A luminescent film and its preparation method and application

Abstract

The present invention discloses a luminescent film and a preparation method and application thereof. The luminescent material comprises the following components: a perovskite material and an organic polymer; wherein the raw materials of the perovskite material comprise the following components: a bromine-containing compound, a compound a and a compound b; wherein the compound a comprises at least one of methylamine lead bromide, cesium lead bromide and methyl ether lead bromide; wherein the compound b comprises at least one of polyethylene oxide, polydimethylsiloxane and thermoplastic polyurethane. The luminescent material of the present invention has low luminescent conditions, can emit light under both white light and ultraviolet excitation light sources, and the light will not decay when leaving the luminescent source.

Description

Technical Field

[0001] The present invention relates to the technical field of thin films, and in particular to a luminescent thin film and a preparation method and application thereof. Background Art

[0002] At present, the preparation of luminescent films on the market is mainly through the following methods: long afterglow material doping, fluorescent coating and fluorescent printing and dyeing. Among them, the main steps of long afterglow material doping are: special treatment of rare earth luminescent materials, doping in the dyeing bath and printing paste in the form of additives to prepare luminescent films; among them, the main steps of fluorescent coating are: using cotton, polyester / cotton or polyester as the base fabric, mixing the luminescent material with the adhesive to form a coating, and then coating it to prepare the luminescent film; among them, the main steps of fluorescent printing and dyeing are: adding fluorescent dyes to the dyeing solution to dye the printed film, so that the printed film emits a fluorescent effect under ultraviolet light, and the luminescent film is prepared by the above methods.

[0003] However, the above methods have defects. Among them, the main defects of long afterglow material doping include: 1. Long afterglow materials come from rare earth non-renewable resources; 2. The performance of long afterglow materials still cannot reach the brightness of night lighting, and the brightness decays rapidly after leaving the excitation light source; 3. Long afterglow materials are colorful, but there are very few materials used in fibers, because long afterglow materials are not resistant to ultraviolet rays and will gradually turn black under ultraviolet irradiation, which greatly limits their scope of use. In addition, the luminous fibers made of long afterglow materials glow in yellow-green at night, which is relatively single. Among them, the main disadvantages of fluorescent coating include: fluorescent coating requires the material to be coated on the base cloth, which is easily affected by the environment and interlayer separation occurs, affecting the luminous effect. Among them, the main disadvantages of fluorescent printing and dyeing include: 1. It is necessary to use dye additives; 2. It is necessary to dye according to different film dyeing mechanisms, such as nylon is mainly dyed with disperse or acid fluorescent dyes, and cotton and polyester / cotton blended films are dyed with active fluorescent dyes.

[0004] In summary, the above methods have their own shortcomings, which makes the above methods have certain limitations in application. Therefore, a new method for preparing light-emitting thin films is urgently needed to solve the above problems and make the preparation of light-emitting thin films adaptable to large-scale, high-efficiency and high-performance production. Summary of the invention

[0005] The first technical problem to be solved by the present invention is:

[0006] A luminescent material is provided.

[0007] The second technical problem to be solved by the present invention is:

[0008] A light-emitting film is provided.

[0009] The third technical problem to be solved by the present invention is:

[0010] A method for preparing the luminescent film is provided.

[0011] The fourth technical problem to be solved by the present invention is:

[0012] Application of the luminescent film.

[0013] In order to solve the first technical problem, the technical solution adopted by the present invention is:

[0014] A light-emitting material comprises the following components: a perovskite material and an organic polymer;

[0015] Among them, the raw materials of perovskite materials include the following components:

[0016] Bromine-containing compounds, compound a and compound b;

[0017] Wherein, compound a comprises at least one of methylamine lead bromide, cesium lead bromide and methyl ether lead bromide;

[0018] Wherein, compound b includes at least one of polyethylene oxide, polydimethylsiloxane and thermoplastic polyurethane.

[0019] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0020] 1. The addition of the compound b can improve the roughness of the surface of the organic polymer fiber, making the surface of the organic polymer fiber smoother, thereby compensating for the bifurcation defect of the organic polymer fiber.

[0021] 2. The compound b contains hydrogen bonds and is easily reacted with water molecules in the atmosphere, making the film unstable. The organic polymer can solve the water absorption problem of the compound b and protect the OH bonds of the compound b from being destroyed by water molecules in the air, thereby preventing the compound b from absorbing water and affecting the stability of the luminescent film on the luminescent film.

[0022] 3. The present invention mixes the perovskite material and the organic polymer so that the polymer fiber and the perovskite material are interwoven and the perovskite material is evenly distributed between the polymer fiber layers, which improves the fluorescence intensity on the one hand; on the other hand, the light-emitting film prepared by the light-emitting material has excellent stability and will not be delaminated due to environmental changes.

[0023] 4. The luminescent material of the present invention has low luminescent conditions and can emit light under both white light and ultraviolet excitation light sources, and the light will not decay when leaving the light source.

[0024] 5. The raw materials used for the luminescent material described in the present invention are all renewable resources and have extremely low costs.

[0025] According to one embodiment of the present invention, the bromine-containing compound includes at least one of methylammonium bromide, cesium bromide and dimethyl ether bromide.

[0026] According to one embodiment of the present invention, the mass ratio of the perovskite material to the organic polymer is 1:2-4.

[0027] According to one embodiment of the present invention, the molar ratio of the bromine-containing compound to the compound a is 3 to 8:1, and the fluorescence intensity of the luminescent material is ensured by adding an excess of the bromine-containing compound.

[0028] According to one embodiment of the present invention, the organic polymer includes at least one of polyacrylonitrile, nylon 6 and polyvinylidene fluoride.

[0029] In order to solve the second technical problem, the technical solution adopted by the present invention is:

[0030] A luminescent film comprises the luminescent material.

[0031] In order to solve the third technical problem, the technical solution adopted by the present invention is:

[0032] A method for preparing the luminescent film comprises the following steps:

[0033] The bromine-containing compound, the compound a and the compound b are mixed to obtain the perovskite material, which is then heated and cooled, and the organic polymer is added to obtain a spinning solution, which is then spun to obtain the luminescent film.

[0034] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0035] 1. The preparation process of the luminescent film is short and environmental factors do not interfere with the preparation process.

[0036] 2. The luminescent film is prepared by electrostatic spinning, and the film luminescence is achieved in one step without the need to prepare a substrate, thus avoiding the dependence of the film substrate on the dye.

[0037] 3. The equipment required for the method is simple in structure, the raw material cost is low, the processing flow is short, and there is no need for post-processing of materials and processes.

[0038] According to one embodiment of the present invention, the heating temperature is 50-80°C.

[0039] According to one embodiment of the present invention, the heating time is 30 to 60 minutes.

[0040] According to one embodiment of the present invention, after the spinning solution is left to stand for 15 to 30 hours, the perovskite crystal particles are further refined so that the components of the solution are fully mixed before electrostatic spinning.

[0041] According to one embodiment of the present invention, the method for preparing the light-emitting film comprises the following steps:

[0042]

[0043]

[0044]

[0045] Among them, CH2Cl2 is dichloromethane; PBC is a mixed solution of methylammonium bromide (MABr) and perovskite (Pervoskite) in different proportions; PPC is a mixed solution of PBC and PEO (polyethylene oxide) in different proportions; 3PC is a mixed solution of PPC and PAN (polyacrylonitrile); DMF is dimethylformamide.

[0046] Another aspect of the present invention also relates to the application of the luminous film in wearable luminous technology, including the luminous film as described in the second embodiment. Since the application adopts all the technical solutions of the luminous film of the above embodiment, it has at least all the beneficial effects brought by the technical solutions of the above embodiment.

[0047] Another aspect of the present invention also relates to the application of the luminous film in a brightness enhancement film of a liquid crystal backlight screen, including the luminous film as described in the second embodiment. Since the application adopts all the technical solutions of the luminous film of the above embodiment, it has at least all the beneficial effects brought by the technical solutions of the above embodiment.

[0048] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0050] Figure 1 This is a luminescence test diagram of the luminescent film of Example 1.

[0051] Figure 2 This is a fluorescence intensity test diagram of the luminescent film of Example 1.

[0052] Figure 3These are scanning electron microscope test images of the luminescent film of Example 1 and the luminescent film of the comparative example. DETAILED DESCRIPTION

[0053] Embodiments of the present invention are described in detail below, examples of the above embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and cannot be understood as limiting the present invention.

[0054] In the description of the present invention, if there is a description of first, second, etc., it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.

[0055] In the description of the present invention, it should be understood that descriptions involving orientation, such as orientation or positional relationship indicated as up, down, etc., are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0056] In the description of the present invention, it should be noted that, unless otherwise clearly defined, terms such as setting, installing, connecting, etc. should be understood in a broad sense, and technicians in the relevant technical field can reasonably determine the specific meanings of the above terms in the present invention in combination with the specific content of the technical solution.

[0057] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of the present invention.

[0058] Example 1

[0059] A method for preparing a luminescent film comprises the following steps:

[0060] MABr (methylammonium bromide) and MAPbBr3 (methylamine lead bromide) are mixed in a DMF (dimethylformamide) solution in a molar ratio of 3:1 to obtain a first solution;

[0061] Dissolve 0.01 g of PEO (polyethylene oxide) in DMF to obtain a second solution;

[0062] Stirring the first solution and the second solution at about 55° C. for about 50 minutes respectively, and then mixing and stirring at room temperature for about 50 hours to prepare a perovskite quantum dot solution;

[0063] 0.3 g PAN (polyacrylonitrile) was dissolved in DMF, heated to about 55°C and stirred for about 55 minutes, and then the perovskite quantum dot solution was added and stirred thoroughly to prepare a spinning solution;

[0064] The spinning solution was electrospun under the following conditions: high voltage of about 20 KV, spinning speed of about 1 mL / h, distance between nozzle and roller of 10 cm and receiving roller of 10 cm / s;

[0065] The electrospun film was collected and the temperature was controlled at about 55° C. on a temperature stage for 60 seconds to obtain a luminescent film.

[0066] The obtained luminescent film changes from white to yellow under natural light, and exhibits high-brightness fluorescence under ultraviolet 256nm and 365nm excitation.

[0067] Example 2

[0068] The difference between Example 2 and Example 1 is that the molar ratio of MABr to MAPbBr3 is different, wherein the molar ratio of Example 1 is 3:1, and the molar ratio of Example 2 is 8:1.

[0069] A method for preparing a luminescent film comprises the following steps:

[0070] MABr and MAPbBr3 were mixed in a DMF solution at a molar ratio of 8:1 to obtain a first solution;

[0071] Dissolve 0.01 g of PEO in DMF to obtain a second solution;

[0072] Stirring the first solution and the second solution at about 55° C. for about 50 minutes respectively, and then mixing and stirring at room temperature for about 50 hours to prepare a perovskite quantum dot solution;

[0073] 0.3 g PAN was dissolved in DMF, heated to about 55°C and stirred for about 55 minutes, and then the perovskite quantum dot solution was added and stirred thoroughly to prepare a spinning solution;

[0074] The spinning solution was electrospun under the following conditions: high voltage of about 20 KV, spinning speed of about 1 mL / h, distance between nozzle and roller of 10 cm and receiving roller of 10 cm / s;

[0075] The electrospun film was collected and the temperature was controlled at about 55° C. on a temperature stage for 60 seconds to obtain a luminescent film.

[0076] The obtained luminescent film changes from white to yellow under natural light, and exhibits high-brightness fluorescence under ultraviolet 256nm and 365nm excitation.

[0077] Example 3

[0078] The difference between Example 3 and Example 1 is that the components and raw materials are different. The bromine-containing compound in Example 3 is cesium bromide, compound a is cesium lead bromide, compound b is polydimethylsiloxane, and the organic polymer is polyvinylidene fluoride.

[0079] A method for preparing a luminescent film comprises the following steps:

[0080] Cesium bromide and cesium lead bromide are mixed in a DMF solution at a molar ratio of 3:1 to obtain a first solution;

[0081] Dissolve 0.01 g of polydimethylsiloxane in DMF to obtain a second solution;

[0082] Stirring the first solution and the second solution at about 55° C. for about 50 minutes respectively, and then mixing and stirring at room temperature for about 50 hours to prepare a perovskite quantum dot solution;

[0083] 0.3 g of polyvinylidene fluoride was dissolved in DMF, heated to about 55°C and stirred for about 55 minutes, and then the perovskite quantum dot solution was added and stirred thoroughly to prepare a spinning solution;

[0084] The spinning solution was electrospun under the following conditions: high voltage of about 20 KV, spinning speed of about 1 mL / h, distance between nozzle and roller of 10 cm and receiving roller of 10 cm / s;

[0085] The electrospun film was collected and the temperature was controlled at about 55° C. on a temperature stage for 60 seconds to obtain a luminescent film.

[0086] The obtained luminescent film changes from white to yellow under natural light, and exhibits high-brightness fluorescence under ultraviolet 256nm and 365nm excitation.

[0087] Comparative Example

[0088] The difference between the comparative example and Example 1 is that the comparative example does not contain a PEO solution.

[0089] A method for preparing a luminescent film comprises the following steps:

[0090] MABr and MAPbBr3 are mixed in a DMF solution at a molar ratio of 3 to 8:1 to obtain a first solution;

[0091] The first solution is stirred at about 55° C. for about 50 minutes, and then mixed and stirred at room temperature for about 50 hours to prepare a perovskite quantum dot solution;

[0092] 0.3 g PAN was dissolved in DMF, heated to about 55°C and stirred for about 55 minutes, and then the perovskite quantum dot solution was added and stirred thoroughly to prepare a spinning solution;

[0093] The spinning solution was electrospun under the following conditions: high voltage of about 20 KV, spinning speed of about 1 mL / h, distance between nozzle and roller of 10 cm and receiving roller of 10 cm / s;

[0094] The electrospun film was collected and the temperature was controlled at about 55° C. on a temperature stage for 60 seconds to obtain a luminescent film.

[0095] Performance Test:

[0096] The luminescent film of Example 1 was tested for luminescence. The test results are as follows: Figure 1 shown. Figure 1 a and Figure 1 b in the figure is a schematic diagram of the luminescent film under natural light. Figure 1 a in the equation is room temperature. Figure 1 b in the figure is after the temperature is raised to 50°C. It can be seen that after the temperature is raised, the color of the spinning membrane changes from white to yellow. Figure 1 c and Figure 1 The d in the figure is a schematic diagram of the luminescent film under ultraviolet light. Figure 1 Where c is room temperature, Figure 1 d in the figure is after the temperature is raised to 50°C. It can be seen that after the temperature is raised, the color of the spinning membrane changes from light blue to green under ultraviolet light excitation.

[0097] The fluorescence intensity test of the luminescent film of Example 1 was carried out. The samples before and after heating were placed in the solid fixture of the fluorescence sample chamber of the fluorescence spectrophotometer (model RF-3600), and then the chamber door was closed. The excitation wavelength was 365nm, and the fluorescence emission spectrum was received in the visible light range of 450-650nm to obtain the fluorescence intensity value before and after heating. The test results are as follows: Figure 2 As shown. Figure 2 It can be seen that when the temperature rises, the fluorescence intensity of the luminescent film will increase, which is manifested as a deepening of the fluorescence color of the luminescent film.

[0098] The luminescent film of Example 1 and the luminescent film of the comparative example were tested by scanning electron microscope. The test results are as follows: Figure 3 As shown. Among them, Figure 3 a in the figure is the spun fiber of the comparative example, Figure 3 b is the spun fiber of Example 1. It can be seen that the addition of PEO can repair the fiber defects of PAN, and PAN can also enhance the stability of the PEO film.

[0099] The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A luminescent material, characterized in that: The invention comprises the following components: a perovskite material and an organic polymer; Among them, the raw materials of perovskite materials include the following components: Bromine-containing compounds, compound a and compound b; Wherein, compound a comprises at least one of methylamine lead bromide, cesium lead bromide and methyl ether lead bromide; Wherein, compound b is polyethylene oxide; The organic polymer is polyacrylonitrile; The bromine-containing compound includes at least one of methylammonium bromide, cesium bromide and methyl ether bromide.

2. A luminescent material according to claim 1, characterized in that: The mass ratio of the perovskite material to the organic polymer is 1:2-4.

3. A luminescent material according to claim 1, characterized in that: The molar ratio of the bromine-containing compound to the compound a is 3-8:

1.

4. A luminous film, characterized in that: The method comprises the luminescent material according to any one of claims 1 to 3.

5. A method for preparing the light-emitting film according to claim 4, characterized in that: The following steps are involved: The bromine-containing compound, the compound a and the compound b are mixed to obtain the perovskite material, which is then heated and cooled, and the organic polymer is added to obtain a spinning solution, which is then spun to obtain the luminescent film.

6. The method according to claim 5, characterized in that: The heating temperature is 50-80°C.

7. The method according to claim 5, characterized in that: After obtaining the spinning solution, the solution is allowed to stand for 15 to 30 hours before electrospinning.

8. Application of the luminous film as claimed in claim 4 in wearable luminous technology or brightness enhancement film of liquid crystal backlight screen.

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