CN103013502B - Silicate-based fluorescent material and synthetic method thereof - Google Patents
Silicate-based fluorescent material and synthetic method thereof Download PDFInfo
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- CN103013502B CN103013502B CN201210505959.1A CN201210505959A CN103013502B CN 103013502 B CN103013502 B CN 103013502B CN 201210505959 A CN201210505959 A CN 201210505959A CN 103013502 B CN103013502 B CN 103013502B
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Abstract
The invention discloses a silicate-based fluorescent material and a synthetic method thereof. The chemical formula of the silicate-based fluorescent material is (Ae1-xEux)3SiO5, wherein Ae is one or more of Sr<2+>, Ba<2+>, Ca<2+>, Zn<2+>, Sm<2+>, Nd<2+> and Tm<2+>; and x is equal to 0.5-5%. The silicate-based fluorescent material is prepared by adopting a solid phase reaction method. The chemical stability of the silicate-based fluorescent material Ae3SiO5:Eu<2+> is good, the peak value of the emission spectrum can be red-shifted to 600nm, the red spectral component produced when a blue light chip is matched with a yellow fluorescent powder for packaging a white-light LED (Light-Emitting Diode) can be effectively made up for, and the color rendering index can be improved.
Description
One, technical field
The present invention relates to a kind of fluorescent material and synthetic method thereof, specifically a kind of silicate-base fluorescent material and synthetic method thereof, this material can effectively reduce colour temperature and improve colour rendering index for white light LEDs.The a small amount of nanometer SiO of this synthetic method utilization
2with conventional SiO
2micro mist mixture, as silicon source, wherein adds a small amount of nanometer SiO
2be conducive to the formation of nucleus, and then impel at high temperature Fast Growth of crystal grain, finally obtain high efficient luminous material.
Two, background technology
From 1994 Nian Ya companies, report first and utilize blue chip to coordinate Y
3al
5o
12: Ce
3+(YAG) since yellow fluorescent powder produces white light, the performance of white light LEDs product, technology of preparing and range of application have obtained marked improvement.Except being applied to indoor and outdoor large screen display screen, information display backlight and outside landscape ornamental, in recent years, LED luminescent lamp, bulb lamp, street lamp start to replace conventional fluorescent and high-pressure mercury lamp one after another.With regard to the number of chips and fluorescent material of utilizing with regard to production white light LEDs, white light LEDs preparation method can be divided into two large classes, and a class is to utilize R-G-B or blue-yellow multi-chip technology; Another kind of is to utilize LED chip utilizing emitted light excitated fluorescent powder to produce.Because multi-chip technology is limited by light decay that cost, lower, the different chip light emitting of green luminescence efficiency produce with temperature and the problem such as aging resistance is inconsistent, can be expected that, in following significant period of time, utilizing single-chip excitation fluorescent material is still the mainstream technology of white light LEDs, and fluorescent material is to produce the indispensable crucial starting material of white light LEDs.
The fluorescent material that is applied to white light LEDs mainly contains yellow fluorescent powder YAG:Ce
3+(Sr, Ba)
2siO
4: Eu
2+, green Lu
3al
5o
12: Ce
3+(LuAG
+) and (Ba, Sr)
2siO
4: Eu
2+, red M
2si
5n
8: Eu
2+and CaAlSiN
3: Eu
2+, and be suitable for the blue colour fluorescent powder Sr that near ultraviolet wavelength excites
3mgSi
2o
8:: Eu
2+and BaMgAl
10o
17: Eu
2+(BAM).At lighting field large power white light LED used, be mainly to utilize blue chip to coordinate YAG encapsulation to form, its efficiency is high.But the emission wavelength peak value of pure YAG fluorescent material is conventionally in 534nm left and right, and the white light that the blue chip that is 460nm in conjunction with emission wavelength peak thus encapsulates is that cold white light (claims again: positive white light).In order to obtain warm white, conventionally to YAG fluorescent material, add Gd or Ga element, make its emission wavelength peak move to 560 or 570nm.Utilize emission wavelength peak for (Y, the Gd) of 560nm left and right
3(Al, Ga)
5o
12: Ce
3+although coordinate blue chip can encapsulate out the warm colour light that colour temperature is 3000-5000K, owing to lacking red spectrum composition in spectrum, its colour rendering index is still very low.In order to obtain high color rendering index (CRI), conventionally in yellow fluorescent powder, sneak into suitable red fluorescence powder, but Nitride phosphor price is high.Aspect encapsulation small power white light LEDs, also someone uses sulfide red fluorescent material, but sulphide fluorescent material poor chemical stability, and thermal quenching is serious.
(Sr
0.8ba
0.2)
3siO
5: Eu
2+emmission spectrum be peak value in the wideband spectrum of 590-600nm, can meet the requirement that white light LEDs reduces colour temperature and improves colour rendering index, still (Sr, Ba)
3siO
5: Eu
2+synthesis temperature is high, is generally 1550 ℃, at 1450 ℃, can not get below pure phase.In industrial production, in order to reduce the synthesis temperature of fluorescent material, conventionally add a certain amount of fusing assistant.The synthesis by solid state reaction of adding fusing assistant claims again high temperature solid-state solution method, and fusing assistant is in a liquid state at high temperature, and the fusing assistant of melting is being coated crystal grain and is growing, but for (Sr, Ba)
3siO
5: Eu
2+, add fusing assistant and be easy to cause (Sr, Ba)
2siO
4the generation of phase.(Sr, Ba)
2siO
4the generation of phase not only seriously reduces luminous intensity, and makes emmission spectrum blue shift, glow color variable color.Therefore, for (Sr, Ba)
3siO
5: Eu
2+synthesizing of fluorescent material, must strictly can control kind and the consumption of fusing assistant.
Three, summary of the invention
The present invention aims to provide a kind of silicate-base fluorescent material and synthetic method thereof, technical problem to be solved be overcome in material building-up process incident from (Sr, Ba)
3siO
5(Sr, Ba) in opposite directions
2siO
4the phase transformation of phase, purifies association phase impurity, improves luminous efficiency and the chemical stability of fluorescent material; By the adjusting to luminescence center different case relative luminous intensities in lattice dot matrix, realize the regulation and control of glow color.
The chemical general formula of silicate-base fluorescent material of the present invention is: (Ae
1-xeu
x)
3siO
5, be abbreviated as Ae
3siO
5: Eu
2+; Wherein Ae is Sr
2+, Ba
2+, Ca
2+, Zn
2+, Sm
2+, Nd
2+, Tm
2+in one or more; X=0.5%-5%, x represents that the atom number of Eu is the 0.5-5% of Eu and Ae total atom number, luminescence center Eu
2+in lattice dot matrix, occupy Ae case.The crystalline network of fluorescent material of the present invention is (Sr, Ba)
3siO
5.
Silicate-base fluorescent material of the present invention adopts solid reaction process preparation, it is characterized in that:
By proportional quantity, take each raw material, after being ground, obtain compound, oxygenatedchemicals and silicon source material that described each raw material is Ae and Eu, described silicon source material is nanometer SiO
2with micron SiO
2mixture; Described proportional quantity refers to by general formula (Ae
1-xeu
x)
asi
bo
a+2bthe material rate limiting, 3.0≤a≤3.1 wherein, 0.9≤b≤1.0,3≤a/b≤3.2, x=0.5%-5%;
Described compound is packed in crucible, in 800-1000 ℃ of (Sr
2siO
4become below phase temperature) calcining 2-5 hour, remove the carbide impurity adsorbing in raw material, after grinding, obtain normal pressure calcining material;
Described normal pressure calcining material is packed in crucible, after adding a cover, puts into tube furnace, under nitrogen and hydrogen mixture atmosphere in 1400-1700 ℃ of calcining 4-20 hour, grind and sieve after obtain fluorescent material.
In nitrogen and hydrogen mixture atmosphere, the volume ratio of hydrogen and nitrogen is 95-75:5-25.
Nanometer SiO in described silicon source material
2quality optimization be the 10-50% of silicon source material quality.
It is oxygenatedchemicals that fluorescent material of the present invention adopts raw material, wherein the preferred carbonate of the raw material of alkaline earth element Sr, Ba and Ca, oxide compound, nitrate or oxalate; Eu
2+raw material preferential oxidation europium (Eu
2o
3) or europium nitrate [Eu (NO
3)
35H
2o].
The glow color of silicate-base fluorescent material of the present invention is at near-white, yellow controllable, with low cost in a big way to orange, and luminous efficiency is high, and Heat stability is good.
Silicate-base fluorescent material Ae of the present invention
3siO
5: Eu
2+crystalline network be (Sr, Ba)
3siO
5, in preparation process, Optimum Regulation Ae/Si atomic ratio is non-stoichiometric (3≤Ae/Si≤3.2), and synthetic like this material crystalline phase is purer, and luminous intensity is higher.
The present invention adopts nanometer SiO
2the conventional micron of Substitute For Partial SiO
2, nano raw material surface can be high, and reaction activity is low, can promote grain nucleation to carry out with reacting, and significantly improves luminous efficiency.
The present invention utilizes rare earth element Sm
2+regulation and control (Sr, Ba)
3siO
5in lattice dot matrix, occupy the Eu of different cases
2+luminous, can realize the luminous of different colours, what have special meaning is that this utilizing emitted light is to be multispectrally with luminously, can realize warm white output in single-matrix.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, compare fluorescent material Ae of the present invention with the widely used nitride red fluorescent material of current white light LEDs
3siO
5: Eu
2+price is super cheap, and fluorescent material Ae of the present invention
3siO
5: Eu
2+emission Spectrum Peals can red shift to 600nm, can effectively make up the red spectrum composition that blue chip coordinates yellow fluorescent powder encapsulation white light LEDs to produce not enough, effectively improve colour rendering index.
2, with CaS:Eu that at present white light LEDs is used
2+and La
2o
2s:Eu
3+sulfide red fluorescent material is compared, fluorescent material Ae of the present invention
asi
bo
a+2b: Eu
2+chemical stability is good.
3, (Sr, the Ba) reporting with existing related documents
3siO
5: Eu
2+luminescent properties is compared, and the present invention is by adding nanometer SiO
2control the nucleation and growth of crystal grain, significantly improve the luminous intensity of fluorescent material.
4, (Sr, the Ba) reporting with existing related documents
3siO
5: Eu
2+luminescent properties is compared, and the fame component of fluorescent material of the present invention (being ingredient proportion) is imperfect stoichiometric ratio, and Ae is excessive a little with respect to Si atomic ratio, synthesized Sr
3siO
5material crystalline phase is purer, and can significantly improve the luminous intensity of sample.
5, (Sr, the Ba) reporting with existing related documents
3siO
5: Eu
2+luminescent properties is compared, fluorescent material Emission Spectrum Peals of the present invention can red shift to 600nm, and document relevant (Sr, Ba)
3siO
5: Eu
2+the report of emission spectrometry peak value has a lot, and as 562nm, 570nm and 580nm, the cause that produces many different peak value reports is the Sr with high-alkali (soil)/silicon ratio
3siO
5: Eu
2+material is difficult to into phase, and synthetic material crystalline phase is impure because from low temperature to high temperature rise temperature process, SrCO
3with SiO
2mixture always at 1300 ℃, start to generate Sr
2siO
4phase, just may form Sr with the further rising of temperature
3siO
5phase.Once composition and temperature adjusting are bad, the so preferential Sr generating
2siO
4dephasign is difficult to eliminate, and Sr
2siO
4: Eu
2+emission Spectrum Peals in about 544nm, work as Sr
2siO
4: Eu
2+the shared ratio of dephasign is more, and emmission spectrum blue shift is more serious.
6, the present invention utilizes nanometer SiO
2with conventional SiO
2the mixture of particle is as silicon source, nanometer SiO
2surface can be high, and be first easy to reaction and form nucleus, nucleus Fast Growth under hot conditions then, profit has significantly improved the luminous efficiency of fluorescent material in this way.
7, rare earth element Sm of the present invention
2+can regulate and control different case Eu
2+relative luminous intensity, not only can regulate and control glow color, and the power loss having reduced from high energy case to low energy case transmittance process, improves energy efficiency.Therefore, the fluorescent material luminous efficiency after the present invention improves is higher, and glow color variable range is larger.
8, in research process of the present invention, find, fusing assistant is to improving (Sr, Ba)
3siO
5: Eu
2+luminous intensity is without benefit, and easily generates Sr
2siO
4: Eu
2+dephasign, should strictly control the use of fusing assistant.
Four, accompanying drawing explanation
Fig. 1 is the synthetic (Sr of high temperature solid-state reduction at 1300 ℃
0.99eu
0.01)
3siO
5the emmission spectrum of fluorescent material under 460nm excites.
Fig. 2 is the synthetic (Sr of high temperature solid-state reduction under differing temps
0.99eu
0.01)
3siO
5the XRD figure spectrum of fluorescent material.
Fig. 3 is the synthetic (Sr of high temperature solid-state reduction at 1400 ℃
0.99eu
0.01)
3siO
5the emmission spectrum of fluorescent material under 460nm excites.
Fig. 4 is the synthetic (Sr of high temperature solid-state reduction at 1450 ℃
0.99eu
0.01)
3siO
5the emmission spectrum of fluorescent material under 460nm excites.
Fig. 5 is the synthetic (Sr of high temperature solid-state reduction at 1500 ℃
0.99eu
0.01)
3siO
5the emmission spectrum of fluorescent material under 460nm excites.
Fig. 6 different content nanometer SiO that adulterates
2(the Sr synthesizing at 1500 ℃
0.99eu
0.01)
3siO
5fluorescent material natural light (left figure) and under 365nm excites the luminous photo of (right figure).
Fig. 7 is (Sr
0.99eu
0.01)
3siO
5fluorescent material relative luminous intensity is with temperature and nanometer SiO
2the variation of doping.
Fig. 8 is different Sr/Si comparison (Sr
0.99eu
0.01)
asi
bo
a+2bthe impact of emmission spectrum.
Fig. 9 adopts different Sr/Si than synthesized (Sr
0.99eu
0.01)
asi
bo
a+2bthe crystalline structure of material.
Figure 10 is different content Ba
2+to [(Sr
1-yba
y)
0.99eu
0.01]
3siO
5the impact of (y=0,0.05,0.10,0.15,0.20,0.25 and 0.30) emmission spectrum.
Figure 11 different content Ba synthesized fluorescent material [(Sr that adulterates
1-yba
y)
0.99eu
0.01]
3siO
5color under natural light.
Figure 12 is the synthetic [(Sr of high temperature solid-state reduction at 1500 ℃
1-xca
x)
0.99eu
0.01]
3siO
5the emmission spectrum of (x=0,0.1,0.2,0.3,0.4,0.5,0.6,1.0) fluorescent material under 365nm excites.
Figure 13 is different content fusing assistant BaF
2to [(Sr
0.85ba
0.15)
0.99eu
0.01]
3siO
5the impact of emmission spectrum.
Figure 14 is fusing assistant NH
4cl content is to [(Sr
0.85ba
0.15)
0.99eu
0.01]
3siO
5the impact of emmission spectrum.
Figure 15 is fusing assistant H
3bO
3content is to [(Sr
0.85ba
0.15)
0.99eu
0.01]
3siO
5the impact of emmission spectrum.
Figure 16 is different content Sm
2+to Sr
3siO
5: Eu
2+the impact of luminescent properties.
Figure 17 sample (Sr
0.98sm
0.01eu
0.01)
3siO
5(Sr
0.94sm
0.05eu
0.01)
3siO
5emmission spectrum chromaticity coordinates.
Figure 18 is different content Nd
2+to Sr
3siO
5: Eu
2+the impact of luminescent properties.
Five, embodiment
Embodiment 1:
The chemical formula of the present embodiment fluorescent material is (Sr
0.99eu
0.01)
3siO
5.
The present embodiment is with SrCO
3, SiO
2and Eu
2o
3raw material, wherein SiO
2for conventional micro-powder, after fully grinding, batch mixing product is packed into corundum crucible, after adding a cover, put into tube furnace, tighten in the backward stove of flange and pass into H
2/ N
2=5/95 reducing gas.High Temperature Furnaces Heating Apparatus sintering schedule is: first with 5 ℃/min, from room temperature, be warming up to 600 ℃, then with 4 ℃/min, be warming up to 900 ℃, with 3 ℃/min, be warming up to 1300 ℃ again, 1300 ℃ insulation 4 hours after, with 4 ℃/min, be cooled to 900 ℃, then 5 ℃/min is cooled to 600 ℃, powered-down, sample cools to room temperature with the furnace, finally closes reducing gas.After sample is come out of the stove, grind, adopt the F4600 of Hitachi spectrograph and Rigaku D/max-IIIA X-ray diffractometer, characterize respectively emmission spectrum and the crystalline structure of sample.Its emmission spectrum is a wideband structural, and peak value is at 545nm, as shown in Figure 1.From XRD diffraction peak, judge, as Fig. 2 (a), material synthetic under this temperature condition is mainly Sr
2siO
4phase.
Embodiment 2:
The present embodiment synthetic chemical general formula is (Sr
0.99eu
0.01)
3siO
5.
The present embodiment synthesizes five samples, wherein nanometer SiO
2the per-cent of shared silicon source material total mass is respectively 0,10%, 30%, 50% and 70%, according to the ratio of sample composition shown in table 1, takes respectively raw material SrCO
3, nanometer SiO
2, conventional SiO
2micro mist and Eu
2o
3, then various raw materials are fully ground, batch mixing product is packed into corundum crucible, under atmospheric environment, in 1000 ℃ of calcinations 2 hours, after coming out of the stove, again sample is ground, then again sample is packed into corundum crucible, after adding a cover, put into tube furnace, at H
2/ N
2under=25/75 reducing atmosphere, in 1400 ℃ of high-temperature calcinations 4 hours, until being cooled to room temperature, furnace temperature closes reducing gas.After sample is come out of the stove, grind, classification is sieved, and finally obtains finished product.
Adopt the emmission spectrum of the F4600 of Hitachi spectrograph sign sample, as shown in Figure 3.10% nanometer SiO adulterates
2with the nanometer SiO that undopes
2the luminous intensity of sample is very nearly the same; As nanometer SiO
2when doping is 30%, luminous intensity significantly promotes, and luminous intensity reaches maximum value, and its luminous intensity is not add nanometer SiO
2206% of sample; As nanometer SiO
2when doping is 50%, luminous intensity starts to reduce, and when doping is 70%, luminous intensity further reduces, but the luminous intensity of doping 50% and 70% sample is still high than the luminous intensity of the sample that undopes.This enforcement synthesized nanometer SiO that undopes
2the XRD figure spectrum of sample is as shown in Fig. 2 (b), and main thing is Sr mutually
3siO
5.
Sample composition formula in table 1 embodiment 2
| Sample number into spectrum | Nanometer SiO 2Per-cent | SrCO 3 (g) | Nanometer SiO 2 (g) | SiO 2 (g) | Eu 2O 3 (g) |
| 1 | 0% | 2.2145 | 0 | 0.303 | 0.0264 |
| 2 | 10% | 2.2145 | 0.0303 | 0.2727 | 0.0264 |
| 3 | 30% | 2.2145 | 0.0909 | 0.2121 | 0.0264 |
| 4 | 50% | 2.2145 | 0.1515 | 0.1515 | 0.0264 |
| 5 | 70% | 2.2145 | 0.2121 | 0.0909 | 0.0264 |
Embodiment 3:
The present embodiment synthetic chemical general formula is (Sr
0.99eu
0.01)
3siO
5.
The preparation method of the present embodiment is with embodiment 2, and different is at H
2/ N
2under=25/75 reducing atmosphere in 1450 ℃ of high-temperature calcinations 4 hours.The emmission spectrum of the present embodiment synthetic sample as shown in Figure 4.The luminous intensity of sample is with nanometer SiO
2the increase of doping and increasing, doping is that the undope luminous intensity of sample of the luminous strength ratio of 10% sample significantly promotes; Work as SiO
2when usage quantity is 30%, luminous intensity reaches maximum, and its luminous intensity is 161% of the sample that undopes; As nanometer SiO
2content increases to 50%, and luminous intensity slightly reduces; Doping is that the luminous intensity of 50% and 70% two sample is very nearly the same.This enforcement synthesized nanometer SiO that undopes
2the XRD figure spectrum of sample is as shown in Fig. 2 (c), and main thing is Sr mutually
3siO
5.
Embodiment 4:
The present embodiment synthetic chemical general formula is (Sr
0.99eu
0.01)
3siO
5.
The preparation method of the present embodiment is with embodiment 2, and different is at H
2/ N
2under=25/75 reducing atmosphere in 1500 ℃ of high-temperature calcinations 4 hours.The emmission spectrum of the present embodiment synthesized sample as shown in Figure 5.Luminous intensity is with nanometer SiO
2doping from zero to 10% increase gradually, then with nanometer SiO
2the increase of doping and reducing gradually; The strongest luminous sample is nanometer SiO
2doping is 10% sample.Than the nanometer SiO that undopes
2sample is compared, doping 10%, 30%, 50% and 70% nanometer SiO
2make respectively luminous intensity improve 32%, 30%, 19% and 6%.
This enforcement synthesized nanometer SiO that undopes
2the XRD figure spectrum of sample is as shown in Fig. 2 (d), and main thing is Sr mutually
3siO
5.
Fig. 6 has provided pattern and the luminous photo under 365nm ultraviolet excitation thereof of 5 samples of the present embodiment synthesized under natural light.Under natural light, sample is micro-yellow; Under 365nm UV-irradiation, sample presents bright-coloured Yellow luminous.
Table 2 and table 3 have been summed up Emission Spectrum Peals and the relative luminous intensity of embodiment 2,3 and 4 synthesized samples.Fig. 7 provides intuitively through 1400 ℃, 1450 ℃ and 1500 ℃ of synthetic (Sr
0.99eu
0.01)
3siO
5fluorescent material luminous intensity is with nanometer SiO
2the variation of doping, under equal conditions, synthesis temperature is higher, luminous stronger; Dopen Nano SiO
2the luminous intensity of sample is luminous strong than the sample that undopes all; Temperature is higher, the required nanometer SiO of corresponding the strongest luminous sample
2doping is fewer and feweri.Dopen Nano SiO
2not only contribute to improve luminous intensity, and contribute to make red shift of the emission spectra.
The Emission Spectrum Peals of each sample in table 2 embodiment 2,3 and 4
The relative luminous spectral intensity of each sample in table 3 embodiment 2,3 and 4
Embodiment 5:
The present embodiment synthetic sample is pressed general formula (Sr
0.99eu
0.01)
asi
bo
a+2bthe ratio limiting feeds intake, wherein a:b=3:0.9; 3:0.95; 3:1; 3:1.05; 3:1.1.
According to chemical formula, take SrCO
3, SiO
2(nanometer SiO
2account for total SiO
2the per-cent of quality is 20%) and Eu
2o
3, after fully being ground, various raw materials pack corundum crucible into, under atmospheric environment, in 1000 ℃ of calcinations 2 hours, after coming out of the stove, again sample is ground, then again sample is packed into corundum crucible, and after adding a cover, put into tube furnace, at H
2/ N
2under=25/75 reducing atmosphere, in 1500 ℃ of high-temperature calcinations 4 hours, until being cooled to room temperature, furnace temperature closes reducing gas.After sample is come out of the stove, grind, classification is sieved, and finally obtains finished product.Adopt the emmission spectrum of the F4600 of Hitachi spectrograph sign sample, as shown in Figure 8.Luminous the strongest be that Sr:Si mol ratio is the sample of a:b=3:0.95, be secondly the sample of a:b=3:1.05.With the Sr:Si mol ratio desirable sample Sr that is a:b=3:1
3siO
5: Eu
2+compare, although a:b=3:1.05 sample luminous intensity promote to some extent, its Emission Spectrum Peals blue shift.What luminous intensity was the most weak is a:b=3:0.9 sample.When a:b=3:1.1, Emission Spectrum Peals blue shift is more serious, and luminous intensity is also very low.The XRD figure of amplifying from part is composed, and as shown in Figure 9, when a:b=3:0.9, has a little unreacted SrO to exist; When a:b=3:1.05 and 3:1.1, in product, there is trace Sr
2siO
4material generates, and along with SiO
2the increase of ratio and increasing.Sr content is excessive a little with respect to Si, is conducive to obtain the good luminous and optimal luminescent color of high strength.
Embodiment 6:
The present embodiment synthetic sample general formula is [(Sr
1-yba
y)
0.99eu
0.01]
3siO
5(y=0,0.05,0.10,0.15,0.20,0.25 and 0.30).
The present embodiment is with SrCO
3, BaCO
3, Eu
2o
3, nanometer SiO
2with the micron-sized SiO of routine
2, nanometer SiO wherein
2account for total SiO
2the per-cent of quality is 20%.The synthetic method of the present embodiment fluorescent material is identical with embodiment 4.Figure 10 is the emmission spectrum of the present embodiment synthesized sample under 460nm excites, therefrom visible, works as Ba
2+when doping is 0.1M, luminous intensity is maximum, after this with Ba
2+the increase of doping slightly reduces; With regard to Emission Spectrum Peals, along with Ba
2+when doping increases to 0.20M from 0, Emission Spectrum Peals is from 582nm red shift to 601nm, with Ba
2+doping further increases, and Emission Spectrum Peals is blue shifted to 599nm on the contrary.Color from the sample shown in Figure 11 under natural light can clearly be found out, along with Ba
2+content increases to y=0.15 from y=0, and the color of sample has become orange from yellow.After this along with Ba
2+content continues to increase y=0.30 from y=0.20, and the color of sample turns dim from orange again.In order to obtain the required red spectrum of high colour developing white light LEDs, Ba
2+doping should be controlled at 0.15-0.20M.
Embodiment 7:
The present embodiment synthetic sample general formula is [(Sr
1-xca
x)
0.99eu
0.01]
3siO
5(x=0,0.1,0.2,0.3,0.4,0.5,0.6,1.0).
The present embodiment synthetic method is identical with embodiment 6.As shown in figure 12, along with the increase of Ca doping, emmission spectrum gradually blue shift and luminous intensity sharply reduces the emmission spectrum that excites lower employing ocean optics (Ocean Optics) USB4000 sample that fluorescence spectrophotometer is tested at 365nm.When Ca doping is 0.6M, Emission Spectrum Peals is 580nm Yellow luminously changes the green emitting that peak value is 520nm into.
Embodiment 8:
The present embodiment synthetic sample general formula is [(Sr
0.85ba
0.15)
0.99eu
0.01]
3siO
5, add account for raw materials quality per-cent be respectively 0,1%, 1.5% and 2.0%BaF
2as fusing assistant.
The present embodiment synthetic method is identical with embodiment 1, but difference is to add in the present embodiment BaF
2as fusing assistant and sintering temperature, it is 1450 ℃.Adopt the emmission spectrum of the F4500 of Hitachi sample that fluorescence spectrophotometer is tested under 460nm excites as shown in figure 13.As can be seen here, add and account for raw materials quality per-cent 1.0%BaF
2sample, its luminous intensity is suitable with the fusing assistant sample luminous intensity of not adding; When the addition of fusing assistant is when being 1.5%, its luminous intensity significantly reduces; When fusing assistant addition is 2%, its luminous intensity reduces more serious, and emmission spectrum blue shift.After the amount of fusing assistant strengthens, sample caking is serious, and it is very hard that sample becomes, and under natural light, looks black, and this may be that sample interior occurs due to more lattice defect.In addition, excessive BaF
2add and cause emmission spectrum blue shift, may be because product generates Sr
2siO
4mutually.
Embodiment 9:
The present embodiment synthetic sample general formula is [(Sr
0.85ba
0.15)
0.99eu
0.01]
3siO
5, add account for raw materials quality per-cent be respectively 0,2.5%, 5% and 7.5%NH
4cl is as fusing assistant.
The present embodiment synthetic method is identical with embodiment 8, but difference is to add in the present embodiment NH
4cl is as fusing assistant.The emmission spectrum that excites lower employing ocean optics USB4000 sample that fluorescence spectrophotometer is tested at 365nm as shown in figure 14.With NH
4the interpolation of Cl doping, the firstth, luminous intensity sharply reduces, and the secondth, emmission spectrum is blue shift gradually.This is because reaction product generates Sr
2siO
4mutually.Therefore, synthetic (Sr, Ba)
3siO
5thing phase, should forbid adopting NH
4cl is as fusing assistant.
Embodiment 10:
The present embodiment synthetic sample general formula is [(Sr
0.85ba
0.15)
0.99eu
0.01]
3siO
5, interpolation accounts for raw materials quality per-cent and is respectively 0,0.5%, 1% and 1.5% H
3bO
3as fusing assistant.
The present embodiment synthetic method is identical with embodiment 8, but difference is to add in the present embodiment H
3bO
3as fusing assistant.The emmission spectrum of sample under 365nm excites as shown in figure 15.With H
3bO
3the interpolation of doping, although Emission Spectrum Peals does not have blue shift, luminous intensity sharply reduces.Explanation thus, adds H
3bO
3as fusing assistant, for the synthetic of fluorescent material, be no advantage.
Embodiment 11:
The present embodiment synthetic sample general formula is [(Sr
1-xsm
x)
0.99eu
0.01]
3siO
5(x=0.01,0.05,0.10 and 0.15).
The present embodiment is with SrCO
3, SiO
2, Eu
2o
3and Sm
2o
3raw material, wherein SiO
2for conventional micro-powder, after fully grinding, batch mixing product is packed into corundum crucible, in tube furnace in H
2/ N
2under=25/75 reducing atmosphere, carry out sintering.Sintering process is: first with 5 ℃/min, from room temperature, be warming up to 600 ℃, then with 4 ℃/min, be warming up to 900 ℃, with 3 ℃/min, be warming up to 1450 ℃ again, 1450 ℃ insulation 4 hours after, with 4 ℃/min, be cooled to 900 ℃, then 5 ℃/min is cooled to 600 ℃, powered-down, sample cools to room temperature with the furnace, finally closes reducing gas.After sample is come out of the stove, grind, adopt the F4600 of Hitachi spectrograph to characterize the luminescent properties of sample, its emmission spectrum as shown in figure 16.For Sm
2+doping is 0.01 and the sample of 0.05M, and its emmission spectrum is obviously to consist of two emission bands, one of them emission band wavelength peak be 472nm another be the warm gold-tinted of 579nm.From generating white light principle, as long as rationally regulate the relative intensity of two emission bands, can modulate white light by gold-tinted and blue light.Sample (Sr
0.98sm
0.01eu
0.01)
3siO
5(Sr
0.94sm
0.05eu
0.01)
3siO
5numbering is designated as respectively 1 and 2, and as shown in figure 17, therefrom visible its glow color is close to white light for its corresponding CIE chromaticity coordinates.Colour temperature difference 3539 and 5587K, the warm colour light presenting with sunlight is consistent, is good warm colour light.
Table 4 sample (Sr
0.98sm
0.01eu
0.01)
3siO
5(Sr
0.94sm
0.05eu
0.01)
3siO
5emmission spectrum chromaticity coordinates, colour temperature and development index
| Numbering | Sample composition | Chromaticity coordinates | Colour temperature | Colour rendering index |
| 1 | (Sr 0.98Sm 0.01Eu 0.01) 3SiO 5 | CIE(0.4232, 0.4447) | 3539K | 58.67 |
| 2 | (Sr 0.94Sm 0.05Eu 0.01) 3SiO 5 | CIE(0.3303, 0.3827) | 5587K | 67.61 |
Embodiment 12:
The present embodiment synthetic sample general formula is [(Sr
1-xnd
x)
0.99eu
0.01]
3siO
5(x=0,0.025,0.05,0.10 and 0.15).
The present embodiment synthetic method is identical with embodiment 11.Sample emmission spectrum as shown in figure 18.Nd
2+mix and first cause Sr
3siO
5: Eu
2+emission wavelength peak blue shift, second sharply reduces luminous intensity, and these two kinds of phenomenons are all along with Nd
2+the increase of doping and aggravating.Known by comparing with the various embodiments described above, in peak value 500nm left and right, there is Nd
2+characteristic emission peak.
[analytic explanation]
Embodiment 1 explanation temperature is mainly Sr lower than the material of 1300 ℃ of synthesizeds
2siO
4phase, in conjunction with the embodiments synthesized Sr under 2,3 and 4 differing tempss
3siO
5: Eu
2+phase, as shown in Figure 2, in temperature from being low to moderate pyroprocess, Sr
2siO
4preferentially generate mutually, synthesize Sr
3siO
5pure phase, temperature is preferably in more than 1500 ℃.Embodiment 2,3 and 4 explanations, used part nanometer SiO
2replace SiO
2, can significantly improve Sr
3siO
5: Eu
2+luminous intensity, nanometer SiO
2optimum doping amount be 10-30%.Embodiment 5 explanation, Sr contributes to synthetic Sr with respect to Si is excessive a little
3siO
5pure phase, and improve luminous intensity.Embodiment 6 illustrates, mixes the Ba of 15-20%M
2+, can make Sr
3siO
5: Eu
2+red shift of the emission spectra, wherein peak value maximum is adjustable to 600nm.Embodiment 7 explanations, should strictly control Ca
2+doping.Embodiment 8,9 and 10 explanations, add fusing assistant for improving (Sr, Ba)
3siO
5: Eu
2+luminescent properties is unhelpful, therefore, should strictly control the use of fusing assistant.This also illustrates that the present invention adopts nanometer SiO
2improve unique R&D expense of luminescent properties.Embodiment 11 explanations, utilize Sm
2+can regulate and control Sr
3siO
5in lattice dot matrix, occupy different Sr
2+the Eu of case
2+luminous, and this embodiment modulate that single wavelength excites can output warm white.Embodiment 12 can regulate and control the luminous of different case luminescence center after not all bivalent rare earth ion doping is described from the negative.
Claims (3)
1. a preparation method for silicate-base fluorescent material, adopts solid reaction process, it is characterized in that:
According to proportional quantity, take SrCO
3, SiO
2and Eu
2o
3, after fully being ground, various raw materials pack corundum crucible into, under atmospheric environment, in 1000 ℃ of calcinations 2 hours, after coming out of the stove, again sample is ground, then again sample is packed into corundum crucible, and after adding a cover, put into tube furnace, at volume ratio H
2/ N
2under=25/75 reducing atmosphere, in 1500 ℃ of high-temperature calcinations 4 hours, until furnace temperature is cooled to room temperature, close reducing gas, grind and sieve after obtain fluorescent material;
Described proportional quantity refers to by chemical formula (Sr
0.99eu
0.01)
asi
bo
a+2bthe ratio limiting, wherein a:b=3:0.95;
Described SiO
2for nanometer SiO
2with micron SiO
2mixture, nanometer SiO wherein
2account for total SiO
2the per-cent of quality is 20%.
2. a preparation method for silicate-base fluorescent material, adopts solid reaction process, it is characterized in that:
According to proportional quantity, take SrCO
3, BaCO
3, SiO
2and Eu
2o
3, after fully being ground, various raw materials pack corundum crucible into, under atmospheric environment, in 1000 ℃ of calcinations 2 hours, after coming out of the stove, again sample is ground, then again sample is packed into corundum crucible, and after adding a cover, put into tube furnace, at volume ratio H
2/ N
2under=25/75 reducing atmosphere, in 1500 ℃ of high-temperature calcinations 4 hours, until furnace temperature is cooled to room temperature, close reducing gas, grind and sieve after obtain fluorescent material;
Described proportional quantity refers to by chemical formula [(Sr
1-yba
y)
0.99eu
0.01]
3siO
5the ratio limiting, wherein y=0.15 or 0.20;
Described SiO
2for nanometer SiO
2with micron SiO
2mixture, nanometer SiO wherein
2account for total SiO
2the per-cent of quality is 20%.
3. a preparation method for silicate-base fluorescent material, adopts solid reaction process, it is characterized in that:
According to proportional quantity, take SrCO
3, micron SiO
2, Eu
2o
3and Sm
2o
3, after various raw materials are fully ground, pack corundum crucible into, in tube furnace in H
2/ N
2under=25/75 reducing atmosphere, carry out sintering; Sintering process is: first with 5 ℃/min, from room temperature, be warming up to 600 ℃, then with 4 ℃/min, be warming up to 900 ℃, with 3 ℃/min, be warming up to 1450 ℃ again, 1450 ℃ of insulations, after 4 hours, with 4 ℃/min, be cooled to 900 ℃, then 5 ℃/min is cooled to 600 ℃, powered-down, sample cools to room temperature with the furnace, finally closes reducing gas, and sample grinds and obtains fluorescent material after coming out of the stove;
Described proportional quantity refers to by chemical formula [(Sr
1-xsm
x)
0.99eu
0.01]
3siO
5the ratio limiting, wherein x is 0.01 or 0.05.
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| Title |
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| 张翼 等.白光LED用碱土金属硅酸盐荧光粉的光谱性质.《发光学报》.2008,第29卷(第5期),第800-804页. |
| 白光LED用碱土金属硅酸盐荧光粉的光谱性质;张翼 等;《发光学报》;20081015;第29卷(第5期);第800-804页 * |
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