A batch manufacturing method of a rapid solid-phase perovskite quantum dot fluorescent powder

Abstract

The application belongs to the technical field of semiconductor material preparation, and particularly relates to a batch manufacturing method of rapid solid-phase perovskite quantum dot fluorescent powder. The application takes micro-powder polymer with rich surface environment as a dispersion carrier to ensure uniform dispersion of quantum dots and avoid fluorescence quenching caused by clustering. The application adds perovskite precursors into the micro-powder polymer, uses high-speed crushing force as a reaction driving force to induce the perovskite precursors to uniformly and rapidly nucleate and grow on the surface of the micro-powder polymer, and prepares perovskite quantum dot materials with high luminous efficiency and uniform morphology. The manufacturing method provided by the application can realize 100% raw material utilization, has no chemical waste, the synthesis rate can reach 1 kg / min, and the quantum yield can reach 90%. The application provides a solvent-free manufacturing method with high efficiency, full solid state, high yield, low cost, green environmental protection, scalability and industrialization, and realizes efficient batch preparation of perovskite quantum dot materials.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of semiconductor material preparation, and particularly relates to a batch manufacturing method of rapid solid-phase perovskite quantum dot fluorescent powder. BACKGROUND

[0002] Due to the characteristics of low energy consumption, high efficiency and long service life, solid-state lighting has replaced traditional incandescent lamps and fluorescent lamps and is widely used in daily life. The mainstream perovskite quantum dot material used in solid-state lighting currently faces challenges such as low quantum yield, high preparation cost and harsh synthesis conditions, and there is an urgent need to develop new perovskite quantum dot materials to meet the needs of modern solid-state lighting.

[0003] Metal halide perovskite quantum dot materials have become a strong competitor for the next generation of lighting technology due to their high luminous efficiency, easily adjustable optical band gap and low preparation cost, and have very high development value. However, most of the current synthesis methods for perovskite quantum dots use solution processes, which will face problems such as waste liquid treatment of organic solvents during industrial production (Science Bulletin 2017, 62(5), 369.), limiting their application and promotion in industrialization.

[0004] Therefore, researchers have developed solid-phase direct synthesis technology for perovskite quantum dots, which avoids the problem of waste liquid treatment of organic solvents, such as ball milling (ACS Applied Nano Materials 2018, 1(3), 1300) or solid-phase sintering (Journal of Materials Chemistry C, 2021, 9(36): 12303-12313). However, the current solid-phase method has problems such as low synthesis rate (usually several hours are needed), which cannot meet the needs of industrial application. SUMMARY

[0005] The purpose of the present application is to provide a batch manufacturing method of rapid solid-phase perovskite quantum dot fluorescent powder. The manufacturing method provided by the present application is efficient, and the synthesis rate can reach 1 kg / min.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] The present application provides a batch manufacturing method of rapid solid-phase perovskite quantum dot fluorescent powder, comprising the following steps:

[0008] (1) mixing organic cesium salt, organic lead salt, organic ligand and polymer micro powder to obtain perovskite precursor; the first mixing rate is 10000-20000 rpm;

[0009] (2) ionization reaction of the organic halide salt and the perovskite precursor to obtain the perovskite quantum dot material; the speed of the second mixing is 10000-20000 rpm.

[0010] Preferably, in step (1), the temperature of the first mixing is room temperature, the atmosphere is air atmosphere, and the reaction time is 1-2 min.

[0011] Preferably, in step (2), the temperature of the ionization reaction is room temperature, the atmosphere is air atmosphere, and the reaction time is 1-5 min.

[0012] Preferably, in step (1), the organic cesium salt includes one or more of cesium stearate and cesium acetate; the mass ratio of the organic cesium salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder, and the organic halide salt is 0.004-0.020:1.

[0013] Preferably, in step (1), the organic lead salt includes one or more of lead stearate and lead acetate; the mass ratio of the organic lead salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder, and the organic halide salt is 0.01-0.06:1.

[0014] Preferably, in step (1), the organic ligand includes one or more of organic amine and organic acid; the molar ratio of the organic ligand to the organic lead salt is 0.1-2.0:1.

[0015] Preferably, in step (1), the polymer micro powder includes one or more of polyolefin and its derivative, polyester, polyaldehyde, polyamide, polyalcohol, and polynitrile; the mass ratio of the polymer micro powder to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder, and the organic halide salt is 0.9-1.0:1.

[0016] Preferably, in step (2), the organic halide salt includes one or more of tribromopyridinium, dibromotriphenylphosphonium, oleylamine chloride, oleylamine iodine, octadecylamine chloride, and octadecylamine iodine; the mass ratio of the organic halide salt to the polymer micro powder is 0.01-0.05:1.

[0017] The application further provides the perovskite quantum dot material obtained by the batch manufacturing method described in the above scheme, with a chemical formula of CsPbX3, wherein X is a halogen element; the luminescent efficiency of the perovskite quantum dot material is 50%-90%, and the particle size distribution is 5-15 nm.

[0018] The application further provides the application of the perovskite quantum dot material described in the above scheme in the field of lighting and display.

[0019] The application provides a batch manufacturing method of a quick solid-phase perovskite quantum dot fluorescent powder.

[0020] The manufacturing method provided by the application can realize 100% raw material utilization, has no chemical waste, has a synthesis rate of 1 kg / min, and has a quantum yield of 90%.

[0021] The application provides a solvent-free manufacturing method with high efficiency, full solid state, high yield, low cost, green environmental protection, scalability and industrialization, realizes efficient batch preparation of perovskite quantum dot materials, and can realize universal synthesis of multi-color materials such as red, green and blue multi-band perovskite quantum dot materials by adjusting the types of halogen salts and polymers, and has great development value and commercial prospect.

[0022] The application also provides perovskite quantum dot materials prepared by the manufacturing method.

[0023] The application also provides applications of the perovskite quantum dot materials in the fields of lighting and display. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the drawings needed in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the application, and those skilled in the art can also obtain other drawings according to these drawings without creative effort.

[0025] Figure 1 A real photo and a fluorescence spectrum diagram of the perovskite quantum dot materials prepared for Example 1;

[0026] Figure 2 A fluorescence spectrum diagram of the perovskite quantum dot materials prepared for Example 2;

[0027] Figure 3 A fluorescence spectrum diagram of the perovskite quantum dot materials prepared for Example 3;

[0028] Figure 4 A physical photo of the perovskite quantum dot material prepared for Example 4;

[0029] Figure 5 A fluorescence quantum yield diagram of the perovskite quantum dot material prepared for Example 1. DETAILED DESCRIPTION

[0030] The application provides a batch manufacturing method for rapidly solidifying perovskite quantum dot fluorescent powder, comprising the following steps:

[0031] (1) first mixing organic cesium salt, organic lead salt, organic ligand and polymer micro powder to obtain perovskite precursor; the first mixing rate is 10000-20000 rpm;

[0032] (2) second mixing organic halide salt with the perovskite precursor to carry out ionic combination reaction, so as to obtain perovskite quantum dot material; the second mixing rate is 10000-20000 rpm.

[0033] The application first mixes organic cesium salt, organic lead salt, organic ligand and polymer micro powder to obtain perovskite precursor.

[0034] In the application, in step (1), the organic cesium salt preferably comprises one or more of cesium stearate and cesium acetate.

[0035] In the application, in step (1), the organic lead salt preferably comprises one or more of lead stearate and lead acetate.

[0036] In the application, in step (1), the organic ligand preferably comprises one or more of organic amine and organic acid; the organic amine preferably comprises one or more of oleylamine, octylamine and octadecylamine; the organic acid preferably comprises one or more of oleic acid and octanoic acid.

[0037] In the application, in step (1), the polymer micro powder preferably comprises one or more of polyolefin and its derivative, polyester, polyaldehyde, polyamide, polyalcohol and polynitrile.

[0038] In the application, the polyolefin and its derivative preferably comprises one or more of polystyrene (PS), polyethylene (PE), polypropylene (PP), polyethylene oxide (PEO), ethylene-vinyl acetate copolymer (EVA), polyvinylidene fluoride (PVDF), ethylene acrylic acid copolymer (EAA), polyvinyl chloride (PVC) and polyvinylpyrrolidone (PVP); the polyethylene is preferably low-density polyethylene (LDPE).

[0039] In the present application, the polyester preferably includes one or more of polymethyl methacrylate (PMMA), polylactic acid (PLA), polyurethane (TPU), polyethylene terephthalate (PET), polycaprolactone (PCL), and polyhydroxybutyrate (PHB).

[0040] In the present application, the polyaldehyde preferably includes one or both of polyoxymethylene (POM) and polyvinyl butyral (PVB).

[0041] In the present application, the polyamide preferably includes one or both of polyamide 6 (PA6) and polyacrylamide (PHIII).

[0042] In the present application, the polyalcohol is preferably polyvinyl alcohol (PVA); and the polynitrile is preferably polyacrylonitrile (PAN).

[0043] In the present application, in step (1), the ratio of the mass of the organic cesium salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder, and the organic halogenated salt is preferably 0.004-0.020:1, more preferably 0.008-0.018:1, and further preferably 0.012-0.015:1.

[0044] In the present application, in step (1), the ratio of the mass of the organic lead salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder, and the organic halogenated salt is preferably 0.01-0.06:1, more preferably 0.02-0.05:1, and further preferably 0.03-0.04:1.

[0045] In the present application, in step (1), the molar ratio of the organic ligand to the organic lead salt is preferably 0.1-2.0:1, more preferably 0.4-1.7:1, and further preferably 0.8-1.4:1.

[0046] In the present application, in step (1), the ratio of the mass of the polymer micro powder to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder, and the organic halogenated salt is preferably 0.9-1.0:1, more preferably 0.92-0.98:1, and further preferably 0.94-0.96:1.

[0047] In the present application, in step (1), the rate of the first mixing is preferably 12000-20000 rpm, more preferably 14000-20000 rpm, and further preferably 16000-18000 rpm; and the device of the first mixing is preferably a high-speed ultra-fine powder crusher.

[0048] In the present application, the temperature of the first mixing is preferably room temperature, the atmosphere is preferably air atmosphere, and the reaction time is preferably 1-2 min, more preferably 1.5 min.

[0049] After obtaining the perovskite precursor, the organic halide salt is secondarily mixed with the perovskite precursor to perform an ion combination reaction, thereby obtaining the perovskite quantum dot material. In the present application, the speed of the second mixing is preferably 12000-20000 rpm, more preferably 15000-20000 rpm, and further preferably 17000-20000 rpm; and the device for the second mixing is preferably a high-speed superfine powder crusher.

[0050] In the present application, in step (2), the organic halide salt preferably comprises one or more of tribromopyridinium, dibromotriphenylphosphonium, oleylamine chloride, oleylamine iodine, octadecylamine chloride and octadecylamine iodine.

[0051] In the present application, in step (2), the mass ratio of the organic halide salt to the polymer micro-powder is preferably 0.01-0.05:1, more preferably 0.02-0.04:1, and further preferably 0.03:1.

[0052] In the present application, in step (2), the temperature of the ion combination reaction is preferably room temperature, the atmosphere is preferably air atmosphere, and the reaction time is preferably 1-5 min, more preferably 2-4 min, and further preferably 3 min. The batch manufacturing method provided by the present application is operated in room temperature atmosphere throughout the whole process, without the need of heating or inert gas protection.

[0053] The present application also provides the perovskite quantum dot material obtained by the batch manufacturing method described in the above scheme, which has the chemical formula CsPbX3, wherein X is a halogen element; the luminescent efficiency of the perovskite quantum dot material is 50%-90%, and the particle size distribution is 5-15 nm.

[0054] The perovskite quantum dot material provided by the present application has the advantages of high stability, uniform appearance and high luminescence efficiency, thereby improving the quality of the perovskite quantum dot material.

[0055] The present application also provides the application of the perovskite quantum dot material described in the above scheme in the field of lighting and display.

[0056] The perovskite quantum dot material provided by the present application provides high-quality luminescent materials for the field of lighting and display, and has a positive promoting effect on the development of the new generation of lighting and new display field.

[0057] In order to further illustrate the present application, the schemes of the present application are described in detail below in combination with the drawings and examples, but they should not be understood as limiting the scope of protection of the present application.

[0058] Example 1

[0059] (1) In the air atmosphere at room temperature, 1.5 mmol (0.62 g) of cesium stearate, 2.5 mmol (1.94 g) of lead stearate, 100 μL of octylamine and 100 g of PE powder were placed in a high-speed ultrafine powder crusher, and stirred at 15000 rpm for 1 min to obtain a perovskite precursor;

[0060] (2) In the air atmosphere at room temperature, 2.5 mmol (0.8 g) of pyridinium tribromide was added to the perovskite precursor described in step (1), and an ion combination reaction was carried out in a high-speed ultrafine powder crusher at 15000 rpm for 1 min to obtain a CsPbBr3 perovskite quantum dot material.

[0061] Example 2

[0062] The same manufacturing method as in Example 1 was used, with the only difference being that the pyridinium tribromide in Example 1 step (2) was replaced with oleylamine iodine, and other conditions remained the same.

[0063] Example 3

[0064] The same manufacturing method as in Example 1 was used, with the only difference being that the pyridinium tribromide in Example 1 step (2) was replaced with a mixture of pyridinium tribromide and oleylamine chloride in a mass ratio of 1:1, and other conditions remained the same.

[0065] Example 4

[0066] The same manufacturing method as in Example 1 was used, with the only difference being that the amount of cesium stearate, lead stearate, octylamine and PE powder in Example 1 step (1) and the amount of pyridinium tribromide in step (2) were all increased by 20 times, and other conditions remained the same.

[0067] Example 5

[0068] The same manufacturing method as in Example 1 was used, with the only difference being that the cesium stearate in Example 1 step (1) was replaced with cesium acetate, the lead stearate was replaced with lead acetate, the octylamine was replaced with oleic acid, and the PE was replaced with PMMA, and other conditions remained the same.

[0069] Example 6

[0070] The same manufacturing method as in Example 1 was used, with the only difference being that the PE in Example 1 step (1) was replaced with POM, and other conditions remained the same.

[0071] Example 7

[0072] The same manufacturing method as in Example 1 was adopted, with the only difference being that the PE in step (1) of Example 1 was replaced by PA6, and other conditions remained unchanged.

[0073] Example 8

[0074] The same manufacturing method as in Example 1 was adopted, with the only difference being that the PE in step (1) of Example 1 was replaced by PVA, and other conditions remained unchanged.

[0075] Example 9

[0076] The same manufacturing method as in Example 1 was adopted, with the only difference being that the PE in step (1) of Example 1 was replaced by PAN, and other conditions remained unchanged.

[0077] Example 10

[0078] The same manufacturing method as in Example 1 was adopted, with the only difference being that the high-speed stirring at 15000 rpm for 1 min in step (1) of Example 1 was replaced by high-speed stirring at 10000 rpm for 2 min; and the continuous stirring at 15000 rpm for 1 min in step (2) of Example 1 was replaced by high-speed stirring at 10000 rpm for 5 min for the ionic combination reaction, and other conditions remained unchanged.

[0079] Example 11

[0080] The same manufacturing method as in Example 1 was adopted, with the only difference being that the high-speed stirring at 15000 rpm for 1 min in step (1) of Example 1 was replaced by high-speed stirring at 20000 rpm for 1.5 min; and the continuous stirring at 15000 rpm for 1 min in step (2) of Example 1 was replaced by high-speed stirring at 20000 rpm for 3 min for the ionic combination reaction, and other conditions remained unchanged.

[0081] Example 12

[0082] The same manufacturing method as in Example 1 was adopted, with the only difference being that in step (1), the mass ratio of the organic cesium salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micropowder, and the organic halide salt was 0.004:1, the mass ratio of the organic lead salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micropowder, and the organic halide salt was 0.01:1, the molar ratio of the organic ligand to the organic lead salt was 0.1:1, and the mass ratio of the polymer micropowder to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micropowder, and the organic halide salt was 0.9:1, and other conditions remained unchanged.

[0083] Example 13

[0084] The same manufacturing method as in Example 1 was adopted, except that in step (1), the mass ratio of the organic cesium salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder and the organic halide salt was 0.020:1, the mass ratio of the organic lead salt to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder and the organic halide salt was 0.06:1, the molar ratio of the organic ligand to the organic lead salt was 2.0:1, the mass ratio of the polymer micro powder to the total mass of the organic cesium salt, the organic lead salt, the organic ligand, the polymer micro powder and the organic halide salt was 1.0:1, and other conditions remained unchanged.

[0085] The perovskite quantum dot material prepared in Examples 1-4 was subjected to morphology and fluorescence spectrum detection, and the results are shown in Figures 1-4

[0086] According to Figure 1 It can be seen that the green perovskite quantum dot material prepared by the method of the present application has large yield and pure spectrum without other impurity peaks.

[0087] According to Figure 2 It can be seen that by changing the type of halogen and replacing the bromide salt with an iodide salt, the preparation of red perovskite quantum dot material can be realized.

[0088] According to Figure 3 It can be seen that by replacing the bromide salt with a mixture of chloride salt and bromide salt, the preparation of blue perovskite quantum dot material can be realized, and it can be seen that the method proposed in the present application has universality.

[0089] According to Figure 4 It can be seen that the present application can realize mass production of perovskite quantum dot material, and the single preparation yield can reach 2 kg, and it can be seen that the method provided in the present application has considerable industrialization prospect.

[0090] The detection results of the perovskite quantum dot material prepared in Examples 5-13 are similar to those of Examples 1-4.

[0091] The quantum yield and luminescent performance of the perovskite quantum dot material of Example 1 of the present application were tested, and the results are shown in Figure 5 According to Figure 5 It can be seen that the quantum yield of the perovskite quantum dot material prepared by the present application can reach 90%, and the product has high luminescent performance.

[0092] The detection results of Examples 2-13 are similar to those of Example 1, and will not be described here.

[0093] ​From the above examples, the manufacturing method provided by the application can realize 100% raw material utilization rate, does not need to be purified, has no chemical waste, the synthesis rate can reach 1 kg / min, and the quantum yield can reach 90%, is a high-efficiency, all-solid-state, high-yield, low-cost, green, environmentally friendly, scalable and industrialized solvent-free manufacturing method, realizes efficient batch preparation of perovskite quantum dot materials, can realize universal synthesis of multi-color materials, and the prepared perovskite quantum dot material has the advantages of high stability, uniform appearance, high-efficiency light emission and the like, and can be directly used for optical devices.

[0094] Although the above examples make a detailed description of the application, it is only a part of the embodiments of the application, not all the embodiments, and other embodiments can be obtained under the premise of no creativity according to the embodiments, and these embodiments all belong to the protection scope of the application.

Claims

1. A method for preparing perovskite quantum dot materials, characterized in that, Includes the following steps: (1) The organic cesium salt, organic lead salt, organic ligand and polymer powder are first mixed to obtain a perovskite precursor; the first mixing rate is 10,000~20,000 rpm; (2) The organic halide salt and the perovskite precursor are subjected to an ionization reaction to obtain perovskite quantum dot material; the second mixing rate is 10000~20000 rpm. The first mixing device is a high-speed ultrafine powder crusher; The second mixing device is a high-speed ultrafine powder crusher; In step (2), the temperature of the ionization reaction is room temperature, the atmosphere is air, and the reaction time is 1~5 min; In step (2), the organic halide salt includes one or more of tribromopyridinium, dibromotriphenylphosphine, oleylamine chloride, oleylamine iodine, octadecylamine chloride and octadecylamine iodine; the mass ratio of the organic halide salt to the polymer micro powder is 0.01~0.05:

1.

2. The preparation method according to claim 1, characterized in that, In step (1), the temperature of the first mixture is room temperature, the atmosphere is air, and the reaction time is 1~2 min.

3. The preparation method according to claim 1 or 2, characterized in that, In step (1), the organic cesium salt includes one or more of cesium stearate and cesium acetate; the mass ratio of the organic cesium salt to the total mass of the organic cesium salt, organic lead salt, organic ligand, polymer micro powder and organic halide salt is 0.004~0.020:

1.

4. The preparation method according to claim 1 or 2, characterized in that, In step (1), the organic lead salt includes one or more of lead stearate and lead acetate; the mass ratio of the organic lead salt to the total mass of the organic cesium salt, organic lead salt, organic ligand, polymer powder and organic halide salt is 0.01~0.06:

1.

5. The preparation method according to claim 1 or 2, characterized in that, In step (1), the organic ligand includes one or more of organic amines and organic acids; the molar ratio of the organic ligand to the organic lead salt is 0.1~2.0:

1.

6. The preparation method according to claim 1 or 2, characterized in that, In step (1), the polymer powder includes one or more of polyolefins and their derivatives, polyesters, polyaldehydes, polyamides, polyols and polynitriles; the mass ratio of the polymer powder to the total mass of the organic cesium salt, organic lead salt, organic ligand, polymer powder and organic halide salt is 0.9~1.0:

1.

7. The perovskite quantum dot material obtained by the preparation method according to any one of claims 1 to 6 has the chemical formula CsPbX3, wherein X is a halogen element; the luminous efficiency of the perovskite quantum dot material is 50% to 90%, and the particle size distribution is 5 to 15 nm.

8. The application of the perovskite quantum dot material of claim 7 in the fields of lighting and display.

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