A copper-zinc-tin-sulfur micro-nano secondary array structure, preparation method and application thereof

Abstract

The present invention discloses a copper-zinc-tin-sulfur micro-nano secondary array structure, which is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps, wherein the semiconductor is copper-zinc-tin-sulfur with a single crystal structure; the diameter of the regularly arranged micron-sized spherical caps is 0.05-50 μm, and the spacing between the spherical caps is 0.01-100 μm. The radially grown semiconductor nanotubes in the micro-nano secondary array structure have a larger specific surface area and significantly enhance the absorption of light compared to the nanowire array; at the same time, since the nanotubes outside the micron-sized semiconductor spherical caps grow radially, light incident from all angles can be well absorbed, reducing the sensitivity of the micro-nano secondary array to the angle of incidence of light. When applied in the photovoltaic field, the micro-nano secondary array structure of the present invention can increase the absorption of light by solar cells, reduce the cost of solar cells, and improve the photoelectric conversion efficiency of solar cells.

Description

Technical Field

[0001] The present invention belongs to the technical field of solar photovoltaic cells, and in particular relates to a copper-zinc-tin-sulfur micro-nano secondary array structure, a preparation method and applications thereof. Background Art

[0002] In recent years, China has introduced numerous subsidy and support policies, including the Solar Roof Program and the Golden Sun Project. With these policies, China is poised to launch a massive solar cell market. However, current solar cells still face challenges such as high production costs and low photoelectric conversion efficiency. With the advancement of nanotechnology, the use of semiconductor nanowires in solar cell fabrication has been shown to play a crucial role in reducing costs and improving photoelectric conversion efficiency. Among various semiconductor nanowire materials, copper zinc tin sulfur (Cu2ZnSnS4, CZTS) has attracted widespread attention in the photovoltaic field due to its direct bandgap semiconductor material, offering numerous advantages such as adjustable bandgap width and high light absorption coefficient.

[0003] Chinese patent CN202111328388.4 discloses a copper-zinc-tin-sulfur (CuZnS) absorber layer film, its preparation, and a solar cell containing the same. This method uses an oxygen-containing CuZnSnS prefabricated layer film and an optimized sulfurization process to effectively reduce leakage channels and reduce the thickness of MoS2, thereby preparing a CuZnSnS absorber layer film that is copper-poor and zinc-rich and meets the requirements of solar cells. However, the CZTS thin film obtained in this method is prone to carrier recombination when used in the photovoltaic field, which can easily cause solar cell performance degradation.

[0004] Chinese patent CN201210135807.7 discloses a nanostructured CZTS thin-film photovoltaic cell and its preparation method. This method adjusts the composition, phase structure, and energy band structure of the absorber layer nanowire array by controlling the type and order of deposited elements, the method of heat treatment, and other subsequent processes, thereby producing solar photovoltaic cells with different structures and performances. The CZTS thin-film photovoltaic cell prepared by this method has reduced light reflection, excellent light capture capability, and improved band gap adjustment. However, when used in the photovoltaic field, the nanowire array is sensitive to the incident angle of sunlight, and the angle of the solar panel needs to be continuously adjusted to increase the absorption of incident light from different directions, which undoubtedly increases the cost of using nanowire solar cells.

[0005] According to existing literature, nanoarrays applied in the photovoltaic field can improve light absorption over thin films, thereby increasing photoelectric conversion efficiency. While various nanoarrays have been prepared using solvent-thermal in-situ growth methods and template-based gas-solid reaction methods, there is currently no method that is simple, low-cost, and suitable for large-area nanowire arrays. Furthermore, currently prepared nanoarray solar cells also require the orientation of the solar panel to continuously change as the sun's position changes, increasing the cost of the solar cell. Summary of the Invention

[0006] In order to solve the above problems, the purpose of the present invention is to provide a copper-zinc-tin-sulfur micro-nano secondary array structure. The application of this array in the photovoltaic field can effectively solve the problems of low photoelectric conversion efficiency of solar cells, easy recombination of photogenerated carriers, sensitivity to light incident angle, and high cost.

[0007] The present invention also provides a preparation method of the copper-zinc-tin-sulfur micro-nano secondary array structure and its application.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A copper-zinc-tin-sulfur micro-nano secondary array structure is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surfaces of the spherical caps.

[0010] In the above-mentioned copper zinc tin sulfur micro-nano secondary array structure, the semiconductor is copper zinc tin sulfur (CZTS) with a single crystal structure; the diameter of the regularly arranged micron-scale spherical caps is 0.05-50μm, and the interval between the spherical caps is 0.01-100μm.

[0011] In the above-mentioned copper-zinc-tin-sulfur micro-nano secondary array structure, the outer diameter of the radially grown semiconductor nanotubes is 10 nm-500 nm, and the length is 20 nm-50 μm.

[0012] The present invention provides a method for preparing the above-mentioned copper-zinc-tin-sulfur micro-nano secondary array structure, which comprises the following steps:

[0013] 1) Using electrochemical deposition to deposit a conductive film on a clean substrate;

[0014] 2) Using electrochemical deposition, a zinc oxide film is deposited on the conductive film. The substrate with the conductive film and zinc oxide film deposited thereon is then placed in hydrogen sulfide or an oxygen-hydrogen sulfide mixture at 0-200°C for 1-500 hours to convert the zinc oxide into a ZnS micro-nano secondary array.

[0015] 3) Using a solvothermal method to replace part of the zinc in the ZnS micro-nano secondary array with copper and tin, and then generating a CZTS micro-nano secondary array structure through sulfurization; specifically, preparing a triethylene glycol precursor solution containing copper and tin ions, and then placing the triethylene glycol precursor solution and the product of step 2) into a reactor, sealing the reactor and reacting at 10-200°C for 0.5-50h, so that the zinc in the ZnS micro-nano secondary array is replaced by copper and tin; after the reaction is completed, placing the product in an H2S atmosphere and heating it at 400-500°C for 0.1-50h.

[0016] Specifically, in step 1), the substrate is one of a metal sheet, a conductive glass, a stainless steel sheet, etc.

[0017] Furthermore, in step 1), the conductive film is one of aluminum, copper, nano-indium tin metal oxide ITO, silver, titanium, etc., and the thickness of the conductive film is 20nm-1μm.

[0018] Furthermore, in step 1) and step 2), the electrochemical deposition method is pulse electrochemical deposition, constant voltage electrochemical deposition or constant current electrochemical deposition.

[0019] Specifically, in step 2), the thickness of the zinc oxide film is 50 nm-50 μm.

[0020] Furthermore, in step 2), the volume ratio of oxygen to hydrogen sulfide in the oxygen-hydrogen sulfide mixture is 1:0.01-100. In step 3), copper chloride, stannous chloride, or the like can be used to prepare the triethylene glycol precursor solution containing copper and tin ions. The concentration of copper chloride in the triethylene glycol precursor solution is 0.3-4.5 mM, and the concentration of stannous chloride is 0.15-6 mM.

[0021] The present invention also provides the application of the copper-zinc-tin-sulfur micro-nano secondary array structure in the photovoltaic field.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1) The present invention is a simple method for preparing a single-crystal CZTS micro-nano secondary array structure on a substrate deposited with a conductive film through electrochemical deposition, gas-solid reaction, and solvothermal methods. The entire preparation process does not require the use of a template, ensuring the subsequent large-scale preparation of CZTS micro-nano secondary arrays. The deposition voltage, electrolyte concentration, and deposition time during the electrochemical deposition process can affect the growth of the micron array. By adjusting the concentration of the precursor solution, reaction temperature, and time during the solvothermal process, the nanotube morphology and ratio of the constituent elements in the micro-nano secondary array can be adjusted, achieving controllable growth of the nanoarray.

[0024] 2) The present invention has the advantages of a simple synthesis method, low requirements for synthesis conditions and equipment, low cost, controllable synthesis conditions, and the reaction products can be easily applied on a large scale. Since no catalyst or template is required during the preparation process, the prepared micro-nano secondary array is not restricted by the template and can be prepared on a large scale at low cost.

[0025] 3) In the micro-nano secondary array synthesized by the present invention, the radially grown nanotube array has a tubular structure with a small diameter, large length and density, which greatly increases the specific surface area of ​​the material, thereby increasing the light absorption area of ​​the micro-nano secondary array structure, making its light absorption significantly enhanced compared to the nanowire array; at the same time, the tubular structure of the nanotube itself determines that when it is used in solar cells, the absorption of light and the separation of photogenerated carriers are along two mutually perpendicular directions, which can effectively solve the problem of photogenerated carrier recombination in solar cells. This performance is better than that of nanowire arrays with the same diameter (the light absorption rate is increased by nearly 7%-10%). In addition, because the nanotubes grow radially on the outside of the micron-sized semiconductor spherical cap, light incident from all angles can be well absorbed, reducing the sensitivity of the nanofilm to the angle of incidence of light. When used in the photovoltaic field, it can avoid the problem of reduced battery performance due to changes in the position of the sun, or the need to continuously change the angle of the solar cell with changes in the angle of illumination, which leads to increased costs;

[0026] 4) The synthesized micro-nano secondary array exhibits orderly arrangement, good periodicity, and excellent light absorption performance (average absorption rate of 96.4%-98%). When the incident light changes from perpendicular to the sample surface to a 45-degree angle, the absorption rate only decreases by 3.5%-4.2%. Furthermore, because the array can be grown simultaneously over large areas on different substrates, it can be used to fabricate high-efficiency, large-area solar cells. When applied in the photovoltaic field, the micro-nano secondary array structure of the present invention can enhance the light absorption of solar cells, reduce solar cell costs, and improve the photoelectric conversion efficiency of solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a schematic diagram of the copper-zinc-tin-sulfur micro-nano secondary array structure of the present invention (vertical section); wherein 1-substrate, 2-conductive film, 3-radially grown CZTS nanotubes, 4-CZTS micron-scale spherical cap;

[0028] Figure 2 This is a scanning electron microscope image of nanotubes in the copper-zinc-tin-sulfur micro-nano secondary array of Example 3 of the present invention. DETAILED DESCRIPTION

[0029] The specific embodiments of the present invention are further described in detail below with reference to the examples.

[0030] In the following examples, unless otherwise specified, the raw materials used are common commercial products that can be directly purchased in the art. Methods not mentioned in detail, such as pulse electrochemical deposition, constant voltage electrochemical deposition or constant current electrochemical deposition, can all be completed using conventional techniques in the art.

[0031] Example 1

[0032] A copper-zinc-tin-sulfur micro-nano secondary array structure, the preparation method of which comprises the following steps:

[0033] (1) The substrate copper sheet was polished with sandpaper No. 0-6 and ultrasonically cleaned with alcohol, acetone, and deionized water for 5 min each. Then, a layer of Ti was deposited on the clean copper sheet by pulse electrochemical deposition. The thickness of Ti was 50 nm.

[0034] (2) A 1 μm thick ZnO film was deposited on a copper sheet with a Ti layer by pulse electrochemical deposition. The copper sheet with the ZnO film was then placed in an oxygen-hydrogen sulfide mixed gas (the volume ratio of oxygen to hydrogen sulfide was 1:2) at 11°C for 16 hours to transform the ZnO film into a ZnS micro-nano secondary array.

[0035] (3) Prepare a triethylene glycol solution containing 2.4 mM copper chloride and 0.18 mM stannous chloride as a precursor solution, put the precursor solution and the product of step (2) into a reactor, seal the reactor, and place it in a 60°C forced air drying oven to react for 6 hours; after the reaction is completed, transfer the substrate into a ceramic tube, introduce argon gas to expel the air in the tube, and then introduce H2S to place the ceramic tube in an H2S atmosphere. After the ceramic tube is sealed, heat it at 500°C for 2 hours to generate a CZTS micro-nano secondary array.

[0036] The CZTS micro-nano secondary array prepared in this example is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps. The semiconductor is copper, zinc, tin, and sulfur with a single crystal structure. Figure 1 The diameter of the regularly arranged micron-sized spherical caps is 600 nm, the spacing between the caps is 50 nm, the outer diameter of the nanotubes is 50 nm, and the length is 500 nm.

[0037] The resulting CZTS micro-nano secondary array has a significantly larger specific surface area than the nanowire array, resulting in a larger light absorption area and less sensitivity to the angle of incidence. The structure's average light absorptivity reaches 96.4%, an increase of nearly 18% compared to a CZTS film of the same thickness. When the incident light angle changes from perpendicular to the sample surface to 45°, the absorptivity decreases by only 3.9%. Compared to a nanowire array of the same diameter, the absorptivity increases by nearly 10%.

[0038] Example 2

[0039] A copper-zinc-tin-sulfur micro-nano secondary array structure, the preparation method of which comprises the following steps:

[0040] (1) The substrate conductive glass was ultrasonically cleaned with alcohol, acetone, and deionized water for 10 min each, and then a layer of copper as a conductive film was deposited on the clean conductive glass by constant voltage electrochemical deposition. The thickness of the copper was 160 nm.

[0041] (2) A 500 nm thick ZnO film was deposited on a conductive glass layer with a copper layer by constant voltage electrochemical deposition. The conductive glass with the ZnO film was placed in an oxygen-hydrogen sulfide mixed gas (the volume ratio of oxygen to hydrogen sulfide was 1:100) at 0°C for 500 h, so that the ZnO film was transformed into a ZnS micro-nano secondary array.

[0042] (3) Prepare a triethylene glycol solution containing 2.4 mM copper chloride and 0.18 mM stannous chloride as a precursor solution, put the precursor solution and the product of step (2) into a reactor, seal the reactor, and place it in an 80°C forced air drying oven for reaction for 10 hours; after the reaction is completed, transfer the substrate into a ceramic tube, introduce argon gas to expel the air in the tube, and then introduce H2S to place the ceramic tube in an H2S atmosphere. After the ceramic tube is sealed, heat it at 500°C for 10 hours to generate a CZTS micro-nano secondary array.

[0043] The CZTS micro-nano secondary array prepared in this example is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps. The semiconductor is copper, zinc, tin, and sulfur with a single crystal structure. Figure 1 The diameter of the regularly arranged micron-sized spherical caps is 400 nm, the spacing between the caps is 20 nm, the outer diameter of the nanotubes is 80 nm, and the length is 200 nm.

[0044] The resulting CZTS micro-nano secondary array has a significantly larger specific surface area than the nanowire array, resulting in a larger light absorption area and less sensitivity to the angle of incidence. The structure's average light absorptivity reaches 96.5%, an increase of nearly 18% compared to a CZTS film of the same thickness. When the incident light angle changes from perpendicular to the sample surface to 45°, the absorptivity decreases by only 4.2%. Compared to a nanowire array of the same diameter, the absorptivity increases by nearly 9.5%.

[0045] Example 3

[0046] A copper-zinc-tin-sulfur micro-nano secondary array structure, the preparation method of which comprises the following steps:

[0047] (1) The substrate stainless steel sheet was polished with sandpaper No. 0-6 in sequence, and ultrasonically cleaned with alcohol, acetone, and deionized water for 5 minutes each. Then, a layer of copper as a conductive film was deposited on the clean stainless steel sheet by constant current electrochemical deposition. The thickness of the copper was 160 nm.

[0048] (2) A 2 μm thick ZnO film was deposited on a copper-deposited stainless steel sheet using a constant current electrochemical deposition method. The stainless steel sheet with the zinc oxide film was placed in an oxygen-hydrogen sulfide mixed gas (the volume ratio of oxygen to hydrogen sulfide was 1:0.01) at 200°C for 12 hours to convert the ZnO into a ZnS micro-nano secondary array.

[0049] (3) Prepare a triethylene glycol solution containing 3 mM copper chloride and 6 mM stannous chloride as a precursor solution, put the precursor solution and the product of step (2) into a reactor, seal the reactor, and place it in a 180°C forced air drying oven for reaction for 10 hours; after the reaction is completed, transfer the substrate into a ceramic tube, introduce argon gas to expel the air in the tube, and then introduce H2S to place the ceramic tube in an H2S atmosphere. After the ceramic tube is sealed, heat it at 450°C for 2 hours to generate a CZTS micro-nano secondary array.

[0050] The CZTS micro-nano secondary array prepared in this example is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps. The semiconductor is copper, zinc, tin, and sulfur with a single crystal structure. Figure 1 The diameter of the regularly arranged micron-sized spherical caps is 1.5 μm, the spacing between the caps is 500 nm, the outer diameter of the nanotubes is 100 nm, and the length is 1 μm (see the scanning electron microscope image). Figure 2 ).

[0051] The resulting CZTS micro-nano secondary array has a significantly larger specific surface area than the nanowire array, resulting in a larger light absorption area and less sensitivity to the angle of incidence. The structure's average light absorptivity reaches 98%, a nearly 20% increase compared to a CZTS film of the same thickness. When the incident light angle changes from perpendicular to the sample surface to 45°, the absorptivity decreases by only 3.8%. Compared to a nanowire array of the same diameter, the absorptivity increases by nearly 7%.

[0052] Example 4

[0053] A copper-zinc-tin-sulfur micro-nano secondary array structure, the preparation method of which comprises the following steps:

[0054] (1) The substrate conductive glass was ultrasonically cleaned with alcohol, acetone, and deionized water for 5 min each, and then a layer of Ag as a conductive film was deposited on the clean conductive glass using a constant current electrochemical deposition method. The thickness of Ag was 1 μm.

[0055] (2) A ZnO film with a thickness of 50 μm was deposited on the conductive glass deposited with Ag by constant current electrochemical deposition. The conductive glass deposited with the ZnO film was placed in an oxygen-hydrogen sulfide mixed gas (the volume ratio of oxygen to hydrogen sulfide was 1:2.5) and placed at 26°C for 12 hours to transform the ZnO film into a ZnS micro-nano secondary array.

[0056] (3) Prepare a triethylene glycol solution containing 0.3 mM copper chloride and 0.15 mM stannous chloride as a precursor solution, put the precursor solution and the product of step (2) into a reactor, seal the reactor, and place it in a 180°C forced air drying oven to react for 10 hours; after the reaction is completed, transfer the substrate into a ceramic tube, introduce argon gas to expel the air in the tube, and then introduce H2S to place the ceramic tube in an H2S atmosphere. After the ceramic tube is sealed, heat it at 400°C for 4 hours to generate a CZTS micro-nano secondary array structure.

[0057] The CZTS micro-nano secondary array prepared in this example is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps. The semiconductor is copper, zinc, tin, and sulfur with a single crystal structure. Figure 1 The diameter of the regularly arranged micron-sized spherical caps is 40 μm, the interval between the spherical caps is 1 μm, the outer diameter of the nanotubes is 500 nm, and the length is 10 μm.

[0058] The resulting CZTS micro-nano secondary array has a significantly larger specific surface area than the nanowire array, resulting in a larger light absorption area and less sensitivity to the incident angle of light. The structure's average light absorptivity reaches 97%, an increase of nearly 19% compared to a CZTS film of the same thickness. When the incident light angle changes from perpendicular to the sample surface to 45°, the absorptivity decreases by only 3.5%. Compared to a nanowire array of the same diameter, the absorptivity increases by nearly 7%.

[0059] Example 5

[0060] A copper-zinc-tin-sulfur micro-nano secondary array structure, the preparation method of which comprises the following steps:

[0061] (1) The substrate conductive glass was ultrasonically cleaned with alcohol, acetone, and deionized water for 10 min each, and then a layer of Al as a conductive film was deposited on the clean conductive glass using a constant current deposition method. The thickness of Al was 700 nm.

[0062] (2) A 50 nm thick ZnO film was deposited on a conductive glass sheet deposited with Al using a pulse electrochemical deposition method. The conductive glass sheet deposited with the ZnO film was placed in an oxygen-hydrogen sulfide mixed gas (the volume ratio of oxygen to hydrogen sulfide was 1:50) and placed at 100°C for 125 hours to transform the ZnO film into a ZnS micro-nano secondary array.

[0063] (3) Prepare a triethylene glycol solution containing 4.5 mM copper chloride and 0.15 mM stannous chloride as a precursor solution, put the precursor solution and the product of step (2) into a reactor, seal the reactor, and place it in a 180°C forced air drying oven to react for 10 hours; after the reaction is completed, transfer the substrate into a ceramic tube, introduce argon gas to expel the air in the tube, and then introduce H2S to place the ceramic tube in an H2S atmosphere. After the ceramic tube is sealed, heat it at 500°C for 6 hours to generate a CZTS micro-nano secondary array structure.

[0064] The CZTS micro-nano secondary array prepared in this example is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps. The semiconductor is copper, zinc, tin, and sulfur with a single crystal structure. Figure 1 The diameter of the regularly arranged micron-sized spherical caps is 50 nm, the interval between the spherical caps is 15 nm, the outer diameter of the nanotubes is 10 nm, and the length is 50 nm.

[0065] The resulting CZTS micro-nano secondary array has a significantly larger specific surface area than the nanowire array, resulting in a larger light absorption area and less sensitivity to the angle of incidence. The structure's average light absorptivity reaches 96.6%, a nearly 19% increase compared to a CZTS film of the same thickness. When the incident light angle changes from perpendicular to the sample surface to 45°, the absorptivity decreases by only 4.2%. Compared to a nanowire array of the same diameter, the absorptivity increases by nearly 8%.

[0066] The above description is merely the best embodiment of the present invention. For those skilled in the art, the present invention may be modified and varied in various ways. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A method for preparing a copper-zinc-tin-sulfur micro-nano secondary array structure, characterized in that: The copper-zinc-tin-sulfur micro-nano secondary array structure is composed of regularly arranged micron-sized semiconductor spherical caps and semiconductor nanotubes radially grown on the surface of the spherical caps; The semiconductor is copper, zinc, tin, and sulfur with a single crystal structure; the diameter of the regularly arranged micron-sized spherical caps is 0.05-50 μm, and the interval between the spherical caps is 0.01-100 μm; The radially grown semiconductor nanotubes have an outer diameter of 10 nm to 500 nm and a length of 20 nm to 50 μm; The copper-zinc-tin-sulfur micro-nano secondary array structure is prepared by the following steps: 1) Using electrochemical deposition to deposit a conductive film on a clean substrate; 2) Using electrochemical deposition, a zinc oxide film is deposited on the conductive film, and then placed in hydrogen sulfide or an oxygen-hydrogen sulfide mixture at 0-200°C for 1-500 hours to convert the zinc oxide into a ZnS micro-nano secondary array; 3) Using a solvothermal method to replace part of the zinc in the ZnS micro-nano secondary array with copper and tin, and then sulfiding the resulting product; specifically, preparing a triethylene glycol precursor solution containing copper and tin ions, and then placing the triethylene glycol precursor solution and the product of step 2) into a reactor, sealing the reactor and reacting at 10-200° C. for 0.5-50 hours; after the reaction is completed, placing the product in an H2S atmosphere and heating it at 400-500° C. for 0.1-50 hours.

2. The method for preparing the copper-zinc-tin-sulfur micro-nano secondary array structure according to claim 1, characterized in that: In step 1), the substrate is one of a metal sheet and conductive glass.

3. The method for preparing the copper-zinc-tin-sulfur micro-nano secondary array structure according to claim 1, characterized in that: In step 1), the conductive film is one of aluminum, copper, nano-indium tin metal oxide ITO, silver, and titanium, and the thickness of the conductive film is 20 nm-1 μm.

4. The method for preparing the copper-zinc-tin-sulfur micro-nano secondary array structure according to claim 1, characterized in that: In step 1) and step 2), the electrochemical deposition method is pulse electrochemical deposition, constant voltage electrochemical deposition or constant current electrochemical deposition.

5. The method for preparing the copper-zinc-tin-sulfur micro-nano secondary array structure according to claim 1, characterized in that: In step 2), the thickness of the zinc oxide film is 50 nm-50 μm.

6. The method for preparing the copper-zinc-tin-sulfur micro-nano secondary array structure according to claim 1, characterized in that: In step 2), the volume ratio of oxygen to hydrogen sulfide in the oxygen-hydrogen sulfide mixed gas is 1:0.01-100.

7. Application of the copper-zinc-tin-sulfur micro-nano secondary array structure prepared by the preparation method according to any one of claims 1 to 6 in the photovoltaic field.

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