CN103773367B - Fluorescent material for white light LED (Light Emitting Diode) and preparation method thereof - Google Patents

Fluorescent material for white light LED (Light Emitting Diode) and preparation method thereof Download PDF

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CN103773367B
CN103773367B CN201410009169.3A CN201410009169A CN103773367B CN 103773367 B CN103773367 B CN 103773367B CN 201410009169 A CN201410009169 A CN 201410009169A CN 103773367 B CN103773367 B CN 103773367B
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fluorescent material
white light
calcine
iii
combination
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CN103773367A (en
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田莲花
刘晓萌
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Yanbian University
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Yanbian University
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Abstract

The invention discloses a fluorescent material for a white light LED (Light Emitting Diode). The chemical expression of the fluorescent material is AM<I>M<II>M<III>O6:cR, wherein c means that the molar ratio of R to AM<I>M<II>M<III>O6 is c:1, c is greater than or equal to 0.001 and less than or equal to 0.75, A is one or combination of Na, Li, K and Ag, M<I> is one or combination of Ca, Mg, Sr, Ba, Zn and Pb, M<II> is one or combination of Ti, Zr, Si and Ge, M<III> is one or combination of Nb, Ta and V, and R is one or combination of Pr, Sm, Eu, Tb, Dy, Mn and Bi. The excitation band of the fluorescent material covers a range of 200-500nm, the emission band is narrow, that is, the full width at half maximum is narrow, and visible light can be emitted after the fluorescent material is excited through ultraviolet, near-ultraviolet and blue light, so that the fluorescent material can be combined with other appropriate fluorescent materials of different colors to manufacture white light emitting devices. The fluorescent material is cheap and easy in obtaining of the raw materials, and simple in manufacturing process and is an ideal candidate fluorescent material for the white light LED. The invention further discloses a preparation method of the fluorescent material for the white light LED.

Description

For fluorescent material and the preparation method of white light LEDs
Technical field
The invention belongs to the technical field of fluorescent material science, be specifically related to a kind of fluorescent material for white light LEDs that effectively can be excited by ultraviolet, near ultraviolet and blue light and preparation method.
Background technology
White light LEDs is the photochromic photodiode for white sent, and white light is made up of the light of multiple wavelength.It has efficiency high, use power consumption less, low-voltage power supply, suitability are strong, stability is high, the time of response is short, environmentally safe, multicolor luminous etc. advantage.White light LEDs is after research and development in 1977, and the development white light LEDs through decades achieves considerable progress in all many-sides such as luminous efficiencies.Nowadays it is widely used in our life, as car light, illumination, LCD display and screen backlight.But current its is still mainly used in screen display, also because its manufacturing cost is slightly high, responsive to temperature requirement, so want alternative existing light source still to need certain improvement.White light LEDs adopts two kinds of methods to be formed usually, one to be coordinated with fluorescent material by " Blue-Ray technology " to form white light, according to the research of people to visible ray, the white light that eye can be shown in, at least need the mixing of two kinds of light, i.e. the pattern of blue light and sodium yellow or blue light, green light and red light.The white light of above-mentioned two kinds of patterns, all needs blue light, so the method for picked-up blue light has become the key manufacturing white light, i.e. so-called Blue-Ray technology; The second is multiple monochromatic ray blending means, and namely by the LED photodiode of different colors, the feature utilizing its driving voltage, luminous output, temperature profile and life-span different is to produce white light.The mode generally adopting blue-ray LED to add YAG fluorescent powder at present makes white light LEDs, although its manufacture craft is comparatively simple, technical costs is lower, and its colour rendering index is also relatively low.Adopt near ultraviolet LED to add RGB three primary colors fluorescent powder and can obtain any colour temperature and the white light LEDs compared with high color rendering index (CRI) in theory, but not yet ripe for the technology of ultraviolet LED fluorescent material at present.And the absorbing wavelength narrow range that the fluorescent material that can be applicable to white light LEDs at present has causes efficiency of conversion low, some poor stabilities, as although the Eu fluorescent material of mixing containing N excites bandwidth but its emission band is also wide, can not meet the needs of high performance device, so research and develop a kind of new and effective fluorescent material for bias light purposes there is certain research and actual application value.
Summary of the invention
The object of the invention is to cause efficiency of conversion low to solve the absorbing wavelength narrow range had for the fluorescent material of white light LEDs at present, some poor stabilities, as the Eu fluorescent material of mixing containing N for white light LEDs excites bandwidth but its emission band is also wide, can not meet the problem such as to need of high performance device, and provide a kind of excitation band to cover 200 ~ 500 nm scopes, emission band is narrower, and namely halfwidth is narrow, and can by the fluorescent material for white light LEDs that effectively can be excited by ultraviolet, near ultraviolet and blue light.
Object of the present invention additionally provides a kind of preparation method of the fluorescent material for white light LEDs.
For realizing the object of the invention, the present invention takes following technical scheme,
For a fluorescent material for white light LEDs, its chemical expression is AM im iIm iIIo 6: cR, wherein, described A is one in Na, Li, K, Ag or its combination;
M ifor Ca, M g, the one in Sr, Ba, Zn, Pb or its combination;
M iIfor the one in Ti, Zr, Si, Ge or its combination;
M iIIfor the one in Nb, Ta, V or its combination;
O is oxygen element;
C represents R and AM im iIm iIIo 6the ratio of amount of substance be c:1, and 0.001≤c≤0.75;
R is one in Pr, Sm, Eu, Tb, Dy, Mn, Bi or its combination.
Described fluorescent material is Na further 1-xa xcaTiNbO 6: cPr (A=Li, K or Ag, 0≤x≤1),
NaCa 1-xm i xtiNbO 6: cPr (M =Mg, Sr, Ba, Zn or Pb, 0≤x≤1),
NaCaTi 1-xm iI xnbO 6: cPr (M iI=Zr, Si or Ge, 0≤x≤1),
NaCaTiNb 1-xm iII xo 6: cPr (M iII=Ta or V, 0≤x≤1),
Or NaCaTiNbO 6: cR 1, cR 2(R 1, R 2=Pr, Sm, Eu, Tb, Dy, Mn or Bi).
This type of fluorescent material can realize the VISIBLE LIGHT EMISSION comprising the visible ray such as ruddiness, yellowish-white light, as NaCaTiTaO 6: 0.005Pr has red emission, NaCaTiNbO 6: 0.01Dy has yellowish-white light emission etc., and this type of fluorescent material includes but not limited to, preferred fluorescent material what follows: LiCaTiNbO 6: 0.005Pr, NaCaTiNbO 6: 0.005Pr, KCaTiNbO 6: 0.005Pr, Na 0.99li 0.01caTiNbO 6: 0.005Pr, Na 0.9ag 0.1caTiNbO 6: 0.005Pr, NaMgTiNbO 6: 0.005Pr, NaSrTiNbO 6: 0.005Pr, NaBaTiNbO 6: 0.005Pr, NaZnTiNbO 6: 0.005Pr, NaCa 0.99mg 0.01tiNbO 6: 0.005Pr, NaCa 0.99ba 0.01tiNbO 6: 0.005Pr, NaCa 0.99sr 0.01tiNbO 6: 0.005Pr, NaCa 0.99zn 0.01tiNbO 6: 0.005Pr, NaCa 0.99pb 0.01tiNbO 6: 0.005Pr, NaCaZrNbO 6: 0.005Pr, NaCaGeNbO 6: 0.005Pr, NaCaSiNbO 6: 0.005Pr, NaCaTiTaO 6: 0.005Pr, NaCaTiNbO 6: 0.02Sm, NaCaTiNbO 6: 0.07Eu, NaCaTiNbO 6: 0.01Dy, NaCaTiNbO 6: 0.1Bi, NaCaTiNbO 6: 0.01Pr, 0.01Bi, NaCaTiNbO 6: 0.005Pr, 0.005Sm, NaCaTiNbO 6: 0.005Pr, 0.005Mn.
Described above for a preparation method for the fluorescent material of white light LEDs, comprise the following steps:
A, to prepare burden by any one in described fluorescent material composition chemical expression according to the activator R of substrate material and use;
B, load joining raw material in step a after fine grinding in corundum crucible with cover through 30 minutes, be placed in calcining furnace and calcine, calcining temperature is 1100 ~ 1300 ° of C, and the firing time is 7 ~ 10 hours, by cooling, broken, and grinding obtains this fluorescent material again.
For a preparation method for the fluorescent material of white light LEDs, specifically comprise the following steps further:
A, will containing the oxide compound of A or carbonate, containing M oxide compound or carbonate, containing M iIoxide compound or carbonate, containing M iIIoxide compound or carbonate, carry out mix containing the oxide compound of R or carbonate according to any one in described fluorescent material composition chemical expression;
B, the mix porphyrize by above-mentioned a step, mixing, load in corundum crucible with cover, be placed in calcining furnace and calcine, and calcining temperature is 1100 ~ 1300 ° of C, and the firing time is 7 ~ 10 hours, by cooling, broken, and grinding obtains this fluorescent material again.
Experimental program of the present invention is summarized as follows:
1. the preparation of material
The raw material of described fluorescent material is the inorganic salt of each element, includes but not limited to oxide compound, carbonate nitrate, and all adopts high temperature solid-state method to obtain.Concrete dosage is calculated by the chemical formula of this fluorescent material, the difference of foundation fluorescent material basic material and activator, we select to calcine 10 minutes at its fusing point place of various starting material, burning temperature is 1100 ~ 1300 ° of C, preparation time is 7 ~ 10 hours, process comprises weighing, calcining, and after the crystal then formed is cooled through break process, carefully grinding obtains fluorescent material of the present invention.
2. performance evaluation
Optical absorption emission characteristic: at the F-7000 FL Spectrophotometer of HIT, its ultraviolet-ray visible absorbing emmission spectrum is tested to the fluorescent material sample of gained of the present invention.The present invention relates in a word and UV-light, near-ultraviolet light and blue light be converted to the higher visible ray of brightness, can be used for white-light LED fluorescence material.The material of fluorescence of the present invention can be used for white light LEDs and be correlated with display, illuminating device.Starting material of the present invention are simple and easy to get, and manufacture craft is simple, is desirable white light LED fluorescent powder candidate material.
Accompanying drawing explanation
Fig. 1 is NaCaTiNbO in the embodiment of the present invention 1 6: 0.01Pr, NaCaTiNbO 6: the excitation spectrum (λ of 0.01Pr, 0.01Bi material em=615 nm) and emmission spectrum (λ ex=357 nm).
Fig. 2 is NaCaTiNbO in the embodiment of the present invention 5 6: the excitation spectrum (λ of 0.02Sm material em=567 nm ;λ em=602 nm) and emmission spectrum (λ ex=408 nm).
Fig. 3 is NaCaTiNbO in the embodiment of the present invention 6 6: the excitation spectrum (λ of 0.07Eu material em=617 nm) and emmission spectrum (λ ex=398 nm).
Fig. 4 is NaCaTiNbO in the embodiment of the present invention 7 6: the excitation spectrum (λ of 0.01Dy material em=485 nm ;λ em=576 nm) and emmission spectrum (λ ex=390 nm).
Fig. 5 is Li in the embodiment of the present invention 15 0.01na 0.99caTiNbO 6: the excitation spectrum (λ of 0.005Pr material em=615 nm) and emmission spectrum (λ ex=357 nm).
Fig. 6 is NaCa in the embodiment of the present invention 16 0.495mg 0.5tiNbO 6: the excitation spectrum (λ of 0.005Pr material em=613 nm) and emmission spectrum (λ ex=343 nm).
Fig. 7 is NaCa in the embodiment of the present invention 17 0.495ba 0.5tiNbO 6: the excitation spectrum (λ of 0.005Pr material em=613 nm) and emmission spectrum (λ ex=276 nm).
Fig. 8 is NaCaTi in the embodiment of the present invention 18 0.9zr 0.1nbO 6: the excitation spectrum (λ of 0.005Pr material em=615 nm) and emmission spectrum (λ ex=344 nm).
Fig. 9 is NaCaTiNb in the embodiment of the present invention 19 0.8ta 0.2o 6: the excitation spectrum (λ of 0.005Pr material em=615 nm) and emmission spectrum (λ ex=358 nm).
Embodiment
Introduce embodiment of the present invention below, but the present invention is only limitted to embodiment absolutely not
Embodiment 1:
by raw material Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Pr 2o 3by NaCaTiNbO 6: 0.01Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTiNbO 6: 0.01Pr fluorescent material.Test result is shown in Fig. 1.
Embodiment 2:
By raw material Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Pr 2o 3, Bi 2o 3by NaCaTiNbO 6: 0.01Pr, 0.01Bi stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaBaTiNbO 6: 0.01Pr, 0.01Bi fluorescent material.Test result is shown in Fig. 1.
Embodiment 3:
By raw material Li 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Pr 2o 3by LiCaTiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 618 ° of C(Li 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1200 ° of C.Through overcooling, fine grinding obtains LiCaTiNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 4:
By raw material K 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Pr 2o 3by KCaTiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 891 ° of C(K 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains KCaTiNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 5:
By raw material Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Sm 2o 3by NaCaTiNbO 6: 0.02Sm stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTiNbO 6: 0.02Sm fluorescent material.Test result is shown in Fig. 2.
Embodiment 6:
By raw material Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Eu 2o 3by NaCaTiNbO 6: 0.07Eu stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTiNbO 6: 0.07Eu fluorescent material.Test result is shown in Fig. 3.
Embodiment 7:
By raw material Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Dy 2o 3by NaCaTiNbO 6: 0.01Dy stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTiNbO 6: 0.01Dy fluorescent material.Test result is shown in Fig. 4.
Embodiment 8:
By raw material Na 2cO 3, CaCO 3, ZrO 2, Nb 2o 5, Pr 2o 3by NaCaZrNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaZrNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 9:
By raw material Na 2cO 3, MgO, TiO2, Nb 2o 5, Pr 2o 3by NaMgTiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1100 ° of C.Through overcooling, fine grinding obtains NaMgTiNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 10:
By raw material Na 2cO 3, ZnO, TiO 2, Nb 2o 5, Pr 2o 3by NaZnTiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes, calcine 2 hours at 1100 ° of C.Through overcooling, fine grinding obtains NaZnTiNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 11:
By raw material Na 2cO 3, SrCO 3, TiO 2, Nb 2o 5, Pr 2o 3by NaSrTiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 1100 ° of C(SrCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaSrTiNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 12:
By raw material Na 2cO 3, CaCO 3, SiO 2, Nb 2o 5, Pr 2o 3by NaCaSiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1100 ° of C.Through overcooling, fine grinding obtains NaCaSiNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 13:
by raw material Na 2cO 3, CaCO 3, GeO 2, Nb 2o 5, Pr 2o 3by NaCa GeNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1100 ° of C.Through overcooling, fine grinding obtains NaCa GeNbO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 14:
By raw material Na 2cO 3, CaCO 3, TiO 2, Ta 2o 5, Pr 2o 3by NaCaTiTaO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, 851 ° of C(Na 2cO 3fusing point), at 825 ° of C(CaCO 3fusing point), 1115 ° of C (GeO 2fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTiTaO 6: 0.005Pr fluorescent material.It effectively can send ruddiness under burst of ultraviolel.
Embodiment 15:
By raw material Li 2cO 3, Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Pr 2o 3by Li 0.01na 0.99caTiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 618 ° of C(Li 2cO 3fusing point), 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains Li 0.01na 0.99caTiNbO 6: 0.005Pr fluorescent material.Test result is shown in Fig. 5.
Embodiment 16:
By raw material Na 2cO 3, CaCO 3, MgO, TiO 2, Nb 2o 5, Pr 2o 3by NaCa 0.495mg 0.5tiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCa 0.495mg 0.5tiNbO 6: 0.005Pr fluorescent material.Test result is shown in Fig. 6.
Embodiment 17:
By raw material Na 2cO 3, CaCO 3, BaCO 3, TiO 2, Nb 2o 5, Pr 2o 3by NaCa 0.495ba 0.5tiNbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCa 0.495ba 0.5tiNbO 6: 0.005Pr fluorescent material.Test result is shown in Fig. 7.
Embodiment 18:
By raw material Na 2cO 3, CaCO 3, TiO 2, ZrO 2, Nb 2o 5, Pr 2o 3by NaCaTi 0.9zr 0.1nbO 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTi 0.9zr 0.1nbO 6: 0.005Pr fluorescent material.Test result is shown in Fig. 8.
Embodiment 19:
By raw material Na 2cO 3, CaCO 3, TiO 2, Nb 2o 5, Ta 2o 5, Pr 2o 3by NaCaTiNb 0.8ta 0.2o 6: 0.005Pr stoichiometric ratio weighs, in mortar, carry out Homogeneous phase mixing, and duration is 30 minutes, and gained split loads corundum crucible with cover and then puts into calcining furnace and calcine, at 825 ° of C(CaCO 3fusing point), 851 ° of C(Na 2cO 3fusing point) calcine 10 minutes respectively, calcine 2 hours at 1300 ° of C.Through overcooling, fine grinding obtains NaCaTiNb 0.8ta 0.2o 6: 0.005Pr fluorescent material.Test result is shown in Fig. 9.

Claims (5)

1., for a fluorescent material for white light LEDs, its chemical expression is AM m iIm iIIo 6: cR, wherein,
Described A is one in Na, Li, K, Ag or its combination;
M for Ca, M g, the one in Sr, Ba, Zn, Pb or its combination;
M iIfor the one in Ti, Zr, Si, Ge or its combination;
M iIIfor the one in Nb, Ta, V or its combination;
O is oxygen element;
C represents R and AM im iIm iIIo 6the ratio of amount of substance be c:1, and 0.001≤c≤0.75;
R is one in Pr, Sm, Eu, Tb, Dy, Mn, Bi or its combination.
2. a kind of fluorescent material for white light LEDs according to claim 1, is characterized in that described fluorescent material is Na 1-xa xcaTiNbO 6: cPr, wherein A=Li, K or Ag, 0≤x≤1;
NaCa 1-xm xtiNbO 6: cPr, wherein M =Mg, Sr, Ba, Zn or Pb, 0≤x≤1;
NaCaTiNb 1-xm iII xo 6: cPr, wherein M iII=Ta or V, 0≤x≤1;
Or NaCaTiNbO 6: cR 1, cR 2, wherein R 1, R 2=Pr, Sm, Eu, Tb, Dy, Mn or Bi.
3. a kind of fluorescent material for white light LEDs according to claim 1, is characterized in that described fluorescent material is one of following: LiCaTiNbO 6: 0.005Pr, NaCaTiNbO 6: 0.01Pr, KCaTiNbO 6: 0.005Pr, Na 0.99li 0.01caTiNbO 6: 0.005Pr, NaMgTiNbO 6: 0.005Pr, NaSrTiNbO 6: 0.005Pr, NaZnTiNbO 6: 0.005Pr, NaCaZrNbO 6: 0.005Pr, NaCaGeNbO 6: 0.005Pr, NaCaSiNbO 6: 0.005Pr, NaCaTiTaO 6: 0.005Pr, NaCaTiNbO 6: 0.02Sm, NaCaTiNbO6:0.07Eu, NaCaTiNbO6:0.01Dy, NaCaTiNbO6:0.01Pr, 0.01Bi, NaCa0.495Mg0.5TiNbO6:0.005Pr, NaCa0.495Ba0.5TiNbO6:0.005Pr, NaCaTi0.9Zr0.1NbO6:0.005Pr, NaCaTiNb0.8Ta0.2O6:0.005Pr.
4., as claimed in claim 1 for a preparation method for the fluorescent material of white light LEDs, comprise the following steps:
A, to prepare burden by any one in described fluorescent material composition chemical expression according to the activator of substrate material and use;
B, load joining raw material in step a after fine grinding in corundum crucible with cover through 30 minutes, be placed in calcining furnace and calcine, calcining temperature is 1100 ~ 1300 ° of C, and the firing time is 7 ~ 10 hours, by cooling, broken, and grinding obtains this fluorescent material again.
5. the preparation method of a kind of fluorescent material for white light LEDs according to claim 4, comprises the following steps:
A, will containing the oxide compound of A or carbonate, containing M oxide compound or carbonate, containing M iIoxide compound or carbonate, containing M iIIoxide compound or carbonate, carry out mix containing the oxide compound of R or carbonate according to any one in described fluorescent material composition chemical expression;
B, the mix porphyrize by above-mentioned a step, mixing, load in corundum crucible with cover, be placed in calcining furnace and calcine, and calcining temperature is 1100 ~ 1300 ° of C, and the firing time is 7 ~ 10 hours, by cooling, broken, and grinding obtains this fluorescent material again.
CN201410009169.3A 2014-01-09 2014-01-09 Fluorescent material for white light LED (Light Emitting Diode) and preparation method thereof Expired - Fee Related CN103773367B (en)

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