CN105038784A - Red phosphor and preparation method thereof - Google Patents

Red phosphor and preparation method thereof Download PDF

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CN105038784A
CN105038784A CN201510507958.4A CN201510507958A CN105038784A CN 105038784 A CN105038784 A CN 105038784A CN 201510507958 A CN201510507958 A CN 201510507958A CN 105038784 A CN105038784 A CN 105038784A
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raw materials
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red fluorescence
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CN105038784B (en
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彭明营
李鹏飞
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South China University of Technology SCUT
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Abstract

The invention discloses a preparation method of red phosphor. The preparation method of the red phosphor comprises the following steps: (1) respectively weighing compound raw materials containing lithium, sodium, germanium, manganese and boron in a molar ratio of elements that Li:Na:Ge:Mn:B is equal to 1:1:4(1-x):4x:4y, wherein x is more than or equal to 0.005% and less than or equal to 2%, and y is more than or equal to 0 and less than or equal to 25%; (2) grinding the raw materials, uniformly mixing, preburning in oxidizing atmosphere; (3) taking out a preburned sample, grinding, uniformly mixing, and firing in the oxidizing atmosphere; and (4) taking out a sample obtained through firing in the step (3), grinding, uniformly mixing, and firing for 1-15 hours in the oxidizing atmosphere again under the condition that temperature is higher or equal to 700 DEG C and lower than or equal to 950 DEG C, so that the red phosphor is obtained. The preparation method of the red phosphor is simple and also has the advantages of low cost, environmental friendliness and mild preparation conditions. The prepared red phosphor has high quantum efficiency.

Description

A kind of red fluorescence powder and preparation method thereof
Technical field
The present invention relates to luminescent material, particularly a kind of red fluorescence powder and preparation method thereof.
Background technology
The white light LEDs (hereinafter referred to as WLED) of current commercialization adopts blue light InGaNLED chip and Y 3al 5o 12: Ce 3+the combination (hereinafter referred to as BLED+YAG:Ce) of this binary tone of yellow fluorescent powder realizes white light, its concrete mechanism is that a light part that blue chip sends impinges upon yellow fluorescence bisque and makes it send gold-tinted, and the gold-tinted complementation that remainder blue light sends with it through phosphor powder layer forms white light.The weak point of this WLED is that it is more weak in red spectral region luminescence, this directly results in commercial WLED colour temperature higher (being usually located at 4500-6500K), colour rendering index (hereinafter referred to as CRI) is on the low side, usually be less than 80, be the white light that a kind of light is dazzling, tone is sombre compared with incandescent light.For addressing this problem, two kinds of methods can be adopted: one, add a kind of have in blue light region comparatively strong absorb red fluorescence powder; Another alternative method is combined blueness, green and red fluorescence powder and a ultraviolet chip (usual emission wavelength is at 380 ~ 420nm).Can find out, these two kinds of solutions all need exploitation can by ultraviolet or blue-light excited efficient red emitting material.Substantially, manufacture warm white LED aforesaid method and just need efficient red fluorescence powder.
Under the guide of research and development red fluorescence powder tight demand, effectively have stimulated the discovery of a series of red fluorescence powder, as with rare earth luminous ions such as expensive europium, samarium and praseodymiums, the transition metal ions such as divalence bismuth are the fluorescent material of luminescence center.For rear-earth-doped, as Eu 2+the red illuminating material such as nitride, oxynitride, silicate, aluminate of doping is by wide coverage in succession.Wherein nitride or oxynitride have especially excellent spectral quality, and quantum yield, more than 70%, is considered to the fluorescent material of most potentiality.But synthesizing these fluorescent material must carry out under the conditions such as high temperature and high pressure, as red fluorescence powder CaAlSiN 3: Eu 2+need synthesize under 1800 DEG C, 10 normal atmosphere, nitrogen atmosphere.Harsh preparation process condition and high cost of material hinder the commercialization process of these fluorescent material; These have the Eu of blue light absorption simultaneously 2+ion doping red fluorescence powder, also has strong absorption in green Region, and it just inevitably again absorbs the green portions in the white light that white light LEDs sends and lowers efficiency.The f-d transition of rare earth ion nature of fluorescent RE powder and cannot fundamentally overcome these drawbacks.
If the valence state of transition metal Mn ion is controlled at+4 valencys in luminescent material, also can ultraviolet or blue-light excited under, present emitting red light.Commercial is 3.5MgO.0.5MgF 2.GeO 2: Mn 4+, launch peak position and be positioned at 658nm, limit its range of application because it there is no obviously absorption in blue region (450 ~ 480nm).And the focus studied at present mainly concentrates on Mn 4+the fluorochemical of doping, the KTiF of people's reports such as such as Setlur 6: Mn 4+red fluorescence powder, with the warm white LED device that it is obtained, its efficiency is 85%, and colour rendering index is 90, colour temperature 3088K, is much better than BLED+YAG:Ce.Consider from environment protection angle, the preparation of fluorochemical needs to use hydrofluoric acid environment being had to high risks, and chemically stability is considered, fluorochemical is less stable in normal circumstances.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide a kind of preparation method of red fluorescence powder, preparation condition is extremely gentle, and calcination temperature, lower than 1000 DEG C, is convenient to volume production.
Another object of the present invention is to provide a kind of red fluorescence powder, luminous efficiency is high.
Object of the present invention is achieved through the following technical solutions:
A preparation method for red fluorescence powder, comprises the following steps:
(1) by elemental mole ratios Li:Na:Ge:Mn:B=1:1:4 (1-x): 4x:4y, wherein 0.005%≤x≤2%, 0≤y≤25%; Take respectively the raw materials of compound containing lithium, the raw materials of compound containing sodium, germanic raw materials of compound, containing the raw materials of compound of manganese and the raw materials of compound of boracic;
(2) pre-burning in an oxidizing atmosphere after raw mill mixing step (1) taken, temperature is 400 ~ 650 DEG C, and the time is 2 ~ 10 hours;
(3) taken out by the sample after step (2) pre-burning, calcination in an oxidizing atmosphere after being ground, temperature is 700 ~ 950 DEG C, and the time is 1 ~ 5 hour;
(4) taken out by the sample after step (3) calcination, calcination under oxidizing atmosphere again after being ground, temperature is 700≤T≤950 DEG C, and the time is 1≤t≤15 hour, obtains red fluorescence powder LiNaGe 4o 9: Mn 4+.
Step (3) described oxidizing atmosphere is air atmosphere or oxygen atmosphere.
The described raw materials of compound containing lithium of step (1) is any one in Quilonum Retard, Lithium Oxide 98min, lithium nitrate, lithium oxalate and Lithium Acetate.
The described raw materials of compound containing sodium of step (1) is any one in sodium carbonate, sodium bicarbonate, sodium oxide, SODIUMNITRATE, sodium oxalate and sodium-acetate.
The described germanic raw materials of compound of step (1) is any one in germanium oxide, nitric acid germanium and hydroxide germanium.
The described raw materials of compound containing manganese of step (1) is any one in manganese monoxide, manganese oxide, Manganse Dioxide and manganous carbonate.
The raw materials of compound of described boracic is the one in boric acid, boron trioxide and borate compound.
The preparation method of described red fluorescence powder, x=0.05%, T=850 DEG C, t=3h.
Described red fluorescence powder is LiNaGe 4o 9crystalline phase.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) red fluorescence pink light emitting efficiency of the present invention is high, and 295nm wavelength excites lower luminous intensity to be germanate business powder 3.5MgO0.5MgF 2geO 2: Mn 4+1.1 times, it is 2.67 times of business powder that 462nm wavelength excites down; It is 47% that 300nm wavelength excites lower quantum yield to be that 77%, 460 ~ 470nm wavelength excites down.
(2) red fluorescence powder of the present invention has broad ultraviolet and blue light absorption (230 ~ 500nm).
(3) red fluorescence powder of the present invention has the emitting red light in covering 600nm ~ 750nm interval under ultraviolet excitation.
(4) red fluorescence powder of the present invention blue-light excited under there is the emitting red light in covering 600nm ~ 750nm interval.
(5) the red fluorescence pink light emitting life-span of the present invention is long, is about at 1.1 ~ 1.4 milliseconds.
(6) the present invention does not adopt rare earth as luminescence center, do not adopt harsh preparation condition, as High Temperature High Pressure, under very gentle reaction conditions, under lesser temps (700 ~ 950 degrees Celsius), normal pressure, utilize cheap manganese as activator, controlling its valence state is+4 valencys, obtained red illuminating material LiNaGe 4o 9: Mn 4+chromaticity coordinates be x=0.727, y=0.273, to environment without harm.
Accompanying drawing explanation
Fig. 1 is the powder x-ray diffraction spectrum of the proportioning (1) of embodiment 1, (4), (5), (7), (9) sample.
Fig. 2 is the luminescent spectrum of proportioning (4) sample of embodiment 1.
Fig. 3 is that proportioning (4) sample of embodiment 1 is at the blue-light excited lower comparison diagram with business powder luminous intensity.
Fig. 4 is the excitation spectrum of proportioning (4) sample of embodiment 1.
Fig. 5 is the decay of luminescence curve of proportioning (4) sample of embodiment 1.
Fig. 6 is that the different Mn ion contents of embodiment 1 are to the influence curve of luminous intensity.
Fig. 7 is that the different Mn ion contents of embodiment 1 are to the influence curve of luminescent lifetime.
Fig. 8 is that the different calcination times of embodiment 3 are to the influence curve of luminous intensity.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Choose Quilonum Retard, sodium carbonate, germanium oxide and manganous carbonate and make initial compounds raw material, by each element mol ratio, take four kinds of raw materials of compound respectively, totally 9 groups, proportioning is as follows:
(1) Li:Na:Ge:Mn=1:1:3.9998:0.0002, corresponding x=0.005%, y=0;
(2) Li:Na:Ge:Mn=1:1:3.9996:0.0004, corresponding x=0.010%, y=0;
(3) Li:Na:Ge:Mn=1:1:3.9992:0.0008, corresponding x=0.020%, y=0;
(4) Li:Na:Ge:Mn=1:1:3.9980:0.0020, corresponding x=0.050%, y=0;
(5) Li:Na:Ge:Mn=1:1:3.9960:0.0040, corresponding x=0.100%, y=0;
(6) Li:Na:Ge:Mn=1:1:3.9880:0.0120, corresponding x=0.300%, y=0;
(7) Li:Na:Ge:Mn=1:1:3.9800:0.0200, corresponding x=0.500%, y=0;
(8) Li:Na:Ge:Mn=1:1:3.9600:0.0400, corresponding x=1.000%, y=0;
(9) Li:Na:Ge:Mn=1:1:3.9200:0.0800, corresponding x=2.000%, y=0;
Control mixture total weight and be 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 500 DEG C of pre-burnings 5 hours.Sample after pre-burning is taken out, after being again ground, puts into crucible, 850 DEG C of calcinations 5 hours under air, take out again grind even after, 850 DEG C of calcinations 5 hours under air, with stove naturally cooling, i.e. obtained red illuminating material LiNaGe 4o 9: Mn 4+.
Fig. 1 is the powder x-ray diffraction spectrum of the proportioning (1) of the present embodiment, (4), (5), (7), (9) sample, spectral line adopts Japanese RigakuD/max-IIIAX x ray diffractometer x to measure, test voltage 40kV, sweep velocity 1.2 °/min, test current 40mA, select Cu-K α 1X ray, wavelength is x-ray diffraction analysis shows that it is LiNaGe 4o 9phase, belongs to rhombic system, and the doping of manganese does not affect the formation of crystalline phase.The X-ray diffraction spectrogram of all the other proportioning samples is similar.
Fig. 2 is the luminescent spectrum of proportioning (4) sample of the present embodiment, Edinburgh, Britain FLS920 stability and transient luminescence spectrometer is adopted to measure, xenon lamp power is 450 watts, detector is Japanese Hamamatsu refrigeration mode R928P photomultiplier (operating voltage-1250 volt), data gathering integral time is 0.2 second, and scanning step is 1nm.The corresponding excitation wavelength of curve a is 295nm, and the corresponding excitation wavelength of curve b is 462nm; Because of other wavelength excite the luminescent spectrum of lower generation and 295, that 462nm excites is similar, so only provide 295 spectrum excited with 462nm herein.As shown in Figure 2, sample all can produce the emitting red light that peak position is positioned at 661nm under UV-light or blue light excite respectively, luminous covering 600-750nm spectral region, corresponding 2e → 4a 2transition, corresponding chromaticity coordinates is x=0.727, y=0.273.The luminescent spectrum of all the other proportioning samples is similar.
Fig. 3 be the present embodiment the luminous intensity of proportioning (4) sample under 462nm is blue-light excited (curve a) with business powder 3.5MgO0.5MgF 2geO 2: Mn 4+the comparison of luminous intensity (curve b), its integrated intensity is 2.67 times of business powder; It is 1.1 times of business powder that 295nm wavelength excites down.
Fig. 4 is the excitation spectrum of proportioning (4) sample of the present embodiment, corresponding emission wavelength 661nm; Edinburgh, Britain FLS920 stability and transient luminescence spectrometer is adopted to measure, xenon lamp power is 450 watts, detector is Japanese Hamamatsu refrigeration mode R928P photomultiplier (operating voltage-1250 volt), and data gathering integral time is 0.2 second, and scanning step is 1nm.As shown in Figure 4, the excitation spectrum of corresponding 661nm luminescence covers the absorption in 230 ~ 500nm interval, and peak position is positioned at 295 and 462nm, shows that sample has broad absorption in UV-light or blue light.The excitation spectrum of all the other proportioning samples is similar.
Fig. 5 is the decay of luminescence curve of proportioning (4) sample of the present embodiment, and corresponding excitation wavelength is 295nm, and emission wavelength is 661nm; Adopt Edinburgh, Britain FLS920 stability and transient luminescence spectrometer to measure, microsecond pulse xenon lamp mean power is 60 watts, and repetition rate is set to 20Hz, and detector is Japanese Hamamatsu refrigeration mode R928P photomultiplier (operating voltage-1250 volt).As shown in Figure 5, the decay of luminescence under wavelength 295nm excites, 661nm luminescent lifetime is 1242 μ s.
As shown in Figures 6 and 7, with the change of Mn ion content, luminous intensity slightly changes, and reach the strongest when x=0.05%, luminescent lifetime changes between 1195 ~ 1244 μ s.Quantum yield test shows, it is 47% that the strongest sample of luminescence excites lower quantum yield to be that 77%, 460 ~ 470nm wavelength excites down at 300nm wavelength.
Embodiment 2
Choose Quilonum Retard, sodium carbonate, germanium oxide and manganous carbonate and make initial compounds raw material, by each element mol ratio Li:Na:Ge:Mn=1:1:3.9980:0.0020, corresponding x=0.050%, y=0; Take four kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 500 DEG C of pre-burnings 5 hours.Sample after pre-burning is taken out, after being again ground, temperature T (T=700,750,800,850,900,950 DEG C) calcination 5 hours under air, take out again grind even after, again temperature T (T=700,750,800,850,900,950 DEG C) calcination 5 hours under air, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1, and when T=850 DEG C, luminescence is the strongest.
Embodiment 3
Choose Quilonum Retard, sodium carbonate, germanium oxide and manganous carbonate and make initial compounds raw material, by each element mol ratio Li:Na:Ge:Mn=1:1:3.9980:0.0020, corresponding x=0.050%, y=0; Take four kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 500 DEG C of pre-burnings 5 hours.Sample after pre-burning is taken out, after being again ground, at 850 DEG C of calcination t (t=1,2,3,4,5,7,10,15) hour under air, take out again grind even after, at 850 DEG C of calcination t (t=1,2,3,4,5,7,10,15) hour again under air, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.As shown in Figure 8, with the change of calcination time, luminous intensity slightly changes, and when t=3h, luminescence is the strongest.
Embodiment 4
Choose Lithium Oxide 98min, sodium bicarbonate, germanium oxide, manganese monoxide and boric acid make starting raw material, and by each element mol ratio, take five kinds of raw materials of compound respectively, totally 4 groups, proportioning is as follows:
(1) Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:0, corresponding x=0.050%, y=0;
(2) Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:0.2, corresponding x=0.050%, y=5%;
(3) Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:0.4, corresponding x=0.050%, y=10%;
(4) Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:1.0, corresponding x=0.050%, y=25%;
Control mixture total weight and be 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 400 DEG C of pre-burnings 10 hours.Sample after pre-burning is taken out, after being again ground, puts into crucible, 800 DEG C of calcinations 5 hours under air, again grind even after, 800 DEG C of calcinations 5 hours under air, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.
X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.
Embodiment 5
Choose lithium nitrate, sodium oxide, nitric acid germanium and manganese oxide make starting raw material, by each element mol ratio Li:Na:Ge:Mn=1:1:3.9980:0.0020, and corresponding x=0.050%, y=0; Take four kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 650 DEG C of pre-burnings 2 hours.Sample after pre-burning is taken out, after being again ground, 850 DEG C of calcinations 7 hours under oxygen, take out again grind even after, 850 DEG C of calcinations 7 hours under oxygen, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.
Embodiment 6
Choose lithium oxalate, SODIUMNITRATE, hydroxide germanium and Manganse Dioxide make starting raw material, by each element mol ratio Li:Na:Ge:Mn=1:1:3.9980:0.0020, and corresponding x=0.050%, y=0; Take four kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 600 DEG C of pre-burnings 4 hours.Sample after pre-burning is taken out, after being again ground, 900 DEG C of calcinations 2 hours under air, take out again grind even after, 900 DEG C of calcinations 2 hours under air, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.
Embodiment 7
Choose Lithium Acetate, sodium oxalate, germanium oxide, starting raw material made by manganous carbonate and boron trioxide, by each element mol ratio Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:0.6, and corresponding x=0.050%, y=15%; Take five kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 550 DEG C of pre-burnings 7 hours.Sample after pre-burning is taken out, after being again ground, 700 DEG C of calcinations 12 hours under air, take out again grind even after, 700 DEG C of calcinations 12 hours under air, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.
Embodiment 8
Choose Quilonum Retard, sodium-acetate, germanium oxide, manganese oxide and lithium tetraborate (Li 2b 4o 7) make starting raw material, by each element mol ratio Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:0.2, corresponding x=0.050%, y=5.0%; Take five kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 450 DEG C of pre-burnings 8 hours.Sample after pre-burning is taken out, after being again ground, 750 DEG C of calcinations 10 hours under oxygen, take out again grind even after, 750 DEG C of calcinations 10 hours under oxygen, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.
Embodiment 9
Choose Quilonum Retard, sodium carbonate, germanium oxide, Manganse Dioxide and borax (Na 2b 4o 7.10H 2o) starting raw material is made, by each element mol ratio Li:Na:Ge:Mn:B=1:1:3.9980:0.0020:0.2, corresponding x=0.050%, y=5.0%; Take five kinds of raw materials respectively, controlling mixture total weight is 10 grams.10 grams of mixtures, after being ground, being put into corundum crucible, then crucible are put into high-temperature electric resistance furnace.Accurate control temperature rise rate, sample was 450 DEG C of pre-burnings 8 hours.Sample after pre-burning is taken out, after being again ground, 750 DEG C of calcinations 10 hours under oxygen, take out again grind even after, 750 DEG C of calcinations 10 hours under oxygen, with stove naturally cooling, i.e. obtained tetravalent manganese ion doping germanate red illuminating material.X-ray diffraction analysis shows that it is LiNaGe 4o 9crystalline phase.The spectral quality of fluorescent material is with similar in embodiment 1.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (9)

1. a preparation method for red fluorescence powder, is characterized in that, comprises the following steps:
(1) by elemental mole ratios Li:Na:Ge:Mn:B=1:1:4 (1-x): 4x:4y, wherein 0.005%≤x≤2%, 0≤y≤25%; Take respectively the raw materials of compound containing lithium, the raw materials of compound containing sodium, germanic raw materials of compound, containing the raw materials of compound of manganese and the raw materials of compound of boracic;
(2) pre-burning in an oxidizing atmosphere after raw mill mixing step (1) taken, temperature is 400 ~ 650 DEG C, and the time is 2 ~ 10 hours;
(3) taken out by the sample after step (2) pre-burning, calcination in an oxidizing atmosphere after being ground, temperature is 700 ~ 950 DEG C, and the time is 1 ~ 5 hour;
(4) taken out by the sample after step (3) calcination, calcination under oxidizing atmosphere again after being ground, temperature is 700≤T≤950 DEG C, and the time is 1≤t≤15 hour, obtains red fluorescence powder.
2. the preparation method of red fluorescence powder according to claim 1, is characterized in that, step (3) described oxidizing atmosphere is air atmosphere or oxygen atmosphere.
3. the preparation method of red fluorescence powder according to claim 1, is characterized in that, the described raw materials of compound containing lithium of step (1) is any one in Quilonum Retard, Lithium Oxide 98min, lithium nitrate, lithium oxalate and Lithium Acetate.
4. the preparation method of red fluorescence powder according to claim 1, is characterized in that, the described raw materials of compound containing sodium of step (1) is any one in sodium carbonate, sodium bicarbonate, sodium oxide, SODIUMNITRATE, sodium oxalate and sodium-acetate.
5. the preparation method of red fluorescence powder according to claim 1, is characterized in that, the described germanic raw materials of compound of step (1) is any one in germanium oxide, nitric acid germanium and hydroxide germanium.
6. the preparation method of red fluorescence powder according to claim 1, is characterized in that, the described raw materials of compound containing manganese of step (1) is any one in manganese monoxide, manganese oxide, Manganse Dioxide and manganous carbonate.
7. the preparation method of red fluorescence powder according to claim 1, is characterized in that, the raw materials of compound of step (1) described boracic is the one in boric acid, boron trioxide and borate compound.
8. the preparation method of red fluorescence powder according to claim 1, is characterized in that, x=0.05%, T=850 DEG C, t=3h.
9. the red fluorescence powder that obtains of the preparation method of red fluorescence powder according to claim 1, it is characterized in that, described red fluorescence powder is LiNaGe 4o 9crystalline phase.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080061674A1 (en) * 2006-09-12 2008-03-13 National Chiao Tung University Highly saturated red-emitting Mn (IV) activated phosphors and method of fabricating the same
CN104087298A (en) * 2014-06-20 2014-10-08 华南理工大学 Light conversion material and light conversion film, and preparation methods thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080061674A1 (en) * 2006-09-12 2008-03-13 National Chiao Tung University Highly saturated red-emitting Mn (IV) activated phosphors and method of fabricating the same
CN104087298A (en) * 2014-06-20 2014-10-08 华南理工大学 Light conversion material and light conversion film, and preparation methods thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K S OMELCHENKO: "Photoluminescence of Manganese Doped LiNaGe4O9 Crystals", 《PHYSICS OF THE SOLID STATE》 *

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