WO2022206038A1 - Dispositif de cellule solaire semi-transparente cuivre-zinc-étain-soufre-sélénium et procédé de préparation associé - Google Patents

Dispositif de cellule solaire semi-transparente cuivre-zinc-étain-soufre-sélénium et procédé de préparation associé Download PDF

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WO2022206038A1
WO2022206038A1 PCT/CN2021/138795 CN2021138795W WO2022206038A1 WO 2022206038 A1 WO2022206038 A1 WO 2022206038A1 CN 2021138795 W CN2021138795 W CN 2021138795W WO 2022206038 A1 WO2022206038 A1 WO 2022206038A1
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zinc
fto
tin
copper
sulfur
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Chinese (zh)
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辛颢
周亚格
龚元才
朱强
相春旭
代琪
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南京邮电大学
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    • 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
    • H01L31/06—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 characterised by potential barriers
    • H01L31/072—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
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    • 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
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
    • H—ELECTRICITY
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    • 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
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
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    • 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
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • 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

Definitions

  • the invention belongs to the technical field of solar energy, and in particular relates to a copper-zinc-tin-sulfur-selenium translucent solar cell device and a preparation method thereof, in particular to an efficient copper-zinc-tin-sulfur-selenium translucent solar cell device prepared by using FTO or FTO - MoO3 as a back electrode method of solar cells.
  • CZTS Cu 2 ZnSnS 4
  • CZTSe Cu 2 ZnSnSe 4
  • a CuZnSinS2 solar cell with tunable band gap in the range of 1.0-1.5 eV can also be fabricated.
  • the biggest advantage of copper-zinc-tin-sulfur solar cells is that they have a wide source of elements, high abundance and low toxicity. They are ideal green photovoltaic materials.
  • the preparation methods of copper-zinc-tin-sulfur film materials are mainly divided into two categories: vacuum method and solution method.
  • the traditional vacuum preparation method is based on a high vacuum environment, and the material preparation process has high energy consumption and low material utilization rate.
  • the solution method is based on a chemical solution, does not require a vacuum environment, has low energy consumption, can be used for large-area film formation, and has the advantages of improving material utilization and low-temperature processing.
  • conventional CZTSSe-based solar cells usually use a metallic Mo back electrode, so that light cannot pass through the back electrode.
  • a transparent conductive oxide is used as the back electrode of CZTSSe instead of Mo to achieve substrate transparency.
  • TCO transparent conductive oxide
  • the high thermal stability compared to other TCOs such as AZO and ITO
  • high light transmittance of fluorine-doped tin oxide FTO
  • the efficiency is much lower than the value of CZTSSe devices fabricated on standard opaque SLG/Mo substrates.
  • MoO3 can enhance the ohmicity of the interface and improve the device performance by reducing the valence band offset.
  • the present invention will disclose a simple and novel translucent FTO or FTO-MoO 3 as the back electrode, and a high-efficiency copper-zinc-tin-sulfur-selenium semitransparent solar cell with an efficiency of over 11% is prepared by the precursor solution method.
  • the present invention provides a copper-zinc-tin-sulfur-selenium translucent solar cell device and a preparation method thereof, based on the use of translucent FTO/FTO-MoO 3 as the back electrode, and at the same time, based on The FTO/FTO-MoO 3 back electrode prepared by solution method doping with monovalent sodium salt has good crystallinity, few defects, no secondary phase, and high optoelectronic performance.
  • one purpose of the present invention is to provide a copper-zinc-tin-sulfur-selenium translucent solar cell device, which is made of translucent fluorine-doped tin oxide FTO or plated with MoO 3
  • the FTO is FTO-MoO 3 as the back electrode, which is sequentially composed of soda-lime glass, FTO/FTO-MoO 3 back electrode, copper-zinc-tin-sulfur-selenium absorber layer, cadmium sulfide buffer layer, high resistance intrinsic zinc oxide window layer, low resistance Indium tin oxide window layer and nickel aluminum or silver electrodes.
  • the soda lime glass, FTO, MoO 3 copper zinc tin sulfur selenium absorption layer, cadmium sulfide buffer layer, high resistance intrinsic zinc oxide window layer, low resistance indium tin oxide window layer, nickel aluminum or silver electrode
  • the thicknesses are 2.2mm, 500nm, 0-100nm, 1-2 ⁇ m, 10-50nm, 10-50nm, 100-250nm, 10-500nm, respectively.
  • the conductivity type of the MoO 3 , the cadmium sulfide buffer layer, the high-resistance intrinsic zinc oxide window layer and the low-resistance indium tin oxide window layer is n-type, and the conductivity type of the copper-zinc-tin-sulfur-selenium absorption layer is p type; the square resistance of the FTO is less than or equal to 7 ⁇ /sq, and the light transmittance is more than or equal to 80%.
  • Another object of the present invention is to provide a method for preparing a copper-zinc-tin-sulfur - selenium translucent solar cell device, which uses FTO conductive glass or FTO conductive glass plated with MoO3 as a substrate, and after cleaning, sequentially Prepare copper-zinc-tin-sulfur-selenium absorber layer, cadmium sulfide buffer layer, high-resistance intrinsic zinc oxide window layer, low-resistance indium-tin oxide window layer, nickel-aluminum or silver electrodes to obtain a translucent backside with FTO/FTO - MoO3 Electrodes for copper-zinc-tin-sulfur-selenium semitransparent solar cell devices.
  • the preparation method of the translucent back electrode the steps are as follows:
  • FTO back electrode Clean the surface of the FTO back electrode.
  • the cleaning method is as follows: Cut the commercial 10cm ⁇ 10cm FTO conductive glass into 2cm ⁇ 2cm with a laboratory glass cutter, and cut the cut SLG-FTO The substrates were cleaned in an ultrasonic bath at 25°C for 10-25 minutes in the order of acetone and isopropanol, and dried under a stream of N 2 .
  • the number to be displayed is stable at Open the main baffle (that is, the large baffle below the SLG-FTO substrate), the film thickness meter is cleared to zero, and the evaporation material begins to be deposited on the SLG-FTO substrate.
  • the main baffle that is, the large baffle below the SLG-FTO substrate
  • the film thickness meter is cleared to zero
  • the evaporation material begins to be deposited on the SLG-FTO substrate.
  • FTO-MoO 3 Another back electrode was obtained: FTO-MoO 3 . Since the properties of MoO 3 may be affected by air exposure, it needs to be put into the glove box immediately after preparation.
  • the thickness of MoO 3 can be 0, 5, 10, 20...100nm.
  • the preparation method of the copper-zinc-tin-sulfur-selenium absorption layer is to directly spin-coat the precursor solution on the substrate formed by FTO/FTO-MoO 3 , anneal, and selenide to prepare the copper-zinc-tin-sulfur-selenium absorption layer.
  • the specific steps are as follows:
  • the precursor solution is prepared by using dimethyl sulfoxide DMSO or N,N-dimethylformamide DMF as a solvent, and the precursor compound as a solute mixed solution;
  • the precursor compound is composed of It is composed of metal complex, metal salt and thiourea, wherein the metal complex is copper complex, and the metal salt is Zn(CH 3 COO) 2 and SnCl 4 ; wherein, the amount of copper element substance: zinc element and tin element
  • the sum of the amount of substances is (0.5 ⁇ 1.0): 1; the amount of zinc element substances: the amount of tin element substances is (0.9 ⁇ 1.5): 1;
  • the preparation method of the copper complex is: dissolving thiourea in deionized water, adding copper salt to the solution after the thiourea is completely dissolved, and the ratio of the amount of the added thiourea to the copper salt is 3. : 1, the reaction process solution temperature is 70 degrees Celsius; After dissolving, the solution is filtered, left standing, slowly cooled, and the target product copper complex crystal is separated out from the solution, and the above-mentioned crystal product is taken out and dried.
  • the preparation of the precursor solution method as required, a certain amount of sodium salt or other metal compounds can be added to the solution for doping and stirred at room temperature until it is completely dissolved.
  • the sodium salt is monovalent sodium.
  • the metal compound includes, but is not limited to, a combination of one or more of sodium salts, potassium salts, lithium salts, and silver salts.
  • the preparation method of the cadmium sulfide buffer layer is to adopt a chemical bath deposition process: add 150 mL of ultrapure water to a water-jacketed beaker, immerse the substrate prepared with the copper-zinc-tin-sulfur-selenium absorption layer in the ultrapure water, A good amount of 20ml of 1.65mmol/L CdSO 4 aqueous solution and 28ml of ammonia water were successively added to the water-jacketed beaker, stirred, and the water pump was turned on.
  • the preparation method of the high-resistance intrinsic zinc oxide window layer and the low-resistance indium tin oxide window layer sputtering a layer of intrinsic zinc oxide (i-ZnO) with a thickness of 10-50 nm on the surface of the sample by a magnetron sputtering method And 100-250nm indium tin oxide (ITO) window layer: vacuum degree is below 4 ⁇ 10 ⁇ -2Torr, under argon atmosphere, pressure 0.2-1Pa, sputtering power 60-100W, Ar gas flow 50-100sccm.
  • i-ZnO intrinsic zinc oxide
  • ITO indium tin oxide
  • a layer of Ni:Al or Ag top electrode was thermally evaporated on the surface of the sample by thermal evaporation method.
  • Another object of the present invention is to provide an application of a copper-zinc-tin-sulfur-selenium translucent solar cell device, including application to the exterior walls of modern buildings, which include windows, facades, skylights, and the like.
  • the technical scheme adopted in the present invention is to use translucent FTO/FTO-MoO 3 as the back electrode, and is composed of soda lime glass SLG, FTO/FTO-MoO 3 , copper-zinc-tin-sulfur-selenium absorption layer, cadmium sulfide buffer layer, high A resistive intrinsic zinc oxide window layer, a low-resistance indium tin oxide window layer, and nickel-aluminum or silver electrodes form a copper-zinc-tin-sulfur semitransparent solar cell device.
  • the method has the following advantages:
  • the present invention discloses the use of translucent back electrodes instead of molybdenum back electrodes to prepare high-efficiency copper-zinc-tin-sulfur-selenium translucent solar cells. Especially, on the FTO-MoO 3 back electrode, the efficiency of CuZnSnSSe semitransparent solar cells prepared with the precursor solution has been greatly improved.
  • the use of semi-transparent back electrodes adds many possibilities for thin-film solar cell applications, including generating electricity from the back side, thus becoming bifacial devices with great potential for industrial applications.
  • the metal sodium salt-doped precursor solution disclosed in the present invention can prepare high-quality, impurity-free, and precise element ratio copper-zinc-tin-sulfur - selenium absorbing layer materials.
  • the efficiency of zinc-tin-sulfur-selenium semitransparent solar cells is comparable to that on molybdenum glass.
  • Fig. 1 is a schematic structural diagram of the copper-zinc-tin-sulfur-selenium semitransparent solar cells prepared by using FTO or FTO-20nm MoO 3 as the back electrode in Examples 1 and 2.
  • FIG. 2 is a physical diagram of the FTO back electrode in the first embodiment.
  • FIG. 4 is a physical diagram of the copper complex Cu(Tu) 3 Cl formed by cuprous chloride and thiourea in Example 1.
  • FIG. 4 is a physical diagram of the copper complex Cu(Tu) 3 Cl formed by cuprous chloride and thiourea in Example 1.
  • FIG. 7 is the X-ray diffraction pattern of the absorber layer film of the FTO back electrode in Example 1.
  • FIG. 8 is the X-ray diffraction pattern of the FTO-20nm MoO 3 back electrode absorber layer film in Example 2.
  • FIG. 9 is a scanning electron microscope image (film layer cross-section) of the absorber layer thin film with FTO as the back electrode in Example 1.
  • FIG. 9 is a scanning electron microscope image (film layer cross-section) of the absorber layer thin film with FTO as the back electrode in Example 1.
  • FIG. 10 is a scanning electron microscope image (film layer cross section) of the absorber thin film with FTO-20nm MoO 3 as the back electrode in Example 2.
  • FIG. 10 is a scanning electron microscope image (film layer cross section) of the absorber thin film with FTO-20nm MoO 3 as the back electrode in Example 2.
  • FIG. 11 the voltage-current characteristic curve of the copper-zinc-tin-sulfur-selenium translucent solar cell device in Example 1 under the AM1.5G standard sunlight intensity.
  • Fig. 12 is the voltage-current characteristic curve of the copper-zinc-tin-sulfur-selenium translucent solar cell device in Example 2 under the AM1.5G standard sunlight intensity.
  • Figure 13 shows the voltage-current characteristic curves of the copper-zinc-tin-sulfur-selenium semitransparent solar cell device in Example 3 and the copper-zinc-tin-sulfur-selenium solar cell device in Example 4 under AM1.5G standard sunlight intensity.
  • the invention discloses a high-efficiency copper-zinc-tin-sulfur semitransparent solar cell device and a preparation method thereof.
  • the invention discloses two types of translucent back electrodes, which can achieve good stability and repeatability by using the solution method at the same time, and can be used to prepare copper-zinc-tin-sulfur thin-film light-absorbing materials with high crystal quality, good film morphology and no impurity phase.
  • the prepared copper-zinc-tin-sulfur semitransparent thin film solar cell has high photoelectric conversion efficiency.
  • the precursor solution is prepared and the copper-zinc-tin-sulfur-selenium translucent thin film solar cell is prepared.
  • the surface of the FTO back electrode was cleaned, and the cleaning method was as follows: the commercial 10cm ⁇ 10cm FTO conductive glass was cut into 2cm ⁇ 2cm with a laboratory glass cutter, and the cut SLG-FTO substrate was in the order of acetone and isopropanol. Ultrasonic bath cleaning treatment at 25 °C was performed for 15 min, and dried under N 2 flow.
  • the absorber layer film that has been selenized in step 5 is taken out and soaked in deionized water for 3 minutes.
  • the CdS buffer layer is deposited by chemical bath deposition (CBD).
  • CBD chemical bath deposition
  • Step 7 Preparation of Window Layer (i-ZnO/ITO)
  • i-ZnO intrinsic zinc oxide
  • ITO indium tin oxide
  • Metal 50nm Ni and 500nm Al were evaporated on the sample obtained in step 7 by thermal evaporation method.
  • the precursor solution was prepared and prepared copper-zinc-tin-sulfur-selenium translucent thin films Solar battery.
  • Step 1 Preparation of FTO-20nm MoO 3 back electrode:
  • Place the cleaned SLG/FTO substrate in the designated position of the vapor deposition chamber use the mechanical pump and the molecular pump to pump the air pressure in the chamber to 4 ⁇ 10 ⁇ -4 Torr, turn on the evaporation power switch corresponding to the evaporation boat, and click the screen Open the corresponding boat baffle, adjust the current knob, slowly increase the working current of the power supply to 39A, and the working voltage to 2.7V, and observe the rate indication of the film thickness meter at all times.
  • the number to be displayed is stable at Open the main baffle (that is, the large baffle below the SLG-FTO substrate), the film thickness meter is cleared to zero, and the evaporation material begins to be deposited on the SLG-FTO substrate.
  • Steps 2-8 The operator is the same as Steps 2-8 in Example 1.
  • back electrodes with different thicknesses of MoO 3 can be prepared, such as FTO-10nm MoO 3 back electrodes and FTO-30nm MoO 3 back electrodes.
  • the precursor solutions were prepared and sodium-doped Copper-zinc-tin-sulfur semitransparent thin-film solar cells.
  • the specific operation steps are as follows:
  • Step 1 The operator is the same as Step 1 in the second implementation example.
  • Step 2 The operator is the same as that of Step 2 in Example 1.
  • Step 3 Preparation of the precursor solution.
  • Steps 4-8 The operator is the same as Steps 4-8 in Example 1.
  • Step 1 Clean the surface of the molybdenum glass.
  • the cleaning method is as follows: Cut the commercial 10cm ⁇ 10cm molybdenum glass into 2cm ⁇ 2cm with a laboratory glass cutter, and cut the cut molybdenum glass in the order of acetone and isopropanol. Ultrasonic bath cleaning treatment at 25 °C for 15 min and drying under N2 flow.
  • Steps 2-8 The operator is the same as Steps 2-8 in Example 1.
  • the embodiment of the present invention provides two translucent back electrodes, FTO and FTO-MoO 3 , and a method for preparing high-efficiency copper-zinc-tin-sulfur-selenium semitransparent thin-film solar cells by a solution method, that is, by using metal complexes and metal salts as precursors
  • the precursor solution prepared by the compound can prepare copper-zinc-tin-sulfur thin film light-absorbing materials with high crystal quality, good film morphology and no impurity phase, and can prepare high-efficiency copper-zinc-tin-sulfur semitransparent solar cells by further doping with metal salts .
  • FIG. 1 is a schematic structural diagram of the copper-zinc-tin-sulfur-selenium semitransparent solar cells prepared by using FTO/FTO-MoO 3 as the back electrode in Examples 1 and 2.
  • FIG. 2 and FIG. 3 are actual photos of the translucent back electrode FTO and FTO-MoO 3 in Example 1, respectively.
  • FIG. 4 is a real photo of the copper complex in Example 1, and its chemical composition is Cu(Tu) 3 Cl as analyzed by an elemental analyzer.
  • FIG. 5 shows the light transmittance of the FTO back electrode and the FTO-MoO 3 back electrode with different thicknesses (10, 20 and 30 nm) of MoO 3 deposited in Examples 1 and 2.
  • the transmittances of these two back electrodes are basically the same, indicating that the transmittance of MoO3 is very high.
  • FIG. 6 is the X-ray diffraction pattern of the semi-transparent FTO back electrode in Example 1, and all the diffraction peaks correspond to the SnO 2 peaks of the FTO back electrode.
  • FIG. 7 and FIG. 8 are respectively the X-ray diffraction patterns of the copper-zinc-tin-sulfur-selenium absorption layer films formed by the selenization reaction of two different substrates FTO and FTO-MoO precursor films in Examples 1 and 2, respectively.
  • FIG. 9 and FIG. 10 are scanning electron microscope (SEM) images of cross-sections of CuZnSnS thin films prepared with different back electrodes in Example 1 and Example 2, respectively.
  • the SEM image in Fig. 9 shows that the upper layer of the CZTSSe absorber layer is formed by a dense and uniform large-grain layer, and the middle and bottom of the absorber layer are small-grain layers with poor crystallinity.
  • the absorber layer exhibits a clear double-layer structure, both of which are composed of well-packed large grains, but with a layer of small grains in the middle.
  • the presence of the MoSe interfacial layer induces a high-quality CZTSSe absorber layer to a large extent.
  • the two groups of light-absorbing films were prepared into solar cell devices and their photovoltaic performance was tested. Their voltage-current characteristic curves are shown in Figures 11 and 12.
  • the photoelectric conversion efficiency of the device with FTO as the back electrode was 4.72%, while The photoelectric conversion efficiency of the device with FTO - MoO3 as the back electrode is 9.70%.
  • the device with FTO - MoO3 as the back electrode has higher optoelectronic performance, which is mainly due to the generation of the MoSe2 interface layer between the FTO and the absorber layer, which improves the ohmic contact and prevents the diffusion of Sn element.
  • Figure 13 shows the photoelectric conversion efficiency of the device prepared by using FTO-MoO 3 as the back electrode and doped with sodium formate in the precursor solution in Example 3 and the device prepared on molybdenum glass in Example 4, with FTO-MoO 3 as the back electrode.
  • the electrode PCE is as high as 11.17%, exceeding 11%, reaching the international advanced level, which is comparable to that of molybdenum glass.
  • the technical solution of the present invention prepares translucent FTO and FTO-MoO 3 back electrodes, and prepares copper-zinc-tin-sulfur-selenium translucent thin film materials and photovoltaic devices by doping by solution method, and finally obtains high crystal quality, Good morphology, no impurity phase copper-zinc-tin-sulfur-selenium translucent thin film material and photovoltaic device with energy conversion efficiency over 11%, indicating the remarkable advancement of the invention.

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  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Sont divulgués dans la présente invention, un dispositif de cellule solaire semi-transparente cuivre-zinc-étain-soufre-sélénium et un procédé de préparation associé. Le dispositif de cellule solaire semi-transparente cuivre-zinc-étain-soufre-sélénium utilise de l'oxyde d'étain dopé au fluor semi-transparent (FTO) ou FTO-MoO3 en tant qu'électrode arrière et est constitué de verre sodocalcique, de l'électrode arrière FTO/FTO-MoO3, d'une couche d'absorption cuivre-zinc-étain-soufre-sélénium, d'une couche tampon de sulfure de cadmium, d'une couche de fenêtre d'oxyde de zinc intrinsèque à haute résistance, d'une couche de fenêtre d'oxyde d'étain d'indium à faible résistance et d'une électrode de nickel-aluminium ou d'argent. Le procédé de préparation consiste à nettoyer le verre conducteur FTO commercial, à déposer le MoO3 de différentes épaisseurs sur le verre conducteur FTO et à préparer de manière séquentielle des couches de film mince pour obtenir un dispositif de cellule solaire semi-transparent cuivre-zinc-étain-soufre-sélénium qui utilise du FTO/FTO-MoO3 en tant qu'électrode arrière. L'utilisation d'une électrode arrière semi-transparente ajoute une pluralité de possibilités pour l'application d'une cellule solaire à film mince, consistant à générer de l'énergie électrique à partir d'une surface arrière. Par conséquent, la cellule solaire à film mince devient un dispositif à double-face et présente ainsi des potentiels d'application industriels importants.
PCT/CN2021/138795 2021-03-29 2021-12-16 Dispositif de cellule solaire semi-transparente cuivre-zinc-étain-soufre-sélénium et procédé de préparation associé WO2022206038A1 (fr)

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