CN105295906A - LED red fluorescent powder, preparation method of composition containing LED red fluorescent powder and product and application - Google Patents
LED red fluorescent powder, preparation method of composition containing LED red fluorescent powder and product and application Download PDFInfo
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- CN105295906A CN105295906A CN201510885206.1A CN201510885206A CN105295906A CN 105295906 A CN105295906 A CN 105295906A CN 201510885206 A CN201510885206 A CN 201510885206A CN 105295906 A CN105295906 A CN 105295906A
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Abstract
The invention provides a preparation method of LED red fluorescent powder. The fluorescent powder is represented by a general formula I: A2M1-xF6:xMn4+ (I), wherein A is selected from one or two of K and Na; M is selected from one or two of Si and Ti; x is 0.02-0.3; and the preparation method comprises the following steps: (1) dissolving A2MnF6 into hydrofluoric acid to obtain a solution containing Mn; and (2) adding A2MF6 to the solution containing the Mn obtained in the step (1), adding a dispersing agent, fully heating, stirring, cooling, aging and filtering the dispersing agent to obtain a solid, sequentially washing the solid with a little of pure water and an organic solvent, and drying the solid to obtain the LED red fluorescent powder. The invention further provides a preparation method of the composition containing the fluorescent powder, the LED red fluorescent powder or the composition containing the LED red fluorescent powder prepared by the method, and an application of the fluorescent powder or the composition containing the fluorescent powder in LED backlight elements or equipment.
Description
Technical field
The present invention relates to a kind of preparation method of fluorescent material, be specifically related to a kind of preparation method of LED red fluorescence powder, the preparation method of the composition containing this LED red fluorescence powder, the LED red fluorescence powder using above-mentioned preparation method to obtain or containing the composition of this LED red fluorescence powder, and this LED red fluorescence powder or containing its purposes of composition in LED-backlit element or equipment.
Background technology
Photodiode (Light-EmittingDiode, referred to as LED) is a kind of is the semiconductor electronic component of luminous energy by electric energy conversion.This electronic component occurred as far back as 1962, can only send the ruddiness of low luminosity in early days, develop other monochromatic versions afterwards, the light that can send even to this day is throughout visible ray, infrared rays and ultraviolet, range is also thus lifted to higher level, is called as " forth generation light source ".There is due to it advantages such as energy-saving and environmental protection, safety, life-span length, be now widely used in all respects in industry and life, comprised the fields such as instruction, display, decoration, backlight, general lighting.
For application more widely white LED lamp, the method realizing white light LEDs at present mainly contains three kinds: (1) applies yellow fluorescent powder on blue chip, mainly YAG:Ce, utilizes blue light to become white light with yellow light mix; (2) encapsulated by the chip portfolio of red, green, blue three kinds of colors, the luminescence of chip institute is directly mixed into white light; (3) fluorescent material of red, green, blue three kinds of colors is excited to be mixed into white light with near-ultraviolet light chip.In these three kinds of methods, 1st kind of method is current maturation the most is also the method for main flow, but the product colour rendering index of the method is on the low side, general about 70, colour temperature is higher, general at more than 5500K, require to there is certain deviation with the optimum visual of human eye, therefore need to mix a certain amount of red fluorescence powder.And other two kinds of methods also need to use red fluorescence powder, to send required ruddiness.In addition, in the LED light source or device of other kinds many, also red fluorescence powder can be used.Therefore, there is the larger market requirement for red fluorescence powder in LED industry.
The comparatively ripe red fluorescence powder of better performances, application is in the market mainly rear-earth-doped nitride or nitric oxide fluorescent powder.But this fluorescent material needs rear-earth-doped, and ingredient requirement is comparatively special, usually needs High Temperature High Pressure to prepare, preparation condition is harsh.Not only energy consumption is high, and yield rate is also on the low side, and thus its production cost is high, price is very expensive.Therefore, develop the red fluorescence powder of new component, and the synthetic method improving present stage red fluorescence powder receives the extensive concern of people.
Summary of the invention
Therefore, the object of the invention is to improve in prior art the weak point of producing red fluorescence powder, provide a kind of method preparing LED red fluorescence powder in short period at normal temperatures, its technique simply, not needs the severe condition such as High Temperature High Pressure, be applicable to suitability for industrialized production, and obtained LED red fluorescence powder colour gamut is wide, functional, has a extensive future.Present invention also offers the preparation method of the composition containing this LED red fluorescence powder, the LED red fluorescence powder using above-mentioned preparation method to obtain or containing the composition of this LED red fluorescence powder, and this LED red fluorescence powder or containing its purposes of composition in LED-backlit element or equipment.
For achieving the above object, the invention provides a kind of preparation method of LED red fluorescence powder, described LED red fluorescence powder is represented by general formula I:
A
2M
1-xF
6:xMn
4+(I)
Wherein, A be selected from K and Na one or both, M be selected from Si and Ti one or both, x=0.02 ~ 0.3, preferably, x=0.02 ~ 0.15 can be such as 0.02 ~ 0.07;
Described preparation method comprises the following steps:
(1) by A
2mnF
6be dissolved in hydrofluoric acid, obtain containing Mn solution;
(2) by A
2mF
6join that step (1) obtains containing in Mn solution, add appropriate dispersion agent, ageing of lowering the temperature after abundant heated and stirred, filter and obtain solid, then use solid described in a small amount of pure water and organic solvent washing successively, dry, obtain described LED red fluorescence powder;
Wherein, the A in step (1)
2mnF
6with the A in step (2)
2mF
6between mol ratio be 0.02 ~ 0.3:1, be preferably 0.02 ~ 0.15:1, such as 0.02 ~ 0.07:1; The concentration of the hydrofluoric acid in step (1) is 60 ~ 80wt%, is preferably 75 ~ 80wt%, is more preferably 80wt%.The present inventor finds, as embodiment 1 ~ 4 hereafter show, when other conditions are constant, the optical efficiency of fluorescent material obtained when hydrofluoric acid concentration is 80wt% is the highest.
Preparation in accordance with the present invention, wherein, in step (1), described A
2mnF
6be 1:10 ~ 100 with the mass ratio of hydrofluoric acid.
Preparation in accordance with the present invention, wherein, in step (2), described dispersion agent can be the polymeric dispersant of steric hindrance type, as PVP, polyvinyl alcohol and polyoxyethylene glycol etc., or long-chain dispersion agent, as one or more in oleic acid, Sodium dodecylbenzene sulfonate etc., but be not limited to several dispersion agents of illustrating out; Preferably, described dispersion agent and A
2mF
6mass ratio be 1:100 ~ 300, be preferably 1:200 ~ 250.The present inventor finds, the fluorescent powder grain not adding dispersion agent (such as PVP-K30) during preparation is uneven, and particle is many, and package brightness is on the low side.
Preparation in accordance with the present invention, wherein, in step (2), described stirring is at 1 ~ 80 DEG C, and at being preferably 10 ~ 80 DEG C, more preferably carry out at 60 DEG C, the time of stirring is 5 ~ 60min, is preferably 20 ~ 60min.Preferably, described ageing is at 1 ~ 80 DEG C, preferably carries out at 5 DEG C, and the time of ageing is 5 ~ 300min, is preferably 60 ~ 90min.
Preparation in accordance with the present invention, wherein, in step (2), described organic solvent be selected from ethanol, Virahol and acetone one or more.Preferably, the temperature of described oven dry is 50 ~ 150 DEG C, is preferably 80 ~ 100 DEG C.
Preparation in accordance with the present invention, wherein, the A in step (1)
2mnF
6prepare according to step (1a):
(1a) by AMnO
4be dissolved in hydrofluoric acid with KF, dropwise add hydrogen peroxide, after reaction, suction filtration, washing, oven dry, obtain A
2mnF
6.Wherein, can with an organic solvent wash, these organic solvents can be one or more in alcoholic solvent, ketones solvent and ether solvent, are preferably ethanol, Virahol, acetone etc.Oven dry at 50 ~ 100 DEG C, can be preferably 60 ~ 80 DEG C, such as, carries out at 70 DEG C.
Preparation in accordance with the present invention, wherein, in step (1a), AMnO
4and the mass ratio between hydrofluoric acid is 1:10 ~ 15, preferably, the concentration of described hydrofluoric acid is 35 ~ 45wt%, is preferably 38wt%.
Preparation in accordance with the present invention, wherein, in step (1a), the concentration of described hydrogen peroxide is 20 ~ 40wt%, is preferably 30wt%; Preferably, described AMnO
4be 1:1 ~ 2.5 with the mass ratio of hydrogen peroxide, be preferably 1:1.2 ~ 1.5.
Present invention also offers a kind of preparation method of the composition containing fluorescent material, described composition comprises the LED red fluorescence powder using above-mentioned preparation method of the present invention to obtain; Described preparation method comprises: use aforesaid method of the present invention to prepare LED red fluorescence powder, and is mixed mutually with solid or liquid medium by described LED red fluorescence powder.
Solid in the present invention or liquid medium, only otherwise realizing the performance damaging this fluorescent material within the scope of object, be not particularly limited.Such as curable material can be used.Curable material is a kind of flow-like (such as liquid or gel state) material, and it solidifies because of certain solidification treatment.Curable material only can use one, can use two or more with arbitrary combination and ratio.This curable material can also provide extra effect, such as, the light that luminous element (as excitaton source) sends is guided to fluorescent material.This curable material can be inorganic based material, such as metal alkoxide, by the solution of sol-gel method by the solution hydrolytie polycondensation containing ceramic precursor polymkeric substance or metal alkoxide, aforesaid combination solidification after inorganic based material (such as there is the inorganic based material of siloxane bond) etc.; Also can be organic system material, such as thermoplastic resin, thermosetting resin, light-cured resin, be specifically as follows the cellulose-based resin such as the styrene resins such as acrylic resin, polystyrene, styrene-acrylonitrile copolymer, polycarbonate resin, vibrin, phenoxy resin, butyral resin, polyvinyl alcohol, ethyl cellulose, rhodia, cellulose acetate butyrate, epoxy resin, phenol resins, the silicone resins etc. such as poly-(methyl) methyl acrylate.
Present invention also offers the LED red fluorescence powder using above-mentioned preparation method of the present invention to obtain or the composition containing fluorescent material, described LED red fluorescence powder has emission peak in the wavelength region of 610 ~ 650nm, preferably has emission peak at 636nm place.
Present invention also offers the LED red fluorescence powder using above-mentioned preparation method of the present invention to obtain, the composition containing fluorescent material using above-mentioned preparation method of the present invention to obtain or LED red fluorescence powder provided by the invention or the purposes of composition in LED-backlit element or device containing fluorescent material provided by the invention.
Technical scheme provided by the invention can synthesize LED red fluorescence powder at relatively low temperatures efficiently, and technique is simple, and preparation condition is gentle, easy and simple to handle, requires lower to production unit.Use Mn
4+excite and instead of rare earth ion and excite, starting material are cheap and easy to get, and compared with conventional LED Nitride phosphor, its production cost significantly reduces, and economical effectiveness is higher.The good dispersity of prepared LED red fluorescence powder, launch that peak shape is sharp-pointed, colour gamut is wide, purity of color is high, can be used for LED-backlit field.In addition, its physicochemical property are stablized, and are easy to long-term preservation.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 shows X-ray diffractogram and the standard card of the obtained LED red fluorescence powder of embodiment 1.
Fig. 2 shows SEM (scanning electronic microscope) picture of the obtained LED red fluorescence powder of embodiment 1.
Fig. 3 shows the spectrogram of the obtained LED red fluorescence powder of embodiment 1.Wherein, excitation wavelength 460nm, emission wavelength 636nm.The emission peak of 636nm is Mn
4+'s
2e
g→
4a
2conversion, proves Mn
4+successfully adulterate.
Fig. 4 shows the SEM picture of the obtained LED red fluorescence powder of comparative example 1.
Fig. 5 shows the SEM picture of the obtained LED red fluorescence powder of comparative example 2.
Fig. 6 shows X-ray diffractogram and the standard card of the obtained LED red fluorescence powder of embodiment 9.
Fig. 7 shows the SEM picture of the obtained LED red fluorescence powder of embodiment 9.
Fig. 8 shows the spectrogram of the obtained LED red fluorescence powder of embodiment 9.
Embodiment
Further illustrate the present invention below by specific embodiment, but should be understood to, these embodiments are only used for the use specifically described more in detail, and should not be construed as limiting the present invention in any form.
General description is carried out to the material used in the present invention's test and test method in this part.Although for realizing many materials that the object of the invention uses and working method is well known in the art, the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and working method are well known in the art.
A used in the present invention
2mnF
6the method preparation can recorded according to prior art document, also can prepare according to method provided by the invention.
Such as, can according to NewExperimentalChemistrySeries#8, " SynthesisofInorganicCompoundIII ", MaruzenCo., the 1166th page, the step recorded in 1977 prepares K
2mnF
6: the central dividing plate of the reaction vessel fluoro-resin ion-exchange membrane of vinyl chloride resin is divided into two chambers.In two chambers separated by ion-exchange membrane, platinum plate is installed as anode and negative electrode.The hydrofluoric acid aqueous solution being wherein dissolved with manganese (II) fluorochemical is delivered in the chamber of anode side, and hydrofluoric acid aqueous solution is delivered in cathode side chamber.Power supply is connected to electrode to carry out electrolysis under the voltage of 3V and the electric current of 0.75A.At the end of electrolysis, the hydrofluoric acid aqueous solution containing saturated level Potassium monofluoride is joined in the reaction soln of anode side chamber with excessive, forms yellow solid product thus, to be filtered and as K
2mnF
6reclaim.
embodiment 1
The present embodiment is for illustration of the preparation method of LED red fluorescence powder of the present invention, and the LED red fluorescence powder using the method obtained.
(1a) by 3.5gKMnO
4be dissolved in 50g38wt% hydrofluoric acid with 1.3gKF, dropwise add the hydrogen peroxide of 4.5g30wt%, suction filtration after reaction, use washing with alcohol, then dry at 70 DEG C, obtain the K of 5.2g
2mnF
6.
(1) 0.5g (~ 0.002mol) K is taken
2mnF
6be dissolved in the hydrofluoric acid of 50g60wt%, obtain containing Mn solution.
(2) by 22.3gK
2siF
6(~ 0.1mol) (purchased from KeYu fluorine chemical raw material company limited of Changshu City) joins above-mentioned containing in Mn solution, add 0.1 gram of PVP-K30,20min is stirred at 60 DEG C, then ageing 60min at being cooled to 5 DEG C, filtration obtains solid, then use solid described in a small amount of pure water and washing with alcohol successively, dry at 90 DEG C, obtain 14.5gK
2si
0.98f
6: 0.02Mn
4+powder.
Recorded the XRD figure (see Fig. 1) of this powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.
Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) record the SEM picture (see Fig. 2) of gained powder, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.
Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm (see Fig. 3), have obvious emission peak at 636nm place.The emission peak of 636nm is Mn
4+'s
2e
g→
4a
2conversion, proves Mn
4+successfully adulterate.
embodiment 2
The present embodiment is for illustration of the preparation method of LED red fluorescence powder of the present invention, and the LED red fluorescence powder using the method obtained.
The preparation method that the present embodiment adopts is identical with embodiment 1, and the concentration of the hydrofluoric acid that difference is in step (1) is 70wt%, obtains 14.5gK
2si
0.98f
6: 0.02Mn
4+powder.
Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 3
The present embodiment is for illustration of the preparation method of LED red fluorescence powder of the present invention, and the LED red fluorescence powder using the method obtained.
The preparation method that the present embodiment adopts is identical with embodiment 1, and the concentration of the hydrofluoric acid that difference is in step (1) is 75wt%, obtains 14.5gK
2si
0.98f
6: 0.02Mn
4+powder.
Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 4
The present embodiment is for illustration of the preparation method of LED red fluorescence powder of the present invention, and the LED red fluorescence powder using the method obtained.
The preparation method that the present embodiment adopts is identical with embodiment 1, and the concentration of the hydrofluoric acid that difference is in step (1) is 80wt%, obtains 14.6gK
2si
0.98f
6: 0.02Mn
4+powder.
Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 5
The preparation method that the present embodiment adopts is identical with embodiment 1, and difference is the K in step (2)
2siF
6consumption be 8.9g (~ 0.04mol), obtain 5.7gK
2si
0.95f
6: 0.05Mn
4+powder.Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 6
The preparation method that the present embodiment adopts is identical with embodiment 1, and difference is the K in step (2)
2siF
6consumption be 5.6g (~ 0.025mol), obtain 3.7gK
2si
0.92f
6: 0.08Mn
4+powder.
Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 7
The preparation method that the present embodiment adopts is identical with embodiment 1, and difference is the K in step (2)
2siF
6consumption be 4g (~ 0.018mol), obtain 2.6gK
2si
0.89f
6: 0.11Mn
4+powder.
Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 8
The preparation method that the present embodiment adopts is identical with embodiment 1, and difference is the K in step (2)
2siF
6consumption be 3.2g (~ 0.0145mol), obtain 2gK
2si
0.86f
6: 0.14Mn
4+powder.
Recorded the XRD figure of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2siF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) to record gained powder SEM picture, show that this powder is formed primarily of the cubic granules of the relatively uniform size with about 25 ~ 30 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak at 636nm place.
embodiment 9
The present embodiment is for illustration of the preparation method of LED red fluorescence powder of the present invention, and the LED red fluorescence powder using the method obtained.
The preparation method that the present embodiment adopts is identical with embodiment 1, and difference is that the doping matrix in step (2) is K
2tiF
6(purchased from Nantong Venus fluorine chemistry company limited), obtains 15gK
2ti
0.98f
6: 0.02Mn
4+powder.
Recorded the XRD figure (see Fig. 6) of gained powder by x-ray powder diffraction instrument (model D8-ADVANCE, purchased from German Brooker company), show that it has and K
2tiF
6corresponding crystalline structure.Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) record gained powder SEM picture (see Fig. 7), show that this powder is formed primarily of the platy shaped particle of the relatively uniform size with about 30 ~ 40 μm.Use fluorescence spectrophotometer (model USB4000, purchased from American Ocean Optics) to record the emission wavelength of above-mentioned powder under the excitation wavelength of 460nm, have obvious emission peak (see Fig. 8) at 634nm place.
comparative example 1
This comparative example is used for contrasting with the preparation method of embodiment and products obtained therefrom.
The preparation method that this comparative example adopts is identical with embodiment 1, and the concentration of the hydrofluoric acid that difference is in step (1) is 49wt%, obtains 14.8gK
2si
0.98f
6: 0.02Mn
4+powder.
Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) record gained powder SEM picture (see Fig. 4), show that this powder is by the uneven granulometric composition of 1 ~ 4 μm of size, and granule-morphology very irregular.
comparative example 2
This comparative example is used for contrasting with the preparation method of embodiment and products obtained therefrom.
The preparation method that this comparative example adopts is identical with embodiment 1, and difference is not add dispersion agent PVP-K30 in step (2), obtains 14.8gK
2si
0.98f
6: 0.02Mn
4+powder.
Use scanning electron microscope (model KYKY2800B, purchased from Beijing KYKY Technology Development Co., Ltd.) record gained powder SEM picture (see Fig. 5), show that this powder is by the uneven granulometric composition of 5 ~ 30 μm of sizes, and granule-morphology very irregular, chopped cooked entrails of sheep particle is more.
Contriver encapsulates the fluorescent material that above embodiment and comparative example obtain respectively, packaged type is: adopt this fluorescent material and the yellowish green powder hybrid package of oxynitride in blue chip, and adopt ultraviolet-visible-near-infrared spectrum analytical system instrument (model PMS-80, purchased from a distant place, Hangzhou Photoelectric Co., Ltd.) to measure respectively, result is as follows:
The colour temperature of fluorescent material prepared by table 1 embodiment and comparative example, tristimulus coordinates, optical efficiency and colour rendering index
| Sequence number | Colour temperature (K) | CIE-X | CIE-Y | Optical efficiency (lm/w) | Colour rendering index |
| Embodiment 1 | 17181 | 0.2546 | 0.2695 | 106 | 82 |
| Embodiment 2 | 17318 | 0.2539 | 0.2702 | 108 | 81 |
| Embodiment 3 | 17298 | 0.2542 | 0.2700 | 111 | 82 |
| Embodiment 4 | 17029 | 0.2545 | 0.2696 | 112 | 83 |
| Embodiment 5 | 17203 | 0.2543 | 0.2698 | 110 | 83 |
| Embodiment 6 | 17191 | 0.2547 | 0.2694 | 109 | 84 |
| Embodiment 7 | 17302 | 0.2538 | 0.2703 | 114 | 82 |
| Embodiment 8 | 17298 | 0.2540 | 0.2701 | 111 | 81 |
| Comparative example 1 | 17189 | 0.2546 | 0.2695 | 100 | 79 |
| Comparative example 2 | 17182 | 0.2544 | 0.2697 | 103 | 81 |
Above data show, the luminous efficiency of embodiment 1 ~ 8 is all better than comparative example 1 and 2, and wherein the performance of embodiment 4 and 7 is more outstanding.This shows, improve the luminescent properties that hydrofluoric acid concentration can significantly improve fluorescent material of the present invention.In addition, Mn
4+doping also has an impact to fluorescent material performance, due to concentration quenching effect, along with Mn
4+the increase of doping, its luminous efficiency first increases rear reduction.Do not add dispersion agent PVP-K30 in comparative example 2, the fluorescent powder grain of preparation is uneven, and particle is many, and package brightness is on the low side.
Although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.
Claims (10)
1. a preparation method for LED red fluorescence powder, is characterized in that, described LED red fluorescence powder is represented by general formula I:
A
2M
1-xF
6:xMn
4+(I)
Wherein, A be selected from K and Na one or both, M be selected from Si and Ti one or both, x=0.02 ~ 0.3, preferably, x=0.02 ~ 0.15;
Described preparation method comprises the following steps:
(1) by A
2mnF
6be dissolved in hydrofluoric acid, obtain containing Mn solution;
(2) by A
2mF
6join that step (1) obtains containing in Mn solution, add appropriate dispersion agent, ageing of lowering the temperature after abundant heated and stirred, filter and obtain solid, then use solid described in a small amount of pure water and organic solvent washing successively, dry, obtain described LED red fluorescence powder;
Wherein, the A in step (1)
2mnF
6with the A in step (2)
2mF
6between mol ratio be 0.02 ~ 0.3:1, be preferably 0.02 ~ 0.15:1; The concentration of the hydrofluoric acid in step (1) is 60 ~ 80wt%, is preferably 75 ~ 80wt%, is more preferably 80wt%.
2. preparation method according to claim 1, is characterized in that, in step (1), and described A
2mnF
6be 1:10 ~ 100 with the mass ratio of hydrofluoric acid.
3. preparation method according to claim 1, is characterized in that, in step (2), described dispersion agent is steric hindrance type polymeric dispersant and/or long-chain dispersion agent; Preferably, described steric hindrance type polymeric dispersant be selected from PVP, polyvinyl alcohol and polyoxyethylene glycol one or more, described long-chain dispersion agent be selected from oleic acid and Sodium dodecylbenzene sulfonate one or both; More preferably, described dispersion agent and A
2mF
6mass ratio be 1:100 ~ 300, be preferably 1:200 ~ 250;
Preferably, described stirring is at 1 ~ 80 DEG C, preferably at 10 ~ 80 DEG C, more preferably carries out at 60 DEG C, and the time of stirring is 5 ~ 60min, is preferably 20 ~ 60min; More preferably, described ageing is at 1 ~ 80 DEG C, preferably carries out at 5 DEG C, and the time of ageing is 5 ~ 300min, is preferably 60 ~ 90min.
4. preparation method according to claim 1, is characterized in that, in step (2), described organic solvent be selected from ethanol, Virahol and acetone one or more; Preferably, the temperature of described oven dry is 50 ~ 150 DEG C, is preferably 80 ~ 100 DEG C.
5. preparation method according to any one of claim 1 to 4, is characterized in that, the A in step (1)
2mnF
6prepare according to step (1a):
(1a) by AMnO
4be dissolved in hydrofluoric acid, dropwise add hydrogen peroxide, after reaction, suction filtration, washing, oven dry, obtain A
2mnF
6;
Preferably, with an organic solvent wash; More preferably, described organic solvent is one or more in alcoholic solvent, ketones solvent and ether solvent, one or more more preferably in ethanol, Virahol and acetone;
More preferably, described oven dry, at 50 ~ 100 DEG C, is preferably carried out at 60 ~ 80 DEG C.
6. preparation method according to claim 5, is characterized in that, in step (1a), and AMnO
4and the mass ratio between hydrofluoric acid is 1:10 ~ 15, preferably, the concentration of described hydrofluoric acid is 35 ~ 45wt%, is preferably 38wt%.
7. preparation method according to claim 5, is characterized in that, in step (1a), the concentration of described hydrogen peroxide is 20 ~ 40wt%, is preferably 30wt%; Preferably, described AMnO
4be 1:1 ~ 2.5 with the mass ratio of hydrogen peroxide, be preferably 1:1.2 ~ 1.5.
8. containing a preparation method for the composition of fluorescent material, it is characterized in that, described composition comprises the LED red fluorescence powder using the preparation method according to any one of claim 1 to 7 to obtain; Described preparation method comprises: use the method according to any one of claim 1 to 7 to prepare LED red fluorescence powder, and mixed mutually with solid or liquid medium by described LED red fluorescence powder.
9. the LED red fluorescence powder using the preparation method according to any one of claim 1 to 7 to obtain or the composition containing fluorescent material using the preparation method described in claim 8 to obtain, it is characterized in that, described LED red fluorescence powder has emission peak in the wavelength region of 610 ~ 650nm, preferably has emission peak at 636nm place.
10. the LED red fluorescence powder using the preparation method according to any one of claim 1 to 7 to obtain, the composition containing fluorescent material using the preparation method described in claim 8 to obtain, LED red fluorescence powder according to claim 9 or the purposes of composition in LED-backlit element or equipment containing fluorescent material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353899A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application |
| CN107541206A (en) * | 2017-02-28 | 2018-01-05 | 江苏罗化新材料有限公司 | It is fluorinated matter fluorescent powder and preparation method thereof |
| CN107964401A (en) * | 2016-10-19 | 2018-04-27 | 隆达电子股份有限公司 | Fluoride fluorescent powder containing flaky crystal and preparation method and application thereof |
| CN111003726A (en) * | 2019-12-17 | 2020-04-14 | 云南民族大学 | Oxyfluoride structural material with uniform appearance and preparation method thereof |
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2015
- 2015-12-03 CN CN201510885206.1A patent/CN105295906B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107964401A (en) * | 2016-10-19 | 2018-04-27 | 隆达电子股份有限公司 | Fluoride fluorescent powder containing flaky crystal and preparation method and application thereof |
| CN107541206A (en) * | 2017-02-28 | 2018-01-05 | 江苏罗化新材料有限公司 | It is fluorinated matter fluorescent powder and preparation method thereof |
| CN107353899A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application |
| CN111003726A (en) * | 2019-12-17 | 2020-04-14 | 云南民族大学 | Oxyfluoride structural material with uniform appearance and preparation method thereof |
| CN111003726B (en) * | 2019-12-17 | 2024-01-09 | 云南民族大学 | Oxyfluoride structural material with uniform morphology and preparation method thereof |
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