CN105623656B - Red fluorescence powder, the preparation method of red fluorescence powder and light-emitting device - Google Patents
Red fluorescence powder, the preparation method of red fluorescence powder and light-emitting device Download PDFInfo
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Abstract
The invention discloses a kind of red fluorescence powder, the preparation method of red fluorescence powder and light-emitting device.The component of the red fluorescence powder is A(2‑x)Dx[X(1‑x‑y)AlxF6]：yMn4+, wherein, A is selected from Li+、Na+And K+Any of or it is a variety of, D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+And Ti4+Any of or a variety of, and 0.001≤x≤0.5,0.001≤y≤0.3.The present invention is by using Al3+Part X is replaced, and introduces D to reduce due to Al3+Lattice dilatation caused by replacing X simultaneously balances Al3+The valence state of system after replacement X, so as to influence centre of luminescence Mn4+The crystalline field of ion, and then the Photochromic Properties of red fluorescence powder can be adjusted, and improve the Photochromic Properties of red fluorescence powder.
Description
Technical field
The present invention relates to technical field of semiconductors, in particular to the preparation of a kind of red fluorescence powder, red fluorescence powder
Method and light-emitting device.
Background technology
In recent years, liquid crystal display (LCD) technology is developed rapidly, and it is in mobile phone, notebook computer, HDTV field
It is widely applied.Because liquid crystal material does not light in itself, therefore backlight is just indispensable as liquid crystal display device
Key element.At present, LCD backlight mainly has cold-cathode lamp (CCFL) and white light-emitting diodes (LED) two ways.It is and white
Light LED has numerous advantages such as color reducibility good, low in energy consumption, long-life, therefore it is in the city in LCD backlight source field
Market share increases rapidly.
White LED device mainly has a two types, it is a kind of be by glow red light emitting diodes, the green of green light
The blue LED of light emitting diode and blue light-emitting combines, and forms white light by feux rouges, green glow and blue light；Separately
One kind is combined by the light emitting diode and luminescent coating of blue light-emitting (460-480nm), and is sent by light emitting diode
Blue light excited fluophor layer after produce white light.In the white light LEDs of the first type, red light emitting diodes, green emitting
Diode and blue LED need respective control circuit, therefore control circuit can be caused more complicated, and manufacturing cost
Also it is higher., can be only with a kind of light emitting diode in the white light LEDs of second of type, therefore control circuit only needs one
Kind, so that manufacturing cost is minimized.Therefore, the white light LEDs of second of type turn into the main flow side of white LED device
Formula.
At present, the fluorescent material applied to white light LEDs mainly has aluminate, silicate, fluoride and nitride/nitrogen oxidation
Thing.Wherein, there is the aluminate YAG of garnet structure：Ce has that luminous efficiency is high, heat endurance is good and steady chemical structure etc.
Advantage, it is presently the most classical liquid crystal display yellow fluorescent powder.And green emitting phosphor is mainly based on silicate fluorescent powder,
Red fluorescence powder is based on fluoride and nitride/nitrogen oxides.What the white light LEDs being currently used on liquid crystal display device used
Most of the combining by blue chip and green emitting phosphor and red fluorescence powder of luminescent coating, wherein the green fluorescence used
Powder is (La, Ce, Tb) PO4、β-sialon-Eu2+, silicate etc., the red fluorescence powder used is MAlSiN3：Eu (M Ca,
It is one or more in Sr, Ba) etc..
Existing fluoride red fluorescence powder is mainly prepared using wet method, and its main flow technology of preparing includes etching method and raw material
Direct precipitation method.Wherein, etching method is developed by Japanese Qun Ma universities, and raw material direct precipitation method is developed by GE companies of the U.S.
.The component of prepared fluoride red fluorescence powder is Ax[MFy]：Mn4+, wherein A is selected from Li, Na, K, Rb, Cs and NR4In
One or more, one or more of the M in Si, Ge, Sn, Ti, Zr, Ga, In, Sc, Y, La, Nb, Ta and Bi, R be H or
Low alkyl, x are the absolute value of [MFy] valence state, and y is equal to 5,6 or 7.However, the component structure of existing fluoride red fluorescence powder is difficult
Effectively to adjust so that the Photochromic Properties of fluoride red fluorescence powder are poor.In view of the above-mentioned problems, there is presently no effective solution
Certainly method.
The content of the invention
The present invention is intended to provide the preparation method and light-emitting device of a kind of red fluorescence powder, red fluorescence powder, red to improve
The Photochromic Properties of color fluorescent material.
Therefore, the invention provides a kind of red fluorescence powder, the component of red fluorescence powder is A(2-x)Dx[X(1-x-y)AlxF6]：
yMn4+, wherein, A is selected from Li+、Na+And K+Any of or it is a variety of, D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or
A variety of, X is selected from Si4+、Ge4+And Ti4+Any of or a variety of, and 0.001≤x≤0.5,0.001≤y≤0.3.
Further, A K+, X Si4+。
Further, D is selected from Sr2+、Ca2+And Mg2+Any of.
Further, A K+, X Ge4+。
Further, D Ba2+。
Further, 0.03≤y≤0.2.
Further, 0.03≤x≤0.1.
Further, x/y≤1.
Meanwhile present invention also offers a kind of preparation method of red fluorescence powder, the preparation method to comprise the following steps：Press
A is weighed respectively according to stoichiometric proportion2MnF6、A2[XF6], salt containing D and salt containing Al, wherein, A is selected from Li+、Na+And K+In any
Kind is a variety of, and D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+And Ti4+Any of
It is or a variety of；By A2MnF6It is dissolved in the first HF solution to obtain the first solution, by A2[XF6] be dissolved in the 2nd HF solution to obtain
Second solution, D salt will be contained and be dissolved in the 3rd HF solution to obtain the 3rd solution, and will contain Al salt be dissolved in the 4th HF solution with
Obtain the 4th solution；By the first solution, the second solution, the 3rd solution and the 4th solution, dropwise reaction is molten to obtain mixing simultaneously
Liquid；Mixed solution is filtered to obtain sediment, the component of sediment is A(2-x)Dx[X(1-x-y)AlxF6]：yMn4+, wherein,
0.001≤x≤0.5,0.001≤y≤0.3, and sediment are red fluorescence powder.
Further, the concentration of the first HF solution, the 2nd HF solution, the 3rd HF solution and the 4th HF solution is identical and is
20wt%~60wt%.
Further, the concentration of the first HF solution, the 2nd HF solution, the 3rd HF solution and the 4th HF solution is identical and is
23wt%~25wt%.
Further, the temperature of dropwise reaction is -20 DEG C~100 DEG C, and the time of dropwise reaction is 10min~5h.
Further, the temperature of dropwise reaction is 50 DEG C~55 DEG C, and the time of dropwise reaction is 2h~2.5h.
Further, before the step of being filtered to mixed solution, preparation method also includes stirring mixed solution
The step of mixing and stirring standing.
Meanwhile present invention also offers a kind of light-emitting device, including blue LED and luminescent coating, luminescent coating
Including red fluorescence powder provided by the invention, wherein, red fluorescence powder is red fluorescence powder provided by the invention.
The present invention is by using Al3+Replace part X (X Si4+、Ge4+And Ti4+Any of or it is a variety of), and introduce
D (D Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of) with reduce due to Al3+Lattice dilatation caused by replacing X, and put down
Weigh Al3+The valence state of system after replacement X, so as to influence centre of luminescence Mn4+The crystalline field of ion, and then red fluorescence can be adjusted
The Photochromic Properties of powder, and improve the Photochromic Properties of red fluorescence powder.Further, used using red fluorescence powder provided by the invention
The display gamut range of light-emitting device is remarkably improved during the backlight for making light-emitting device.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the K in comparative example 12SiF6:Mn4+The SEM spectrum of fluorescent material；
Fig. 2 shows the K in embodiment 51.91Ba0.09(Ge0.81Al0.09)F6:0.1Mn4+The SEM spectrum of fluorescent material；
Fig. 3 shows the K in comparative example 12SiF6:Mn4+The XRD spectrum of fluorescent material；
Fig. 4 shows the K in comparative example 12SiF6:Mn4+The excitation spectrum and emission spectrum of fluorescent material；
Fig. 5 is the K of the embodiment of the present invention 51.91Ba0.09(Ge0.81Al0.09)F6:0.1Mn4+Fluorescent material XRD spectrum；And
Fig. 6 is the K of the embodiment of the present invention 51.91Ba0.09(Ge0.81Al0.09)F6:0.1Mn4+Phosphor emission spectrum.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.The present invention is described in detail below in conjunction with embodiment.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
From background technology, the component structure of existing fluoride red fluorescence powder is difficult to effectively adjust so that fluoride
The Photochromic Properties of red fluorescence powder are poor.The present inventor is studied regarding to the issue above, it is proposed that a kind of red glimmering
Light powder.The component of the red fluorescence powder is A(2-x)Dx[X(1-x-y)AlxF6]：yMn4+, wherein, A is selected from Li+、Na+And K+In any
Kind is a variety of, and D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+And Ti4+Any of
Or it is a variety of, and 0.001≤x≤0.5,0.001≤y≤0.3.
The present invention is by using Al3+Replace part X (X Si4+、Ge4+And Ti4+Any of or it is a variety of), and introduce
D (D Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of) with reduce due to Al3+Lattice dilatation caused by replacing X, and put down
Weigh Al3+The valence state of system after replacement X, so as to influence centre of luminescence Mn4+The crystalline field of ion, and then red fluorescence can be adjusted
The Photochromic Properties of powder, and improve the Photochromic Properties of red fluorescence powder.Further, used using red fluorescence powder provided by the invention
The display gamut range of light-emitting device is remarkably improved during the backlight for making light-emitting device.
In above-mentioned red fluorescence powder, in order to reduce Al3+(ionic radius r is) lattice dilatation caused by X is replaced,
Preferably, A K+, X Si4+(ionic radius r is) or Ge4+(ionic radius is).Meanwhile by introducing D, example
Such as Ca2+(ionic radius r is)、Sr2+(ionic radius r is)、Ba2+(ionic radius r is)、Mg2+(ion half
Footpath r is) to solve Al3+System valence state imbalance problem caused by replacing X.
According to above-mentioned Al3+Mn in red fluorescence powder M can accordingly be adjusted by replacing X amount4+Substitute X amount.Preferably, at this
Mn in red fluorescence powder4+Substitute X (X Si4+、Ge4+Or Ti4+) amount be 0.1%-30%.
In Al3+Replace Si4+Red fluorescence powder system in, in order to reduce replace after lattice dilatation (Al3+、Mn4+From
Sub- radius and Si4+Ionic radius difference it is larger) and realize the charge balance of system, prioritizing selection ionic radius is less than K+
(its ionic radius) Ca2+、Sr2+Or Mg2+.Centre of luminescence Mn can be influenceed by above-mentioned ionic compartmentation4+The crystalline substance of ion
Body field, so as to realize that the Photochromic Properties to red fluorescence powder are adjusted.Meanwhile inventor also demonstrate,proves by lot of experiments
It is real, when A is K+, X Si4+, D is selected from Sr2+、Ca2+And Mg2+Any of when, red fluorescence powder has more preferable photochromism
Energy.
In Al3+Replace Ge4+Red fluorescence powder system in, in order to as far as possible reduce replace after lattice dilatation (Al3+From
Sub- radius and Si4+Ionic radius differ larger, Mn4+Ionic radius and Si4+Ionic radius it is suitable) and realize system
Charge balance, prioritizing selection ionic radius and K+(ionic radius) suitable Ba2+ By it is above-mentioned from
Son substitution can influence centre of luminescence Mn4+The crystalline field of ion, so as to realize that the Photochromic Properties to red fluorescence powder are adjusted.Together
When replacement of the aluminium element to Ge element can reduce cost.Moreover, inventor also confirms that by lot of experiments, when A is K+, X
For Ge4+, D Ba2+When, red fluorescence powder has more preferable Photochromic Properties.
In order to further improve the Photochromic Properties of red fluorescence powder, it is preferable that 0.03≤y≤0.2；It is further preferable that
0.03≤x≤0.1.Meanwhile in a preferred embodiment, x/y≤1, now the crystal structure of red fluorescence powder is more steady
It is fixed, and the red-emitting phosphors have more preferable Photochromic Properties.
Meanwhile present invention also offers a kind of preparation method of red fluorescence powder, the preparation method to comprise the following steps：Press
A is weighed respectively according to stoichiometric proportion2MnF6、A2[XF6], salt containing D and salt containing Al, wherein, A is selected from Li+、Na+And K+In any
Kind is a variety of, and D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+And Ti4+Any of
It is or a variety of；By A2MnF6It is dissolved in the first HF solution to obtain the first solution, by A2[XF6] be dissolved in the 2nd HF solution to obtain
Second solution, D salt will be contained and be dissolved in the 3rd HF solution to obtain the 3rd solution, and will contain Al salt be dissolved in the 4th HF solution with
Obtain the 4th solution；By the first solution, the second solution, the 3rd solution and the 4th solution, dropwise reaction is molten to obtain mixing simultaneously
Liquid；Mixed solution is filtered to obtain sediment, the component of sediment is A(2-x)Dx[X(1-x-y)AlxF6]：yMn4+, wherein,
0.001≤x≤0.5,0.001≤y≤0.3, and sediment are red fluorescence powder.
In above-mentioned preparation method, red fluorescence powder is formed by using Al3+Replace part X, and introduce D with reduce by
In Al3+Lattice dilatation caused by replacing X, and balance Al3+The valence state of system after replacement X, so as to influence centre of luminescence Mn4+Ion
Crystalline field, and then the Photochromic Properties of red fluorescence powder can be adjusted, and improve the Photochromic Properties of red fluorescence powder.
The exemplary embodiment party of the preparation method according to red fluorescence powder provided by the invention is described in more detail below
Formula.However, these illustrative embodiments can be implemented by many different forms, and should not be construed to be limited solely to
Embodiments set forth herein.It should be appreciated that these embodiments are provided so that disclosure herein is thorough
And it is complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
First, A is weighed respectively according to stoichiometric proportion2MnF6、A2[XF6], salt containing D and salt containing Al, wherein, A is selected from Li+、
Na+And K+Any of or it is a variety of, D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+With
Ti4+Any of or it is a variety of.Wherein, it is so-called to refer to according to stoichiometric proportion according in the red fluorescence powder being finally prepared
The content ratio of each element.Salt containing D can be chlorate or nitrate containing D etc., and salt containing Al can be containing Al3+Chlorate or
Nitrate etc..
Then, by A2MnF6It is dissolved in the first HF solution to obtain the first solution, by A2[XF6] be dissolved in the 2nd HF solution
To obtain the second solution, D salt will be contained and be dissolved in the 3rd HF solution to obtain the 3rd solution, and Al salt will contained to be dissolved in the 4th HF molten
To obtain the 4th solution in liquid.Wherein, the concentration of the first HF solution, the 2nd HF solution, the 3rd HF solution and the 4th HF solution can
To be set according to the actual requirements.Preferably, the first HF solution, the 2nd HF solution, the 3rd HF solution and the 4th HF solution
Concentration is all identical and is 20wt%~60wt%.Can have prepared red-emitting phosphors from the HF solution of above-mentioned concentration
There is luminous intensity high effect.
Next, the first solution, the second solution, the 3rd solution and the 4th solution are stoichiometrically subjected to dropwise reaction
To obtain mixed solution.In this step, the temperature and time of dropwise reaction can be set according to actual process demand.It is excellent
Selection of land, the temperature of dropwise reaction is -20 DEG C~100 DEG C, and the time of dropwise reaction is 10min~5h.It is further preferable that it is added dropwise anti-
The temperature answered is 50 DEG C~55 DEG C, and the time of dropwise reaction is 2h~2.5h.
Finally, mixed solution is filtered to obtain sediment, the component of sediment is A(2-x)Dx[X(1-x-y)AlxF6]：
yMn4+, wherein, 0.001≤x≤0.5,0.001≤y≤0.3, and sediment is red fluorescence powder.Wherein, the mode of suction filtration
It can be vacuum filtration etc..Preferably, before the step of being filtered to mixed solution, preparation method also includes to mixed solution
The step of being stirred and standing.The specific process parameter of above-mentioned technique is referred to prior art progress, will not be repeated here.
So far, you can acquisition component is A(2-x)Dx[X(1-x-y)AlxF6]：yMn4+Red fluorescence powder, wherein, A is selected from Li+、
Na+And K+Any of or it is a variety of, D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+With
Ti4+Any of or a variety of, and 0.001≤x≤0.5,0.001≤y≤0.3.
Meanwhile present invention also offers a kind of light-emitting device, including blue LED and luminescent coating, luminescent coating
Including red fluorescence powder, wherein, red fluorescence powder is red fluorescence powder provided by the invention.In the light-emitting device, due to red
The Photochromic Properties of fluorescent material are improved so that the display gamut range of light-emitting device is significantly improved.
Further illustrate beneficial effects of the present invention below in conjunction with specific embodiments.
Luminous intensity and chromaticity coordinates in the following example and comparative example is quick in high precision using Hangzhou distant place HAAS-2000
Spectral radiometer detects to obtain；
SEM spectrum is to be collected using the SEM of HITACHI S-1510 models；
XRD spectrum carries out the powder x-ray diffraction of material phase analysis using X ' Pert PRO MPD to the fluorescent material of synthesis
Collect；
Excitation spectrum and emission spectrum use the highly sensitive integral type of the FluoroMax-4 models using Horiba companies glimmering
Photothermal spectroscopic analyzer collects；
The detection of gamut range and luminous flux detects in using for the photoelectric test system of the ZWL-600 models of company
Arrive.
Comparative example 1
The chemical formula of fluoride red fluorescence material is prepared by this comparative example：K2SiF6:Mn4+.Its preparation method is：Press
According to K2Si0.85F6:0.15Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2SiF6It is molten that 20wt%HF is dissolved in respectively Deng raw material
The hydrofluoric acid solution of fluorine potassium manganate and the hydrofluoric acid solution of potassium fluosilicate are obtained in liquid, by the hydrofluoric acid solution and fluorine of fluorine potassium manganate
The hydrofluoric acid solution of potassium silicate is added dropwise simultaneously at 20 DEG C, and mixed solution is added dropwise after 0.5h is stirred through standing, being filtered by vacuum, obtains
Obtain golden yellow precipitate, as red fluorescence powder.
Detected by SEM, XRD detections and emission spectrum detection, the SEM spectrum of above-mentioned red fluorescence powder, XRD spectrum with
And emission spectrum is shown as shown in Figure 1, Figure 3 and Figure 4 respectively, from figure 1 it appears that synthetic product granule-morphology shows corner angle point
Bright polyhedral structure, surface are very bright and clean.
From figure 3, it can be seen that the product prepared using the precipitation method has and K2SiF6Identical phase structure, its diffraction spectra
Figure (upper row) and K2SiF6PDF diffraction card (07-0217) control peak (lower arrange) unanimously, in the absence of any dephasign, and peak type point
It is sharp, it is higher to indicate wet chemistry method synthetic product purity.
Figure 4, it is seen that in the case where wavelength is 460nm exciting light, the fluorescence spectrum of the red fluorescence powder is shown
The characteristics of wide excitation spectrum and narrow emission spectrum, particularly 440-460nm blue regions have it is very strong excite, show this
Fluorescent material is especially suitable for being excited by blue-ray LED；Its emission spectrum has very strong narrow emission in 630nm or so red light region,
And without other non-red emissions, high color purity feux rouges can be launched by showing that the fluorescent material excites in blue light, available for high-quality liquid
Crystalline substance shows LED backlight.
Embodiment 1
According to K1.95Sr0.05(Si0.77Al0.05)F6:0.18Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2SiF6、
AlF3And SrF2It is dissolved in respectively in 35wt%HF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2SiF6、
AlF3And SrF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 80 DEG C, mixing is added dropwise
Solution, through standing, being filtered by vacuum, obtains golden yellow precipitate, as fluoride rouge and powder after 2h is stirred.
Embodiment 2
According to K1.96Ca0.04(Si0.91Al0.04)F6:0.05Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2SiF6、
AlF3And SrF2It is dissolved in respectively in 40wt%HF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2SiF6、
AlF3And SrF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 60 DEG C, mixing is added dropwise
Solution, through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence powder after 1.5h is stirred.
Embodiment 3
According to K1.98Ca0.02(Si0.85Al0.02)F6:0.03Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2SiF6、
AlF3And CaF2It is dissolved in respectively in 25%HF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2SiF6、AlF3
And CaF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 45 DEG C, it is molten that mixing is added dropwise
Liquid, through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence powder after 4h is stirred.
Embodiment 4
According to K1.9Sr0.1(Si0.7Al0.1)F6:0.2Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2SiF6、AlF3
And SrF2It is dissolved in respectively in 55%wtHF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2SiF6、AlF3With
SrF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 100 DEG C, mixed solution is added dropwise
Through standing, being filtered by vacuum after 5h is stirred, golden yellow precipitate, as red fluorescence powder are obtained.
Embodiment 5
According to K1.91Ba0.09(Ge0.81Al0.09)F6:0.1Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2GeF6、
AlF3And BaF2It is dissolved in respectively in 30wt%HF solution Deng raw material, obtains the hydrofluoric acid solution A and K of fluorine potassium manganate respectively2GeF6、
AlF3And SrF2Fluorspar acid solution B, both mixed solutions are proportionally uniformly added dropwise at 55 DEG C, mixed solution is added dropwise and passes through 1h
Through standing, being filtered by vacuum after stirring, golden yellow precipitate, as red fluorescence powder are obtained.
Embodiment 6
According to K1.97Ba0.03(Ge0.77Al0.03)F6:0.2Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2GeF6、
AlF3And BaF2It is dissolved in respectively in 35wt%HF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2GeF6、
AlF3And SrF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 55 DEG C, mixing is added dropwise
Solution, through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence powder after 2.5h is stirred.
Embodiment 7
According to Na1.999Ca0.001Si0.949Al0.001F6:0.05Mn4+Stoichiometric proportion weigh respectively fluorine sodium manganate,
Na2SiF6、AlF3And CaF2Be dissolved in respectively in 50wt%HF solution Deng raw material, respectively obtain fluorine potassium manganate hydrofluoric acid it is molten and
Na2SiF6、AlF3And CaF2Two kinds of mixed solutions of hydrofluoric acid solution, both mixed solutions are proportionally uniform at 70 DEG C
It is added dropwise, mixed solution is added dropwise after 3h is stirred through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence powder.
Embodiment 8
According to Na1.5Sr0.01Ti0.81Al0.01F6:0.18Mn4+Stoichiometric proportion weigh fluorine sodium manganate, Na respectively2TiF6、
AlF3And SrF2It is dissolved in respectively in 55%wtHF solution Deng raw material, obtains the hydrofluoric acid solution and Na of fluorine potassium manganate respectively2TiF6、
AlF3And SrF2Two kinds of mixed solutions of hydrofluoric acid solution, by both mixed solutions 100 DEG C proportionally uniformly be added dropwise, drop
Mixed solution is added, through standing, being filtered by vacuum, to obtain golden yellow precipitate, as red fluorescence powder after 4.5h is stirred.
Embodiment 9
According to K1.99Mg0.01Ti0.69Al0.01F6:0.3Mn4+Stoichiometric proportion weigh fluorine potassium manganate, K respectively2TiF6、
AlF3And MgF2It is dissolved in respectively in 40%wtHF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2TiF6、
AlF3And MgF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 30 DEG C, mixing is added dropwise
Solution, through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence powder after 5h is stirred.
Embodiment 10
According to Na1.5Mg0.5Ge0.42Al0.5F6:0.08Mn4+Stoichiometric proportion weigh fluorine sodium manganate, Na respectively2GeF6、
AlF3And MgF2It is dissolved in respectively in 45wt%HF solution Deng raw material, obtains the hydrofluoric acid solution and K of fluorine potassium manganate respectively2GeF6、
AlF3And MgF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniformly added dropwise at 85 DEG C, mixing is added dropwise
Solution, through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence powder after 5h is stirred.
Embodiment 11
According to Li1.9K0.09Mg0.01Ti0.79Al0.01F6:0.2Mn4+Stoichiometric proportion weigh respectively fluorine sodium manganate,
K2TiF6、Na2TiF6、AlF3And MgF2It is dissolved in respectively in 60wt%HF solution Deng raw material, obtains the hydrofluoric acid of fluorine sodium manganate respectively
Solution and Na2TiF6、Na2TiF6、AlF3And MgF2Two kinds of mixed solutions of fluorspar acid solution, by both mixed solutions 30 DEG C according to
Ratio uniform is added dropwise, and mixed solution is added dropwise after 5h is stirred through standing, being filtered by vacuum, obtains golden yellow precipitate, is red
Fluorescent material.
Embodiment 12
According to K1.9Sr0.05Ba0.05(Si0.72Al0.1)F6:0.18Mn4+Stoichiometric proportion weigh respectively fluorine potassium manganate,
K2SiF6、AlF3、BaF2And SrF2It is dissolved in respectively in 35wt%HF solution Deng raw material, obtains the hydrofluoric acid solution of fluorine potassium manganate respectively
And K2SiF6、AlF3、BaF2And MgF2Two kinds of mixed solutions of fluorspar acid solution, both mixed solutions are proportionally uniform at 80 DEG C
It is added dropwise, mixed solution is added dropwise after 10min is stirred through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence
Powder.
Embodiment 13
According to K1.9Sr0.1(Si0.64Ge0.08Al0.1)F6:0.18Mn4+Stoichiometric proportion weigh respectively fluorine potassium manganate,
K2SiF6、K2GeF6、AlF3And SrF2It is dissolved in respectively in 35wt%HF solution Deng raw material, the hydrofluoric acid for obtaining fluorine potassium manganate respectively is molten
Liquid and K2SiF6、K2GeF6、AlF3And SrF2Two kinds of mixed solutions of fluorspar acid solution, by both mixed solutions at 80 DEG C proportionally
Uniformly it is added dropwise, mixed solution is added dropwise after 2h is stirred through standing, being filtered by vacuum, obtains golden yellow precipitate, as red fluorescence
Powder.
The comparative example 1 of table 1 and embodiment 1-13 red fluorescence powders and its optics output performance data
| Chemical composition | Reaction temperature | Reaction time | HF concentration | Luminous intensity | |
| Comparative example 1 | K2Si0.85F6:0.15Mn4+ | 25℃ | 0.5h | 20wt% | 100 |
| Embodiment 1 | K1.95Sr0.05(Si0.77Al0.05)F6:0.18Mn4+ | 80℃ | 2h | 35wt% | 108 |
| Embodiment 2 | K1.96Ca0.04(Si0.91Al0.04)F6:0.05Mn4+ | 60℃ | 1.5h | 40wt% | 107 |
| Embodiment 3 | K1.98Ca0.02(Si0.85Al0.02)F6:0.03Mn4+ | 45℃ | 4h | 25wt% | 109 |
| Embodiment 4 | K1.9Sr0.1(Si0.7Al0.1)F6:0.2Mn4+ | 50℃ | 5h | 55wt% | 112 |
| Embodiment 5 | K1.91Ba0.09(Ge0.81Al0.09)F6:0.1Mn4+ | 55℃ | 1h | 30wt% | 108 |
| Embodiment 6 | K1.97Ba0.03(Ge0.77Al0.03)F6:0.2Mn4+ | 55℃ | 2.5h | 35wt% | 112 |
| Embodiment 7 | Na1.999Ca0.001Si0.949Al0.001F6:0.05Mn4+ | 70℃ | 3h | 50wt% | 104 |
| Embodiment 8 | Na1.5Sr0.01Ti0.81Al0.01F6:0.18Mn4+ | 100℃ | 4.5h | 55wt% | 105 |
| Embodiment 9 | K1.99Mg0.01Ti0.69Al0.01F6:0.001Mn4+ | -20℃ | 5h | 40wt% | 103 |
| Embodiment 10 | Na1.5Mg0.5Ge0.42Al0.5F6:0.08Mn4+ | 85℃ | 5h | 45wt% | 102 |
| Embodiment 11 | Li1.9K0.09Mg0.01Ti0.79Al0.01F6:0.2Mn4+ | 30℃ | 5h | 60wt% | 105 |
| Embodiment 12 | K1.9Sr0.05Ba0.05(Si0.72Al0.1)F6:0.18Mn4+ | 80℃ | 10min | 35wt% | 108 |
| Embodiment 13 | K1.9Sr0.1(Si0.64Ge0.08Al0.1)F6:0.18Mn4+ | 80℃ | 2h | 35wt% | 108 |
It can be seen from upper table 1 compared with comparative example 1, above-described embodiment 1-13 is by using Al3+Replace part Si4+、
Ge4+Or Ti4+, and introduce Ba2+、Sr2+、Ca2+And Mg2+Any of or a variety of reduce due to Al3+Replace X (X Si4 +、Ge4+Or Ti4+In one or more) caused by lattice dilatation, and balance Al3+The valence state of system after replacement X, so that institute
The luminous intensity of the red fluorescence powder of acquisition improves 2%~16%.
In addition, the red fluorescence powder that inventor is also obtained to the various embodiments described above carries out SEM and XRD detections and transmitting
Spectral detection, it is found that the red fluorescence powder prepared by above-described embodiment at least has diffraction maximum in the range of 10-90 °, and launch
Spectrum is high compared with the intensity of comparative example 1.
Wherein, Fig. 2 shows the SEM spectrum of the red fluorescence powder prepared by embodiment 5；Fig. 5 shows that embodiment 5 is made
The XRD spectrum of standby red fluorescence powder, from figure 5 it can be seen that the diffraction maximum collection of illustrative plates (upper row) of the product prepared by embodiment 5
With K2GeF6Standard PDF diffraction cards (24026-p3m1) diffraction maximum collection of illustrative plates (lower arrange) it is similar, show that synthetic product has
K2GeF6Pure phase structure.
Fig. 6 shows the emission spectrum of the red fluorescence powder prepared by embodiment 5, it can be seen that in 460nm excitation wavelengths
Under, the emission spectrum of the red fluorescence powder of embodiment 5 has the Mn that wire is launched4+Ion characteristic emission peak, peak wavelength are
628nm。
As can be seen here, according to the Al of the present invention3+Replace part X (X Si4+、Ge4+And Ti4+Any of or it is a variety of),
And introduce D (D Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of) with reduce due to Al3+Lattice caused by replacing X
Expansion, and balance Al3+Replace X after system valence state invention thought prepared by red fluorescence powder, by by above-mentioned composition it
Between ratio control in scope preferred for this invention, there is the high beneficial effect of luminous intensity.
Embodiment 14
The red fluorescence powder that the embodiment of the present invention 1 is obtained and β-SiAlON:Eu2+Green emitting phosphor presses 1:1 mass ratio is equal
Even to be distributed in organic silica gel, the mixture obtained after blended deaeration processing is coated in (launch wavelength on blue-ray LED
450nm), encapsulation is completed by 150 DEG C and 3 hours of drying.The blue light and the feux rouges of phosphor emission of blue-ray LED transmitting and green
Light is mixed to get white light LEDs, and tests its Photochromic Properties.
Embodiment 15
The fluoride rouge and powder that the embodiment of the present invention 3 is obtained and β-SiAlON:Eu2+Green powder presses 1:1 mass ratio is dispersed
Into organic silica gel, the mixture obtained after blended deaeration processing passes through coated in (launch wavelength 450nm) on blue-ray LED
Encapsulation is completed in 150 DEG C and 3 hours of drying.The blue light of blue-ray LED transmitting and the feux rouges and green glow of phosphor emission are mixed to get
White light LEDs, and test its Photochromic Properties.
Embodiment 16
The fluoride rouge and powder that the embodiment of the present invention 5 is obtained and β-SiAlON:Eu2+Green powder presses 1:1 mass ratio is dispersed
Into organic silica gel, the mixture obtained after blended deaeration processing passes through coated in (launch wavelength 450nm) on blue-ray LED
Encapsulation is completed in 150 DEG C and 3 hours of drying.The blue light of blue-ray LED transmitting and the feux rouges and green glow of phosphor emission are mixed to get
White light LEDs, and test its Photochromic Properties.
Comparative example 2
The red fluorescence powder that comparative example 1 of the present invention is obtained and β-SiAlON:Eu2+Green emitting phosphor presses 1:1 mass ratio is equal
Even to be distributed in organic silica gel, the mixture obtained after blended deaeration processing is coated in (launch wavelength on blue-ray LED
450nm), encapsulation is completed by 150 DEG C and 3 hours of drying.The blue light and the feux rouges of phosphor emission of blue-ray LED transmitting and green
Light is mixed to get white light LEDs, and tests its Photochromic Properties.
The component and its optics output performance data of the comparative example 2 of table 2 and embodiment 14-16 white light LEDs
As can be seen from the above embodiments, the above-mentioned example of the present invention realizes following technique effect：The present invention is by adopting
Use Al3+Replace part X (X Si4+、Ge4+And Ti4+Any of or it is a variety of), and introduce D (D Ba2+、Sr2+、Ca2+With
Mg2+Any of or it is a variety of) with reduce due to Al3+Lattice dilatation caused by replacing X, and balance Al3+System after replacement X
Valence state, so as to influence centre of luminescence Mn4+The crystalline field of ion, and then the Photochromic Properties of red fluorescence powder can be adjusted, and improve
The Photochromic Properties of red fluorescence powder.And from table 2 it can be seen that light-emitting device is used as using red fluorescence powder provided by the invention
Backlight when be remarkably improved the display gamut range of light-emitting device.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (12)
1. a kind of red fluorescence powder, it is characterised in that the component of the red fluorescence powder is A(2-x)Dx[X(1-x-y)AlxF6]：yMn4 +, wherein, A is selected from Li+、Na+And K+Any of or it is a variety of, D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is more
Kind, X is selected from Si4+、Ge4+And Ti4+Any of or a variety of, and 0.001≤x≤0.5,0.03≤y≤0.2, x/y≤1.
2. red fluorescence powder according to claim 1, it is characterised in that A K+, X Si4+。
3. red fluorescence powder according to claim 2, it is characterised in that D is selected from Sr2+、Ca2+And Mg2+Any of.
4. red fluorescence powder according to claim 1, it is characterised in that A K+, X Ge4+。
5. red fluorescence powder according to claim 4, it is characterised in that D Ba2+。
6. red fluorescence powder according to claim 5, it is characterised in that 0.03≤x≤0.1.
7. a kind of preparation method of red fluorescence powder, it is characterised in that the preparation method comprises the following steps：
A is weighed respectively according to stoichiometric proportion2MnF6、A2[XF6], salt containing D and salt containing Al, wherein, A is selected from Li+、Na+And K+In
Any one or more, D is selected from Ba2+、Sr2+、Ca2+And Mg2+Any of or it is a variety of, X is selected from Si4+、Ge4+And Ti4+In appoint
It is one or more；
By the A2MnF6It is dissolved in the first HF solution to obtain the first solution, by the A2[XF6] be dissolved in the 2nd HF solution with
The second solution is obtained, the salt containing D is dissolved in the 3rd HF solution to obtain the 3rd solution, and the salt containing Al is dissolved in
To obtain the 4th solution in four HF solution；
By first solution, second solution, the 3rd solution and the 4th solution simultaneously dropwise reaction to obtain
Mixed solution；
The mixed solution is filtered to obtain sediment, the component of the sediment is A(2-x)Dx[X(1-x-y)AlxF6]：
yMn4+, wherein, 0.001≤x≤0.5,0.03≤y≤0.2, x/y≤1, and the sediment is the red fluorescence powder.
8. preparation method according to claim 7, it is characterised in that the first HF solution, the 2nd HF solution, institute
It is identical with the concentration of the 4th HF solution and be 20wt%~60wt% to state the 3rd HF solution.
9. preparation method according to claim 7, it is characterised in that the temperature of the dropwise reaction is -20 DEG C~100
DEG C, the time of the dropwise reaction is 10min~5h.
10. preparation method according to claim 7, it is characterised in that the temperature of the dropwise reaction is 50 DEG C~55 DEG C,
The time of the dropwise reaction is 2h~2.5h.
11. the preparation method according to any one of claim 7 to 10, it is characterised in that carried out to the mixed solution
Before the step of suction filtration, the preparation method is also including the step of mixed solution is stirred and stood.
12. a kind of light-emitting device, including blue LED and luminescent coating, the luminescent coating includes red fluorescence powder,
Characterized in that, the red fluorescence powder is the red fluorescence powder any one of claim 1 to 6.
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