Dual-band light-emitting fluorescent powder and preparation method and application thereof
By synthesizing KSF powder and CsPbBr3 quantum dots in the template agent, it ensures that the quantum dots grow and crystallize with the red phosphor, forming a dual-band luminescent phosphor, solving the process complexity and stability problems of traditional phosphors in complex spectral applications, and achieving efficient, thermally stable and widely used phosphor materials.
Patent Information
- Application Number
- CN202510102327.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-22
- Publication Date
- 2025-05-06
AI Technical Summary
Traditional phosphors can only emit light in a specific single wavelength range, resulting in the need to mix multiple different phosphors in complex spectral or multi-color display applications, increasing process complexity and cost, and affecting the stability and consistency of luminous performance.
A template agent with a pore is used to set green perovskite quantum dots and red phosphors inside, and through the technical route of synthesizing KSF powder and CsPbBr3 quantum dots, it is ensured that at least some of the CsPbBr3 quantum dots grow and crystallize with the red phosphor, thereby forming a dual-band luminescent phosphor.
The phosphor material with high dual-band luminescence efficiency, good thermal stability and relatively simple preparation process has been achieved, which has expanded its application in the field of modern lighting and display technology, and has solved the water resistance and thermal stability challenges of commercially doped Mn4+ red light luminescence phosphors.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of phosphor synthesis, and in particular relates to a dual-band luminescent phosphor and a preparation method and application thereof. Background Art
[0002] Phosphor is a photoluminescent material that can convert the color of excitation light and plays a vital role in the field of modern lighting and display technology. Phosphor includes ions that emit light, such as manganese ions (Mn 2+ ) can produce orange or green light, semiconductor luminescent BaZn2(BO3)2 phosphors, perovskite quantum dots, cadmium quantum dots, InP, etc., are widely used in lighting and LCD (liquid crystal display) fields.
[0003] However, traditional phosphors can only emit light within a specific single wavelength range, which requires mixing a variety of different phosphors in the construction of complex spectra or multi-color display applications. This not only increases the complexity and cost of the process, but also easily affects the stability and consistency of the luminous performance due to differences in the phosphor ratio. In addition, some existing fluorescent materials have deficiencies in energy conversion efficiency, luminous intensity, and thermal stability, which limits their application in scenarios such as high-power lighting and long-term display. Therefore, developing a new method for preparing dual-band luminescent phosphors to overcome the limitations of existing technologies has become a hot topic and key to current phosphor technology research. Summary of the invention
[0004] The purpose of the present invention is to provide a dual-band luminescent phosphor and a preparation method and application thereof, aiming to obtain a dual-band luminescent phosphor material with high luminous efficiency, good thermal stability and relatively simple preparation process, so as to promote the further development of lighting and display technology.
[0005] To achieve the above object, the technical solution adopted by the present invention is:
[0006] A dual-band luminescent phosphor comprises a template having pores, wherein the pores of the template are provided with green perovskite quantum dots and red phosphor;
[0007] At least a portion of the green perovskite quantum dots grow and crystallize on the red phosphor.
[0008] Furthermore, the green perovskite quantum dots are CsPbBr3, and the red phosphor is KSF powder.
[0009] Furthermore, the template is one of molecular sieve and silicon oxide.
[0010] A method for preparing a dual-band luminescent phosphor comprises the following steps:
[0011] A1. Synthesize KSF powder in template:
[0012] (1) dissolving an excess amount of template in a hydrofluoric acid solution, heating and stirring until dissolved to obtain an emulsion A;
[0013] (2) adding potassium permanganate and potassium fluoride to a hydrofluoric acid solution, heating and stirring until dissolved to obtain a solution B;
[0014] (3) Emulsion A and solution B were mixed and stirred evenly, and hydrogen peroxide was slowly added dropwise until the solution turned yellow-brown. After washing with acetone, the solution was dried in an oven to obtain a light yellow powder.
[0015] A2. Resynthesize green perovskite quantum dots in the template.
[0016] By adopting the above technical solution: First, whether the template is a molecular sieve or silicon oxide, its main component is silicon dioxide, and silicon dioxide will react in a hydrofluoric acid solution to form H2SiF6 that is easily soluble in water. At this time, part of the template is consumed by the hydrofluoric acid solution to form H2SiF6, which is used to react with potassium fluoride to form K2SiF6 in the later stage, and K2SiF6 is the raw material for synthesizing KSF powder. At the same time, the excess template acts as a carrier for the KSF generated in the later reaction to diffuse and adsorb into the pores.
[0017] Secondly, the excess template of the present invention provides a synthetic KSF powder (K2SiF6: Mn 4+ ) and participate in the synthesis process of KSF powder. On the other hand, it also serves as the "shell" of the synthesized KSF powder.
[0018] At the same time, this application selects the technical route of first synthesizing KSF powder in the template and then synthesizing perovskite quantum dots. And the choice of this technical route is unique and specific.
[0019] The subsequent technical route for synthesizing and diffusing perovskite quantum dots in the template pores is not unique, and this application uses the following examples, but is not limited to them. The following is a detailed description:
[0020] Furthermore, the step A2 is to synthesize green perovskite quantum dots in the gas phase, including the following:
[0021] The CsPbBr3 solid phase precursor and the light yellow powder obtained in the A1 step are ground and mixed, and then the mixed powder is heated to 450-580°C in an air atmosphere, maintained for at least 0.5 hour, and finally cooled to allow rapid crystallization, so that the gas phase lead, cesium and halogen atoms react to form CsPbBr3 quantum dots; at least part of the CsPbBr3 quantum dots grow and crystallize attached to the red phosphor.
[0022] The present invention provides another technical route for synthesizing green perovskite quantum dots in a template, wherein the step A2 is to synthesize green perovskite quantum dots by microwave heating, which includes the following steps:
[0023] Mixing the CsPbBr3 solid phase precursor solution and the light yellow powder obtained in step A1, so that the CsPbBr3 solid phase precursor solution is adsorbed into the pores of the template, and obtaining a spatially confined CsPbBr3 solid phase precursor solution, i.e., an intermediate product;
[0024] Then, the intermediate product is placed in a microwave oven, the microwave is turned on, the power is adjusted to 50-100W, the microwave time is set to 1-8min, and the CsPbBr3 solid phase precursor is reacted in the template pores to form CsPbBr3 quantum dots through microwave heating;
[0025] The solute of the CsPbBr3 solid phase precursor solution is CsPbBr3 solid phase precursor, and the solvent is one of ethanolamine and trimethoxypropylamine.
[0026] In the above, the solvents are ethanolamine and trimethoxypropylamine. On the one hand, they satisfy the requirement of dissolving the CsPbBr3 solid phase precursor as a qualified carrier solvent; on the other hand, ethanolamine and trimethoxypropylamine can be adsorbed into the pores of the template; on the third hand, ethanolamine and trimethoxypropylamine solve the defect of KSF being afraid of water.
[0027] In the above-mentioned technical route of synthesizing green perovskite quantum dots in the template, whether it is gas phase synthesis or liquid phase microwave synthesis, the CsPbBr3 solid phase precursor is easily attached to the red phosphor to grow and crystallize to form CsPbBr3 quantum dots after being adsorbed into the pores of the template, and at least part of the CsPbBr3 quantum dots grow and crystallize attached to the red phosphor.
[0028] Further, the CsPbBr3 solid phase precursor includes a Cs source precursor, a Pb source precursor and a Br source precursor;
[0029] The Cs source precursor is one or more of cesium halide and cesium carbonate;
[0030] The Pb source precursor is one or more of lead halide and lead acetate;
[0031] The Br source precursor comes from the Br source provided by the cesium halide or lead halide.
[0032] Furthermore, the heating conditions of the emulsion A in step A1 are: temperature 30-80° C., stirring time 30-60 min;
[0033] The heating conditions of the solution B in step A1 are: temperature 30-80° C., stirring time 30 min-60 min.
[0034] Furthermore, the potassium fluoride in step A1 includes potassium fluoride, potassium bifluoride and a combination thereof.
[0035] Furthermore, the dual-band luminescent phosphor can be applied to perovskite diffuser plates, inkjet printing, wavelength conversion films, quantum dot films or Micro LEDs.
[0036] The beneficial effects of the present invention are mainly reflected in: the present invention successfully obtains a phosphor that can stably emit light in two different bands, expanding the application of phosphors in the field of modern lighting and display technology. At the same time, the phosphor obtained by the present invention has good water resistance and thermal stability of luminescence, which solves the problem of commercial Mn doping. 4+ The great challenges facing red light emitting phosphors. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 The spectrum of the sample obtained in Example 1 of the present invention;
[0038] Figure 2 The spectrum of the sample obtained for Comparative Example 1 of the present invention. DETAILED DESCRIPTION
[0039] In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific implementation methods described herein are only used to explain the present invention and are not used to limit the present invention.
[0040] Embodiment 1:
[0041] Step 1: Dissolve 1.2 g of MCM in 3 mL of hydrofluoric acid (40% wt) solution, heat and stir at 40° C. for 30 min to obtain emulsion A.
[0042] Step 2: Dissolve 79 mg potassium permanganate and 4.5 g potassium bifluoride in 4 mL hydrofluoric acid (40% wt), heat and stir at 40°C for 30 min to obtain solution B. Stir and mix the emulsion A obtained in step 1 and solution B evenly, slowly add hydrogen peroxide until the solution changes from purple to yellow-brown, wash with acetone three times, and dry in an oven at 60°C to obtain a light yellow powder.
[0043] Step 3: Grind and mix 127.7 mg of cesium bromide and 220.2 mg of lead bromide powder to obtain the corresponding CsPbBr3 solid phase precursor;
[0044] Step 4: Grind and mix the CsPbBr3 solid phase precursor and the light yellow powder obtained in step 2 thoroughly, then heat the mixed powder in an air atmosphere at 560°C for 1 hour; cool and crystallize to allow gas phase lead, cesium and halogen atoms to react and form halide perovskite.
[0045] Embodiment 2:
[0046] Step 1: Dissolve 1.2 g of MCM in 3 mL of hydrofluoric acid (40%) solution, heat and stir at 40° C. for 30 min to obtain emulsion A.
[0047] Step 2: Dissolve 158 mg potassium permanganate and 4.5 g potassium bifluoride in 4 mL hydrofluoric acid (40%), heat and stir at 40°C for 30 min to obtain solution B. Stir and mix the emulsion A obtained in step 1 and solution B evenly, slowly add hydrogen peroxide until the solution changes from purple-red to yellow-brown, wash with acetone three times, and dry in an oven at 60°C to obtain a light yellow powder.
[0048] Step 3: Grind and mix 127.7 mg of cesium bromide and 220.2 mg of lead bromide powder to obtain the corresponding CsPbBr3 solid phase precursor;
[0049] Step 4: Grind and mix the CsPbBr3 solid phase precursor and the light yellow powder obtained in step 2 thoroughly, then heat the mixed powder in an air atmosphere at 560°C for 1 hour; cool and crystallize to allow gas phase lead, cesium and halogen atoms to react and form halide perovskite.
[0050] Embodiment 3:
[0051] Step 1: Dissolve 1.2 g of MCM in 3 mL of hydrofluoric acid (40% wt) solution, heat and stir at 40° C. for 30 min to obtain emulsion A.
[0052] Step 2: Dissolve 79 mg potassium permanganate and 4.5 g potassium bifluoride in 4 mL hydrofluoric acid (40% wt), heat and stir at 40°C for 30 min to obtain solution B. Stir and mix the emulsion A obtained in step 1 and solution B evenly, slowly add hydrogen peroxide until the solution changes from purple to yellow-brown, wash with acetone three times, and dry in an oven at 60°C to obtain a light yellow powder.
[0053] Step 3: Grind and mix 127.7 mg of cesium bromide and 220.2 mg of lead bromide powder to obtain the corresponding CsPbBr3 solid phase precursor, and dissolve the CsPbBr3 solid phase precursor in 4 mL of ethanolamine to obtain a CsPbBr3 solid phase precursor solution.
[0054] Step 4: Fully mix the CsPbBr3 solid phase precursor solution and the light yellow powder obtained in step 2, so that the CsPbBr3 solid phase precursor solution is adsorbed into the pores of the MCM to obtain a spatially confined CsPbBr3 solid phase precursor solution, i.e., an intermediate product;
[0055] Then, the intermediate product is placed in a microwave oven, the microwave is turned on, the power is adjusted to 80 W, the microwave time is set to 8 minutes, and the CsPbBr3 solid phase precursor is reacted in the template pores through microwave heating to form CsPbBr3 quantum dots.
[0056] Comparative Example 1:
[0057] The difference from Example 1 is that step 3 and step 4 do not exist.
[0058] Step 1: Dissolve 1.2 g of MCM in 3 mL of hydrofluoric acid (40%) solution, heat and stir at 40° C. for 30 min to obtain emulsion A.
[0059] Step 2: Dissolve 79 mg potassium permanganate and 4.5 g potassium bifluoride in 4 mL hydrofluoric acid (40%), heat and stir at 40°C for 30 min to obtain solution B. Stir and mix the emulsion A obtained in step 1 and solution B evenly, slowly add hydrogen peroxide until the solution changes from purple-red to yellow-brown, wash with acetone three times, and dry in an oven at 60°C to obtain a light yellow powder.
[0060] Experimental analysis: Take Example 1 ( Figure 1 ) and Comparative Example 1 ( Figure 2 ) were used to prepare the final products. The PL of each product under 450nm blue light laser is as shown in the following table.
[0061] Comparative Example 2:
[0062] The difference from Example 1 is that there is no KSF powder.
[0063] Step 1: Grind and mix 127.7 mg of cesium bromide and 220.2 mg of lead bromide powder to obtain the corresponding CsPbBr3 solid phase precursor.
[0064] Step 2: Grind and mix the CsPbBr3 solid phase precursor and 1.2g MCM thoroughly. Then, heat the mixed powder in an air atmosphere at 560°C for 1 hour; cool and crystallize to make the gas phase lead, cesium and halogen atoms react and form halide perovskite.
[0065] Table 1 shows the stability and PLQY of the final products of various embodiments and comparative examples in high temperature environments of 60°C and 100°C.
[0066]
[0067]
[0068] Table 1
[0069] The present invention illustrates the detailed preparation method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed preparation method, that is, it does not mean that the present invention must rely on the above-mentioned products and detailed preparation methods to be implemented. It should be clear to those skilled in the art that any improvement of the present invention, the combination or equivalent replacement of the raw materials of the product of the present invention, all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A dual-band luminescent phosphor, characterized in that: It comprises a template having pores, wherein green perovskite quantum dots and red phosphor are arranged in the pores of the template; At least a portion of the green perovskite quantum dots grow and crystallize on the red phosphor.
2. The dual-band luminescent phosphor according to claim 1, characterized in that: The green perovskite quantum dots are CsPbBr3, and the red phosphor is KSF powder.
3. The dual-band luminescent phosphor according to claim 1, characterized in that: The template is one of molecular sieve and silicon oxide.
4. A method for preparing a dual-band luminescent phosphor according to any one of claims 1 to 3, characterized in that: The steps include: A1. Synthesize KSF powder in template: (1) dissolving an excess amount of template in a hydrofluoric acid solution, heating and stirring until dissolved to obtain an emulsion A; (2) adding potassium permanganate and potassium fluoride to a hydrofluoric acid solution, heating and stirring until dissolved to obtain a solution B; (3) Emulsion A and solution B were mixed and stirred evenly, and hydrogen peroxide was slowly added dropwise until the solution turned yellow-brown. After washing with acetone, the solution was dried in an oven to obtain a light yellow powder. A2. Resynthesize green perovskite quantum dots in the template.
5. The method for preparing a dual-band luminescent phosphor according to claim 4, characterized in that: The step A2 is to synthesize green perovskite quantum dots in the gas phase, including the following: The CsPbBr3 solid phase precursor and the light yellow powder obtained in the A1 step are ground and mixed, and then the mixed powder is heated to 450-580°C in an air atmosphere, maintained for at least 0.5 hour, and finally cooled to allow rapid crystallization, so that the gas phase lead, cesium and halogen atoms react to form CsPbBr3 quantum dots; at least part of the CsPbBr3 quantum dots grow and crystallize attached to the red phosphor.
6. The method for preparing a dual-band luminescent phosphor according to claim 4, characterized in that: The step A2 is to synthesize green perovskite quantum dots by microwave heating, which includes the following steps: Mixing the CsPbBr3 solid phase precursor solution and the light yellow powder obtained in step A1, so that the CsPbBr3 solid phase precursor solution is adsorbed into the pores of the template, and obtaining a spatially confined CsPbBr3 solid phase precursor solution, i.e., an intermediate product; Then, the intermediate product is placed in a microwave oven, the microwave is turned on, the power is adjusted to 50-100W, the microwave time is set to 1-8min, and the CsPbBr3 solid phase precursor is reacted in the template pores to form CsPbBr3 quantum dots through microwave heating; The solute of the CsPbBr3 solid phase precursor solution is CsPbBr3 solid phase precursor, and the solvent is one of ethanolamine and trimethoxypropylamine.
7. The method for preparing a dual-band luminescent phosphor according to claim 5 or 6, characterized in that: The CsPbBr3 solid phase precursor includes a Cs source precursor, a Pb source precursor and a Br source precursor; The Cs source precursor is one or more of cesium halide and cesium carbonate; The Pb source precursor is one or more of lead halide and lead acetate; The Br source precursor comes from the Br source provided by the cesium halide or lead halide.
8. The method for preparing a dual-band luminescent phosphor according to claim 4, characterized in that: The heating conditions of the emulsion A in step A1 are: temperature 30-80°C, stirring time 30-60 min; The heating conditions of the solution B in step A1 are: temperature 30-80° C., stirring time 30 min-60 min.
9. The method for preparing a dual-band luminescent phosphor according to claim 4, characterized in that: The potassium fluoride in step A1 includes potassium fluoride, potassium bifluoride and a combination thereof.
10. The use of a dual-band luminescent phosphor according to any one of claims 1 to 3, characterized in that: The dual-band luminescent phosphor can be applied to perovskite diffuser plates, inkjet printing, wavelength conversion films, quantum dot films or Micro LEDs.