CN104087300A - Thiophosphate phosphor and application thereof - Google Patents
Thiophosphate phosphor and application thereof Download PDFInfo
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- CN104087300A CN104087300A CN201410103517.3A CN201410103517A CN104087300A CN 104087300 A CN104087300 A CN 104087300A CN 201410103517 A CN201410103517 A CN 201410103517A CN 104087300 A CN104087300 A CN 104087300A
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- fluor
- thiophosphate
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- twinkler
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- HWKUMLHNWXPOSD-UHFFFAOYSA-N P(O)(O)(O)=S.P Chemical compound P(O)(O)(O)=S.P HWKUMLHNWXPOSD-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 4
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- -1 thiophosphate fluor Chemical compound 0.000 claims description 23
- 238000001228 spectrum Methods 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 abstract description 8
- 230000000171 quenching effect Effects 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241001025261 Neoraja caerulea Species 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JWXBNWNTLAMNRC-UHFFFAOYSA-N S=O.[F] Chemical compound S=O.[F] JWXBNWNTLAMNRC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a thiophosphate phosphor and application thereof. The phosphor has a chemical composition general formula of: (M1-aREa)2b+cAbDxOyEz, wherein M is at least one of Ba, Sr, Ca, Mg, Zn, Sc, Y, Gd, La and Lu; RE is at least one of Eu, Ce, Yb, Dy, Nd, Pr, Sm, Ho, Er, Tb, Mn, Cr, Bi, Pb, Sn, Sb, Ni, Cu and Ag; A is at least one of P, B, Si and contains P; D is at least one of Li, Na, K, Hf, Zr, Ti, Al, Ga, In, Ge, V, Nb and Ta; E is at least one of S, Se, N, F, Cl, Br, OH and at least contains S; 0 is oxygen; and a is greater than 0 and smaller than or equal to 0.5, b is greater than or equal to 1 and smaller than or equal to 3, c is greater than or equal to 0 and smaller than or equal to 300, x is greater than or equal to 0 and smaller than or equal to 200, y is greater than 0 and smaller than or equal to 800, z is greater than 0 and smaller than or equal to 500. The phosphor provided by the invention shows high brightness luminescence and excellent temperature quenching characteristics under blue light excitation.
Description
Technical field
The present invention relates to solid luminescent material field, relate in particular to a kind of thiophosphate fluor, also relate to the luminous element, pigment and the UV light absorber that contain this fluor.
Background technology
Fluor is applied to illumination and the every field showing, especially along with the development of semiconductor lighting technology, the fluor being applied in white light LEDs has been subject to paying close attention to more and more widely.White light LEDs photoelectric transformation efficiency is high, energy-conserving and environment-protective, long service life, safe and reliable, is acknowledged as green illumination light source of future generation.The current white light LEDs of realizing mainly contains 3 kinds of approach, the first is to be combined to form white light by red, green and blue look LED chip, but it is more difficult to realize by this method white light, because will consider the drive characteristic of three different colours chips, very complicated in circuit layout.The second is to use quantum effect, uses the same semi-conductor of different-grain diameter size to prepare LED chip to realize white light, and the white light LEDs that this method realizes has higher efficiency, but cost is higher, simultaneously technical also immature.The third is to add that with the LED chip of sending out UV-light or blue light fluor realizes white light, and this method is the most simple, is also the most ripe method simultaneously.
LED has been subject to showing great attention to of countries in the world as the green illumination light source of energy-conserving and environment-protective of new generation, utilize ultraviolet or blue-ray LED excited fluophor and produce the main flow that white light is current white light LEDs development, the performance of fluor directly affects brightness, colour temperature, thermostability and the color developing etc. of white light LEDs.Along with the development of white light LEDs to high-power direction, the working temperature of LED is more and more higher, and the working temperature of current great power LED chips can reach 180 ℃, and this just requires the fluor being applied in white light LEDs must possess excellent temperature quenching characteristic.
The fluor using in white light LEDs is at present mainly blue-light excited YAG:Ce bloom, and it can effectively absorb near blue light 460nm, excited by it and launches gold-tinted, and produce white light with LED blue light.But owing to lacking red and green spectral composition in the emmission spectrum of YAG:Ce bloom, the white light LEDs colour rendering index made from it is low, can not truly show the color of object; Simultaneously the temperature quenching characteristic of YAG:Ce bloom is not outstanding, when its luminous intensity is room temperature in the time of 150 ℃, drops to 74% 87%, 200 ℃ of luminous intensity time, can not meet the application demand of large power white light LED.
The LuAG fluor that LED newly developed mainly contains silicate phosphor, nitride and oxynitride fluor and improves on YAG basis with fluor in recent years.Silicate phosphor has wider adjustable emission wavelength, and luminous efficiency is also higher, but existing silicate phosphor temperature profile is poor, as Sr
3siO
5: Eu
2and Sr
2siO
4: Eu
2luminance factor room temperature at 150 ℃ declines respectively 32% and 62%, thereby the practical application of current silicate phosphor few.
Nitride and oxynitride fluor be because having wider excitation spectrum and emmission spectrum, and heatproof characteristic and chemical stability be all better than YAG bloom, received the very big concern of white light LEDs industry.With regard to current nitride and oxynitride fluor, fluor that can be practical is mainly Sr
2si
5n
8: Eu rouge and powder and CaAlSiN
3: Eu rouge and powder.Sr
2si
5n
8: the luminosity of Eu rouge and powder is higher, but because self physical and chemical stability is with respect to CaAlSiN
3: Eu rouge and powder is slightly poor, and its luminosity at 150 ℃ is 74% while being 86%, 200 ℃ under room temperature, has limited to a certain extent it and has applied on a large scale.CaAlSiN
3: Eu rouge and powder has good physical and chemical stability and temperature quenching characteristic, and its luminosity at 150 ℃ is 82% while being 90%, 200 ℃ under room temperature, but its transmitting main peak is 650nm, in dark red wave band, luminosity is not enough, awaits further raising.
Improved LuAG:Ce fluor on the basis of YAG:Ce bloom, there is good luminous efficiency and excellent temperature quenching characteristic, its luminous efficiency under blue-ray LED excites is about 90%, luminosity at 150 ℃ is 97% under room temperature, in the time of 200 ℃, be 90%, but the LuAG:Ce fluor prices of raw and semifnished materials are more expensive, and synthesis technique is comparatively complicated.
And, conventionally by fluor for throw light on or the situation of indicating meter under, except requiring luminous efficiency height, also hope can be selected the fluor of any emission wavelength.Its reason is, under lighting condition, according to working conditions, color developing is preferential sometimes, and optical throughput is preferential sometimes.Therefore can obtain the fluor that emission wavelength is arbitrary value, useful to the design freedom of raising means of illumination.In addition, fluor, in the situation of indicating meter, can be changed to Color reproduction scope according to purposes, improve the degree of freedom of display equipment design.
In sum, the aspects such as the luminous efficiency of the fluor using at present under ultraviolet LED or blue-ray LED excite and temperature cancellation characteristic can't meet the needs of practical application completely, so the efficient LED of development of new becomes the focus of domestic and international research with fluor.
Summary of the invention
The object of the invention is for the problems referred to above, the fluor that a kind of physical and chemical stability is good is provided, it has higher luminous efficiency than existing all kinds of fluor, more excellent temperature cancellation characteristic, and the kind or the proportioning that only change its raw material can change emission wavelength.
Another object of the present invention be use that this fluor provides that luminous efficiency is high, Heat stability is good, luminous element that design freedom is good.
Another object of the present invention is to provide pigment and the UV light absorber of having used this fluor.
In order to solve above-mentioned problem, the present inventor conducts in-depth research various sulfide and oxysulfide fluor, found that, the thiophosphate fluor that contains specific chemical constitution is the excellent fluor that solves above-mentioned problem, thereby has realized the present invention.
The object of the invention is to be achieved through the following technical solutions:
The 1st invention is a kind of thiophosphate fluor, it is characterized in that: chemical constitution general formula is: (M
1-arE
a)
2b+ca
bd
xo
ye
z, wherein, M is at least one in Ba, Sr, Ca, Mg, Zn, Sc, Y, Gd, La, Lu; RE is at least one in Eu, Ce, Yb, Dy, Nd, Pr, Sm, Ho, Er, Tb, Mn, Cr, Bi, Pb, Sn, Sb, Ni, Cu, Ag; A be in P, B, Si at least one and at least contain P; D is at least one in Li, Na, K, Hf, Zr, Ti, Al, Ga, In, Ge, V, Nb, Ta; E be in S, Se, N, F, Cl, Br, OH at least one and at least contain S; O is oxygen; 0 < a≤0.5,1≤b≤3,0≤c≤300,0≤x≤200,0 < y≤800,0 < z≤500.
The 2nd invention is the related thiophosphate fluor of the 1st invention, it is characterized in that: in RE, at least contain Eu.
The 3rd invention is the related thiophosphate fluor of the 1st invention, it is characterized in that: in RE, at least contain Ce.
The 4th invention is that 1st～3 any one are invented related thiophosphate fluor, it is characterized in that: in M, at least contain Sr.
The 5th invention is that 1st～3 any one are invented related thiophosphate fluor, it is characterized in that: in M, at least contain Ca.
The 6th invention is that 1st～5 any one are invented related thiophosphate fluor, it is characterized in that: 0.5≤c≤100,0≤x≤60,2≤y≤300,0 < z≤60; Preferred 1≤c≤60,0≤x≤40,3≤y≤200,0 < z≤40; 2≤c≤20 more preferably, 0≤x≤10,4≤y≤50,0 < z≤10.
The 7th invention is a kind of luminous element, it comprises the 1st twinkler and the 2nd twinkler, the 1st twinkler sends the light with the 1st luminescent spectrum, the 2nd twinkler has at least a portion of the light of the 1st luminescent spectrum described in absorbing, and sends the light with 2nd luminescent spectrum different with described the 1st luminescent spectrum; It is characterized in that: as the 2nd twinkler, contain the described thiophosphate fluor of 1st～6 any one invention.
The 8th invention is the related luminous element of the 7th invention, it is characterized in that: as the 1st twinkler, especially use photodiode or laser diode, or the discharge lamp based on low pressure or high pressure, or electroluminescent lamp.
The 9th invention is a kind of pigment, it is characterized in that: contain the described thiophosphate fluor of 1st～6 any one invention.
The 10th invention is a kind of UV light absorber, it is characterized in that: contain the described thiophosphate fluor of 1st～6 any one invention.
Thiophosphate fluor of the present invention can also with for example blue light OLED use that is associated of other ultraviolet source or blue light source, or be combined with blue light EL luminescent material.EL represents electroluminescent.
Accompanying drawing explanation
Fig. 1 is the excitation spectrum of the embodiment of the present invention 1 fluor and the 460nm wavelength utilizing emitted light spectrogram under blue-light excited.
Fig. 2 is the embodiment of the present invention 1 fluor and comparative example CaAlSiN
3: the temperature quenching performance diagram of the commercial fluor of Eu under 460nm wavelength is blue-light excited.
Embodiment
Thiophosphate fluor of the present invention can adopt the technique preparations such as high temperature solid phase synthesis, coprecipitation method, sol-gel method, microwave sintering synthesis method, the technological process of its high temperature solid phase synthesis is: the simple substance or the compound that according to chemical formula component, take respective element, and add boric acid, halogenide, alkaline carbonate at least one as fusing assistant, the addition of fusing assistant is 0.01～10% of raw material total mass.Ground and mixed evenly after, in reducing atmosphere at 800 ℃～1800 ℃ sintering 1～30 hour, obtain product.In addition, in order to obtain the uniform fluor of crystalline phase, also the fluor obtaining can be repeated to pulverize, fire again.Described reducing atmosphere is at least one in charcoal, sulphur, carbon monoxide, hydrogen, nitrogen, ammonia, dithiocarbonic anhydride and hydrogen sulfide.
Below by embodiment, the present invention is described more specifically, but only otherwise exceed aim of the present invention, the present invention is not subject to any restriction of following embodiment.
Embodiment 1:Sr
6.8mgY
2p
2siO
17s:Eu
0.2synthesizing of fluor:
At chemical constitution general formula (M
1-arE
a)
2b+ca
bd
xo
ye
zin, set M=(Sr, Mg, Y), RE=Eu, A=(P, Si), E=S, weighs various raw materials, is Sr: Mg: Y: P: Si: O: S: Eu=6.8: 1: 2: 2: 1: 17: 1: 0.2 (a=0.02, b=3, c=4, x=0, y=17, z=1) so that form the mol ratio of ion.
Take 5.6gSrCO
3, 3.67gSrHPO
4, 1.83gSrSO
4, 0.4gMgO, 2.25gY
2o
3, 0.6gSiO
2, 0.35gEu
2o
3, and add 0.12gH
3bO
3as solubility promoter, after abundant ground and mixed is even, pack alumina crucible roasting in reducing atmosphere into, in 1450 ℃ of insulations 2 hours, obtain described fluor.Its excitation spectrum and emmission spectrum are shown in Fig. 1, and emmission spectrum halfwidth is about 55nm, and transmitting main peak is in the ruddiness region of 630nm; Excitation spectrum is a broadband excitation spectrum, and the ultraviolet ray within the scope of 200～500nm or visible ray all can effectively excite; Its luminous intensity is in Table 1, the fluor that the present invention makes as can be seen from Table 1, and the luminous intensity of luminous intensity during its room temperature and 200 ℃ is all higher than comparative example CaAlSiN
3: the commercial fluor of Eu.
Fig. 2 is embodiment 1Sr
6.8mgY
2p
2siO
17s:Eu
0.2fluor and comparative example CaAlSiN
3: the temperature quenching performance diagram of the commercial fluor of Eu under 460nm wavelength is blue-light excited.Embodiment 1 fluor has excellent temperature quenching characteristic as can be seen from Figure 2, and within the scope of 300 ℃, its luminous intensity almost remains unchanged with the rising of temperature.
Embodiment 2～16:
At chemical constitution general formula (M
1-arE
a)
2b+ca
bd
xo
ye
zin, set M=(Sr, Ca, Ba, Mg, Zn, Y, La), RE=Eu, A=(P, B, Si), E=S, forms and takes various raw materials by the concrete chemical formula of each embodiment in table 1, and preparation process is identical with embodiment 1, and the characteristics of luminescence of the fluor obtaining is in Table 1.
The chemical formula of table 1 embodiment 1～16 and the characteristics of luminescence thereof (excitation wavelength is 460nm)
Embodiment 17～31:
In chemical constitution formula M
1-arE
a)
2b+ca
bd
xo
ye
zin, set M=(Sr, Ca, Mg, Y), RE=(Eu, Ce, Ho, Er, Nd), A=P, E=S, forms and takes various raw materials by the concrete chemical formula of each embodiment in table 2, and preparation process is identical with embodiment 1, and the characteristics of luminescence of the fluor obtaining is in Table 2.
The chemical formula of table 2 embodiment 17～31 and the characteristics of luminescence thereof (excitation wavelength is 460nm)
Embodiment 32～41:
At chemical constitution general formula (M
1-arE
a)
2b+ca
bd
xo
ye
zin, set M=(Sr, Ca, Mg, Zn, Y), RE=Eu, A=(P, Si), D=(Al, Li, Zr), E=(S, F, Cl), forms and takes various raw materials by the concrete chemical formula of each embodiment in table 3, and preparation process is identical with embodiment 1, and the characteristics of luminescence of the fluor obtaining is in Table 3.
The chemical formula of table 3 embodiment 32～41 and the characteristics of luminescence thereof (excitation wavelength is 460nm)
Fluor of the present invention shows than luminous, the more excellent thermal stability of the higher briliancy of existing fluor, so it is suitable for white light emitting device, lighting fixtures, VFD, FED, PDP, CRT etc.In addition, fluor of the present invention can easily be adjusted the peak width of emission wavelength and glow peak, so practicality is industrially large, can expect that from now on flexible Application is in the design of material of various light-emitting devices, illumination, image display device, the development of Promoting Industrial.
Although utilize specific mode to understand in detail the present invention, it will be apparent to those skilled in the art that and can carry out multiple change in the intent and scope of the present invention not departing from.
Claims (10)
1. a thiophosphate fluor, is characterized in that: the chemical constitution general formula of described fluor is:
(M
1-arE
a)
2b+ca
bd
xo
ye
z, wherein, M is at least one in Ba, Sr, Ca, Mg, Zn, Sc, Y, Gd, La, Lu; RE is at least one in Eu, Ce, Yb, Dy, Nd, Pr, Sm, Ho, Er, Tb, Mn, Cr, Bi, Pb, Sn, Sb, Ni, Cu, Ag; A be in P, B, Si at least one and at least contain P; D is at least one in Li, Na, K, Hf, Zr, Ti, Al, Ga, In, Ge, V, Nb, Ta; E be in S, Se, N, F, Cl, Br, OH at least one and at least contain S; O is oxygen; 0 < a≤0.5,1≤b≤3,0≤c≤300,0≤x≤200,0 < y≤800,0 < z≤500.
2. thiophosphate fluor according to claim 1, is characterized in that: in RE, at least contain Eu.
3. thiophosphate fluor according to claim 1, is characterized in that: in RE, at least contain Ce.
4. according to the thiophosphate fluor described in claim 1～3 any one, it is characterized in that: in M, at least contain Sr.
5. according to the thiophosphate fluor described in claim 1～3 any one, it is characterized in that: in M, at least contain Ca.
6. according to the thiophosphate fluor described in claim 1～5 any one, it is characterized in that: 0.5≤c≤100,0≤x≤60,2≤y≤300,0 < z≤60; Preferred 1≤c≤60,0≤x≤40,3≤y≤200,0 < z≤40; 2≤c≤20 more preferably, 0≤x≤10,4≤y≤50,0 < z≤10.
7. a luminous element, it comprises the 1st twinkler and the 2nd twinkler, the 1st twinkler sends the light with the 1st luminescent spectrum, has at least a portion of the light of the 1st luminescent spectrum, and send the light with 2nd luminescent spectrum different with described the 1st luminescent spectrum described in the 2nd twinkler absorbs; It is characterized in that: as the 2nd twinkler containing the thiophosphate fluor described in good grounds claim 1～6 any one.
8. luminous element according to claim 7, is characterized in that: as the 1st twinkler, use photodiode or laser diode, or the discharge lamp based on low pressure or high pressure, or electroluminescent lamp.
9. a pigment, is characterized in that: described pigment is containing the thiophosphate fluor described in good grounds claim 1～6 any one.
10. a UV light absorber, is characterized in that: described UV light absorber is containing the thiophosphate fluor described in good grounds claim 1～6 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410103517.3A CN104087300B (en) | 2014-03-20 | 2014-03-20 | A kind of thiophosphate fluorophor and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410103517.3A CN104087300B (en) | 2014-03-20 | 2014-03-20 | A kind of thiophosphate fluorophor and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104087300A true CN104087300A (en) | 2014-10-08 |
| CN104087300B CN104087300B (en) | 2017-03-15 |
Family
ID=51635065
Family Applications (1)
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| CN201410103517.3A Expired - Fee Related CN104087300B (en) | 2014-03-20 | 2014-03-20 | A kind of thiophosphate fluorophor and its application |
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| CN106047347A (en) * | 2016-06-29 | 2016-10-26 | 东台市天源荧光材料有限公司 | Manganese-ion-activated yttrium calcium phosphate fluorescent powder and preparation method thereof |
| CN106634997A (en) * | 2016-09-21 | 2017-05-10 | 王海容 | Composite phosphate fluorophor and application thereof |
| CN106634996A (en) * | 2016-09-21 | 2017-05-10 | 王海容 | Fluorophor and application method thereof |
| CN108503353A (en) * | 2017-11-27 | 2018-09-07 | 福鼎市溥昱电子科技有限公司 | A kind of composite phosphate series microwave dielectric ceramic and preparation method thereof |
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| CN104087300B (en) | 2017-03-15 |
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