction is finished, and preparing the growth of the second step;
the second step is that: the temperature of the substrate is raised to the reaction temperature within 5 minutes, and the Cu source baffle is opened to start the deposition of Cu, the temperature of the Cu source is set above the melting point, the Cu deposited on the substrate is connected with the first layer (In, Ga) 2 Se 3 Starting the film reaction to generate a CIGS film layer, immediately closing a Cu baffle when the temperature of the temperature controller is reduced after the CIGS film layer reaches the stoichiometric ratio, and continuing the growth of the third step after in-situ annealing;
and thirdly, continuously depositing a layer of In and Ga at the substrate temperature of 560-595 ℃ and In the Se atmosphere, wherein the further grown In, Ga and Se react with the film of the last step to finally form the copper-poor CIGS film absorption layer.
In some embodiments, the step of performing laser local heating passivation on the copper indium gallium selenide thin film absorption layer specifically includes:
performing surface treatment on the film absorption layer in an etching solution for 10-120s, wherein the concentration is 0.01M-3M, the treatment temperature is 25-70 ℃, and the etching solution can be one or more than two mixed acid solutions of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid;
washing the treated sample with deionized water, keeping the temperature of a water bath between 25 and 50 ℃ under the irradiation of laser, carrying out water-soluble reaction on the sample and a passivation solution to form a passivation layer on the surface of a CIGS absorption layer, wherein the concentration of the passivation solution is 0.01 to 1M, and the passivation solution is selected from AlCl 3 Solution, InCl 3 Solution, GaCl 3 One or more than two solutions;
washing the sample after water bath with deionized water, putting the sample into a vulcanizing liquid, and eliminating dangling bonds generated by laser irradiation, wherein the concentration of the vulcanizing liquid is 0.01-1M, the treatment temperature is 0-25 ℃, the treatment time is 10-300s, and the vulcanizing liquid is one or more than two of thiourea solution, thioacetamide solution and sodium sulfide solution.
In some embodiments, the step of growing a CdS buffer layer on the passivated CIGS thin film specifically includes:
and uniformly growing a CdS buffer layer material on a mixed solution formed by the passivated film absorption layer and cadmium sulfate, ammonia water and thiourea solution by using a chemical water bath method.
In some embodiments, the step of forming the window layer on the surface of the CdS buffer layer specifically includes the following steps:
sending a sample of the growing CdS buffer layer into an i-ZnO and AZO chamber, introducing Ar, igniting the i-ZnO at the power of 120-500W-120W, then sputtering for 16-40 circles at 220-750W, then introducing Ar and H2, sputtering for 6-36 circles of 220W at 500-900W for 20 circles after igniting the AZO target at 120-500W, then introducing Ar and H2, and sputtering for 20 circles at 750W after igniting the AZO target at 500W to obtain a 300-400nm window layer, wherein the window layer comprises intrinsic zinc oxide and aluminum-doped zinc oxide. In some embodiments, in the step of forming the metal gate electrode on the surface of the window layer, the structure of the metal gate electrode is Ni/Al/Ni.
In addition, the application also provides a copper indium gallium selenide thin-film solar cell which is prepared by the preparation method.
By adopting the technical scheme, the invention has the following technical effects:
the preparation method of the CIGS thin-film solar cell comprises the steps of preparing a thin-film absorption layer on a substrate, carrying out laser local heating passivation on the thin-film absorption layer, growing a CdS buffer layer on the passivated thin-film absorption layer, forming a window layer on the surface of the CdS buffer layer, and forming a metal gate electrode on the surface of the window layer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention or the description of the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flowchart illustrating steps of a method for manufacturing a copper indium gallium selenide thin-film solar cell according to an embodiment of the invention;
fig. 2 is a schematic structural diagram of a passivation reaction device provided in an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "horizontal", "inside", "outside", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Referring to fig. 1, a flowchart of steps of a method for manufacturing a copper indium gallium selenide thin-film solar cell according to an embodiment of the invention includes the following steps:
step S110: a substrate is provided.
In some of these embodiments, the substrate is a molybdenum substrate.
Specifically, a cleaned soda-lime glass substrate or a Si sheet is placed in a vacuum molybdenum chamber, the pressure in the Ar gas control chamber is controlled to be 2.0Pa, 350W power direct current is used for sputtering for 8 circles, then 1000W power is used for sputtering for 16 circles under the pressure of 0.3Pa, the Ar gas is closed, and a sample is taken out after cooling for 5-10min, so that a Mo substrate with the thickness of about 800nm is obtained and used as a bottom electrode.
Step S120: and preparing a thin film absorption layer on the substrate.
In some of these embodiments, the thin film absorber layer comprises CIGS or CZTS or CIS.
Specifically, the substrate taken out in the step 110 is sent into an MBE vacuum coating cavity, a three-step co-evaporation method is adopted to prepare the CIGS absorbing layer, and the background vacuum of the cavity is kept at 1x10 -5 The purity of the used source materials is 99.999 percent below Pa, and the specific three-step method experimental process is as follows:
in a first step, an In source and a Ga source are evaporated at a lower substrate temperature. Firstly, turning on the Se source heater, and manually setting a temperature controller to heat; setting the In source temperature at 840-985 ℃ and the Ga source temperature at 880-970 ℃, simultaneously setting the substrate to heat, and controlling the temperature controller to uniformly heat the sources. After the temperature of each source reaches a set value, opening an In source baffle, a Ga source baffle and a sample rack baffle, simultaneously opening a needle valve of the Se furnace, and starting a first layer (In, Ga) 2 Se 3 The growth of the film, closing the In and Ga baffles after the reaction is finished, and preparing the growth of the second step;
step two, setting the temperature of the substrate to rise to the reaction temperature within 5 minutes, simultaneously opening a Cu source baffle to evaporate Cu, setting the temperature of the Cu source at a certain temperature above the melting point, enabling the evaporated Cu to react with the previous layer of film to start to generate a CIGS layer, immediately closing the Cu baffle when the temperature of the CIGS film reaches the stoichiometric ratio and displaying that the temperature drops when a temperature controller prevents excessive Cu from depositing on the surface of the film, slightly enriching Cu in the film, and continuing the growth of the step three after in-situ annealing for 1 minute;
thirdly, continuing to deposit a layer of In and Ga at the substrate temperature of 560 ℃ and 595 ℃ and In Se atmosphere. The temperature of the In source and the Ga source is consistent with that of the first step, and In, Ga and Se grown In the first step react with the thin film grown In the last step to finally form the copper-poor CIGS absorption layer. And (3) closing each source baffle after the evaporation is finished, annealing in situ for 1 minute in the Se atmosphere, then closing the sample baffle and the Se furnace valve, and taking out the sample from the chamber when the sample is cooled to about 150 ℃.
Step S130: and carrying out laser local heating passivation on the thin film absorption layer.
In the step of performing laser local heating passivation on the thin film absorption layer, the following steps are specifically performed:
step S131: performing surface treatment on the film absorption layer in an etching solution for 10-120s, wherein the concentration is 0.01M-3M, the treatment temperature is 25-70 ℃, and the etching solution can be one or more than two mixed acid solutions of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid;
step S132: washing the treated sample with deionized water, keeping the temperature of a water bath between 25 and 50 ℃ under the irradiation of laser, carrying out water-soluble reaction on the sample and a passivation solution to form a passivation layer on the surface of the CIGS absorption layer, wherein the concentration of the passivation solution is 0.01 to 1M, and the passivation solution is selected from AlCl 3 Solution, InCl 3 Solution, GaCl 3 One or more of the solutions, please refer to fig. 2, which is a schematic structural diagram of the passivation reaction.
Step S133: washing the sample after water bath with deionized water, putting the sample into a vulcanizing liquid, and eliminating dangling bonds generated by laser irradiation, wherein the concentration of the vulcanizing liquid is 0.01-1M, the treatment temperature is 0-25 ℃, the treatment time is 10-300s, and the vulcanizing liquid is one or more than two of thiourea solution, thioacetamide solution and sodium sulfide solution.
It can be understood that the CIGS thin film absorption layer is subjected to laser local heating passivation, so that the crystal interface of the CIGS thin film absorption layer is passivated, and the recombination of carriers at a grain boundary surface is inhibited.
Step S140: and growing a CdS buffer layer on the passivated film absorption layer.
In some embodiments, a mixed solution of the passivated thin film absorption layer and cadmium sulfate, ammonia water and thiourea solution is used for uniformly growing the CdS buffer layer material by a chemical water bath method.
Specifically, a mixed solution of cadmium sulfate and ammonia water is prepared, thiourea solution is poured into a reactor, the passivated film absorption layer is placed in the center of the reactor and placed into a water bath kettle with the constant temperature of 69 ℃, a stirrer is opened, a chemical water bath method is used for uniformly growing a CdS buffer layer material, after 9.5min of reaction, the instrument is closed, a sample is taken out, the sample is quickly washed by deionized water, and N is used for washing the sample by the deionized water 2 Blow-drying, and annealing in an oven at 160 deg.C for 2 min.
Step S150: and forming a window layer on the surface of the CdS buffer layer.
In some embodiments, a sample of the growing CdS buffer layer is sent into an i-ZnO and AZO chamber, Ar is introduced, i-ZnO is ignited under the power of 120-500W 120W, sputtering is carried out for 16-40 circles under the power of 220-750W, Ar and H2 are introduced, after the AZO target is ignited under the power of 120-500W, sputtering is carried out for 6-36 circles under the power of 500-900W for 220W for 20 circles, then Ar and H2 are introduced, after the AZO target is ignited under the power of 500W, sputtering is carried out for 20 circles under the power of 750W, and a window layer with the size of 300-400nm is obtained, wherein the window layer comprises intrinsic zinc oxide and aluminum-doped zinc oxide.
Furthermore, the window layer of the CIGS thin-film solar cell is composed of two parts, namely intrinsic zinc oxide (i-ZnO) and aluminum-doped zinc oxide (AZO), which respectively play different roles, the high-resistance i-ZnO is an important component of the detector mainly because the high-resistance i-ZnO can form a good n region with the CdS buffer layer, and the low-resistance AZO has high transmittance, and the double-layer window has the advantages that the window layer not only can be well matched with the CdS buffer layer in lattice mode, but also can be in good ohmic contact with a top electrode.
Step S160: and forming a metal gate electrode on the surface of the window layer.
It can be understood that, because the sheet resistance of the AZO transparent electrode is too large to collect charges effectively, a metal gate electrode is needed at this time, the structure of the gate electrode is generally Ni/Al/Ni, the Ni is used to increase the adhesion and resist oxidation, the thickness of the Al electrode is important for collecting charges, and the thickness of Al is 8 μm in this embodiment.
The preparation method of the CIGS thin-film solar cell comprises the steps of preparing a thin-film absorption layer on a substrate, carrying out laser local heating passivation on the thin-film absorption layer, growing a CdS buffer layer on the passivated thin-film absorption layer, forming a window layer on the surface of the CdS buffer layer, and forming a metal gate electrode on the surface of the CdS buffer layer.
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is not to be construed in any way as limiting the scope of the invention. Any modifications, equivalents and improvements made within the spirit and principles of the invention and other embodiments of the invention without the exercise of inventive faculty will be appreciated by those skilled in the art and are intended to be included within the scope of the invention.
Claims (8)
1. A preparation method of a copper indium gallium selenide thin-film solar cell is characterized by comprising the following steps:
providing a substrate;
preparing a thin film absorption layer on the substrate;
carrying out laser local heating passivation on the thin film absorption layer;
growing a CdS buffer layer on the passivated film absorption layer;
forming a window layer on the surface of the CdS buffer layer; and
forming a metal gate electrode on the surface of the window layer;
the method specifically comprises the following steps of carrying out laser local heating passivation on the thin film absorption layer:
performing surface treatment on the film absorption layer in an etching solution for 10-120s, wherein the concentration is 0.01M-3M, the treatment temperature is 25-70 ℃, and the etching solution is one or more than two mixed acid solutions selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and citric acid;
washing the treated sample with deionized water, keeping the temperature of a water bath between 25 and 50 ℃ under the irradiation of laser, carrying out water-soluble reaction on the sample and a passivation solution to form a passivation layer on the surface of a CIGS absorption layer, wherein the concentration of the passivation solution is 0.01 to 1M, and the passivation solution is selected from AlCl 3 Solution, InCl 3 Solution, GaCl 3 One or more than two solutions;
washing the sample after water bath with deionized water, putting the sample into a vulcanizing solution, and eliminating dangling bonds generated by laser irradiation, wherein the concentration of the vulcanizing solution is 0.01-1M, the treatment temperature is 0-25 ℃, the treatment time is 10-300s, and the vulcanizing solution is one or more than two of thiourea solution, thioacetamide solution and sodium sulfide solution.
2. The method according to claim 1, wherein in the step of providing a substrate, the substrate is a molybdenum substrate.
3. The method of claim 1, wherein in the step of fabricating a thin film absorber layer on the substrate, the thin film absorber layer comprises CIGS.
4. The method according to claim 3, wherein the step of preparing the thin film absorption layer on the substrate comprises the following steps:
the first step is as follows: opening the Se source heater, setting a temperature controller for heating, setting the In source temperature at 840-985 ℃ and the Ga source temperature at 880-970 ℃, simultaneously heating the substrate, controlling the sources to uniformly heat by the temperature controller, opening the In source, the Ga source baffle and the sample frame baffle after the source temperatures reach the set values, simultaneously opening a needle valve of the Se furnace, and starting the first layer (In, Ga) 2 Se 3 Growing the film, closing the In and Ga baffles after the reaction is finished, and preparing for the growth of the second step;
the second step is that: the temperature of the substrate is raised to the reaction temperature within 5 minutes, and the Cu source baffle is opened to start the deposition of Cu, the temperature of the Cu source is set above the melting point, the Cu deposited on the substrate is connected with the first layer (In, Ga) 2 Se 3 Starting the film reaction to generate a CIGS film layer, immediately closing a Cu baffle when the temperature of the temperature controller is reduced after the CIGS film layer reaches the stoichiometric ratio, and continuing the growth of the third step after in-situ annealing;
and thirdly, continuously depositing a layer of In and Ga at the substrate temperature of 560-595 ℃ and under the Se atmosphere, wherein the further grown In, Ga and Se react with the film of the previous step to finally form the copper-poor CIGS film absorption layer.
5. The method for preparing a copper indium gallium selenide thin-film solar cell according to claim 1, wherein the step of growing a CdS buffer layer on the passivated thin film absorption layer specifically comprises the following steps:
and uniformly growing a CdS buffer layer material on a mixed solution formed by the passivated film absorption layer and cadmium sulfate, ammonia water and thiourea solution by using a chemical water bath method.
6. The method for preparing the copper indium gallium selenide thin-film solar cell according to claim 1, wherein the step of forming the window layer on the surface of the CdS buffer layer specifically comprises the following steps:
sending the sample of the growing CdS buffer layer into the i-ZnO and AZO chambers, introducing Ar, and subjecting the i-ZnO to the reaction under the power of 120-500WStarting luminance, sputtering for 16-40 circles at 220-750W, and then introducing Ar and H 2 After the AZO target is ignited under the conditions of 120-500W, sputtering is carried out for 6-36 circles under the conditions of 500-900W to obtain a 300-400nm window layer, and the window layer comprises intrinsic zinc oxide and aluminum-doped zinc oxide.
7. The method according to claim 1, wherein in the step of forming the metal gate electrode on the surface of the window layer, the metal gate electrode has a structure of Ni/Al/Ni.
8. A copper indium gallium selenide thin-film solar cell, characterized by being prepared by the preparation method of any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110017020.XA CN112736150B (en) | 2021-01-07 | 2021-01-07 | Copper indium gallium selenide thin-film solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110017020.XA CN112736150B (en) | 2021-01-07 | 2021-01-07 | Copper indium gallium selenide thin-film solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112736150A CN112736150A (en) | 2021-04-30 |
| CN112736150B true CN112736150B (en) | 2022-08-19 |
Family
ID=75590974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110017020.XA Active CN112736150B (en) | 2021-01-07 | 2021-01-07 | Copper indium gallium selenide thin-film solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112736150B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115498052B (en) * | 2022-09-22 | 2024-02-09 | 深圳先进技术研究院 | CIGS solar cell preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102893404A (en) * | 2010-01-29 | 2013-01-23 | 弗劳恩霍弗实用研究促进协会 | Method for local high-doping and contacting of a semiconductor structure which comprises a solar cell or a precursor of a solar cell |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709163B (en) * | 2012-05-24 | 2016-02-24 | 中山大学 | A kind of crystalline silicon etching technique based on laser interference induced reaction |
| KR101459041B1 (en) * | 2013-03-04 | 2014-11-10 | 엘에스엠트론 주식회사 | Thin film solar cell and Method of fabricating the same |
| CN104143587A (en) * | 2014-07-22 | 2014-11-12 | 苏州瑞晟纳米科技有限公司 | Surface passivation technology capable of improving performance of copper indium gallium selenium thin-film solar cells |
| CN109225080B (en) * | 2018-08-24 | 2019-09-13 | 天津大学 | Microballoon controllable preparation and method of operating based on optical tweezer |
| CN111435686A (en) * | 2018-12-25 | 2020-07-21 | 东泰高科装备科技有限公司 | Copper indium gallium selenide thin-film solar cell and preparation method thereof |
| CN110224037A (en) * | 2019-06-03 | 2019-09-10 | 深圳先进技术研究院 | Copper-zinc-tin-sulfur film solar cell and preparation method thereof |
-
2021
- 2021-01-07 CN CN202110017020.XA patent/CN112736150B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102893404A (en) * | 2010-01-29 | 2013-01-23 | 弗劳恩霍弗实用研究促进协会 | Method for local high-doping and contacting of a semiconductor structure which comprises a solar cell or a precursor of a solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112736150A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110828602B (en) | Antimony selenide thin film solar cell and preparation method thereof | |
| CN110416356B (en) | Preparation method of antimony selenide thin-film solar cell | |
| CN113078225A (en) | Copper-zinc-tin-sulfur-selenium semitransparent solar cell device and preparation method thereof | |
| CN107623046B (en) | Post-processing method of copper-indium-gallium-selenium absorption layer and solar cell preparation method based on post-processing method | |
| CN113078239B (en) | Antimony selenide thin film solar cell and preparation method thereof | |
| CN112736150B (en) | Copper indium gallium selenide thin-film solar cell and preparation method thereof | |
| JP2004015039A (en) | Compound thin film solar cell and method for manufacturing the same | |
| CN110224037A (en) | Copper-zinc-tin-sulfur film solar cell and preparation method thereof | |
| CN113745359A (en) | Preparation method of cadmium telluride gradient absorption layer and solar cell | |
| CN112201699A (en) | Antimony selenide solar cell with back contact structure and preparation method and application thereof | |
| CN112259620A (en) | Sb2Se3Thin film solar cell and preparation method thereof | |
| CN105895735A (en) | Method for preparing CZTS (copper zinc tin sulfide) thin-film solar cell through zinc oxide target sputtering | |
| CN112071941B (en) | Functional module and preparation method and application thereof | |
| CN108550657A (en) | A method of improving cadmium telluride solar cell properties | |
| CN116154007A (en) | Transition metal doped MoSe 2 Membrane, preparation method and application thereof, and CZTSSe battery | |
| CN110571155B (en) | Preparation method of light absorption layer of thin-film solar cell | |
| CN110565060B (en) | Preparation method of light absorption layer of thin-film solar cell | |
| CN112225468B (en) | Method for preparing CZTS absorption layer by combining electrodeposition method and sol-gel method | |
| CN109841697B (en) | Solar cell based on CuO/Se composite material film | |
| CN114122169A (en) | Method for preparing copper-zinc-tin-selenium absorption layer film by selenide target sputtering and application | |
| CN114203842A (en) | Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell | |
| CN113036000A (en) | Preparation method of broadband near-infrared detector and broadband near-infrared detector | |
| CN103268906B (en) | Cadmium sulphide membrane and there is the preparation method of the solar cell of cadmium sulphide membrane | |
| CN112259623A (en) | Method for improving crystallinity of light absorption layer of Copper Indium Gallium Selenide (CIGS) thin-film solar cell | |
| CN106684210B (en) | Film and include the solar cell of the film prepared by a kind of copper zinc tin sulfur selenium method for manufacturing thin film for solar cell, this method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |