CN110257065B - Red fluorescent powder with waterproof performance and preparation method thereof - Google Patents
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Abstract
The general formula of the red fluorescent powder with self-contained waterproof performance is as follows: k2MxNyF6：zMn4+In which K is2MxNyF6M N in the matrix is any two of Si, Ge and Ti ions, 0<x<1、0<y<1, and x + y =1, 0<z ≦ 0.2. The red fluorescent powder with waterproof performance is K at normal temperature and normal pressure2MxNyF6As a substrate, with KMnO4And HF solution. The method for preparing the fluorescent powder is rapid, simple and efficient, the red fluorescent powder prepared by the method is emitted in a narrow band, has high luminous efficiency, good color development effect and uniform fluorescent powder particles, has waterproofness, solves the problem of rapid performance attenuation of the fluorescent powder in a traditional waterproof means for protecting a coating, does not need a waterproof coating, saves the production cost, and can be widely applied to a humid environment.
Description
Technical Field
The invention relates to the technical field of luminescence, in particular to red fluorescent powder with self-contained waterproof performance and a preparation method thereof.
Background
The development of white light diodes (LEDs) is of great importance for saving global energy, and they are widely used in the display and lighting fields because of their advantages of long lifetime, high energy conversion efficiency, good stability, small size, light weight, compact structure, etc. Currently, the most commercially available WLEDs are produced by mixing InGaN blue chips with YAG: Ce3+A yellow phosphor, and blue light emitted from GaN excites YAG to obtain yellow lightThe YAG fluorescent powder which emits yellow light under the excitation of blue light or purple light is the most used fluorescent powder at present because the absorbed blue light and yellow light are compounded to obtain white light, but the YAG fluorescent powder which emits yellow light under the excitation of the blue light or the purple light is the most used fluorescent powder because of the fact that the Ce is mixed with the YAG3+The red component in the emission spectrum is insufficient, so that the WLED color rendering index is low, the correlated color temperature is high, and the general requirements for illumination cannot be met. To achieve high performance high power WLEDs with high color rendering and adjustable color temperature, red phosphor is also needed to compensate for the red color. At present, the red phosphor is mainly a rare earth doped nitride phosphor, such as Ca (Sr, Ba)2Si5N8:Eu2+、CaAlSiN3:Eu2+And the like, but they are synthesized under severe conditions, resulting in high cost, and the occurrence of reabsorption results in low luminous efficiency. In addition, some phosphors are significantly out of the human eye's sensitivity range, making it difficult to increase the light emitting efficiency of a WLED. Therefore, new narrow red phosphors with excellent performance have been sought after for their luminescent properties under simple or mild synthesis conditions.
In recent years, Mn4+Doping with fluorine compounds, e.g. A2XF6:Mn4+(A ═ NH4, K, Na, Rb, Cs ═ Si, Ge, Sn, Ti, Zr) appeared as novel non-rare earth red phosphors, and compared to red nitride phosphors, series A2XF6:Mn4+The red fluorescent powder has the following advantages: first, they exhibit efficient narrow-band red emission, most of which is less than 650nm, which ensures better color purity and visual colorimetric parameters; secondly, they exhibit very high quantum efficiencies; thirdly, they have very good hot quenching performance and high thermal stability; finally, the synthesis conditions are relatively simple, which makes them cost effective. But the phosphor includes a halide and an alkaline earth element (e.g., Cl)-、F-、Na+、K+Etc.) are easily affected with moisture, so that the luminous performance of the fluorescent powder is reduced, although researchers propose to perform coating protection on the surface of the fluorescent powder or use a surface coating scheme to prevent the fluorescent powder from directly contacting with water, so as to improve the water resistance of the fluorescent powder, the method causes the fluorescent powder to have poor weather resistance and fast performance attenuation under high temperature or ultraviolet environment. It has also been shown by H2O2Or H2C2O4And passivation treatment is carried out to construct an inactivation layer as an isolation film, which can not solve the fundamental problem all the time, and the fluorescent powder is required to have the function of water resistance in some humid environments for illumination.
Disclosure of Invention
The invention aims to provide red fluorescent powder with waterproof performance.
Still another object of the present invention is to provide a method for preparing the above red phosphor with self-water-proofing property.
The invention is realized by the following technical scheme:
a red fluorescent powder with self-contained waterproof performance is characterized in that: the general formula of the red fluorescent powder with the waterproof performance is as follows: k2MxNyF6：zMn4+In which K is2MxNyF6As a matrix, MN in the matrix is any two combinations of Si, Ge and Ti ions, wherein x, y and z are M, N and Mn respectively4+Mole fraction of (1), 0<x<1、0<y<1, and x + y is 1, 0<z≦0.2。
More preferably, the general formula of the red fluorescent powder with self-waterproof performance is K2M0.3N0.7F6：0.1Mn4+。
K above2MxNyF6The matrix is not reported in the prior art literature. The inventors have developed the above-mentioned host in their research and doped Mn4+The red phosphor K obtained2MxNyF6：zMn4+The fluorescent powder has the characteristics of high luminous efficiency, good color development effect and the like, has very good waterproof effect and high waterproof stability, and can be used in a humid environment for a long time.
Further, a red fluorescent powder with waterproof performance is characterized in that: the fluorescent powder is represented by K2MxNyF6As a substrate, and KMnO4Mixing and reacting with HF solution to obtain the final product; said K2MxNyF6The matrix is composed of soluble potassium salt and H2AF6Prepared by reacting according to the molar ratio of 1: 2-15, wherein H is2AF6The solution is H2SiF6、H2GeF6、H2TiF6The soluble potassium salt can be KCl or K2CO3、KNO3Or one of KOH.
Furthermore, the fluorescent powder is prepared by K at normal temperature and normal pressure2MxNyF6As a substrate, with KMnO4After mixing with HF solution according to K2MxNyF6：KMnO4: reacting for 10-20 h with HF (1: 0.1-0.5: 1-300) in a molar ratio, vacuum filtering, washing with absolute ethyl alcohol, and vacuum drying for 8-10 h by using a vacuum drying oven at 80 ℃ to obtain K2MxNyF6:zMn4+And (3) fluorescent powder.
A preparation method of red fluorescent powder with self-contained waterproof performance is characterized in that: the fluorescent powder is prepared from soluble potassium salt and H at normal temperature and pressure2AF6Reacting according to the molar ratio of 1: 2-15 to prepare K2MxNyF6In which H is2AF6Is H2SiF6、H2GeF6、H2TiF6Any two mixed solutions in the solution; at normal temperature and pressure, and K2MxNyF6As a substrate, with KMnO4After mixing with HF solution according to K2MxNyF6： KMnO4: reacting for 10-20 h with HF (1: 0.1-0.5: 1-300) in a molar ratio, performing vacuum filtration, washing with absolute ethyl alcohol for 1-3 times, and performing vacuum drying for 8-10 h with a vacuum drying oven at 80 ℃ to obtain K2MxNyF6:zMn4+And (3) fluorescent powder.
More preferably, the above soluble potassium salt is reacted with H2AF6The molar ratio of (A) to (B) is 1: 2-10; k above2MxNyF6、 KMnO4And HF in a molar ratio of K2MxNyF6：KMnO4：HF＝1:0.1～0.2:50～150。
Further preferably, the above-mentioned H2AF6The mass percentage concentration of the solution is 30-50%, and the mass percentage concentration of the soluble sylvite solution is 10-40%; the mass percentage concentration of the HF aqueous solution is 30-40%.
If the control is not good in the preparation process of the waterproof fluorescent powder, the red fluorescent powder can not be obtained, the prepared red fluorescent powder is soaked in distilled water, the layer of the fluorescent powder on the surface which is firstly contacted with the water does not emit light at all, and although a part of the intermediate powder emits light, the light emitting effect is suddenly reduced until the fluorescent powder is completely blackened. The red fluorescent powder with remarkable waterproofness and good stability is successfully prepared by adopting the preparation method.
Meanwhile, in the research, the defect that the uniformity of the prepared fluorescent powder particles is poor due to poor control in the preparation process and the fluorescent powder prepared by the method has certain influence on the luminous effect of the fluorescent powder in water is found, and the technical problem is well solved by the fluorescent powder prepared by the method disclosed by the invention.
More particularly, the preparation method of the red fluorescent powder with the self-contained waterproof performance comprises the following steps:
(1) h with the mass percentage concentration of 30-50% is added under normal temperature and normal pressure2AF6Slowly dripping the solution into a soluble sylvite solution with the mass percentage concentration of 10-40%, regularly stirring in the same direction while dripping, and stirring at the rotating speed of 60-80 r/min to prepare K2MxNyF6The base solution of (1), wherein the soluble potassium salt is mixed with H2AF6The molar ratio of (A) to (B) is 1: 2-15;
(2) vacuum filtering with a vacuum pump, washing with distilled water to neutrality, drying in an oven at 90 deg.C for 8-10 hr to obtain K2MxNyF6A matrix powder;
(3) k prepared in the step (2)2MxNyF6Powder and KMnO4Mixing, addingReacting in 40 percent of HF aqueous solution by mass percentage, wherein K2MxNyF6、KMnO4The molar ratio of HF to HF is 1: 0.1-0.5: 1-300; the reaction time is 10-20 h at normal temperature and normal pressure, and a target product K is generated2MxNyF6:zMn4+A precipitate;
(4) performing suction filtration by using a vacuum pump filter, washing with absolute ethyl alcohol for 1-3 times, and performing vacuum drying for 8-10 hours by using a vacuum drying oven at 80 ℃ to obtain a target product K2MxNyF6:zMn4+And (3) fluorescent powder.
Further, H in the above step (1)2AF6After the solution is dripped into the soluble sylvite solution, the solution needs to be continuously stirred for 30-40 min.
The invention has the following beneficial effects:
the invention provides red fluorescent powder with self-contained waterproof performance and a preparation method thereof, and the method for preparing the red fluorescent powder is simple and efficient, does not need steps such as high-temperature calcination and the like, and can be prepared under the conditions of normal temperature and normal pressure; the red fluorescent powder is emitted in a narrow band, is uniform in particles, has the outstanding advantages of high luminous efficiency, good color development effect, good waterproof effect and the like, well solves the problem that the traditional red fluorescent powder is easy to damp and hydrolyze, has stable waterproof performance, can be kept stable and not attenuated for a long time in a wet environment, and can keep the final luminous intensity to be more than 80% of the original luminous intensity, so that the problem that the performance of the fluorescent powder is attenuated quickly in a waterproof means protected by a traditional coating is solved, a waterproof coating is not needed, the production cost is saved, and the red fluorescent powder is widely suitable for the wet environment.
Drawings
FIG. 1: the XRD spectrum of the red phosphor described in inventive example 1;
FIG. 2: excitation spectrum of the red phosphor described in inventive example 1;
FIG. 3: emission spectrum of the red phosphor described in example 1 of the present invention;
FIG. 4 is a schematic view of: excitation spectrum of the red phosphor described in inventive example 3;
FIG. 5: emission spectrum of the red phosphor described in inventive example 3;
FIG. 6: comparative graphs of luminescence intensity after immersion of the red phosphors described in inventive examples 1, 2 and 3.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the present disclosure.
Example 1
A preparation method of red fluorescent powder with self-contained waterproof performance comprises the following steps:
(1) taking H with the mass percentage concentration of 50 percent at normal temperature and normal pressure2TiF6And H2GeF6Mixed acid solution of composition wherein H2TiF6：H2GeF6The molar ratio of the mixed solution is 1:9, and the mixed solution is slowly dropped into KNO with the mass percentage concentration of 40 percent3In solution, KNO3The molar ratio of the mixed acid solution to the application amount of the mixed acid solution is 1:2, the mixed acid solution is stirred in the same direction in a circumferential rule while being dropwise added, the stirring is continued for 30min after the dropwise addition is finished, and the stirring speed is 80 r/min, so that the K-containing solution is prepared2Ge0.9Ti0.1F6The substrate solution of (1);
(2) filtering with circulating water type multi-purpose vacuum pump, washing with distilled water to neutrality, drying in oven at 90 deg.C for 10 hr to obtain K2Ge0.9Ti0.1F6A substrate;
(3) taking the K prepared in the step (2)2Ge0.9Ti0.1F6Powder and KMnO4After being uniformly mixed, adding an HF solution with the mass percentage concentration of 40%; reacting for 20 hours at normal temperature and normal pressure to generate a target product K2Ge0.9Ti0.1F6： 0.15Mn4+Wherein the molar ratio of each reactant is K2Ge0.9Ti0.1F6：KMnO4：HF＝1:0.15:150；
(4) Removing upper suspension, suction filtering with circulating water type multi-purpose vacuum pump, washing with anhydrous ethanol for 3 times, and drying at 80 deg.C for 10 hr to obtain target product K2Ge0.9Ti0.1F6：0.15Mn4+And (3) fluorescent powder.
K obtained in example 12Ge0.9Ti0.1F6：0.15Mn4+The waterproof red phosphor was immersed in distilled water, left standing for a while, and the emission of the red phosphor in water was observed and detected as shown in FIG. 6.
As shown in fig. 1, 2, 3 and 6: example 1K obtained by the Process according to the invention2Ge0.9Ti0.1F6：0.15Mn4+The excitation peak of the red fluorescent powder is located at 362.8nm and 462.8nm, the emission spectrum is narrow-band emission between 580-680 nm, 5 cross emission peaks of 590.4nm, 603.2nm, 616.0nm, 634.8nm and 650.6nm are provided, wherein 634.8nm is the strongest peak, and the half-peak width of the strongest peak is 10 nm. The fluorescent powder has slightly reduced luminous intensity in a short time along with the increase of the soaking time, tends to be stable after being reduced to a certain degree, still has good luminous effect, and the luminous performance is not attenuated any more.
Example 2
A preparation method of red fluorescent powder with self-contained waterproof performance comprises the following steps:
(1) taking H with the mass percentage concentration of 30 percent at normal temperature and normal pressure2TiF6And H2SiF6Mixed acid solution of composition in mole ratio of H2TiF6:H2SiF6Slowly dripping into 10% KCl solution with a molar ratio of 1:10, stirring in the same direction while dripping, and stirring at 60 r/min for 40min to obtain the final product containing K2Ti0.5Si0.5F6The substrate solution of (1);
(2) pumping and filtering with circulating water type multi-purpose vacuum pump, washing with distilled water to neutrality, and filtering with vacuum pumpDrying for 8h in a vacuum drying oven at 90 ℃ to obtain a matrix K2Ti0.5Si0.5F6；
(3) Taking the K prepared in the step (2)2Ti0.5Si0.5F6Powder and KMnO4After being mixed evenly, the mixture is added into HF mixed solution with the mass percentage concentration of 30 percent for reaction, and the molar ratio of each reactant is K2Ti0.5Si0.5F6： KMnO4: HF is 1:0.2:80, and after reaction for 20 hours at normal temperature and normal pressure, a target product K is generated2Ti0.5Si0.5F6:0.2Mn4+；
(4) Removing the upper suspension, vacuum filtering with circulating water type multi-purpose vacuum pump, washing with anhydrous ethanol for 1 time, and drying in 80 deg.C vacuum drying oven for 8 hr to obtain target product K2Ti0.5Si0.5F6:0.2Mn4+And (3) fluorescent powder.
K obtained in example2Ti0.5Si0.5F6:0.2Mn4+The waterproof red phosphor was immersed in distilled water, left standing for a while, and the emission of the red phosphor in water was observed and detected as shown in FIG. 6.
Example 2K obtained by the Process according to the invention2Ti0.5Si0.5F6:0.2Mn4+The red fluorescent powder has excitation peaks at 336.4.0nm and 469.2nm, an emission spectrum in a narrow band between 580-680 nm, and 5 cross emission peaks at 590.2nm, 605.6nm, 617.2nm, 636.2nm and 651.4nm, wherein 636.2nm is the strongest peak, and the half-peak width of the strongest peak is 10 nm. As shown in fig. 6, as the soaking time increases, the luminescent intensity of the phosphor slightly decreases in a short time, and becomes stable after decreasing to a certain extent, and the phosphor still has good luminescent effect, and the luminescent performance is not attenuated any more.
Example 3
A preparation method of red fluorescent powder with self-contained waterproof performance comprises the following steps:
(1) taking H with the mass percentage concentration of 40% at normal temperature and normal pressure2SiF6And H2GeF6Mixed solution of composition in mole ratio of H2GeF6:H2SiF6Slowly dropping KOH solution with the mass percentage concentration of 26%, wherein the molar ratio of the KOH to the mixed acid solution is 1:6, stirring the mixed acid solution in the same direction in a circumferential manner while dropping, continuing stirring for 35min after the dropping is finished, and stirring at the rotating speed of 70 revolutions per minute to obtain the K-containing solution2Si0.7Ge0.3F6The substrate solution of (1);
(2) pumping and filtering with circulating water type multi-purpose vacuum pump, washing with distilled water to neutrality, and drying in 90 deg.C vacuum drying oven for 9 hr to obtain matrix K2Si0.7Ge0.3F6；
(3) Taking the K prepared in the step (2)2Si0.7Ge0.3F6Powder and KMnO4After being uniformly mixed, the mixture is added into HF mixed solution with the mass percentage concentration of 36 percent for reaction, wherein the molar ratio of each reactant is K2Si0.7Ge0.3F6：KMnO4: HF is 1:0.1:50, and after reaction for 12 hours at normal temperature and normal pressure, a target product K is generated2Si0.7Ge0.3F6：0.1Mn4+；
(4) Removing upper suspension, vacuum filtering with circulating water type multi-purpose vacuum pump, cleaning with anhydrous ethanol for 3 times, and drying in 80 deg.C vacuum drying oven for 9 hr to obtain target product K2Si0.7Ge0.3F6：0.1Mn4+And (3) fluorescent powder.
K obtained in example 32Si0.7Ge0.3F6：0.1Mn4+The water-proof red phosphor is immersed in distilled water, left standing for a while, and the light emission of the red phosphor in water is observed and detected as shown in fig. 6.
As shown in fig. 4, 5 and 6: example 3K obtained by the Process according to the invention2Si0.7Ge0.3F6：0.1Mn4+Red phosphor with K as matrix2Si0.7Ge0.3F6Excitation peaks at 358.0nm and 460.0nm, emission spectrumNarrow-band emission is carried out between 580-680 nm, and 6 cross emission peaks of 590.4nm, 600.8nm, 615.2nm, 623.8nm, 633.6nm and 649.8nm are provided, wherein 633.6nm is the strongest peak, and the half-peak width of the strongest peak is 10 nm. The fluorescent powder has slightly reduced luminous intensity in the calculation time along with the increase of the soaking time, tends to be stable after being reduced to a certain degree, still has good luminous effect, and the luminous performance is not attenuated any more.
Through multiple tests and detections, the excitation peaks of the waterproof red fluorescent powder are 360nm +/-10 nm and 460nm +/-10 nm, and the emission spectrum of the waterproof red fluorescent powder emits in a narrow band between 580-680 nm: 5-6 crossed emission peaks exist;
when the value of 0< z > is less than or equal to 0.1, 6 emission peaks appear, wherein the peak positions are 590nm +/-2 nm, 602nm +/-2 nm, 616nm +/-2 nm, 625nm +/-2 nm, 635nm +/-2 nm and 650nm +/-2 nm respectively, the strongest peak is 635nm +/-2 nm, and the half-peak width of the strongest peak is 10nm +/-2 nm.
When the value of z is more than 0.1 and less than or equal to 0.2, 5 emission peaks appear, the peak positions are 590nm +/-2 nm, 603nm +/-3 nm, 616nm +/-2 nm, 635nm +/-2 nm and 650nm +/-2 nm respectively, wherein the strongest peak is 635nm +/-2 nm, and the half-peak width of the strongest peak is 10nm +/-2 nm.
Claims (3)
1. A red fluorescent powder with self-contained waterproof performance is characterized in that: the general formula of the red fluorescent powder with the waterproof performance is as follows: k2MxNyF6：zMn4+In which K is2MxNyF6As a matrix, MN in the matrix is any two combinations of Si, Ge and Ti ions, wherein x, y and z are M, N and Mn respectively4+Mole fraction of (1), 0<x<1、0<y<1, and x + y =1, 0<z ≦ 0.2; the fluorescent powder is represented by K2MxNyF6As a substrate, and KMnO4The catalyst is prepared by reacting with HF solution after mixing, and specifically comprises the following steps:
(1) h with the mass percentage concentration of 30-50% is added under normal temperature and normal pressure2AF6Slowly dripping the solution into a soluble sylvite solution with the mass percentage concentration of 10-40%, regularly stirring in the same direction while dripping, and stirring at the rotating speed of 60-80 r/min to prepare the potassium sylvite water dispersible granuleTo obtain K2MxNyF6The base solution of (1), wherein the soluble potassium salt is mixed with H2AF6The molar ratio of (A) to (B) is 1: 2-15;
(2) performing suction filtration by using a vacuum pump filter, washing the obtained product to be neutral by using distilled water, and drying the obtained product for 8-10 hours at 90 ℃ by using an oven to obtain the K2MxNyF6A matrix powder;
(3) k prepared in the step (2)2MxNyF6Powder and KMnO4After being mixed evenly, the mixture is added into HF aqueous solution with the mass percentage concentration of 40 percent for reaction, wherein K2MxNyF6、KMnO4The molar ratio of HF to HF is 1: 0.1-0.5: 1-300; the reaction time is 10-20 h at normal temperature and normal pressure, and a target product K is generated2MxNyF6:zMn4+A precipitate;
(4) performing suction filtration by using a vacuum pump filter, washing with absolute ethyl alcohol for 1-3 times, and performing vacuum drying for 8-10 hours by using a vacuum drying oven at 80 ℃ to obtain a target product K2MxNyF6:zMn4+Fluorescent powder;
wherein H2AF6The solution is H2SiF6、H2GeF6、H2TiF6Two mixed solutions in the solution, the soluble sylvite is KCl and K2CO3、KNO3Or KOH.
2. The method for preparing the red fluorescent powder with self-water-proofing property according to claim 1, which is characterized by comprising the following steps:
(1) h with the mass percentage concentration of 30-50% is added under normal temperature and normal pressure2AF6Slowly dripping the solution into a soluble sylvite solution with the mass percentage concentration of 10-40%, regularly stirring in the same direction while dripping, and stirring at the rotating speed of 60-80 r/min to prepare K2MxNyF6The base solution of (1), wherein the soluble potassium salt is mixed with H2AF6The molar ratio of (A) to (B) is 1: 2-15;
(2) performing suction filtration by using a vacuum pump filter, washing the obtained product to be neutral by using distilled water, and drying the obtained product for 8-10 hours at 90 ℃ by using an oven to obtain the K2MxNyF6A matrix powder;
(3) k prepared in the step (2)2MxNyF6Powder and KMnO4After being evenly mixed, the mixture is added into HF aqueous solution with the mass percentage concentration of 40 percent for reaction, wherein K2MxNyF6、KMnO4The molar ratio of HF to HF is 1: 0.1-0.5: 1-300; the reaction time is 10-20 h at normal temperature and normal pressure, and a target product K is generated2MxNyF6:zMn4+A precipitate;
(4) performing suction filtration by using a vacuum pump filter, washing with absolute ethyl alcohol for 1-3 times, and performing vacuum drying for 8-10 hours by using a vacuum drying oven at 80 ℃ to obtain a target product K2MxNyF6:zMn4+And (3) fluorescent powder.
3. The method according to claim 2, wherein the step (1) is H2AF6After the solution is dripped into the soluble sylvite solution, the solution is continuously stirred for 30-40 min.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013014715A (en) * | 2011-07-06 | 2013-01-24 | Nichia Corp | Fluoride phosphor and light-emitting device obtained using the fluoride phosphor |
| CN103003388A (en) * | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture-resistant phosphor and associated method |
| CN103980896A (en) * | 2014-04-29 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method of fluoride fluorescent powder material |
| CN105733575A (en) * | 2015-12-28 | 2016-07-06 | 温州大学 | Tetravalent manganese ion doped ammonium salt red light material and preparation method thereof |
| CN105980523A (en) * | 2014-01-30 | 2016-09-28 | 信越化学工业株式会社 | Method for producing and method for processing complex fluoride phosphor |
| CN106085428A (en) * | 2015-03-10 | 2016-11-09 | 重庆文理学院 | A kind of fluorescent material being applicable to LED illumination |
| JP2016210950A (en) * | 2015-04-28 | 2016-12-15 | 株式会社ネモト・ルミマテリアル | Fluoride phosphor and production method thereof, and semiconductor light-emitting device |
| CN106433626A (en) * | 2016-09-22 | 2017-02-22 | 陕西师范大学 | Method for preparing Mn(IV)-activated fluoride red fluorescent powder |
| CN106929015A (en) * | 2015-12-29 | 2017-07-07 | 有研稀土新材料股份有限公司 | Red fluorescence powder, its preparation method and the luminescent device comprising the red fluorescence powder |
| CN107236543A (en) * | 2017-06-15 | 2017-10-10 | 华南理工大学 | One kind improves Mn4+The method of doped fluoride red fluorescence powder material moisture resistance properties |
| WO2018215204A1 (en) * | 2017-05-23 | 2018-11-29 | Osram Opto Semiconductors Gmbh | Wavelength conversion element, light emitting device and method for producing a wavelength conversion element |
| CN109135739A (en) * | 2017-06-16 | 2019-01-04 | 隆达电子股份有限公司 | Manganese-doped red fluoride fluorescent powder, light-emitting device and backlight module |
-
2019
- 2019-06-28 CN CN201910571374.1A patent/CN110257065B/en active Active
Patent Citations (12)
| 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 |
| JP2013014715A (en) * | 2011-07-06 | 2013-01-24 | Nichia Corp | Fluoride phosphor and light-emitting device obtained using the fluoride phosphor |
| CN105980523A (en) * | 2014-01-30 | 2016-09-28 | 信越化学工业株式会社 | Method for producing and method for processing complex fluoride phosphor |
| CN103980896A (en) * | 2014-04-29 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method of fluoride fluorescent powder material |
| CN106085428A (en) * | 2015-03-10 | 2016-11-09 | 重庆文理学院 | A kind of fluorescent material being applicable to LED illumination |
| JP2016210950A (en) * | 2015-04-28 | 2016-12-15 | 株式会社ネモト・ルミマテリアル | Fluoride phosphor and production method thereof, and semiconductor light-emitting device |
| CN105733575A (en) * | 2015-12-28 | 2016-07-06 | 温州大学 | Tetravalent manganese ion doped ammonium salt red light material and preparation method thereof |
| CN106929015A (en) * | 2015-12-29 | 2017-07-07 | 有研稀土新材料股份有限公司 | Red fluorescence powder, its preparation method and the luminescent device comprising the red fluorescence powder |
| CN106433626A (en) * | 2016-09-22 | 2017-02-22 | 陕西师范大学 | Method for preparing Mn(IV)-activated fluoride red fluorescent powder |
| WO2018215204A1 (en) * | 2017-05-23 | 2018-11-29 | Osram Opto Semiconductors Gmbh | Wavelength conversion element, light emitting device and method for producing a wavelength conversion element |
| CN107236543A (en) * | 2017-06-15 | 2017-10-10 | 华南理工大学 | One kind improves Mn4+The method of doped fluoride red fluorescence powder material moisture resistance properties |
| CN109135739A (en) * | 2017-06-16 | 2019-01-04 | 隆达电子股份有限公司 | Manganese-doped red fluoride fluorescent powder, light-emitting device and backlight module |
Non-Patent Citations (3)
| Title |
|---|
| 20170621;陈文威;《厦门大学硕士学位论文》;20170621;第1-69页 * |
| Synthesis and photoluminescence properties of octahedral;JIN Yuming et al.,;《JOURNAL OF RARE EARTHS》;20161230;第34卷(第12期);第1173-1178页 * |
| 陈文威.20170621.《厦门大学硕士学位论文》.2017,第1-69页. * |
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