CN111762808B - Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell - Google Patents

Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell Download PDF

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CN111762808B
CN111762808B CN201910244593.9A CN201910244593A CN111762808B CN 111762808 B CN111762808 B CN 111762808B CN 201910244593 A CN201910244593 A CN 201910244593A CN 111762808 B CN111762808 B CN 111762808B
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CN111762808A (en
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刘晟楠
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Zishi Energy Co ltd
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Abstract

The invention relates to the technical field of solar cells, in particular to a copper-tin-sulfur thin film absorption layer of a solar cell, a preparation method of the absorption layer and the solar cell. The preparation method of the copper-tin-sulfur film absorption layer provided by the invention is characterized in that a precursor liquid containing copper acetate, stannous chloride and thiourea and taking methanol and ethanol as solvents is used as a raw material, the precursor liquid is atomized, sprayed and deposited on the surface of a substrate by adopting a high-pressure gas spray pyrolysis method, and then the copper-tin-sulfur film absorption layer is prepared by annealing treatment. The method provided by the invention successfully prepares the copper-tin-sulfur film which has the advantages of good crystallization property, proper crystal grain size, smooth surface, high uniformity, excellent optical property and electrical property and capability of meeting the performance requirement of the absorption layer of the solar cell, has the advantages of cheap and easily obtained raw materials, high utilization rate, safety, environmental friendliness, no need of a vacuum preparation process, suitability for large-area film preparation and suitability for industrial production of the solar cell.

Description

Solar cell copper-tin-sulfur thin film absorption layer, preparation method thereof and solar cell
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for preparing a copper-tin-sulfur film absorption layer of a solar cell by high-pressure gas spray pyrolysis.
Background
Copper zinc tin sulfide (Cu) 2 ZnSnS 4 CZTS) is considered as a new thin-film solar cell material with great development potential, and has a large light absorption coefficient and a forbidden bandwidth of about 1.45eV, which is well matched with the solar spectrum. In recent years, CZTS thin film solar cells have been widely studied and have made great progress. However, as quaternary compound semiconductors, CZTS readily produces secondary phases such as Cu during fabrication 2 S、SnS 2 And Cu 2 SnS 3 Etc., adversely affecting the optical and electrical properties of the film. In contrast, ternary copper tin sulfide (Cu) 2 SnS 3 CTS) compound has few element types, the component proportion is easier to control, and the CTS is also a direct band gap semiconductor with the band gap value of about 1.0eV, has large light absorption coefficient and P-type conductivity, and is suitable for being used as an absorption layer material of a thin film solar cell. The theoretical conversion efficiency of the CTS thin film solar cell is about 30%.
The preparation method of the thin film material of the thin film solar cell material mainly comprises a Metal Organic Chemical Vapor Deposition (MOCVD) method, a spray pyrolysis method and the like. The MOCVD method for preparing the film has the advantages of low deposition temperature, high deposition rate, uniform prepared film and compatibility with a semiconductor process, so the method is widely used for preparing semiconductor materials. However, the metal organic source (MO source) used in the MOCVD method is a gas or liquid having a high vapor pressure, so that the preparation and purification are difficult, and the present species are limited, and the use and transportation are inconvenient, thereby limiting the development of MOCVD to a certain extent. In order to overcome the defects of the MOCVD method, researchers are developing a new MO source on one hand, and searching a method which has the characteristics of a Chemical Vapor Deposition (CVD) method and does not need the MO source on the other hand. Spray Pyrolysis (Spray Pyrolysis, SP method) was followed. The spray pyrolysis method combines the advantages of the liquid phase method and the gas phase method film preparation technology to a certain extent, the preparation process does not need vacuum conditions, the raw materials are nontoxic, the crust reserves are rich, and the method has a wide application prospect. The spray pyrolysis method comprises an ultrasonic spray pyrolysis method and a high-pressure gas spray pyrolysis method, the ultrasonic spray pyrolysis method adopts expensive ultrasonic atomization equipment, and precursor liquid is atomized by utilizing ultrasonic waves, so that the uniformity of a prepared film can be well ensured, but the preparation cost is high, and the method is not suitable for wide popularization and application. The high-pressure gas spray pyrolysis method (carrier gas flow spray pyrolysis method) utilizes high-pressure carrier flow to atomize the precursor liquid to form aerosol, and the preparation cost is far lower than that of the ultrasonic spray pyrolysis method. However, when the high-pressure gas spray pyrolysis method is used for preparing a thin film of a multicomponent compound such as CTS, the uniformity of the grain size and the uniformity of the surface of the thin film are low, and the light absorption rate and the photoelectric conversion efficiency of the thin film absorption layer are affected. Therefore, there is a need to develop a more efficient method for preparing a CTS film absorbing layer by high pressure gas spray pyrolysis with excellent film properties.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a method for preparing a copper-tin-sulfur thin film absorption layer of a solar cell by high-pressure gas spray pyrolysis.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a copper-tin-sulfur film absorption layer of a solar cell, which takes a precursor liquid containing copper acetate, stannous chloride and thiourea as a raw material and adopts a high-pressure gas spray pyrolysis method for preparation; the precursor solution takes methanol and ethanol as solvents.
The invention discovers that when the high-pressure gas spray pyrolysis method is adopted to prepare the copper-tin-sulfur film absorbing layer, copper acetate, stannous chloride and thiourea are taken as raw materials, and a mixture of methanol and ethanol is taken as a solvent, so that the low-temperature stable solubility of the raw materials of metal salt and thiourea in the solvent, the atomization efficiency of the precursor liquid sprayed by high-pressure gas, the reaction rate of the metal salt and thiourea in the deposition process and the crystallization film forming efficiency can be obviously improved, the pollution of impurities such as chloride ions and carbon atoms to the film is reduced, other impure phases are reduced, the uniformity of the formed crystal grain size and the surface flatness and uniformity of the copper-tin-sulfur film are improved, and the optical and electrical properties of the solar cell absorbing layer are effectively improved.
Preferably, in the precursor solution, the molar ratio of copper acetate to stannous chloride is (1-5): 1. the molar ratio of the metal salts can better ensure the interaction between the metal salts in the crystallization and nucleation processes, and further improve the crystallization performance of the film.
More preferably, the molar ratio of the copper acetate to the stannous chloride is (1-3): 1.
preferably, the molar concentration of the copper acetate in the precursor solution is 0.25-1.5 mol/L; the molar concentration of the stannous chloride is 0.25-1.5 mol/L; the molar concentration of the thiourea is 0.5-5 mol/L.
More preferably, the molar concentration of the copper acetate in the precursor solution is 0.25 to 0.75mol/L; the molar concentration of the stannous chloride is 0.25-0.5 mol/L; the molar concentration of the thiourea is 0.5-1.5 mol/L.
Preferably, in the precursor liquid, the volume ratio of methanol to ethanol is 11:1 to 2:1; more preferably 11:1 to 5:1. by adopting the proportion of the methanol and the ethanol, the stable dissolution of the metal salt can be more effectively realized, the atomization efficiency of high-pressure gas spraying can be improved, and the reaction rate of the metal salt and the thiourea in the deposition process can be increased.
The preparation method of the high-pressure gas spray pyrolysis method comprises the following steps: and atomizing the precursor liquid by adopting high-pressure gas, spraying and depositing the precursor liquid on the surface of the high-temperature substrate, and annealing the substrate.
Preferably, the temperature of the substrate during the deposition process is 100-400 ℃. By adopting the substrate temperature, the crystallization and nucleation speeds of decomposed substances can be effectively controlled while the full decomposition reaction of copper acetate and stannous chloride is ensured, and uniform film formation is promoted.
Further preferably, the temperature of the substrate during the deposition is 100-300 ℃.
Preferably, in the spraying deposition process, the distance from the nozzle to the substrate is 5-15 cm.
Preferably, in the spray deposition process, nitrogen or argon is used as a carrier gas, and the flow rate of the carrier gas is 5-45 mL/min.
Preferably, the temperature of the annealing treatment is 300-500 ℃, and the annealing time is 30-60 min. The annealing temperature and the annealing time can be adopted to better ensure the uniformity of film formation.
Further preferably, the temperature of the annealing treatment is 300-400 ℃, and the annealing time is 45-60 min.
Preferably, the temperature rise time in the annealing process is 0.5-10min, and the temperature drop time is 1-60min.
Further preferably, the temperature rise time in the annealing process is 0.5-5 min, and the temperature drop time is 1-10 min.
Preferably, in the annealing process, nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1-4%, hydrogen sulfide diluted gas with the hydrogen sulfide volume percentage of 0.1-15%, and high-purity nitrogen or argon are used as protective gas.
Preferably, the thickness of the copper tin sulfur thin film absorption layer is 1-10 μm.
As a preferred embodiment of the present invention, the method for preparing the copper tin sulfide thin film absorption layer of the solar cell includes the following steps:
(1) Preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11:1 to 5:1, the concentration of copper acetate is 0.25-0.75 mol/L, the concentration of stannous chloride is 0.25-0.5 mol/L, and the concentration of thiourea is 0.5-1.5 mol/L;
(2) Atomization spraying deposition: atomizing the precursor solution prepared in the step (1) into gas under high pressure, taking nitrogen or argon as a carrier, wherein the flow rate of the carrier is 5-45 mL/min, the distance from a nozzle to a substrate is 5-15 cm, the temperature of the substrate is 100-300 ℃, and carrying out atomization spraying deposition on the surface of the substrate;
(3) Annealing treatment: after the deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage content of 0.1-1% as protective gas, and annealing at 300-400 ℃ for 0.5-5 min, 45-60 min and 1-10 min.
The invention further provides a copper tin sulfur thin film absorption layer of the solar cell prepared by the preparation method.
The invention also provides a solar cell containing the copper-tin-sulfur thin film absorption layer.
As a preferable embodiment of the present invention, the solar cell includes, in order from bottom to top, a substrate, a dense layer, a buffer layer, an absorber layer, and an upper electrode.
Preferably, the substrate is FTO conductive glass as a substrate.
Preferably, the dense layer is a titanium dioxide film or a zinc oxide film.
Further preferably, the thickness of the dense layer is 20nm to 200nm.
Preferably, the buffer layer is a cadmium sulfide thin film, a zinc oxide thin film, a magnesium oxide thin film, a zinc sulfide thin film or an antimony-doped indium sulfide thin film.
Further preferably, the buffer layer has a thickness of 20nm to 200nm.
Preferably, the upper electrode is a layered structure prepared from graphite, silver, gold and molybdenum electrodes.
Further preferably, the thickness of the upper electrode is 50nm to 150nm.
The invention also provides a preparation method of the solar cell, which comprises the following steps:
(1) Preparing a substrate: cleaning and drying the FTO conductive glass to be used as a substrate;
(2) Preparing a compact layer: titanium isopropoxide solution or zinc isopropoxide solution is used as precursor solution, the precursor solution is atomized into gas under high pressure, compressed air, nitrogen or argon is used as carrier gas, and titanium dioxide film or zinc oxide film with the thickness of 20nm-200nm is formed by spray pyrolysis deposition on the surface of the FTO substrate;
(3) Preparing a buffer layer: preparing a cadmium sulfide film, a zinc oxide film, a magnesium oxide film, a zinc sulfide film or an antimony-doped indium sulfide film with the thickness of 20nm-200nm on the surface of the compact layer by adopting spray pyrolysis or chemical bath to serve as a buffer layer;
(4) Preparation of an absorption layer: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11:1 to 5:1, so that the concentration of copper acetate is 0.25-0.75 mol/L, the concentration of stannous chloride is 0.25-0.5 mol/L, and the concentration of thiourea is 0.5-1.5 mol/L, thereby obtaining a precursor solution; atomizing the precursor liquid into gas at high pressure, taking nitrogen or argon as a carrier, wherein the flow rate of the carrier is 5-45 mL/min, the distance from a nozzle to a substrate is 5-15 cm, the temperature of the substrate is 100-300 ℃, and carrying out atomization spraying on the surface of the substrate to deposit a copper-tin-sulfur film with the thickness of 1-10 mu m; after deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1-1% as protective gas, and annealing at 300-400 ℃ for 0.5-5 min, 45-60 min and 1-10 min;
(5) Preparing an upper electrode: printing graphite slurry or silver slurry on the surface of the absorption layer by adopting a screen printing method and carrying out annealing treatment, or evaporating silver, gold, molybdenum and molybdenum disulfide on the surface of the absorption layer by adopting a vacuum thermal evaporation method or an electron beam evaporation method to prepare an upper electrode with the thickness of 50nm-150 nm; wherein the current of vacuum thermal evaporation or electron beam evaporation is 80A-120A; during annealing treatment, nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1-4%, hydrogen sulfide diluent gas with the hydrogen sulfide volume percentage of 0.1-15%, and high-purity nitrogen or argon are introduced as protective gas, the annealing temperature is 300-600 ℃, the temperature rise time is 0.5-10min, the annealing time is 5-60min, and the temperature reduction time is 1-60min.
The invention has the beneficial effects that:
(1) According to the invention, the copper tin sulfur film which has the advantages of good crystallization property, proper crystal grain size, smooth surface, high uniformity, excellent optical property and electrical property (forbidden bandwidth of 0.97eV and conversion efficiency of 1.05%) and can meet the performance requirement of the solar cell absorption layer is successfully prepared by selecting and optimizing the preparation raw materials for preparing the copper tin sulfur film absorption layer by the high-pressure gas spray pyrolysis method and adaptively carrying out the integral optimization of the whole set of preparation process.
(2) The preparation method of the copper tin sulfur film absorption layer provided by the invention has the advantages of cheap and easily-obtained raw materials, high utilization rate, safety, environmental friendliness, no need of a vacuum preparation process and suitability for large-area film preparation, obviously improves the production efficiency of the copper tin sulfur film absorption layer, reduces the production cost and is suitable for industrial production of solar film batteries.
Drawings
FIG. 1 is a graph showing the results of X-ray diffraction (XRD) analysis of a CTS thin film in Experimental example 1 of the present invention.
FIG. 2 is a Raman spectrum of a CTS film in Experimental example 1 of the present invention.
FIG. 3 is a surface topography of a CTS film in Experimental example 2 of the present invention.
FIG. 4 shows a CTS film (. Alpha.h v) in Experimental example 3 of the present invention 2 And h ν.
Fig. 5 is a graph showing J-V characteristics of a CTS thin film solar cell in experimental example 4 of the present invention.
Fig. 6 is a schematic structural diagram of a CTS thin film solar cell in embodiment 7 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The embodiment provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which comprises the following specific steps:
(1) Preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11:1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5mol/L;
(2) Atomization spraying deposition: atomizing the precursor liquid prepared in the step (1) into gas at high pressure, wherein the gas source for high-pressure atomization is air, and the pressure is 0.1MPa; carrying out atomization spraying on the surface of a substrate at the temperature of 300 ℃ by taking nitrogen as a carrier, wherein the flow rate of the carrier is 15mL/min, the distance from a nozzle to the substrate is 5cm, and a copper-tin-sulfur film with the thickness of 1 micrometer is deposited;
(3) Annealing treatment: and after the deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1% as protective gas, and annealing at 300 ℃, wherein the temperature rise time is 0.5min, the annealing time is 60min, and the temperature reduction time is 1min.
Example 2
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from embodiment 1 only in step (1), specifically as follows:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11:1, preparing a precursor solution with the concentration of copper acetate of 0.6mol/L, the concentration of stannous chloride of 0.3mol/L and the concentration of thiourea of 1 mol/L.
Example 3
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from the embodiment 1 only in the step (1), and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11:1, preparing a precursor solution with the concentration of copper acetate of 0.75mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 1.5mol/L.
Example 4
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from the embodiment 1 only in the step (1), and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 5:1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L.
Example 5
This example provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from example 1 only in that the substrate temperature of the spray deposition in step (2) is 250 ℃.
Example 6
The embodiment provides a method for preparing a copper-tin-sulfur thin film absorber layer of a solar cell, which is different from the method in embodiment 1 only in that the annealing temperature in the step (3) is 400 ℃ and the annealing time is 60min.
Example 7
The embodiment provides a method for preparing a solar cell with a copper-tin-sulfur film as an absorption layer, which comprises the following specific steps:
(1) Preparing a substrate: the method comprises the following steps of taking FTO conductive glass as a substrate, putting the substrate into a beaker, firstly, ultrasonically cleaning for 0.5h by using a washing powder solution, then ultrasonically cleaning for 15min by using a saturated sodium hydroxide-ethanol solution, then ultrasonically cleaning until no alkali liquor residue exists on the surface by using tap water, then ultrasonically cleaning by using deionized water, and finally drying by using nitrogen for later use.
(2) Preparing a compact layer: titanium isopropoxide and ethanol are mixed according to a molar ratio of 1:1, uniformly mixing to prepare a titanium isopropoxide solution, spraying, pyrolyzing and depositing on the surface of the FTO conductive glass substrate by taking compressed air as a carrier gas to form a titanium dioxide film with the thickness of 20nm, wherein the deposition temperature is 400 ℃, and the distance from a nozzle to a hot platform is 5cm;
(3) Preparing a buffer layer: adding cadmium acetate and thiourea into distilled water to prepare a precursor solution, wherein the concentration of the cadmium acetate is 0.05mol/L, the concentration of the thiourea is 0.2mol/L, spraying and pyrolyzing on the surface of the compact layer by taking nitrogen as carrier gas to prepare a cadmium sulfide thin film buffer layer with the thickness of 20nm, the deposition temperature is 300 ℃, and the distance from a nozzle to a hot platform is 5cm;
(4) Preparation of an absorption layer: adding copper acetate, stannous chloride and thiourea into methanol and ethanol at a volume ratio of 11:1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5mol/L; atomizing the prepared precursor liquid into gas at high pressure, taking nitrogen as a carrier, controlling the flow rate of the carrier gas to be 15mL/min, controlling the distance from a nozzle to a hot table to be 5cm, controlling the temperature of a substrate to be 300 ℃, and carrying out atomization spraying on the surface of the substrate to deposit a copper-tin-sulfur film with the thickness of 1 mu m; and after the deposition is finished, introducing nitrogen-hydrogen mixed gas with the hydrogen volume percentage of 0.1% as protective gas, and annealing at 300 ℃ for 0.5min, 60min and 1min.
(5) Preparing an upper electrode: and (2) performing gold evaporation plating on the surface of the absorption layer by using gold (Au) with the purity of 99.99% as a raw material by adopting a vacuum thermal evaporation method, and then performing annealing treatment to obtain an upper electrode with the thickness of 100nm, wherein high-purity nitrogen is introduced as a protective gas during the annealing treatment, the annealing temperature is 400 ℃, the temperature rise time is 5min, the annealing time is 30min, and the temperature reduction time is 15min.
The embodiment also provides a solar cell prepared by the method, and the structural schematic diagram of the solar cell is shown in fig. 6.
Comparative example 1
The comparative example provides a preparation method of a solar cell copper-tin-sulfur thin film absorption layer, which is different from example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper chloride, stannous chloride and thiourea into the mixture according to the volume ratio of 11:1, preparing a precursor solution with the concentration of copper chloride of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L.
Comparative example 2
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper sulfate, tin chloride and thiourea into the mixture according to the volume ratio of 11:1, preparing a precursor solution with copper sulfate concentration of 0.25mol/L, tin chloride concentration of 0.25mol/L and thiourea concentration of 0.5 mol/L.
Comparative example 3
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into methanol to prepare a precursor solution with the concentration of 0.25mol/L of copper acetate, the concentration of 0.25mol/L of stannous chloride and the concentration of 0.5mol/L of thiourea.
Comparative example 4
The comparative example provides a preparation method of a solar cell copper-tin-sulfur thin film absorption layer, which is different from example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper acetate, stannous chloride and thiourea into the mixture according to the volume ratio of 11:1, preparing a precursor solution with the concentration of copper acetate of 1.5mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 1.0 mol/L.
Comparative example 5
The comparative example provides a preparation method of a copper-tin-sulfur thin film absorption layer of a solar cell, which is different from the method of example 1 only in the step (1) and specifically comprises the following steps:
preparing a precursor solution: adding copper sulfate, tin chloride and thiourea into the mixture according to the volume ratio of 1:1, preparing a precursor solution with the concentration of copper acetate of 0.25mol/L, the concentration of stannous chloride of 0.25mol/L and the concentration of thiourea of 0.5 mol/L.
Experimental example 1 Crystal Structure analysis of film
The X-ray diffractometer is adopted to respectively detect the crystal structures of the CTS films prepared by the methods of examples 1-6 and comparative examples 1-5, and the results show that the CTS films prepared by the examples 1-6 are CTS films with a Kesterite structure, have no hetero-phase peak and have the grain size of 1 mu m; the CTS films prepared in comparative examples 1 to 5 have weak X-ray diffraction peaks, which indicates that the crystallinity is not good enough; wherein the X-ray diffraction pattern of the CTS thin film prepared in example 1 is shown in fig. 1.
The internal structures of the CTS films prepared by the methods of examples 1 to 6 and comparative examples 1 to 5 are analyzed by Raman spectroscopy (Raman), and the results show that the films prepared by examples 1 to 6 and comparative examples 1 to 5 are CTS films, but compared with comparative examples 1 to 5, the Raman spectroscopy peaks of examples 1 to 6 are stronger, which indicates that the CTS films of the examples have better quality; the raman spectrum result of the CTS film prepared in example 1 is shown in fig. 2.
Experimental example 2 surface morphology analysis of film
The surface appearance of the CTS films prepared by the methods of examples 1-6 and comparative examples 1-5 is observed by a scanning electron microscope, and the results show that the CTS films of examples 1-6 have compact and flat surfaces, no crack defects and high quality; the films prepared by the methods of comparative examples 1 to 5 have poor surface compactness, holes and smaller grain size; the results of the CTS film prepared in example 1 are shown in FIG. 3.
Experimental example 3 optical Properties of film
The ultraviolet-visible spectrometer is adopted to analyze the optical properties of the CTS films prepared by the methods of the examples 1-6 and the comparative examples 1-5, and the result shows that the forbidden bandwidth of the CTS films prepared by the examples 1-6 is within the range of 0.95-1 eV; the forbidden band width prepared by the comparative examples 1-5 is less than 0.90eV; the detection result of the ultraviolet-visible spectrometer of the CTS film prepared in example 1 is shown in fig. 4, and the forbidden bandwidth is 0.97eV.
Experimental example 4 analysis of electrical properties of CTS thin film solar cell
The electrical properties of the CTS thin-film solar cell prepared by the method of example 7 were measured by an IV tester and analyzed, and the current density-voltage (J-V) characteristic curve thereof is shown in fig. 5, and the conversion efficiency thereof was calculated to be 1.05%.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (8)

1. A preparation method of a copper tin sulfur film absorption layer of a solar cell is characterized in that a precursor liquid containing copper acetate, stannous chloride and thiourea is used as a raw material, and a high-pressure gas spray pyrolysis method is adopted for preparation; the precursor solution takes methanol and ethanol as solvents;
in the precursor liquid, the molar ratio of copper acetate to stannous chloride is (1-3): 1;
in the precursor solution, the molar concentration of the copper acetate is 0.25-0.75 mol/L; the molar concentration of the stannous chloride is 0.25-0.5 mol/L; the molar concentration of the thiourea is 0.5-1.5 mol/L;
in the precursor liquid, the volume ratio of methanol to ethanol is 11:1 to 5:1.
2. the method of claim 1, wherein the high pressure gas spray pyrolysis method comprises: and atomizing the precursor liquid by adopting high-pressure gas, spraying and depositing the precursor liquid on the surface of a high-temperature substrate, and annealing the substrate.
3. The method of claim 2, wherein the substrate is at a temperature of 100 to 400 ℃ during the spray deposition.
4. The method of claim 3, wherein the substrate is at a temperature of 100 to 300 ℃ during the spray deposition.
5. The method according to any one of claims 2 to 4, wherein the distance from the nozzle to the substrate during the spray deposition is 5 to 15cm.
6. The preparation method according to claim 5, wherein during the spray deposition, nitrogen or argon is used as a carrier gas, and the flow rate of the carrier gas is 5-45 mL/min.
7. The production method according to any one of claims 2 to 4 and 6, wherein the temperature of the annealing treatment is 300 to 500 ℃ and the annealing time is 30 to 60min.
8. The method according to claim 7, wherein the annealing temperature is 300 to 400 ℃ and the annealing time is 45 to 60min.
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