CN104073257B - A kind of thiosilicic acid salt fluorophor and application thereof - Google Patents
A kind of thiosilicic acid salt fluorophor and application thereof Download PDFInfo
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- CN104073257B CN104073257B CN201410103520.5A CN201410103520A CN104073257B CN 104073257 B CN104073257 B CN 104073257B CN 201410103520 A CN201410103520 A CN 201410103520A CN 104073257 B CN104073257 B CN 104073257B
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Abstract
The present invention relates to a kind of thiosilicic acid salt fluorophor and application thereof, this fluorophor chemical composition formula is: (M1‑aREa)bDxSiOyEz, 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 is at least one in S, Se, N, F, Cl, Br, OH and at least contains S；O is oxygen；0 < a≤0.5,3.5≤b≤200,0≤x≤100,0 < y≤500,0 < z≤200.The fluorophor of the present invention shows the luminescence of high briliancy and good temperature quenching feature under ultraviolet and blue light excite.
Description
Technical field
The present invention relates to solid luminescent material field, relate in particular to a kind of thiosilicic acid salt fluorophor, further relate to containing this
Plant light-emitting component, pigment and the ultra-violet absorber of fluorophor.
Background technology
Fluorophor is applied to the every field of illumination and display, especially with the development of semiconductor illumination technique, is applied to
Fluorophor in white light LEDs receives increasingly to be paid close attention to widely.White light LEDs photoelectric transformation efficiency height, energy-conserving and environment-protective, make
It by life-span length, safe and reliable, is acknowledged as green illumination light source of future generation.Currently realize that white light LEDs mainly has 3 kinds of approach,
The first is to form white light by the combination of red, green and blue look LED chip, but realizes that white light is relatively difficult by this method,
Because it is very complicated in circuit design in view of the drive characteristic of three different colours chips.The second is to use quantum effect,
The same semiconductor using different-grain diameter size prepares LED chip to realize white light, the white light LEDs tool that this method realizes
There is higher efficiency, but relatively costly, simultaneously technically also immature.The third is to use to send out ultraviolet light or blue light
LED chip realizes white light plus fluorophor, and this method is the most simple, is also method the most ripe simultaneously.
LED receives the highest attention of countries in the world as the green illumination light source of a new generation's energy-conserving and environment-protective, utilizes ultraviolet or indigo plant
Light LED excited fluophor and produce white light be current white light LEDs development main flow, the performance of fluorophor directly affects white light LEDs
Brightness, colour temperature, heat endurance and colour rendering etc..As white light LEDs is to the development in high-power direction, the work temperature of LED
Spending more and more higher, the operating temperature of current great power LED chips can reach 180 DEG C, and this requires to be applied to white light LEDs
In fluorophor must possess excellent temperature quenching characteristic.
The fluorophor using in current white light LEDs is mainly blue light activated YAG: Ce bloom, and it is attached that it can effectively absorb 460nm
Near blue light, is excited by it and launches gold-tinted, and produces white light with LED blue light.But due to YAG: Ce bloom
Emission spectrum lacks red and green spectral components, low with its white light LEDs colour rendering index made, it is impossible to truly to show thing
The color of body；The temperature quenching characteristic of YAG: Ce bloom is not outstanding simultaneously, and when 150 DEG C, its luminous intensity is sent out when being room temperature
The 87% of luminous intensity, then drops to 74%, it is impossible to meet the application demand of large power white light LED when 200 DEG C.
LED fluorophor newly developed in recent years mainly have silicate phosphor, nitride and nitrogen oxides fluorophor and
The LuAG fluorophor of improvement on the basis of YAG.Silicate phosphor has wider adjustable transmission wavelength, and luminous efficiency also compares
Height, but existing silicate phosphor temperature characterisitic is poor, such as Sr3SiO5∶Eu2And Sr2SiO4∶Eu2Brightness ratio at 150 DEG C
Room temperature declines 32% and 62% respectively, thus the actual application of current silicate phosphor is simultaneously few.
Nitride and nitrogen oxides fluorophor are because having wider excitation spectrum and emission spectrum, and temperature-resistance characteristic and chemically stable
Property be superior to YAG bloom, receive the very big concern of white light LEDs industry.With regard to current nitride and nitrogen oxides fluorophor
For, fluorophor that can be practical is mainly Sr2Si5N8: Eu rouge and powder and CaAlSiN3: Eu rouge and powder.Sr2Si5N8: Eu rouge and powder
Luminosity is higher, but owing to the physical and chemical stability of self is relative to CaAlSiN3: Eu rouge and powder is slightly poor, and it is 150
Luminosity at DEG C is 86% under room temperature, is 74% when 200 DEG C, limits its large-scale application to a certain extent.
CaAlSiN3: Eu rouge and powder has good physical and chemical stability and temperature quenching characteristic, and its luminosity at 150 DEG C is
Under room temperature 90%, is 82% when 200 DEG C, but its transmitting main peak is 650nm, is in dark red wave band, and luminosity is not enough,
Await improving further.
Improved LuAG: Ce fluorophor on the basis of YAG: Ce bloom, has preferable luminous efficiency and excellent temperature is sudden
Going out characteristic, its luminous efficiency under blue-ray LED excites is about 90%, and the luminosity at 150 DEG C is 97% under room temperature,
It is 90% when 200 DEG C, but LuAG: the Ce fluorophor prices of raw materials are costly, and synthesis technique is complex, relatively costly.
And, in the case of generally fluorophor being used for illumination or display, in addition to requiring that luminous efficiency is high, it is also desirable to energy
Enough select the fluorophor of any emission wavelength.Its reason is, under lighting condition, according to the condition of use, sometimes develops the color
Property preferential, luminous flux is preferential sometimes.Therefore if obtaining the fluorophor that emission wavelength is arbitrary value, to raising lighting device
Design freedom useful.In the case of in addition, fluorophor is used for display, Color reproduction scope can be changed according to purposes,
Improve the free degree of display equipment design.
In sum, luminous efficiency ultraviolet LED or blue-ray LED excite under for the fluorophor using at present and temperature cancellation spy
The aspects such as property can't fully meet the needs of actual application, and therefore developing new and effective LED fluorophor becomes domestic and international
The focus of research.
Content of the invention
It is an object of the invention to, for the problems referred to above, provide the fluorophor of a kind of physical and chemical stability and good thermal stability,
It has a higher luminous efficiency than existing all kinds of fluorophor, and only changes the species of its raw material or proportioning can change luminescence
Wavelength.
Another object of the present invention is to use this fluorophor to provide luminous efficiency height, Heat stability is good, design freedom good
Light-emitting component.
It is a further object to provide pigment and the ultra-violet absorber employing this fluorophor.
In order to solve above-mentioned problem, various sulfide and oxysulfide fluorophor are deeply ground by the present inventor
Study carefully, it was found that the thiosilicic acid salt fluorophor containing specified chemical composition is the excellent fluorophor solving above-mentioned problem, from
And achieve the present invention.
It is an object of the invention to be achieved through the following technical solutions:
1st invention is a kind of thiosilicic acid salt fluorophor, it is characterised in that: chemical composition formula is: (M1-aREa)bDxSiOyEz, wherein, M is at least one in Ba, Sr, Ca, Mg, Zn, Sc, Y, Gd, La, Lu；RE is
Eu、Ce、Yb、Dy、Nd、Pr、Sm、Ho、Er、Tb、Mn、Cr、Bi、Pb、Sn、Sb、Ni、Cu、Ag
Middle at least one；D is at least one in Li, Na, K, Hf, Zr, Ti, Al, Ga, In, Ge, V, Nb, Ta；
E is at least one in S, Se, N, F, Cl, Br, OH and at least contains S；O is oxygen；0 < a≤0.5,3.5≤b≤200,
0≤x≤100,0 < y≤500,0 < z≤200.
2nd invention is the involved thiosilicic acid salt fluorophor of the 1st invention, it is characterised in that: RE at least contains Eu.
3rd invention is the involved thiosilicic acid salt fluorophor of the 1st invention, it is characterised in that: RE at least contains Ce.
4th invention is the involved thiosilicic acid salt fluorophor of the 1st～3 any one invention, it is characterised in that: M at least contains
There is Sr.
5th invention is the involved thiosilicic acid salt fluorophor of the 1st～3 any one invention, it is characterised in that: M at least contains
There is Ca.
6th invention is the involved thiosilicic acid salt fluorophor of the 1st～5 any one invention, it is characterised 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.
7th invention is a kind of light-emitting component, and it includes the 1st illuminator and the 2nd illuminator, and the 1st illuminator sends has the
The light of 1 luminescent spectrum, the 2nd illuminator absorb described in there is at least a portion of light of the 1st luminescent spectrum, and send and have
The light of 2nd luminescent spectrum different with described 1st luminescent spectrum；It is characterized in that: contain the 1st～6 as the 2nd illuminator
The described thiosilicic acid salt fluorophor of any one invention.
8th invention is the involved light-emitting component of the 7th invention, it is characterised in that: especially use luminescence as the 1st illuminator
Diode or laser diode, or the discharge lamp based on low pressure or high pressure, or electroluminescent lamp.
9th invention is a kind of pigment, it is characterised in that: containing the described thiosilicic acid salt fluorophor of the 1st～6 any one invention.
10th invention is a kind of ultra-violet absorber, it is characterised in that: containing the sulphur described in the 1st～6 any one invention for silicon
Hydrochlorate fluorophor.
Thiosilicic acid salt fluorophor of the present invention can also be related to other ultraviolet sources or blue light source such as Nan dian Yao
Connection uses, or is used in combination with blue light EL luminescent material.EL represents electroluminescent.
Brief description
Fig. 1 is the excitation spectrum of the embodiment of the present invention 1 fluorophor and 460nm wavelength blue light excite under emission spectrum figure.
Fig. 2 is the embodiment of the present invention 1 fluorophor and comparative example CaAlSiN3: Eu is commercial, and fluorophor swashs at 460nm wavelength blue light
The temperature quenching performance diagram given.
Detailed description of the invention
Thiosilicic acid salt fluorophor of the present invention can use high temperature solid phase synthesis, coprecipitation, sol-gal process, microwave
Prepared by the techniques such as sintering synthetic method, the technical process of its high temperature solid phase synthesis is: weigh respective element according to chemical formula component
Simple substance or compound, and add boric acid, halide, at least one of alkali carbonate as flux, flux
Addition is the 0.01～10% of raw material gross mass.After ground and mixed is uniform, burn at 800 DEG C～1800 DEG C in reducing atmosphere
Tie 1～30 hour, i.e. obtain product.In addition, in order to obtain the uniform fluorophor of crystalline phase, it is also possible to the fluorophor that will obtain
Carry out repeating to pulverize, fire again.Described reducing atmosphere is charcoal, sulphur, carbon monoxide, hydrogen, nitrogen, ammonia, curing
At least one in carbon and hydrogen sulfide.
Further illustrating the present invention below by embodiment, but as long as without departing from spirit of the invention, the present invention is not
Any restriction by following embodiment.
Embodiment 1:Sr6.6MgY2Al2SiO15S∶Eu0.4The synthesis of fluorophor:
At chemical composition formula (M1-aREa)bDxSiOyEzIn, set M=(Sr, Mg, Y), RE=Eu, D=Al, E=S, claim
Measure various raw material, so that the mol ratio constituting ion 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)。
Weigh 8.26gSrCO3、1.83gSrSO4、0.4gMgO、2.25gY2O3、1.02gAl2O3、0.6gSiO2、0.7gEu2O3,
And add 0.12gH3BO3It as flux, is fully ground after mixing, load alumina crucible roasting in reducing atmosphere,
It is incubated 2 hours in 1450 DEG C, obtain described fluorophor.Its excitation spectrum and emission spectrum are shown in Fig. 1, emission spectrum halfwidth
It is about 75nm, launch main peak in the red light region of 635nm；Excitation spectrum is a broadband excitation spectrum, 200～500nm model
Ultraviolet in enclosing or visible ray all can effectively excite；Its luminous intensity is shown in Table 1, and the present invention prepares as can be seen from Table 1
Fluorophor, the luminous intensity of luminous intensity during its room temperature and 200 DEG C is above comparative example CaAlSiN3: the commercial fluorophor of Eu.
Fig. 2 is embodiment 1Sr6.6MgY2Al2SiO15S∶Eu0.4Fluorophor and comparative example CaAlSiN3: Eu is commercial, and fluorophor exists
460nm wavelength blue light excite under temperature quenching performance diagram.Sr as can be seen from Figure 26.6MgY2B2SiO15S∶Eu0.4Fluorescence
Body has good temperature quenching characteristic, and the luminous intensity at 150 DEG C is 92% under room temperature, is 85% when 200 DEG C.
Embodiment 2～13:
At chemical composition formula (M1-aREa)bDxSiOyEzIn, set M=(Sr, Ca, Ba, Mg, Zn, Y, La), RE=Eu, D
=Al, E=S, weigh various raw material by the concrete chemical formula composition of each embodiment in table 1, and preparation process is same as in Example 1,
The characteristics of luminescence of the fluorophor obtaining is shown in Table 1.
The chemical formula of table 1 embodiment 1～13 and the characteristics of luminescence (excitation wavelength is 460nm) thereof
Embodiment 14～24:
At chemical composition formula (M1-aREa)bDxSiOyEzIn, set M=(Sr, Ca, Mg, Y), RE
=(Eu, Ce, Ho, Er, Nd), E=S, weigh various raw material, preparation process by the concrete chemical formula composition of each embodiment in table 2
Same as in Example 1, the characteristics of luminescence of the fluorophor obtaining is shown in Table 2.
The chemical formula of table 2 embodiment 14～24 and the characteristics of luminescence (excitation wavelength is 460nm) thereof
Embodiment 25～30:
At chemical composition formula (M1-aREa)bDxSiOyEzIn, set M=(Sr, Ca, Mg, Zn, Y), RE=Eu, D
=(Al, Li, Zr), E=(S, F, Cl), weigh various raw material by the concrete chemical formula composition of each embodiment in table 3, preparation process with
Embodiment 1 is identical, and the characteristics of luminescence of the fluorophor obtaining is shown in Table 3.
The chemical formula of table 3 embodiment 25～30 and the characteristics of luminescence (excitation wavelength is 460nm) thereof
The fluorophor of the present invention shows the luminescence of the higher briliancy than existing fluorophor, good thermal stability, so it is fitted
Share in white light emitting device, ligthing paraphernalia, VFD, FED, PDP, CRT etc..In addition, the fluorescence physical efficiency of the present invention
It is enough easily adjusted the peak width of emission wavelength and glow peak, so practicality industrially is big, can expect flexibly should from now on
For various light-emitting devices, illumination, the design of material of image display device, the development of Promoting Industrial.
Although utilizing specific mode to be described in detail by the present invention, it will be evident to those skilled in the art that can be without departing from this
It is variously changed in the intention of invention and scope.
Claims (5)
1. a thiosilicic acid salt fluorophor, it is characterised in that: the chemical formula of described fluorophor is:
Sr6.6MgY2Al2SiO15S:Eu0.4；
2. a light-emitting component, it includes the 1st illuminator and the 2nd illuminator, and the 1st illuminator sends has the 1st luminous light
The light of spectrum, the 2nd illuminator absorb described in there is at least a portion of light of the 1st luminescent spectrum, and send and have and described the
The light of the 2nd different luminescent spectrum of 1 luminescent spectrum；It is characterized in that: contain according to claim 1 as the 2nd illuminator
Described thiosilicic acid salt fluorophor.
3. light-emitting component according to claim 2, it is characterised in that: as the 1st illuminator use light emitting diode or
Laser diode, or the discharge lamp based on low pressure or high pressure, or electroluminescent lamp.
4. a pigment, it is characterised in that: described pigment contains thiosilicic acid salt fluorophor according to claim 1.
5. a ultra-violet absorber, it is characterised in that: described ultra-violet absorber contains sulphur according to claim 1
For silicate phosphor.
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| 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 |
| WO2020188913A1 (en) * | 2019-03-15 | 2020-09-24 | パナソニックＩｐマネジメント株式会社 | Solid electrolyte material and battery using same |
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 |
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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 (2)
| Title |
|---|
| Crystal structure and luminescence properties of a cyan emitting Ca10(SiO4)3(SO4)3F2:Eu2+ phosphor;Meidan Que et al.;《CrystEngComm》;20130531;6389-6394 * |
| Tunable orange red phosphors: S2--doped high temperature phase Ca3SiO4Cl2:Eu2+ for solid-state lighting;Xin Zhao et al.;《RSC Advances》;20121128;1965-1969 * |
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