CN109054814B - Ultraviolet-excited white-light multi-element non-lead perovskite fluorescent powder and preparation method thereof - Google Patents
Ultraviolet-excited white-light multi-element non-lead perovskite fluorescent powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses ultraviolet excited white light multielement non-lead perovskite fluorescent powder and a preparation method thereof2B1 xB2 1‑xB3 yB4 1‑ yX1 mX2 nX3 6‑m‑nWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, m is more than 0 and less than or equal to 6, n is more than 0 and less than or equal to 6, and 0-m-n is more than or equal to 6 and less than or equal to 6; in addition, A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Are respectively F‑、Cl‑、Br‑. According to the invention, through key composition of the multi-element non-lead perovskite fluorescent powder, the whole process set of the corresponding preparation method and parameter conditions adopted in each step are improved, compared with the prior art, the type of the single-matrix fluorescent powder excited by near ultraviolet can be effectively expanded, the function of continuously adjusting an excitation spectrum and an absorption spectrum is realized, and the adjustment of the luminous color temperature of the LED is realized.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to ultraviolet-excited white-light multielement non-lead perovskite fluorescent powder and a preparation method thereof.
Background
With the development of economy in recent years, the living standard and quality are continuously improved, the requirement on an illumination light source is continuously improved, and an energy-saving, environment-friendly and efficient illumination mode is more and more attracted by various parties. White light LED LEDs have the significant advantages of small size, low power consumption, fast response, long lifetime, no pollution, etc., and are considered as a new generation of lighting technology that is promising for replacing conventional lighting sources.
The light emitting diode is a monochromatic light source, and therefore, fluorescent powder needs to be excited by mixing or matching different light sources, so that the whole spectrum contains three source colors, and photosensitive cells of human eyes are stimulated. At present, white light LED illumination is mainly realized by matching an LED chip and corresponding fluorescent powder, and a common and widely-used white light LED is formed by combining a blue light-emitting diode and yellow fluorescent powder. The color of the white LED device will vary with the driving voltage applied to the device and the thickness of the phosphor. And the current commercial white light LED has poor color reducibility and low color rendering index, and the illumination efficiency is influenced by the aging of the blue light LED. Therefore, the composite white light obtained by exciting the visible light fluorescent powder by the near ultraviolet LED chip can effectively solve the phenomenon of a series of color rendering indexes and color temperature deterioration caused by aging of the blue LED. Therefore, it is necessary to research the single-matrix fluorescent powder excited by near ultraviolet.
Related researches on non-lead perovskite phosphor also exist in the prior art, such as Sr3Ti2O7:Eu3+、M2TiO4(M ═ Ca, Sr, Ba) and other conventional non-lead perovskite phosphor powdersAlthough the mineral fluorescent powder can replace the traditional yellow fluorescent powder, the problem of poor stability of the traditional LED caused by the fact that white light is multi-color light mixed cannot be solved. The single-matrix non-lead perovskite fluorescent powder provided by the invention can well solve the problem of aging stability of the LED, and has a great potential market.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide the ultraviolet excited white light multi-element non-lead perovskite fluorescent powder and the preparation method thereof, wherein the key components (including the types of the chemical elements and the proportion thereof) of the multi-element non-lead perovskite fluorescent powder, the whole process setting of the corresponding preparation method and the parameter conditions (such as the temperature, the time and the like of a sintering reaction) adopted in each step are improved, compared with the prior art, the types of the near ultraviolet excited single-matrix fluorescent powder can be effectively expanded, the function of continuously adjusting an excitation spectrum and an absorption spectrum (the peak position of the excitation spectrum can cover 380 nm-630 nm) is realized, and the luminous color temperature of an LED (the color temperature can cover 2200K-7500K) is adjusted. In addition, aiming at the problems of low yield, high cost and the like of liquid phase synthesis adopted by the prior art, the invention also improves the preparation method, and prepares the multielement perovskite white-light fluorescent material with higher quality by utilizing a solid phase synthesis method. Broad spectrum white light due to self-confined excitation (self-trapped excitation) of the material, and by introducing Na in the B-position+Ion, Bi3+The intensity of the self-confinement effect is regulated and controlled by ions, and the electronic latitude in the perovskite is reduced, so that the fluorescence yield of the white light multielement non-lead perovskite fluorescent powder is improved, and high-quality white light is realized. The fluorescent yield of the novel fluorescent powder obtained by the invention is up to 90%, the product purity is high, the product generates warm white light, the LED color rendering index is up to 98, and the novel fluorescent powder has a good application prospect.
To achieve the above objects, according to one aspect of the present invention, there is provided an ultraviolet excited white light multi-element non-lead perovskite phosphor, wherein the phosphorThe optical powder has perovskite structure and chemical formula of the optical powder satisfies A2B1 xB2 1-xB3 yB4 1- yX1 mX2 nX3 6-m-nWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, m is more than 0 and less than or equal to 6, n is more than 0 and less than or equal to 6, and 0-m-n is more than or equal to 6 and less than or equal to 6; in addition, A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Are respectively F-、Cl-、Br-。
As a further preferred feature of the present invention, the phosphor has a chemical formula satisfying Cs2Na0.4Ag0.6InCl6、Cs2Na0.4Ag0.6InF0.6Cl5.4、Cs2Na0.4Ag0.6InF1Cl5、Cs2Na0.4Ag0.6InF2.8Cl3.2、Cs2Na0.4Ag0.6InF3.6Cl2.4、Cs2Na0.4Ag0.6InF6、Cs2Na0.4Ag0.6In0.99Bi0.01Cl6。
As a further preferred aspect of the present invention, the excitation wavelength of the phosphor is 340-410nm, and the emission wavelength is 380-750 nm; preferably, the excitation wavelength of the fluorescent powder is 365 nm.
According to another aspect of the present invention, the present invention provides a method for preparing the above ultraviolet excited white light multielement non-lead perovskite fluorescent powder, which is characterized by comprising the following steps:
(1) according to A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nRespectively weighing AX powder and B powder according to the stoichiometric ratio of the chemical formula1X powder, B2X powder, B3X3Powder and B4X3Powder, wherein X is X1、X2、X3Any one of the above; then, uniformly mixing the powders with each other to obtain a powder mixture, namely a reaction precursor;
(2) placing the reaction precursor obtained in the step (1) in a crucible, heating for sintering reaction, and cooling to obtain a synthetic solid;
(3) grinding and crushing the synthetic solid obtained in the step (2), then putting the synthetic solid in a crucible again to repeat the sintering reaction in the step (2), and cooling to obtain the synthetic solid again;
(4) and (4) crushing the synthetic solid obtained in the step (3) to obtain the ultraviolet excited white light multielement non-lead perovskite fluorescent powder.
As a further preferred aspect of the present invention, in the step (2), the sintering reaction is carried out at a temperature of 360-470 ℃.
In a further preferred embodiment of the present invention, in the step (2), the sintering time of the sintering reaction is 5 to 10 hours.
As a further preferred aspect of the present invention, in the step (4), the pulverization treatment is specifically grinding pulverization or ball mill pulverization.
According to another aspect of the invention, the ultraviolet excited white light multielement non-lead perovskite fluorescent powder is used as ultraviolet excited matrix fluorescent powder to be applied to fluorescent devices.
As a further preference of the present invention, the fluorescent device is specifically a white LED device, and preferably, the ultraviolet excited white light multi-component non-lead perovskite fluorescent powder is applied to the white LED device together with an ultraviolet chip as an ultraviolet excited single substrate.
Through the technical scheme, compared with the prior art, the multielement non-lead halogen perovskite material A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-n(0≤x≤1，0≤y≤1，0＜m≤6，0＜n≤6，0≤6-m-n≤6, and A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Are respectively F-、Cl-、Br-) Compared with the conventional lead-containing perovskite material ABX3(A：Cs+、CH3NH3 +；B:Pb2+；X:Cl-、Br-、I-) Compared with the prior art, the material does not contain organic matters and lead elements, thereby being a novel environment-friendly material. For the application of an LED, the white light fluorescent powder provided by the invention can realize single-matrix warm white light, and has extremely high fluorescence quantum yield (more than 80%) and color rendering index (more than 90). Meanwhile, in the multielement non-lead halogen perovskite material, B site and X site can be continuously adjusted at any proportion1X and B2Ratio of X and B3X3And B4X3The ratio of (A) to (B) is continuously controlled (wherein X can be F with any molar ratio-、Cl-、Br-) Thereby regulating and controlling the strength of the self-confinement effect and the quantum confinement effect in the multielement non-lead perovskite material, and further achieving the effect of continuously adjusting the absorption spectrum and the emission spectrum of the fluorescent powder. By the regulation and control in the mode, 520-630 nm of peak position coverage of the luminescence spectrum can be realized, and the adjustable color temperature interval is 2200-7500K.
Furthermore, the invention also provides a new application of the multielement non-lead perovskite material, and the multielement non-lead perovskite material can be applied to ultraviolet excited fluorescent devices, such as ultraviolet LEDs and the like. The multi-element non-lead perovskite material is used as fluorescent powder and applied to an ultraviolet excited LED, and the defects of poor stability, poor color rendering property and the like of a traditional white light LED device with a blue light chip and yellow fluorescent powder can be overcome. The ultraviolet excited white light multi-element non-lead perovskite fluorescent powder reported in the patent can perfectly solve the defects of the traditional white light LED and realize stable white light with high color reduction degree. The fluorescent powder can be used as single-matrix fluorescent powder, particularly has the characteristic of adjustable color temperature, for example, the fluorescent powder and an ultraviolet chip can be combined into a white light LED, and the novel white light LED has great potential market. In addition, the solid phase method reported in the patent has simple production process, lower manufacturing cost and wide application prospect and market. In addition, the single-matrix non-lead perovskite fluorescent powder emits white light instead of the white light emitted by mixing the blue light and the yellow light, so that the phenomenon of white light color drift caused by aging of a chip and weakening of the blue light is avoided; namely, the single-matrix multi-element non-lead perovskite fluorescent powder provided by the invention can solve the problem of stability of the existing white light LED, and has outstanding advantages.
The invention adopts a solid phase method for synthesis, and has simple preparation method and environmental protection. The preparation method adopts a solid phase method and takes inorganic metal halide as raw material (A: Cs)+；B1、B2：Na+、Ag+；B3、B4：In3+、Bi3+；X1、X2、X3：F-、Cl-、Br-) The perovskite is prepared by uniformly mixing, grinding and then taking the mixture as a precursor and calcining the precursor at high temperature. And grinding the precursor into powder, and calcining for the second time to prepare the high-quality novel multielement non-lead perovskite white light fluorescent powder.
The invention relates to a multielement all-inorganic non-lead halogen perovskite white light fluorescent powder AB1B2B3B4X1X2X3Whose composition is continuously adjustable, i.e. A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nWherein x, y, m and n can be continuously changed (for example, when one of x or y is 0 or 1, the other can still be continuously adjustable), and the fluorescent powder obtained by continuously changing can be used as a single ultraviolet excitation substrate. Correspondingly, in the starting materials used in the preparation process, monovalent metal halides B1X and B2X is continuously adjustable in any proportion, trivalent metal halide B3X3And B4X3Is in any proportionContinuously adjustable, wherein X represents X1(i.e. F)-)、X2(i.e., Cl)-)、X3(i.e. Br)-) The three halogen ions are also continuously adjustable in any proportion; and, a monovalent metal halide B1X and B2Ratio of X and B3X3And B4X3Are independent of each other as long as B is satisfied1X and B2The sum of the amounts of X and B3X3And B4X3The sum of the amounts of substance(s) of (c) is equal and is preferably half the sum of the amounts of substance(s) of AX.
In the invention A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nThe ultraviolet excited white light multielement non-lead perovskite fluorescent powder can change the element proportion at the B position and adjust; and at the X position, a plurality of halogen ions are also innovatively introduced, and the adjustment range of the spectral peak position from 520nm to 630nm is realized by changing the proportion of various halogen ions. Meanwhile, the multi-element non-lead perovskite is used as ultraviolet excited fluorescent powder for the first time, and the white light device with the color temperature continuously adjustable from 2200K to 7500K is realized. The novel multi-element perovskite system originally invented by the invention is in the traditional perovskite ABX3On the basis, the self-limiting effect is triggered by the doping combination of the B site and the X site, so that the half-peak width of the traditional perovskite about 60nm is increased to about 170nm, and the wide-spectrum white light is realized. And the combined doping of the B site and the X site improves the quantum yield and realizes the spectrum adjustability.
The invention also provides a preparation method of a solid phase method for the novel multi-element non-lead perovskite fluorescent powder, particularly, the sintering temperature and the sintering time are preferably controlled, a good target ultraviolet excited white-light multi-element non-lead perovskite fluorescent powder product can be obtained only by two sintering processes, and the defects of complex process, high cost, liquid pollution and the like of the traditional liquid phase synthesis method are overcome.
In conclusion, the multielement all-inorganic metal non-lead halogen perovskite fluorescent powder material disclosed by the invention generates warm white light, has an LED color rendering index as high as 98, and has a good application prospect. The invention provides a solid phase method for synthesis, which has the advantages of low energy consumption, high yield, low production cost and no waste liquid treatment problem, and perfectly solves the defects of complicated flow, waste liquid pollution and the like of the existing hydrothermal method. The method provided by the invention is more beneficial to industrial large-scale production and application.
Drawings
FIG. 1 is A prepared in examples 1 to 72B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nX-ray diffraction pattern of the phosphor (wherein X is 0. ltoreq. x.ltoreq.1, y is 0. ltoreq. y.ltoreq.1, m is 0. ltoreq. m.ltoreq.6, n is 0. ltoreq. n.ltoreq.6, 0. ltoreq. 6-m-n.ltoreq.6, and A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively as follows: f-，Cl-，Br-)。
FIG. 2 shows A prepared in examples 1 to 72B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nPhotoluminescence spectrum of the phosphor (wherein x is 0. ltoreq. x.ltoreq.1, y is 0. ltoreq. y.ltoreq.1, m is 0. ltoreq. m.ltoreq.6, n is 0. ltoreq. n.ltoreq.6, 0. ltoreq. 6-m-n.ltoreq.6. furthermore, A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively as follows: f-，Cl-，Br-)。
FIG. 3 shows Cs prepared in example 72Na0.4Ag0.6In0.99Bi0.01Cl6Absorption spectrum and emission spectrum of the phosphor.
FIG. 4 shows Cs after being ground and milled by agate crucible2Na0.4Ag0.6In0.99Bi0.01Cl6And (3) fluorescent powder.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention relates to a multi-element non-lead perovskite white light fluorescent powder with continuously adjustable components and a single ultraviolet excited matrix, wherein the multi-element non-lead perovskite white light fluorescent powder with the single ultraviolet excited matrix is of a perovskite structure, and the expression of the multi-element non-lead perovskite white light fluorescent powder with the single ultraviolet excited matrix is as follows: a. the2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, m is more than or equal to 0 and less than or equal to 6, n is more than or equal to 0 and less than or equal to 6, and 0-m-n is more than or equal to 6. In addition, A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively as follows: f-，Cl-，Br-。
The invention adopts a solid phase method to prepare the fluorescent powder, and the method comprises the following steps:
(1) according to the mass ratio x: 1-x weighing B1X and B2X, the mass ratio of the substances y: 1-y weighing B3X3And B4X3While ensuring B1X and B2The sum of the amounts of X and B3X3And B4X3The sum of the amounts of substances is equal. Then weighing and B3X3，B4X3，B1X，B2CsX with equal substance amount of X, mixing the basic materials, grinding into powder to obtainPreparing a precursor;
for example, specifically weighing B at room temperature1X mmol and B2X (1-X) mmol, and B is weighed3X3x mmol and B4X3(1-x) mmol, weighing 2mmol AX, mixing uniformly, and grinding into powder to obtain a reaction precursor. A is Cs+，B1、B2Is Na+、Ag+，B3、B4Is In3+、Bi3+X represents X1、X2、X3Is F-、Cl-、Br-. In particular, X1，X2，X3Can be selected according to the type and proportion of the required halogen anions.
(2) Placing the reaction precursor in a crucible, then placing the crucible in a muffle furnace, heating to a temperature T, keeping the temperature for T hours, and cooling to room temperature along with the furnace to obtain a synthetic solid;
for example, the reaction precursor is placed in a crucible, then placed in a muffle furnace at 360-470 ℃ for reaction for 5-10h, and then cooled to room temperature along with the furnace to obtain the synthetic solid.
(3) And (3) grinding and crushing the obtained white solid again, putting the white solid into the crucible again, putting the crucible into a muffle furnace, and repeating the sintering process in the step 2.
(4) The obtained synthetic powder is crushed and sieved to obtain the target perovskite white phosphor A2B1 xB2 1- xB3 yB4 1-yX1 mX2 nX3 6-m-n。
The following are specific examples:
example 1
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.3366g CsCl, 0.0234g NaCl, 0.0861g AgCl, 0.221g InCl were weighed out3Mixing, grinding with mortar, and standingAnd putting into a crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6InCl6And (3) fluorescent powder.
Example 2
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.3366g CsCl, 0.0234g NaCl, 0.0762g AgF, 0.221g InCl were weighed out3Mixing, grinding with mortar, and placing into crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6InF0.6Cl5.4And (3) fluorescent powder.
Example 3
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.3366g CsCl, 0.0168g NaF, 0.0762g AgF, 0.221g InCl were weighed out3Mixing, grinding with mortar, and placing into crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6InF1Cl5And (3) fluorescent powder.
Example 4
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.3366g CsCl, 0.0168g NaF, 0.0762g AgF, 0.0886g InCl were weighed out3，0.1032gInF3Mixing, grinding with mortar, and placing into crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6InF2.8Cl3.2And (3) fluorescent powder.
Example 5
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.3366g CsCl, 0.0234g NaCl, 0.0762g AgF, 0.172g InF were weighed out3Mixing, grinding with mortar, and placing into crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6InF3.6Cl2.4And (3) fluorescent powder.
Example 6
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.304g CsCl, 0.0168g NaF, 0.0762g AgF, 0.172g InF were weighed out3Mixing, grinding with mortar, and placing into crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6InF6And (3) fluorescent powder.
Example 7
The preparation method of the perovskite fluorescent powder in the embodiment specifically comprises the following steps:
a) the crucible was cleaned with deionized water for 3min and then blow dried with a nitrogen gun.
b) 0.3366g CsCl, 0.0234g NaCl, 0.0861g AgCl, 0.2193g InCl were weighed out3，0.0032gBiCl3Mixing, grinding with mortar, and placing into crucible.
c) And (3) placing the crucible in a muffle furnace, setting the temperature of the muffle furnace to be 30 ℃, raising the temperature to 460 ℃ after 1h, preserving the temperature for 5h, and then naturally cooling to room temperature.
d) Taking out the crucible in the muffle furnace, taking out the powder in the crucible, and uniformly grinding in a mortar. And then put into a crucible to perform operation c.
e) Taking out the crucible in the muffle furnace, and taking out the powder in the crucible to obtain Cs2Na0.4Ag0.6In0.99Bi0.01Cl6And (3) fluorescent powder.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The ultraviolet excited white light multielement non-lead perovskite fluorescent powder is characterized in that the fluorescent powder has a perovskite structure, and the chemical formula of the fluorescent powder satisfies A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nWherein x is greater than 0 and less than 1, y is greater than 0 and less than or equal to 1, m is greater than 0 and less than 6, n is greater than 0 and less than 6, (6-m-n) is greater than or equal to 0 and less than 6; in addition, A is Cs+；B1、B2、B3、B4Are respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Are respectively F-、Cl-、Br-；
The excitation wavelength of the fluorescent powder is 340-410nm, and the emission wavelength is 380-750 nm.
2. The multi-element non-lead perovskite phosphor of claim 1, wherein the phosphor has a chemical formula satisfying Cs2Na0.4Ag0.6InF0.6Cl5.4、Cs2Na0.4Ag0.6InF1Cl5、Cs2Na0.4Ag0.6InF2.8Cl3.2、Cs2Na0.4Ag0.6InF3.6Cl2.4。
3. The ultraviolet-excited white-light multi-element non-lead perovskite phosphor of claim 2, wherein the excitation wavelength of the phosphor is 365 nm.
4. The method for preparing the ultraviolet excited white light multielement non-lead perovskite fluorescent powder as described in any one of claims 1 to 3, which comprises the following steps:
(1) according to A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nRespectively weighing AX powder and B powder according to the stoichiometric ratio of the chemical formula1X powder, B2X powder, B3X3Powder and B4X3Powder, wherein X is X1、X2、X3Any one of the above; then, uniformly mixing the powders with each other to obtain a powder mixture, namely a reaction precursor;
(2) placing the reaction precursor obtained in the step (1) in a crucible, heating for sintering reaction, and cooling to obtain a synthetic solid;
(3) grinding and crushing the synthetic solid obtained in the step (2), then putting the synthetic solid in a crucible again to repeat the sintering reaction in the step (2), and cooling to obtain the synthetic solid again;
(4) and (4) crushing the synthetic solid obtained in the step (3) to obtain the ultraviolet excited white light multielement non-lead perovskite fluorescent powder.
5. The method as set forth in claim 4, wherein the sintering reaction is performed at a temperature of 360-470 ℃ in step (2).
6. The method of claim 4, wherein in the step (2), the sintering time of the sintering reaction is 5-10 h.
7. The method according to claim 4, wherein in the step (4), the pulverization treatment is specifically grinding pulverization or ball mill pulverization.
8. The ultraviolet-excited white-light multi-element non-lead perovskite phosphor as claimed in any one of claims 1 to 3, which is used as an ultraviolet-excited matrix phosphor in a fluorescent device.
9. The use according to claim 8, wherein the fluorescent device is a white LED device, and the uv-excited white light multi-component non-lead perovskite fluorescent powder is used as a uv-excited single matrix and is applied to the white LED device together with a uv chip.
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