Perovskite quantum dot bridged silane composite luminescent film and preparation method thereof

Abstract

The application belongs to the technical field of luminescent materials, and relates to a preparation method of a perovskite quantum dot bridged silane composite luminescent film. Perovskite quantum dots of a silicon-based ligand are obtained at room temperature, the perovskite quantum dots are added into an organic bridged polysilsesquioxane colloid, the colloid is aged to a certain degree, and then the colloid is formed into a film at room temperature to obtain a perovskite quantum dot / organic bridged polysilsesquioxane composite transparent flexible film. The organic bridged polysilsesquioxane film matrix protects the perovskite quantum dots from contacting the surrounding environment, and solves the problem of poor stability of existing perovskite quantum dots in a water system and under high-temperature conditions. The luminescent film can be stably stored for months under environmental conditions; the fluorescence effect is not affected after being placed at 100 DEG C for 2 days and soaked in water for 6 days. Meanwhile, the whole experimental process is simple in operation, low in reaction temperature, short in preparation time and green in environment protection, and has great significance for constructing new flexible and foldable luminescent materials.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of luminescent materials, and particularly relates to a perovskite quantum dot bridged silane composite luminescent film and a preparation method thereof. BACKGROUND

[0002] Perovskite quantum dots can be applied to liquid crystal display, light-emitting diode, solar cell and x-ray field due to their excellent optical properties, including high photoluminescence quantum yield, narrow emission peak and adjustable emission wavelength (full spectrum luminescence can be achieved by adjusting the proportion of halogen). However, perovskite quantum dots are very unstable under the stimulation of water vapor, temperature change, oxygen and light due to their inherent ionic properties and low formation energy, especially in water system, perovskite quantum dots will decompose to cause the attenuation of fluorescence intensity or even quenching.

[0003] To improve the stability of perovskite quantum dots, researchers generally start from two aspects, the first is to passivate surface defects through ligands to enhance the luminescent performance and stability of quantum dots, but this improvement method is limited; the second is to embed quantum dots into a stable polymer matrix to protect perovskite quantum dots, so as to avoid contact with air and thus avoid stimulation by moisture, oxygen and ultraviolet light. Chen et al. proposed a simple method to improve the stability of CsPbX3 PeNCs by encapsulating in a superhydrophobic organic bridged polysilsesquioxane poly(styrene-ethylene-butylene-styrene) (SEBS) matrix, which can protect PeNCs from contacting the surrounding environment, and blue-green-red emitting CsPbX3@SEBS (X = Cl / Br, Br, Br / I) composite films exhibit high moisture and thermal stability (Chen Y, Liang X, Liu J, et al. Environmentally Friendly and Ultrastable Narrow-Band Emitter: CsPbX3@SEBS Flexible Film for Light-Emitting Diode Displays [J]. ACS Sustainable Chemistry & Engineering, 2021, 9(30): 10291-10298.). Ge et al. proposed a strategy of thermoplastic polyurethane encapsulating perovskite quantum dots to improve their thermal degradation and moisture resistance performance, this cheap and convenient method not only greatly reduces the intensity loss of photoluminescence, but also exhibits excellent photoluminescence performance in water (Shi GD, Ge W Y, Gao W X, et al. Enhanced Thermal Stability of Halide Perovskite CsPbX3 Nanocrystals by a Facile TPU Encapsulation [J]. Advanced Optical Materials, 2019, 8(4): 1901516.). Although these encapsulation barrier materials can have some protective effect, they will all have problems such as poor flexibility, low transparency, poor stability in water systems and high-temperature environments, and this solvent evaporation film forming method will cause the volatile toluene with high toxicity to volatilize into the air and cause environmental pollution. SUMMARY

[0004] The object of the present application is to provide a perovskite quantum dot bridged silane composite luminescent film and a preparation method thereof, which solves the problem of poor stability of existing perovskite quantum dots in water systems and under high-temperature conditions.

[0005] The application is realized by the following technical scheme:

[0006] A preparation method of a perovskite quantum dot bridged silane composite light-emitting film, comprising the following steps:

[0007] (1) adding perovskite raw material components and a silicon-based ligand to an organic solvent, and stirring uniformly to obtain a perovskite quantum dot precursor;

[0008] The molar ratio of the silicon-based ligand to the perovskite raw material components is (0.27-2.2):1;

[0009] The perovskite raw material components comprise a perovskite raw material first component and a perovskite raw material second component; the molar ratio of the perovskite raw material first component to the perovskite raw material second component is (0.8-1):1;

[0010] (2) injecting part of the perovskite quantum dot precursor into an anti-solvent under stirring to obtain a perovskite quantum dot solution, and obtaining perovskite quantum dots after cleaning, ultrasonic treatment and centrifugation;

[0011] (3) mixing a bridged silane precursor, a solvent, deionized water and an acidic catalyst according to a volume ratio of 1:(2-10):(0.2-0.5):(0.01-0.03), stirring uniformly, and then aging to prepare an organic bridged polysilsesquioxane colloid;

[0012] (4) adding the perovskite raw material first component to the organic bridged polysilsesquioxane colloid, then adding the perovskite quantum dots, stirring uniformly, and forming a film after the colloid is aged to obtain a perovskite quantum dot bridged silane composite light-emitting film;

[0013] The molar ratio of the perovskite quantum dots to the perovskite raw material first component is 1:(0.5-1.5).

[0014] Further, in step (1), the molecular formula structure of the perovskite raw material first component is AX; wherein A is one of a methylamine cation CH3NH3 + (MA + ), a formamidinium cation CH(NH2) 2+ (FA + ), and X is at least one of halogen ions including Cl - , Br - , and I - .

[0015] The molecular formula structure of the perovskite raw material second component is BX2; wherein B is any one of Pb 2+ , Sn 2+ , and Ge 2+ , and X is halogen ions including Cl - , Br- , I - at least one of I and II.

[0016] Further, in step (1), the silicon-based ligand is any one of 3-aminopropyl triethoxysilane and 3-aminopropyl trimethoxysilane.

[0017] Further, in step (1), the solvent in the perovskite precursor solution is any one of dimethylformamide, dimethyl sulfoxide or a mixed solution of dimethylformamide and dimethyl sulfoxide.

[0018] Further, in step (1), the stirring time is 1-12 h.

[0019] Further, in step (2), the anti-solvent is toluene, benzene, ethyl acetate or methyl acetate.

[0020] Further, in step (2), the centrifugal speed is 1500-5000 r / min, and the ultrasonic time is 5-15 min.

[0021] Further, in step (3), the solvent is ethanol, and the acidic catalyst is acetic acid, phytic acid, hydrochloric acid or formic acid.

[0022] Further, in step (4), when the perovskite quantum dots are MAPbX3, MASnX3 or MAGeX3, the first component of the perovskite raw material added in the organically bridged polysilsesquioxane colloidal is MAX, and the molar ratio of the perovskite quantum dots to the first component of the perovskite raw material is 1:(0.5-1.5).

[0023] Further, in step (4), the colloidal film forming method is spin coating, dip coating, solution sinking, spraying or casting.

[0024] The application further discloses the perovskite quantum dot bridged silane composite luminescent film prepared by the preparation method.

[0025] Compared with the prior art, the application has the following beneficial technical effects:

[0026] The application discloses a preparation method of a perovskite quantum dot bridged silane composite luminescent film, first obtains perovskite quantum dots of a silicon-based ligand at room temperature, then adds the perovskite quantum dots into an organic bridged polysilsesquioxane colloid, and after the colloid is aged to a certain degree, the colloid is formed into a film at room temperature, so that a perovskite quantum dot / organic bridged polysilsesquioxane composite transparent flexible film with high stability and excellent luminescent performance is obtained, and the organic bridged polysilsesquioxane film matrix protects the perovskite quantum dots from contacting the surrounding environment, thereby solving the problem of poor stability of existing perovskite quantum dots in a water system and under high-temperature conditions.

[0027] The perovskite quantum dot bridged silane composite luminescent film prepared by the application not only has excellent luminescent performance of quantum dots, but also has good flexibility and excellent optical performance of the organic bridged polysilsesquioxane film, and also has high stability, can be stably stored for months under environmental conditions, and has no influence on fluorescence effect after being placed at 100 DEG C for 2 days or soaked in water for 6 days, which is of great significance for research and application of the new type of flexible luminescent material in photoelectric devices. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 Fig. 1 is a fluorescence optical photo comparison diagram of quantum dots dispersed in ethanol after ethanol cleaning in the comparative example 1 and the example 1, wherein a is the fluorescence optical photo before and after ethanol cleaning in the comparative example 1, and b is the fluorescence optical photo before and after ethanol cleaning in the example 1.

[0029] Figure 2 Fig. 2 is a colloid fluorescence optical photo in the comparative example 2 and the example 1, wherein a is the fluorescence optical photo after adding quantum dots in step 4 in the comparative example 2, and b is the fluorescence optical photo after adding MABr and then adding quantum dots in step 4 in the example 1.

[0030] Figure 3is the fluorescence optical photo of the flexible, transparent perovskite quantum dot bridged silane composite light-emitting thin film obtained by adding the quantum dots obtained in Example 1 into the colloid by the flow casting method;

[0031] Figure 4 is the fluorescence optical photo of the light-emitting thin film after being placed at 100℃ for 2 days;

[0032] Figure 5 is the fluorescence optical photo of the light-emitting thin film after being placed at -8℃ for 5 days;

[0033] Figure 6 is the fluorescence optical photo of the light-emitting thin film after being immersed in water. DETAILED DESCRIPTION

[0034] In order to make the objects, technical solutions and advantages of the present application clearer, further detailed description will be made in combination with the accompanying drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application, that is, the described examples are only a part of the examples of the present application, but not all the examples.

[0035] The components described and shown in the accompanying drawings and examples of the present application can be arranged and designed in various different configurations, therefore, the detailed description of the examples of the present application provided in the following accompanying drawings is not intended to limit the scope of the claimed present application, but only to represent a selected embodiment of the present application. Based on the accompanying drawings and examples of the present application, all other examples obtained by those skilled in the art without making creative efforts, are within the protection scope of the present application.

[0036] The present application discloses a preparation method of a perovskite quantum dot bridged silane composite light-emitting thin film, comprising the following steps:

[0037] Step 1, preparation of perovskite quantum dot precursor

[0038] A sample bottle with a magnet is added with a first component of perovskite raw materials, a second component of perovskite raw materials, the molar ratio of the first component and the second component is (0.8-1):1, and a certain amount of organic solvent is added to obtain a precursor, and after adding a silicon-based ligand in the precursor under stirring, the stirring is continued for 1-12h to obtain a perovskite quantum dot precursor;

[0039] The molar ratio of the silicon-based ligand to the precursor is (0.27-2.2):1;

[0040] The first component of the perovskite raw material is at least one of MABr, MACI, MAI, FABr, FACl, FAI, the second component is at least one of PbBr2, PbCl2, PbI2, SnBr2, SnCl2, SnI2, GeBr2, GeCl2, GeI2, the organic solvent is any one of N, N dimethylformamide, dimethyl sulfoxide or a mixed solution of dimethylformamide and dimethyl sulfoxide, and the silicon-based ligand is any one of 3-aminopropyl trimethoxysilane and 3-aminopropyl triethoxysilane;

[0041] Step 2, preparation of perovskite quantum dots

[0042] Part of the perovskite quantum dot precursor is injected into an anti-solvent under stirring to obtain a perovskite quantum dot solution, which is cleaned with ethanol, and perovskite quantum dots are obtained after multiple ultrasonic treatment and centrifugation;

[0043] The anti-solvent is toluene, benzene, ethyl acetate or methyl acetate;

[0044] Step 3, preparation of organically bridged polysilsesquioxane colloids

[0045] A reagent bottle with a lid is sequentially added with solvent ethanol, deionized water, an acidic catalyst and a bridged silane precursor in a proportion of 1: (2-10): (0.2-0.5): (0.01-0.03) in volume ratio, and after being stirred uniformly, it is aged at room temperature to obtain the bridged polysilsesquioxane colloids;

[0046] Step 4, preparation of perovskite quantum dot bridged silane composite luminescent film

[0047] The first component of the perovskite raw material is added to the bridged polysilsesquioxane colloids and stirred uniformly, and then the perovskite quantum dots prepared in step 2 are added and stirred again, and the molar ratio of the perovskite quantum dots to the first component of the perovskite raw material is 1: (0.5-1.5), and after being stirred uniformly, it is left to stand, and after the colloids are aged to a certain extent, a film is formed by spin coating, dip-coating, solution sinking, spraying or casting.

[0048] Comparative Example 1

[0049] Step 1, 0.16 mmol of MABr, 0.20 mmol of PbBr2 and 1 mL of N, N dimethylformamide are sequentially added to a sample bottle with a magnet and stirred for 6 h to obtain perovskite quantum dot precursors;

[0050] Step 2, 500 μL of the perovskite quantum dot precursor solution is added dropwise to 10 mL of anti-solvent toluene under stirring for 4 h to obtain a perovskite quantum dot solution, which is cleaned with ethanol, and perovskite quantum dots are obtained after multiple ultrasonic treatment and centrifugation;

[0051] Step 3, add solvent ethanol, deionized water, acidic catalyst phytic acid and bridged silane precursor 3-trimethoxysilylpropyl-2-methyl-3-[(3-trimethoxysilyl)propylthio]propionate into the reagent bottle with a cover in proportion, the volume ratio of precursor, ethanol, water and phytic acid is 1:3:0.25:0.02, stir uniformly, and then age at room temperature to prepare a bridged polysilsesquioxane sol;

[0052] Step 4, add 0.16 mmol of MABr into the organic bridged polysilsesquioxane colloid and stir uniformly, then add the quantum dots in step 2 into the colloid and stir again, and then stand until the colloid is aged to a certain extent, and then film forming is performed by a casting method or the like.

[0053] Comparative Example 2

[0054] Step 1, add 0.16 mmol of MABr, 0.20 mmol of PbBr2 and 1 mL of N,N dimethylformamide into a sample bottle with a magnet, and then add 20 μL of 3-aminopropyltriethoxysilane under stirring, and continue to stir for 6 h to obtain perovskite quantum dot precursors;

[0055] Step 2, add 500 μL of the perovskite quantum dot precursor solution into 10 mL of antisolvent toluene under stirring, and continue to stir for 4 h to obtain a perovskite quantum dot solution, and then clean with ethanol, and obtain perovskite quantum dots after multiple ultrasonic treatment and centrifugation;

[0056] Step 3, add solvent ethanol, deionized water, acidic catalyst phytic acid and bridged silane precursor 3-trimethoxysilylpropyl-2-methyl-3-[(3-trimethoxysilyl)propylthio]propionate into the reagent bottle with a cover in proportion, the volume ratio of precursor, ethanol, water and phytic acid is 1:3:0.25:0.02, stir uniformly, and then age at room temperature to prepare a bridged polysilsesquioxane colloid;

[0057] Step 4, add the quantum dots in step 2 into the organic bridged polysilsesquioxane colloid, stir uniformly, and then stand until the colloid is aged to a certain extent, and then film forming is performed by a casting method or the like.

[0058] The features and performances of the present application are further described in detail in combination with the following examples.

[0059] Example 1

[0060] Step 1, add 0.16 mmol of MABr, 0.20 mmol of PbBr2 and 1 mL of N,N dimethylformamide in sequence into a sample bottle with a magnet, to obtain a precursor, then add 20 μL of 3-aminopropyltriethoxysilane into the precursor, and continue to stir for 6 h to obtain a perovskite quantum dot precursor;

[0061] Step 2, take 500 μL of the perovskite quantum dot precursor solution, and drop it into 10 mL of anti-solvent toluene under stirring for 4 h to obtain a perovskite quantum dot solution, then clean it with ethanol, and obtain the perovskite quantum dots after multiple ultrasonic treatment and centrifugation;

[0062] Step 3, add solvent ethanol, deionized water, acid catalyst phytic acid and 3-trimethoxysilylpropyl-2-methyl-3-[(3-trimethoxysilyl)propylthio]propionate in sequence into a reagent bottle with a lid in a proportion of 1:3:0.25:0.02, and stir uniformly, then age at room temperature to obtain an organic bridged polysilsesquioxane colloid;

[0063] Step 4, add 0.16 mmol of MABr into the organic bridged polysilsesquioxane colloid and stir uniformly, then add the perovskite quantum dots in step 2 into it and stir again, and then stand until the colloid is aged to a certain extent, and then perform film formation by a casting method or the like.

[0064] Figure 1 In the figure, a is the fluorescence optical photograph before and after cleaning with ethanol in the comparative example 1, and b is the fluorescence optical photograph before and after cleaning with ethanol in the example 1. It can be seen from the figure that the fluorescence of the quantum dots without using a silicon-based ligand disappears in ethanol, while the perovskite quantum dots prepared by using 3-aminopropyltriethoxysilane as the ligand can stably exist in ethanol, which indicates that the presence of the silicon-based ligand plays a key role in the stable existence of the quantum dots in ethanol.

[0065] Figure 2 In the figure, a is the fluorescence optical photograph after adding the quantum dots in step 4 of the comparative example 2, and b is the fluorescence optical photograph after adding MABr first and then adding the quantum dots in step 4 of the example 1. It can be found that the fluorescence disappears after directly adding the quantum dots into the colloid, but the colloid has strong fluorescence effect after adding a certain amount of MABr into the colloid first and then adding the quantum dots, which indicates that the excess MABr can cause the reversible reaction of MAPbBr3, and effectively avoid the decomposition of MAPbBr3.

[0066] Figure 3is the fluorescence optical photo of the flexible, transparent perovskite quantum dot bridged silane composite luminescent film obtained by the flow casting method with the quantum dots obtained in Example 1 added into the colloid. As can be seen from the figure, the luminescent film has excellent transparency, luminescent performance and flexibility.

[0067] Figure 4 and Figure 5 are the fluorescence optical photos of the luminescent film obtained in Example 1 after being placed at 100°C for 2 days and after being placed at -8°C for 5 days respectively, and as can be seen from the figures, the film also has excellent luminescent performance, further indicating that the luminescent film has excellent thermal stability.

[0068] Figure 6 is the fluorescence optical photo of the luminescent film obtained in Example 1 after being immersed in water for different times, and it can be seen that the fluorescence effect of the film hardly changes over time, indicating that the fluorescence film has excellent stability.

[0069] Example 2

[0070] Step 1, sequentially add 0.16 mmol MAI, 0.20 mmol PbI2 and 1 mL N,N dimethylformamide into a sample bottle with a magnetic bar to obtain a precursor, and then add 30 μL 3-aminopropyl triethoxysilane into the precursor and continue to stir for 6 h to obtain a perovskite quantum dot precursor;

[0071] Step 2, take 500 μL of the perovskite quantum dot precursor solution and drop it into an anti-solvent toluene under stirring for 4 h to obtain a perovskite quantum dot solution, and then clean it with ethanol, and obtain the perovskite quantum dots after multiple ultrasonic treatment and centrifugation;

[0072] Step 3, sequentially add solvent ethanol, deionized water, acidic catalyst phytic acid and 3-trimethoxysilylpropyl-2-methyl-3-[(3-trimethoxysilyl)propylthio]propionate into a reagent bottle with a lid in proportion, the volume ratio of the precursor, ethanol, water and phytic acid is 1:3:0.25:0.02, and then stir uniformly and place at room temperature for aging to prepare an organic bridged polysilsesquioxane sol;

[0073] Step 4, add 0.10 mmol MAI into the organic bridged polysilsesquioxane colloid and stir uniformly, then add the quantum dots in Step 2 into it and stir again, and then place it after aging to a certain extent, and then perform film formation by the flow casting method or the like.

[0074] Example 3

[0075] Step 1, add 0.2 mmol MABr, 0.20 mmol PbBr2 and 1 mL N,N dimethylformamide into a sample bottle with a magnet in sequence to obtain a precursor, and then add 40 μL 3-aminopropyltriethoxysilane into the precursor and continue to stir for 5 h to obtain a perovskite quantum dot precursor;

[0076] Step 2, take 500 μL perovskite quantum dot precursor solution and drop it into 10 mL anti-solvent toluene under stirring for 4 h to obtain a perovskite quantum dot solution, and then clean it with ethanol, and obtain the perovskite quantum dots after multiple ultrasonic treatment and centrifugation;

[0077] Step 3, add solvent ethanol, deionized water and acidic catalyst phytic acid and 3-trimethoxysilylpropyl-2-methyl-3-[(3-trimethoxysilyl)propylthio]propionate into a reagent bottle with a lid in sequence according to the volume ratio of 1:5:0.3:0.01, and then stir uniformly and place at room temperature for aging to obtain an organic bridged polysilsesquioxane sol;

[0078] Step 4, add 0.20 mmol MABr into the organic bridged polysilsesquioxane sol and stir uniformly, then add the quantum dots in step 2 into it and stir again, and then place it after aging to a certain extent, and then perform film forming by using a casting method or the like.

[0079] Example 4

[0080] In this example, step 1, the silane ligand is 3-aminopropyltrimethoxysilane, the stirring time is 2 h, and the other steps are the same as those in example 1.

[0081] Example 5

[0082] In this example, step 1, the organic solvent is a mixture of N,N dimethylformamide and dimethyl sulfoxide in a ratio of 9:1, and the other steps are the same as those in example 1.

[0083] Example 6

[0084] In this example, step 1, the amount of 3-aminopropyltriethoxysilane added is 30 μL, and the other steps are the same as those in example 1.

[0085] Example 7

[0086] In this example, step 2, ethyl acetate is used as an anti-solvent, and the other steps are the same as those in example 1.

[0087] Example 8

[0088] In this example, step 4, MABr is 0.10 mmol, and the other steps are the same as those in example 1.

[0089] Example 9

[0090] In this example, in step 3, the volume ratio of precursor, ethanol, water and phytic acid is 1:7:0.3:0.02, and other steps are the same as example 1.

[0091] Example 10

[0092] In this example, in step 3, the volume ratio of precursor, ethanol, water and phytic acid is 1:7:0.3:0.02, and other steps are the same as example 1.

[0093] Similarly, the luminescent film prepared in examples 2 to 10 is verified, and the fluorescent optical photo of the flexible and transparent perovskite quantum dot bridged silane composite luminescent film obtained by the casting method has excellent transparency, luminescent performance and flexibility.

[0094] The luminescent film is placed at 100°C for 2 days to obtain the fluorescent optical photo, and at -8°C for 5 days to obtain the fluorescent optical photo, from which it can be seen that the film also has excellent luminescent performance, and further indicates that the luminescent film has excellent thermal stability.

[0095] Figure 6 Also applicable to examples 2-10, it can be seen that the fluorescent effect of the film hardly changes over time, indicating that the prepared fluorescent film has excellent stability.

[0096] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit it, although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that: the specific embodiments of the present application can be modified or replaced by the same, without departing from the spirit and scope of the present application, any modification or equivalent replacement, which should be covered in the protection scope of the claims of the present application.

Claims

1. A method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film, characterized in that, Includes the following steps: (1) Add the perovskite raw material components and silicon-based ligands to an organic solvent and stir until homogeneous to obtain a perovskite quantum dot precursor; The molar ratio of silicon-based ligands to perovskite raw material components is (0.27~2.2):1; The perovskite raw material consists of a first component and a second component; the molar ratio of the first component to the second component is (0.8~1):

1. (2) Take a portion of the perovskite quantum dot precursor and inject it into an antisolvent under stirring to obtain a perovskite quantum dot solution. After washing, sonicating and centrifuging, perovskite quantum dots are obtained. (3) The bridged silane precursor, solvent, deionized water and acid catalyst are mixed in a volume ratio of 1:(2~10):(0.2~0.5):(0.01~0.03), stirred evenly and aged to prepare organic bridged polysilsesquioxane colloid; (4) The first component of the perovskite raw material was added to the organic bridged polysilsesquioxane colloid, and then perovskite quantum dots were added. The mixture was stirred evenly and the colloid was aged before being formed into a film to obtain a perovskite quantum dot bridged silane composite luminescent film. The molar ratio of perovskite quantum dots to the first component of perovskite raw material is 1: (0.5~1.5). In step (1), the molecular formula of the first component of the perovskite raw material is AX; where A is a methylamine cation CH3NH3. + (MA + ), formamidinium cation CH(NH2) + (FA + One of them; X is a halide ion, including Cl. - ,Br - I - At least one of them; The molecular formula of the second component of the perovskite feedstock is BX2; where B is Pb. 2+ Sn 2+ 、Ge 2+ Any one of them; X is a halide ion, including Cl. - ,Br - I - At least one of them; In step (4), when the perovskite quantum dots are MAPbX3, MASnX3, and MAGeX3, the first component of the perovskite raw material added to the organic bridged polysilsesquioxane colloid is MAX.

2. The method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film according to claim 1, characterized in that, In step (1), the silicon-based ligand is either 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane; The solvent in the perovskite precursor solution is any one of dimethylformamide, dimethyl sulfoxide, or a mixture of dimethylformamide and dimethyl sulfoxide.

3. The method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film according to claim 1, characterized in that, In step (1), the stirring time is 1~12 h.

4. The method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film according to claim 1, characterized in that, In step (2), the antisolvent is toluene, benzene, ethyl acetate or methyl acetate.

5. The method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film according to claim 1, characterized in that, In step (2), the centrifugation speed is 1500~5000 r / min and the ultrasonic duration is 5~15 min.

6. The method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film according to claim 1, characterized in that, In step (3), the solvent is ethanol, and the acidic catalyst is acetic acid, phytic acid, hydrochloric acid, or formic acid.

7. The method for preparing a perovskite quantum dot-bridged silane composite luminescent thin film according to claim 1, characterized in that, In step (4), the colloidal film formation methods include spin coating, dip-coating, solution sinking, spraying, or casting.

8. The perovskite quantum dot-bridged silane composite luminescent film prepared by the preparation method according to any one of claims 1-7.

Images