Antimony sulfide photovoltaic device interface modification method

Abstract

The invention discloses an antimony sulfide photovoltaic device interface modification method, which is characterized in that an ultrathin zinc oxide (ZnO) seed crystal layer is rapidly prepared under a low-temperature condition through a magnetron sputtering process, and an interface between a conductive substrate and an antimony sulfide absorption layer is modified. The method has the advantages that 1) nucleation sites can be provided for the growth of antimony sulfide by utilizing an interface modification process, the problem of difficulty in uniform growth caused by lattice mismatch of the conductive substrate and the antimony sulfide material is solved, and the performance of a photovoltaic device is improved; (2) the zinc oxide seed crystal layer is prepared by utilizing a magnetron sputtering method, the advantages of high sputtering yield, high deposition speed, no need of annealing treatment and the like are achieved, seed crystal deposition can be completed within 1 minute, and (3) the zinc oxide interface layer is low in crystallization temperature, compatible with a low-temperature preparation process, high in light transmittance (gt and 90% in a visible light range), low in resistivity, rich in reserves and low in material cost.

Description

Technical Field

[0001] The present invention relates to a preparation technology of solar cells, specifically a method for modifying the interface of antimony sulfide photovoltaic devices, belonging to the field of solar energy technology. Background Art

[0002] Indoor photovoltaics, as a sustainable power supply solution for Internet of Things (IoT) terminal devices, has attracted much attention in recent years due to the exponential growth of IoT technology. Different from traditional outdoor photovoltaics, the spectrum of indoor light sources (such as LEDs) is concentrated in the range of 400 - 700 nm, and the intensity is only 0.1% - 1% of standard sunlight, which requires photovoltaic materials to have an ideal bandgap of 1.8 - 2.0 eV to achieve high conversion efficiency (Adv. Funct. Mater. 2021, 31(27): 2100265). Antimony sulfide (Sb 2 S 3 ) has become an ideal candidate material for indoor photovoltaics due to its bandgap of 1.7 - 1.8 eV, high absorption coefficient (>10 4 cm -1 ), and environmentally friendly characteristics. Its quasi-one-dimensional (Q1D) crystal structure and low melting point (about 550 °C) characteristics not only facilitate the directional transport of carriers but also support the preparation of low-temperature flexible devices. Currently, some studies have achieved a conversion efficiency of 17.55% under 1000 lux indoor light and successfully driven IoT sensors to work continuously (Light Sci Appl 13, 281 (2024)).

[0003] Close-Spaced Sublimation (CSS), as a mature thin-film deposition technology, has been successfully applied to the preparation of semiconductor materials such as CdTe and Sb 2 S 3 (IEEE J. Photovoltaics 2014, 4, 954). Compared with solution methods (such as spin coating and hydrothermal methods), the close-spaced sublimation method has the advantages of fast deposition rate, simple operation, and easy large-scale production. It is a thin-film preparation method suitable for large-scale production (Sol. RRL 2018, 2, 1800128), which can achieve large-area (>5 cm 2 ), dense and uniform thin-film deposition, and the all-vacuum process avoids the risk of pollution by toxic solvents. By precisely controlling the sublimation temperature of the source material (500 - 600 °C) and the substrate spacing, an Sb 2 S 3 absorption layer with excellent crystallization quality can be obtained.

[0004] In the preparation of antimony sulfide photovoltaic devices, the substrate type and surface properties have a great influence on the quality of the antimony sulfide absorption layer film. Since antimony sulfide belongs to the orthorhombic system (space group Pbnm), while conductive electrodes such as fluorine-doped tin oxide (FTO) have a tetragonal rutile structure (space group P4 2 / mnm), the difference in the crystal lattice constants of the two is significant, and the quality of the absorption layer film directly deposited on the conductive substrate is poor. The traditional process usually adds a buffer layer between the conductive electrode and the antimony sulfide absorption layer, such as cadmium sulfide (CdS) or titanium oxide (TiO 2 ) prepared by the solution method, which greatly increases the process complexity and manufacturing cost and is not conducive to large-scale production. Therefore, exploring a suitable process to modify the substrate / absorption layer interface is expected to improve the quality of the absorption layer film and even enhance the device performance.

[0005] To meet the continuously growing energy demand and the increasingly severe environmental pollution, many efforts have been made to find emerging photovoltaic technologies. However, the current mainstream solar cell preparation technologies still face problems such as pollution in the production process and expensive materials. There is an urgent need to find more environmentally friendly materials and more convenient processes to meet the continuous growth in the future new energy field. Summary of the Invention

[0006] The present invention aims at the pain points in the above-mentioned solar cell preparation technology and provides a method for modifying the interface of an antimony sulfide photovoltaic device. The present invention modifies the interface between the conductive substrate prepared by magnetron sputtering of a zinc oxide seed layer and the antimony sulfide absorption layer film prepared by close-spaced sublimation. This method has the advantages of high cell efficiency, environmental friendliness, convenient and time-saving process, and easy industrialization.

[0007] The method for modifying the interface of the antimony sulfide photovoltaic device of the present invention is to prepare a 10-20 nm ultra-thin zinc oxide seed layer between the conductive substrate and the antimony sulfide absorption layer through a magnetron sputtering process, providing nucleation sites for the growth of antimony sulfide and enabling the uniform growth of antimony sulfide to improve the performance of the photovoltaic device.

[0008] Specifically, it includes the following steps:

[0009] Step 1: Preparation of zinc oxide seed layer by magnetron sputtering

[0010] First, open the cavity of the vacuum coating machine, fix the conductive substrate on the substrate table with tape, then install the zinc oxide target and adjust its height so that the distance between the target and the substrate is 10 cm. Control of the magnetron sputtering vacuum: Turn on the power of the magnetron sputtering equipment, then turn on the mechanical pump switch and the foreline valve switch in sequence to start pumping vacuum. When the vacuum reaches 10 Pa, open the cut-off valve, then open the gas cylinder and the gas flow meter, and introduce argon at a small flow rate (5 sccm) to dredge the pipeline (10 - 15 seconds). When the vacuum is pumped to 5 Pa, turn on the molecular pump until it is pumped to 5×10 -3High vacuum. Introduce oxygen and argon (ratio 1:2), and adjust the working pressure to 1.3 Pa. Then turn on the RF power supply, set the sputtering power to 70 - 100 W, and the sputtering time to 30 - 60 seconds. After sputtering, turn off the molecular pump and mechanical pump in sequence. After the equipment stops completely, open the gas release valve and take out the substrate.

[0011] Step 2: Sintering of the antimony sulfide source plate powder compact

[0012] Use the lifting rod to raise the upper cover of the furnace chamber, take out the lower graphite plate of the near - space sublimation equipment, spread antimony sulfide powder on it and compact it with a quartz plate to obtain an antimony sulfide powder compact, and then put it back into the quartz furnace cavity; lower the lifting rod, open the vacuum pump to seal the cavity, and when the vacuum degree is less than 1 Pa, turn on the water cooler; set and start the sintering program: heat the lower graphite plate for 3 - 5 minutes through an infrared heat source to raise the temperature to 550 °C and keep it warm for 10 - 20 minutes to make the loose antimony sulfide powder compact fuse and become dense; after the program ends, wait for the water cooler to cool the cavity to room temperature.

[0013] Step 3: Preparation of antimony sulfide thin film by near - space sublimation method

[0014] Turn on the equipment power supply, place the conductive substrate with the conductive surface facing down in the upper graphite plate of the quartz furnace, then fix the upper graphite plate in the upper infrared heat source area. After fixing, use the lifting rod to close the furnace chamber, then close the intake valve, open the exhaust valve and turn on the vacuum pump to evacuate the quartz furnace chamber; when the vacuum degree is less than 1 Pa, turn on the water cooler, set the evaporation program required for deposition, and start the deposition of the thin film; after the program ends, use the water cooler to cool the equipment to room temperature, turn off the water cooler and the vacuum pump, open the intake valve, and take out the thin film when the furnace chamber pressure is the same as the atmospheric pressure.

[0015] Step 4: Preparation of metal electrodes

[0016] Place the sample prepared in Step 3 in a thermal evaporation device, evaporate the metal electrodes, with the evaporation current being 120 - 130 A, the evaporation voltage being 3 - 4 V, and the evaporation time being 5 - 10 minutes. Finally, the preparation of the antimony sulfide thin - film solar cell is completed.

[0017] In Step 1, the conductive substrate needs to be pretreated before use. Specifically, cut the conductive substrate according to the required size, and ultrasonically clean it with deionized water, acetone, and ethanol for 15 - 20 minutes in sequence. After cleaning, dry it with a nitrogen gas gun, and then treat it with an ultraviolet ozone cleaner for 20 - 30 minutes.

[0018] In Step 1, the conductive substrate is selected from FTO or ITO conductive substrates.

[0019] In Step 1, the oxygen - argon ratio is preferably 1:2.

[0020] In Step 1, during the deposition process, the power is preferably 70 - 100 W.

[0021] In Step 1, the sputtering time is preferably 30 - 60 seconds.

[0022] In Step 2, during the deposition, the constant temperature of the substrate is preferably 300 - 320 °C, the deposition temperature of the evaporation source is preferably 520 - 540 °C, and the deposition time is preferably 1 - 2 minutes.

[0023] In Step 3, when preparing the antimony sulfide source plate, 5 - 10 g of powder is placed, and the standard for compaction with a quartz plate is that the powder is evenly spread on the central area of the graphite plate without obvious gaps.

[0024] In Step 4, the metal electrode is an electrode such as gold, silver, or aluminum.

[0025] During the vacuum treatment and thin film sputtering process of the present invention, the water cooler is always in the open state. During the vacuum treatment and thin film deposition process of the present invention, the vacuum pump is always in the open state.

[0026] For the top - substrate - structured solar cell proposed by the present invention, its device structure from bottom to top is successively a conductive substrate / zinc oxide seed layer / antimony sulfide absorption layer / back electrode.

[0027] Compared with the existing technology, the innovation points and advantages of the present invention are mainly reflected in the following aspects:

[0028] (1) Interface modification to improve device performance: Using the interface modification process can provide nucleation sites for the growth of antimony sulfide, solve the problem of difficult uniform growth caused by the lattice mismatch between the conductive substrate and the antimony sulfide material, and achieve the improvement of the performance of photovoltaic devices.

[0029] (2) High - efficiency preparation technology: Using the magnetron sputtering method to prepare the zinc oxide seed layer has the advantages of high sputtering yield, fast deposition speed, and no need for annealing treatment, and the seed crystal deposition can be completed within 1 minute.

[0030] (3) Advantages of zinc oxide material: The zinc oxide interface layer has a low crystallization temperature, is compatible with low - temperature preparation processes, and at the same time has a high transmittance (>90% in the visible light range) and low resistivity, and is rich in reserves and low in material cost.

[0031] (4) Process compatibility: Different from the traditional solution method, this interface modification process has excellent convenience and can be vertically integrated with the vacuum processes (such as near - space sublimation) adopted by other functional layers of the device, facilitating large - scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a schematic diagram of the structure of the antimony sulfide thin - film solar cell of the present invention. From bottom to top, it is successively a conductive substrate, a zinc oxide seed layer, an antimony sulfide absorption layer, and a metal electrode.

[0033] Figure 2 It is a scanning electron microscope (SEM) photograph of the cross-section of a conductive substrate / zinc oxide seed layer / antimony sulfide absorption layer / gold film. The film is flat, dense, and the grain boundaries are clear. Among them, the zinc oxide seed layer adopts an optimized process, that is, sputtering for 40 seconds with a radio frequency power supply of 70 W.

[0034] Figure 3 The left is a scanning electron microscope (SEM) photograph of the surface of a conductive substrate without a zinc oxide seed layer, and the right is a scanning electron microscope (SEM) photograph of the surface of a conductive substrate with a zinc oxide seed layer. By comparing the two, similar surface morphologies can be seen, but the conductive substrate after the growth of the zinc oxide seed is rougher.

[0035] Figure 4 It is an X-ray diffraction (XRD) spectrogram of the magnetron sputtered zinc oxide seed layer. It can be seen from the figure that compared with the stronger diffraction peaks of the conductive substrate, the zinc oxide seed layer is extremely thin and only weak diffraction signals can be detected.

[0036] Figure 5 The left is a scanning electron microscope (SEM) photograph of the surface of an antimony sulfide absorption layer without a modified interface of a zinc oxide seed layer, and the right is a scanning electron microscope (SEM) photograph of the surface of an antimony sulfide absorption layer with a modified interface of a zinc oxide seed layer. By comparing the two, a huge difference in surface morphology can be seen. The surface of the antimony sulfide absorption layer after the modified interface is denser, the pores are significantly reduced, and the grain size is larger.

[0037] Figure 6 It is the photocurrent density-voltage (J-V) curve of a zinc oxide seed layer interface-modified antimony sulfide solar cell under one sun (AM1.5G, 100 mW / cm 2 ) irradiation, and the device efficiency can reach 3.06%.

[0038] Figure 7 It is the photocurrent density-voltage (J-V) curve of a zinc oxide seed layer interface-modified antimony sulfide solar cell under 1000 lux irradiation, and the device efficiency can reach 8.57%. Specific embodiments

[0039] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0040] Example 1: Comparison of device performance with and without a zinc oxide seed layer

[0041] 1. Cleaning of the Conductive Substrate

[0042] Cut the FTO substrate to the required size, and ultrasonically clean it with deionized water, acetone, and ethanol for 15 minutes in sequence. After cleaning, dry the glass with a nitrogen gas gun, and further treat it with an ultraviolet ozone cleaner for 20 minutes, then take it out for standby.

[0043] 2. Preparation of the Zinc Oxide Seed Layer

[0044] Deposit a zinc oxide thin film by magnetron sputtering. Fix the cleaned FTO substrate in step one on the rotating disk, and fix the titanium target in the cavity of the magnetron sputtering coating machine. Adjust the height of the target so that the distance between the target and the substrate is 10 cm, and then close the lid. Conduct vacuum treatment on the cavity of the magnetron sputtering coating machine. When the vacuum degree is 5×10 -3 Pa, introduce oxygen and argon in a ratio of 1:2 to adjust the air pressure to 1.3 Pa, turn on the radio frequency power supply, adjust the voltage and current buttons to a power of 70 W, and sputter for 40 seconds. After sputtering, turn off the molecular pump and mechanical pump in sequence, open the air release valve, and take out the substrate when the air pressure in the sputtering cavity is the same as the atmospheric pressure; the control group does not go through this step.

[0045] 3. Sintering of the Antimony Sulfide Source Plate Powder Green Body

[0046] Raise the upper cover of the furnace chamber with the lifting rod, take out the lower graphite plate in the near-space sublimation equipment, spread 15 g of antimony sulfide powder on it and compact it with a quartz plate to obtain an antimony sulfide powder green body, and then put it back into the quartz furnace chamber; lower the lifting rod, open the vacuum pump to seal the cavity, and when the vacuum degree is less than 1 Pa, turn on the water cooler; set and start the sintering program: heat the lower graphite plate for 3 minutes through an infrared heat source to raise the temperature to 550 °C and keep it warm for 10 minutes to make the loose antimony sulfide powder green body fuse and become dense; after the program ends, wait for the water cooler to cool the cavity to room temperature.

[0047] 4. Preparation of the Antimony Sulfide Absorption Layer

[0048] Prepare the antimony sulfide absorption layer using the above-mentioned near-space sublimation equipment. Place the thin film prepared in step 2 in the upper graphite plate, put the lower graphite plate on which the antimony sulfide powder green body sintering is completed in step 3 back into the quartz furnace chamber, and adjust the distance between the upper and lower graphite plates through the lifting rod. Close the intake valve, evacuate with a vacuum pump for 15 minutes, and then start the deposition of the thin film. Turn on the water cooler, set the evaporation program required for deposition, and start the deposition of the thin film. The evaporation process is as follows: heat the upper and lower layers of graphite to 300 °C in 2 minutes and keep it warm for 15 minutes to make the source and the substrate heat evenly; then, raise the source temperature to 540 °C in 60 seconds while keeping the substrate temperature unchanged, and deposit for 1.5 minutes until the program ends. After the program ends, use the water cooler to cool the equipment to room temperature, turn off the water cooler and the vacuum pump, open the intake valve, and take out the substrate when the air pressure in the furnace chamber is the same as the atmospheric pressure.

[0049] 5. Preparation of metal electrodes: Place the sample obtained in Step 4 in a thermal evaporation device, deposit a metal gold electrode, and finally complete the preparation of a large-area antimony sulfide thin-film solar cell.

[0050]

[0051] As can be seen from Table 1, after modifying the interface between the zinc oxide seed layer and the conductive substrate / antimony sulfide absorption layer, the device performance has been significantly improved.

[0052] Example 2: Optimization of the sputtering time of the zinc oxide seed layer

[0053] 1. Cleaning of the conductive substrate

[0054] Cut the FTO substrate to the required size, and ultrasonically clean it with deionized water, acetone, and ethanol for 15 minutes in sequence. After cleaning, dry the glass with a nitrogen air gun, and further treat it with an ultraviolet ozone cleaner for 20 minutes, then take it out for standby.

[0055] 2. Preparation of the zinc oxide seed layer

[0056] Deposit the zinc oxide seed layer by magnetron sputtering. Fix the cleaned FTO substrate in Step 1 on the rotating disk, fix the titanium target in the cavity of the magnetron sputtering coating machine, adjust the height of the target so that the distance between the target and the substrate is 10 cm, and close the lid. Vacuum-treat the cavity of the magnetron sputtering coating machine. When the vacuum degree is 5×10 -3 Pa, introduce oxygen and argon in a ratio of 1:2 to adjust the air pressure to 1.3 Pa, turn on the radio frequency power supply, adjust the voltage and current buttons to a power of 70 W, and sputter for 30 - 60 seconds. After sputtering, turn off the molecular pump and mechanical pump in sequence, open the air release valve, and take out the substrate when the air pressure in the sputtering cavity is the same as the atmospheric pressure.

[0057] 3. Sintering of the antimony sulfide source plate powder compact

[0058] Use the lifting rod to raise the upper cover of the furnace chamber, take out the lower graphite plate of the near-space sublimation equipment, spread 15 g of antimony sulfide powder on it and compact it with a quartz plate to obtain an antimony sulfide powder compact, and then put it back into the quartz furnace chamber; lower the lifting rod, open the vacuum pump to seal the cavity, and when the vacuum degree is less than 1 Pa, turn on the water cooler; set and start the sintering program: heat the lower graphite plate for 3 minutes through an infrared heat source to raise the temperature to 550 °C and keep it warm for 10 minutes to fuse and densify the loose antimony sulfide powder compact; after the program ends, wait for the water cooler to cool the cavity to room temperature.

[0059] 4. Preparation of the antimony sulfide absorption layer

[0060] The antimony sulfide absorption layer is prepared using the above-mentioned near-space sublimation equipment. Place the film obtained in Step 2 in the upper graphite plate, and put the lower graphite plate on which the antimony sulfide powder green body was sintered in Step 3 back into the quartz furnace cavity. Adjust the distance between the upper and lower graphite plates through the lifting rod. Close the intake valve, evacuate the air using a vacuum pump for 15 minutes, and then start the deposition of the film. Turn on the water cooler, set the evaporation program required for deposition, and start depositing the film. The evaporation process is as follows: Heat the upper and lower layers of graphite to 300 °C within 2 minutes and keep it at this temperature for 15 minutes to ensure uniform heating of the source and the substrate; then, raise the source temperature to 540 °C within 60 seconds while keeping the substrate temperature unchanged, and deposit for 1.5 minutes. When the program ends, use the water cooler to cool the equipment to room temperature, turn off the water cooler and the vacuum pump, open the intake valve, and take out the film when the furnace pressure is the same as the atmospheric pressure.

[0061] 5. Preparation of the metal electrode: Place the sample obtained in Step 4 in a thermal evaporation device, deposit the metal gold electrode, and finally complete the preparation of the large-area antimony sulfide thin-film solar cell.

[0062]

[0063] As can be seen from Table 2, the sputtering time has a great influence on the device performance when preparing the zinc oxide seed layer. The device performance is the best when the sputtering time of the zinc oxide seed layer is 40 seconds.

[0064] Example 3: Optimization of the argon-oxygen ratio for sputtering the zinc oxide seed layer

[0065] 1. Cleaning of the conductive substrate

[0066] Cut the FTO substrate to the required size, and ultrasonically clean it with deionized water, acetone, and ethanol for 15 minutes in sequence. After cleaning, dry the glass with a nitrogen air gun, and further treat it with an ultraviolet ozone cleaner for 20 minutes, then take it out for standby.

[0067] 2. Preparation of the zinc oxide seed layer

[0068] Deposit the zinc oxide thin film using the magnetron sputtering method. Fix the cleaned FTO substrate in Step 1 on the rotating disk, and fix the titanium target in the cavity of the magnetron sputtering coating machine. Adjust the height of the target so that the distance between the target and the substrate is 10 cm, and then close the lid. Conduct vacuum treatment on the cavity of the magnetron sputtering coating machine. When the vacuum degree is 5×10 -3 Pa, introduce oxygen and argon in a ratio of 1:10 - 1:2 to adjust the air pressure to 1.3 Pa, turn on the radio frequency power supply, adjust the voltage and current buttons to a power of 70 W, and sputter for 40 seconds. After sputtering is completed, turn off the molecular pump and the mechanical pump in sequence, open the air release valve, and take out the substrate when the sputtering cavity pressure is the same as the atmospheric pressure.

[0069] 3. Sintering of the antimony sulfide source plate powder green body

[0070] Raise the furnace top cover using the lifting rod, take out the lower graphite plate of the near-space sublimation equipment, spread 15 g of antimony sulfide powder evenly on it, and compact it with a quartz plate to obtain an antimony sulfide powder green body. Then, put it back into the quartz furnace cavity; lower the lifting rod, close the vacuum pump to seal the cavity, and turn on the water cooler when the vacuum degree is less than 1 Pa; set and start the sintering program: heat the lower graphite plate for 3 minutes through an infrared heat source to raise the temperature to 550 °C and keep it warm for 10 minutes to fuse and densify the loose antimony sulfide powder green body; after the program ends, wait for the water cooler to cool the cavity to room temperature. The control group only spreads 15 g of antimony sulfide powder on the lower graphite plate and compacts it with a quartz plate for standby.

[0071] 4. Preparation of the antimony sulfide absorption layer

[0072] Prepare the antimony sulfide absorption layer using the above-mentioned near-space sublimation equipment. Place the film prepared in Step 2 in the upper graphite plate, put the lower graphite plate that has completed the sintering of the antimony sulfide powder green body in Step 3 back into the quartz furnace cavity, and adjust the distance between the upper and lower graphite plates through the lifting rod. Close the intake valve, evacuate the vacuum for 15 minutes using the vacuum pump, and then start the film deposition. Turn on the water cooler, set the evaporation program required for deposition, and start the film deposition. The evaporation process is as follows: heat the upper and lower graphite plates to 300 °C within 2 minutes and keep them warm for 15 minutes to make the source and the substrate heat evenly; then, raise the source temperature to 540 °C in 60 seconds while keeping the substrate temperature unchanged, and deposit for 1.5 minutes until the program ends. After the program ends, use the water cooler to cool the equipment to room temperature, turn off the water cooler and the vacuum pump, open the intake valve, and take out the film when the furnace pressure is the same as the atmospheric pressure.

[0073] 5. Preparation of the metal electrode: Place the sample prepared in Step 4 in a thermal evaporation device, evaporate the metal gold electrode, and finally complete the preparation of the large-area antimony sulfide thin-film solar cell.

[0074]

[0075] As can be seen from Table 3, the atmosphere has a great influence on the device performance when preparing the zinc oxide seed layer. Increasing the oxygen ratio, when the argon-oxygen ratio is 1:2, the device performance is the best.

Claims

1. A method for modifying the interface of an antimony sulfide photovoltaic device, characterized in that: A 10-20nm ultra-thin zinc oxide seed layer is prepared between the conductive substrate and the antimony sulfide absorption layer through a magnetron sputtering process to provide nucleation sites for the growth of antimony sulfide, allowing antimony sulfide to grow uniformly, thereby improving the performance of photovoltaic devices.

2. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 1, characterized in that: The device structure of the antimony sulfide photovoltaic device is, from bottom to top, a conductive substrate, a zinc oxide seed crystal layer, an antimony sulfide absorption layer, and a back electrode.

3. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 2, characterized in that The zinc oxide seed crystal layer is prepared by a method comprising the following steps: The conductive substrate is fixed on the substrate table, and then the zinc oxide target is installed and the height is adjusted, the vacuum degree of magnetron sputtering is controlled, and then a mixed gas of oxygen and argon is introduced, and magnetron sputtering is performed under the working gas pressure to prepare a zinc oxide seed crystal layer on the conductive substrate.

4. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 3, characterized in that: The distance between the target and the substrate is 10 cm.

5. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 3, characterized in that: The conductive substrate is selected from FTO or ITO conductive substrate.

6. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 3, characterized in that: The volume ratio of oxygen to argon is 1:10-1:2, and the working gas pressure is 1.3 Pa.

7. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 6, characterized in that: The volume ratio of oxygen to argon is 1:

2.

8. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 3, characterized in that: The sputtering power was 70-100 W and the sputtering time was 30-60 seconds.

9. The method for modifying the interface of antimony sulfide photovoltaic devices according to claim 8, characterized in that: The sputtering power was 70 W and the sputtering time was 40 seconds.

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