CN114988715B - Preparation method of copper zinc tin sulfide film - Google Patents

Preparation method of copper zinc tin sulfide film Download PDF

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CN114988715B
CN114988715B CN202210574612.6A CN202210574612A CN114988715B CN 114988715 B CN114988715 B CN 114988715B CN 202210574612 A CN202210574612 A CN 202210574612A CN 114988715 B CN114988715 B CN 114988715B
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CN114988715A (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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    • 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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—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
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01—INORGANIC CHEMISTRY
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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 sulfide film by means of inverted annealing. Spin-coating a precursor solution containing copper salt, zinc salt and tin salt on cleaned molybdenum glass; then placing the wet film face down on a hot table for inversion annealing, and repeating for a plurality of times to obtain a copper zinc tin sulfide preset layer film; and finally, putting the preset layer film into a rapid thermal annealing furnace for vulcanization annealing treatment to obtain the copper zinc tin sulfide film. The invention utilizes the dual functions of the covering effect of the substrate and the hot plate and the gravity to regulate and optimize the CZTS preset layer film, so that elements are uniformly dispersed in the preset layer, and the high-quality copper zinc tin sulfur absorbing 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 sulfide 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 sulfide film, which is particularly used for preparing a photovoltaic device.
Background
Energy is a basic stone for people to enjoy modern comfortable life. With the continuous progress of the life quality of people and the high-speed development of industry, the energy consumption is accelerated to increase. The traditional fossil energy has increasingly serious environmental problems in the processes of exploitation, processing and use, and the irreversible damage to ecology is attracting more and more attention, so that the development of various renewable green energy sources has become the most important common problem and research hotspot in the present society. Solar energy is clean and pollution-free, and is considered to be the most ideal renewable green energy source. Solar cell photovoltaic power generation technology is in turn considered to be the most attractive solution for utilizing solar energy.
The copper zinc tin sulfur thin film solar cell is used as a member of a thin film solar cell family, and has the following characteristics compared with a crystalline silicon cell: (1) High light absorption coefficient, copper zinc tin sulfide (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) as a direct bandgap semiconductor material with an optical absorption coefficient of up to 10 4 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the (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; and (3) the elements contained in the copper zinc tin sulfide are nontoxic and have abundant reserves. Based on the above discussion, copper zinc tin sulfur solar cells are receiving a great deal of attention because of their good photovoltaic properties, which are considered to be one of the new types of solar cells with development prospects.
The morphology and crystal quality of the copper zinc tin sulfur film are one of the most critical factors determining the photovoltaic performance of the copper zinc tin sulfur solar cell. There are many methods for preparing copper zinc tin sulfide thin films, among which, the solution method is the most promising method for large-scale industrial production at present, the method has the advantages that no nano particles are needed to be synthesized, the thin film components can be adjusted by the feeding ratio in the solution, and the material utilization rate is high. The specific implementation method comprises the steps of directly dissolving molecular precursors containing Cu, zn, sn and S in a proper solvent to form a uniform precursor solution, depositing the precursor solution on a substrate by spin coating or spray pyrolysis and other methods to obtain a film, then carrying out baking-cooling-spin coating circulation to obtain a preset layer film, and finally carrying out high-temperature annealing or selenizing/vulcanizing to convert the amorphous preset layer film into a crystalline absorption layer film.
However, copper zinc tin sulfide thin films prepared by conventional bake-chill spin coating processes are generally composed of small randomly oriented grains, the smaller grain size is unfavorable for charge transfer, and too many grain boundaries between the small grains can generate recombination centers to deteriorate device performance.
In view of the foregoing, it would be desirable to provide a method for preparing high quality copper zinc tin sulfide films with high crystallinity, large grain size, and low surface defect density.
Disclosure of Invention
The invention aims to provide a method for preparing a high-quality copper-zinc-tin-sulfur film by adopting an inversion annealing mode, so as to solve the problem of poor performance of a copper-zinc-tin-sulfur solar cell caused by defects of a vertical structure of the film and non-ideal surface morphology.
In order to achieve the above purpose, the preparation method of the copper zinc tin sulfide 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 table with the 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 film;
and 4) carrying out vulcanization annealing on the preset layer film to obtain the copper zinc tin sulfur absorption layer film.
Preferably, the molar ratio of the elements in the precursor solution in 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 subjected to the following treatments: the molybdenum glass is immersed in common detergent, deionized water and ethanol solution in sequence, and then dried by a nitrogen gun for standby.
Preferably, in the step 1), the spin-coating rotation speed is 600-5000 rpm, and the time is 10-360 s.
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, in the inversion annealing process in the step 2), a piece of weighing paper is placed on the hot stage in advance, and the film is placed on the weighing paper to avoid being polluted by the hot stage.
Preferably, the number of repetitions in step 3) is between 6 and 15.
Preferably, the target temperature of the vulcanization annealing in the step 4) is 500-600 ℃, the heating speed is 0.1-15 ℃ per second, and the annealing is performed for 1-20 min at the target temperature.
Preferably, after the annealing process in the step 4), a temperature-controlled cooling mode is adopted to reach the room temperature.
Preferably, the specific steps of the vulcanization annealing in step 4) are as follows:
placing the preset layer film in a quartz disc, 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 quartz disc until the air pressure in the cavity is 600mBar;
heating is started, and annealing is carried out at a target temperature;
after the annealing process is completed, the cooling mode is carried out to room temperature.
According to the invention, the copper zinc tin sulfur preset layer film is prepared by adopting an inversion annealing mode, and residual solvents and some elements can be prevented from escaping 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 crystal growth is promoted, the crystallinity of the film is improved, the charge transmission efficiency is improved, the charge recombination is inhibited, and the performance of the copper zinc tin sulfur solar cell is improved.
In the process of applying the inversion annealing technology, the surface morphology of the copper zinc tin sulfur film can be controlled by regulating and controlling the annealing temperature and the annealing time, so that the device performance is improved, and the method has high application value for researching the performance optimization of the copper zinc tin sulfur solar cell and developing industrialization thereof.
Drawings
FIG. 1 is a schematic diagram of an inversion annealing process according to the present invention.
Fig. 2 is SEM images of the copper zinc tin sulfide 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 graph of a copper zinc tin sulfide solar cell J-V 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 sulfide film. The copper-zinc-tin-sulfur preset layer film is obtained by placing the spin-coated wet film surface downwards on a hot table for inversion annealing, and the copper-zinc-tin-sulfur preset layer film can be subjected to vulcanization annealing 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 film solar cell has high photoelectric conversion efficiency.
The invention will now be further illustrated by way of example for a better understanding of the invention.
Comparative example 1
1) Sequentially immersing molybdenum glass into a common detergent, deionized water and an ethanol solution, and then drying by a nitrogen gun for standby;
2) Precursor solution prepared in advance (element molar ratio 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 performed on molybdenum glass by adopting a spin coating method, wherein the spin coating rotating speed is 3000rpm, and the time is 120s.
3) And placing the wet film obtained in the steps on a hot table with the molybdenum glass facing upwards, wherein the baking temperature is 280 ℃ and the baking time is 3min.
4) Repeating the step 2) and the step 3) for 9 times to obtain the preset layer film.
5) And placing the obtained preset layer film in a quartz disc, simultaneously adding 0.4g of sulfur and 0.2g of stannous sulfide, pumping gas in the quartz disc to below 30mBar, then filling nitrogen gas until the air pressure in the cavity is 600mBar, selecting a rapid thermal annealing furnace as a heating source, heating at a rate of 2 ℃/s, finally keeping the temperature at 580 ℃, preserving 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 scanning electron microscope cross-section view is shown in fig. 2 (a), and it can be seen from the figure that the absorption layer comprises two layers of small crystal grain layer and large crystal grain layer, the existence of the small crystal grain layer is unfavorable for charge transfer, and too many crystal grain boundaries among the small crystal grains can generate recombination centers so as to deteriorate the device performance.
6) Placing the absorbing layer material into a water jacket beaker containing ammonia water, cadmium sulfate and thiourea solution, reacting under heating, and depositing a layer of CdS on the surface of the absorbing layer; sequentially sputtering ZnO and ITO on the surface of the sample by using a magnetron sputtering technology to serve as a window layer; finally, metal Ag is evaporated on the surface of the sample by a thermal evaporation method to serve as a cathode, and the copper zinc tin sulfur solar cell device A is obtained.
Example 1
1) Sequentially immersing molybdenum glass into a common detergent, deionized water and an ethanol solution, and then drying by a nitrogen gun for standby;
2) Precursor solution prepared in advance (element molar ratio 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 performed on molybdenum glass by adopting a spin coating method, wherein the spin coating rotating speed is 3000rpm, and the time is 120s.
3) The wet film obtained in the above steps was faced down, and molybdenum glass was placed on a hot table with weighing paper laid up, with an annealing temperature of 280 ℃ and an annealing time of 3min.
4) Repeating the step 2) and the step 3) for 9 times to obtain the preset layer film.
5) And placing the obtained preset layer film in a quartz disc, simultaneously adding 0.4g of sulfur and 0.2g of stannous sulfide, pumping gas in the quartz disc to below 30mBar, then filling nitrogen gas until the air pressure in the cavity is 600mBar, selecting a rapid thermal annealing furnace as a heating source, heating at a rate of 2 ℃/s, finally keeping the temperature at 580 ℃, preserving 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. The scanning electron microscope section view is shown in fig. 2 (b), and the absorption layer is composed of large crystal grains penetrating through the absorption layer, is perfect in crystallization, has high compactness, is favorable for charge transmission, and can optimize the performance of the device to a certain extent.
6) Placing the absorbing layer material into a water jacket beaker containing ammonia water, cadmium sulfate and thiourea solution, reacting under heating, and depositing a layer of CdS on the surface of the absorbing layer; sequentially sputtering ZnO and ITO on the surface of the sample by using a magnetron sputtering technology to serve as a window layer; finally, metal Ag is evaporated on the surface of the sample by a thermal evaporation method to serve as a cathode, and the copper zinc tin sulfur solar cell device B is obtained.
The graphs of the copper zinc tin sulfide thin film solar cells J-V prepared in the embodiment 1 and the comparative example 1 are shown in fig. 3, and 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%, so that the preset layer prepared by the inversion annealing method can obtain an absorption layer thin film structure with high compactness and high crystallinity after vulcanization annealing, and the photoelectric conversion efficiency of the device is improved.

Claims (9)

1. A preparation method of a copper zinc tin sulfide 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 table with the 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 film;
step 4), carrying out vulcanization annealing on the preset layer film to prepare a copper zinc tin sulfur absorption layer film;
in the inversion annealing process in the step 2), a piece of weighing paper is placed on a hot table in advance, and a film is placed on the weighing paper to avoid being polluted by the hot table.
2. The method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: the molar ratio of the elements in the precursor solution in the step 1) is as follows: 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.
3. the method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: the molybdenum glass in the step 1) is sequentially subjected to the following treatment: the molybdenum glass is immersed in common detergent, deionized water and ethanol solution in sequence, and then dried by a nitrogen gun for standby.
4. The method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: in the step 1), the spin coating rotating speed is 600-5000 rpm, and the time is 10-360 s.
5. The method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: the annealing temperature in the inversion annealing process in the step 2) is 200-300 ℃, and the annealing time is 2-6 min.
6. The method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: the repetition number in the step 3) is 6 to 15.
7. The method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: the target temperature of the vulcanization annealing in the step 4) is 500-600 ℃, the heating speed is 0.1 ℃/s-15 ℃/s, and the annealing is performed for 1-20 min at the target temperature.
8. The method for preparing the copper-zinc-tin-sulfur film according to claim 1, which is characterized in that: and after the annealing procedure in the step 4) is finished, adopting a temperature control cooling mode to reach room temperature.
9. The method for preparing the copper-zinc-tin-sulfur film according to claim 7 or 8, which is characterized in that:
the specific steps of the vulcanization annealing in the step 4) are as follows:
placing the preset layer film in a quartz disc, 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 quartz disc until the air pressure in the cavity is 600mBar;
heating is started, and annealing is carried out at a target temperature;
after the annealing process is completed, the cooling mode is carried out to room temperature.
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Citations (5)

* 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
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3001467B1 (en) * 2013-01-29 2016-05-13 Imra Europe Sas PROCESS FOR PREPARING THIN FILM OF SULFIDE (S) COPPER, ZINC AND TIN SULFIDE ABSORBER, RECESSED THIN LAYER AND PHOTOVOLTAIC DEVICE OBTAINED

Patent Citations (5)

* 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
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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