CN109423276B - Efficient and stable Mn4+Doped fluoride luminescent material and preparation method thereof - Google Patents

Efficient and stable Mn4+Doped fluoride luminescent material and preparation method thereof Download PDF

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CN109423276B
CN109423276B CN201710791365.4A CN201710791365A CN109423276B CN 109423276 B CN109423276 B CN 109423276B CN 201710791365 A CN201710791365 A CN 201710791365A CN 109423276 B CN109423276 B CN 109423276B
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朱浩淼
黄得财
卢灿忠
陈学元
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Xiamen Institute of Rare Earth Materials
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Abstract

The invention discloses efficient and stable modified Mn4+Doped fluoride luminescent materials and methods for their preparation, which allow for the efficient synthesis of A at temperatures in the range of 0-120 deg.C2MF6Compound coated A2MF6:Mn4+Fluoride phosphor to avoid Mn4+The fluorescent powder is directly contacted with the external environment for degradation, has high temperature stability and good moisture resistance, and further improves the luminous efficiency of the fluorescent powder. The method has the advantages of low preparation temperature, short time and easily controlled process, and is suitable for industrial large-scale preparation.

Description

Efficient and stable Mn4+Doped fluoride luminescent material and preparation method thereof
Technical Field
The invention relates to the technical field of rare earth luminescent materials and illumination display, in particular to efficient and stable Mn4+Doped fluoride luminescent material and preparation method thereof.
Background
White light LED is a novel solid-state light source, compared with traditional incandescent lamps, fluorescent lamps and other light sources, it has the advantages of environmental protection, energy conservation, high efficiency, quick response and the like, and is known as a fourth generation green light source after three major light sources of incandescent lamps, fluorescent lamps and high-pressure gas discharge lamps. In an LED light source, the performance of the phosphor determines the technical indexes of the LED, such as luminous efficiency, color rendering index, color temperature, and service life, so the phosphor plays a significant role in a white LED and is receiving much attention. The most common method at present is to combine the blue LED chip (with the emission wavelength of 440-. However, only a cold white device with a Correlated Color Temperature (CCT) of more than 4500K can be obtained in this way, and the Color Rendering Index (CRI) is also low, usually less than 80. The main reason is that the red light component in the emission spectrum of the commonly used yellow fluorescent powder is insufficient, so that it is difficult to obtain a white light LED device with low color temperature, warm tone and high color rendering index, which is the key point that the white light LED can be applied indoors. To achieve this goal, an effective method is to add appropriate red phosphor powder to the white LED device to enhance the red emission of the device.
Mn4+The ion-activated fluoride material has a narrow emission peak and a small half-peak width, and is a research hotspot of the current red light emitting material. Patent US2009/7497973 discloses Mn4+Activated A2MF6(A is K, Na, Rb, etc.; M is Ti, Si, Sn, Ge, etc.) red-light fluorescent powder; dissolving raw materials in high-concentration hydrofluoric acid, and then heating, volatilizing and co-crystallizing to obtain a product; patent WO2009/119486 discloses dissolving a metal such as Si in a solution of hydrofluoric acid and potassium permanganate, the reaction resulting in a fluoride product; patent CN102732249A discloses that the product is obtained by first preparing a first solution containing a fluoride of metal M and a second solution containing a or a compound of a in solid form, mixing the two solutions, and reacting to generate a precipitate; the fluoride luminescent materials prepared by the methods have the advantages of high luminescent efficiency and good thermal stability. However, these methods do not overcome the disadvantage that the fluoride luminescent material is easily hydrolyzed, and the fluoride luminescent material is easily hydrolyzed in a long-term use or a humid environment, so that the luminous efficiency is reduced or even fails. US 2007/0125984A 1 reports that the surface of fluoride is coated with a layer of inorganic material (such as TiO)2、Al2O3、SiO2) Protective film against Mn4+Directly contacting with water to generate hydrolysis; patent CN 106479485A also discloses that coating a layer of potassium silicate-sodium carboxymethylcellulose-polyethylene glycol mixture on the surface of fluorescent powder particles improves the high temperature and high humidity resistance of the fluorescent powder; these publications all describe methods that are effective in improving the moisture resistance of the phosphor, but, on the other hand, reduce the luminous efficiency of the material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide efficient and stable Mn4+Doped fluoride luminescent materials and preparation thereofThe method solves the defect that the fluoride luminescent material has insufficient high temperature resistance and humidity resistance, and can effectively improve the luminous efficiency of the fluorescent powder. The method has the characteristics of simple preparation process, wide raw material source and low hydrofluoric acid consumption, and is suitable for industrial large-scale preparation.
The purpose of the invention is realized by the following technical scheme:
modified Mn4+Preparation method of doped fluoride luminescent material, wherein the surface of the luminescent material is coated with A2MF6Coated Mn4+Doped fluoride A2MF6:Mn4+；
Wherein, A is selected from one or the combination of alkali metals Li, Na, K, Rb and Cs;
m is selected from one or the combination of Ti, Si, Ge, Sn and Zr;
Mn4+is a luminescence center ion;
characterized in that the method comprises the following steps:
(1) a is to be2MF6Dissolving in HF solution to form saturated solution;
(2) mixing the saturated solution with A2MF6:Mn4+Mixing the luminescent materials, stirring, soaking, filtering, and drying to obtain the product A2MF6:Mn4+Powder;
(3) mixing the saturated solution obtained in the step (1) with the A obtained after filtering and drying in the step (2)2MF6:Mn4+Mixing the powders, stirring and soaking again, filtering and drying to obtain A after secondary treatment2MF6:Mn4+Powder, repeating the steps to prepare the modified Mn4+Doped fluoride luminescent materials.
According to the invention, in step (3), the number of times of repeating the steps is 1 to 6 times, preferably 2 to 5 times.
According to the invention, said M is preferably Si and/or Ti.
According to the invention, the alkali metal A is preferably Na and/or K.
According to the inventionMn described above4+Doped fluoride A2MF6:Mn4+Is selected from K2SiF6:Mn4+、 K2TiF6:Mn4+、K2SnF6:Mn4+、Cs2SiF6:Mn4+、Rb2GeF6:Mn4+、Rb2SiF6:Mn4+、 Na2TiF6:Mn4+、Na2SiF6:Mn4+、Na2ZrF6:Mn4+、K2GeF6:Mn4+Preferably Na2TiF6:Mn4+、Na2SiF6:Mn4+、K2TiF6:Mn4+、K2SiF6:Mn4+。
According to the invention, A is2MF6Are corresponding matrix compounds.
According to the invention, A is2MF6Is selected from K2SiF6、K2TiF6、K2SnF6、Cs2SiF6、Rb2GeF6、 Rb2SiF6、Na2TiF6、Na2SiF6、Na2ZrF6、K2GeF6Preferably Na2TiF6、Na2SiF6、K2TiF6、 K2SiF6。
According to the invention, in the step (1), the mass percentage of the hydrofluoric acid is preferably 20-50%.
According to the present invention, in step (1), the saturated solution is preferably formed at 20 ℃ to 120 ℃.
According to the invention, the temperature of the stirring and soaking in steps (2) and (3) is 0-120 ℃, preferably 20-50 ℃.
According to the invention, in the steps (2) and (3), the stirring and soaking can be carried out under the condition of heat preservation or under the condition of slow cooling, preferably, the slow cooling rate is 0.1-10 ℃/min, and further preferably 0.5-5 ℃/min.
According to the invention, in the steps (2) and (3), the stirring and soaking time is 2min-2h, preferably 5min-1 h.
According to the invention, in steps (2) and (3), A is2MF6And A2MF6:Mn4+In a molar ratio of 1-5: 1.
According to the present invention, in steps (2) and (3), the filtered product may be further washed with an organic solvent such as absolute ethanol or acetone to remove residual acid solution on the surface, and dried.
In the invention, A is obtained by the method2MF6:Mn4+Mn of the surface4+And saturation of A2MF6M in solution4+Realize ion exchange and remove A2MF6:Mn4+Mn of the surface4+Forming A on the surface of the phosphor2MF6Protective layer of compound with reduction of active ion Mn4+In A2MF6:Mn4+Defects formed on the surface of the phosphor.
In the invention, when the stirring and soaking process is carried out under the heat preservation condition, the surface layer of the powder sample after filtration and drying is A2MF6A of the Compound2MF6:Mn4+Fluoride phosphor, the phosphor particle size is unchanged, in the process, A2MF6:Mn4+Mn of fluoride phosphor surface layer4+And M ions in the solution, and thus, the size of the phosphor particles is not changed.
In the invention, when the stirring and soaking process is carried out under the condition of slow temperature reduction, the surface layer of the powder sample after filtration and drying is A2MF6A of the Compound2MF6:Mn4+Fluoride phosphor, the phosphor particle size increases, in the process, A2MF6:Mn4+The fluoride fluorescent powder is mainly subjected to crystallization coating, namely A in solution2MF6The compound is separated out and coated on A along with the change of temperature2MF6:Mn4+A fluoride phosphor surface layer, and thus, the phosphor particle size increases.
The invention also provides modified Mn4+The doped fluoride luminescent material is prepared by the method.
The invention has the beneficial effects that:
the invention provides efficient and stable modified Mn4+Doped fluoride luminescent materials and methods for their preparation, which allow for the efficient synthesis of A at temperatures in the range of 0-120 deg.C2MF6Compound coated A2MF6:Mn4+Fluoride phosphor to avoid Mn4+The fluorescent powder is directly contacted with the external environment for degradation, has high temperature stability and good moisture resistance, and further improves the luminous efficiency of the fluorescent powder. The method has the advantages of low preparation temperature, short time and easily controlled process, and is suitable for industrial large-scale preparation.
Drawings
FIG. 1 example 2 of the present invention, K2TiF6:Mn4+XRD diffraction pattern of the fluorescent powder.
FIG. 2K in example 2 of the present invention2TiF6:Mn4+Excitation spectrum and emission spectrum of the phosphor.
FIG. 3K in example 6 of the present invention2SiF6:Mn4+XRD diffraction pattern of the fluorescent powder.
FIG. 4K in example 6 of the present invention2SiF6:Mn4+Excitation spectrum and emission spectrum of the phosphor.
Detailed description of the preferred embodiments
The present invention will be further described with reference to the following examples. However, it is understood by those skilled in the art that the following examples are not intended to limit the scope of the present invention, and any modifications and variations based on the present invention are within the scope of the present invention.
Example 1: k2TiF6:Mn4+Preparation of phosphor
0.4000g K2MnF6Dissolved in 6mL hydrofluoric acid (49 wt.%) solution and stirredAn orange-yellow transparent solution was obtained for 5 minutes, and 5.1850g K was then added2TiF6Adding the powder to the solution, stirring at room temperature for 30min, stopping stirring, filtering with filter paper, washing with acetone to remove any residual HF, and drying to obtain K2TiF6:Mn4+And (3) powder. The excitation and emission spectra of the products as well as the fluorescence quantum yield and absorption efficiency were measured by an FLS980 (Edinburgh Instrument) fluorescence spectrometer.
Example 2: modified K2TiF6:Mn4+Preparation of phosphor
By adding K to 10ml of 49% HF solution2TiF6The compound was filtered until no more dissolved (about 1.7000g, room temperature), and the undissolved K was filtered2TiF6Obtaining K2TiF6Saturated solution in 49% HF solution. The saturated solution was then added to the flask containing K obtained in example 12TiF6:Mn4+The phosphor was kept stirred at room temperature for 30min in a container. Then carrying out vacuum filtration; repeating the stirring and soaking steps for 2 times, finally filtering, washing with acetone for a plurality of times, removing residual HF, and drying at 70 ℃ for 2 hours to obtain the fluorescent powder. X-ray powder diffraction shows that the product is still hexagonal phase K2TiF6Structure (fig. 1); excitation and emission spectra and internal fluorescence quantum yield of the product were measured by an FLS980 (Edinburgh Instrument) fluorescence spectrometer, the excitation and emission spectra are shown in FIG. 2, and important physicochemical and optical performance parameters, including Mn, of the prepared phosphor are shown in Table 14+The doping concentration, the preparation raw material ratio and the fluorescence quantum yield and absorption efficiency of the sample.
Example 3: modified K2TiF6:Mn4+Preparation of phosphor
By adding K to 10ml of 49% HF solution2TiF6The compound, solution was heated to 70 ℃ with constant stirring until no more dissolved (about 2.3000g), and undissolved K was filtered2TiF6Obtaining K2TiF6Saturated solution in 49% HF solution at 70 ℃. Subsequently mixing the saturated solutionIs charged with K obtained in example 12TiF6:Mn4+And (3) slowly cooling the fluorescent powder in a container at a cooling speed of 0.5 ℃/min, and continuously stirring the fluorescent powder to room temperature. And then carrying out vacuum filtration, washing with acetone for several times, removing residual HF, and drying at 70 ℃ for 2h to obtain the fluorescent powder. Table 1 shows the important physicochemical and optical performance parameters of the prepared phosphor, including Mn4+The doping concentration, the preparation raw material ratio and the fluorescence quantum yield and absorption efficiency of the sample.
Example 4: stability test
The phosphor samples prepared in example 1, example 2 and example 3 were respectively soaked in water for a certain period of time, and the luminescence intensity values thereof were measured and compared. 0.5000g of the phosphor powder samples of example 1, example 2 and example 3 were respectively taken, 1ml of distilled water was measured and added to the samples, and the samples were respectively soaked for 10min, and after being filtered and dried, the luminous intensities after soaking in water were respectively measured and are shown in table 1.
TABLE 1K2TiF6:Mn4+Comparison of fluorescent Properties before and after phosphor treatment
Figure BDA0001399324900000061
As can be seen from the table, the quantum yield of the phosphor is improved after the modification treatment, more importantly, the moisture resistance stability of the phosphor is improved, and the luminous intensity decay is reduced after the phosphor is soaked in water.
Example 5: k2SiF6:Mn4+Preparation of phosphor
0.3250g K2MnF6Dissolved in 4mL of hydrofluoric acid (49%) solution, stirred for 5 minutes to obtain an orange-yellow transparent solution, and then 5.5000g K was added2SiF6Adding the powder into the solution, stirring at room temperature for 3 hr, stopping stirring, and filtering with filter paper to obtain K2SiF6:Mn4+Powder, X-ray powder diffraction shows that the product has a cubic phase K2SiF6The structure is that under the excitation of blue light, the fluorescent powder emits bright red light.
Example 6: modified K2SiF6:Mn4+Preparation of phosphor
By adding K to 10ml of 49% HF solution2SiF6The compound was filtered until no more dissolved (about 0.1750g, room temperature), and the undissolved K was filtered2SiF6Obtaining K2SiF6Saturated solution in 49% HF solution. The K obtained in example 5 is subsequently2SiF6:Mn4+The phosphor was added to the saturated solution and stirring was continued at room temperature for 30 min. And then carrying out vacuum filtration, repeating the stirring and soaking steps for 2 times, finally filtering, washing with acetone for several times, removing residual HF, and drying at 70 ℃ for 2 hours to obtain the fluorescent powder. X-ray powder diffraction shows that the product is still hexagonal phase K2SiF6Structure (fig. 3); excitation and emission spectra and internal fluorescence quantum yield of the product were measured by an FLS980 (Edinburgh Instrument) fluorescence spectrometer, the excitation and emission spectra are shown in FIG. 4, and important physicochemical and optical performance parameters, including Mn, of the prepared phosphor are shown in Table 24+The doping concentration, the preparation raw material ratio and the fluorescence quantum yield and absorption efficiency of the sample.
Example 7: modified K2SiF6:Mn4+Preparation of phosphor
By adding K to 10ml of 49% HF solution2SiF6The compound, solution was heated to 70 ℃ with constant stirring until no more dissolved (about 0.2200g), and undissolved K was filtered2SiF6Obtaining K2SiF6Saturated solution in 49% HF solution at 70 ℃. The saturated solution was then added to the flask containing K obtained in example 52SiF6:Mn4+And (3) slowly cooling the fluorescent powder in a container at a cooling speed of 0.5 ℃/min, and continuously stirring the fluorescent powder to room temperature. And then carrying out vacuum filtration, washing with acetone for several times, removing residual HF, and drying at 70 ℃ for 2h to obtain the fluorescent powder. Table 2 shows the important physicochemical and optical performance parameters of the prepared phosphors, including Mn4+Doping concentration, preparation raw material ratio and fluorescence quantum yield and absorption of sampleEfficiency.
Example 8: stability test
The phosphor samples prepared in example 5, example 6 and example 7 were respectively soaked in water for a certain period of time, and the luminescence intensity values thereof were measured and compared. 0.5000g of the phosphor samples of example 5, example 6 and example 7 were respectively taken, 1ml of distilled water was measured and added to the samples, and the samples were respectively soaked for 10min, and after being filtered and dried, the luminous intensities after soaking in water were respectively measured and shown in table 2.
TABLE 2K2SiF6:Mn4+Comparison of fluorescent Properties before and after phosphor treatment
Figure BDA0001399324900000081
As can be seen from the table, the quantum yield of the phosphor is improved after the modification treatment, more importantly, the moisture resistance stability of the phosphor is improved, and the luminous intensity decay is reduced after the phosphor is soaked in water.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. Modified Mn4+Preparation method of doped fluoride luminescent material, wherein the surface of the luminescent material is coated with A2MF6Coated Mn4+Doped fluoride A2MF6:Mn4+；
Wherein, A is selected from one or the combination of alkali metals Li, Na, K, Rb and Cs;
m is selected from one or the combination of Ti, Si, Ge, Sn and Zr;
Mn4+is a luminescence center ion;
characterized in that the method comprises the following steps:
(1) a is to be2MF6Dissolving in HF solution to form saturated solution;
(2) mixing the saturated solution with A2MF6:Mn4+Mixing the luminescent materials, stirring, soaking, filtering, and drying to obtain the product A2MF6:Mn4+Powder;
(3) mixing the saturated solution obtained in the step (1) with the A obtained after filtering and drying in the step (2)2MF6:Mn4+Mixing the powders, stirring and soaking again, filtering and drying to obtain A after secondary treatment2MF6:Mn4+Powder, repeating the steps to prepare the modified Mn4+A doped fluoride luminescent material;
wherein, the stirring and soaking are carried out under the condition of slow cooling, and the slow cooling rate is 0.1-10 ℃/min.
2. The method according to claim 1, wherein in the step (3), the number of times of repeating the step is 1 to 6 times.
3. The method according to claim 1, wherein in the step (3), the number of times of repeating the step is 2 to 5 times.
4. The method according to claim 1, wherein M is Si and/or Ti.
5. The method according to claim 1, wherein the alkali metal A is Na and/or K.
6. The method according to claim 1, wherein the Mn is4+Doped fluoride A2MF6:Mn4+Is selected from K2SiF6:Mn4+、K2TiF6:Mn4+、K2SnF6:Mn4+、Cs2SiF6:Mn4+、Rb2GeF6:Mn4+、Rb2SiF6:Mn4+、Na2TiF6:Mn4 +、Na2SiF6:Mn4+、Na2ZrF6:Mn4+、K2GeF6:Mn4+。
7. The method according to claim 1, wherein A is2MF6Is a corresponding matrix compound, the A2MF6Is selected from K2SiF6、K2TiF6、K2SnF6、Cs2SiF6、Rb2GeF6、Rb2SiF6、Na2TiF6、Na2SiF6、Na2ZrF6、K2GeF6。
8. The method according to claim 1, wherein in the step (1), the hydrofluoric acid is preferably 20 to 50% by mass.
9. The method according to claim 1, wherein in the step (1), the saturated solution is formed at 20 ℃ to 120 ℃.
10. The method according to claim 1, wherein the temperature of the agitation soaking in the steps (2) and (3) is 20 to 50 ℃.
11. The method according to claim 1, wherein the slow cooling rate is 0.5 ℃/min to 5 ℃/min in the steps (2) and (3).
12. The preparation method according to claim 1, wherein the stirring and soaking time in steps (2) and (3) is 2min-2 h.
13. The method according to claim 1, wherein in steps (2) and (3), A is2MF6And A2MF6:Mn4+In a molar ratio of 1-5: 1.
14. The method according to any one of claims 1 to 13, wherein in steps (2) and (3), the filtered product is further washed with absolute ethanol or acetone to remove residual acid solution on the surface, and dried.
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CN111471456A (en) * 2020-04-11 2020-07-31 厦门市钛科创科技有限公司 Fluoride red fluorescent powder and luminescent device based on same
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103003388A (en) * 2010-07-27 2013-03-27 通用电气公司 Moisture-resistant phosphor and associated method
CN103429701A (en) * 2011-03-23 2013-12-04 通用电气公司 Color stable manganese-doped phosphors
CN104024374A (en) * 2012-12-28 2014-09-03 信越化学工业株式会社 Method for surface treatment of phosphor
CN105038776A (en) * 2015-06-18 2015-11-11 北京宇极科技发展有限公司 Preparation method of Mn<4+> doped fluoride fluorescent powder material and method for surface modification of Mn<4+> doped fluoride fluorescent powder material
CN105189696A (en) * 2013-03-15 2015-12-23 通用电气公司 Color stable red-emitting phosphors
CN105452418A (en) * 2013-08-22 2016-03-30 通用电气公司 Processes for preparing color stable manganese-doped phosphors

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102337406B1 (en) * 2014-12-09 2021-12-13 삼성전자주식회사 Fluoride phosphor, method of manufacturing the same, light emitting device, display apparatus and illumination apparatus

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103003388A (en) * 2010-07-27 2013-03-27 通用电气公司 Moisture-resistant phosphor and associated method
CN103429701A (en) * 2011-03-23 2013-12-04 通用电气公司 Color stable manganese-doped phosphors
CN104024374A (en) * 2012-12-28 2014-09-03 信越化学工业株式会社 Method for surface treatment of phosphor
CN105189696A (en) * 2013-03-15 2015-12-23 通用电气公司 Color stable red-emitting phosphors
CN105452418A (en) * 2013-08-22 2016-03-30 通用电气公司 Processes for preparing color stable manganese-doped phosphors
CN105038776A (en) * 2015-06-18 2015-11-11 北京宇极科技发展有限公司 Preparation method of Mn<4+> doped fluoride fluorescent powder material and method for surface modification of Mn<4+> doped fluoride fluorescent powder material

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