CN113155754B - Luminous film, oxygen detection device and manufacturing method thereof - Google Patents

Abstract

The invention discloses a luminescent film, an oxygen detection device and a manufacturing method thereof, which belong to the technical field of optical sensing and can solve the problems of relatively complicated preparation methods and slow response speed of the existing oxygen detection device. The oxygen detection device includes an excitation light source, a spectrum detector, a processor, and a luminescent film; the luminescent film includes a perovskite nanomaterial; the general formula of the perovskite nanomaterial is A ₂ (Ma, Fa) _m-1 B _m X _3m+1 , where A represents organic long-chain macromolecules, B represents divalent metal cations, X represents halogen ions, and m represents the number of layers of metal cations between organic chains. The light emitted by the excitation light source is irradiated on the luminescent film to excite the luminescent film to generate a light signal; the spectrum detector is used to detect the intensity of the light signal; the processor is used to calculate the oxygen concentration of the environment where the luminescent film is located according to the intensity of the light signal. The invention is used for the measurement of oxygen concentration.

Description

Luminescent film, oxygen detection device and manufacturing method thereof

technical field

The invention relates to a luminescent film, an oxygen detection device and a manufacturing method thereof, belonging to the technical field of optical sensing.

Background technique

As an important gas, oxygen has been widely used in fields such as biochemistry, medical care, marine and space science, biotechnology and aerospace. When oxygen is used in daily life and production, its concentration must meet the requirements for use. If the oxygen concentration does not meet the standard or the control is inaccurate, it will lead to serious safety hazards. The traditional detection methods of oxygen concentration include Winkler titration method, Clark electrode method, zirconia method, ultrasonic method and electrochemical method, etc. These methods have the disadvantages of slow detection process, electrode consumption, and inability to realize real-time monitoring. In recent years, fiber optic oxygen sensors have developed rapidly. Compared with traditional oxygen sensors, fiber optic oxygen sensors have unique advantages in many aspects, including high detection accuracy, high sensitivity, and short response time, and can realize long-distance, real-time and continuous monitoring of oxygen concentration. , and its research has received great attention in recent years. There are many sensing mechanisms for optical fiber oxygen sensors, among which the optical oxygen sensor based on the principle of fluorescence quenching has been widely studied because of its simple detection method and easy miniaturization of devices. The optical oxygen sensor consists of an oxygen sensitive probe and a probe fixing material. Therefore, the preparation and development of oxygen-sensitive probes with sensitive oxygen response, high precision and good stability, and the construction of immobilized materials with good oxygen permeability, high light transmittance and good optical properties are the key to determine the optical oxygen sensor. So far, most oxygen probes in optical oxygen sensors are based on organic dyes, polycyclic aromatic hydrocarbons, and metal-organic complexes. However, the preparation method of this type of oxygen probe is relatively complicated, and it only has high sensitivity to phosphorescence, which increases the response time of the probe to changes in oxygen concentration to a certain extent.

Contents of the invention

The invention provides a luminescent film, an oxygen detection device and a manufacturing method thereof, which can solve the problems of complicated preparation methods and slow response speed of the existing oxygen detection device.

In one aspect, the present invention provides a luminescent film, the luminescent film includes a perovskite nanomaterial; the general formula of the perovskite nanomaterial is A ₂ (Ma,Fa) _m-1 B _m X _3m+1 , where A represents organic long-chain macromolecules, B represents divalent metal cations, X represents halide ions, and m represents the number of layers of metal cations between organic chains.

Compared with the three-dimensional tin-based perovskite quantum dots, the tin-based perovskite nanomaterials in this application can effectively protect the tin-based perovskite due to the introduction of long-chain organic cations to form a two-dimensional structure, and significantly improve the performance of the tin-based perovskite. The structure is stable, and due to the quantum well confinement effect, the fluorescence quantum yield is significantly improved.

In order to obtain the two-dimensional structure with directional orientation described in this application, additives are used in the synthesis process, and in order to obtain a dense structure, after the two-step spin coating, vacuum first and then thermal annealing.

Optionally, the A is selected from one of PEA, TEA, BA, OA, DA; the B is selected from one of Sn, Sn/Pb, Sn/Mn; X is selected from Cl, Br, I One of.

Optionally, the perovskite nanomaterial has a size of 2 nm to 50 nm in at least one dimension.

Optionally, the luminescence peak of the perovskite nanomaterial is between 500nm and 1000nm.

Optionally, the luminescent film also includes a polymer material; the polymer material is selected from the group consisting of: silicone rubber, fluorosilicone, polystyrene (PS), ethyl cellulose, organically modified silica gel, polyvinylidene fluoride At least one of vinyl (PVDF), polyethylene terephthalic acid (PET), and polymethyl methacrylate (PMMA). Among them, polystyrene (PS) and polyethylene terephthalic acid (PET) have a fixed emission wavelength under the irradiation of UV excitation light source, the emission wavelength will not change with the change of oxygen concentration, and can be used as a fluorescent reference probe The ratiometric fluorescent probes were constructed with needles, which significantly enhanced the accuracy of the luminescent film.

The in-situ preparation of the perovskite nanomaterial/polymer material composite material provided by the present application realizes the in-situ generation of the perovskite nanomaterial in the polymer matrix during the spin coating process. By selecting the polymer, the concentration range in which the material is linearly sensitive to oxygen can be adjusted. In addition, the perovskite nanomaterials/polymer composites prepared in situ not only have the advantages of high luminous purity of perovskite nanomaterials, and the wavelength can be adjusted according to the composition, but also have the advantages of easy processing, high mechanical strength, and flexibility of polymer components. Good, good water insulation performance and so on.

Optionally, the luminescent film further includes a substrate, and the perovskite nanomaterial or the composite material of the perovskite nanomaterial and the polymer material is disposed on the substrate.

Optionally, the substrate may be selected from at least one of glass sheet, silicon sheet, silicon oxide, polyethylene terephthalate, polyvinyl chloride, polyethylene, polypropylene, and polystyrene.

In another aspect, the present invention provides an oxygen detection device, comprising an excitation light source, a spectrum detector, a processor, and any one of the luminescent films described above; the light emitted by the excitation light source is irradiated on the luminescent film , used to excite the luminescent film to generate a light signal; the spectrum detector is used to detect the intensity of the light signal; the processor is used to calculate the oxygen concentration of the environment where the luminescent film is located according to the intensity of the light signal.

Optionally, the wavelength of the excitation light source can be adjusted in the range from ultraviolet to visible light.

Optionally, the device also includes a Y-shaped optical fiber, the Y-shaped optical fiber includes an input end, a first output end, and a second output end; the excitation light source is connected to the input end of the Y-shaped optical fiber; the Y-shaped optical fiber The first output end of the Y-shaped optical fiber faces the luminescent film; the light emitted by the excitation light source passes through the input end and the first output end of the Y-shaped optical fiber and then irradiates on the luminescent film to excite the luminescent film to generate Optical signal; the spectral detector is connected to the second output end of the Y-shaped optical fiber, and the spectral detector is used to detect the intensity of the optical signal through the second output end of the Y-shaped optical fiber.

In another aspect, the present invention provides an oxygen detection device, including a digital source meter, a processor, and any one of the luminescent films described above; the digital source meter is used to supply power to the luminescent film to excite the The luminescent film generates light signals; the digital source meter is also used to measure the electrical conductivity of the luminescent film after excitation; the processor is used to calculate the oxygen in the environment where the luminescent film is located according to the electrical conductivity of the luminescent film concentration.

In yet another aspect, the present invention provides an oxygen detection device, comprising an excitation light source, a spectrum detector, a digital source meter, a processor, and any of the luminescent films described above; the light emitted by the excitation light source is irradiated on the The luminescent film is used to excite the luminescent film to generate a light signal; the spectral detector is used to detect the intensity of the light signal; the digital source meter is used to measure the conductivity of the luminescent film after excitation; the The processor is used to calculate the oxygen concentration of the environment where the luminescent film is located according to the intensity of the light signal and the conductivity of the luminescent film.

Optionally, the wavelength of the excitation light source can be adjusted in the range from ultraviolet to visible light.

Optionally, the device also includes a Y-shaped optical fiber, the Y-shaped optical fiber includes an input end, a first output end, and a second output end; the excitation light source is connected to the input end of the Y-shaped optical fiber; the Y-shaped optical fiber The first output end of the Y-shaped optical fiber faces the luminescent film; the light emitted by the excitation light source passes through the input end and the first output end of the Y-shaped optical fiber and then irradiates on the luminescent film to excite the luminescent film to generate Optical signal; the spectral detector is connected to the second output end of the Y-shaped optical fiber, and the spectral detector is used to detect the intensity of the optical signal through the second output end of the Y-shaped optical fiber.

Optionally, a casing is also included, and the luminescent film is arranged in the casing.

Optionally, a bracket is arranged inside the housing; the luminescent film is arranged on the bracket.

Optionally, the support angle of the bracket is adjustable.

In another aspect, the present invention provides a manufacturing method applied to any one of the oxygen detection devices described above, the manufacturing method comprising: drying the perovskite precursor solution to obtain a luminescent film; The sealing treatment of blocking water and dust to obtain a sealed luminescent film; setting the sealed luminescent film on the exit light path of the excitation light source, and setting the spectrum detector on the exit light path of the sealed luminescent film; And/or, a digital source meter is connected to opposite ends of the sealed luminescent film.

Among them, the perovskite precursor solution is dried to obtain a luminescent film, which specifically includes:

(1) obtain the anti-solvent and the precursor solution containing the perovskite precursor;

(2) Adding the anti-solvent to the precursor solution, and shaping the precursor solution to obtain a luminescent film.

Optionally, the perovskite precursor solution includes: an organic solvent, AX and BX ₂ ; wherein, A represents an organic long-chain macromolecule, B represents a divalent metal cation, and X represents a halogen ion.

Wherein, the organic solvent is at least one selected from N,N-dimethylformamide, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate, N-methylpyrrolidone, and dimethylacetamide.

Optionally, the molar ratio of the AX to the BX ₂ is 1.5-10:1; the concentration of the perovskite precursor solution is 0.1M-1.2M.

Optionally, the perovskite solution further includes a polymer material; the mass ratio of the polymer material to the perovskite precursor is 100:0.01-30.

Optionally, the perovskite solution also includes additives; the additives are selected from trimethylbutyric acid, n-butyric acid, acetic acid, propiolic acid, 2-methylpropionic acid, pentanoic acid, 2-methylbutyric acid acid, at least one of 2,2-dimethylpropanoic acid, hexanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, and heptanoic acid.

The added additive is an aliphatic carboxylic acid containing a functional group carbonyl (-C=O-), the tin cation can be stabilized by the electron-rich oxygen atom on the carbonyl, and the halide is simultaneously stabilized by the proton hydrogen. During the nucleation process, unstable halides and free Sn ²⁺ at the edge can also be stabilized with carboxylic acids. The other binding surface of the carboxylic acid can attract free ions in the solution, and these free ions enter the surface of the successively grown perovskite and leave the bondage of the carboxylic acid group. The carboxylic acid then rebonds to the unstable surface atoms. This repeated process accelerates the nucleation process and largely reduces the oxidation of Sn ²⁺ on the core surface. After many experiments, it was found that aliphatic carboxylic acids can significantly improve the quality of tin halide perovskite nanomaterials and increase the quantum yield.

Optionally, the ratio of the additive to the organic solvent is 1:50-100.

Optionally, the molding in step (2) is specifically:

The precursor solution is transferred to a template and shaped to obtain a luminescent film.

Optionally, the transfer includes at least one of a spin coating method, a dipping and pulling method, an electrospinning method, a solution sinking method, a spray coating method, a scraping method, and a casting method.

The beneficial effects that the present invention can produce include:

(1) The luminescent film provided by the present invention adopts an in-situ preparation method. The luminescent film formed in situ has a layered two-dimensional structure, has a higher fluorescence quantum yield than the three-dimensional lead-free perovskite and is stable in air. Stability; and by changing the halogen composition to achieve tunable emission wavelength and other characteristics. In addition, the tin-based perovskite of the present invention shows a good linear or exponential decay in fluorescence intensity under a certain concentration of oxygen, and the recovery of fluorescence intensity can be achieved by vacuuming and in an inert atmosphere environment. The fluorescence intensity is reversible under a certain range of oxygen concentration.

(2) The luminescent film provided by the present invention has a perovskite nanomaterial with a general formula of A ₂ (Ma, Fa) _m-1 B _m X _3m+1 , which has good luminescence performance and is resistant to oxygen With ultra-high sensitivity, the fluorescence intensity changes linearly or exponentially with the oxygen concentration.

(3) In the oxygen detection device provided by the present invention, by irradiating the light emitted by the exciting light source on the luminescent film, the luminescent film is excited to generate a light signal, and the spectrum detector receives the light signal. The oxygen concentration changes, so the processor can obtain the corresponding oxygen concentration value according to the intensity of the light signal detected by the spectral detector, and then achieve the purpose of oxygen detection. The oxygen detection device of the present invention has simple preparation process, low cost and can be applied on a large scale.

(4) The oxygen detection device provided by the present invention, by utilizing the digital source meter to supply power to the luminescent film, to stimulate the luminescent film to generate an optical signal; and utilize the digital source meter to measure the electrical conductivity of the excited luminescent film; As the oxygen concentration in the outside world changes, the processor can obtain the corresponding oxygen concentration value according to the conductivity measured by the digital source meter, and then achieve the purpose of oxygen detection. The oxygen detection device of the present invention has simple preparation process, low cost and can be applied on a large scale.

Description of drawings

Fig. 1 is the fluorescence emission spectrum of the luminescent film provided by the embodiment of the present invention;

Fig. 2 is the XRD structural diagram of the luminescent thin film provided by the embodiment of the present invention;

Fig. 3 is the fluorescence emission spectrum of the luminescent film provided by the embodiment of the present invention under different oxygen concentrations;

Fig. 4 is the curve that the fluorescence spectrum of the luminescent thin film provided by the embodiment of the present invention varies with the oxygen concentration;

Figure 5 shows the reversibility of the fluorescence intensity of the luminescent film provided by the embodiment of the present invention under low oxygen concentration;

Fig. 6 is the change curve of the fluorescence spectrum of the luminescent film provided by the embodiment of the present invention under low oxygen concentration;

Fig. 7 is a schematic structural diagram of an oxygen detection device provided by an embodiment of the present invention;

Fig. 8 is a schematic structural diagram of an oxygen detection device provided by another embodiment of the present invention;

Fig. 9 is a schematic structural diagram of an oxygen detection device provided by another embodiment of the present invention.

List of parts and reference numbers:

11. Substrate/housing; 12. Exciting light source; 13. Luminescent film; 14. Optical fiber probe; 15. Spectral detector; 16. Digital source meter.

Detailed ways

The present invention will be described in detail below in conjunction with the embodiments and accompanying drawings 1 to 9, but the present invention is not limited to these embodiments.

Unless otherwise specified, the raw materials in the examples of the present application were purchased through commercial channels.

Example 1

Mix polyvinylidene fluoride (PVDF) with PEAI and SnI ₂ powder; control mass ratio: polymer: (PEAI+SnI ₂ )=100:10, control drug PEAI:SnI ₂ molar mass ratio: 10～1.5: 1. Mix the powder evenly with low-speed mechanical stirring for 0.5h. Then the mixed powder and the organic solvent (DMF:DMSO) were miscible together at a mass ratio of 1:7.2:1.8, stirred on a magnetic stirrer for 12 hours, and then spin-coated to form a film. The rotation speed was 3500, and the time was 60s. Add anti-solvent dropwise before nucleation, vacuumize for 3-5 minutes after spin-coating to form a film, and then anneal at 100°C for 15 minutes to obtain a dense and uniform red film.

Example 2

After mixing PEAI and _SnI2 powders with a molar mass ratio of 10-1.5:1, dissolve it in an organic solvent (DMF:DMSO=4:1) to obtain a 0.1M-1M precursor solution; place it in a magnetic stirrer After stirring for 12 hours, a more clear and transparent precursor solution was obtained after filtration. Use 2-step spin coating to form a film. The first step is at a speed of 1000 and the time is 10s. ), annealing at 90-100°C for 15 minutes after spin coating to form a film to obtain a brown to dark brown film with dense and uniform distribution.

Example 3

According to another aspect of the present application, an oxygen detection device based on the principle of fluorescence quenching is provided, as shown in FIG. A light source 12 (such as LED), a luminescent film 13, and an optical fiber probe 14 for detecting fluorescent signals.

As shown in Figure 7, the luminescent film 13 based on tin perovskite spin-coated on the glass slide is placed on the fixed bracket in the housing 11, the angle of the bracket is adjusted to about 45°, and the light beam emitted by the LED light source passes through the Y-shaped optical fiber Irradiated on the luminescent film 13, the light emitted by the luminescent film 13 is received by the Y-shaped optical fiber probe 14. Since the oxygen concentration in the outside world to be measured is different, the fluorescent light intensity of the luminescent film 13 will be attenuated to varying degrees, so the optical fiber probe 14 Receive signals of different sizes of fluorescent light intensities, the optical fiber probe 14 transmits the received optical signals to the spectral detector through the Y-shaped optical fiber, and the spectral detector converts the optical signals to output digital signals (fluorescent light intensity of the luminescence peak), by The processor calculates and outputs the corresponding oxygen concentration value according to the previously detected light intensity attenuation function with the oxygen concentration, and displays the value through the display unit for easy reading.

It should be noted that after detecting the oxygen concentration of the external air, vacuumize the luminescent film 13 for 30 minutes and then fill the housing 11 with nitrogen gas to restore the fluorescence intensity of the luminescent film 13 and protect the luminescent film 13 . The built-in fluorescence intensity as a function of oxygen concentration needs to be updated periodically.

Example 4

According to another aspect of the present application, another oxygen detection device based on the change of the electrical properties of the luminescent film with the oxygen concentration is provided, as shown in FIG. The luminescent film 13 on the glass or silicon/silicon dioxide substrate coated with electrodes on the surface is connected with a digital source meter 16 (Keithley sourcemeter) through wires.

As shown in Figure 8, the tin-based perovskite luminescent film 13 that is spin-coated on the glass substrate coated with electrodes on the surface is placed on the fixed support in the housing 11, and it is connected with the Keithley sourcemeter digital source meter 16 by wires. Connected, and set the opening voltage (O ~ 5V). As the oxygen concentration increases, the hole concentration increases, and in the low oxygen concentration range, the conductivity of the luminescent film 13 tends to increase exponentially with the increase of the oxygen concentration. The processor calculates and outputs the corresponding oxygen concentration value according to the function formula of the change of the conductivity with the oxygen concentration detected in advance, and displays the value through the display unit for easy reading.

Example 5

According to another aspect of the present application, in order to improve measurement accuracy, a composite reference oxygen concentration detection device is provided. The oxygen concentration detecting device of this compound parameter is as shown in Figure 9, comprises base/housing 11, is placed on or in the excitation light source 12 (such as LED), luminescent film 13, the Y-shaped optical fiber probe 14 of detecting fluorescent signal , spectral detector 15 and digital source meter 16. The part where the LED excites the luminescent film 13 is an electrodeless module, which ensures that the fluorescence emitted by the luminescent film 13 is not affected by the reflectivity of the electrode material plated on the substrate. Usually, the single-wavelength fluorescence intensity detection mode is easily affected by the environment and the instrument itself, so the combination of the fluorescence intensity and electrical properties of the luminescent film with a certain relationship with the change of oxygen concentration can effectively make up for the lack of single-wavelength fluorescence detection. The method of constructing composite parameters greatly improves the accuracy of the oxygen concentration detection device.

The above are only a few embodiments of the application, and do not limit the application in any form. Although the application is disclosed as above with preferred embodiments, it is not intended to limit the application. Any skilled person familiar with this field, Without departing from the scope of the technical solution of the present application, any changes or modifications made using the technical content disclosed above are equivalent to equivalent implementation cases, and all belong to the scope of the technical solution.

Claims (19)

1. A method of manufacturing an oxygen detection device, the method comprising:

spin-coating the perovskite precursor solution into a film to obtain a luminescent film;

sealing the light-emitting film to block water and dust to obtain a sealed light-emitting film;

the sealed light-emitting film is arranged on an emergent light path of an excitation light source, and a spectrum detector is arranged on the emergent light path of the sealed light-emitting film; and/or connecting a digital source meter to the electrode output end of the sealed electrode-plated light-emitting film;

the luminescent film comprises perovskite nano-materials;

the general formula of the perovskite nano material is A ₂ (Ma,Fa) _m-1 B _m X _3m+1 Wherein A represents an organic long chain macromolecule, B represents a divalent metal cation, X represents a halogen ion, and m represents the number of metal cation layers between organic chains;

the A is selected from one of PEA, TEA, BA, OA, DA; the B is selected from one of Sn, sn/Pb and Sn/Mn; x is selected from one of Cl, br and I;

the perovskite nano material has a size of 2 nm-50 nm in at least one dimension;

the luminescence peak of the perovskite nano material is between 500nm and 1000 nm.

2. The method of claim 1, wherein the luminescent film further comprises a polymeric material;

the polymeric material is selected from: at least one of organic silicon rubber, fluorosilicone, polystyrene, ethyl cellulose, organic modified silica gel, polyvinylidene fluoride, poly terephthalic acid and polymethyl methacrylate.

3. The method of claim 2, wherein the luminescent film further comprises a substrate, and the perovskite nanomaterial or the composite of the perovskite nanomaterial and the polymer material is disposed on the substrate.

4. The method of claim 3, wherein the substrate is at least one selected from the group consisting of glass flakes, silicon wafers, silicon oxides, polyethylene terephthalate, polyvinyl chloride, polyethylene, polypropylene, and polystyrene.

5. The oxygen detecting device obtained by the manufacturing method according to any one of claims 1 to 4, comprising an excitation light source, a spectrum detector, a processor, and a light-emitting thin film;

the light emitted by the excitation light source irradiates the light-emitting film and is used for exciting the light-emitting film to generate light signals;

the spectrum detector is used for detecting the intensity of the optical signal;

the processor is used for calculating the oxygen concentration of the environment where the luminous film is located according to the intensity of the optical signal.

6. The oxygen detecting apparatus according to claim 5, wherein the wavelength of the excitation light source is adjustable in a range from ultraviolet to visible light.

7. The oxygen detection device of claim 5, further comprising a Y-fiber comprising an input end, a first output end, and a second output end;

the excitation light source is connected with the input end of the Y-shaped optical fiber; the first output end of the Y-shaped optical fiber faces the light-emitting film; the light emitted by the excitation light source irradiates the light-emitting film after passing through the input end and the first output end of the Y-shaped optical fiber so as to excite the light-emitting film to generate light signals;

the spectrum detector is connected with the second output end of the Y-shaped optical fiber and is used for detecting the intensity of the optical signal through the second output end of the Y-shaped optical fiber.

8. The oxygen detecting device obtained by the manufacturing method according to any one of claims 1 to 4, comprising a digital source meter, a processor, and a light emitting film;

the digital source meter is used for supplying power to the light-emitting film so as to excite the light-emitting film to generate light signals;

the digital source meter is also used for measuring the conductivity of the excited luminescent film;

the processor is used for calculating the oxygen concentration of the environment where the luminescent film is located according to the conductivity of the luminescent film.

9. The oxygen detecting device obtained by the manufacturing method according to any one of claims 1 to 4, comprising an excitation light source, a spectrum detector, a digital source meter, a processor, and a light-emitting film;

the light emitted by the excitation light source irradiates the light-emitting film and is used for exciting the light-emitting film to generate light signals;

the spectrum detector is used for detecting the intensity of the optical signal;

the digital source meter is used for measuring the conductivity of the excited luminescent film;

the processor is used for calculating the oxygen concentration of the environment where the luminescent film is located according to the intensity of the light signal and the conductivity of the luminescent film.

10. The oxygen detection device of claim 9, wherein the wavelength of the excitation light source is adjustable in the ultraviolet to visible range.

11. The oxygen detection device of claim 9, further comprising a Y-fiber comprising an input end, a first output end, and a second output end;

the excitation light source is connected with the input end of the Y-shaped optical fiber; the first output end of the Y-shaped optical fiber faces the light-emitting film; the light emitted by the excitation light source irradiates the light-emitting film after passing through the input end and the first output end of the Y-shaped optical fiber so as to excite the light-emitting film to generate light signals;

the spectrum detector is connected with the second output end of the Y-shaped optical fiber and is used for detecting the intensity of the optical signal through the second output end of the Y-shaped optical fiber.

12. The oxygen detection device of any one of claims 5 to 11, further comprising a housing, the luminescent film being disposed within the housing.

13. The oxygen detection device of claim 12, wherein a bracket is disposed within the housing; the luminous film is arranged on the bracket.

14. The oxygen detecting apparatus according to claim 13, wherein a supporting angle of the bracket is adjustable.

15. The method of claim 1, wherein the perovskite precursor solution comprises: organic solvent, AX and BX ₂ The method comprises the steps of carrying out a first treatment on the surface of the Wherein A represents an organic long chain macromolecule, B represents a divalent metal cation, and X represents a halogen ion.

16. The method of claim 15, wherein AX and BX are the same ₂ The molar ratio of (2) is 1.5-10: 1, a step of;

the concentration of the perovskite precursor solution is 0.1M-1.2M.

17. The method of making according to claim 15, wherein the perovskite precursor solution further comprises a polymeric material;

the mass ratio of the polymer material to the perovskite precursor is 100:0.01 to 30.

18. The method of making according to claim 15, wherein the perovskite precursor solution further comprises an additive;

the additive is at least one of trimethyl butyric acid, n-butyric acid, acetic acid, propiolic acid, 2-methylpropanoic acid, valeric acid, 2-methylbutanoic acid, 2-dimethylpropionic acid, caproic acid, 3-methylpentanoic acid, 4-methylpentanoic acid and heptanoic acid.

19. The method of claim 18, wherein the ratio of the additive to the organic solvent is 1:50 to 100.

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