CN116065301A

CN116065301A - Perovskite polymer fiber film and preparation method thereof

Info

Publication number: CN116065301A
Application number: CN202211679851.4A
Authority: CN
Inventors: 汪国平; 张振宇; 陈滢; 孙燕明
Original assignee: Shenzhen University
Current assignee: Shenzhen University
Priority date: 2022-12-26
Filing date: 2022-12-26
Publication date: 2023-05-05

Abstract

The application relates to the technical field of perovskite semiconductor materials, and provides a preparation method of a perovskite polymer fiber film, which comprises the following steps: preparing a perovskite precursor solution; adding a polymer into the perovskite precursor solution to obtain an electrostatic spinning solution; carrying out electrostatic spinning on the electrostatic spinning solution on a receiving substrate to obtain an initial perovskite polymer fiber film; the initial perovskite polymer fiber film is etched by laser to form a perovskite polymer fiber film with a specific pattern. The perovskite crystal can be embedded on the microscale polymer fiber by adopting the electrostatic spinning process, the coating structure can improve the luminous waterproofness of the perovskite fluorescent film, strong electrostatic adsorption capacity exists between microscale perovskite polymer fibers obtained by electrostatic spinning, excellent self-adhesion capacity is given to the surface of the fiber film, and the laser etching technology is adopted for patterning the fiber film, so that the operation stability is greatly improved.

Description

Perovskite polymer fiber film and preparation method thereof

Technical Field

The application belongs to the technical field of perovskite semiconductor materials, and particularly relates to a perovskite polymer fiber film and a preparation method thereof.

Background

Metal halide perovskite is a novel semiconductor material with unique optical and optoelectronic properties. The novel crystal has the advantages of low cost of raw materials, low temperature liquid phase synthesis, adjustable transition band gap, high defect tolerance, high exciton binding energy and the like, and brings great interest to researchers in multiple fields of materials science, chemistry, physics and the like, and the research hot trend of the novel crystal in the fields of Light Emitting Diodes (LEDs) and novel photoelectric display devices thereof is raised.

In recent years, many researchers have improved the stability of metal-halogen perovskite in the environment based on chemical regulation methods, but most of currently existing light-emitting devices are exposed to humid environments, even when exposed to aqueous media, the metal-halogen perovskite will lose its original chemical structural integrity, and excellent device performance will be degraded therewith. Overall, earlier studies report that the current relatively advanced technology is to form a layered quasi-two-dimensional lattice structure in a three-dimensional cubic perovskite by adopting different hydrophobic organic macromolecules to be intercalated, so that the performance of the perovskite is ensured as much as possible, and meanwhile, the moisture resistance of the perovskite crystal is improved, but the ending of the perovskite crystal which is completely decomposed by water vapor in the long-term use process is still difficult to fundamentally change. The very previous international research reports that the perovskite quantum dots are wrapped in the organic microspheres, so that the perovskite quantum dots are stable in an aqueous medium, and unfortunately, the fluorescence intensity of the perovskite quantum dots prepared by the technology is reduced to 60% of the original fluorescence intensity after 20 days in the aqueous medium, and the luminous performance is seriously weakened by the erosion of water molecules. Therefore, a need exists for new inventive techniques to realize commercial applications of perovskite light emitting display devices in aqueous media.

In addition, another impediment to limited commercial use of perovskite-based luminescence displays is poor flexibility and harsh fabrication substrates, most of the current experimental processes are based on a variety of rigid planar substrates, hardly bendable folding, and difficult to uniformly fabricate over large areas by spin-coating techniques, resulting in very limited practical application outside the laboratory. The current report on the front edge of the flexible perovskite film preparation field is mainly based on the growth of perovskite crystals on organic flexible substrates, and although the perovskite crystals can provide certain flexibility, the perovskite crystals grown on the substrates have poor wettability, are easy to separate from the substrates to form island crystal grains instead of continuous films, seriously weaken the stable storage property and the luminous performance of the films, and limit the competitiveness of the films in commercial application. Meanwhile, the perovskite-based display device depending on the substrate is prepared through multi-step procedures, the preparation process is complex, the packaging structure is relatively heavy, the perovskite-based display device cannot be adhered and taken down at any time and any place when being used for luminous display on the wall surfaces made of different materials, and the installation and the disassembly processes of the display device are still complicated in practical life application, so that a novel technology of a flexible perovskite fluorescent film which is simple in synthetic method and has no substrate and can be adhered and taken at any time is required.

At present, technologies such as ink-jet printing, spraying technology, three-dimensional laser lithography and the like are often adopted to realize the color patternability of the perovskite polymer composite material. Although they exhibit good stability and processability in the laboratory, they are severely substrate dependent, cannot be used as stand alone patterned displays, and liquid phase spray processes also require subsequent curing. These techniques are also disadvantageous in terms of multi-color module stitching and lightweight displays, and thus there is a need to develop new and economical processes to overcome these drawbacks.

Based on the method, the preparation method of the flexible substrate-free patternable perovskite fluorescent film with stable aqueous medium environment is very important, and the method is also an urgent need for solving the problem that the current lead halogen perovskite material is applied to the field of luminous display in a large-scale commercial way.

Disclosure of Invention

The invention aims to provide a perovskite polymer fiber film and a preparation method thereof, and aims to solve the problems that the perovskite fluorescent film is poor in waterproofness and insufficient in flexibility, and multicolor module splicing and light display are difficult to realize.

In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:

in a first aspect, the present application provides a method for preparing a perovskite polymer fiber film, comprising the steps of:

Preparing a perovskite precursor solution;

adding a polymer into the perovskite precursor solution to obtain an electrostatic spinning solution;

carrying out electrostatic spinning on the electrostatic spinning solution on a receiving substrate to obtain an initial perovskite polymer fiber film;

the initial perovskite polymer fiber film is etched by laser to form a perovskite polymer fiber film with a specific pattern.

In a second aspect, the present application provides a perovskite polymer fiber film, prepared by the method for preparing the perovskite polymer fiber film provided in the first aspect.

According to the preparation method of the perovskite polymer fiber film, firstly, an electrostatic spinning process is adopted to embed perovskite crystals on micro-scale polymer fibers, and the perovskite polymer fiber film is formed by spinning and stacking, and the perovskite micro-scale cladding structure can completely isolate the embedded perovskite crystals from external water environment in physical space, so that the luminous waterproofness of the perovskite fluorescent film is improved, and the permanent luminous waterproofness can be almost realized. The micro-scale perovskite-polymer fibers obtained by electrostatic spinning have strong electrostatic adsorption capability, and can be aggregated into an integral independent film by a plurality of layers of superimposed microfibers, so that the perovskite polymer fiber film surface can be endowed with excellent self-adhesion capability, the perovskite polymer fiber film can be self-adhered to the surface of any material, the application scene of the fiber film is greatly widened, and the mechanical operation of adhesion at any time can be performed. In addition, the initial perovskite polymer fiber film is subjected to patterning treatment by adopting a laser etching technology, the perovskite polymer fiber film can be melted and resolidified after laser scanning under the action of thermal ablation, the perovskite polymer fiber film is separated from the original film, and lamellar fibers at the edge of the pattern can be sewn into a whole in the curing process, so that the mechanical operation stability of the pattern is greatly improved.

The perovskite polymer fiber film provided by the second aspect of the application is prepared by the preparation method provided by the first aspect, and the preparation method can effectively prepare the perovskite polymer fiber film which has the advantages of luminescence and water resistance, self adhesion, flexibility and modularized pattern treatment, endows the prepared fiber film with stable luminescence and water resistance in a severe water environment, can be applied to multi-scene self adhesion luminescence patterning display, and is beneficial to the wide application of perovskite materials in the luminescence display field.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is an SEM image of a perovskite polymer fiber film provided by an embodiment of the present application;

FIG. 2 is a graph of a test of the water repellency of a perovskite polymer fiber film provided by an embodiment of the application;

FIG. 3 is a flexible crimp graph of a perovskite polymer fiber film provided by an embodiment of the application;

FIG. 4 is a graph of a flexible curl test of perovskite polymer fiber films provided by embodiments of the invention;

FIG. 5 is an application scenario diagram of a perovskite polymer fiber film provided by an embodiment of the invention;

FIG. 6 is a comparison of manual cropping and laser etching provided by an embodiment of the present invention;

FIG. 7 is a laser etched pattern of a perovskite polymer fiber film provided by an embodiment of the invention.

Detailed Description

In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.

In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.

It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.

The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.

The term "PMMA" is an abbreviation for polymethyl methacrylate and the term "DMF" is an abbreviation for N, N-dimethylformamide.

In a first aspect, an embodiment of the present application provides a method for preparing a perovskite polymer fiber film, including the following steps:

s1, preparing perovskite precursor solution;

s2, adding a polymer into the perovskite precursor solution to obtain an electrostatic spinning solution;

s3, carrying out electrostatic spinning on the electrostatic spinning solution on a receiving substrate to obtain an initial perovskite polymer fiber film;

s4, forming the perovskite polymer fiber film with a specific pattern by laser etching the initial perovskite polymer fiber film.

According to the preparation method of the perovskite polymer fiber film, firstly, an electrostatic spinning process is adopted to embed perovskite crystals on micro-scale polymer fibers, and the perovskite polymer fiber film is formed by spinning and stacking, and the perovskite micro-scale cladding structure can completely isolate the embedded perovskite crystals from external water environment in physical space, so that the luminous waterproofness of the perovskite fluorescent film is improved, and the permanent luminous waterproofness can be almost realized. The micro-scale perovskite-polymer fibers obtained by electrostatic spinning have strong electrostatic adsorption capability, and can be aggregated into an integral independent film by a plurality of layers of superimposed microfibers, so that the perovskite polymer fiber film surface can be endowed with excellent self-adhesion capability, the perovskite polymer fiber film can be self-adhered to the surface of any material, the application scene of the fiber film is greatly widened, and the mechanical operation of adhesion at any time can be performed. In addition, the initial perovskite polymer fiber film is subjected to patterning treatment by adopting a laser etching technology, the perovskite polymer fiber film is melted and resolidified after laser scanning under the action of thermal ablation, the perovskite polymer fiber film is separated from the original film, and the layered fiber layer is stitched into a whole at the edge of the pattern again in the resolidification process, so that the mechanical operation stability of the pattern is greatly improved.

In some embodiments, in step S1, the perovskite precursor solution includes an organic solvent and a perovskite precursor, the concentration of the perovskite precursor being from 1mg/ml to 100mg/ml. According to the perovskite precursor solution, the content of perovskite in a fiber film formed by subsequent electrostatic spinning can be influenced, and then the waterproof property or the flexibility of the prepared fiber film is influenced. Preferably, the concentration of perovskite precursor is 1mg/ml to 50mg/ml. Specifically, the concentration of perovskite precursor may be typical but non-limiting values of 1mg/ml, 5mg/ml, 10mg/ml, 15mg/ml, 20mg/ml, 30mg/ml, 40mg/ml, 50mg/ml, 100mg/ml, etc.

In some embodiments, the perovskite precursor includes a molar ratio of lead halide to organic ammonium halide of 0.9 to 1.1:1. In particular, organic ammonium halides include, but are not limited to, CH ₃ NH ₃ Cl、CH ₃ NH ₃ Br、CH ₃ NH ₃ I、CH ₂ (NH ₃ ) ₂ Cl、CH ₂ (NH ₃ ) ₂ Br and CH ₂ (NH ₃ ) ₂ At least one of I. In the embodiment of the application, the organic ammonium halide and lead halide can form APbX with the chemical formula of APbX by a solution method in an organic solvent ₃ Wherein A comprises CH ₃ NH ₃ And CH (CH) ₂ (NH ₃ ) ₂ X comprises at least one halogen of chlorine, bromine and iodine. The method ensures that the lead halide and the organic ammonium halide can fully react and the synthesized calcium is obtained by controlling the proportion range of the lead halide and the organic ammonium halideThe titanium ore crystal is fully dissolved in the organic solvent, and the precursor solution is ensured not to be separated out of the perovskite crystal at normal temperature (about 25 ℃).

In some embodiments, the organic solvent is at least one of N, N-dimethylformamide and 1, 4-butyrolactone. The organic solvent has better solubility to lead halide and organic ammonium halide, and can ensure that the lead halide and the organic ammonium halide can smoothly react to obtain perovskite crystals with high purity.

In some embodiments, in step S2, the polymer is at least one of polymethyl methacrylate, polyvinylidene fluoride, polyurethane, polystyrene, and polyvinylpyrrolidone. The polymer not only can coat perovskite crystals, the formed microscale coating structure can completely isolate the perovskite crystals from external water environment in physical space, and the fiber film is endowed with permanent luminous waterproof performance, but also has strong electrostatic adsorption capability between microscale perovskite polymer fibers formed by electrostatic spinning, and can agglomerate a plurality of layers of stacked microfibers into an integral independent film, and endow the fiber film with excellent self-adhesion capability.

In some embodiments, in step S2, the concentration of polymer in the electrospinning solution is 50mg/ml to 100mg/ml. The concentration of the polymer in the electrostatic spinning solution can influence the film forming property and flexibility of the fiber film formed by the subsequent electrostatic spinning, the concentration range of the polymer can ensure that the polymer can form a film smoothly in the electrostatic spinning process, a large number of bead particles are prevented, and excellent flexibility and self-adhesion capability can be endowed to the fiber film. In particular, the concentration of the polymer may be, but is not limited to, typical values of 50mg/ml, 60mg/ml, 70mg/ml, 80mg/ml, 90mg/ml, 100mg/ml, etc.

In some embodiments, in step S3, the electrospinning solution is electrospun onto a receiving substrate to obtain an initial perovskite polymer fiber film. Specifically, the electrostatic spinning solution is extracted by the injector, and the injector is required to discharge redundant air when the electrostatic spinning solution is extracted, so that uneven spraying in the electrostatic spinning process is avoided. Then selecting a syringe needle with proper inner diameter, connecting the needle with positive voltage, connecting a roller collector of a spinning machine with negative voltage, applying voltage between a receiver and the needle, pushing the syringe by the spinning machine, spraying spinning solution from the needle, volatilizing organic solvent in a space, and obtaining the perovskite polymer fiber film at the collector. According to the embodiment of the application, through controlling and optimizing the voltage of electrostatic spinning, the spinning distance (the distance between the syringe needle and the roller receiver), the flow rate of the electrostatic spinning solution and the spinning temperature, the ultra-long microscale perovskite polymer fiber can be formed into a film framework through repeated superposition, so that the perovskite polymer fiber film can be manufactured in a high-efficiency repeated large-area manner and is endowed with excellent flexibility and skin touchability. In addition, the spinning technology is not limited to the traditional hard plane substrate, so that the perovskite photoelectric device can adapt to more complex conditions, such as a curved substrate, a special display pattern, even a suspended scene and the like. Other conditions may be realized by modifying the drum collector to an appropriately curved surface.

In some embodiments, the voltage of the electrospinning is 8kV to 20kV. The syringe needle is connected with positive voltage, the roller collector of the spinning machine is connected with negative voltage, and the voltage difference between the two is the spinning voltage. The method controls the spinning voltage to be 8 kV-20 kV, ensures that the electrostatic spinning solution is smoothly sprayed in the electrostatic spinning process, and if the voltage is too high, the polymer is easy to have insufficient time to perform regular winding arrangement due to the fact that the spraying speed of the electrostatic spinning solution is too high and the spraying duration (namely the time from the spraying of the solution from the syringe needle to the arrival of the solution at the roller collector) is reduced, so that the spinning is unstable and uniform fibers are difficult to obtain; if the voltage is too low, the electrostatic spinning solution is not sprayed out, and the fiber film cannot be prepared. In particular, the voltage of the electrospinning may be a typical but non-limiting value of 8kV, 9kV, 10kV, 15kV, 20kV, etc.

In some embodiments, the electrospinning liquid feed advancing speed is 0.01-0.2 mm/min and the liquid feed translating speed is 300-700 mm/min. The pushing speed of the injector is the liquid feeding pushing speed, and the translational speed of the injector in the horizontal direction is the liquid feeding translational speed. According to the embodiment of the application, through optimizing and controlling the liquid supply propelling speed and the liquid supply translation speed, the continuity of the spinning fiber is ensured, so that the ultra-long microscale perovskite polymer fiber can form a film structure through repeated superposition, and excellent flexibility and self-adhesion are provided for the fiber film. Specifically, the feed advance speed is a typical but non-limiting value such as 0.01mm/min, 0.05mm/min, 0.1mm/min, 0.2mm/min, etc., and the feed translation speed is a typical but non-limiting value such as 300mm/min, 400mm/min, 500mm/min, 600mm/min, 700mm/min, etc.

In some embodiments, the spinning distance of the electrospinning is 12cm to 16cm. The distance between the needle of the injector and the roller collector is the spinning distance, if the spinning distance is too short, the solvent cannot be volatilized sufficiently, so that the fibers on the receiving substrate are easy to bond with each other; if the spinning distance is too long, the electrostatic spinning solution is easy to cause that the electrostatic spinning solution cannot perform normal spinning. Thus, the embodiment of the application can obtain polymer fibers with uniform diameters on the receiving substrate through optimizing and controlling the spinning distance. In particular, the spinning distance may be typical, but not limiting, values of 12cm, 13cm, 14cm, 15cm, 16cm, etc.

In some embodiments, the receiving drum speed of the electrospinning is 60rpm to 100rpm. The rotation speed of the receiving roller can ensure that the polymer fibers are fully stretched and split and deposited on the receiving substrate, so that the fiber films can be effectively and repeatedly overlapped, and the fiber films can roll with the roller collector, so that the flexible continuous perovskite polymer fiber films with larger areas can be prepared. Specifically, the receiving drum rotation speed is typical but not limiting of 60rpm, 70rpm, 80rpm, 90rpm, 100rpm, etc.

In some embodiments, the time of electrospinning is 30min to 3h. If the time of the electrostatic spinning is too long, the thickness of the formed fiber film is larger, and if the time of the electrostatic spinning is too short, the thickness of the formed fiber film is smaller. According to the embodiment of the application, through optimizing and controlling the electrostatic spinning time, the fiber film with moderate thickness is ensured to be obtained, and the perovskite polymer fiber film is endowed with excellent flexibility and self-adhesion. Specifically, the time of electrospinning is a typical but non-limiting value of 30min, 1h, 2h, 3h, etc.

In some embodiments, the temperature of electrospinning is from 25 ℃ to 50 ℃. According to the embodiment of the application, through controlling and optimizing the electrostatic spinning temperature, the effect that the electrostatic spinning solution is solidified to affect the electrostatic spinning can be avoided. Specifically, the temperature of the electrospinning may be a typical but non-limiting value such as 25 ℃, 30 ℃, 40 ℃, 50 ℃.

In some embodiments, the electrospun receiving substrate is a release paper. According to the method, the release paper with a smooth surface is prepared at the roller receiver to serve as the receiving substrate, and the prepared fiber film has excellent self-adhesion capability, so that the prepared fiber film is easy to remove from the receiving substrate.

In some embodiments, the electrospun needle model is 21G, 22G, or 23G. In the electrostatic spinning, electrostatic spinning solution is sprayed out from a needle of a syringe, and forms micro jet flow between positive and negative electrodes under high voltage, and finally the micro jet flow is solidified on a receiving substrate to form the perovskite polymer fiber film. According to the embodiment of the application, the model of the needle is optimized and controlled, so that the spinning solution sprayed from the needle can be sufficiently stretched and split, and finally the flexible self-adhesive perovskite polymer fiber film is obtained.

In some embodiments, the electrospun syringe gauge is 10ml.

In some embodiments, in step S4, the specific process of forming the perovskite polymer fiber film of the specific pattern by laser etching is as follows:

s41, predefining the edge contour of a specific pattern by adopting a CAD two-dimensional graphic file;

s42, fixing the initial perovskite polymer fiber film on an operating platform of laser lithography equipment;

s43, starting the laser lithography equipment, and opening equipment software to read the manufactured CAD file;

s44, moving the position of the laser cutting head and positioning the laser cutting head above the fiber film, enabling the laser to emit laser, focusing the laser at a focus through a lens to form tiny light spots, irradiating the fiber film at the focus by the laser light spots with high power density, and melting the irradiated film due to local high temperature; along with the position control of the vibrating mirror system by the numerical control machine, laser can ablate and cut the perovskite polymer film according to CAD file routing, and the patterning processing of the initial perovskite polymer fiber film is completed after the edge is cured again.

In step S41, the laser etched pattern can be designed according to human will, and various large-scale complex fluorescent patterns and display devices thereof can be manufactured by splicing film pattern modules with different colors; wherein the color of the perovskite polymer fiber film is not only adjustable from blue green to yellow green, and the perovskite solution component (halogen type) is changed, and the spectrum range can cover the whole visible light range and even the near infrared light wave band.

As an example, the process for preparing the "flower" type perovskite polymer fiber film as shown in fig. 7 is as follows:

(1) Designing CAD files of round pistils, polygonal petals and leaf outlines of the round pistils according to the shape of a specific pattern flower;

(2) Fixing the initial perovskite polymer fiber film with the target color on a laser lithography equipment operating platform;

(3) Introducing the designed CAD file into software of a laser photoetching machine, and controlling and moving a laser cutting head in the software to be positioned above the initial perovskite polymer fiber film to be cut, wherein the platform precision is less than 10 mu m;

(4) Enabling a 355nm spectrum physical laser, pressing a 'positioning' key, then pressing a 'frame' to determine the working range of the machine, finally pressing a 'start/pause' button, and controlling a mechanical arm on a numerical control system to move the position of a vibrating mirror so as to control laser routing and start processing the perovskite polymer fiber film;

(5) The laser spot is about 15 mu m, and the perovskite polymer fiber film is cracked along the laser action position by means of the thermal effect of laser and then resolidified to form a specific pattern, and meanwhile, the air cooling device is used for cooling equipment in the processing process.

In some embodiments, laser etching uses laser wavelengths of 355nm to 1550nm.

The laser wavelength and the laser frequency are key parameters of the perovskite polymer fiber film in laser etching, and the etched fiber film has the maximum absorptivity under the laser wavelength and the laser frequency in the embodiment of the application, so that the fiber film can be melted and resolidified, and further, the initial perovskite polymer fiber film can form a specific pattern. In particular, the laser wavelength may be, but is not limited to, typical values of 355nm, 405nm, 633nm, 980nm, 1550nm, and the like.

In some embodiments, the laser spot of the laser etch has a diameter of 15 μm to 20 μm. The laser spot is the minimum linewidth of laser etching, and can influence the uniformity and consistency of laser etching. The size of the laser light spot can be flexibly selected according to the design requirement of the pattern, so that the fiber film can be stitched into a whole at the edge of the pattern, thereby forming a specific pattern and further improving the mechanical operation stability of the pattern colorization. In particular, the laser spot may be of typical but non-limiting value of 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, etc.

In some embodiments, the laser etching uses a galvanometer model number F511 long focus. The key of laser vibration is fine adjustment of focal length, so that the pattern forming effect is optimal. The vibrating mirror model selected by the embodiment of the application can enable the patterning processing of the fiber film to be smoother, and can be used for processing a large format to form multi-color complex figures or display marks.

In some embodiments, the specific pattern is pre-designed using AUTO CAD program. The initial perovskite fiber film can form various specific patterns, such as different shapes of Chinese knot patterns, different number combinations-0123456789, different letter combinations CHINA, different letter combinations ABCDE or multicolor spliced safflower and the like as shown in figure 7, and the initial perovskite fiber film can be specifically designed flexibly according to actual requirements, and various large-scale complex fluorescent patterns and display devices thereof can be manufactured by splicing film pattern modules with different colors. The AUTO CAD program is convenient to design, and can be designed in advance by adopting the program.

In a second aspect, the embodiments of the present application provide a perovskite polymer fiber film, which is prepared by the preparation method of the perovskite polymer fiber film provided in the first aspect.

The perovskite polymer fiber film provided by the second aspect of the application is prepared by the preparation method provided by the first aspect, and the preparation method can effectively prepare the perovskite polymer fiber film which has the advantages of luminescence, water resistance, self adhesion, flexibility and modularized pattern treatment, so that the prepared fiber film has stable luminescence and water resistance in a severe water environment, and can be applied to an atmospheric environment, an aqueous medium environment and even a flowing aqueous medium environment; meanwhile, due to the low melting point of the polymer fiber, the perovskite polymer fiber film can be subjected to patterning treatment through a laser etching technology, so that the mechanical operation stability of the fiber film is greatly improved, the fiber film can be applied to multi-scene self-adhesion luminous patterning display, and the perovskite material can be widely applied to the luminous display field. It is noted that the luminescent color of the perovskite fiber film can be adjusted by the halogen type and content, so that the fiber film can realize the display of multi-color complex patterns.

In some embodiments, the perovskite polymer fiber film has a thickness of 0.05mm to 0.3mm and a bending strain of 0.1% to 4%. The thickness of the fiber film is a key factor influencing the flexibility and self-adhesion, and the embodiment of the application endows the fiber film with excellent flexibility and self-adhesion performance through optimizing and controlling the thickness so that the full strain of the fiber film reaches 4 percent.

The following description is made with reference to specific embodiments.

Example 1

The embodiment of the invention provides a perovskite polymer fiber film and a preparation method thereof.

A method for preparing a perovskite polymer fiber film, comprising the following steps:

s1, preparing perovskite precursor solution:

15.32mg of PbBr are reacted ₂ Dissolved in 10ml of DMFStirring uniformly at the speed of 800rpm at room temperature, then adding 4.86mg of methyl amine bromide, and stirring uniformly at the speed of 800rpm at room temperature to obtain a methylamine lead bromide precursor solution, wherein the concentration of the methylamine lead bromide precursor is 2mg/ml.

S2, adding a polymer into the lead bromide precursor solution of methylamine, and uniformly mixing to obtain an electrostatic spinning solution:

and adding PMMA into the lead bromide precursor solution of methylamine, and stirring for 3 hours until the solution is in a clear state, so as to prepare the electrostatic spinning solution with the PMMA concentration of 100 mg/ml.

setting the environment temperature in the electrostatic spinning equipment to be 30 ℃, adding the electrostatic spinning solution into an electrostatic spinning machine by adopting an injector with the specification of 10ml, and carrying out electrostatic spinning, wherein the parameters of the electrostatic spinning are as follows: the type of the needle head is 23G, the spinning distance is 14cm, the spinning voltage is 10kV, the liquid supply propelling speed is 0.04mm/min, the liquid supply translational speed is 300mm/min, the rotating speed of the receiving roller is 80rpm, the spinning time is 120min, and the initial methylamine lead bromide/PMMA fiber film is formed on the surface of the release paper by solidification.

S4, forming the perovskite polymer fiber film with a specific pattern by laser etching the initial perovskite polymer fiber film:

designing CAD files of different digital combination outlines according to the shapes of different digital combination of specific patterns;

fixing the initial perovskite polymer fiber film on a laser lithography equipment operation table;

the designed CAD file is imported into software of a laser photoetching machine, and a laser cutting head is controlled and moved in the software to be positioned above the initial perovskite polymer fiber film to be cut, and the platform precision is smaller than 10 mu m;

f511 long-focal-length vibrating mirrors are subjected to laser processing, 355nm spectrum physical lasers are started, a 'positioning' key is pressed, a 'frame' is pressed to determine the working range of the machine, finally a 'start/pause' button is pressed, a mechanical arm is controlled on a numerical control system to move the positions of the vibrating mirrors, so that laser routing is controlled, and the perovskite polymer fiber film is started to be processed;

the laser spot is about 15 mu m, and the initial perovskite polymer fiber film is cracked along the laser action position by the thermal effect of the laser, and then resolidified to form the perovskite polymer fiber film with different digital combination patterns.

The perovskite polymer fiber film is prepared by adopting the preparation method of the perovskite polymer fiber film, and the thickness of the fiber film is 0.07mm, and the maximum bending strain rate is 4%.

Example 2

s1, preparing perovskite precursor solution:

76.62mg of PbBr ₂ Dissolving in 10ml of DMF, stirring uniformly at the speed of 800rpm at room temperature, then adding 23.38mg of methyl amine bromide, stirring uniformly at the speed of 800rpm at room temperature, and obtaining a methylamine lead bromide precursor solution, wherein the concentration of the methylamine lead bromide precursor is 10mg/ml.

adding PMMA into the lead bromide precursor solution of methylamine, stirring for 3 hours until the solution is in a clear state, the electrostatic spinning solution with PMMA concentration of 100mg/ml is prepared.

setting the environmental temperature in the electrostatic spinning equipment to be 35 ℃, adding the electrostatic spinning solution into an electrostatic spinning machine by adopting an injector with the specification of 10ml, and carrying out electrostatic spinning, wherein the parameters of the electrostatic spinning are as follows: the type of the needle head is 23G, the spinning distance is 14cm, the spinning voltage is 12kV, the liquid supply propelling speed is 0.04mm/min, the liquid supply translational speed is 400mm/min, the rotating speed of the receiving roller is 80rpm, the spinning time is 120min, and the initial methylamine lead bromide/PMMA fiber film is formed on the surface of the release paper by solidification.

designing a CAD file of the contour of the Chinese knot according to the shape of the Chinese knot of the specific pattern;

the laser spot is about 15 mu m, and the initial perovskite polymer fiber film is cracked along the laser action position by the thermal effect of the laser, and then resolidified to form the perovskite polymer fiber film with the Chinese knot pattern.

The perovskite polymer fiber film is prepared by adopting the preparation method of the perovskite polymer fiber film, the thickness of the fiber film is 0.12mm, and the maximum bending strain rate is 3.5%.

Example 3

s1, preparing perovskite precursor solution:

153.24mg of PbBr ₂ Dissolved in 10mAnd (3) uniformly stirring the mixture in DMF at the room temperature at the speed of 800rpm, then adding 46.76mg of methyl amine bromide, and uniformly stirring the mixture at the room temperature at the speed of 800rpm to obtain a methylamine lead bromide precursor solution, wherein the concentration of the methylamine lead bromide precursor is 20mg/ml.

setting the environment temperature in the electrostatic spinning equipment to be 40 ℃, adding the electrostatic spinning solution into an electrostatic spinning machine by adopting an injector with the specification of 10ml, and carrying out electrostatic spinning, wherein the parameters of the electrostatic spinning are as follows: the model of the needle head is 22G, the spinning distance is 14cm, the spinning voltage is 14kV, the liquid supply propelling speed is 0.06mm/min, the liquid supply translational speed is 500mm/min, the rotating speed of the receiving roller is 80rpm, the spinning time is 80min, and the initial methylamine lead bromide/PMMA fiber film is formed on the surface of the release paper by solidification.

designing CAD files of different letter combination outlines according to the shapes of different letter combination CHINA of a specific pattern;

the laser spot is about 15 mu m, and the initial perovskite polymer fiber film is cracked along the laser action position by the aid of the thermal effect of laser, and then resolidified to form the perovskite polymer fiber film with different letter combination CHINA patterns, and the perovskite polymer fiber film shows green fluorescence under the irradiation of a ultraviolet lamp.

The perovskite polymer fiber film is prepared by adopting the preparation method of the perovskite polymer fiber film, the thickness of the fiber film is 0.1mm, and the maximum bending strain rate is 3.33%.

Example 4

s1, preparing perovskite precursor solution:

383.09mg of PbBr ₂ Dissolving in 10ml of DMF, stirring uniformly at the speed of 800rpm at room temperature, then adding 116.91mg of methyl amine bromide, stirring uniformly at the speed of 800rpm at room temperature to obtain a methylamine lead bromide precursor solution, wherein the concentration of the methylamine lead bromide precursor is 50mg/ml.

setting the environment temperature in the electrostatic spinning equipment to be 45 ℃, adding the electrostatic spinning solution into an electrostatic spinning machine by adopting an injector with the specification of 10ml, and carrying out electrostatic spinning, wherein the parameters of the electrostatic spinning are as follows: the model of the needle head is 22G, the spinning distance is 14cm, the spinning voltage is 16kV, the liquid supply propelling speed is 0.08mm/min, the liquid supply translational speed is 500mm/min, the rotation speed of the receiving roller is 80rpm, the spinning time is 60min, and the initial methylamine lead bromide/PMMA fiber film is formed on the surface of the release paper by solidification.

designing CAD files of different letter combination outlines according to the shapes of different letter combination ABCDEs of a specific pattern;

the laser spot is about 15 μm, and the initial perovskite polymer fiber film is cracked along the laser action position by the thermal effect of the laser, and then resolidified to form the perovskite polymer fiber film with different letter combination ABCDE patterns, wherein the letter patterns can be self-adhered on the rough hard paper sheet.

The perovskite polymer fiber film is prepared by adopting the preparation method of the perovskite polymer fiber film, and the thickness of the fiber film is 0.09mm, and the maximum bending strain rate is 3%.

Example 5

s1, preparing perovskite precursor solution:

666.18mg of PbBr ₂ Dissolving in 10ml of DMF, stirring uniformly at the speed of 800rpm at room temperature, then adding 233.82mg of methyl amine bromide, stirring uniformly at the speed of 800rpm at room temperature to obtain a methylamine lead bromide precursor solution, wherein the concentration of the methylamine lead bromide precursor is 100mg/ml.

and adding PMMA into the lead bromide precursor solution of methylamine, and stirring for 3 hours until the solution is in a clear state, so as to prepare the electrostatic spinning solution with the PMMA concentration of 100mg/ml.

setting the environment temperature in the electrostatic spinning equipment to be 50 ℃, adding the electrostatic spinning solution into an electrostatic spinning machine by adopting an injector with the specification of 10ml, and carrying out electrostatic spinning, wherein the parameters of the electrostatic spinning are as follows: the model of the needle head is 21G, the spinning distance is 14cm, the spinning voltage is 18kV, the liquid supply propelling speed is 0.10mm/min, the liquid supply translational speed is 600mm/min, the rotation speed of the receiving roller is 80rpm, the spinning time is 48min, and the initial methylamine lead bromide/PMMA fiber film is formed on the surface of the release paper by solidification.

designing CAD files of different letter combination outlines according to the shapes of different letter combinations of a specific pattern;

the laser spot is about 15 mu m, the initial perovskite polymer fiber film is cracked along the laser action position by the thermal effect of the laser, and then is resolidified to form the perovskite polymer fiber film with different letter combination patterns, wherein the letter combination patterns can float on the water surface and show green fluorescence under the irradiation of a ultraviolet lamp.

The perovskite polymer fiber film is prepared by adopting the preparation method of the perovskite polymer fiber film, and the thickness of the fiber film is 0.08mm, and the maximum bending strain rate is 2.6%.

Performance testing

(1) Microstructure of microstructure

The initial methylamine lead bromide/PMMA fiber films prepared in examples 1 to 5 were examined by SEM, and the results are shown in FIG. 1, wherein a is example 1, b is example 2, c is example 3, d is example 4, and e is example 5.

As can be seen from SEM images, the methylamine lead bromide nanocrystals in the initial methylamine lead bromide/PMMA fiber films prepared in examples 1 to 3 were not attached to the surface of the polymer PMMA fiber but were all embedded in the smooth microstructure, thus achieving microstructure encapsulation of the perovskite crystals by the polymer. Namely, hydrophobic PMMA polymer fiber successfully performs microscopic physical isolation on perovskite crystals and the external environment, and efficiently blocks contact and hydration reaction of water molecules and the perovskite crystals so as to achieve perfect waterproof effect. After filling the polymer fiber micro space with the methylamine lead bromide in the initial methylamine lead bromide/PMMA fiber films prepared in examples 4 to 5, a small amount of methylamine lead bromide was attached to the surface of the polymer fiber and crystallized.

(2) Waterproof test

The initial methylamine lead bromide/PMMA fiber films prepared in examples 1 to 5 were subjected to waterproof capability detection.

The specific detection process comprises the following steps:

s10, respectively cutting the initial lead methylamine bromide/PMMA fiber films prepared in the examples 1-5 with the length of 2cm multiplied by 2cm, respectively fixing the fiber films in a culture dish by using an adhesive tape, testing the initial fluorescence intensity (without adding water) by using a fluorescence spectrometer, and recording the initial fluorescence intensity, which is recorded as 'Original';

step S20, respectively adding water into the culture dishes to immerse the fiber film, pumping out the water after the fiber film is soaked in the water for one minute, naturally airing the fiber film in the air for 2 hours, testing the fluorescence luminous intensity of the fiber film by using a fluorescence spectrometer, and recording as day 0;

after the test fluorescence spectrum of the step S30 and the step S20 is finished, water is injected into the culture dish again to completely soak the perovskite polymer fiber film, and the fluorescence luminous intensity of the film is tested by the same method on the 1 st, 2 nd, 3 rd, 4 th, 5 th, 7 th, 9 th, 11 th, 13 th, 17 th, 26 th, 30 th, 35 th, 45 th and 90 th days after the soaking of the water;

step S40, normalizing the fluorescence intensity data after soaking to the initial fluorescence intensity (Original) (namely dividing the fluorescence intensity after soaking by the initial fluorescence intensity, and normalizing the initial fluorescence intensity to be 1). The resulting distribution of fluorescence intensity is shown as a in FIG. 2, and the normalized value results are shown in Table 1.

The fluorescence spectrometer test equipment is a Renisshaw inVia spectrometer; the wavelength of the excitation laser was 405nm.

TABLE 1

As can be seen from the data analysis of a in fig. 2 and table 1, the initial methylamine lead bromide/PMMA fiber films prepared in examples 1 to 4 can maintain the fluorescence intensity floating range within 1±0.1 from day 0 to day 90 of soaking in water, thereby demonstrating that the fiber films prepared in the present application are excellent in waterproof effect and have excellent fluorescence stability. The waterproof effect of the films prepared in example 5 was slightly weaker but still allowed to float in the range of 0.694 to 1.073, and the above results demonstrate that the perovskite films prepared in examples 1 to 5 all had good fluorescence stability over a period of 90 days.

B in fig. 2 is a photograph of the initial perovskite polymer fiber film prepared in example 1 cut to a size of 2cm x 2cm and fixed to the bottom of a petri dish with tape, and a large amount of water was added to submerge the film. As can be seen from b in fig. 2, the perovskite fiber film remains intact when immersed in water, and is not decomposed by water, demonstrating the potential of the film for stable application in water.

In fig. 2, c is a physical diagram of the film prepared in example 1 under a fluorescent lamp after being immersed in water, and as can be seen from c in fig. 2, the perovskite polymer fiber film still has a good photoluminescence effect after being immersed in water, which indicates that the film can be applied to fluorescent display in water, and can realize a three-dimensional fluorescent display due to the fact that the film is lighter than water in density.

D in FIG. 2 is a physical image of the films prepared in examples 1 to 5, which were immersed in water for

days

0, 1, 5, 30 and 90 by irradiation with a violet lamp, respectively. As can be seen from d in FIG. 2, the fiber films prepared in examples 1 to 5 have excellent waterproof ability, and the fluorescent effect on

days

1, 5, 30, and 90 of the fiber film bubble in water is not visually distinguished from the fluorescent intensity effect on day 0. Therefore, the perovskite polymer fiber film has strong water-proof capability and can be stably fluorescent in water environment for a long time.

(3) Flexible test

The initial perovskite polymer fiber films prepared in examples 1 to 4 were subjected to a flexibility test.

In fig. 3: a, a ₁ ～d ₁ A is the plan development of the initial perovskite polymer fiber films prepared in examples 1 to 4, respectively ₂ ～d ₂ Flexible curl patterns of the initial perovskite polymer fiber films prepared in examples 1 to 4, respectively, on the surface of a metal rod having a diameter of 26mm, wherein a ₁ 、a ₂ Is example 1, b ₁ 、b ₂ Is example 2, c ₁ 、c ₂ Is example 3, d ₁ 、d ₂ Is example 4. As can be seen from the figures, the initial perovskite polymer fiber films prepared in examples 1 to 4 were smooth in surface, and could be curled multiple times on the surface of a 26mm diameter metal rod without generating cracks. The perovskite polymer fiber film can be independently stored away from a substrate, has extremely high flexibility and can be repeatedly curled, and the characteristic is critical in the fields of curved surface display and flexible wearable display devices.

The initial perovskite polymer fiber film prepared in example 5 was smooth in surface when developed in a flat state, but was inferior in flexibility to examples 1 to 4, and a small number of turns could be curled on the surface of a metal rod having a diameter of 60mm without generating cracks.

The initial perovskite polymer fiber film prepared in example 3 was subjected to bending strain test, and the thickness of the fiber film was 0.1mm. The fiber films were subjected to a flexible curl test on the surfaces of metal rods having diameters of 3mm, 14mm, 26mm and 60mm, respectively, as shown in fig. 4, and the flexible curl test results are shown in table 2 below.

Table 2 flexibility test results

The flexibility of a perovskite polymer fiber film refers to the ability of the film to withstand deformation caused by external forces, and the direct parameter characterizing the flexibility of the film is the bending radius R of curvature, with smaller R indicating better flexibility of the film. At the same time, the film thickness h is also another important parameter characterizing the film flexibility. The film bending strain (. Epsilon.) can be evaluated using the formula:

and (5) performing calculation.

As can be seen from Table 2, the perovskite fiber film is bent on the metal surface with the radius of 1.5mm-30mm without generating cracks, and can be repeatedly bent and unfolded without damage, and the bending strain epsilon can be as high as 3.33%. The flexibility function is not limited to the perovskite polymer fiber film prepared in the embodiment 3, the concentration of the perovskite precursor is between 1 and 100mg/ml, and the perovskite polymer fiber film prepared in the PMMA concentration is between 50 and 100mg/ml has good flexibility.

(4) Self-adsorption capability test

The perovskite polymer fiber film prepared in example 3 was cut out to obtain a film to be tested (mass: 23 mg) having a size of 3cm×8cm, the film to be tested was adhered to the surface of a centrifuge rotor made of a metal material (rotor radius r: 115 mm), and the film was centrifuged at different rotational speeds to test the centrifugal force, i.e., the adsorption force of the film. When the adsorption force is tested, the rotation speed of the centrifugal machine starts to be tested from 100r/min, the duration of each centrifugal machine is 1min, and the centrifugal machine is repeated three times. The rotational speed n is increased in sequence with a step size of 50r/min until the membrane is detached from the centrifuge rotor surface. The adsorption force of the film to be measured can be expressed by the formula F=mω ² r is calculated, wherein ω is the angular velocity, r is the rotor radius, and m is the mass of the film to be measured. The results of the self-adsorption capacity test are shown in table 3 below.

TABLE 3 self-adsorption Capacity test results

As can be seen from table 3, the perovskite polymer fiber film is adsorbed on the metal rotor of the centrifuge, and the film is not detached if it is to be effectively adsorbed when the centrifuge is rotated, and the adsorption force provides centripetal force. When the rotational speed of the centrifuge increases to a certain value, the adsorption force of the membrane cannot provide a larger centripetal force, and the membrane flies away along the tangential direction of the movement, so that the membrane is separated from the contact surface of the rotor. In the experimental process, the rotating speed of the rotor of the centrifugal machine is in the range of 100-450r/min, and the films can be attached on the surface without separation, so that the film adsorption force can reach 18.696mN, which is almost 8.129 times of the self gravity of the film to be detected. Therefore, when the external force in the horizontal direction is less than 8 times of the self weight of the film, the film can be well adsorbed on the metal surface and does not fall off.

The flexible perovskite polymer fiber film without the substrate can be curled on the surface of a sphere to realize curved surface fluorescence display, and the patterned film with self-adhesion property can be optionally adhered on the metal surface, the glass surface and a rough wall surface to display multiple scenes. Therefore, the perovskite fluorescent film which can be patterned, is flexible and has no substrate and is simply stuck in multiple scenes is prepared, and the defect that a modern display device cannot be conveniently and multi-functionally displayed is overcome. Specifically, the perovskite polymer fiber film is respectively adsorbed on different materials, such as a cardboard, a metal surface, a glass material or a rough wall surface, as shown in fig. 5, in fig. 5: a is a hard board, b is a metal surface, c is a glass material, and d is a rough wall surface. Therefore, the perovskite polymer fiber film has rich application scenes and good adsorption effect.

(5) Comparison test of manual cutting and laser etching

The initial perovskite polymer fiber film prepared in example 2 was patterned by manual cutting and laser etching, respectively, wherein the parameters of the laser etching were S4 in example 2.

A in FIG. 6 ₁ ～a ₂ For a manually tailored perovskite polymer fiber film, from a in FIG. 6 ₁ It can be seen that delamination of the film after manual cutting occurs and the edges of the film are observed under a microscope as a in FIG. 6 ₂ The figure shows that the manually cut film edges are rough and have no stitching effect.

B in FIG. 6 ₁ ～b ₂ Is a perovskite polymer fiber film processed by laser etching. B in FIG. 6 ₁ The side surface of the film processed by laser etching has no layering effect, and the edge profile is obvious. B in FIG. 6 ₂ The film is an optical picture observed under a microscope, point ablation marks of laser processing are visible in the picture, and the edge of the film has a good sewing effect. This demonstrates that the perovskite polymer fiber film processed by laser etching has excellent processing effect.

The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.

Claims

1. A method for preparing a perovskite polymer fiber film, which is characterized by comprising the following steps:

preparing a perovskite precursor solution;

and (3) etching the initial perovskite polymer fiber film by laser to form a perovskite polymer fiber film with patterns.

2. The method for preparing the perovskite polymer fiber film according to claim 1, wherein the laser etching adopts a laser wavelength of 355 nm-1550 nm; and/or

The diameter of the laser spot of the laser etching is 15-20 mu m.

3. The method for preparing the perovskite polymer fiber film according to claim 1, wherein the laser etching adopts a galvanometer model of F511 long focal length; and/or

The pattern was pre-designed using AUTO CAD program.

4. The method for preparing a perovskite polymer fiber film according to claim 1, wherein the voltage of the electrostatic spinning is 8 kV-20 kV, the feed liquid advancing speed is 0.01-0.2 mm/min, the feed liquid translating speed is 300-700 mm/min, the spinning distance is 12 cm-16 cm, the rotating speed of a receiving roller is 60 rpm-100 rpm, and the time is 30 min-3 h.

5. The method of preparing a perovskite polymer fiber film according to claim 1, wherein the temperature of electrospinning is 25 ℃ to 50 ℃; and/or

The receiving substrate of the electrostatic spinning is release paper; and/or

The type of the electrostatic spinning needle head is 21G, 22G or 23G; and/or

The specification of the electrospun syringe is 10ml.

6. The method for producing a perovskite polymer fiber film according to claim 1, wherein the perovskite precursor solution comprises an organic solvent and a perovskite precursor, and the concentration of the perovskite precursor is 1mg/ml to 100mg/ml.

7. The method of preparing a perovskite polymer fiber film according to claim 6, wherein the perovskite precursor comprises lead halide and organic ammonium halide in a molar ratio of 0.9 to 1.1:1; and/or

The organic solvent is at least one of N, N-dimethylformamide and 1, 4-butyrolactone.

8. The method of preparing a perovskite polymer fiber film as claimed in claim 1, wherein the polymer is at least one of polymethyl methacrylate, polyvinylidene fluoride, polyurethane, polystyrene and polyvinylpyrrolidone; and/or

The concentration of the polymer in the electrostatic spinning solution is 50mg/ml to 100mg/ml.

9. A perovskite polymer fiber film prepared by the method of any one of claims 1-8.

10. The perovskite polymer fiber film as claimed in claim 9, wherein the thickness of the perovskite polymer fiber film is 0.05mm to 0.3mm and the bending strain rate is 0.1% to 4%.