CN104073257A - Glucosinolate silicate phosphor and application thereof - Google Patents
Glucosinolate silicate phosphor and application thereof Download PDFInfo
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- CN104073257A CN104073257A CN201410103520.5A CN201410103520A CN104073257A CN 104073257 A CN104073257 A CN 104073257A CN 201410103520 A CN201410103520 A CN 201410103520A CN 104073257 A CN104073257 A CN 104073257A
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- fluor
- acid salt
- twinkler
- light
- thiosilicic acid
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Abstract
The invention relates to a glucosinolate silicate phosphor and an application thereof. The general formula of the chemical composition of the phosphor is (M1-aREa)bDxSiOyEz, 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; 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 and OH, and at least contains S; O is oxygen; a is smaller than or equal to 0.5 and greater than 0; b is smaller than or equal to 200 and greater than or equal to 3.5; x is smaller than or equal to 100 and greater than or equal to 0; y is smaller than or equal to 500 and greater than 0; z is smaller than or equal to 200 and greater than 0. The phosphor disclosed by the invention can show high-brightness luminescence characteristics and good quenching temperature characteristics under ultraviolet and blue light excitation.
Description
Technical field
The present invention relates to solid luminescent material field, relate in particular to a kind of thiosilicic acid salt 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 white light LEDs is to the development of 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 DEG C, and this fluor that just requires to be 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, it can effectively absorb near blue light 460nm, excited by it and launches gold-tinted, and produce white light with LED blue light.But due to YAG: lack red and green spectral composition in the emmission spectrum of Ce bloom, the white light LEDs colour rendering index made from it is low, can not truly show the color of object; Simultaneously YAG: the temperature quenching characteristic of Ce bloom is not outstanding, drops to 74% 87%, 200 DEG C of luminous intensity time when its luminous intensity is room temperature in the time of 150 DEG C, 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 DEG C 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 DEG C is 74% while being 86%, 200 DEG C 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 DEG C is 82% while being 90%, 200 DEG C under room temperature, but its transmitting main peak is 650nm, in dark red wave band, luminosity deficiency, awaits further raising.
At YAG: improved LuAG on the basis of Ce bloom: Ce fluor, there is good luminous efficiency and excellent temperature quenching characteristic, its luminous efficiency under blue-ray LED excites is about 90%, luminosity at 150 DEG C is 97% under room temperature, 200 DEG C time, be 90%, but LuAG: the Ce fluor prices of raw and semifnished materials are more expensive, and synthesis technique is comparatively complicated, and cost is higher.
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 aspect such as luminous efficiency and temperature cancellation characteristic of the fluor using at present under ultraviolet LED or blue-ray LED excite can't meet the needs of practical application completely, and therefore 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 of a kind of physical and chemical stability and good thermal stability is provided, it has higher luminous efficiency than existing all kinds of fluor, 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 the pigment and the UV light absorber that have 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 thiosilicic acid salt 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 thiosilicic acid salt fluor, it is characterized in that: chemical constitution general formula is: (M
1-arE
a)
bd
xsiO
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; 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≤0.5,3.5≤b≤200,0≤x≤100,0<y≤500,0<z≤200.
The 2nd invention is the related thiosilicic acid salt fluor of the 1st invention, it is characterized in that: in RE, at least contain Eu.
The 3rd invention is the related thiosilicic acid salt 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 thiosilicic acid salt fluor, it is characterized in that: in M, at least contain Sr.
The 5th invention is that 1st～3 any one are invented related thiosilicic acid salt fluor, it is characterized in that: in M, at least contain Ca.
The 6th invention is that 1st～5 any one are invented related thiosilicic acid salt fluor, it is characterized in that: 3.5≤b≤100,0≤x≤50,2≤y≤300,0<z≤100; Preferably 3.5≤b≤50,0≤x≤20,3≤y≤100,0<z≤30; More preferably 3.5≤b≤20,0≤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: contain the described thiosilicic acid salt fluor of 1st～6 any one invention as the 2nd twinkler.
The 8th invention is the related luminous element of the 7th invention, it is characterized in that: especially use photodiode or laser diode as the 1st twinkler, or 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 thiosilicic acid salt 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 thiosilicic acid salt fluor of 1st～6 any one invention.
The thiosilicic acid salt fluor of the present invention use that can also be associated with other ultraviolet source or for example blue light OLED of blue light source, or be combined with blue light EL luminescent material.EL represents electroluminescent.
Brief description of the drawings
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
Thiosilicic acid salt 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 take respective element according to chemical formula component, 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 DEG C～1800 DEG C 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
6.6mgY
2al
2siO
15s: Eu
0.4synthesizing of fluor:
At chemical constitution general formula (M
1-arE
a)
bd
xsiO
ye
zin, set M=(Sr, Mg, Y), RE=Eu, D=Al, E=S, weighs various raw materials, is Sr: Mg: Y: Al: Si: O: S: Eu=6.6: 1: 2: 2: 1: 15: 1: 0.4 (a=0.04, b=10, x=2, y=15, z=1) so that form the mol ratio of ion.
Take 8.26gSrCO
3, 1.83gSrSO
4, 0.4gMgO, 2.25gY
2o
3, 1.02gAl
2o
3, 0.6gSiO
2, 0.7gEu
2o
3, and add 0.12gH
3bO
3as fusing assistant, after abundant ground and mixed is even, pack alumina crucible roasting in reducing atmosphere into, in 1450 DEG C of insulations 2 hours, obtain described fluor.Its excitation spectrum and emmission spectrum are shown in Fig. 1, and emmission spectrum halfwidth is about 75nm, and transmitting main peak is in the ruddiness region of 635nm; 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 when its room temperature and 200 DEG C is all higher than comparative example CaAlSiN
3: the commercial fluor of Eu.
Fig. 2 is embodiment 1Sr
6.6mgY
2al
2siO
15s: Eu
0.4fluor and comparative example CaAlSiN
3: the temperature quenching performance diagram of the commercial fluor of Eu under 460nm wavelength is blue-light excited.Sr as can be seen from Figure 2
6.6mgY
2b
2siO
15s: Eu
0.4fluor has good temperature quenching characteristic, and the luminous intensity at 150 DEG C is 85% while being 92%, 200 DEG C under room temperature.
Embodiment 2～13:
At chemical constitution general formula (M
1-arE
a)
bd
xsiO
ye
zin, set M=(Sr, Ca, Ba, Mg, Zn, Y, La), RE=Eu, D=Al, E=S, the chemical formula composition concrete by each embodiment in table 1 takes various raw materials, 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 1～13 and the characteristics of luminescence thereof (excitation wavelength is 460nm)
Embodiment 14～24:
At chemical constitution general formula (M
1-arE
a)
bd
xsiO
ye
zin, set M=(Sr, Ca, Mg, Y), RE=(Eu, Ce, Ho, Er, Nd), E=S, the chemical formula composition concrete by each embodiment in table 2 takes various raw materials, 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 14～24 and the characteristics of luminescence thereof (excitation wavelength is 460nm)
Embodiment 25～30:
At chemical constitution general formula (M
1-arE
a)
bd
xsiO
ye
zin, set M=(Sr, Ca, Mg, Zn, Y), RE=Eu, D=(Al, Li, Zr), E=(S, F, Cl), the chemical formula composition concrete by each embodiment in table 3 takes various raw materials, 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 25～30 and the characteristics of luminescence thereof (excitation wavelength is 460nm)
Fluor of the present invention shows than luminous, the good 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 thiosilicic acid salt fluor, is characterized in that: the chemical constitution general formula of described fluor is:
(M
1-arE
a)
bd
xsiO
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; 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≤0.5,3.5≤b≤200,0≤x≤100,0<y≤500,0<z≤200.
2. thiosilicic acid salt fluor according to claim 1, is characterized in that: in RE, at least contain Eu.
3. thiosilicic acid salt fluor according to claim 1, is characterized in that: in RE, at least contain Ce.
4. according to the thiosilicic acid salt fluor described in claim 1～3 any one, it is characterized in that: in M, at least contain Sr.
5. according to the thiosilicic acid salt fluor described in claim 1～3 any one, it is characterized in that: in M, at least contain Ca.
6. according to the thiosilicic acid salt fluor described in claim 1～5 any one, it is characterized in that: 3.5≤b≤100,0≤x≤50,2≤y≤300,0<z≤100; Preferably 3.5≤b≤50,0≤x≤20,3≤y≤100,0<z≤30; More preferably 3.5≤b≤20,0≤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 thiosilicic acid salt fluor described in good grounds claim 1～6 any one.
8. luminous element according to claim 7, is characterized in that: use photodiode or laser diode as the 1st twinkler, or discharge lamp based on low pressure or high pressure, or electroluminescent lamp.
9. a pigment, is characterized in that: described pigment is containing the thiosilicic acid salt 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 thiosilicic acid salt fluor described in good grounds claim 1～6 any one.
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|---|---|---|---|
| CN201410103520.5A CN104073257B (en) | 2014-03-20 | 2014-03-20 | A kind of thiosilicic acid salt fluorophor and application thereof |
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|---|---|---|---|
| CN201410103520.5A CN104073257B (en) | 2014-03-20 | 2014-03-20 | A kind of thiosilicic acid salt fluorophor and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018088A (en) * | 2015-07-06 | 2015-11-04 | 河北大学 | Silicate-based rare-earth ion doped visible-ultraviolet up-conversion luminescent material, and preparation method and application thereof |
| JPWO2020188913A1 (en) * | 2019-03-15 | 2020-09-24 |
Citations (2)
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|---|---|---|---|---|
| CN101397498A (en) * | 2006-09-28 | 2009-04-01 | 佳能株式会社 | Electron beam-excited blue phosphor |
| CN102719245A (en) * | 2012-06-25 | 2012-10-10 | 重庆文理学院 | Secondary excitation type orange-red fluorescent powder and preparation method thereof |
-
2014
- 2014-03-20 CN CN201410103520.5A patent/CN104073257B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397498A (en) * | 2006-09-28 | 2009-04-01 | 佳能株式会社 | Electron beam-excited blue phosphor |
| CN102719245A (en) * | 2012-06-25 | 2012-10-10 | 重庆文理学院 | Secondary excitation type orange-red fluorescent powder and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| MEIDAN QUE ET AL.: "Crystal structure and luminescence properties of a cyan emitting Ca10(SiO4)3(SO4)3F2:Eu2+ phosphor", 《CRYSTENGCOMM》 * |
| MEIDAN QUE ET AL.: "Crystal structure and luminescence properties of a cyan emitting Ca10(SiO4)3(SO4)3F2:Eu2+ phosphor", 《CRYSTENGCOMM》, 31 May 2013 (2013-05-31) * |
| XIN ZHAO ET AL.: "Tunable orange red phosphors: S2--doped high temperature phase Ca3SiO4Cl2:Eu2+ for solid-state lighting", 《RSC ADVANCES》 * |
| XIN ZHAO ET AL.: "Tunable orange red phosphors: S2--doped high temperature phase Ca3SiO4Cl2:Eu2+ for solid-state lighting", 《RSC ADVANCES》, 28 November 2012 (2012-11-28) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018088A (en) * | 2015-07-06 | 2015-11-04 | 河北大学 | Silicate-based rare-earth ion doped visible-ultraviolet up-conversion luminescent material, and preparation method and application thereof |
| JPWO2020188913A1 (en) * | 2019-03-15 | 2020-09-24 |
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|---|---|
| CN104073257B (en) | 2016-11-09 |
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