WO2022206038A1 - Copper-zinc-tin-sulfur-selenium semi-transparent solar cell device and preparation method therefor - Google Patents

Copper-zinc-tin-sulfur-selenium semi-transparent solar cell device and preparation method therefor 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 at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier 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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    • H01L21/02365—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
    • 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
    • H01L31/022408—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
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    • 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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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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.

Abstract

Disclosed in the present invention are a copper-zinc-tin-sulfur-selenium semi-transparent solar cell device and a preparation method therefor. The copper-zinc-tin-sulfur-selenium semi-transparent solar cell device uses semi-transparent fluorine doped tin oxide (FTO) or FTO-MoO3 as a back electrode, and consists of soda-lime glass, the FTO/FTO-MoO3 back electrode, a copper-zinc-tin-sulfur-selenium absorption layer, a cadmium sulfide buffer layer, a high-resistance intrinsic zinc oxide window layer, a low-resistance indium tin oxide window layer, and a nickel-aluminum or silver electrode. The preparation method comprises cleaning commercial FTO conductive glass, depositing MoO3 of different thicknesses on the FTO conductive glass, and sequentially preparing thin film layers to obtain a copper-zinc-tin-sulfur-selenium semi-transparent solar cell device which uses FTO/FTO-MoO3 as a back electrode. The use of a semi-transparent back electrode adds a plurality of possibilities for the application of a thin film solar cell, including generating electric energy from a back surface. Therefore, the thin film solar cell becomes a double-sided device, and thus has great industrial application potentials.

Description

一种铜锌锡硫硒半透明太阳能电池器件及其制备方法A copper-zinc-tin-sulfur-selenium translucent solar cell device and preparation method thereof 技术领域technical field
本发明属于太阳能技术领域，具体涉及一种铜锌锡硫硒半透明太阳能电池器件及其制备方法，尤其是一种以FTO或FTO-MoO 3为背电极制备高效的铜锌锡硫硒半透明太阳能电池的方法。 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.
背景技术Background technique
随着经济的快速发展，人们对能源和环境问题越来越关注。解决日益突出的能源短缺和环境污染问题是实现可持续发展、提高人民生活质量的迫切需要。因此，可再生能源的开发和大规模应用已经上升到了国家发展战略的高度。太阳能是一种取之不尽、用之不竭的可再生能源，具有清洁、无污染、可永续利用、储量巨大和分布广泛等优点。在过去的几十年中，基于CdTe和Cu(In,Ga)Se 2(CIGS)吸收层材料的薄膜太阳能电池得到了非常快速的发展，目前CdTe太阳电池的实验室效率为22.1％，CIGS太阳电池的目前实验室效率为23.35％，而且已经实现了商业化。但是，由于Cd有毒，In，Ga，Te为稀有金属，导致基于这些薄膜材料光伏器件的产业化受到了制约。因此，寻找一种安全环保、原料储量丰富的薄膜材料成为了研究热点。四元化合物Cu 2ZnSnS 4(CZTS)和Cu 2ZnSnSe 4(CZTSe)半导体材料有望成为目前商业化的太阳能电池吸收层CdTe和Cu(In,Ga)Se 2(CIGS)的理想替代品。CZTS为直接带隙半导体，拥有超过10 4cm -1的光吸收系数，理论转换效率达32.2％。利用同为Ⅵ族的Se代替CZTS中的S，还可以制备出带隙在1.0～1.5eV范围内可调的铜锌锡硫硒太阳能电池。铜锌锡硫类太阳能电池最大的优势就在于其元素组成来源广、丰度高、毒害低，是一种理想的绿色光伏材料。 With the rapid economic development, people pay more and more attention to energy and environmental issues. Solving the increasingly prominent problems of energy shortage and environmental pollution is an urgent need to achieve sustainable development and improve people's quality of life. Therefore, the development and large-scale application of renewable energy has risen to the height of the national development strategy. Solar energy is an inexhaustible renewable energy, with the advantages of clean, non-polluting, sustainable utilization, huge reserves and wide distribution. Thin-film solar cells based on CdTe and Cu(In,Ga)Se 2 (CIGS) absorber materials have been developed very rapidly in the past few decades, and the laboratory efficiency of CdTe solar cells is currently 22.1%, CIGS solar cells The current laboratory efficiency of the battery is 23.35% and it has already been commercialized. However, since Cd is toxic and In, Ga, and Te are rare metals, the industrialization of photovoltaic devices based on these thin-film materials is restricted. Therefore, it has become a research hotspot to find a safe and environmentally friendly thin film material with abundant raw material reserves. The quaternary compounds Cu 2 ZnSnS 4 (CZTS) and Cu 2 ZnSnSe 4 (CZTSe) semiconductor materials are expected to be ideal substitutes for the currently commercialized solar cell absorber layers CdTe and Cu(In,Ga)Se 2 (CIGS). CZTS is a direct bandgap semiconductor with a light absorption coefficient over 10 4 cm -1 and a theoretical conversion efficiency of 32.2%. By replacing S in CZTS with Se, which is also in Group VI, 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.
铜锌锡硫膜层材料的制备方法主要分为真空法和溶液法两大类。传统的真空制备法以高真空环境为基础，其材料制备过程能耗高，材料利用率较低。溶液法以化学溶液为基础，无需真空环境，其能耗较低，可用于大面积成膜，还具备提高材料利用率和低温加工等优点。同时，基于常规的CZTSSe的太阳能电池，通常使用金属Mo背电极，使得光无法穿过背电极。透明背电极在光伏应用中的使用为薄膜设备系列增加了许多可能的技术应用，也包括从背面产生电能，因此成为双面设备，而且对一些先进的光伏应用(如建筑物集成和高效串联设备)也非常重要。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. Meanwhile, conventional CZTSSe-based solar cells usually use a metallic Mo back electrode, so that light cannot pass through the back electrode. The use of transparent back electrodes in photovoltaic applications adds many possible technical applications to the family of thin-film devices, also including the generation of electricity from the back, thus becoming bifacial devices, but also for some advanced photovoltaic applications such as building integration and high-efficiency tandem devices. ) is also very important.
通常，使用透明导电氧化物(TCO)作为CZTSSe的背电极，来替代Mo以实现基底透明。在不同的TCO中，氟掺杂的氧化锡(FTO)的高热稳定性(与其他TCO(如AZO和ITO)相比)与高透光率使其成为基于Kesterite的器件的理想选择。直接使用FTO进行CZTSSe太阳能电池器件制备，效率远低于在标准不透明SLG/Mo基底上制造的CZTSSe器件的值。主要原因在于p-kesterite/n-TCO界面之间的非欧姆的复杂行为可能阻碍电荷提取。其中，MoO 3可以增强界面的欧姆性，以及通过减少价带偏移提高器件性能。 Typically, a transparent conductive oxide (TCO) is used as the back electrode of CZTSSe instead of Mo to achieve substrate transparency. Among the different TCOs, the high thermal stability (compared to other TCOs such as AZO and ITO) and high light transmittance of fluorine-doped tin oxide (FTO) make it ideal for Kesterite-based devices. Directly using FTO for CZTSSe solar cell device fabrication, the efficiency is much lower than the value of CZTSSe devices fabricated on standard opaque SLG/Mo substrates. The main reason is that the non-ohmic complex behavior between the p-kesterite/n-TCO interface may hinder charge extraction. Among them, MoO3 can enhance the ohmicity of the interface and improve the device performance by reducing the valence band offset.
综上，本发明将公开一种简单、新颖的以半透明FTO或FTO-MoO 3为背电极，并通过前驱体溶液法制备得到效率超过11％的高效铜锌锡硫硒半透明太阳能电池。 To sum up, 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.
发明内容SUMMARY OF THE INVENTION
发明目的：为了克服现有技术中存在的不足，本发明提供一种铜锌锡硫硒半透明太阳能电池器件及其制备方法，基于以半透明FTO/FTO-MoO 3为背电极，同时，基于FTO/FTO-MoO 3背电极通过溶液法掺杂一价钠盐制备的铜锌锡硫硒吸收层结晶性好，缺陷少，无二次相，光电性能高。 Purpose of the invention: In order to overcome the deficiencies in the prior art, 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.
技术方案：为实现上述目的，本发明采用的技术方案为：本发明的一个目的是，提供一种铜锌锡硫硒半透明太阳能电池器件，以半透明掺氟氧化锡FTO或镀有MoO 3的FTO即FTO-MoO 3为背电极，依次由钠钙玻璃、FTO/FTO-MoO 3背电极、铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层和镍铝或银电极组成。 Technical scheme: In order to achieve the above purpose, the technical scheme adopted in the present invention is: 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.
进一步的，所述钠钙玻璃、FTO、MoO 3、铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层、镍铝或银电极的厚度分别为2.2mm、500nm、0-100nm、1-2μm、10-50nm、10-50nm、100-250nm、10-500nm。 Further, 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, 1-2μm, 10-50nm, 10-50nm, 100-250nm, 10-500nm, respectively.
进一步的，所述MoO 3、硫化镉缓冲层、高阻本征氧化锌窗口层和低阻氧化铟锡窗口层的导电类型为n型，所述铜锌锡硫硒吸收层的导电类型为p型；所述FTO的方阻≤7Ω/sq，透光率≥80％。 Further, 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 7Ω/sq, and the light transmittance is more than or equal to 80%.
本发明的另一个目的是，提供一种铜锌锡硫硒半透明太阳能电池器件的制备方法，以FTO导电玻璃或镀有MoO 3的FTO导电玻璃为基底，清洗后，在所述基底表面依次制备铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层、镍铝或银电极，得到以FTO/FTO-MoO 3为半透明的背电极的铜锌锡硫硒半透明太阳能电 池器件。 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.
进一步的，半透明背电极的制备方法，步骤如下：Further, the preparation method of the translucent back electrode, the steps are as follows:
1)FTO背电极的制备：对FTO背电极表面进行清洗，清洗方法如下：将商用的10cm×10cm的FTO导电玻璃用实验室用玻璃切割器切成2cm×2cm，将切好的SLG-FTO基底按照丙酮、异丙醇顺序进行25℃的超声波浴清洗处理10-25分钟，并在N 2气流下干燥。 1) Preparation of 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 .
2)FTO-MoO 3背电极的制备：将洗净的SLG-FTO基底放在蒸镀仪腔室指定位置，分别用机械泵和分子泵将腔体中气压抽至4×10^-4Torr以下，开启蒸发舟对应的蒸发电源开关，点击屏幕打开对应的舟挡板，调节电流旋钮，缓慢升高电源工作电流至30-50A，工作电压为2-5V，并时刻观察膜厚仪速率示数。待示数稳定在
Figure PCTCN2021138795-appb-000001
打开主挡板(即SLG-FTO基底下方大挡板)，膜厚仪示数清零，蒸发料开始在SLG-FTO基底上沉积。时刻关注蒸发速率变化，直至目标膜厚达到，关闭主挡板,蒸发停止。到达目标膜厚后，缓慢降低电源工作电流至零,关闭蒸发电源。获得另一背电极：FTO-MoO 3。由于MoO 3的性质可能受空气暴露的影响，制备好之后需立马放进手套箱。 2) Preparation of FTO-MoO 3 back electrode: Place the cleaned SLG-FTO substrate in the designated position of the vapor deposition chamber, and use a mechanical pump and a molecular pump to pump the air pressure in the chamber to below 4×10^-4 Torr, respectively. , turn on the evaporation power switch corresponding to the evaporation boat, click the screen to open the corresponding boat baffle, adjust the current knob, slowly increase the working current of the power supply to 30-50A, the working voltage is 2-5V, and always observe the film thickness meter rate indication . The number to be displayed is stable at
Figure PCTCN2021138795-appb-000001
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. Always pay attention to the change of evaporation rate until the target film thickness is reached, close the main baffle, and the evaporation will stop. After reaching the target film thickness, slowly reduce the working current of the power supply to zero, and turn off the evaporation power supply. 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.
进一步的，FTO-MoO 3背电极的制备，MoO 3的厚度可以为0，5，10，20…100nm。 Further, for the preparation of the FTO-MoO 3 back electrode, the thickness of MoO 3 can be 0, 5, 10, 20...100nm.
进一步的，铜锌锡硫硒吸收层的制备方法为直接在由FTO/FTO-MoO 3形成的基底上旋涂前驱体溶液，退火，硒化制备铜锌锡硫硒吸收层，具体步骤如下： Further, 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:
1)前驱体溶液的配制：以二甲基亚砜DMSO或N,N-二甲基甲酰胺DMF为溶剂，前驱体化合物为溶质混合溶液配制得到所述前驱体溶液；所述前驱体化合物由金属配合物、金属盐和硫脲组成，其中，所述金属配合物为铜配合物，金属盐为Zn(CH 3COO) 2和SnCl 4；其中，铜元素物质的量：锌元素与锡元素物质的量之和为(0.5～1.0)：1；锌元素物质的量：锡元素物质的量为(0.9～1.5)：1； 1) Preparation of precursor solution: 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;
2)铜锌锡硫前驱体薄膜的制备：采用溶液旋涂法，将FTO/FTO-MoO 3背电极放置于手套箱中的旋涂仪上，用上述1)制备的前驱体溶液进行旋涂，转速为1000-3000rpm/min，旋转时间为30-60s；旋涂后置于退火温度为200-400℃的热台上，退火0.5-10min，重复以上旋涂-退火过程进行多次旋涂沉积，至背电极上铜锌锡硫前驱体薄膜的厚度为0.5-2μm； 2) Preparation of copper-zinc-tin-sulfur precursor thin film: using solution spin coating method, the FTO/FTO-MoO 3 back electrode was placed on the spin coater in the glove box, and the precursor solution prepared in the above 1) was used for spin coating , the rotation speed is 1000-3000rpm/min, and the rotation time is 30-60s; after spin coating, it is placed on a hot table with an annealing temperature of 200-400°C, and annealed for 0.5-10min, and the above spin coating-annealing process is repeated for several times. deposition, the thickness of the CuZnSnS precursor thin film on the back electrode is 0.5-2μm;
3)铜锌锡硫硒吸光层制备：将旋涂有铜锌锡硫前驱体薄膜的背电极置于石墨盒中，四周放置0.2-0.5g硒粒，然后将石墨盒缓慢装入管式炉中；用机械泵将管式炉中气压抽 至4×10^-2Torr以下，然后向管式炉中冲入氩气至大气压；气体流量为0-20ml/min；启动程序，升温至500-600℃，硒化5-60min，即得制备有铜锌锡硫硒吸光层的基底。3) Preparation of copper-zinc-tin-sulfur-selenium light-absorbing layer: the back electrode spin-coated with the copper-zinc-tin-sulfur precursor film is placed in a graphite box, 0.2-0.5 g of selenium particles are placed around it, and then the graphite box is slowly loaded into a tube furnace in the tube furnace; use a mechanical pump to pump the air pressure in the tube furnace to below 4×10^-2 Torr, and then pour argon into the tube furnace to atmospheric pressure; the gas flow is 0-20ml/min; start the program, and heat up to 500- 600° C., selenization for 5-60 min, to prepare a substrate with a copper-zinc-tin-sulfur-selenium light-absorbing layer.
更进一步的，铜配合物的制备方法为：将硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度；溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出，取出上述晶体产物并烘干。Further, 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.
更进一步的，前驱体溶液法的配制：按照需求可以在该溶液中加入一定量的钠盐或者其他金属化合物进行掺杂并在室温下搅拌至完全溶解其中，所述钠盐为一价钠的化合物，包括但不限于卤素钠盐、乙酸钠、硝酸钠、硫酸钠其中一种或多种的组合，且钠元素的物质的量：铜元素的物质的量为：(0～0.1):1；所述金属化合物包括但不限于钠盐、钾盐、锂盐、银盐其中一种或多种的组合。Further, 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. Compounds, including but not limited to a combination of one or more of sodium halide, sodium acetate, sodium nitrate, and sodium sulfate, and the amount of sodium element: the amount of copper element is: (0～0.1):1 ; 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.
进一步的，硫化镉缓冲层的制备方法为采用化学浴沉积工艺：在水夹套烧杯中加入150mL的超纯水，将制备有铜锌锡硫硒吸收层的基底浸没在超纯水中，在水夹套烧杯中依次加入量好的20ml的1.65mmol/L的CdSO 4水溶液，28ml氨水，搅拌，打开水泵，随后，向水夹套烧杯的夹层中通入温度为65℃的热水；1min后，加入20ml的0.825mol/L的硫脲水溶液，沉积5-15min，CdS厚度为10-50nm。 Further, 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. Subsequently, hot water with a temperature of 65°C was passed into the interlayer of the water-jacketed beaker; 1min After that, 20 ml of 0.825 mol/L thiourea aqueous solution was added to deposit for 5-15 min, and the thickness of CdS was 10-50 nm.
进一步的，高阻本征氧化锌窗口层和低阻氧化铟锡窗口层的制备方法：通过磁控溅射法在样品表面溅射一层10-50nm厚的本征氧化锌(i-ZnO)和100-250nm的氧化铟锡(ITO)窗口层：：真空度为4×10^-2Torr以下，氩气氛围下，气压0.2-1Pa，溅射功率60-100W，Ar气流量50-100sccm。Further, 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.
进一步的，通过热蒸镀方法在样品表面，最后热蒸镀一层Ni:Al或者Ag顶电极。Further, a layer of Ni:Al or Ag top electrode was thermally evaporated on the surface of the sample by thermal evaporation method.
本发明的另一个目的是，提供一种铜锌锡硫硒半透明太阳能电池器件的应用，包括应用于现代建筑外墙，所述现代建筑外墙包括窗户、立面和天窗等。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.
有益效果：本发明采取的技术方案是以半透明FTO/FTO-MoO 3为背电极，由钠钙玻璃SLG、FTO/FTO-MoO 3、铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层、镍铝或银电极组成铜锌锡硫半透明太阳能电池器件。该方法与现有技术相比较，具有以下优点： Beneficial effects: 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. Compared with the prior art, the method has the following advantages:
1、本发明公开了运用半透明背电极代替钼背电极来制备高效铜锌锡硫硒半透明太阳能电池。尤其，在FTO-MoO 3背电极上，用前驱体溶液制备的铜锌锡硫硒半透明太阳 能电池效率有很大的提升。半透明背电极的使用为薄膜太阳能电池的应用增加了许多可能，包括从背面产生电能，因此成为双面设备，具有极大的工业应用潜力。 1. 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.
2、本发明公开的金属钠盐掺杂的前驱体溶液可以制备得到高质量、无杂相、元素配比精准的铜锌锡硫硒吸收层材料，以FTO-MoO 3为基底制备得到的铜锌锡硫硒半透明太阳能电池效率与在钼玻璃上不相上下。 2. 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.
附图说明Description of drawings
图1、实施例一、二中以FTO或FTO-20nm MoO 3为背电极制备的铜锌锡硫硒半透明太阳能电池结构示意图。 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.
图2、实施例一中的FTO背电极实物图。FIG. 2 is a physical diagram of the FTO back electrode in the first embodiment.
图3、实施例一中的FTO-20nm MoO 3背电极实物图。 Figure 3. The actual picture of the FTO-20nm MoO 3 back electrode in Example 1.
图4、实施例一中氯化亚铜与硫脲的生成的铜配合物Cu(Tu) 3Cl的实物图。 FIG. 4 is a physical diagram of the copper complex Cu(Tu) 3 Cl formed by cuprous chloride and thiourea in Example 1. FIG.
图5、实施例一和实施例二中FTO和FTO-20nm MoO 3背电极的透光率图谱。 Figure 5. Light transmittance spectra of FTO and FTO-20nm MoO 3 back electrodes in Example 1 and Example 2.
图6、实施例一中的FTO背电极X射线衍射图谱。Figure 6. The X-ray diffraction pattern of the FTO back electrode in the first embodiment.
图7、实施例一中的FTO背电极吸收层薄膜的X射线衍射图谱。FIG. 7 is the X-ray diffraction pattern of the absorber layer film of the FTO back electrode in Example 1. FIG.
图8、实施例二中的FTO-20nm MoO 3背电极吸收层薄膜的X射线衍射图谱。 FIG. 8 is the X-ray diffraction pattern of the FTO-20nm MoO 3 back electrode absorber layer film in Example 2. FIG.
图9、实施例一中的以FTO为背电极的吸收层薄膜的扫描电镜图(膜层横截面)。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.
图10、实施例二中的以FTO-20nm MoO 3为背电极的吸收层薄膜的扫描电镜图(膜层横截面)。 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.
图11、实施例一中的铜锌锡硫硒半透明太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。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.
图12、实施例二中的铜锌锡硫硒半透明太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。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.
图13、实施例三中的铜锌锡硫硒半透明太阳能电池器件和实施例四中的铜锌锡硫硒太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。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.
具体实施方式Detailed ways
本发明公开了一种高效铜锌锡硫半透明太阳能电池器件及其制备方法。本发明公开了两类半透明背电极，同时使用溶液法可达到稳定性和重复性好，可用来制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，以此制备的铜锌锡硫半透明薄膜太阳能电池光电转化效率高。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.
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实例。The embodiments of the present invention will be described in detail below. The present embodiment is implemented on the premise of the technical solution of the present invention, and provides a detailed implementation manner and a specific operation process, but the protection scope of the present invention is not limited to the following examples. .
根据下述实施例，可以更好的理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。The present invention can be better understood from the following examples. However, those skilled in the art can easily understand that the specific material ratios, process conditions and results described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims. .
实施示例一：Implementation example one:
以FTO为背电极，DMSO为溶剂，以一价铜配合物、二价锌盐配合物、四价锡盐为原料，配制前驱体溶液并制备的铜锌锡硫硒半透明薄膜太阳能电池。Using FTO as the back electrode, DMSO as the solvent, using monovalent copper complex, divalent zinc salt complex and tetravalent tin salt as raw materials, the precursor solution is prepared and the copper-zinc-tin-sulfur-selenium translucent thin film solar cell is prepared.
步骤一：FTO背电极的制备Step 1: Preparation of FTO Back Electrode
对FTO背电极表面进行清洗，清洗方法如下：将商用的10cm×10cm的FTO导电玻璃用实验室用玻璃切割器切成2cm×2cm，将切好的SLG-FTO基底按照丙酮、异丙醇顺序进行25℃的超声波浴清洗处理15分钟，并在N 2气流下干燥。 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.
步骤二：铜配合物的制备Step 2: Preparation of copper complexes
称取45.67g(0.6mol)硫脲溶解于100ml去离子水中，加热搅拌保持溶液温度为70℃，待硫脲完全溶解，称取19.8g(0.2mol)氯化亚铜加入其中，所加入的硫脲与铜盐的物质的量之比为3:1；反应30分钟后，大部分氯化亚铜溶解，将溶液热过滤，将滤液静置，自然冷却。一段时间后滤液中析出无色透明晶体即为目标产物铜配合物晶体Cu(Tu) 3Cl，过滤取出上述晶体产物，烘干。 Weigh 45.67g (0.6mol) of thiourea and dissolve it in 100ml of deionized water, heat and stir to keep the solution temperature at 70°C, until the thiourea is completely dissolved, weigh 19.8g (0.2mol) of cuprous chloride and add it, the added The substance ratio of thiourea to copper salt was 3:1; after 30 minutes of reaction, most of the cuprous chloride was dissolved, the solution was filtered hot, the filtrate was allowed to stand, and cooled naturally. After a period of time, the colorless and transparent crystals precipitated in the filtrate are the target product copper complex crystals Cu(Tu) 3 Cl, and the above crystal products are taken out by filtration and dried.
步骤三：前驱体溶液的制备Step 3: Preparation of Precursor Solution
量取4mL DMSO至试剂瓶1中，称取2.1g(6.41mmol)步骤二中制备的铜配合物，再加入0.3g硫脲，搅拌至澄清。在试剂瓶2中加入1.04g的SnCl 4(4.00mmol)，并将小瓶密封以防止SnCl 4蒸发。然后，通过注射器将4mL的DMSO注入试剂瓶2中。SnCl 4与DMSO剧烈反应，形成白色沉淀。然后将0.84g的Zn(OAc) 2(4.58mmol)添加到SnCl 4-DMSO悬浮液中并搅拌直到形成澄清溶液。然后将该溶液与试剂瓶1溶液混合，得到浅黄色溶液。 Measure 4 mL of DMSO into reagent bottle 1, weigh 2.1 g (6.41 mmol) of the copper complex prepared in step 2, add 0.3 g of thiourea, and stir until clear. 1.04 g of SnCl 4 (4.00 mmol) was added to vial 2 and the vial was sealed to prevent SnCl 4 from evaporating. Then, 4 mL of DMSO was injected into Reagent Bottle 2 via a syringe. SnCl4 reacted violently with DMSO to form a white precipitate. Then 0.84 g of Zn(OAc) 2 (4.58 mmol) was added to the SnCl 4 -DMSO suspension and stirred until a clear solution formed. This solution was then mixed with the Reagent Bottle 1 solution, resulting in a pale yellow solution.
步骤四：前驱体薄膜的制备Step 4: Preparation of Precursor Thin Films
在手套箱中，将FTO背电极放置于旋涂仪上，将步骤三中配制的前驱体溶液置于样品上进行旋涂，旋涂速度为2000转/分，旋涂时间60s。旋涂完将样品放到380℃的热台上退火90s。重复以上旋涂-退火操作8次，得到铜锌锡硫前驱体薄膜。In the glove box, place the FTO back electrode on the spin coater, and place the precursor solution prepared in step 3 on the sample for spin coating at a spin coating speed of 2000 rpm and a spin coating time of 60 s. After spin coating, the samples were annealed on a hot stage at 380 °C for 90 s. The above spin coating-annealing operation was repeated 8 times to obtain a copper-zinc-tin-sulfur precursor thin film.
步骤五：吸收层薄膜的制备Step 5: Preparation of Absorber Layer Film
将步骤四得到的前驱体薄膜取两片(2cm×2cm)放入石墨盒中，在样品四周对称放置0.35g的硒粒。将石墨盒置于管式炉中，关好阀门，用机械泵抽真空使管内真空度达到3×10^-2Torr以下，关掉机械泵，充入氩气至大气压，重复以上操作三次以排净管内的空气。启动管式炉的加热程序，目标温度为550℃，升温速度为2℃/s，退火时间为20分钟。退火结束后，样品自然冷却到室温。Two pieces (2cm×2cm) of the precursor film obtained in step 4 were put into a graphite box, and 0.35g of selenium particles were placed symmetrically around the sample. Put the graphite box in the tube furnace, close the valve, use a mechanical pump to evacuate the tube to make the vacuum degree below 3 × 10^-2 Torr, turn off the mechanical pump, fill with argon to atmospheric pressure, repeat the above operation three times to drain Clean the air in the pipe. The heating program of the tube furnace was started, the target temperature was 550°C, the heating rate was 2°C/s, and the annealing time was 20 minutes. After annealing, the samples were naturally cooled to room temperature.
步骤六：缓冲层CdS的制备Step 6: Preparation of buffer layer CdS
将步骤五硒化完的吸收层薄膜取出置于去离子水中浸泡3min，浸泡完，采用化学水浴沉积法(CBD)沉积CdS缓冲层。首先，量取150ml的超纯水置于夹层烧杯中，将样品用模具固定好放于夹层烧杯中；然后，加入20ml的1.65mmol/L的CdSO 4水溶液，28ml氨水，搅拌，打开水泵，向水浴烧杯中通入温度为65℃的热水；1min后，加入20ml的0.825mol/L的硫脲水溶液，沉积8分钟。最后，用去离子水冲洗样品表面除去表面吸附的硫化镉颗粒，并用氮气枪将样品吹干。 The absorber layer film that has been selenized in step 5 is taken out and soaked in deionized water for 3 minutes. After soaking, the CdS buffer layer is deposited by chemical bath deposition (CBD). First, measure 150ml of ultrapure water and place it in the interlayer beaker, fix the sample with a mold and place it in the interlayer beaker; then, add 20ml of 1.65mmol/L CdSO4 aqueous solution, 28ml of ammonia water, stir, turn on the water pump, and add Pour hot water at a temperature of 65°C into the water bath beaker; after 1 min, add 20 ml of a 0.825 mol/L thiourea aqueous solution, and deposit for 8 minutes. Finally, the surface of the sample was rinsed with deionized water to remove the adsorbed cadmium sulfide particles, and the sample was blown dry with a nitrogen gun.
步骤七：窗口层(i-ZnO/ITO)的制备Step 7: Preparation of Window Layer (i-ZnO/ITO)
通过磁控溅射法在步骤六得到的样品上溅射窗口层：本征氧化锌(i-ZnO)和氧化铟锡(ITO)。溅射i-ZnO：氩气氛围下，气压0.5Pa，溅射功率80W，膜层厚度50nm；溅射ITO：氩气氛围下，气压0.5Pa，溅射功率60W，膜层厚度200nm。Window layers: intrinsic zinc oxide (i-ZnO) and indium tin oxide (ITO) are sputtered on the sample obtained in step six by magnetron sputtering. Sputtering i-ZnO: under argon atmosphere, pressure 0.5Pa, sputtering power 80W, film thickness 50nm; sputtering ITO: under argon atmosphere, pressure 0.5Pa, sputtering power 60W, film thickness 200nm.
步骤八：顶电极Ni/Al的制备Step 8: Preparation of top electrode Ni/Al
通过热蒸镀法在步骤七得到的样品上蒸镀金属50nm Ni和500nm Al。Metal 50nm Ni and 500nm Al were evaporated on the sample obtained in step 7 by thermal evaporation method.
实施示例二：Implementation example two:
以FTO-20nm MoO 3为背电极，DMSO为溶剂，以一价铜配合物、二价锌盐配合物、四价锡盐为原料，配制前驱体溶液并制备的铜锌锡硫硒半透明薄膜太阳能电池。 Using FTO-20nm MoO 3 as the back electrode, DMSO as the solvent, and using monovalent copper complexes, divalent zinc salt complexes, and tetravalent tin salts as raw materials, the precursor solution was prepared and prepared copper-zinc-tin-sulfur-selenium translucent thin films Solar battery.
步骤一：FTO-20nm MoO 3背电极的制备： Step 1: Preparation of FTO-20nm MoO 3 back electrode:
将洗净的SLG/FTO基底放在蒸镀仪腔室指定位置，分别用机械泵和分子泵将腔体中气压抽至4×10^-4Torr，开启蒸发舟对应的蒸发电源开关，点击屏幕打开对应的舟挡板，调节电流旋钮，缓慢升高电源工作电流39A，工作电压为2.7V，并时刻观察膜厚仪速率示数。待示数稳定在
Figure PCTCN2021138795-appb-000002
打开主挡板(即SLG-FTO基底下方大挡板)，膜厚仪示数清零，蒸发料开始在SLG-FTO基底上沉积。时刻关注蒸发速率变化，直至目标膜厚达到，关闭主挡板,蒸发停止。到达目标膜厚
Figure PCTCN2021138795-appb-000003
后，缓慢降低电源工作电流至零, 关闭蒸发电源。获得另一背电极：FTO-20nm MoO 3。由于MoO 3的性质可能受空气暴露的影响，制备好之后需立马放进手套箱。 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
Figure PCTCN2021138795-appb-000002
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. Always pay attention to the change of evaporation rate until the target film thickness is reached, close the main baffle, and the evaporation will stop. Reach target film thickness
Figure PCTCN2021138795-appb-000003
After that, slowly reduce the working current of the power supply to zero, and turn off the evaporation power supply. Another back electrode was obtained: FTO - 20nm MoO3. Since the properties of MoO 3 may be affected by air exposure, it needs to be put into the glove box immediately after preparation.
步骤二-八：操作方同实施示例一中步骤二-八。Steps 2-8: The operator is the same as Steps 2-8 in Example 1.
同理可制备不同MoO 3厚度的背电极，如FTO-10nm MoO 3背电极、FTO-30nm MoO 3背电极。 Similarly, 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.
实施示例三：Implementation example three:
以FTO-20nm MoO 3为背电极，DMSO为溶剂，以一价铜配合物、二价锌盐配合物、四价锡盐和一价钠盐为原料，配制前驱体溶液并制备钠掺杂的铜锌锡硫半透明薄膜太阳能电池。具体操作步骤如下： Using FTO - 20nm MoO3 as the back electrode, DMSO as the solvent, and using monovalent copper complexes, divalent zinc salt complexes, tetravalent tin salts and monovalent sodium salts as raw materials, the precursor solutions were prepared and sodium-doped Copper-zinc-tin-sulfur semitransparent thin-film solar cells. The specific operation steps are as follows:
步骤一：操作方同实施示例二中步骤一。Step 1: The operator is the same as Step 1 in the second implementation example.
步骤二：操作方同实施示例一中步骤二。Step 2: The operator is the same as that of Step 2 in Example 1.
步骤三：前驱体溶液的制备。Step 3: Preparation of the precursor solution.
量取4mL DMSO至试剂瓶1中，称取2.1g(6.41mmol)步骤三中制备的铜配合物，再加入0.3g硫脲，搅拌至澄清。在试剂瓶2中加入1.04g的SnCl 4(4.00mmol)，并将小瓶密封以防止SnCl 4蒸发。然后，通过注射器将4mL的DMSO注入试剂瓶2中。SnCl 4与DMSO剧烈反应，形成白色沉淀。然后将0.84g的Zn(OAc) 2(4.58mmol)添加到SnCl 4-DMSO悬浮液中并搅拌直到形成澄清溶液。然后将该溶液与试剂瓶1溶液混合，得到浅黄色溶液。最后，在该溶液中加入0.0088g甲酸钠HCOONa(0.13mmol)中并在室温下搅拌至完全溶解。 Measure 4 mL of DMSO into reagent bottle 1, weigh 2.1 g (6.41 mmol) of the copper complex prepared in step 3, add 0.3 g of thiourea, and stir until clear. 1.04 g of SnCl 4 (4.00 mmol) was added to vial 2 and the vial was sealed to prevent SnCl 4 from evaporating. Then, 4 mL of DMSO was injected into Reagent Bottle 2 via a syringe. SnCl4 reacted violently with DMSO to form a white precipitate. Then 0.84 g of Zn(OAc) 2 (4.58 mmol) was added to the SnCl 4 -DMSO suspension and stirred until a clear solution formed. This solution was then mixed with the Reagent Bottle 1 solution, resulting in a pale yellow solution. Finally, 0.0088 g of sodium formate HCOONa (0.13 mmol) was added to this solution and stirred at room temperature until complete dissolution.
步骤四-八：操作方同实施示例一中步骤四-八。Steps 4-8: The operator is the same as Steps 4-8 in Example 1.
实施示例四：Implementation example four:
以钼玻璃为背电极，以一价铜配合物、二价锌盐配合物、四价锡盐和一价钠盐为原料，配制前驱体溶液并制备钠掺杂的铜锌锡硫半透明薄膜太阳能电池。具体操作步骤如下：Using molybdenum glass as the back electrode, using monovalent copper complexes, divalent zinc salt complexes, tetravalent tin salts and monovalent sodium salts as raw materials to prepare a precursor solution and prepare a sodium-doped copper-zinc-tin-sulfur translucent thin film Solar battery. The specific operation steps are as follows:
步骤一：对钼玻璃表面进行清洗，清洗方法如下：将商用的10cm×10cm的钼玻璃用实验室用玻璃切割器切成2cm×2cm，将切好的钼玻璃按照丙酮、异丙醇顺序进行25℃的超声波浴清洗处理15分钟，并在N 2气流下干燥。 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.
步骤二-八：操作方同实施示例一中步骤二-八。Steps 2-8: The operator is the same as Steps 2-8 in Example 1.
实施例结果分析Example result analysis
本发明实施例提供了FTO和FTO-MoO 3两种半透明背电极，并用溶液法制备高效铜锌锡硫硒半透明薄膜太阳能电池的制备方法，即通过使用金属配合物和金属盐作为前驱体化合物配制的前驱体溶液，制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，可通过进一步金属盐掺杂，制备出高效率的铜锌锡硫半透明太阳能电池。 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 .
图1为实施例一、二中以FTO/FTO-MoO 3为背电极制备的铜锌锡硫硒半透明太阳能电池结构示意图。图2和图3分别为实施例一中半透明背电极FTO和FTO-MoO 3的实物照片。图4为实施例一中铜配合物的实物照片，经元素分析仪分析其化学组分为Cu(Tu) 3Cl。 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.
图5为实施例一、二中FTO背电极和蒸镀不同厚度(10，20和30nm)MoO 3的FTO-MoO 3背电极的透光率。这两种背电极的透光率基本一致，说明MoO 3的透光率非常高。 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.
图6为实施例一中半透明FTO背电极的X射线衍射图谱，所有的衍射峰均对应FTO背电极的SnO 2峰。图7和图8分别为在实施例一、二中两种不同基底FTO和FTO-MoO 3前驱体薄膜硒化反应形成的铜锌锡硫硒吸收层薄膜的X射线衍射图谱，从图中可以看出两个铜锌锡硫硒吸收层薄膜在2-Theta＝27.2°,45.3°,53.7°处均出现强衍射峰，这些衍射峰分别对应铜锌锡硫硒相(CZTSSe)的(112)，(204)，(312)晶面，表明硒化后的吸收层薄膜均为CZTSSe相，无其他杂相可观测到。 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. It can be seen that there are strong diffraction peaks at 2-Theta=27.2°, 45.3°, and 53.7° for the two Cu-Zn-S-S absorbing layer films, which correspond to the (112) of the Cu-Zn-S-S-Se phase (CZTSSe), respectively. , (204), (312) crystal planes, indicating that the absorber layer films after selenization are all CZTSSe phase, and no other impurity phase can be observed.
图9和图10分别为实施例一和例二中的不同背电极制备的铜锌锡硫薄膜的横截面扫描电子显微镜(SEM)图像。图9中的SEM图像显示CZTSSe吸收层上层是致密且均匀的大晶粒层形成，吸收层中部和底部为结晶性差的小晶粒层。图10中的SEM图像中，吸收层表现出清晰的双层结构，两层均由堆积良好的大晶粒组成，但中间有小晶粒层。显然，MoSe 2界面层的存在在很大程度上诱发了高质量的CZTSSe吸收层。将两组吸光膜层制备成太阳能电池器件并对其进行光伏性能测试，它们的电压-电流特性曲线如图11，12所示，以FTO为背电极的器件的光电转换效率为4.72％，而以FTO-MoO 3为背电极器件的光电转换效率为9.70％。以FTO-MoO 3为背电极的器件有更高的光电性能，这主要是因为FTO和吸收层之间MoSe 2界面层的产生，提高了欧姆接触和阻止Sn元素的扩散。 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. In the SEM image in Figure 10, 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. Apparently, 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.
图13为实施例三中以FTO-MoO 3为背电极且在前躯体溶液中掺了甲酸钠制备的器件与实施例四中在钼玻璃上制备的器件光电转换效率，以FTO-MoO 3为背电极PCE高 达11.17％，超过11％，达到国际先进水平，与在钼玻璃上不相上下。 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.
综上，本发明的技术方案制备了半透明FTO和FTO-MoO 3背电极，并通过溶液法进行掺杂制备铜锌锡硫硒半透明薄膜材料和光伏器件，最终，得到了结晶质量高，形貌好，无杂相的铜锌锡硫硒半透明薄膜材料和能量转化效率超过11％的光伏器件，表明该发明显著的先进性。 In summary, 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.
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only the preferred embodiment of the present invention, it should be pointed out: for those skilled in the art, under the premise of not departing from the principle of the present invention, several improvements and modifications can also be made, and these improvements and modifications are also It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种铜锌锡硫硒半透明太阳能电池器件，其特征在于：以半透明掺氟氧化锡FTO或镀有MoO 3的FTO即FTO-MoO 3为背电极，依次由钠钙玻璃、FTO/FTO-MoO 3背电极、铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层和镍铝或银电极组成。 A copper-zinc-tin-sulfur-selenium translucent solar cell device is characterized in that: a translucent fluorine-doped tin oxide FTO or FTO plated with MoO3, that is, FTO - MoO3, is used as a back electrode, and soda lime glass, FTO/FTO -MoO3 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.
  2. 根据权利要求1所述的铜锌锡硫硒半透明太阳能电池器件，其特征在于：所述钠钙玻璃、FTO、MoO 3、铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层、镍铝或银电极的厚度分别为2.2mm、500nm、0-100nm、1-2μm、10-50nm、10-50nm、100-250nm、10-500nm。 The copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 1, wherein the soda lime glass, FTO, MoO 3 , copper-zinc-tin-sulfur-selenium absorption layer, cadmium sulfide buffer layer, high-resistance intrinsic The thickness of zinc oxide window layer, low resistance indium tin oxide window layer, nickel aluminum or silver electrode is 2.2mm, 500nm, 0-100nm, 1-2μm, 10-50nm, 10-50nm, 100-250nm, 10-500nm respectively .
  3. 根据权利要求1所述的铜锌锡硫硒半透明太阳能电池器件，其特征在于：所述MoO 3、硫化镉缓冲层、高阻本征氧化锌窗口层和低阻氧化铟锡窗口层的导电类型为n型，所述铜锌锡硫硒吸收层的导电类型为p型；所述FTO的方阻≤7Ω/sq，透光率≥80％。 The copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 1, wherein 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 are conductive The type 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 7Ω/sq, and the light transmittance is greater than or equal to 80%.
  4. 根据权利要求1-3任一所述的铜锌锡硫硒半透明太阳能电池器件的制备方法，其特征在于：以FTO导电玻璃或镀有MoO 3的FTO导电玻璃为基底，清洗后，在所述基底表面依次制备铜锌锡硫硒吸收层、硫化镉缓冲层、高阻本征氧化锌窗口层、低阻氧化铟锡窗口层、镍铝或银电极，得到以FTO/FTO-MoO 3为半透明的背电极的铜锌锡硫硒半透明太阳能电池器件。 The method for preparing a copper-zinc-tin-sulfur-selenium semitransparent solar cell device according to any one of claims 1 to 3 , wherein: using FTO conductive glass or FTO conductive glass plated with MoO3 as a substrate, after cleaning, in the A copper-zinc-tin-sulfur-selenium absorber layer, a cadmium sulfide buffer layer, a high-resistance intrinsic zinc oxide window layer, a low-resistance indium-tin oxide window layer, and a nickel-aluminum or silver electrode were sequentially prepared on the substrate surface to obtain FTO/FTO - MoO3 as the Copper-Zn-Sn-Sel-Selenide Translucent Solar Cell Devices with Translucent Back Electrode.
  5. 根据权利要求4所述的铜锌锡硫硒半透明太阳能电池器件的制备方法，其特征在于：所述FTO导电玻璃即SLG-FTO的清洗方法如下：将SLG-FTO切割成2cm×2cm尺寸，将切好的SLG-FTO基底按照丙酮、异丙醇顺序进行25℃的超声波浴清洗处理10-25分钟，并在N 2气流下干燥； The method for preparing a copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 4, wherein the cleaning method of the FTO conductive glass, namely the SLG-FTO is as follows: the SLG-FTO is cut into a size of 2cm×2cm, The cut SLG-FTO substrate was cleaned in an ultrasonic bath at 25°C for 10-25 minutes in the order of acetone and isopropanol, and dried under a N 2 airflow;
    所述FTO-MoO 3背电极的制备方法为：将洗净的SLG-FTO放在蒸镀仪腔室中，腔体中气压抽至4×10^-4Torr以下，调节电源工作电流至30-50A，工作电压为2-5V，待膜厚仪速率示数稳定在
    Figure PCTCN2021138795-appb-100001
    打开主挡板，蒸发料开始在SLG-FTO基底上沉积至目标膜厚。     The preparation method of the FTO-MoO 3 back electrode is as follows: the cleaned SLG-FTO is placed in the chamber of the vapor deposition apparatus, the air pressure in the chamber is pumped to below 4×10^-4 Torr, and the working current of the power supply is adjusted to 30- 50A, the working voltage is 2-5V, and the rate indication of the film thickness gauge is stable at
    Figure PCTCN2021138795-appb-100001
    The main baffle was opened, and the evaporation material began to be deposited to the target film thickness on the SLG-FTO substrate.
  6. 根据权利要求4所述的铜锌锡硫硒半透明太阳能电池器件的制备方法，其特征在于：所述的铜锌锡硫硒吸收层的制备方法，步骤如下：The preparation method of a copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 4, wherein the preparation method of the copper-zinc-tin-sulfur-selenium absorption layer comprises the following steps:
    1)前驱体溶液的配制：以二甲基亚砜DMSO或N,N-二甲基甲酰胺DMF为溶剂，前驱体化合物为溶质混合溶液配制得到所述前驱体溶液；所述前驱体化合物由金属配合物、金属盐和硫脲组成，其中，所述金属配合物为铜配合物，金属盐为Zn(CH 3COO) 2 和SnCl 4；其中， 1) Preparation of precursor solution: 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,
    铜元素物质的量：锌与锡元素物质的量之和为(0.5～1.0)：1；The amount of copper element substances: the sum of the amounts of zinc and tin element substances is (0.5 to 1.0): 1;
    锌元素物质的量：锡元素物质的量为(0.9～1.5)：1。The amount of zinc element substance: the amount of tin element substance is (0.9-1.5):1.
    2)铜锌锡硫前驱体薄膜的制备：将FTO/FTO-MoO 3背电极放置于旋涂仪上，用上述1)制备的前驱体溶液进行旋涂并退火，重复以上旋涂-退火过程，至背电极上铜锌锡硫前驱体薄膜的厚度为0.5-2μm； 2) Preparation of copper-zinc-tin-sulfur precursor thin film: place the FTO/FTO-MoO 3 back electrode on a spin coater, spin-coat and anneal with the precursor solution prepared in 1) above, and repeat the above spin-coating-annealing process , the thickness of the copper-zinc-tin-sulfur precursor film on the back electrode is 0.5-2 μm;
    3)铜锌锡硫硒吸光层制备：将旋涂有铜锌锡硫前驱体薄膜的背电极置于石墨盒中，四周放置硒粒，将石墨盒装入管式炉中；用管式炉中气压抽至4×10^-2Torr以下，然后向管式炉中冲入氩气至大气压，气体流量为0-20ml/min；升温至500-600℃，硒化5-60min。3) Preparation of copper-zinc-tin-sulfur-selenium light-absorbing layer: the back electrode spin-coated with the copper-zinc-tin-sulfur precursor film is placed in a graphite box, selenium particles are placed around, and the graphite box is loaded into a tube furnace; The medium pressure is pumped to below 4×10^-2 Torr, and then argon gas is poured into the tube furnace to atmospheric pressure, and the gas flow rate is 0-20ml/min; the temperature is raised to 500-600°C, and the selenization is performed for 5-60min.
  7. 根据权利要求6所述的铜锌锡硫硒半透明太阳能电池器件的制备方法，其特征在于：铜锌锡硫硒吸收层的掺杂方法为：The method for preparing a copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 6, wherein the doping method of the copper-zinc-tin-sulfur-selenium absorption layer is:
    所述前驱体溶液中加入钠盐或者金属化合物进行掺杂并在室温下搅拌至完全溶解，其中，所述钠盐为一价钠的化合物，包括但不限于卤素钠盐、乙酸钠、硝酸钠、硫酸钠其中一种或多种的组合，且钠元素的物质的量：铜元素的物质的量为：(0～0.1):1；所述金属化合物包括但不限于钠盐、钾盐、锂盐、银盐其中一种或多种的组合。Adding sodium salt or metal compound to the precursor solution for doping and stirring at room temperature until completely dissolved, wherein, the sodium salt is a compound of monovalent sodium, including but not limited to halogen sodium salt, sodium acetate, sodium nitrate , a combination of one or more of sodium sulfate, and the amount of the substance of sodium element: the amount of substance of copper element is: (0 ~ 0.1): 1; the metal compound includes but is not limited to sodium salt, potassium salt, A combination of one or more of lithium salts and silver salts.
  8. 根据权利要求4所述的铜锌锡硫硒半透明太阳能电池器件的制备方法，其特征在于：所述的硫化镉缓冲层的制备方法，采用化学浴沉积工艺，步骤如下：The preparation method of a copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 4, wherein the preparation method of the cadmium sulfide buffer layer adopts a chemical bath deposition process, and the steps are as follows:
    将制备有铜锌锡硫硒吸收层的基底浸没在超纯水中，依次加入CdSO 4水溶液和氨水并搅拌；通入热水，加入硫脲水溶液，沉积得到硫化镉缓冲层的厚度为10-50nm。 The substrate prepared with the copper-zinc-tin-sulfur-selenium absorption layer is immersed in ultrapure water, followed by adding CdSO 4 aqueous solution and ammonia water and stirring; pouring hot water, adding thiourea aqueous solution, and depositing a cadmium sulfide buffer layer with a thickness of 10- 50nm.
  9. 根据权利要求4所述的铜锌锡硫硒半透明太阳能电池器件的制备方法，其特征在于：通过磁控溅射法溅射制备所述高阻本征氧化锌窗口层、低阻氧化铟锡窗口层，The method for preparing a copper-zinc-tin-sulfur-selenium translucent solar cell device according to claim 4, wherein the high-resistance intrinsic zinc oxide window layer and the low-resistance indium tin oxide are prepared by sputtering by a magnetron sputtering method. window layer,
    通过热蒸镀方法热蒸镀一层Ni:Al或者Ag顶电极。A layer of Ni:Al or Ag top electrode is thermally evaporated by thermal evaporation method.
  10. 根据权利要求1-3任一所述的铜锌锡硫硒半透明太阳能电池器件的应用，其特征在于：包括但不限于应用于现代建筑外墙，所述现代建筑外墙包括窗户、立面和天窗。The application of the copper-zinc-tin-sulfur-selenium translucent solar cell device according to any one of claims 1-3, characterized in that: including but not limited to being applied to the exterior walls of modern buildings, and the exterior walls of modern buildings include windows, facades and skylight.
PCT/CN2021/138795 2021-03-29 2021-12-16 Copper-zinc-tin-sulfur-selenium semi-transparent solar cell device and preparation method therefor WO2022206038A1 (en)

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