CN114988715A - Preparation method of copper-zinc-tin-sulfur film - Google Patents

Preparation method of copper-zinc-tin-sulfur film Download PDF

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CN114988715A
CN114988715A CN202210574612.6A CN202210574612A CN114988715A CN 114988715 A CN114988715 A CN 114988715A CN 202210574612 A CN202210574612 A CN 202210574612A CN 114988715 A CN114988715 A CN 114988715A
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copper
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CN114988715B (en
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刘芳洋
杨文通
郑博琳
潘逸宁
蒋良兴
张宗良
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
    • H01L31/0248—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
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract

The invention provides a method for preparing a copper-zinc-tin-sulfur film by an inverted annealing mode. Spin-coating a precursor solution containing copper salt, zinc salt and tin salt on cleaned molybdenum glass; then placing the wet film face downwards on a hot table for inversion annealing, and repeating the steps for a plurality of times to obtain a copper-zinc-tin-sulfur preset layer film; and finally, putting the preset layer of film into a rapid thermal annealing furnace for vulcanization annealing treatment to obtain the copper-zinc-tin-sulfur film. The invention utilizes the dual functions of the covering effect of the substrate and the hot plate and gravity to regulate and optimize the CZTS preset layer film, so that elements are uniformly dispersed in the preset layer, and a high-quality copper-zinc-tin-sulfur absorption layer film with high crystallinity, large grain size and low surface defect state density can be obtained after vulcanization annealing.

Description

Preparation method of copper-zinc-tin-sulfur film
Technical Field
The invention belongs to the technical field of new energy photovoltaic power generation, and particularly relates to a preparation method of a copper-zinc-tin-sulfur film, which is particularly used for preparing a photovoltaic device.
Background
The energy source is the foundation stone for people to enjoy modern comfortable life. With the continuous progress of the quality of life of people and the high-speed development of industry, the energy consumption is increased rapidly. The environmental problems brought by the traditional fossil energy in the processes of mining, processing and using are increasingly serious, the irreversible damage caused by ecology is more and more important to people, and the development of various renewable green energy sources becomes the most important common problem and research hotspot in the current society. Solar energy is considered as the most ideal renewable green energy source because it is clean and pollution-free. Solar cell photovoltaic power generation technology is also considered to be the most attractive solution for utilizing solar energy.
The thin film solar cell as one member of the thin film solar cell family has the following characteristics compared with the crystalline silicon cell: (1) high light absorption coefficient, copper-zinc-tin-sulfur (Cu) 2 ZnSnS 4 CZTS) and copper zinc tin sulfur selenium (Cu) 2 ZnSn(S,Se) 4 CZTSSe) and copper indium gallium selenide (Cu (In, Ga) Se 2 CIGS) is a direct band gap semiconductor material, and the optical absorption coefficient reaches 10 4 cm -1 (ii) a (2) The optical band gap is adjustable within the range of 1.0-1.5 eV, and is very close to the band gap required by the theoretical highest conversion efficiency (32.3%) of the solar cell; (3) the elements contained in the copper-zinc-tin-sulfur are nontoxic and abundant in reserves. Based on the above discussion, the copper zinc tin sulfur solar cell is regarded as one of the new solar cells with development prospect due to its good photovoltaic performance, and is receiving wide attention.
The morphology and the crystal quality of the copper-zinc-tin-sulfur thin film are one of the most critical factors for determining the photovoltaic performance of the copper-zinc-tin-sulfur solar cell. There are many methods for preparing copper zinc tin sulfide thin films, wherein the solution method is the most promising method for large-scale industrial production at present, and the method has the advantages that nanoparticles do not need to be synthesized, the components of the thin film can be adjusted by the feeding ratio of the solution, and the material utilization rate is high. The specific implementation method comprises the steps of directly dissolving a molecular precursor containing Cu, Zn, Sn and S in a proper solvent to form a uniform precursor solution, depositing the precursor solution on a substrate by methods such as spin coating or spray pyrolysis to obtain a film, performing baking-cooling-spin coating circulation to obtain a preset layer film, and finally converting the amorphous preset layer film into a crystalline absorption layer film by high-temperature annealing or selenization/vulcanization.
However, the cu-zn-sn-s thin film prepared by the conventional bake-chill-spin coating process usually consists of randomly oriented small grains, the grain size is small and is not favorable for charge transfer, and excessive grain boundaries between the small grains can generate recombination centers to deteriorate the device performance, and besides, some elements can volatilize along with the solvent during the bake process to cause the element proportion of the thin film to be disordered.
In view of the foregoing, it is desirable to provide a method for producing high quality copper zinc tin sulfide thin films with high crystallinity, large grain size, and low surface defect state density.
Disclosure of Invention
The invention aims to provide a method for preparing a high-quality copper-zinc-tin-sulfur film by adopting an inverted annealing mode, so as to solve the problem of poor performance of a copper-zinc-tin-sulfur solar cell caused by the defects of a vertical structure and the non-ideal surface appearance of the film.
In order to achieve the purpose, the preparation method of the copper-zinc-tin-sulfur film provided by the invention comprises the following steps:
step 1), spin-coating a precursor solution containing copper salt, zinc salt and tin salt on cleaned molybdenum glass;
step 2), placing the wet film obtained in the step 1) on a hot bench with the film surface facing downwards for inverted annealing;
step 3), repeating the step 1) and the step 2) for a plurality of times to obtain a preset layer of film;
and 4) carrying out vulcanization annealing on the preset layer film to prepare the copper-zinc-tin-sulfur absorption layer film.
Preferably, the molar ratio of the elements in the precursor solution in the step 1) is: n (Cu): n (Sn) ═ 1.0 to 2.0: 1, n (Zn): n (Sn) ═ 0.8 to 1.3: 1, n (Cu): n (Zn + Sn) ═ 0.5 to 1.0: 1.
preferably, the molybdenum glass in the step 1) is sequentially treated as follows: the molybdenum glass is sequentially immersed in a common detergent, deionized water and an ethanol solution, and then is dried by a nitrogen gun for later use.
Preferably, in the step 1), the spin coating speed is 600-5000 rpm, and the time is 10-360 seconds.
Preferably, the annealing temperature in the inversion annealing process in the step 2) is 200-300 ℃, and the annealing time is 2-6 min.
Preferably, during the inverted annealing in step 2), a piece of weighing paper is placed on the hot table in advance, and a thin film is placed on the weighing paper to avoid being polluted by the hot table.
Preferably, the repetition times in the step 3) are 6-15 times.
Preferably, the target temperature of the vulcanization annealing in the step 4) is 500-600 ℃, the heating rate is 0.1-15 ℃/s, and the annealing is carried out for 1-20 min at the target temperature.
Preferably, after the annealing procedure in the step 4) is finished, a temperature-controlled cooling mode is adopted to reach room temperature.
Preferably, the specific steps of the sulfide annealing in the step 4) are as follows:
placing the preset layer film in a quartz tray, and simultaneously placing 0.1-0.5 g of sulfur and 0.1-0.3 g of stannous sulfide;
pumping the gas in the quartz disc to be below 30mBar, and then filling nitrogen into the chamber until the air pressure is 600 mBar;
starting heating and annealing at a target temperature;
and after the annealing procedure is finished, cooling to room temperature.
The invention adopts an inversion annealing mode to prepare the copper-zinc-tin-sulfur pre-deposited layer film, and the escape of residual solvent and some elements can be blocked due to the covering effect of the substrate and the hot plate and the gravity action of the molybdenum glass and the film in the inversion annealing process, so that the growth of crystals can be promoted, the crystallinity of the film can be improved, the charge transmission efficiency can be improved, and the charge recombination can be inhibited in the vulcanization annealing process, thereby improving the performance of the copper-zinc-tin-sulfur solar cell.
In the process of applying the inversion annealing technology, the surface appearance of the copper-zinc-tin-sulfur thin film can be controlled by regulating and controlling the annealing temperature and the annealing time, so that the performance of a device is improved, and the method has high application value for the research on the performance optimization of the copper-zinc-tin-sulfur solar cell and the development of industrialization of the copper-zinc-tin-sulfur solar cell.
Drawings
Fig. 1 is a schematic diagram of an inversion annealing process of the present invention.
FIG. 2 is SEM images of Cu-Zn-Sn-S thin films prepared in comparative example 1 and example 1, wherein (a) is comparative example 1 and (b) is example 1.
Fig. 3 is a J-V diagram of the copper zinc tin sulfide solar cell prepared in comparative example 1 and example 1, wherein device a is comparative example 1 and device B is example 1.
Detailed Description
The invention discloses a preparation method of a high-quality copper-zinc-tin-sulfur film. The method comprises the steps of placing a spin-coated wet film face downwards on a hot table for inversion annealing to obtain a copper-zinc-tin-sulfur preset layer film, and carrying out vulcanization annealing on the preset layer film to obtain a high-quality copper-zinc-tin-sulfur absorption layer material with high crystallinity, large grain size and low surface defect state density, so that the prepared copper-zinc-tin-sulfur thin film solar cell is high in photoelectric conversion efficiency.
The present invention will now be further described by way of examples for a better understanding of the invention.
Comparative example 1
1) Sequentially immersing the molybdenum glass into a common detergent, deionized water and an ethanol solution, and then blowing the molybdenum glass by using a nitrogen gun for later use;
2) and a precursor solution prepared in advance (the element molar ratio is n (Cu)): n (sn) ═ 1.7: 1, n (Zn): n (sn) ═ 1.2: 1, n (Cu): n (Zn + Sn) ═ 0.7: 1) the coating is coated on the molybdenum glass by a spin coating method, wherein the spin coating speed is 3000rpm, and the time is 120 s.
3) And placing the wet film obtained in the step with the film surface facing upwards and the molybdenum glass facing downwards on a hot table, wherein the baking temperature is 280 ℃ and the baking time is 3 min.
4) And repeating the step 2) and the step 3) for 9 times to obtain the film with the preset layer.
5) Placing the obtained preset layer film in a quartz disc, adding 0.4g of sulfur and 0.2g of stannous sulfide, pumping gas in the quartz disc to be below 30mBar, then filling nitrogen to the pressure of 600mBar in the cavity, selecting a rapid thermal annealing furnace as a heating source, heating at a rate of 2 ℃/s, finally keeping the temperature at 580 ℃, keeping the temperature for 10min, and then cooling to room temperature by adopting a temperature control cooling mode to obtain the copper-zinc-tin-sulfur absorption layer film. The cross-sectional view of the scanning electron microscope is shown in fig. 2(a), and it can be seen from the figure that the absorption layer includes two layers, namely a small grain layer and a large grain layer, the existence of the small grain layer is not beneficial to charge transfer, and too many grain boundaries between small grains can generate recombination centers to deteriorate the performance of the device.
6) Placing the absorption layer material in a water jacket beaker containing ammonia water, cadmium sulfate and thiourea solution, reacting under a heating condition, and depositing a layer of CdS on the surface of the absorption layer; sequentially sputtering ZnO and ITO on the surface of the sample by a magnetron sputtering technology to form a window layer; and finally, evaporating metal Ag on the surface of the sample by a thermal evaporation method to be used as a cathode, thereby obtaining the copper-zinc-tin-sulfur solar cell device A.
Example 1
1) Sequentially immersing the molybdenum glass into a common detergent, deionized water and an ethanol solution, and then blowing the molybdenum glass by using a nitrogen gun for later use;
2) and preparing a precursor solution (the element molar ratio is n (Cu)): n (sn) ═ 1.7: 1, n (Zn): n (sn) ═ 1.2: 1, n (Cu): n (Zn + Sn) ═ 0.7: 1) the coating is coated on the molybdenum glass by a spin coating method, wherein the spin coating speed is 3000rpm, and the time is 120 s.
3) And placing the wet film obtained in the step with the film surface facing downwards and the molybdenum glass facing upwards on a hot bench paved with weighing paper, wherein the annealing temperature is 280 ℃ and the annealing time is 3 min.
4) And repeating the step 2) and the step 3) for 9 times to obtain the film with the preset layer.
5) Placing the obtained preset layer film in a quartz disc, adding 0.4g of sulfur and 0.2g of stannous sulfide, pumping gas in the quartz disc to be below 30mBar, then filling nitrogen to the pressure of 600mBar in the cavity, selecting a rapid thermal annealing furnace as a heating source, heating at a rate of 2 ℃/s, finally keeping the temperature at 580 ℃, keeping the temperature for 10min, and then cooling to room temperature by adopting a temperature-controlled cooling mode to obtain the copper-zinc-tin-sulfur absorption layer. The section view of a scanning electron microscope is shown in fig. 2(b), and the absorption layer is formed by large penetrating grains, is complete in crystallization, has high compactness, is favorable for charge transmission, and can optimize the performance of a device to a certain degree.
6) Placing the absorption layer material in a water jacket beaker containing ammonia water, cadmium sulfate and thiourea solution, reacting under a heating condition, and depositing a layer of CdS on the surface of the absorption layer; sequentially sputtering ZnO and ITO on the surface of the sample by a magnetron sputtering technology to form a window layer; and finally, evaporating metal Ag on the surface of the sample by a thermal evaporation method to be used as a cathode, thereby obtaining the copper-zinc-tin-sulfur solar cell device B.
Fig. 3 shows J-V diagrams of the copper-zinc-tin-sulfur thin film solar cell prepared in example 1 and comparative example 1, it can be seen that the photoelectric conversion efficiency of the device a is 6.42%, and the photoelectric conversion efficiency of the device B is 9.86%, and thus, after the pre-layer prepared by the inversion annealing method is subjected to vulcanization annealing, an absorption layer thin film structure with high compactness and high crystallinity can be obtained, which is beneficial to improving the photoelectric conversion efficiency of the device.

Claims (10)

1. A preparation method of a copper-zinc-tin-sulfur film is characterized by comprising the following steps: the method comprises the following steps:
step 1), spin-coating a precursor solution containing copper salt, zinc salt and tin salt on cleaned molybdenum glass;
step 2), placing the wet film obtained in the step 1) on a hot bench with the film surface facing downwards for inverted annealing;
step 3), repeating the step 1) and the step 2) for a plurality of times to obtain a preset layer of film;
and 4), carrying out vulcanization annealing on the preset layer film to prepare the copper-zinc-tin-sulfur absorption layer film.
2. The method for preparing a CZTS film as claimed in claim 1, wherein: the molar ratio of elements in the precursor solution in the step 1) is as follows: n (Cu): n (Sn) (1.0-2.0): 1, n (Zn): n (Sn) ═ 0.8 to 1.3: 1, n (Cu): n (Zn + Sn) ═ 0.5 to 1.0: 1.
3. the method for preparing a copper-zinc-tin-sulfur film according to claim 1, wherein the method comprises the following steps: the molybdenum glass in the step 1) is sequentially treated as follows: the molybdenum glass is sequentially immersed in a common detergent, deionized water and an ethanol solution, and then is dried by a nitrogen gun for later use.
4. The method for preparing a CZTS film as claimed in claim 1, wherein: in the step 1), the spin-coating speed is 600-5000 rpm, and the time is 10-360 seconds.
5. The method for preparing a copper-zinc-tin-sulfur film according to claim 1, wherein the method comprises the following steps: the annealing temperature of the inversion annealing process in the step 2) is 200-300 ℃, and the annealing time is 2-6 min.
6. The method for preparing a copper-zinc-tin-sulfur film according to claim 1, wherein the method comprises the following steps: in the process of inversion annealing in the step 2), a piece of weighing paper is placed on the hot table in advance, and a thin film is placed on the weighing paper to avoid being polluted by the hot table.
7. The method for preparing a copper-zinc-tin-sulfur film according to claim 1, wherein the method comprises the following steps: the repetition frequency in the step 3) is 6-15 times.
8. The method for preparing a copper-zinc-tin-sulfur film according to claim 1, wherein the method comprises the following steps: the target temperature of the sulfide annealing in the step 4) is 500-600 ℃, the heating rate is 0.1-15 ℃/s, and the annealing is carried out for 1-20 min at the target temperature.
9. The method for preparing a copper-zinc-tin-sulfur film according to claim 1, wherein the method comprises the following steps: and after the annealing procedure in the step 4) is finished, adopting a temperature-controlled cooling mode to reach room temperature.
10. The method for preparing a copper-zinc-tin-sulfur thin film according to claim 8 or 9, characterized in that:
the specific steps of the sulfurization annealing in the step 4) are as follows:
placing the preset layer of film in a quartz tray, and simultaneously placing 0.1-0.5 g of sulfur and 0.1-0.3 g of stannous sulfide;
pumping the gas in the quartz plate to be below 30mBar, and then filling nitrogen to ensure that the air pressure in the cavity is 600 mBar;
starting heating and annealing at a target temperature;
and after the annealing procedure is finished, cooling to room temperature.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103346215A (en) * 2013-07-09 2013-10-09 北京工业大学 Method for preparing copper-zinc-tin-sulfide solar cell absorbing layer with homogeneous solution method
US20150333212A1 (en) * 2013-01-29 2015-11-19 Imra Europe Sas Method for preparing a thin layer of an absorber made of copper, zinc and tin sulfide(s), annealed thin layer and photovoltaic device thus obtained
CN109802011A (en) * 2019-01-23 2019-05-24 福建师范大学 A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air
CN111755323A (en) * 2020-07-07 2020-10-09 内蒙古大学 Preparation method of copper-zinc-tin-sulfur solar cell absorption layer film
CN113571647A (en) * 2021-06-25 2021-10-29 太原理工大学 Solvent steam assisted inversion annealing method and application thereof
WO2021227362A1 (en) * 2020-05-15 2021-11-18 南京邮电大学 Precursor solution of copper-zinc-tin-sulfur thin film solar cell, preparation method therefor, and use thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150333212A1 (en) * 2013-01-29 2015-11-19 Imra Europe Sas Method for preparing a thin layer of an absorber made of copper, zinc and tin sulfide(s), annealed thin layer and photovoltaic device thus obtained
CN103346215A (en) * 2013-07-09 2013-10-09 北京工业大学 Method for preparing copper-zinc-tin-sulfide solar cell absorbing layer with homogeneous solution method
CN109802011A (en) * 2019-01-23 2019-05-24 福建师范大学 A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air
WO2021227362A1 (en) * 2020-05-15 2021-11-18 南京邮电大学 Precursor solution of copper-zinc-tin-sulfur thin film solar cell, preparation method therefor, and use thereof
CN111755323A (en) * 2020-07-07 2020-10-09 内蒙古大学 Preparation method of copper-zinc-tin-sulfur solar cell absorption layer film
CN113571647A (en) * 2021-06-25 2021-10-29 太原理工大学 Solvent steam assisted inversion annealing method and application thereof

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