CN106883845B - Perovskite microcrystal luminescent material, preparation method and application thereof - Google Patents

Perovskite microcrystal luminescent material, preparation method and application thereof Download PDF

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CN106883845B
CN106883845B CN201710229040.7A CN201710229040A CN106883845B CN 106883845 B CN106883845 B CN 106883845B CN 201710229040 A CN201710229040 A CN 201710229040A CN 106883845 B CN106883845 B CN 106883845B
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luminescent material
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CN106883845A (en
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钟海政
陈小梅
张峰
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Beijing Institute of Technology BIT
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Abstract

The invention provides a hybrid perovskite microcrystal luminescent material, which has a general formula A4BX6Wherein A is CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +Or R2NH3 +B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or MnX is Cl‑、Br‑And I‑Wherein R is2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8. The invention prepares A for the first time4BX6The organic-inorganic hybrid perovskite luminescent material prepared by the method has high luminescent efficiency and good stability. The invention also provides a method for preparing the hybrid perovskite microcrystalline luminescent material, which can be simultaneously applied to preparing inorganic perovskite microcrystalline luminescent materials, and has the advantages of simplicity, strong universality, high yield of the material, capability of reaching more than 90 percent, less impurities, easiness in cleaning and purifying, low cost and high purity of the material.

Description

Perovskite microcrystal luminescent material, preparation method and application thereof
Technical Field
The invention relates to the field of materials, in particular to a perovskite microcrystal luminescent material, a preparation method and application thereof.
Background
In recent years, the appearance of metal halide perovskite materials further promotes the understanding of preparing semiconductor nanocrystalline or quantum dot materials by a solution method, wherein high-quality perovskite quantum dot materials can be obtained by a simple solution preparation method under normal temperature conditions. Aiming at the application requirements of quantum dot materials in display devices, compared with a typical II-VI group CdSe quantum dot system or a III-V group InP quantum dot system, perovskite quantum dots have greater advantages and potentials in the aspects of luminous efficiency, half-peak width, preparation process and the like. For perovskite quantum dot materials, ABX is currently the most studied3Perovskite quantum dots of type structure, relating to ABX3The preparation method, the structure regulation and the application report of the perovskite quantum dot material in various fields are various.
In recent research reports, a new class of perovskite luminescent materials (with the chemical formula of Cs) appears4PbBr6) Such materials having the formula: ABX3The perovskite quantum dot has excellent optical performance comparable to that of perovskite quantum dot and has great application potential. Particularly, as the preparation method of the material is optimized and improved, the semiconductor material called zero-dimensional perovskite is shown to be similar to ABX3Form of calcium titaniumDifferent special photoelectric properties (such as high photoluminescence intensity and large exciton binding energy) of the mine. These novel properties lead to Cs4PbBr6Applications in devices such as light emitting diodes, electroluminescent devices, lasers and photodetectors are in an unprecedented position.
From the structural point of view of the perovskite material, the perovskite material has AnBX2+nThe value of n determines BX6 4-Connectivity of octahedron and dimension of perovskite: when n ═ 1, the perovskite material is typically ABX3Type three-dimensional structure (BX)6 4-Octahedral sharing an angle); when n is 2, the perovskite material is A2BX4Two-dimensional structure of type (BX)6 4-Octahedral planes); when n is 3, the perovskite material is a one-dimensional structure (BX)6 4-Octahedron in chain shape); when n is 4, the perovskite material is A4BX6Zero-dimensional structure of type (BX)6 4-Octahedra are not connected or isolated).
However, only Cs is present in the existing materials4PbBr6The organic-inorganic hybrid perovskite microcrystal luminescent material does not exist, and the preparation method of the organic-inorganic hybrid perovskite microcrystal luminescent material does not exist.
Furthermore, the conventional inorganic A4BX6Most of the preparation methods of perovskite luminescent materials are complicated, so the preparation method is not suitable for preparing the hybrid perovskite microcrystal luminescent materials. As described below, conventional inorganic A4BX6The preparation method of the perovskite luminescent material generally comprises the following steps:
① A method comprises adding a first solution of CsOA (cesium oleate), OA (oleic acid) and n-hexane to a second solution of PbBr2DMF (dimethylformamide), HBr, OA and OLA (oleylamine) are generally involved in more reaction raw materials, and after OA and OLA are added, the subsequent Cs is obtained4PbBr6Purification of perovskite nanocrystals becomes difficult and the fluorescence quantum yield is low, only about 65%.
② similar milk is usedThe liquid method comprises the step of mixing the component PbBr2Adding emulsion of CsBr, DMF, OA, OLA into n-hexane solvent, stirring to obtain precipitate, washing with cyclohexane to obtain Cs4PbBr6Powder (microcrystal), the emulsion preparation is related to in this method, need to add OA, OLA as emulsion stabilizer too, the fluorescence quantum yield is not high too, only about 40-45%.
③ adopts PbBr2Adding poor solvent acetonitrile or methanol into a solution system of CsBr and DMSO (dimethyl sulfoxide) at 50 ℃ to obtain a saturated solution, continuously stirring for 24h to obtain precipitate, namely Cs4PbBr6Powder (microcrystal) and fluorescence quantum yield of about 45 percent.
④ adopts PbBr2CsBr as reaction raw material, adding DMSO as solvent, stirring for one hour, filtering, heating to 120 deg.C, stirring for 3 hr, washing the obtained precipitate with DMSO, and drying to obtain Cs4PbBr6Powder (microcrystals), which has a long reaction time and DMSO has a certain solubility to quantum dots, is not good as a cleaning solvent.
In summary, the present disclosure relates to Cs4PbBr6In the synthesis method of the perovskite luminescent material, DMSO is used as a solvent, reaction raw materials are precipitated after being saturated by adding a poor solvent or heating, and microcrystalline powder is prepared, the reaction period of the method is long, the yield of fluorescent quantum dots is not high, wherein ③ is a byproduct generated in the method for growing perovskite single crystals, the other method is similar to the preparation method of emulsion, DMF is used as a solvent, because CsBr is poor in solubility in DMF, OA and OLA organic matters need to be added to form emulsion, then the emulsion is added into the poor solvent, and the perovskite nano crystals are obtained by demulsification and precipitation of the reaction raw materials.
Thus, currently at A4BX6In the research of type zero-dimensional perovskite materials, organic-inorganic hybrid A is not related4BX6Perovskite material anda corresponding preparation method. And the existing inorganic A4BX6The preparation method of the perovskite material is not only complicated, but also the fluorescence quantum yield of the obtained luminescent material is low, and the method is obviously not suitable for preparing organic-inorganic hybrid A4BX6A perovskite-type material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hybrid perovskite microcrystal luminescent material and a preparation method thereof, the obtained hybrid perovskite microcrystal luminescent material has high luminous efficiency and good stability, and the preparation method can be prepared and applied in a large scale.
Specifically, the invention provides a hybrid perovskite microcrystalline luminescent material, and the general formula of the hybrid perovskite microcrystalline luminescent material is A4BX6Wherein A is CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +Or R2NH3 +B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl-、Br-And I-Wherein R is2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8.
Preferably, the invention provides a preparation method of a hybrid perovskite microcrystalline luminescent material, which comprises the following steps:
s1, respectively adding a perovskite component, an organic solvent component and a catalyst component into a glass container, and uniformly mixing to obtain a solid-liquid two-phase coexisting substance to be reacted, wherein the ratio of the perovskite component to the organic solvent component is 1 (1-25) mol/L, the ratio of the catalyst component to the organic solvent component is (0.2-0.5) 1mol/L, and the perovskite component is composed of a first perovskite component which can be completely dissolved in the organic solvent component and a second perovskite component which is not completely dissolved in the organic solvent component;
s2, reacting the substance to be reacted obtained in the step S1 under one or more reaction conditions of stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, oscillation reaction conditions or heating reaction conditions for 1-60min to obtain a solid material after reaction;
and S3, repeatedly washing and drying the solid material obtained in the S2 by using the organic solvent with the same components as the organic solvent in the S1, and finally obtaining the hybrid perovskite microcrystalline luminescent material.
Preferably, the first perovskite component in S1 is of the general formula ABX3Of the general formula BXnThe second perovskite component is a halide of the general formula AX.
Preferably, wherein A is CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +Or R2NH3 +B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl-、Br-And I-At least one of (1), R2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8.
Preferably, the organic solvent component in S1 is at least one selected from the group consisting of acetonitrile, acetone, methyl ethyl ketone, 2-pentanol, 3-pentanol, propionitrile, t-butanol, ethylenediamine, 1, 2-dichloroethane, butanone, t-pentanol, 2-pentanone, isoamyl ketone, dichloromethane, pyridine, methyl acetate, 4-methyl-2-pentanone, 3-pentanone, ethyl acetate, and diethyl carbonate.
Preferably, the organic solvent component in S1 is at least one selected from acetone, acetonitrile, methyl ethyl ketone, propionitrile, and ethyl acetate.
Preferably, the catalyst component in S1 is at least one selected from hydrohalic acid HX, sodium halide NaX or potassium halide KX, and X is Cl-、Br-Or I-。
Preferably, the general formula is ABX3With a molar ratio of perovskite material of formula AX of 1: (2-3) the general formula is BXnThe molar ratio of the metal halide of (2) to the halide of formula AX is 1 (3-4).
Preferably, the stirring reaction condition in S2 is magnetic stirring, mechanical stirring or high-speed dispersion, wherein the reaction time is 1-60min, and the stirring speed is 50-5000 r/min.
Preferably, the friction reaction condition is a mechanical ball milling method, wherein the reaction time is 1-60min, the rotating speed of the cylinder body is 20-40r/min, and the diameter of the steel ball is 20-60 mm.
Preferably, the reaction time of the ultrasonic reaction condition is 1-60min, the ultrasonic frequency is 20-40kHz, and the power density is 0.3-1W/cm2；
Preferably, the oscillation reaction condition is constant-temperature water bath oscillation, wherein the reaction time is 1-60min, the oscillation frequency is 100-300 times/min, the amplitude is 20-30mm, and the water bath temperature is 30-85 ℃.
Preferably, the heating reaction conditions are for a reaction time of 1-60min and at a temperature in the range of 20-90 ℃.
Preferably, the substance to be reacted obtained in S1 is reacted in S2 under two reaction conditions among stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, shaking reaction conditions or heating reaction conditions.
Preferably, the invention also provides a light-emitting device prepared from the hybrid perovskite microcrystalline luminescent material.
Preferably, the invention also provides a liquid crystal display backlight source which comprises the light-emitting device.
Preferably, the invention also provides a preparation method of the inorganic perovskite microcrystalline luminescent material, which comprises the following steps:
s1, respectively adding a perovskite component, an organic solvent component and a catalyst component into a glass container, and uniformly mixing to obtain a solid-liquid two-phase coexisting substance to be reacted, wherein the ratio of the perovskite component to the organic solvent component is 1 (1-25) mol/L, the ratio of the catalyst component to the organic solvent component is 0.2-0.5) 1mol/L, and the perovskite component is composed of a first perovskite component which can be completely dissolved in the organic solvent component and a second perovskite component which is not completely dissolved in the organic solvent component;
s2, reacting the substance to be reacted obtained in the step S1 under one or more reaction conditions of stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, oscillation reaction conditions or heating reaction conditions for 1-60min to obtain a solid material after reaction;
and S3, repeatedly washing and drying the solid material obtained in the S2 by using the organic solvent with the same components as the organic solvent in the S1, and finally obtaining the hybrid perovskite microcrystalline luminescent material.
Preferably, the first perovskite component in S1 is of the formula MBX3Of the general formula BXnThe second perovskite component is a halide of the general formula MX.
Preferably, where M is Cs+、Ru+Or K+B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl-、Br-And I-At least one of (1), R2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8.
Preferably, the organic solvent component in S1 is dimethylformamide or dimethylacetamide.
Preferably, the catalyst component in S1 is at least one of hydrohalic acid HX, sodium halide NaX or potassium halide KX, and X is Cl-、Br-Or I-。
Preferably, the stirring reaction condition in S2 is magnetic stirring, mechanical stirring or high-speed dispersion, wherein the reaction time is 1-60min, and the stirring speed is 50-5000 r/min.
Preferably, the friction reaction condition is a mechanical ball milling method, wherein the reaction time is 1-60min, the rotating speed of the cylinder body is 20-40r/min, and the diameter of the steel ball is 20-60 mm.
Preferably, the ultrasonic reaction stripThe reaction time of the part is 1-60min, the ultrasonic frequency is 20-40kHz, and the power density is 0.3-1W/cm2。
Preferably, the oscillation reaction condition is constant-temperature water bath oscillation, wherein the reaction time is 1-60min, the oscillation frequency is 100-300 times/min, the amplitude is 20-30mm, and the water bath temperature is 30-85 ℃.
Preferably, the heating reaction conditions are for a reaction time of 1-60min and at a temperature in the range of 20-90 ℃.
Preferably, the substance to be reacted obtained in S1 is reacted in S2 under two reaction conditions among stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, shaking reaction conditions or heating reaction conditions.
Compared with the prior art, the invention has the following beneficial effects:
① the invention prepares A for the first time4BX6Type hybrid perovskite microcrystal luminescent material and preparation method thereof, and A of prepared hybrid perovskite microcrystal luminescent material4BX6The component purity is high, the purity can reach more than 90%, the luminous efficiency is high, the fluorescence quantum yield can reach more than 80%, and the stability is good.
② compared with other methods for preparing Cs, the method for preparing the inorganic perovskite luminescent material of the invention4PbBr6As for the perovskite luminescent material method, the method adopted by the invention is simple, strong in universality, high in material yield which can reach more than 90%, less in impurity, easy to clean and purify and low in cost, and the cleaned Cs4PbBr6The purity of the material components is high (the purity is close to 100 percent), the process amplification is easy, and the preparation of hectogram level is easy to realize at present.
③ when the method is used for preparing the hybrid perovskite luminescent material or inorganic perovskite luminescent material, the adopted organic solvent components are matched with the perovskite components, one of the selected perovskite components can be completely dissolved and dispersed in the organic solvent component, the other perovskite component can not be well dissolved and dispersed in the organic component and exists in a solid phase form, so that a solid-liquid two-phase coexisting body is formed, and the formed solid-liquid two-phase body is stirred, rubbed and ultrasonically treatedThe reaction is started by controlling the conditions of shaking or heating, one perovskite component dispersed in the organic solvent is fully contacted and reacted with the other perovskite component in the solid phase, and the special solid-liquid contact reaction system ensures that the reaction of the perovskite component is carried out towards A4BX6And (4) transforming the type structure. Avoids the situation that the perovskite component of the reaction system in the prior art has a large part of ABX3And (4) transforming the type structure.
④ the method of the invention introduces the catalyst component during the preparation, when reacting, if the solid-liquid contact reaction system is controlled by the conditions of stirring, friction, ultrasound, vibration or heating, the reaction time is longer, generally about 30 minutes4BX6The microcrystal generally can be shortened from 30 minutes to 1 minute in the whole reaction process after the catalyst component is added, so that the efficiency of preparing the perovskite luminescent material is greatly improved.
Drawings
FIG. 1 shows (NH ═ CHNH)3)4PbBr6Fluorescence spectra of perovskite luminescent materials;
FIG. 2 shows (NH ═ CHNH)3)4PbBr6A microscopic spectrum of the perovskite luminescent material;
FIG. 3 is (CH)3NH3)4PbBr6Fluorescence spectra of perovskite luminescent materials;
FIG. 4 shows Cs4PbBr6A microscopic spectrum of the perovskite luminescent material;
FIG. 5 shows Cs4PbBr6An XRD spectrum of the perovskite luminescent material;
FIG. 6 shows Cs4PbBr6EDS spectra of perovskite luminescent materials;
FIG. 7 shows Cs4PbBr6A schematic diagram of a perovskite luminescent material; and
FIG. 8 is a graph based on (NH ═ CHNH)3)4PbBr6Spectrum of backlight of perovskite luminescent material.
Detailed Description
Exemplary embodiments, features and aspects of the present invention will be described in detail below with reference to the accompanying drawings. In the drawings, like reference numbers can indicate functionally identical or similar elements. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a hybrid perovskite microcrystal luminescent material, which has a general formula A4BX6Wherein A is CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +Or R2NH3 +B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl-、Br-And I-Wherein R is2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8.
The invention also provides a preparation method of the perovskite microcrystal luminescent material, which comprises the following steps:
s1, respectively adding a perovskite component, an organic solvent component and a catalyst component into a glass container, and uniformly mixing to obtain a solid-liquid two-phase coexisting substance to be reacted, wherein the ratio of the perovskite component to the organic solvent component is 1 (1-25) mol/L, the ratio of the catalyst component to the organic solvent component is 0.2-0.5) 1mol/L, and the perovskite component is composed of a first perovskite component which can be completely dissolved in the organic solvent component and a second perovskite component which is not completely dissolved in the organic solvent component;
s2, reacting the substance to be reacted obtained in the step S1 under one or more reaction conditions of stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, oscillation reaction conditions or heating reaction conditions for 1-60min to obtain a solid material after reaction;
and S3, repeatedly washing and drying the solid material obtained in the S2 by using the organic solvent with the same components as the organic solvent in the S1, and finally obtaining the hybrid perovskite microcrystalline luminescent material.
Preferably, the first perovskite component in S1 is of the general formula ABX3Of the general formula BXnThe second perovskite component is a halide of the general formula AX.
The stirring reaction condition in the S2 is magnetic stirring, mechanical stirring or high-speed dispersion, wherein the reaction time is 1-60min, and the stirring speed is 50-5000 r/min;
the friction reaction condition is a mechanical ball milling method, wherein the reaction time is 1-60min, the rotating speed of the cylinder body is 20-40r/min, and the diameter of the steel ball is 20-60 mm;
the reaction time under the ultrasonic reaction condition is 1-60min, the ultrasonic frequency is 20-40kHz, and the power density is 0.3-1W/cm2；
The oscillation reaction condition is constant-temperature water bath oscillation, wherein the reaction time is 1-60min, the oscillation frequency is 100-300 times/min, the amplitude is 20-30mm, and the water bath temperature is 30-85 ℃; and
the reaction time of the heating reaction condition is 1-60min, and the temperature range is 20-90 ℃.
The method can be used for preparing a hybrid perovskite microcrystal luminescent material and can also be used for preparing an inorganic perovskite microcrystal luminescent material.
The invention is further illustrated by the following examples:
preparation of hybrid perovskite microcrystalline luminescent material
Example 1(NH ═ CHNH)3)4PbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component PbBr21mmol of organic amine halide salt component NH ═ CHNH3Br 3mmol and organic solvent component acetonitrile 10mL are added into a glass bottle, and then the ratio of the perovskite component to the organic solvent is (1+3) 10mol/L and 1:2.5 mol/L;
s2, performing ultrasonic dispersion for 20min at the temperature of 20 ℃, wherein the ultrasonic frequency is 20kHz, and the turbid liquid is changed from yellow to light green;
s3, centrifuging the light green turbid liquid, discarding the upper layer liquid, and using acetonitrile solvent to dissolve the lower layer solidWashing for 3 times, and drying to obtain (NH ═ CHNH)3)4PbBr6Green powder, blue-green light emitted by the material under 365nm ultraviolet lamp irradiation, as shown in fig. 1, the result of the fluorescence spectrophotometer test shows (NH ═ CHNH)3)4PbBr6The light-emitting wavelength of the perovskite light-emitting material is 505nm, the half-peak width is 21nm, and the quantum yield test result shows that (NH ═ CHNH)3)4PbBr6The absolute fluorescence quantum yield of the perovskite luminescent material is 85%, and fig. 2 shows that (NH ═ CHNH) is obtained by preparation3)4PbBr6The microstructure under SEM of the perovskite luminescent material.
Example 2 (CH)3NH3)4PbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component PbBr24mmol of organic amine halide salt component CH3NH3Br 16mmol and organic solvent component acetone 8mL are added into a stainless steel container and mixed evenly;
s2, adding a steel ball with the diameter of 20mm, and mechanically ball-milling for 30min at the temperature of 30 ℃, wherein the turbid solid-liquid phase is changed from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with acetone solvent for 3 times, and drying to obtain (CH)3NH3)4PbBr6Green powder, the material emits strong green light under 365nm ultraviolet lamp irradiation, as shown in figure 3, the test result of fluorescence spectrophotometer shows (CH)3NH3)4PbBr6The perovskite luminescent material has the luminescent wavelength of 512nm and the half-peak width of 27nm, and the quantum yield test result shows that (CH)3NH3)4PbBr6The absolute fluorescence quantum yield of the perovskite luminescent material is 80%.
Example 3(NH ═ CHNH)3)4PbI6Preparation of perovskite luminescent material
S1 preparation of metal halide component PbI21mmol of organic amine halide salt component NH ═ CHNH3I3.2 mmol, organic solvent component ethyl acetate 10mL into a glass bottlePerforming the following steps;
s2, shaking the mixed solid liquid for 50min under the condition of constant-temperature water bath at 50 ℃, and changing the turbid liquid from yellow to yellow-green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with ethyl acetate solvent for 3 times, and drying to obtain (NH ═ CHNH)3)4PbI6Yellow green powder, yellow green light emitted by the material under 365nm ultraviolet lamp irradiation, and fluorescence emission wavelength of the material is 553nm by using a fluorescence spectrophotometer.
Example 4(NH ═ CHNH)3)4PbCl6Preparation of perovskite luminescent material
S1, adding the metal halide component PbCl21mmol of organic amine halide salt component NH ═ CHNH3Cl 3.4mmol and acetonitrile 40mL of organic solvent component are added into a glass bottle;
s2, performing microwave heating on the mixed solid liquid for 35min to change the turbid liquid from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with acetonitrile solvent for 3 times, and drying to obtain (NH ═ CHNH)3)4PbCl6The material emits blue-green light under the irradiation of a 365nm ultraviolet lamp, and the fluorescence emission wavelength of the material is 492nm by a fluorescence spectrophotometer.
Example 5 (C)6H5NH3)4PbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component PbBr21mmol of organic amine halide salt component C6H5NH3Adding 3.6mmol of Br, 25mL of propionitrile serving as an organic solvent component and 7.5mmol of HBr serving as a catalyst component into a glass bottle;
s2, dispersing the solid-liquid coexisting body at a high speed for 5min at the temperature of 30 ℃, wherein the rotating speed of the high-speed dispersion is 3500r/min, and the turbid liquid is changed from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with propionitrile solvent for 3 times, and dryingTo obtain (C)6H5NH3)4PbBr6Green powder, which emits green light under 365nm ultraviolet lamp irradiation, and the fluorescence emission wavelength of the material is 524nm as measured by a fluorescence spectrophotometer.
Example 6 (CH)2＝CHCH2CH3NH3)4PbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component PbBr21mmol of organic amine halide salt component CH2＝CHCH2CH3NH3Br 3.8mmol, 50mL of organic solvent component methyl ethyl ketone is added into a glass bottle;
s2, stirring the mixed solid-liquid coexisting body at a high speed for 30min at the temperature of 30 ℃, wherein the stirring speed is 500r/min, and the turbid liquid is changed from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with methyl ethyl ketone solvent for 3 times, and drying to obtain (CH)2＝CHCH2CH3NH3)4PbBr6Green powder, which emits green light under 365nm ultraviolet lamp irradiation, and a fluorescence emission wavelength of the material is 519nm by a fluorescence spectrophotometer test.
Example 7(C (NH)2)3)4PbBr6Preparation of perovskite luminescent material
S1, mixing perovskite component C (NH)2)3PbBr31mmol of organic amine halide salt component C (NH)2)3Adding Br 2.9mmol, organic solvent component methanol 20mL and catalyst component KBr 5mmol into a glass bottle;
s2, carrying out ultrasonic treatment on the mixed solid-liquid coexisting body for 3min at the temperature of 30 ℃, wherein the ultrasonic frequency is 30kHz, and the turbid liquid is changed from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with methanol solvent for 3 times, and drying to obtain (C (NH)2)3)4PbBr6Green powder, the material emits green under 365nm ultraviolet lamp irradiationThe fluorescence emission wavelength of the material was 526nm as measured by a fluorescence spectrophotometer.
Example 8(C (NH)2)3)4MnBr6Preparation of perovskite luminescent material
S1, mixing perovskite component C (NH)2)3MnCl31mmol of organic amine halide salt component C (NH)2)3Adding Cl 2.6mmol, organic solvent component methanol 20mL and catalyst component HCl 6mmol into a glass bottle;
s2, carrying out ultrasonic treatment on the mixed solid-liquid coexisting body for 8min at the temperature of 30 ℃, wherein the ultrasonic frequency is 30kHz, and the turbid liquid is changed from milky white to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with methanol solvent for 3 times, and drying to obtain (C (NH)2)3)4MnCl6The material emits blue-green light under the irradiation of a 365nm ultraviolet lamp, and a fluorescence emission wavelength of the material is 486nm through a fluorescence spectrophotometer.
Example 9(NH ═ CHNH)3)4SbBr6Preparation of perovskite luminescent material
S1, converting the perovskite component NH into CHNH3SbBr31mmol of organic amine halide salt component NH ═ CHNH3Adding Br 3mmol, organic solvent component methanol 20mL and catalyst component HBr 6mmol into a glass bottle;
s2, carrying out ultrasonic treatment on the mixed solid-liquid coexisting body for 3min at the temperature of 30 ℃, wherein the ultrasonic frequency is 30kHz, and the turbid liquid is changed from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with methanol solvent for 3 times, and drying to obtain (NH ═ CHNH)3)4SbBr6Green powder, which emits green light under 365nm ultraviolet lamp irradiation, and a fluorescence emission wavelength of the material is 528nm by a fluorescence spectrophotometer.
Example 10(NH ═ CHNH)3)4GeBr6Preparation of perovskite luminescent material
S1, converting the perovskite component NH into CHNH3GeBr31mmol of organic amine halide salt component NH ═ CHNH3Br2.8mmol, 20mL of organic solvent component methanol and catalyst component HBr are added into a glass bottle;
s2, carrying out ultrasonic treatment on the mixed solid-liquid coexisting body for 6min at the temperature of 60 ℃, wherein the ultrasonic frequency is 30kHz, and the turbid liquid is changed from light brown to white;
s3, centrifuging the above white turbid solution, discarding the upper layer liquid, washing the lower layer solid with methanol solvent for 3 times, and drying to obtain (NH ═ CHNH)3)4GeBr6And (3) powder, wherein the material emits weak green light under the irradiation of a 365nm ultraviolet lamp, and a fluorescence emission wavelength of the material is 518nm by using a fluorescence spectrophotometer.
Preparation of inorganic perovskite microcrystal luminescent material
Example 11Cs4PbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component PbBr2Adding 1mmol of cesium halide component CsBr of 3.6mmol and organic solvent component DMF (dimethylformamide) of 15mL into a glass bottle;
s2, ultrasonically dispersing the mixed solid-liquid coexisting body for 25min at the temperature of 25 ℃, wherein the ultrasonic frequency is 25kHz, and the turbid liquid is changed from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with DMF solvent for 3 times, and drying to obtain Cs4PbBr6Green powder, the material emits strong green light under 365nm ultraviolet lamp irradiation, figure 4 is Cs4PbBr6A microscopic spectrum of the perovskite luminescent material; as shown in FIGS. 5 and 6, the fluorescence spectrophotometer test results indicated that Cs4PbBr6The luminescent wavelength of the perovskite luminescent material is 516nm, the half-peak width is 19nm, and the quantum yield test result shows that Cs is4PbBr6The absolute fluorescence quantum yield of the perovskite luminescent material is 90%. FIG. 7 shows the obtained Cs4PbBr6Schematic structural diagram of perovskite luminescent material.
Example 12Cs4PbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component PbBr210mmol of cesium halide component CsBr 38mmol and 50mL of organic solvent component DMAC (dimethylacetamide) are placed in a stainless steel container of a ball mill;
s2, adding a steel ball with the diameter of 30mm, and starting grinding at the temperature of 25 ℃ for 60min, wherein the rotating speed of the cylinder is 40 r/min;
s3, grinding the obtained light yellow mixed solid liquid, taking the lower layer solid, washing the lower layer solid with DMAC solvent for 3 times, and drying to obtain Cs4PbBr6Green powder with a mass of 105g after weighing, the material emits strong green light under the irradiation of a 365nm ultraviolet lamp, and the test result of a fluorescence spectrophotometer shows that Cs4PbBr6The light-emitting wavelength of the perovskite light-emitting material is 525nm, and the half-peak width is 20 nm.
Example 13Cs4SnBr6Preparation of perovskite luminescent material
S1, adding a metal halide component SnBr21mmol, 4mmol of cesium halide component CsBr, 20mL of organic solvent component DMF and 0.25mmol of catalyst component HBr are added into a glass bottle;
s2, ultrasonically dispersing the mixed solid-liquid coexisting body for 10min at the temperature of 70 ℃, and changing the turbid liquid from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with DMF solvent for 3 times, and drying to obtain Cs4SnBr6Light green powder. The material emits yellow green light under the irradiation of 365nm ultraviolet lamp, and the test result of a fluorescence spectrophotometer shows that Cs4SnBr6The light-emitting wavelength of the perovskite light-emitting material is 555nm, and the half-peak width is 35 nm.
Example 14Cs4GeBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component GeBr21mmol, cesium halide component CsBr 4mmol, organic solvent component DMF20mL are added into a glass bottle;
s2, ultrasonically dispersing the mixed solid-liquid coexisting body for 50min at the temperature of 90 ℃, and changing the yellow of the turbid liquid into light yellow;
s3, centrifuging the light yellow turbid liquid, discarding the upper layer liquid, washing the lower layer solid with DMF solvent for 3 times, and drying to obtain Cs4GeBr6A pale yellow powder. The material emits yellow light under the irradiation of 365nm ultraviolet lamp, and the test result of a fluorescence spectrophotometer shows that Cs4GeBr6The light-emitting wavelength of the perovskite light-emitting material is 545nm, and the half-peak width is 34 nm.
Example 15Cs4SbBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component SbBr21mmol, cesium halide component CsBr 4mmol, organic solvent component DMF20mL are added into a glass bottle;
s2, ultrasonically dispersing the mixed solid-liquid coexisting body for 40min at the temperature of 30 ℃, and changing the turbid liquid from yellow to light green;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with DMF solvent for 3 times, and drying to obtain Cs4SbBr6Light green powder. The material emits green light under the irradiation of 365nm ultraviolet lamp, and the test result of a fluorescence spectrophotometer shows that Cs4SbBr6The perovskite luminescent material has the luminescent wavelength of 527nm and the half-peak width of 31 nm.
Example 16Cs4CuBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component CsCuBr31mmol, cesium halide component CsBr2.8mmol, organic solvent component DMF20mL, catalyst component KBr 0.2mmol are added into a glass bottle;
s2, ultrasonically dispersing the mixed solid-liquid coexisting body for 10min at the temperature of 30 ℃, and changing the turbid liquid from yellow green to light brown;
s3, centrifuging the light green turbid solution, discarding the upper layer liquid, washing the lower layer solid with DMF solvent for 3 times, and drying to obtain Cs4CuBr6Light brown powder. The material emits slight yellow light under the irradiation of 365nm ultraviolet lamp, and the test result of a fluorescence spectrophotometer shows that Cs4CuBr6The perovskite luminescent material has the luminescent wavelength of 553nm and the half-peak width of 43 nm.
Example 17Cs4MnBr6Preparation of perovskite luminescent material
S1, mixing the metal halide component MnBr21mmol, cesium halide component CsBr 4mmol, organic solvent component DMF20mL are added into a glass bottle;
s2, ultrasonically dispersing the mixed solid-liquid coexisting body for 45min at the temperature of 50 ℃, and changing the turbid liquid from light brown to light yellow;
s3, centrifuging the light yellow turbid liquid, discarding the upper layer liquid, washing the lower layer solid with DMF solvent for 3 times, and drying to obtain Cs4MnBr6Light brown powder. The material emits yellow green light under the irradiation of 365nm ultraviolet lamp, and the test result of a fluorescence spectrophotometer shows that Cs4MnBr6The light-emitting wavelength of the perovskite light-emitting material is 545nm, and the half-peak width is 38 nm.
Example 18 is based on (NH ═ CHNH)3)4PbBr6Photoluminescent device of perovskite microcrystalline luminescent material and backlight source preparation thereof
Will (NH ═ CHNH)3)4PbBr60.1g of perovskite luminescent material, 0.1g of KSF fluoride fluorescent powder and 0.5g of OE6551A and OE6551B silica gel which are uniformly mixed in a ratio of 1:1 are placed in a small beaker, and are uniformly mixed to obtain glue containing the luminescent material, and the glue is defoamed for later use;
packaging the mixed glue on a 0.5W patch type LED, performing heat curing at 100 ℃ for 30min, and performing post curing at 120 ℃ for 2h to obtain a photoluminescence LED device, wherein the color coordinate of the obtained LED is (0.29, 0.31) and the color temperature is 8400K;
and welding the photoluminescence device on a 55-inch liquid crystal display lamp bar bracket, and then fixing the photoluminescence device in a lateral backlight module to obtain a 55-inch white light backlight source for the liquid crystal display, wherein the color gamut of the backlight source obtained by testing is 1.21 times of the color gamut standard of NTSC.
Example 19 is based on (NH ═ CHNH)3)4PbBr6Preparation of liquid crystal display backlight source of perovskite luminescent material
Will (NH ═ CHNH)3)4PbBr610g of perovskite luminescent material, 10g of KSF fluoride fluorescent powder and 80g of ultraviolet curing glue are placed in a small beaker, uniformly mixed to obtain glue containing the luminescent material, and defoamed for later use;
uniformly coating the mixed glue on a transparent PET substrate through a casting machine, and curing for 45min under the irradiation of an ultraviolet lamp with the wavelength of 320nm to obtain the product based on (NH ═ CHNH)3)4PbBr6An optical thin film of a perovskite luminescent material;
an optical film is arranged right above a 65-inch backlight module light guide plate, a lamp strip of pure blue light is fixed on the side face of the backlight module, the emission wavelength of the blue light lamp strip is 454nm, the lamp strip is fixed by a frame to obtain a 65-inch white light backlight source for a liquid crystal display, the backlight spectrum is shown in FIG. 8, and a test result shows that the color coordinates of the assembled white light backlight source are (0.27, 0.28), the color temperature is 11000K, and the color gamut is 1.22 times of the NTSC standard.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (4)

1. A method for preparing a hybrid perovskite microcrystal luminescent material is characterized by comprising the following steps: the general formula of the hybrid perovskite microcrystal luminescent material is A4BX6Wherein A is NH ═ CHNH3 +、C(NH2)3 +Or R2NH3 +B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl-、Br-And I-Wherein R is2Is a saturated straight chain alkane with the carbon number between 1 and 8A radical or a saturated branched alkyl radical or an unsaturated linear alkyl radical or an unsaturated branched alkyl radical, or R2Is an aromatic group;
the manufacturing method comprises the following steps:
s1, respectively adding a perovskite component, an organic solvent component and a catalyst component into a glass container, uniformly mixing to obtain a solid-liquid two-phase coexisting substance to be reacted, wherein the ratio of the perovskite component to the organic solvent component is 1 (1-25) mol/L, the ratio of the catalyst component to the organic solvent component is 0.2-0.5) 1mol/L, the perovskite component comprises a first perovskite component which can be completely dissolved in the organic solvent component and a second perovskite component which is not completely dissolved in the organic solvent component, the catalyst component in the step S1 is at least one selected from hydrohalic acid HX, sodium halide NaX or potassium halide KX, and X is Cl-、Br-Or I-；
In step S1 the first perovskite component is of the general formula ABX3Of the general formula BXnThe second perovskite component is a halide of the general formula AX;
the organic solvent component in step S1 is at least one selected from the group consisting of acetonitrile, acetone, methyl ethyl ketone, 2-pentanol, 3-pentanol, propionitrile, t-butanol, ethylenediamine, 1, 2-dichloroethane, butanone, t-pentanol, 2-pentanone, isoamyl ketone, dichloromethane, pyridine, methyl acetate, 4-methyl-2-pentanone, 3-pentanone, ethyl acetate, and diethyl carbonate;
s2, reacting the substance to be reacted obtained in the step S1 under one or more reaction conditions of stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, oscillation reaction conditions or heating reaction conditions for 1-60min to obtain a solid material after reaction;
s3, repeatedly washing and drying the solid material obtained in the step S2 by using the same organic solvent as the organic solvent in the step S1 to obtain the hybrid perovskite microcrystalline luminescent material.
2. The method for preparing hybrid perovskite microcrystalline luminescent material according to claim 1, wherein: in step S1, the organic solvent component is at least one selected from acetone, acetonitrile, methyl ethyl ketone, propionitrile, and ethyl acetate.
3. The method for preparing hybrid perovskite microcrystalline luminescent material according to claim 1, wherein: the general formula is ABX3With a molar ratio of perovskite material of formula AX of 1: (2-3) the general formula is BXnThe molar ratio of the metal halide of (2) to the halide of formula AX is 1 (3-4).
4. The method for preparing hybrid perovskite microcrystalline luminescent material according to claim 1, wherein: the stirring reaction condition in the step S2 is magnetic stirring, mechanical stirring or high-speed dispersion, wherein the reaction time is 1-60min, and the stirring speed is 50-5000 r/min;
the friction reaction condition is a mechanical ball milling method, wherein the reaction time is 1-60min, the rotating speed of the cylinder body is 20-40r/min, and the diameter of the steel ball is 20-60 mm;
the reaction time under the ultrasonic reaction condition is 1-60min, the ultrasonic frequency is 20-40kHz, and the power density is 0.3-1W/cm2；
The oscillation reaction condition is constant-temperature water bath oscillation, wherein the reaction time is 1-60min, the oscillation frequency is 100-300 times/min, the amplitude is 20-30mm, and the water bath temperature is 30-85 ℃; and
the reaction time of the heating reaction condition is 1-60min, and the temperature range is 20-90 ℃;
in step S2, the substance to be reacted obtained in step S1 is reacted under two reaction conditions selected from among stirring reaction conditions, friction reaction conditions, ultrasonic reaction conditions, shaking reaction conditions, and heating reaction conditions.
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