Te < 4 + > doped vacancy ordered halide perovskite fluorescent powder and preparation method and application thereof

Abstract

The invention relates to Te < 4 + > doped vacancy ordered halide perovskite fluorescent powder as well as a preparation method and application thereof, and belongs to the technical field of preparation of luminescent materials. The chemical formula of the fluorescent powder is Rb2Hf (1-x) Cl6: xTe < 4 + >, wherein x is more than 0 and less than 1. The fluorescent powder is prepared from TeCl4, HfCl4 and RbCl through a precipitation method at the room temperature, TeCl4 and HfCl4 are accurately weighed according to a certain stoichiometric ratio and fully dissolved in hydrochloric acid, then the dissolved RbCl is dropwise added into the dissolving solution, and magnetic stirring is conducted for several hours so that the raw materials can fully react; and drying the solution precipitate to obtain the fluorescent powder. The excitation wavelength of the fluorescent powder is 250-480 nm, and white light can be obtained through excitation of a blue light chip. The fluorescent powder is high in quantum efficiency, good in stability and simple in synthesis process, and the chromaticity parameter of a WLED assembled by the fluorescent powder is close to that of standard white light.

Description

Technical Field

[0001] The present invention relates to the field of phosphor-converted white light-emitting diodes (WLEDs), and in particular to the synthesis and application of white luminescent phosphors that can be excited by a blue light chip. Background Art

[0002] Excessive energy consumption has become a critical global issue, driving the development of energy-saving technologies such as luminescent materials and solid-state lighting. Phosphor-converted white light-emitting diodes offer significant advantages over traditional incandescent or fluorescent lamps, including high luminous efficiency, low power consumption, long lifespan, and environmental friendliness. Currently, mainstream WLEDs on the market primarily come in two forms.

[0003] One method uses an ultraviolet-near ultraviolet chip to excite a mixture of red, green and blue phosphors to emit white light. Due to the fluorescence reabsorption between different materials, the ratio of the three primary colors is difficult to control, the luminous efficiency is low, and the color reproduction and color stability are also greatly affected. At the same time, the coating process of mixing several phosphors increases the difficulty of making WLEDs, and the production cost remains high. In order to overcome these defects, researchers have tried to introduce different luminescence centers into a matrix material. Chinese patent CN109111912A discloses a method for preparing nanocluster core-shell phosphors for high-power WLEDs, in which nanosilver cluster-modified core-shell fluorescent conversion materials are prepared by a hydrothermal method, and Bi / Mn ion-doped fluoride micron particles are prepared by a microwave method, and the phosphors are regulated to achieve dual absorption in the ultraviolet and blue light regions, while generating emission in the blue, green, yellow and red light regions. However, its preparation process successively undergoes microwave reaction, hydrothermal reaction and high-temperature sintering, and the operation is complicated, making it difficult to achieve large-scale production. Liu et al. used Tm 3+ , green light Tb 3+ and red light Eu 3+ The single-phase white light fluorescent material GdNbO4:xTm was obtained by co-doping ions into the GdNbO4 matrix. 3+ ,yTb 3+ ,zEu 3+

Inorganic Chemistry, 2016, 55: 10383-10396

[0004] Another method is to use a blue light chip to excite a yellow luminescent phosphor. Currently, the popular phosphor on the market is Y3Al5O 12 :Ce 3+ This type of phosphor has the following main defects: (1) low photoluminescence quantum efficiency; (2) the assembled WLED has problems such as poor color rendering index (CRI) and high correlated color temperature (CCT); (3) the phosphor synthesis process is complex and the cost is high. 3+ Doped borate phosphor material. Under the excitation of ultraviolet light, it can produce two strong emission peaks at 485nm (blue) and 575nm (yellow), thereby achieving white light emission. However, its preparation process requires long-term calcination at 1110-1145℃, and the preparation conditions are high, thus limiting its wide application. The Chinese patent publication number CN106590636A discloses a Dy 3+ Doped silicate phosphor material, its emission spectrum color coordinate position is: (x = 0.2983, y = 0.3019), located in the white light region. Currently used to replace Y3Al5O 12 :Ce 3+ One of the strong candidate materials for phosphors is rare earth ion Dy 3+ Doped inorganic luminescent materials. However, the luminescence properties of this type of material are mainly determined by Dy 3+ Provided. 3+ The emission characteristic peak mainly depends on 4 F 9 / 2 Energy level to 6 H 15 / 2 and 6 H 13 / 2 The energy level transition results in peak spectral bands located in the blue and yellow regions, rather than continuous broad-peak emission. Therefore, the color rendering index of WLEDs obtained from such materials is usually low.

[0005] Vacancy-ordered halide perovskite has the advantages of strong absorption coefficient, high quantum efficiency, easy tunability of band gap, good carrier mobility, small exciton binding energy, long carrier diffusion length, etc. It has become one of the candidate materials for the preparation of LEDs and color displays. In recent years, Cs2SnCl6 vacancy-ordered halide perovskite has attracted widespread attention from researchers. The Cs2SnCl6 matrix itself does not emit light and requires ion doping to obtain additional luminescent properties. Tan et al. used Bi 3+ Ion doping of Cs2SnCl6 yielded a blue light emission with a quantum efficiency of 78.9%. 3+ The efficient blue light emission of Cs2SnCl6 doped with bismuth is generated by the defect structure. 3+ Ion-doped Cs2SnCl6 and commercial yellow phosphors produced a WLED with CIE coordinates of (0.36, 0.37) and a color temperature of 4486 K [Advanced Functional Materials, 2018, 28(29): 1801131]. Currently, no materials have been found in vacancy-ordered halide perovskites that can achieve white light emission by stimulating yellow phosphors with blue light chips.

[0006] The present invention provides a fluorescent powder that can use a blue light chip to excite a yellow vacancy-ordered halide perovskite to produce white luminescence and a preparation method thereof. 4+ Yellow luminescent phosphors were obtained by doping vacancy-ordered halide perovskites. Te is located in the fifth period and sixth main group of the periodic table, and its outer electron configuration is [Kr]4d 10 5s 2 5p 4 The present invention has proved through theoretical calculation that Te 4+ Yellow light emission from vacancy-doped ordered halide perovskites is caused by [TeCl6] 2- The 5s energy level of Te in the octahedron directly transitions to the 5p energy level of Te, generating self-trapped excitons, unlike the self-trapped excitons of vacancy-ordered halide perovskite luminescent materials. Compared to existing technologies and products, this phosphor offers advantages such as high quantum efficiency and excellent environmental and thermal stability. The preparation method of the present invention is simple, technically and economically viable, and suitable for low-cost, large-scale deployment. Summary of the Invention

[0007] The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a Te 4+ Vacancy-doped ordered halide perovskite phosphor and its preparation method and application. In the preparation process, Te 4+ Ion doping into A2MX6 vacancy-ordered halide perovskite and combining it with room temperature synthesis method to obtain Te 4+Vacancy-ordered halide perovskite phosphor doped with A2MX6 is excited by a blue light chip to obtain a WLED that can emit white light.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A Te 4+ Vacancy-doped ordered halide perovskite phosphor, the chemical formula of the phosphor is: Rb2Hf 1-x Cl6:xTe 4+ , where 0<x<1.

[0010] The Te 4+ The excitation wavelength of the doped vacancy ordered perovskite phosphor is 250-480nm. ex =460nm) to obtain a phosphor that emits white light.

[0011] Preferably, x=0.03, Te 4+ The chemical formula of the vacancy-doped ordered perovskite phosphor is Rb2Hf 0.97 Cl6:0.03Te 4+ .

[0012] The Te 4+ A method for preparing a vacancy-doped ordered halide perovskite phosphor comprises the following steps:

[0013] (1) Te 4+ The source and compound HfCl4 are added into a container, and then hydrochloric acid is added and dissolved after stirring to obtain solution A;

[0014] Wherein, the amount of hydrochloric acid added corresponding to each xmmol HfCl4 is 1-10mL, and the mass percentage concentration of the hydrochloric acid is 36%-38%;

[0015] The Te 4+ The source is specifically TeCl4 or TeO2;

[0016] (2) Add RbCl to hydrochloric acid to obtain solution B, and add solution B dropwise to solution A with a dropper under vigorous stirring. After the addition of solution B is complete, continue stirring for 20-200 minutes;

[0017] (3) The product obtained in the previous step is washed with an alcohol solvent, and then dried at 25° C.-80° C. for 2-20 hours to finally obtain a perovskite phosphor; the alcohol solvent is anhydrous ethanol, isopropyl alcohol or anhydrous methanol.

[0018] Preferably, the product in step (3) is washed with anhydrous ethanol 6 times and dried at 60° C. for 12 hours.

[0019] The Te 4+ Vacancy-doped ordered halide perovskite phosphors are used to prepare WLEDs.

[0020] The present invention is achieved by Te 4+ Doping Rb2HfCl6 vacancy ordered perovskite obtains a material that can excite yellow phosphor to achieve white luminescence with a blue chip. The phosphor has high PLQY, good stability, and easy-to-obtain raw materials. Te 4+ Doping Rb2HfCl6 phosphor has a simple process, fast reaction and high yield. It is a safe and effective method for preparing vacancy-ordered perovskite, which can reduce the preparation cost while ensuring large-scale production.

[0021] The beneficial effects of the present invention are:

[0022] Te of the present invention 4+ Vacancy-doped ordered perovskite phosphors not only address the technical challenges of existing WLED phosphors, such as low photoluminescence quantum efficiency, poor CRI, and high CCT, but also overcome the complex and costly process for synthesizing these phosphors. This phosphor synthesis method is simple to operate and offers high yields. WLEDs assembled with this phosphor exhibit chromaticity parameters approaching those of standard white light. This is reflected in the following key aspects:

[0023] (1) Te of the present invention 4+ When excited by a blue light chip, the CIE coordinates of the vacancy-doped ordered perovskite phosphor are located at (0.3502, 0.3527) and the correlated color temperature (CCT) is 4814K, close to standard white light. Its color rendering index (CRI) is 75.3, which is higher than that of the commercial yellow phosphor Y3Al5O 12 :Ce 3+ .

[0024] (2) The raw materials used in the present invention are cheap, the room temperature precipitation synthesis process is easy to operate, and the yield is high. 12 :Ce 3+ Compared with yellow phosphor, it has the advantages of simple preparation, energy saving and large-scale production.

[0025] (3) Te of the present invention 4+ Yellow emission from vacancy-doped ordered halide perovskites is induced by the activator [TeCl6] 2- The 5s energy level of Te in the octahedron directly transitions to the 5p energy level of Te, which is different from the self-trapped exciton luminescence of vacancy-ordered halide perovskite luminescent materials. The charge transfer in self-trapped exciton luminescence needs to pass through the matrix and then be transferred to the energy level of the activator, resulting in partial energy consumption. However, the present invention [TeCl6] 2-Te in octahedron 4+ The efficient luminescence of ions is achieved by direct relaxation of the excited state to the ground state. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Rb2Hf in Example 1 0.97 Cl6:0.03Te 4+ The photoluminescence quantum efficiency diagram. According to the following formula, Rb2HfCl6: 3%Te 4+ The quantum efficiency of Yu reached 76.72%.

[0027] Yu=(Ys*Fu*As) / (Fs*Au)

[0028] Yu, Ys-fluorescence quantum efficiency of the test substance and reference standard substance;

[0029] Fu, Fs- are the integrated fluorescence intensities of the test substance and the reference substance;

[0030] Au, As- are the absorbances of the incident light of the test substance and the reference substance at the excitation wavelength (A=εbc).

[0031] Figure 2 This is the emission spectrum of the WLED in Example 1. As can be seen from the figure, the emission spectrum includes two parts: the blue light chip peak and the phosphor yellow light peak.

[0032] Figure 3 1931 chromaticity parameter diagram of the WLED in Example 1. Its CIE coordinates are (0.3502, 0.3527), CCT is 4814K, and CRI is 75.3.

[0033] Figure 4 This is a graph showing the luminous intensity decay of the WLED after continuous operation in Example 1. After continuous operation for 10 hours, the luminous intensity can still be maintained at more than 90%.

[0034] More specifically, the following embodiments of the present invention provide Te 4+ The vacancy-doped ordered perovskite phosphor and its preparation method are described in more detail. DETAILED DESCRIPTION

[0035] The following is a detailed and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0036] Example 1

[0037] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0038] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0039] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0040] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0041] Example 2

[0042] Rb2H 0.99 Cl6:0.01Te 4+ The preparation method is as follows:

[0043] (1) Weigh 0.01 mmol TeCl4 and 0.99 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0044] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0045] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0046] Example 3

[0047] Rb2H 0.95 Cl6:0.05Te 4+ The preparation method is as follows:

[0048] (1) Weigh 0.05 mmol TeCl4 and 0.95 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0049] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0050] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0051] Example 4

[0052] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0053] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), then add 5 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0054] (2) Prepare solution B by mixing 2 mmol of RbCl and 5 mL of 36%-38% hydrochloric acid. Slowly add solution B to solution A with a pipette while stirring. After the addition of solution B is complete, continue stirring for 100 minutes to allow for complete reaction.

[0055] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0056] Example 5

[0057] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0058] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 7 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0059] (2) Solution B was prepared by mixing 2 mmol of RbCl and 7 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0060] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0061] Example 6

[0062] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0063] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0064] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 150 minutes to allow for complete reaction.

[0065] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0066] Example 7

[0067] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0068] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0069] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 200 minutes to allow for complete reaction.

[0070] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 12 hours to obtain phosphor.

[0071] Example 8

[0072] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0073] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0074] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0075] (3) The product was washed with anhydrous ethanol six times and dried at 50°C for 12 hours to obtain phosphor.

[0076] Example 9

[0077] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0078] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0079] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0080] (3) The product was washed with anhydrous ethanol six times and dried at 80°C for 12 hours to obtain phosphor.

[0081] Example 10

[0082] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0083] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0084] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0085] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for eight hours to obtain phosphor powder.

[0086] Example 11

[0087] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0088] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0089] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0090] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 15 hours to obtain phosphor.

[0091] Example 12

[0092] Rb2H 0.97 Cl6:0.03Te 4+ The preparation method is as follows:

[0093] (1) Weigh 0.03 mmol TeCl4 and 0.97 mmol HfCl4 (both with a purity of more than 98%), and then add 10 mL of 36%-38% hydrochloric acid into a beaker as solution A. Seal the beaker and stir for 30 minutes to allow the solution to fully dissolve.

[0094] (2) Solution B was prepared by mixing 2 mmol of RbCl and 10 mL of hydrochloric acid with a mass percentage concentration of 36%-38%. Solution B was slowly added dropwise to solution A using a pipette under stirring. After the addition of solution B was completed, stirring was continued for 100 minutes to allow for complete reaction.

[0095] (3) The product was washed with anhydrous ethanol six times and dried at 60°C for 20 hours to obtain phosphor powder.

[0096] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the embodiments. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is understood that such obvious variations or modifications based on the present invention are still within the scope of protection of the present invention.

Claims

1. A Te 4+ Vacancy-doped ordered halide perovskite phosphor and its preparation method, characterized in that the chemical formula of the phosphor is: Rb2Hf 1-x Cl6:xTe 4+ , where 0<x<1. The phosphor is prepared from TeCl4, HfCl4, and RbCl by a precipitation method at room temperature. TeCl4 and HfCl4 are accurately weighed according to a certain stoichiometric ratio and fully dissolved in hydrochloric acid. The dissolved RbCl is then added dropwise to the solution. The solution is magnetically stirred for several hours to allow the raw materials to fully react and precipitate. The precipitate is dried to obtain the phosphor. The phosphor is used to prepare white light-emitting diodes.

2. Te according to claim 1 4+ Vacancy-doped ordered halide perovskite phosphors characterized by The excitation range of the phosphor is 280-480nm, and white light is obtained under the excitation of a blue light chip, and is used to prepare a white light-emitting diode.

3. Te according to claim 1 4+ Vacancy-doped ordered halide perovskite phosphor, preferably, x=0.03, Te 4+ The chemical formula of the vacancy-doped ordered perovskite phosphor is Rb2Hf 0.97 Cl6:0.03Te 4+ .

4. Te according to claim 1 4+ Preparation method of vacancy-doped ordered halide perovskite phosphor, The method is characterized in that it comprises the following steps: (1) Te 4+ The source and compound HfCl4 are added to a container, and hydrochloric acid is added, stirred and dissolved to obtain solution A; wherein the amount of hydrochloric acid added corresponding to each x mmol HfCl4 is 1.0-10 mL; (2) RbCl Add hydrochloric acid to obtain solution B, and add solution B dropwise to solution A with a dropper under vigorous stirring. After the addition of solution B is completed, continue stirring for 10-200 minutes; (3) The product obtained in the previous step is washed with an alcohol solvent, and then dried at 25°C-80°C for 2-20 hours to finally obtain a double perovskite phosphor; the alcohol solvent is anhydrous ethanol, isopropyl alcohol or anhydrous methanol.

5. The method for preparing the Te4+ doped vacancy ordered halide double perovskite phosphor according to claim 4, characterized in that Preferably, the mass percentage concentration of the hydrochloric acid in step (2) is 36%-38%; in step (3), the product is washed 6 times with anhydrous ethanol and dried at 50-100° C. for 1-12 hours.

6. Te according to claim 4 4+ A method for preparing vacancy-doped ordered halide perovskite phosphor, characterized in that the Te 4+ The source is specifically TeCl4 or TeO2.

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