Manufacturing method of wide-spectrum collaborative complementary thin film solar cell

Abstract

The invention relates to the technical field of solar cells, and discloses a manufacturing method of a wide-spectrum collaborative complementary thin film solar cell, and the manufacturing method comprises the following steps: S1, preparing a substrate and an electron transport layer, selecting conductive glass as the substrate, and preparing a TiO2 electron transport layer by using a chemical bath deposition technology; the Sb2S3 inorganic film and the copper sulfide are used as the light absorption layer, the materials are rich in reserves on the earth and free of toxicity, so that the material cost is relatively low, the thickness of the light absorption layer film is smaller than 2 micrometers, the material consumption is small, the material cost is further reduced, a simple preparation process is adopted, the preparation cost is relatively low, and the light absorption layer is suitable for large-scale production. Through the stacked light absorption layers, the light absorption edge is widened to 900nm, so that a spectrum in a wider range can be absorbed, the utilization rate of sunlight is improved, the transmission path of electrons is optimized, the loss of the electrons in the transmission process is reduced, and the energy conversion efficiency is improved.

Description

Technical Field

[0001] The invention relates to the technical field of solar cells, in particular to a method for manufacturing a wide-spectrum cooperative complementary thin-film solar cell. Background Art

[0002] Solar cells, also known as solar cells or solar chips, are photoelectric semiconductor sheets that use sunlight to directly generate electricity. Solar cells are semiconductor components that can effectively absorb solar energy and convert it into electrical energy. They use the photovoltaic effect, that is, when sunlight shines on semiconductor materials, photons excite electrons in the semiconductor, thereby generating electric current.

[0003] Currently, most solar cells are monocrystalline silicon and polycrystalline silicon solar cells. The production of monocrystalline silicon and polycrystalline silicon solar cells requires thicker silicon materials, generally greater than 200 microns, which not only increases the amount of material used, but also increases the production cost. Due to the indirect bandgap semiconductor characteristics of silicon materials, a certain thickness is required to absorb solar energy, resulting in a large waste of silicon raw materials. The purification and production process of silicon materials requires a large amount of energy, which increases the overall energy consumption of solar cells. The material purity requirements of silicon solar cells are very high, generally required to reach 99.999% or more. Tiny impurities may affect the performance and efficiency of solar cells. This high purity requirement further increases production costs and energy consumption. Monocrystalline silicon and polycrystalline silicon solar cells are not easy to carry out large-area flexible processing due to the limitations of material properties and production processes. Summary of the invention

[0004] The object of the present invention is to provide a method for manufacturing a wide-spectrum cooperative complementary thin-film solar cell to solve the problems raised in the above-mentioned background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: a method for manufacturing a wide spectrum cooperative complementary thin film solar cell, the manufacturing method comprising the following steps:

[0006] S1. Prepare substrate and electron transport layer, select conductive glass as substrate and use chemical bath deposition technology to prepare TiO 2 Electron transport layer;

[0007] S2. Prepare the light absorption layer on TiO 2 A layer of Sb is deposited on the 2 S 3 Thin film, in Sb 2 S 3 A copper sulfide light absorption layer is superimposed on the film by spin coating;

[0008] S3, for Sb 2 S 3The film is doped to improve its conductivity and optoelectronic properties using ion implantation doping techniques, and then a layer of counter electrode material is deposited on the light absorbing layer;

[0009] S4. Assemble the prepared substrate, electron transport layer, light absorption layer and modification layer components to form a complete solar cell structure, and perform performance tests on the packaged solar cells.

[0010] Preferably, in step S1, TiO is prepared 2 The steps of the electron transport layer are:

[0011] S1.1, prepare a plating solution containing titanium ions, adjust the pH value of the plating solution by adding acid or alkali, and heat the plating solution to 300℃-450℃;

[0012] S1.2, TiO will need to be deposited 2 The substrate is cleaned and dried to ensure that its surface is clean, free of impurities and has good adhesion;

[0013] S1.3, immerse the treated substrate in the plating solution and keep it for a period of time, hydrolysis and oxidation reactions occur on the substrate surface to generate TiO 2 and deposited on a substrate;

[0014] S1.4. After the deposition is completed, the substrate is taken out from the plating solution, cleaned and dried, and then the substrate is annealed.

[0015] Preferably, in step S1, TiO 2 After the electron transport layer is prepared, the TiO 2 The electron transport layer is modified by dissolving the deposited material in a solvent and adjusting the pH value, concentration and temperature of the solution. 2 The electron transport layer is immersed in the deposition solution, and the deposited material is deposited on the TiO 2 A uniform coating is formed on the surface of the electron transport layer.

[0016] Preferably, the steps of preparing the Sb2S3 thin film in step S2 are:

[0017] S2.1. Prepare Piranha solution with concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, mix well and set aside, ultrasonically clean the substrate in acetone, anhydrous ethanol and deionized water for 10 minutes respectively, blow dry with nitrogen and immerse in Piranha solution for 5 to 50 minutes, rinse the activated substrate with a large amount of deionized water to ensure that the pH of the substrate surface is 7;

[0018] S2.2, the raw materials for preparing the thin film precursor solution are sodium thiosulfate and antimony trichloride. The substrate activated by the Piranha solution is vertically immersed in the prepared thin film precursor solution and deposited at 30°C for 6 to 8 hours;

[0019] S2.3. After that, the deposits on the surface of the substrate are carefully rinsed with deionized water and dried in air. The substrate with the deposits is heat treated at 200°C and 400°C for 1 h respectively to complete the preparation of the Sb2S3 film.

[0020] Preferably, in step S2, the thickness of the light absorbing layer is controlled to be equal to that of Sb 2 S 3 The film forms a good complementary light absorption effect, which broadens the light absorption edge to 850nm-950nm.

[0021] Preferably, the steps of the doping operation in step S3 are:

[0022] S3.1. Select a boron ion dopant, generate the desired doping ions through an ionization process in an ion implantation device, and accelerate the generated doping ions to 20 kiloelectron volts to 400 kiloelectron volts;

[0023] S3.2, through the focusing and scanning system, the accelerated ion beam is accurately irradiated to Sb 2 S 3 On the surface of the film, an accelerated ion beam of doping ions is irradiated in a vacuum system. 2 S 3 film, thereby forming an injected layer with special properties in the selected area;

[0024] S3.3, during the ion implantation process, the temperature of the film is controlled, and annealing is performed after ion implantation to restore its lattice integrity. 2 S 3 The film is subjected to performance testing and the doping operation is completed.

[0025] Preferably, in step S3, the electrode material is deposited by electrolytic deposition, the light absorbing layer is placed in a deposition device, the deposition process is started, and the transparent conductive oxide is deposited on the light absorbing layer.

[0026] Preferably, the performance test in step S4 includes open circuit voltage, short circuit current, fill factor and energy conversion efficiency, and each step and parameter in the preparation process is optimized and adjusted according to the performance test results and process conditions.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention adopts Sb 2 S 3Inorganic thin films and copper sulfide are used as light absorption layers. These materials are abundant on the earth and are non-toxic, so the material cost is relatively low. The thickness of the light absorption layer film is less than 2μm, and the material consumption is small, which further reduces the material cost. In addition, a simple preparation process is adopted, and the preparation cost is also relatively low. By superimposing light absorption layers, the light absorption edge is widened to 900nm, so that a wider range of spectrum can be absorbed, which improves the utilization rate of sunlight, optimizes the transmission path of electrons, reduces the loss of electrons during transmission, and thus improves the energy conversion efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The present invention is a flow chart of the method. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Embodiment 1:

[0032] A method for manufacturing a wide spectrum cooperative complementary thin film solar cell, the manufacturing method comprising the following steps:

[0033] S1. Prepare substrate and electron transport layer, select conductive glass as substrate and use chemical bath deposition technology to prepare TiO 2 The electron transport layer, TiO 2 After the electron transport layer is prepared, the TiO 2 The electron transport layer is modified by dissolving the deposited material in a solvent and adjusting the pH value, concentration and temperature of the solution. 2 The electron transport layer is immersed in the deposition solution, and the deposited material is deposited on the TiO 2 A uniform coating is formed on the surface of the electron transport layer;

[0034] S2. Prepare the light absorption layer on TiO 2 A layer of Sb is deposited on the 2 S 3 Thin film, in Sb 2 S 3 A copper sulfide light absorption layer is superimposed on the film by spin coating, and the thickness of the light absorption layer is controlled to make it consistent with Sb 2 S 3 The film forms a good complementary light absorption effect, which broadens the light absorption edge to 850nm-950nm;

[0035] S3, for Sb 2 S 3 The film is doped to improve its conductivity and photoelectric properties by using ion implantation doping technology, and then a layer of counter electrode material is deposited on the light absorbing layer. The counter electrode material is deposited by electrolytic deposition. The light absorbing layer is placed in a deposition device, and the deposition process is started to deposit the transparent conductive oxide on the light absorbing layer.

[0036] S4. Assemble the prepared substrate, electron transport layer, light absorption layer and modification layer components to form a complete solar cell structure, and perform performance tests on the packaged solar cells. The performance tests include open circuit voltage, short circuit current, fill factor and energy conversion efficiency. According to the performance test results and process conditions, optimize and adjust each step and parameter in the preparation process.

[0037] Embodiment 2:

[0038] A method for manufacturing a wide spectrum cooperative complementary thin film solar cell, the manufacturing method comprising the following steps:

[0039] S1. Prepare substrate and electron transport layer, select conductive glass as substrate and use chemical bath deposition technology to prepare TiO 2 The electron transport layer, TiO 2 After the electron transport layer is prepared, the TiO 2 The electron transport layer is modified by dissolving the deposited material in a solvent and adjusting the pH value, concentration and temperature of the solution. 2 The electron transport layer is immersed in the deposition solution, and the deposited material is deposited on the TiO 2 A uniform coating is formed on the surface of the electron transport layer to prepare TiO 2 The steps of the electron transport layer are:

[0040] S1.1, prepare a plating solution containing titanium ions, adjust the pH value of the plating solution by adding acid or alkali, and heat the plating solution to 300℃-450℃;

[0041] S1.2, TiO will need to be deposited 2 The substrate is cleaned and dried to ensure that its surface is clean, free of impurities and has good adhesion;

[0042] S1.3, immerse the treated substrate in the plating solution and keep it for a period of time, hydrolysis and oxidation reactions occur on the substrate surface to generate TiO 2 and deposited on a substrate;

[0043] S1.4, after the deposition is completed, the substrate is taken out from the plating solution, cleaned and dried, and then the substrate is annealed;

[0044] S2. Prepare the light absorption layer on TiO 2 A layer of Sb is deposited on the 2 S 3 Thin film, in Sb 2 S 3 A copper sulfide light absorption layer is superimposed on the film by spin coating, and the thickness of the light absorption layer is controlled to make it consistent with Sb 2 S 3 The film forms a good complementary light absorption effect, which broadens the light absorption edge to 850nm-950nm. The steps for preparing the Sb2S3 film are as follows:

[0045] S2.1. Prepare Piranha solution with concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, mix well and set aside, ultrasonically clean the substrate in acetone, anhydrous ethanol and deionized water for 10 minutes respectively, blow dry with nitrogen and immerse in Piranha solution for 5 to 50 minutes, rinse the activated substrate with a large amount of deionized water to ensure that the pH of the substrate surface is 7;

[0046] S2.2, the raw materials for preparing the thin film precursor solution are sodium thiosulfate and antimony trichloride. The substrate activated by the Piranha solution is vertically immersed in the prepared thin film precursor solution and deposited at 30°C for 6 to 8 hours;

[0047] S2.3, then carefully rinse the deposits on the substrate surface with deionized water, dry in air, and heat treat the substrate with deposits at 200°C and 400°C for 1h respectively to complete the preparation of Sb2S3 thin film;

[0048] S3, for Sb 2 S 3 The film is doped to improve its conductivity and photoelectric properties. Ion implantation doping technology is used, and then a layer of counter electrode material is deposited on the light absorbing layer. The deposition of the counter electrode material adopts electrolytic deposition. The light absorbing layer is placed in the deposition equipment, and the deposition process is started to deposit the transparent conductive oxide on the light absorbing layer. The steps of the doping operation are:

[0049] S3.1. Select a boron ion dopant, generate the desired doping ions through an ionization process in an ion implantation device, and accelerate the generated doping ions to 20 kiloelectron volts to 400 kiloelectron volts;

[0050] S3.2, through the focusing and scanning system, the accelerated ion beam is accurately irradiated to Sb 2 S 3 On the surface of the film, an accelerated ion beam of doping ions is irradiated in a vacuum system. 2 S 3 film, thereby forming an injected layer with special properties in the selected area;

[0051] S3.3, during the ion implantation process, the temperature of the film is controlled, and annealing is performed after ion implantation to restore its lattice integrity. 2 S 3 The film is tested for performance and the doping operation is completed;

[0052] S4. Assemble the prepared substrate, electron transport layer, light absorption layer and modification layer components to form a complete solar cell structure, and perform performance tests on the packaged solar cells. The performance tests include open circuit voltage, short circuit current, fill factor and energy conversion efficiency. According to the performance test results and process conditions, optimize and adjust each step and parameter in the preparation process.

[0053] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0054] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for manufacturing a wide spectrum cooperative complementary thin film solar cell, characterized in that: The manufacturing method comprises the following steps: S1. Prepare a substrate and an electron transport layer, select conductive glass as the substrate and use chemical bath deposition technology to prepare a TiO2 electron transport layer; S2, preparing a light absorption layer, depositing a Sb2S3 film on the TiO2 layer, and superimposing a copper sulfide light absorption layer on the Sb2S3 film by spin coating; S3, doping the Sb2S3 film to improve its conductivity and photoelectric properties, using ion implantation doping technology, and then depositing a layer of counter electrode material on the light absorbing layer; S4. Assemble the prepared substrate, electron transport layer, light absorption layer and modification layer components to form a complete solar cell structure, and perform performance tests on the packaged solar cells.

2. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: The steps of preparing the TiO2 electron transport layer in step S1 are: S1.1, prepare a plating solution containing titanium ions, adjust the pH value of the plating solution by adding acid or alkali, and heat the plating solution to 300℃-450℃; S1.

2. Clean and dry the substrate on which TiO2 is to be deposited to ensure that its surface is clean, free of impurities, and has good adhesion; S1.3, immersing the treated substrate in the plating solution and keeping it for a period of time, hydrolysis and oxidation reactions occur on the substrate surface, TiO2 is generated and deposited on the substrate; S1.

4. After the deposition is completed, the substrate is taken out from the plating solution, cleaned and dried, and then the substrate is annealed.

3. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: In the step S1, after the TiO2 electron transport layer is prepared, the TiO2 electron transport layer is modified, the deposition material is dissolved in a solvent, and the pH value, concentration and temperature of the solution are adjusted, the TiO2 electron transport layer is immersed in the deposition solution, and the deposition material forms a uniform coating on the surface of the TiO2 electron transport layer through a chemical reaction.

4. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: The steps of preparing the Sb2S3 film in step S2 are: S2.

1. Prepare Piranha solution with concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3, mix well and set aside, ultrasonically clean the substrate in acetone, anhydrous ethanol and deionized water for 10 minutes respectively, blow dry with nitrogen and immerse in Piranha solution for 5 to 50 minutes, rinse the activated substrate with a large amount of deionized water to ensure that the pH of the substrate surface is 7; S2.2, the raw materials for preparing the thin film precursor solution are sodium thiosulfate and antimony trichloride. The substrate activated by the Piranha solution is vertically immersed in the prepared thin film precursor solution and deposited at 30°C for 6 to 8 hours; S2.

3. After that, the deposits on the surface of the substrate are carefully rinsed with deionized water and dried in air. The substrate with the deposits is heat treated at 200°C and 400°C for 1 h respectively to complete the preparation of the Sb2S3 film.

5. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: In step S2, the thickness of the light absorption layer is controlled so that it forms a good light absorption complementary effect with the Sb2S3 film, and the light absorption edge is widened to 850nm-950nm.

6. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: The steps of the doping operation in step S3 are: S3.

1. Select a boron ion dopant, generate the desired doping ions through an ionization process in an ion implantation device, and accelerate the generated doping ions to 20 kiloelectron volts to 400 kiloelectron volts; S3.2, through the focusing and scanning system, the accelerated ion beam is accurately irradiated onto the surface of the Sb2S3 film. In the vacuum system, the Sb2S3 film is irradiated with the ion beam of the accelerated doped ions, thereby forming an implantation layer with special properties in the selected area; S3.

3. During the ion implantation process, the temperature of the film is controlled. After ion implantation, annealing is performed to restore its lattice integrity. The performance of the doped Sb2S3 film is tested to complete the doping operation.

7. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: In the step S3, the electrode material is deposited by electrolytic deposition, the light absorbing layer is placed in a deposition device, the deposition process is started, and the transparent conductive oxide is deposited on the light absorbing layer.

8. The method for manufacturing a wide spectrum cooperative complementary thin film solar cell according to claim 1, characterized in that: The performance test in step S4 includes open circuit voltage, short circuit current, fill factor and energy conversion efficiency. According to the performance test results and process conditions, each step and parameter in the preparation process is optimized and adjusted.

Images