Monocrystal perovskite absorption layer surface morphology customization method and application

Abstract

The invention discloses a method for customizing the surface morphology of a single-crystal perovskite absorption layer, and belongs to the technical field of single-crystal perovskite solar cells. Comprising the following steps: S1, placing a perovskite single crystal in a regulating agent atmosphere, and standing to soften a surface absorption layer of the perovskite single crystal to form a softened layer; and S2, pressing the softened layer by using a template with a surface microstructure to form a target surface appearance. According to the method, the surface morphology of the perovskite single crystal can be directionally changed by customizing the template, for example, by customizing a semicircular template, the specific surface area of the absorption layer can be increased, the formed semicircular structure is a good hydrophobic structure, and the waterproof effect is more prominent after a waterproof layer is smeared. The method can be applied to redox catalysts, perovskite solar cells, radiation detection and the like.

Description

Technical Field

[0001] The present application relates to a method and application for customizing the surface morphology of a single crystal perovskite absorption layer, and belongs to the technical field of single crystal perovskite solar cells. Background Art

[0002] my country's annual output of petrochemical energy cannot meet its own development needs, so it needs to import a large amount of petrochemical energy from abroad. However, the turbulent foreign situation in recent years has made the development model of relying on imports to meet its own needs no longer applicable to my country's national conditions. Therefore, by developing new energy industries such as the photovoltaic industry, my country can effectively reduce its dependence on external energy and ensure national energy security. Among them, the most promising photovoltaic material at present, perovskite material, perfectly makes up for the shortcomings of low efficiency and high cost of silicon materials. Among perovskite materials, single crystals of perovskite have the advantages of ultra-long carrier diffusion length and no grain boundaries. Directed changes in the surface morphology of perovskite single crystals can increase the light absorption area per unit area, thereby improving the photoelectric conversion efficiency of perovskite solar cells. Summary of the invention

[0003] In order to solve the problems in the prior art of controlling the surface morphology of perovskite single crystals, such as complex process, high cost, difficulty in customizing the morphology, and difficulty in material recycling, the present application provides a method for customizing the surface morphology of a single crystal perovskite absorber layer, which uses a specific volatile atmosphere to soften the surface of the perovskite single crystal, and then uses a template with a customizable morphology to press the surface of the single crystal perovskite absorber layer to form a specific surface morphology structure and pattern.

[0004] This application adopts the following technical solutions:

[0005] According to one aspect of the present application, a method for customizing the surface morphology of a single crystal perovskite absorption layer is provided, comprising the following steps:

[0006] S1. placing the perovskite single crystal in a regulating agent atmosphere and allowing it to stand, so that the surface absorption layer of the perovskite single crystal softens to form a softened layer;

[0007] S2. Use a template with a surface microstructure to press the softened layer to form a target surface morphology.

[0008] Perovskite single crystal absorbs light of different wavelengths, and the penetration ability of light of different wavelengths is different. The depth to which light can penetrate perovskite is also different. The maximum depth that light can penetrate perovskite is the perovskite absorption layer, that is, the technical solution of this application softens the thickness range of light penetration on the surface of perovskite single crystal by regulating the atmosphere of the agent.

[0009] The technical solution of the present application aims to soften the perovskite single crystal first and then use different templates to suppress specific surface morphology structures and patterns to achieve different performance effects. For example, the waterproof layer is directly spin-coated on the perovskite single crystal that is afraid of water erosion, and its waterproof effect is not very good. Because the morphology structure of the surface of the perovskite single crystal is not an ideal hydrophobic structure, this will cause small water droplets to stay on the surface of the perovskite single crystal more easily. Long-term accumulation of moisture will reduce the efficiency of single-crystal perovskite devices. In severe cases, water droplets will erode the waterproof layer into the perovskite single crystal, causing the device to fail. The technical solution of the present application can make the perovskite single crystal have a stronger hydrophobic structure and increase the contact area of ​​the catalyst. It can also increase the light absorption area of ​​the single crystal perovskite to achieve the effect of improving the photoelectric conversion efficiency of solar cells. In addition, many catalysts increase the contact area by grinding. This will make the recovery of the catalyst difficult. Now the contact area of ​​the catalyst can be easily increased by the method of the present application to achieve a better catalytic effect.

[0010] Optionally, in step S1, the regulator atmosphere is formed by volatilizing an alcohol-water mixture containing the regulator;

[0011] The regulating agent is selected from at least one of methylamine and ethanol.

[0012] Optionally, the alcohol-water mixture containing the regulating agent is obtained by mixing the regulating agent aqueous solution and alcohol in a volume ratio of 1:1.0 to 1.5;

[0013] Wherein, the concentration of the regulating agent aqueous solution is 25.0-30.0 wt%.

[0014] Optionally, the static method includes placing the perovskite single crystal 1 to 2.5 cm above the liquid surface of the alcohol-water mixture containing the regulating agent.

[0015] Optionally, in step S1, the standing time is 30 to 40 seconds.

[0016] Optionally, in step S2, the pressing time is 4 to 10 minutes.

[0017] Optionally, in step S2, before pressing, it also includes spraying oil on the template to form an oil film.

[0018] Optionally, in step S2, before pressing, the template is further subjected to ultrasonic cleaning in a water and / or alcohol solution and dried.

[0019] According to another aspect of the present application, there is provided an application of the above-mentioned method for customizing the surface morphology of a single crystal perovskite absorption layer in the field of catalysts, the field of perovskite solar cells, and the field of radiation detection.

[0020] Optionally, the application includes: obtaining a papillary structure or a semicircular structure on the surface of a single crystal perovskite absorption layer by the method to improve hydrophobicity; or, obtaining a wavy structure or a micro-pit structure to increase the light absorption area.

[0021] The surface morphology structure prepared by the application method can produce different effects depending on the structure. For example, by designing a papillary structure or a semicircular structure, the perovskite single crystal can have a stronger waterproof effect, and by designing a wavy structure or a micro-pit structure, the contact area of ​​the catalyst and the light absorption area of ​​the single crystal perovskite solar cell can be increased, thereby improving the catalytic efficiency and the photoelectric conversion efficiency.

[0022] The beneficial effects of this application include:

[0023] The method for customizing the surface morphology of a single crystal perovskite absorption layer provided in the present application has the characteristics of simple operation, low price, high success rate, etc. Different morphology control and customization effects can be achieved by simply softening the perovskite single crystal and then using different templates to press specific surface morphology structures and patterns. In application, the preparation of different morphologies that are easy to carry out according to application needs can produce different effects. The hydrophobicity of the surface of the perovskite single crystal can be adjusted by the surface morphology to avoid the influence of water accumulation on the efficiency of the perovskite device. The specific surface area can also be increased by adjusting the surface morphology, so that it can achieve better adsorption effect when used as a catalyst or achieve a larger absorption area as a solar cell absorption material to improve the conversion efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A preparation process flow chart tailored for the surface morphology of the perovskite single crystal in this application;

[0025] Figure 2 A diagram of a template used in the present application and a perovskite single crystal pressed using the template, wherein (a) is a perovskite single crystal, (b) a softened perovskite single crystal, (c) a pressed perovskite single crystal, and (d) a pressed perovskite single crystal;

[0026] Figure 3 This is a SEM image of a perovskite single crystal with a surface microstructure formed in the present application. DETAILED DESCRIPTION

[0027] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0028] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0029] Unless otherwise specified, conventional methods were used for testing and instrument settings were those recommended by the manufacturer.

[0030] According to one embodiment of the present application, a method for customizing the surface morphology of a single crystal perovskite absorption layer includes the following steps: mixing ethanol and methylamine aqueous solution in a beaker, and then placing the perovskite single crystal one centimeter above the prepared solution, and letting it stand for about thirty seconds. At this time, the surface of the perovskite single crystal will form a state between solid and liquid, and the customized template will be ultrasonically cleaned with water, and then the side of the template with the customized structure will be pressed on the surface absorption layer of the perovskite single crystal, so that the absorption layer surface of the perovskite single crystal will produce a special structure. This method can change the surface morphology of the perovskite single crystal in a direction by customizing the template. For example, by customizing the semicircular template, not only can the specific surface area of ​​the absorption layer be increased, but the semicircular structure formed is a good hydrophobic structure, which will make the waterproof effect more prominent after applying the waterproof layer. This method can be applied to redox catalysts, perovskite solar cells, radiation detection, etc.

[0031] According to one implementation of the present application, Figure 1 As shown, the method for customizing the surface morphology of the single crystal perovskite absorption layer specifically includes the following steps:

[0032] Step S1, mixing ethanol and methylamine aqueous solution in a beaker;

[0033] Step S2, placing the perovskite single crystal on the solution prepared in step S1 and keeping it still for a period of time;

[0034] Step S3, ultrasonically cleaning the customized template with water or ethanol;

[0035] Step S4, placing the cleaned template into a vacuum drying oven;

[0036] Step S5, spraying an oil film on the cleaned template surface for easy demoulding (this step can be omitted);

[0037] Step S6: Press the side of the template with the customized structure onto the surface absorption layer of the perovskite single crystal at room temperature to produce a special customized structure on the surface of the absorption layer of the perovskite single crystal.

[0038] According to one embodiment of the present application, in step S1, the mixed solution of ethanol and methylamine aqueous solution is mixed in a volume ratio of 1:1.

[0039] According to one embodiment of the present application, in step S1, the mass concentration of the methylamine aqueous solution is 25.0-30.0%, and the mass concentration of ethanol is 99.9%.

[0040] According to one embodiment of the present application, in step S2, the distance between the solution and the crystal is 1-2.5 cm.

[0041] According to an implementation of the present application, in step S2, the static time is 30-45 seconds.

[0042] According to one embodiment of the present application, in step S3, the customized template is ultrasonically cleaned with water or ethanol for about 1 hour.

[0043] According to one embodiment of the present application, in step S4, the cleaned template is placed in a vacuum drying oven at 65° C. and dried for 30-50 minutes.

[0044] According to an embodiment of the present application, in step S6, the side of the template with the customized structure is pressed onto the surface absorption layer of the perovskite single crystal at room temperature for about 4-10 minutes.

[0045] Through the above method of the present application, those skilled in the art can design a pattern or morphology structure that meets the requirements on the surface of the perovskite single crystal according to the needs.

[0046] Example 1

[0047] Mix 15 ml of ethanol (99.99%) and 15 ml of methylamine aqueous solution (25 wt%) in a 50 ml beaker to prepare a regulating agent;

[0048] The perovskite single crystal is placed 1 cm above the solution prepared in step S1 and kept still for 30 seconds. At this time, the surface of the perovskite single crystal will form a state between solid and liquid, that is, the surface absorption layer of the perovskite single crystal softens to form a softened layer in the volatile atmosphere of the regulating agent;

[0049] The customized template was ultrasonically cleaned in a mixture of ultrapure water and ethanol for 1 h;

[0050] Place the cleaned template in a vacuum drying oven at 65°C and dry for 30 minutes;

[0051] At room temperature, the side of the template with the customized surface microstructure is pressed onto the surface absorption layer of the perovskite single crystal for 5 minutes to produce a special customized structure on the surface of the absorption layer of the perovskite single crystal, thus completing the morphology customization of the perovskite single crystal.

[0052] The surface changes of the perovskite single crystal in this embodiment are as follows Figure 2 As shown, Figure 2 The perovskite surface shown in (a) has no microstructure before treatment and is smooth. After the perovskite single crystal is treated with a regulator, its surface is Figure 2 (b) is softened (transparent orange part), as shown in Figure 2 (c) shows that the softened perovskite single crystal is placed on a template with a structured side, as shown in FIG. Figure 2 As shown in (d), the surface with microstructure formed by pressing is rough. The SEM image of the perovskite single crystal with surface microstructure is as follows: Figure 3As shown (the scale of the left picture is 200μm, the scale of the right picture is 1μm)

[0053] Example 2

[0054] Ethanol (99.99%) and methylamine aqueous solution (25 wt %) were mixed in a beaker at a volume ratio of 1:1 to prepare a regulating agent;

[0055] The perovskite single crystal is placed 1.5 cm above the solution prepared in step S1 and kept still for 30 seconds. At this time, the surface of the perovskite single crystal will form a state between solid and liquid, that is, the surface absorption layer of the perovskite single crystal softens to form a softened layer in the volatile atmosphere of the regulator;

[0056] The customized template was ultrasonically cleaned in a mixture of water and ethanol for 1 h;

[0057] Place the cleaned template in a vacuum drying oven at 65°C and dry for 30 minutes;

[0058] In order to facilitate demoulding, spray a mineral oil film on the cleaned template surface;

[0059] At room temperature, the side of the template with the customized structure is pressed onto the surface absorption layer of the perovskite single crystal, so that a special customized structure is produced on the surface of the absorption layer of the perovskite single crystal, thus completing the morphology customization of the perovskite single crystal.

[0060] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for customizing the surface morphology of a single crystal perovskite absorption layer, characterized in that: The steps include: S1. placing the perovskite single crystal in a regulating agent atmosphere and allowing it to stand, so that the surface absorption layer of the perovskite single crystal softens to form a softened layer; S2. Use a template with a surface microstructure to press the softened layer to form a target surface morphology.

2. The method according to claim 1, characterized in that In step S1, the regulator atmosphere is formed by volatilizing an alcohol-water mixture containing the regulator; The regulating agent is selected from at least one of methylamine and ethanol.

3. The method according to claim 2, characterized in that The alcohol-water mixed solution containing the regulating agent is obtained by mixing the regulating agent aqueous solution and alcohol in a volume ratio of 1:1.0-1.5; Wherein, the concentration of the regulating agent aqueous solution is 25.0-30.0 wt%.

4. The method according to claim 2, characterized in that: The static placing method includes placing the perovskite single crystal 1 to 2.5 cm above the liquid surface of the alcohol-water mixed liquid containing the regulating agent.

5. The method according to claim 1, characterized in that In step S1, the standing time is 30 to 40 seconds.

6. The method according to claim 1, characterized in that In step S2, the pressing time is 4 to 10 minutes.

7. The method according to claim 1, characterized in that In step S2, before pressing, it also includes spraying oil on the template to form an oil film.

8. The method according to claim 1, characterized in that In step S2, before pressing, the template is placed in a water and / or alcohol solution for ultrasonic cleaning and drying.

9. Application of the method for customizing the surface morphology of a single crystal perovskite absorption layer according to any one of claims 1 to 8 in the fields of catalysts, perovskite solar cells, and radiation detection.

10. The method according to claim 9, characterized in that The application includes: obtaining a papillary structure or a semicircular structure on the surface of a single crystal perovskite absorption layer by the method to improve hydrophobicity; or obtaining a wavy structure or a micro-pit structure to increase the light absorption area.

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