Preparation method of BaZrS3 film
BaZrS3 thin films were prepared by spin coating and high-temperature sulfidation, solving the problem of high preparation cost and obtaining thin films with high crystallinity and high light absorption performance, which promotes the commercial application of optoelectronic devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-05
- Publication Date
- 2026-03-10
AI Technical Summary
The high cost of preparing BaZrS3 thin films limits the large-scale commercial application of optoelectronic devices, and existing methods are insufficient to obtain thin films with high crystallinity and high light absorption performance.
BaZrO3 films were prepared by spin coating, and then BaZrS3 films were obtained by high-temperature curing in an H2S atmosphere. The specific steps included dissolving a mixed solution of barium acetate and zirconium acetate hydroxide, spin coating it onto a substrate, annealing it, and then heating and curing it in an H2S atmosphere. The temperature and gas composition were controlled to obtain high-quality films.
We have achieved low-cost, large-scale preparation of BaZrS3 thin films with high crystallinity and high light absorption performance, which are suitable for applications such as PEC photoanodes, solar cells, and photoelectric detection.
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Figure CN121629445A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of photoelectric thin film materials, and particularly relates to a preparation of a photoelectrochemical catalytic water splitting photoanode thin film material. BACKGROUND
[0002] Photoelectrochemical (PEC) water splitting is considered as a solution for clean and sustainable hydrogen production, which can alleviate the diurnal and intermittent limitations of solar and wind energy and large-scale consumption problems, and convert solar or wind energy into clean, low-carbon and storable hydrogen energy. In order to drive PEC water splitting, photo-generated electrons and holes are guided to the solid-liquid interface of p-type photoelectrode or n-type photoelectrode, respectively, where electrocatalytic reactions are carried out. The preparation of high-efficiency photoelectrode or photoanode material is the key to improve the performance of PEC devices.
[0003] Organic-inorganic halide lead perovskite has a power conversion efficiency of more than 25%, but faces the problems of instability and toxicity. Although metal sulfide perovskite was first reported in the 1980s, in recent years, it has been proposed as a potential solar energy conversion material. Through high-throughput screening calculation, it is found that sulfide perovskite has potential in stability, suitable band gap (1.3-2.0eV), small carrier effective mass (0.2-0.3me) and strong optical absorption (>10 5 cm -1 ) and can be used as a photoelectric conversion material. In addition, the theoretical maximum photoelectric conversion efficiency of sulfide perovskite solar cell has been predicted to be about 30%.
[0004] Among all sulfide perovskites, BaZrS3 as an n-type semiconductor is the most studied compound so far. According to theoretical and experimental reports, it has a suitable band gap of 1.7-2.0eV, a very high absorption coefficient (>10 5 cm −1 ) near the band edge and quite good charge transport properties with a mobility of 13.7cm 2 V −1 s −1This indicates that it can be a good candidate for PEC photoanodes. Most of the data published so far on the synthesis of BaZrS3 is about bulk materials (i.e. powders) and only a few studies have focused on the preparation of BaZrS3 thin films and their application in photovoltaic devices. Wei et al. reported the first example of BaZrS3 thin films in 2020 (Realization of BaZrS3 chalcogenide perovskite thin films for optoelectronics. Nano Energy 2020, 68, 104317.), they deposited BaZrO3 thin films using pulsed laser deposition (PLD) and then sulphurized at temperatures around 1000℃ using CS2. But due to the expensive large equipment, the cost of thin film preparation is high, which affects the large-scale commercial preparation of the photoelectric device. In the present invention, a preparation method of BaZrS3 thin film photoanode is disclosed, which is simple, low in cost and can be prepared on a large scale. The obtained BaZrS3 thin film has good crystallinity, good light absorption performance and high photoelectric conversion efficiency, and is a photoelectric conversion material with great potential, which can not only be applied to PEC photoanodes, but also be applied to solar cells, photoelectric detection and other fields. SUMMARY
[0005] The present application provides a preparation method of BaZrS3 thin film, characterized in that: firstly, a BaZrO3 thin film is prepared by spin coating method, and then the BaZrS3 thin film is obtained by high-temperature sulphurization under H2S atmosphere. The present application adopts the following technical scheme, comprising the following steps: (1) Dissolve ultrapure barium acetate and zirconium acetate hydroxide in a mixture of acetic acid, 2-methoxyethanol and deionized water at 50℃ under stirring to form a transparent solution; (2) Spin-coat the precursor solution in step 1 on the substrate substrate multiple times to achieve the desired film thickness; (3) Anneal the thin film obtained in step 2 in a muffle furnace under air atmosphere for 2 hours to obtain a BaZrO3 perovskite phase; (4) Put the BaZrO3 precursor thin film in step 3 into a quartz boat in the middle of a quartz tube furnace, and heat the furnace to the target temperature at a rate of 5℃ / min. During the heating process, when the furnace temperature rises to 600℃, introduce H2S-containing Ar mixed gas into the tube furnace. Keep the furnace at the target temperature for 2 hours, then stop heating and let the furnace cool naturally. When the furnace cools to 600℃, stop the supply of H2S, and purge the furnace tube with Ar or N2 until the furnace cools to room temperature, to obtain a BaZrS3 thin film grown on the substrate.
[0006] In the above preparation method, in the step (1), the molar ratio of barium acetate and zirconium acetate hydroxide is 1:1; In the above preparation method, in the step (1), the concentration of barium acetate in the solution is 0.5-1.0 mmol / ml; In the above preparation method, in the step (1), the volume ratio of acetic acid, 2-methoxyethanol and deionized water is 2:3:1; In the above preparation method, in the step (2), the spin coating condition is 3000 rpm for 30 seconds; In the above preparation method, in the step (2), the substrate can be selected from one of quartz and silicon; In the above preparation method, in the step (2), the sample is annealed at 200℃ for 2 minutes on a hot plate after each spin coating to evaporate the excess solvent; In the above preparation method, in the step (3), the annealing temperature of the thin film in the muffle furnace is 300-600℃; In the above preparation method, in the step (4), the target temperature for sulfidation of the BaZrO3 precursor is 900-1200℃; In the above preparation method, in the step (4), the volume fraction of H2S in the mixed gas is 10%-30%; In the above preparation method, in the step (4), the flow rate of H2S / Ar mixed gas is 15-50 sccm. BRIEF DESCRIPTION OF DRAWINGS
[0007] Figure 1 XRD patterns of BaZrS3 thin films obtained at different heating temperatures; Figure 2 SEM pattern of BaZrS3. DETAILED DESCRIPTION
[0008] In order to further understand the present application, the preferred embodiments of the present application are described below in conjunction with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present application, and are not limitations to the claims of the present application. EXAMPLE
[0009] A clear solution precursor was formed by stirring and dissolving 0.1709 g of barium acetate and 0.158 g of zirconium acetate hydroxide in a mixture of 1 mL of acetic acid, 1.5 mL of 2-methoxyethanol, and 0.5 mL of deionized water at 50 °C. The precursor solution was dropped 30 μΐ^on a clean quartz substrate (1.8 cm x 2.0 cm) and spun at 3000 rpm for 30 seconds. The quartz substrate was ultrasonically cleaned in acetone and ethanol for 30 minutes each, then dried with nitrogen, and finally cleaned with 02 plasma for 30 minutes. After each spin-coating step, the sample was annealed on a hot plate at 200 °C for 2 minutes to evaporate the excess solvent. This cycle was repeated 5 times to achieve the desired film thickness. Finally, the sample was annealed in air at 550 °C for 2 h in a muffle furnace to obtain the perovskite phase of BaZr03. The BaZr03thin film on quartz was placed in a quartz boat in a tube furnace. The quartz tube was evacuated and purged with argon or nitrogen three times to eliminate air contaminants. The furnace was then heated to 1100 °C at a rate of 5 °C / min. When the temperature reached 600 °C, 20 seem of Ar mixed gas containing 20% H2S was introduced into the tube, and the furnace was kept at 1100 °C for 2 hours, then the heating was stopped and the furnace was allowed to cool naturally. When the furnace cooled to 600 °C, the supply of H2S was stopped, and the tube was purged with Ar until the furnace cooled to room temperature. Example
[0010] A clear solution precursor was formed by stirring and dissolving 0.1709 g of barium acetate and 0.158 g of zirconium acetate hydroxide in a mixture of 1 mL of acetic acid, 1.5 mL of 2-methoxyethanol, and 0.5 mL of deionized water at 50 °C. The precursor solution was dropped 30 μΐ^on a clean quartz substrate (1.8 cm x 2.0 cm) and spun at 3000 rpm for 30 seconds. The quartz substrate was ultrasonically cleaned in acetone and ethanol for 30 minutes each, then dried with nitrogen, and finally cleaned with 02 plasma for 30 minutes. After each spin-coating step, the sample was annealed on a hot plate at 200 °C for 2 minutes to evaporate the excess solvent. This cycle was repeated 5 times to achieve the desired film thickness. Finally, the sample was annealed in air at 550 °C for 2 h in a muffle furnace to obtain the perovskite phase of BaZr03. The BaZr03thin film on quartz was placed in a quartz boat in a tube furnace. The quartz tube was evacuated and purged with argon or nitrogen three times to eliminate air contaminants. The furnace was then heated to 1100 °C at a rate of 5 °C / min. When the temperature reached 600 °C, 20 seem of Ar mixed gas containing 20% H2S was introduced into the tube, and the furnace was kept at 1100 °C for 2 hours, then the heating was stopped and the furnace was allowed to cool naturally. When the furnace cooled to 600 °C, the supply of H2S was stopped, and the tube was purged with Ar until the furnace cooled to room temperature.
[0011] The above description of the embodiments is only for the purpose of helping understand the method of the present application and its core idea. It should be noted that, for those skilled in the art, some improvements and modifications can be made to the present application without departing from the principles of the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application. The above description of the disclosed embodiments enables those skilled in the art to implement or use the present application. Various modifications to the embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method for producing a BaZrS3 thin film, characterized by, First, BaZrO3 thin film is prepared by spin coating method, then BaZrS3 thin film is obtained by high-temperature sulfuration under H2S atmosphere, and the application adopts the following technical scheme and comprises the following steps: (1) Ba acetate and Zr acetate hydroxide are stirred and dissolved in a mixture of acetic acid, 2-methoxyethanol and deionized water at 50 DEG C to form a transparent solution; (2) the precursor solution in step 1 is spin-coated on a substrate substrate multiple times to achieve the required film thickness; (3) the film obtained in step 2 is annealed in a muffle furnace under air atmosphere for 2 hours to obtain BaZrO3 perovskite phase; (4) the BaZrO3 precursor film in step 3 is placed in a quartz boat in the middle of a quartz tube furnace, the furnace is heated to the target temperature at a rate of 5 DEG C / min, during the heating process, when the furnace temperature rises to 600 DEG C, H2S-containing Ar mixed gas is introduced into the tube furnace, the furnace is kept at the target temperature for 2 hours, then the heating is stopped, and the furnace is naturally cooled, when the furnace is cooled to 600 DEG C, the supply of H2S is stopped, and the furnace tube is purged with Ar or N2 until the furnace is cooled to room temperature, and BaZrS3 thin film grown on the substrate is obtained.
2. In the above preparation method, the molar ratio of Ba acetate and Zr acetate hydroxide is 1:1; the concentration of Ba acetate in the solution is 0.5-1.0 mmol / ml; the volume ratio of acetic acid, 2-methoxyethanol and deionized water is 2:3:1; the spin coating condition is 3000 rpm for 30 seconds; the substrate substrate can be selected from one of quartz sheet and silicon sheet; the sample needs to be annealed at 200 DEG C for 2 minutes on a hot plate after each spin coating; multiple spin coating is performed to achieve the desired film thickness; the film is annealed in a muffle furnace at a temperature of 300-600 DEG C; the target temperature of BaZrO3 precursor sulfuration is 900-1200 DEG C; the volume fraction of H2S in the mixed gas is 10%-30%; the flow rate of H2S / Ar mixed gas is 15-50 sccm.