CN107629791B - Mn (manganese)4+Ion-doped red fluorescent powder, preparation method and application - Google Patents

Abstract

The invention discloses Mn⁴⁺Ion-doped red fluorescent powder, and a preparation method and application thereof.The chemical general formula of the fluorescent powder is Cs₃Ge₂Sb₃O₁₃:xMn⁴⁺WhereinxIs Mn⁴⁺The doping molar ratio is more than or equal to 0.0005 and less than or equal to 0.015. The material prepared by the invention can respond in the wavelength range of blue light, near ultraviolet or ultraviolet and the like, emits red fluorescence in the wavelength range of 620-750 nanometers, and can be used for replacing the traditional rare earth-doped red light source; the excitation spectrum range is wide, the absorption is strong at 355 nm, and the excitation spectrum range is matched with the light-emitting waveband of a commercial ultraviolet-blue light chip. The fluorescent powder provided by the invention is simple in preparation method, has the characteristics of wide raw material selectivity, low cost and the like compared with rare earth fluorescent powder, is a red fluorescent material with good luminous performance, and can be applied to manufacturing white light LED fluorescent powder excited by near ultraviolet light or blue light.

Description

Mn (manganese)4+Ion-doped red fluorescent powder, preparation method and application

Technical Field

The invention belongs to the field of solid fluorescent materials, and particularly relates to a manganese (IV) -doped red luminescent material and a specific obtaining way thereof. The prepared luminescent material can be mixed with YAG: the combination of the Ce and the InGaN blue light chips can make up for the defects of high color temperature and poor color rendering index of the traditional commercial white light LED, and can obtain warm white light required by people.

Background

The rapid social development promotes human civilization, and meanwhile, the demand on energy is also increased, and before the novel energy is not developed and utilized, the primary energy sources of the traditional fossil fuels such as petroleum, coal, natural gas and the like are still the main energy sources for obtaining energy from the nature. However, the abuse of fossil fuels aggravates a series of environmental pollution problems such as carbon dioxide emission and haze, and under the condition that the human living environment is threatened, energy conservation is reduced to become a controversial strategy in all countries.

The incandescent lamp brings brightness to human beings at night in over one hundred years, but gradually exits the historical stage due to the defects of high energy consumption, easy damage, environmental pollution and the like. White light LEDs are used as a novel green light source, are widely applied to lighting lamps and displays by virtue of a plurality of advantages, and are a milestone for energy conservation and emission reduction in the field of lighting. Currently, the most common commercial applications are blue light emitted by InGaN and YAG Ce³⁺The yellow light emitted by the fluorescent powder is mixed to obtain white light, but the most fundamental defects of the design are poor color rendering property and high color temperature, and the fundamental cause of the phenomenon is the defect of a red light source. Therefore, theoretically, it is necessary to add a red light-emitting materialBesides, the phosphor of (1) can be effectively excited by blue light. Rare earth ion doped Eu³⁺Is one of the easiest methods to obtain a red light source, but it can only be used under near ultraviolet (A)<365 nm) is excited, and is not matched with blue light chip InGaN (the excitation area is generally 380-470 nm), so the application requirement in WLEDs can not be met, and rare earth is a strategic resource and the price is expensive, so that a low-cost non-rare earth doped red fluorescent powder capable of being excited by short-wavelength light is urgently sought.

Among several transition metal elements, Mn⁴⁺Is a suitable red phosphor activator due to its unique property²E-⁴A₂A spin-forbidden transition, which causes it to emit light in the red band; mn⁴⁺And also has 3d³The electronic configuration can present effective emission and is easy to be excited by near ultraviolet and blue light in a certain coordination environment. In addition to this, Mn⁴⁺The raw material sources of the ions are wide, and the price is much cheaper than that of the rare earth, so that the manufacturing cost of the WLEDs is favorably reduced. Due to Mn⁴⁺The ions have wide application prospect and are paid more and more attention.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a non-rare earth doped material-Mn which can respond to ultraviolet, near-ultraviolet or blue light and other wave bands excited by an excitation light source and can emit red fluorescence⁴⁺Ion-doped red fluorescent powder, and a preparation method and application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is to provide Mn⁴⁺The ion-doped red fluorescent powder has the chemical formula: cs₃Ge₂Sb₃O₁₃:xMn⁴⁺Wherein, in the step (A),xis Mn⁴⁺The mol ratio of doping is less than or equal to 0.0005x≤0.015。

The fluorescent powder emits red fluorescence with the dominant wavelength of 620-750 nanometers under the excitation of near ultraviolet to blue light with the wavelength of 270-480 nanometers.

The technical scheme of the invention also comprises Mn⁴⁺The preparation method of the ion-doped red fluorescent powder adopts a chemical gel method and comprises the following steps:

1. by Cs containing cesium ions⁺Compound of (2), containing germanium ion Ge⁴⁺Compound of (2), antimony ion Sb⁵⁺Compound of (5) and manganese ion containing Mn⁴⁺Is prepared from the compound of formula (I) according to the formula Cs₃Ge_2-2xMn_2xSb₃O₁₃Corresponding stoichiometric ratio, where x is Mn⁴⁺Weighing each raw material, respectively dissolving the weighed raw materials in corresponding solvents, and stirring for more than 3 hours, wherein x is more than or equal to 0.0005 and less than or equal to 0.015;

2. citric acid is taken as a complexing agent, the complexing agent is added according to 0.5-2.0 wt% of the mass of reactants in the raw materials, and the raw materials are stirred for 0.5-5 hours at the temperature of 60-90 ℃;

3. slowly mixing the solutions obtained in the step (2), stirring for 3-6 hours at the temperature of 60-100 ℃, standing, and drying to obtain a fluffy precursor;

4. fully grinding the precursor, preserving heat for 3-5 hours at the temperature of 400-600 ℃, then heating to 950-1250 ℃, and calcining in an air atmosphere for 3-8 hours;

5. naturally cooling the product obtained in the step 4 to obtain Mn⁴⁺Ion-doped red phosphor.

In the above technical scheme, the cesium ions Cs⁺The compound of (A) is cesium nitrate CsNO₃Cesium acetate C₂H₃CsO₂Cesium carbonate Cs₂CO₃One of (1); the Ge ion containing germanium⁴⁺The compound of (A) is germanium oxide GeO₂And germanium tetrachloride GeCl₄One of (1); the antimony-containing ions Sb⁵⁺The compound of (A) is antimony acetate C₆H₉O₆Sb and antimony trichloride SbCl₃One of (1); the manganese ion Mn⁴⁺The compound of (A) is manganese nitrate tetrahydrate Mn (NO)₃)₂·4H₂O, manganese acetate Mn (CH)₃COO)₂MnCl, manganese chloride₂One kind of (1).

One preferred scheme described in step 4 is: the calcination temperature is 1000-1200 ℃, and the calcination time is 3-6 hours.

Mn according to the invention⁴⁺The ion activated red fluorescent powder is used as a red light source and is combined with a blue light chip to obtain warm white light.

Compared with the prior art, the technical scheme of the invention has the advantages that:

1. mn prepared by the invention⁴⁺The ion-doped red fluorescent powder can effectively absorb and emit red light in the range of 620-750 nanometers in near ultraviolet and blue light bands.

2. Mn prepared by the invention⁴⁺The ion-doped red fluorescent powder has high luminous efficiency, has good chemical stability and thermal stability because of inorganic salt, and can be used as a red component of a multi-primary-color energy-saving fluorescent light source to improve the color rendering index and reduce the color temperature.

3. Mn prepared by the invention⁴⁺The ion-doped red fluorescent powder not only has the luminescent characteristic similar to that of rare earth ions, but also has rich raw materials, low cost and good application prospect in the aspect of replacing rare earth elements.

4. The invention has no waste gas and waste liquid discharge, and is an environment-friendly inorganic luminescent material.

Drawings

FIG. 1 shows Cs prepared according to example 1 of the present invention₃Ge_1.999Mn_0.001Sb₃O₁₃X-ray powder diffraction pattern of (a);

FIG. 2 shows Cs prepared according to example 1 of the present invention₃Ge_1.999Mn_0.001Sb₃O₁₃SEM spectra of (a);

FIG. 3 shows Cs prepared according to example 1 of the present invention₃Ge_1.999Mn_0.001Sb₃O₁₃An excitation spectrogram in a near ultraviolet to blue light region is obtained under the monitoring of 656 nm;

FIG. 4 shows Cs prepared according to example 1 of the present invention₃Ge_1.999Mn_0.001Sb₃O₁₃A luminescence spectrum under excitation of 400 nm;

FIG. 5 shows Cs prepared according to example 1 of the present invention₃Ge_1.999Mn_0.001Sb₃O₁₃The luminescence decay curve of (a);

FIG. 6 shows Cs prepared according to example 5 of the present invention₃Ge_1.984Mn_0.016Sb₃O₁₃X-ray powder diffraction pattern of (a);

FIG. 7 shows Cs prepared according to example 5 of the present invention₃Ge_1.984Mn_0.016Sb₃O₁₃SEM spectra of (a);

FIG. 8 shows Cs prepared according to example 5 of the present invention₃Ge_1.984Mn_0.016Sb₃O₁₃An excitation spectrogram in a near ultraviolet to blue light region is obtained under the monitoring of 656 nm;

FIG. 9 shows Cs prepared according to example 5 of the present invention₃Ge_1.984Mn_0.016Sb₃O₁₃A luminescence spectrum under excitation of 400 nm;

FIG. 10 shows Cs prepared according to example 5 of the present invention₃Ge_1.984Mn_0.016Sb₃O₁₃The luminescence decay curve of (1).

Detailed Description

The technical solution of the present invention is further described with reference to the accompanying drawings and examples.

Example 1

Preparation of Cs₃Ge_1.999Mn_0.001Sb₃O₁₃

According to the formula Cs₃Ge_1.999Mn_0.001Sb₃O₁₃Respectively weighing cesium nitrate CsNO according to stoichiometric ratio₃: 2.924 g of germanium oxide GeO₂: 1.045 g; antimony acetate C₆H₉O₆Sb: 4.483 g; manganese nitrate tetrahydrate Mn (NO)₃)₂·4H₂O: 0.001 g; respectively weighing corresponding lemon according to 2.0wt% of the mass of the reactants in the raw materialsCitric acid. Dissolving antimony acetate in a proper amount of glycol solution, and stirring to obtain a solution A; dissolving the rest raw materials in a proper amount of dilute nitric acid, stirring for 3 hours, and adding the weighed citric acid into the mixed solution after the raw materials, particularly germanium oxide, are completely dissolved to obtain a solution B; the solution A is slowly added to the solution B with stirring and stirred in a water bath at 75 ℃ until gelatinous. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, fully grinding the precursor uniformly by using an agate mortar, placing the precursor in a muffle furnace for roasting, keeping the temperature of 500 ℃ for 3 hours, slowly heating to 1200 ℃, roasting for 7 hours, and naturally cooling to obtain the required Mn⁴⁺Ion-doped red phosphor.

Referring to FIG. 1, Cs prepared in accordance with this example₃Ge_1.999Mn_0.001Sb₃O₁₃The XRD test result shows that the prepared sample has good crystallinity and is a single-phase material.

Referring to FIG. 2, Cs prepared in accordance with this example₃Ge_1.999Mn_0.001Sb₃O₁₃The scanning electron microscope image and the SEM test result show that the prepared material particles are slightly agglomerated.

Referring to fig. 3, which shows the excitation spectrum of the sample prepared according to the technical scheme of this embodiment under the condition of monitoring emitted light 656 nm, it can be seen that the excitation source of the red luminescence of the material is mainly in the near ultraviolet to blue region between 270-480 nm.

Refer to FIG. 4, which is a graph of the luminescence spectrum of a sample prepared according to the embodiment under excitation at 400 nm. As can be seen from the figure, the main central luminescence wavelength of the material is a red luminescence band with 656 nm.

Referring to FIG. 5, Cs prepared in accordance with an embodiment of the present invention₃Ge_1.999Mn_0.001Sb₃O₁₃The calculated decay time of the luminescence decay curve of (2) was 31 msec.

Cs provided in this example₃Ge_1.999Mn_0.001Sb₃O₁₃Fluorescent materials are used as red light sources to improve the cool white light resulting from conventional yellow-blue mixing, such as with commercial YAG: the Ce-InGaN blue light chip combination can obtain the warm white light required by people.

Example 2

Preparation of Cs₃Ge_1.998Mn_0.002Sb₃O₁₃

According to the formula Cs₃Ge_1.998Mn_0.002Sb₃O₁₃Respectively weighing cesium nitrate CsNO₃: 2.924 g; germanium tetrachloride GeCl₄: 2.142 g (adding a proper amount of absolute ethyl alcohol into a small beaker, peeling with a balance, and slowly dripping GeCl into the beaker by using a dropper₄Obtaining a solution A); antimony acetate C₆H₉O₆Sb: 4.483 g; manganese acetate Mn (CH)₃COO)₂: 0.002 g; and weighing corresponding citric acid according to 2.0wt% of the mass of the reactants in the raw materials respectively. Dissolving all weighed citric acid in a proper amount of deionized water, and then dissolving cesium nitrate and manganese acetate in a citric acid solution together to obtain a solution B; meanwhile, a proper amount of glycol is taken to be put in another beaker, and the weighed antimony acetate is dissolved to obtain a solution C; then, the solution A and the solution C are slowly added into the solution B by a dropper, the solution B is stirred while adding, after the solution A and the solution C are completely mixed into the solution B, the obtained mixed solution is placed into a water bath kettle at 75 ℃ to be stirred until the mixed solution is colloidal. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, sufficiently grinding the precursor with an agate mortar, roasting the precursor in a muffle furnace at the constant temperature of 500 ℃ for 3 hours, slowly heating the precursor to 1150 ℃, roasting the precursor for 5 hours, and naturally cooling the calcined precursor to obtain the required Mn⁴⁺Ion-doped red phosphor.

The X-ray powder diffraction pattern, the scanning electron microscope pattern, the excitation spectrogram, the luminescence spectrogram and the luminescence attenuation curve of the sample prepared by the technical scheme of the embodiment are similar to those of the sample prepared in the embodiment 1.

Example 3

Preparation of Cs₃Ge_1.994Mn_0.006Sb₃O₁₃

According to the formula Cs₃Ge_1.994Mn_0.006Sb₃O₁₃Respectively weighing cesium acetate C₂H₃CsO₂: 2.879 g; germanium tetrachloride GeCl₄: 2.138 g (adding a proper amount of absolute ethyl alcohol into a small beaker, peeling with a balance, and slowly dripping GeCl into the beaker by using a dropper₄Obtaining a solution A); antimony trichloride SbCl₃: 3.422 g; manganese chloride MnCl₂: 0.005 g; and weighing corresponding citric acid according to 2.0wt% of the mass of the reactants in the raw materials respectively. Dissolving all the weighed citric acid into a proper amount of deionized water, dropwise adding 3ml of 37% concentrated hydrochloric acid, and dissolving cesium acetate, antimony trichloride and manganese chloride into a citric acid solution to obtain a solution B; then, the solution A is slowly added into the solution B by a dropper under stirring, and after the solution A is completely mixed into the solution B, the obtained mixed solution is placed into a water bath kettle at 75 ℃ and stirred until the mixed solution is colloidal. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, sufficiently grinding the precursor with an agate mortar, roasting the precursor in a muffle furnace at the constant temperature of 500 ℃ for 3 hours, slowly heating the precursor to 1200 ℃, roasting the precursor for 8 hours, and naturally cooling the calcined precursor to obtain the required Mn⁴⁺Ion-doped red phosphor.

The X-ray powder diffraction pattern, the scanning electron microscope pattern, the excitation spectrogram, the luminescence spectrogram and the luminescence attenuation curve of the sample prepared by the technical scheme of the embodiment are similar to those of the sample prepared in the embodiment 1.

Example 4

Preparation of Cs₃Ge_1.99Mn_0.01Sb₃O₁₃

According to the formula Cs₃Ge_1.99Mn_0.01Sb₃O₁₃Respectively weighing raw material cesium acetate C₂H₃CsO₂: 2.879 g; germanium oxide GeO₂: 1.041 g; antimony acetate C₆H₉O₆Sb: 4.483 g; manganese nitrate tetrahydrateMn(NO₃)₂·4H₂O: 0.013 g; and weighing corresponding citric acid according to 2.0wt% of the mass of the reactants in the raw materials respectively. Firstly, taking a proper amount of glycol, and adding antimony acetate C₆H₉O₆Dissolving Sb to obtain an ethylene glycol solution, and obtaining a solution A containing antimony ions; then taking a proper amount of nitric acid solution, putting germanium oxide into the nitric acid solution, putting cesium acetate and manganese nitrate into the nitric acid solution after the germanium oxide is fully dissolved, and stirring for 3 hours to obtain solution B; and then slowly dripping the solution A into the solution B while stirring, adding weighed citric acid after the solution A and the solution B are uniformly mixed, and placing the obtained mixed solution into a 75 ℃ water bath kettle to be stirred until the mixed solution is colloidal. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, sufficiently grinding the precursor with an agate mortar, roasting the precursor in a muffle furnace at the constant temperature of 500 ℃ for 3 hours, slowly heating the precursor to 1150 ℃, roasting the precursor for 6 hours, and naturally cooling the calcined precursor to obtain the required Mn⁴⁺Ion-doped red phosphor.

The X-ray powder diffraction pattern, the scanning electron microscope pattern, the excitation spectrogram, the luminescence spectrogram and the luminescence attenuation curve of the sample prepared by the technical scheme of the embodiment are similar to those of the sample prepared in the embodiment 1.

Example 5

Preparation of Cs₃Ge_1.984Mn_0.016Sb₃O₁₃

According to the formula Cs₃Ge_1.984Mn_0.016Sb₃O₁₃Respectively weighing raw material cesium carbonate Cs₂CO₃: 2.444 g; germanium tetrachloride GeCl₄: 2.127 g (adding a proper amount of absolute ethyl alcohol into a small beaker, peeling with a balance, and slowly dripping GeCl into the beaker by using a dropper₄Obtaining a solution A); antimony trichloride SbCl₃: 3.422 g; manganese acetate Mn (CH)₃COO)₂: 0.014 g; and weighing corresponding citric acid according to 2.0wt% of the mass of the reactants in the raw materials respectively. The cesium carbonate is weighed in a glove box, the cesium carbonate is dissolved in a proper amount of dilute hydrochloric acid and taken out of the glove box, and then the cesium carbonate, the hydrochloric acid and the hydrochloric acid are added into the glove boxAdding antimony chloride and manganese acetate into the solution, and stirring until the antimony chloride and the manganese acetate are dissolved to obtain a solution B; slowly dripping the solution A into the solution B while stirring, adding weighed citric acid after the solution A and the solution B are uniformly mixed, and placing the obtained mixed solution into a 75 ℃ water bath kettle to be stirred until the mixed solution is colloidal. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, fully grinding the precursor uniformly by using an agate mortar, placing the precursor in a muffle furnace for roasting, keeping the temperature of 500 ℃ for 3 hours, slowly heating to 1180 ℃, roasting for 7 hours, and naturally cooling to obtain the required Mn⁴⁺Ion-doped red phosphor.

Referring to FIG. 6, Cs prepared according to the embodiment of this example₃Ge_1.984Mn_0.016Sb₃O₁₃The XRD test result shows that the prepared sample has good crystallinity and is a single-phase material.

Referring to the attached figure 7, which is a scanning electron microscope image of a sample prepared according to the technical scheme of the embodiment, an SEM test result shows that the particle size of the prepared material particles is 1-3 microns, and the crystals are perfect.

Referring to fig. 8, which is an excitation spectrum of a sample prepared according to the technical scheme of the embodiment under the condition of monitoring emitted light 656 nm, it can be seen that the excitation source of red light emission of the material is mainly in the near ultraviolet to blue light region between 270-480 nm.

Refer to FIG. 9, which is a graph of the luminescence spectrum of a sample prepared according to the embodiment of the present invention under excitation at a wavelength of 400 nm. As can be seen from the figure, the main central luminescence wavelength of the material is a red luminescence band with 656 nm.

Referring to fig. 10, which is a luminescence decay curve of a sample prepared according to the embodiment of the present invention, the calculated decay time is 34.4 ms.

Example 6

Preparation of Cs₃Ge_1.978Mn_0.022Sb₃O₁₃

According to the formula Cs₃Ge_1.978Mn_0.022Sb₃O₁₃Respectively weighing raw material cesium carbonate Cs₂CO₃: 2.444 g; germanium oxide GeO₂: 1.034 g; antimony acetate C₆H₉O₆Sb: 4.483 g; manganese acetate Mn (CH)₃COO)₂: 0.019 g; and weighing corresponding citric acid according to 2.0wt% of the mass of the reactants in the raw materials respectively. The cesium carbonate is weighed in a glove box, the cesium carbonate is dissolved in excessive dilute nitric acid after weighing, then the cesium carbonate is taken out from the glove box, germanium oxide and manganese acetate are also put into the solution, and the solution A is obtained after stirring until the solid is completely dissolved; taking appropriate amount of ethylene glycol, adding antimony acetate C₆H₉O₆Dissolving Sb to obtain a solution B containing antimony ions; slowly dripping the solution B into the solution A while stirring, adding weighed citric acid after the solution A and the solution B are uniformly mixed, and placing the obtained mixed solution into a 75 ℃ water bath kettle to be stirred until the mixed solution is colloidal. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, sufficiently grinding the precursor with an agate mortar, roasting the precursor in a muffle furnace at the constant temperature of 500 ℃ for 3 hours, slowly heating the precursor to 1100 ℃, roasting the precursor for 8 hours, and naturally cooling the calcined precursor to obtain the required Mn⁴⁺Ion-doped red phosphor.

The X-ray powder diffraction pattern, the scanning electron microscope pattern, the excitation spectrogram, the luminescence spectrogram and the luminescence attenuation curve of the sample prepared by the technical scheme of the embodiment are the same as those of the sample prepared in the embodiment 5.

Example 7

Preparation of Cs₃Ge_1.974Mn_0.026Sb₃O₁₃

According to the formula Cs₃Ge_1.974Mn_0.026Sb₃O₁₃Respectively weighing raw material cesium acetate C₂H₃CsO₂: 2.897 g; germanium tetrachloride GeCl₄: 2.117 g (adding a proper amount of absolute ethyl alcohol into a small beaker, peeling off the skin by a balance, and slowly dripping GeCl into the beaker by a dropper₄Obtaining a solution A); antimony acetate C₆H₉O₆Sb: 4.483 g; manganese acetate Mn: (CH₃COO)₂: 0.022 g, and weighing corresponding citric acid according to 2.0wt% of the reactant in each raw material. Firstly, taking a proper amount of glycol, and dissolving antimony acetate in the glycol to obtain a solution B; dissolving the weighed citric acid in a proper amount of deionized water, adding cesium acetate and manganese acetate, and continuously stirring to obtain a solution C; and (3) dropwise adding the solution A and the solution B into the solution C while stirring, adding weighed citric acid after A, B and the solution C are uniformly mixed, and placing the obtained mixed solution into a 75 ℃ water bath kettle to be stirred until the mixed solution is colloidal. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, sufficiently grinding the precursor with an agate mortar, roasting the precursor in a muffle furnace at the constant temperature of 500 ℃ for 3 hours, slowly heating the precursor to 1150 ℃, roasting the precursor for 6 hours, and naturally cooling the calcined precursor to obtain the required Mn⁴⁺Ion-doped red phosphor.

The X-ray powder diffraction pattern, the scanning electron microscope pattern, the excitation spectrogram, the luminescence spectrogram and the luminescence attenuation curve of the sample prepared by the technical scheme of the embodiment are the same as those of the sample prepared in the embodiment 5.

Example 8

Preparation of Cs₃Ge_1.97Mn_0.03Sb₃O₁₃

According to the formula Cs₃Ge_1.97Mn_0.03Sb₃O₁₃Respectively weighing raw material cesium nitrate CsNO₃: 2.924 g; germanium oxide GeO₂: 1.03 g; antimony acetate C₆H₉O₆Sb: 4.483 g; manganese acetate Mn (CH)₃COO)₂: 0.026 g, and weighing citric acid according to 2.0wt% of the reactant. Firstly, taking a proper amount of glycol, dissolving antimony acetate in the glycol to obtain a solution A, then taking a proper amount of dilute nitric acid, firstly adding germanium oxide into the dilute nitric acid, stirring until the germanium oxide is completely dissolved, then dissolving cesium nitrate and manganese acetate into the solution to obtain a solution B, then dropwise adding the solution A into the solution B while stirring, adding weighed citric acid after the solution A and the solution B are uniformly mixed, and mixing the obtained mixed solutionStirring in 75 deg.C water bath until colloid. The resulting jelly was aged for a period of time and dried in an oven at 100 ℃ for 12 hours to give a fluffy precursor. Taking out the precursor, sufficiently grinding the precursor with an agate mortar, roasting the precursor in a muffle furnace at the constant temperature of 500 ℃ for 3 hours, slowly heating the precursor to 1100 ℃, roasting the precursor for 4 hours, and naturally cooling the calcined precursor to obtain the required Mn⁴⁺Ion-doped red phosphor.

The X-ray powder diffraction pattern, the scanning electron microscope pattern, the excitation spectrogram, the luminescence spectrogram and the luminescence attenuation curve of the sample prepared by the technical scheme of the embodiment are the same as those of the sample prepared in the embodiment 5. Similarly, the fluorescent material provided by the embodiment is used as a red light source and combined with a blue light chip to obtain warm white light.

Claims (6)

1. Mn (manganese)⁴⁺The ion-doped red fluorescent powder is characterized by having a chemical formula as follows: cs₃Ge₂Sb₃O₁₃:xMn⁴⁺Wherein, in the step (A),xis Mn⁴⁺The mol ratio of doping is less than or equal to 0.0005x≤0.015。

2. A Mn according to claim 1⁴⁺The ion-doped red fluorescent powder is characterized in that: the fluorescent powder emits red fluorescence with the dominant wavelength of 620-750 nanometers under the excitation of near ultraviolet to blue light with the wavelength of 270-480 nanometers.

3. An Mn as set forth in claim 1⁴⁺The preparation method of the ion-doped red fluorescent powder is characterized by adopting a chemical gel method and comprising the following steps of:

(1) taking a cesium compound, a germanium compound, an antimony compound and a manganese compound as raw materials according to a chemical formula of Cs₃Ge₂Sb₃O₁₃:xMn⁴⁺The corresponding stoichiometric ratio, wherein,xis Mn⁴⁺The coefficient of mole percentage of (1) is not more than 0.0005xWeighing the raw materials at a ratio of less than or equal to 0.015, and respectively weighing the raw materialsDissolving in corresponding solvent, and stirring for more than 3 hours;

(2) citric acid is taken as a complexing agent, the complexing agent is added according to 0.5-2.0 wt% of the mass of reactants in the raw materials, and the raw materials are stirred for 0.5-5 hours at the temperature of 60-90 ℃;

(3) slowly mixing the solutions obtained in the step (2), stirring for 3-6 hours at the temperature of 60-100 ℃, standing, and drying to obtain a fluffy precursor;

(4) fully grinding the precursor, preserving heat for 3-5 hours at the temperature of 400-600 ℃, then heating to 950-1250 ℃, and calcining in an air atmosphere for 3-8 hours;

(5) naturally cooling the product obtained in the step (4) to obtain Mn⁴⁺Ion-doped red phosphor.

4. A Mn according to claim 3⁴⁺The preparation method of the ion-doped red fluorescent powder is characterized by comprising the following steps: the cesium compound is cesium nitrate CsNO₃Cesium acetate C₂H₃CsO₂Cesium carbonate Cs₂CO₃One of (1); the germanium compound is germanium oxide GeO₂And germanium tetrachloride GeCl₄One of (1); the compound of the antimony element is antimony acetate C₆H₉O₆Sb and antimony trichloride SbCl₃One of (1); the compound of the manganese element is manganese nitrate tetrahydrate Mn (NO)₃)₂·4H₂O, manganese acetate Mn (CH)₃COO)₂MnCl, manganese chloride₂One kind of (1).

5. A Mn according to claim 3⁴⁺The preparation method of the ion-doped red fluorescent powder is characterized by comprising the following steps: and (4) calcining at 1000-1200 ℃ for 3-6 hours.

6. An Mn as set forth in claim 1⁴⁺The application of ion activated red fluorescent powder is characterized in that: the red light source is used as a red light source and is combined with a blue light chip to obtain warm white light.

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