CN105400513A - Red phosphor powder and preparation method thereof - Google Patents
Red phosphor powder and preparation method thereof Download PDFInfo
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- CN105400513A CN105400513A CN201510428924.6A CN201510428924A CN105400513A CN 105400513 A CN105400513 A CN 105400513A CN 201510428924 A CN201510428924 A CN 201510428924A CN 105400513 A CN105400513 A CN 105400513A
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- 239000000843 powder Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 150000004678 hydrides Chemical class 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 37
- 239000012298 atmosphere Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052693 Europium Inorganic materials 0.000 claims description 15
- 150000004767 nitrides Chemical class 0.000 claims description 12
- 229910017083 AlN Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- -1 strontium nitride Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000009877 rendering Methods 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000005121 nitriding Methods 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229910052582 BN Inorganic materials 0.000 description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 7
- 238000013467 fragmentation Methods 0.000 description 7
- 238000006062 fragmentation reaction Methods 0.000 description 7
- 229910010082 LiAlH Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 4
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910016655 EuF 3 Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The present invention discloses red phosphor powder and a preparation method thereof, wherein the chemical structure formula of the red phosphor powder is Ca1-x-ySrxEuyLzAl3O[delta]N4-[delta], L is at least one selected from Li, Na and K, X is more than or equal to 0 and is less than 1, Y is more than 0 and is less than or equal to 0.1, Z is more than or equal to 0.5 and is less than or equal to 1, and [delta] is more than 0 and is less than 0.5. According to the present invention, the trace oxygen is introduced to balance the charge so as to improve the light emitting efficiency of the synthesized red phosphor powder; the phosphor powder can emit narrow brand visible light having the peak value of 630-680 nm under excitation of 400-500 nm violet light or blue light so as to improve the color rendering index of the product and meet the application requirements of the backlight and the display product on the narrow peak emission phosphor powder; and the red phosphor powder is prepared through the multi-step nitriding reaction method of the composite hydride dehydrogenation nitriding, and can be used for high color rendering index illumination, and backlighting and display devices.
Description
Technical field
The present invention relates to lighting engineering, display and field of photoelectric material, particularly relate to a kind of red fluorescence powder and preparation method thereof.
Background technology
The U.S., Japan, Europe and the policy in succession putting into effect restriction incandescent light, mercury lamp and two primary colours luminescent lamps such as Chinese, and the asterisk of american energy standard regulation, colour rendering index CRI >=80 of interior lighting, require CRI >=90 in some high-end application scenarios.LED as solid-state illumination of new generation and technique of display, by the requirement of accomplished in many ways to high-color rendering.Adding high-quality LED red fluorescence powder is a kind of important means wherein.
M
2si
5n
8: Eu
2+(M=Ca, Sr, Ba) and CaAlSiN
3: Eu
2+this kind of nitride red fluorescent powder physico-chemical property is very stable, stablely in empty G&W does not decompose, and has that light decay is little, luminous quantum efficiency advantages of higher.Compared with the former, CaAlSiN
3: Eu
2+have longer emission wavelength, fade resistance also increases.Its excitation spectrum extends to the main excitation peak of 590mm from 200nm and is positioned at 335nm and 450nm. and emission peak system broadband, along with the increase of doping, peak position moves to 680nm from 640nm, is existing primary commercial red fluorescence powder.
To CaAlSiN
3: Eu
2+research, from 1985, ZHEN-KLNHUANG was to CaO-AlN-Si
3n
4phasor is studied; On this basis, Kyotallheda in reported first in 2006 CaAlSiN
3: Eu
2+red fluorescence powder, have studied its spectrum property and quenching temperature. in application publication number CN10217432A and application publication number CN102206491A, and Independent Administrative Institution, matter Materials Research Institution and Mitsubishi chemical Co., Ltd's co-applications CaAlSiN
3for the fluorescent material of principal phase, use this fluorescent material successfully can make the white light-emitting diode of high-level efficiency transmitting warm white.Cree Co adds active ions Ce in publication number CN101451063A patent
3+, also to introduce at atom N place multiple the moon from, but not mentioned these change impacts on performance etc.Intematix Corp. think in application publication number CN102282641A synthesis CaAlSiN
3the F being less than 2% is added in process
-or Cl
-from providing adsorption effect (getteringeffect), and be make oxygen impurities content keep low-level reason.
Up to the present, still there is following defect in this silica-based nitride red fluorescent powder: (1) luminous efficiency is still lower, about being only the half of YAG yellow fluorescent powder brightness.(2) the emmission spectrum due to this series of silicon nitride matter fluorescent powder is wider, is positioned at more than 700nm and still has comparatively multi-emitting, causes the light efficiency of packaged LED lower.(3), due to the relative inertness of nitride fluorescent powder raw material, the synthesis of silica-based nitride fluorescent material needs the severe condition such as active raw material, high temperature and high pressure usually, and this constrains suitability for industrialized production and the application of this series phosphor powder greatly.
Summary of the invention
The object of this invention is to provide a kind of luminous efficiency high, red fluorescence powder that emission wavelength is adjustable and preparation method thereof.
For solving the above technical problem, technical scheme of the present invention is:
A kind of red fluorescence powder, its chemical structural formula is: Ca
1-x-ysr
xeu
yl
zal
3o
δn
4-δ, wherein L is at least one in Li, Na, K, 0≤X < 1,0 < Y≤0.1,0.5≤Z≤1,0 < δ < 0.5.
Preferably, in above-mentioned chemical structural formula, 0 < δ≤0.25, balancing the uneven and disturbance of electric charge in the crystalline network of Tricationic Al, Eu, divalent cation Ca, Sr, Eu and monovalent cation Li, Na, K and nitrogen coordination by introducing micro amount of oxygen, regulating emission wavelength and the luminous efficiency of fluorescent material with this.
The lithium nitride aluminium calcium material of nearest appearance is by effectively can being excited by purple light or blue light after rare earth ion doped and launching the very narrow ruddiness of emission peak halfwidth, compared with traditional alkaline-earth metal silicon aluminum nitrides, be more suitable for the application requiring in backlight and display field, but in this material monovalence, divalence and Tricationic and nitrogen altogether isosteric constructional feature make it easily cause charge unbalance in local structure, defect, orderly/disorder phenomenon and affect the optical excitation of material and emitting performance and stability.
Based on more than, applicant studies discovery: by introducing luminous efficiency and the stability that micro amount of oxygen obviously can improve material in lithium nitride aluminium calcium material, the electric charge effect that is uneven and disturbance that acquisition and the micro amount of oxygen of this effect play in the crystalline network balancing Tricationic Al, Eu, divalent cation Ca, Sr, Eu and monovalent cation Li, Na, K and nitrogen coordination is relevant, thus form a kind of red fluorescence powder disclosed in this invention, have and promote the luminous efficiency of fluorescent material and the feature of stability.
The preparation method of above-mentioned red fluorescence powder, is the multistep nitrogenizing reaction method of a kind of complex hydride dehydrogenation then nitrogenize, comprises following steps successively:
A, by Ca
1-x-ysr
xeu
yl
zal
3o
δn
4-δstoichiometric ratio take raw material, mix;
B, steps A gained material is carried out high-temperature roasting in nitrogen atmosphere or nitrogen and hydrogen mixture atmosphere, maturing temperature 900 ~ 1400 DEG C, roasting time is 1 ~ 10 hour;
C, by step B gained crushing material, to sieve, obtain red fluorescence powder.
Above-mentioned steps A operates in nitrogen glove box.
Preferably, the raw material in steps A comprises CaCl2 or hydrolith, strontium nitride or hydrogenation strontium, nitrogenize europium, europium sesquioxide or europium, aluminium nitride, the hydride of L or the complex hydride of nitride, aluminium and L or nitride.
Further, for enhancing product performance, the europium sesquioxide in steps A or the mole dosage of europium are 0.2% ~ 3% of integral molar quantity.
Preferably, in step B, calcination atmosphere is N
2atmosphere or N
2/ H
2atmosphere.
Further, in step B, calcination atmosphere is N
2/ H
2atmosphere, the volume ratio of nitrogen and hydrogen is (95:5)-(75:25), and atmosphere pressures is 0.1MPa.
For improving product purity, ensureing quality product further, in step C, the material after sieving being washed, drying, obtains red fluorescence powder.
Washing main purpose removes impurity, general washing 2 times.
Above-mentioned fluorescent material is encapsulated, mixes by a certain percentage by this fluorescent material and YAG, and then be coated in blue chip surface by after certain Ratio of filler bitumen mixing, namely can be made into white light LEDs.
A principal feature of the red fluorescence powder that the present invention announces is, it a kind ofly there is micro amount of oxygen and regulate the narrowed emission nitride fluorescent material of emission wavelength and luminous efficiency.In the substrate lattice structure of this nitride material, there is the constitutional features of Tricationic Al, Eu, divalent cation Ca, Sr, Eu and monovalent cation Li, Na, K and nitrogen coordination, this feature be easy to due to the cationic omission of valence states various in structure, unordered, orderly and cause partial charge or valence state uneven and have influence on the exciting of material, emission characteristic.Found through experiments, the introducing of micro amount of oxygen has positive effect to the luminescent properties improving material.The micro amount of oxygen introduced may play the effect of the uneven and disturbance of electric charge in the crystalline network of balance Tricationic Al, Eu, divalent cation Ca, Sr, Eu and monovalent cation Li, Na, K and nitrogen coordination, plays the adjustment emission wavelength of fluorescent material and the effect of luminous efficiency with this.
Thus, the invention discloses this technical scheme being regulated the lithium nitride aluminium calcium fluorescent material of the narrowed emission of emission wavelength and luminous efficiency by micro amount of oxygen, it is in the improvement had on simple narrowed emission lithium nitride aluminium calcium fluorescent material basis and lifting, belongs to a kind of technical scheme of novelty.Fluorescent material stable in properties of the present invention, luminous efficiency significantly improves.Its emmission spectrum spike length is adjustable between 630nm to 670nm, and launch peak width at half height and only have 50nm, be highly suitable for for the very high height colour developing backlight of narrow peak width launch requirements or display device field, luminescent device can be made further, have broad application prospects in display, backlight and general illumination etc.
Accompanying drawing explanation
Fig. 1 is the SEM Electronic Speculum figure of the embodiment of the present invention 1 products obtained therefrom; ,
Fig. 2 is the XRD figure spectrum of the embodiment of the present invention 1 products obtained therefrom;
Fig. 3 is the abosrption spectrogram of the embodiment of the present invention 1 products obtained therefrom;
Fig. 4 is the utilizing emitted light spectrogram of the embodiment of the present invention 1, embodiment 2 and comparative example 1 products obtained therefrom;
Fig. 5 is the utilizing emitted light spectrogram of the embodiment of the present invention 3 and comparative example 2 products obtained therefrom;
Fig. 6 is the thermal quenching Performance comparision figure of the embodiment of the present invention 3 and comparative example 2 products obtained therefrom;
Fig. 7 is the utilizing emitted light spectrogram of the embodiment of the present invention 4 and comparative example 3 products obtained therefrom.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further combined with example below, but content of the present invention is not limited only to the following examples.
The invention provides a kind of red fluorescence powder, its chemical structural formula is: Ca
1-x-ysr
xeu
yl
zal
3o
δn
4- δ, wherein L is at least one in Li, Na, K, 0≤X < 1,0 < Y≤0.1,0.5≤Z≤1,0 < δ < 0.5.
The preparation method of above-mentioned red fluorescence powder is the multistep nitrogenizing reaction of complex hydride dehydrogenation then nitrogenize, comprises the following steps that order connects:
1) by Ca
1-x-ysr
xeu
yl
zal
3o
δn
4-δstoichiometric ratio take raw material, be ground;
2) steps A gained material is carried out high-temperature roasting in reducing atmosphere, temperature is 800 ~ 1300 DEG C, and roasting time is 1 ~ 15 hour;
3) by step B gained crushing material, sieve, obtain nitride red fluorescent powder.
Embodiment 1
Take SrH
2(4N) 0.0996mol, LiAlH
4(4N) 0.1mol, AlN (4N) 0.06667mol, Eu
2o
3(4N) 0.0002mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 900 DEG C of 0.1MpaN
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Sr
0.996eu
0.004liAl
3o
0.006n
3.96.The SEM electron microscopic picture of embodiment 1, XRD figure are composed and abosrption spectrogram is shown in Fig. 1, Fig. 2 and Fig. 3.
Embodiment 2
Take CaH
2(4N) 0.0996mol, LiAlH
4(4N) 0.1mol, AlN (4N) 0.06667mol, Eu
2o
3(4N) 0.0002mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 900 DEG C of 0.1MpaN
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Ca
0.996eu
0.004liAl
3o
0.006n
3.96.
Comparative example 1
Take Sr
3n
2(4N) 0.0332mol, LiAlH
4(4N) 0.1mol, AlN (4N) 0.06667mol, EuF
3(4N) 0.0004mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 900 DEG C of 0.1MpaN
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Sr
0.996eu
0.004liAl
3n
4.The emmission spectrum of embodiment 1 and comparative example 1 and embodiment 2 compares sees Fig. 4.
Embodiment 3
Take SrH
2(4N) 0.0992mol, LiAlH
4(4N) 0.1mol, AlN (4N) 0.06667mol, Eu
2o
3(4N) 0.0004mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 900 DEG C of 0.1MpaN
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Sr
0.996eu
0.008liAl
3o
0.012n
3.92.
Comparative example 2
Take SrH
2(4N) 0.0996mol, LiAlH4 (4N) 0.1mol, AlN (4N) 0.06667mol, Eu
2o
3(4N) 0.0002mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 1200 DEG C of 0.1MpaN
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Sr
0.996eu
0.004liAl
3o
0.006n
3.96.Embodiment 3 compares with the emmission spectrum of comparative example 2 sees Fig. 5.
Embodiment 4
Take SrH
2(4N) 0.0498mol, CaH
2(4N) 0.0498mol, LiAlH
4(4N) 0.1mol, AlN (4N) 0.06667mol, Eu
2o
3(4N) 0.0002mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 900 DEG C of 0.1MpaN
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Sr
0.498ca
0.498eu
0.004liAl
3o
0.006n
3.96.
Comparative example 3
Take SrH
2(4N) 0.0996mol, LiAlH
4(4N) 0.1mol, AlN (4N) 0.06667mol, Eu
2o
3(4N) 0.0002mol; Put into boron nitride crucible after being mixed in glove box by above-mentioned raw materials, then it is moved into rapidly in tube furnace, at 900 DEG C of 0.1Mpa0.9N
2/ 0.1H
2be incubated 4 hours in atmosphere, products obtained therefrom through fragmentation, ion, sieve, dry, obtain fluorescent material Sr
0.996eu
0.004liAl
3o
0.006n
3.96.Embodiment 4 compares with the emmission spectrum of comparative example 3 sees Fig. 6
Embodiment 5-embodiment 8, takes raw material according to stoichiometric ratio and mixes, technique with reference to embodiment 1, the emission peak wavelength of these embodiments and Relative intensity data as shown in table 1.
Table 1: the emmission spectrum of embodiment 5-embodiment 8 and comparative example 1 and spectral intensity:
Claims (10)
1. a red fluorescence powder, its chemical structural formula is: Ca
1-x-ysr
xeu
yl
zal
3o
δn
4-δ, wherein L is at least one in Li, Na, K, 0≤X < 1,0 < Y≤0.1,0.5≤Z≤1,0 < δ < 0.5.
2. red fluorescence powder as claimed in claim 1, is characterized in that: 0 < δ≤0.25.
3. a preparation method for red fluorescence powder as claimed in claim 1 or 2, is characterized in that, it is the multistep nitrogenizing reaction of complex hydride dehydrogenation then nitrogenize, comprises the following steps that order connects:
A, by Ca
1-x-ysr
xeu
yl
zal
3o
δn
4-δstoichiometric ratio take raw material, be ground;
B, steps A gained material is carried out high-temperature roasting in reducing atmosphere, temperature is 800 ~ 1300 DEG C, and roasting time is 1 ~ 15 hour;
C, by step B gained crushing material, to sieve, obtain nitride red fluorescent powder.
4. preparation method as claimed in claim 3, is characterized in that: the raw material in described steps A comprises CaCl2 or hydrolith, strontium nitride or hydrogenation strontium, nitrogenize europium, europium sesquioxide or europium, aluminium nitride, the hydride of L or the complex hydride of nitride, aluminium and L or nitride.
5. preparation method as claimed in claim 4, is characterized in that: in described steps A, the mole dosage of nitrogenize europium, europium sesquioxide or europium is 0.2% ~ 3% of raw material total mole.
6. preparation method as claimed in claim 3, is characterized in that: by oxide compound in raw material select or micro amount of oxygen in the adsorb oxygen on raw material surface or atmosphere realizes mixing of micro amount of oxygen.
7. the preparation method as described in right 3-6 any one, is characterized in that: in described step B, calcination atmosphere is N
2atmosphere or N
2/ H
2atmosphere.
8. preparation method as claimed in claim 7, is characterized in that: in described step B, calcination atmosphere is N
2/ H
2atmosphere, the volume range of nitrogen and hydrogen is (95:5) ~ (75:25), and atmosphere pressures is 0.1MPa.
9. preparation method as claimed in claim 3, is characterized in that: in described step C, by the material after sieving again through washing, dry, obtain red fluorescence powder.
10. comprise the luminescent device of red fluorescence powder according to claim 1.
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|---|---|---|---|
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| JP2018109124A (en) * | 2017-01-05 | 2018-07-12 | 太平洋セメント株式会社 | Method for producing phosphor |
| US10323184B2 (en) * | 2015-11-11 | 2019-06-18 | Nichia Corporation | Method of producing nitride fluorescent material, nitride fluorescent material, and light-emitting device using the same |
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