CN103834392A - Fluorescent material crystal and preparation method thereof - Google Patents
Fluorescent material crystal and preparation method thereof Download PDFInfo
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- CN103834392A CN103834392A CN201210479616.2A CN201210479616A CN103834392A CN 103834392 A CN103834392 A CN 103834392A CN 201210479616 A CN201210479616 A CN 201210479616A CN 103834392 A CN103834392 A CN 103834392A
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Abstract
The invention relates to a fluorescent material crystal, which has a chemical composition expression of Sr2.98 (Al,Ga)0.1Si0.9O5:Sm0.01, Tm0.01, and has X-ray powder diffraction pattern at 2theta of about 6.0, 9.1, 18.8 and 23.3. The fluorescent material crystal has high color purity and improved brightness, and can be excited by optical radiation in required wavelength range.
Description
Technical field
The invention belongs to luminescent material technical field, a kind of purple light excited fluorescent material that has been specifically related to this disclosure of the invention and make each method.
Background technology
Took the lead in the technical breakthrough of blue GaN-LED from 1993, White LED is introduced to the market then, has caused that outer personage pays close attention to greatly in the industry.Because compared with traditional lighting light source, white light LEDs has many advantages, volume is little, less energy consumption, response is fast, the life-span is long, pollution-free etc., be therefore called the 4th generation lighting source.The blue-ray LED chip emission wavelength of traditional commerce is in 460nm left and right at present, because its emission wavelength is longer, inevitably exist the shortcoming o YAG:Ce fluorescent material such as energy is lower, spectral coverage is wide not, color developing is poor as the blue-light excited LED fluorescent material of the most conventional business due to produce time need to use a large amount of rare earths, cause it with high costs, and in emmission spectrum, lack ruddiness composition, after mating with blue-ray LED chip, colour rendering index is lower etc., and these shortcomings have limited the application of blue-light excited LED greatly.
For as above problem; people invest in the shorter purple LED chip o purple LED chip of wavelength sight because himself emission wavelength is 400 ~ 450nm; take the purple light excited LED chip of typical 420nm as example; its energy Ratios blue-ray LED chip exceeds 20% under the same conditions, and this just means after mating with corresponding fluorescent material can obtain efficient white light emission; On the other hand, because purple LED chip emission wavelength is shorter, after mating with fluorescent material, the scope of the covering of spectrum is wider, can obtain the better color developing than blue-light excited LED.Theoretical Calculation is known, mates best fluorescent material emmission spectrum peak position should be near the broadband peak of transmitting main peak 555nm with 420nm purple LED chip, after coupling, can obtain the warm white that colour temperature is lower.
But the fluorescent material that can meet at present this requirement is considerably less, and purple LED chips incorporate direct with conventional blu-ray excitated fluorescent powder, excites matching problem to cause its luminous efficiency extremely low on the one hand; On the other hand, on market, not yet occur there is matched well with purple LED chip
Business fluorescent material.Therefore, LED R&D direction is to seek the warm white fluorescent powder that can effectively be excited by purple LED chip 395nm ~ 450nm at present.Silicic acid three strontium systems are as a kind of novel fluorescence matrix, have very high chemistry and thermally-stabilised ' property, color developing and good temperature quenching effect.Sr at present
3-xsiO
5: Ce fluor, because its emmission spectrum is at 530nm, lacks ruddiness composition, cause its mate with 420nm purple LED after colour temperature higher; Secondly,, because Ce replaces the deficiency that causes fluorescence intensity to Sr, limited actual application.
Summary of the invention
The object of the invention is to the defect existing for prior art, a kind of safety non-toxic is provided, stable chemical nature, easy long-term preservation, fluorescence property are stablized, the fluorescent material of the purple light excited yellow emission of tunable optical, and provide a kind of with low cost, technique is simple and direct, energy-conserving and environment-protective are easy to again the each method of system of suitability for industrialized production.
The chemical constitution expression of described fluorescent material is: Sr
2.98(Al, Ga)
0.1si
0.9o
5: Sm
0.01, Tm
0.01, it has 2 θ at approximately 6.0,9.1,18.8 and 23.3 X-ray powder diffraction figure.
According to a second aspect of the present invention, a kind of preparation method of fluorescent material crystal is provided, comprise the following steps:
1) according to the competent strontium salt of the stoichiometric ratio of each element beyond deoxygenation in above-mentioned fluorescent material, silicon-dioxide, aluminium plus gallium compound, samaric nitrate and thulium nitrate;
2) at ambient temperature by even above-mentioned raw materials ground and mixed;
3) at N
2/ H
2under atmosphere, be warming up to 1300 ℃ ~ 1600 ℃ with the speed of 3 ~ 4 ℃, insulation 4 ~ 8h, again grinds and obtains target product.
Described in step 1), strontium salt is selected from one or both in Strontium carbonate powder and strontium nitrate; The compound of described aluminium plus gallium is that one or more in oxide compound, nitrate, fluorochemical mix with arbitrary proportion;
Step 2) in add dehydrated alcohol assist grind, ground post-drying material powder; The add-on of dehydrated alcohol is 20 ~ 50% of mixture quality.
[0016] step 3) in N
2/ H
2atmosphere is 95% N preferably
2/ 5% H
2, the preferred 8h of soaking time.
In fluorescent material of the present invention, Sr
3siO
5as matrix, and one or more in a small amount of gallium, aluminium, boron can be doped in the lattice of silicon-dioxide, also can free state and silicic acid three strontiums and deposit; Or a part of being doped in the lattice of silicon-dioxide, another part and free silicic acid three strontiums are also deposited.The doping of one or more in gallium, aluminium, boron can be increased in the absorption of visible region, improves the integrity degree of lattice, finally improves luminous intensity.
Gained fluor particle shape looks rule, size is even, is applicable to very much LED encapsulation; The crystal of made each sample and YAG:Ce have identical crystal morphology, but have higher luminous efficiency; Gained fluorescent powder packaging is become to LED, compare with adopting YAG:Ce, there is higher colour rendering index and lower colour temperature.
The preparation method of fluorescent material crystal of the present invention, technique is simple, with low cost, and the fluorescent material crystal of stating making is not introduced other impurity, and quality product is high, can be widely used in the manufacture of luminescent material.
Accompanying drawing explanation
Fig. 1 is Sr prepared by the embodiment of the present invention 1
2.98(Al, Ga)
0.1si
0.9o
5: Sm
0.01, Tm
0.01the emmission spectrum comparison diagram of fluorescent material crystal (representing with 1) and commercially available yttrium aluminium garnet fluorescent powder (representing with 2).
Wherein, utilizing emitted light spectrogram is to obtain through 200 ~ 250nm optical excitation.
Fig. 2 is the characteristic X-ray powder diagram of embodiment 1 fluorescent material crystal.
Embodiment
In powder X-ray ray diffraction (XRD), use Cu K α 1 as X x ray tube, at room temperature use powder X-ray ray diffraction device RINT2200/Ultima+ (RIGAKU) or X'Pert Pro MPD (PANalytical) to measure within the scope of the 2 θ diffraction angle of 2 ° to 35 °.For used each diffraction instrument, measuring condition is as follows.
Diffraction instrument: RINT2200/Ultima+ (RIGAKU)
Tube current: 40mA, tube voltage: 40kV, sweep velocity: 4 °/minute
Diffraction instrument: X'Pert Pro MPD (PANalytical)
Tube current: 40 mA, tube voltage: 45kV, sweep velocity: 40.1 °/minute
Although 2 θ values generally illustrate the error of approximately positive and negative 0.2 °, may cause larger error due to measuring condition etc.
Use thermogravimetric/differential thermal analyzer TG/SDTA851e (TG/DTA) (Mettler Toledo) or differential scanning calorimeter DSC821e (DSC), in the dry nitrogen air-flow of 40ml/ minute and under the intensification degree speed of 10 ℃/min, carry out heat analysis.
Embodiment 1:Sr
2.98(Al, Ga)
0.1si
0.9o
5: Sm
0.01, Tm
0.01the preparation of fluorescent material crystal
1) take SrCO
3(29.75mmol), SiO
2(10mmol), (0.01mmol) samaric nitrate and (0.01mmol) thulium nitrate;
2) in stink cupboard, precursor is mixed, add 50% ethanol liquid of sample total mass, be ground;
3), in air dry oven, at 80 ℃ of temperature, dry;
4) above powder is put into tube furnace and is passed into 95%N simultaneously
2/ 5%H
2mixed atmosphere, is warming up to 1400 ℃ with the speed of 3 ~ 4 ℃/min, after calcination 6h, cooling rapidly, grinds a little and obtain target product.
Fig. 1 is Sr prepared by the embodiment of the present invention 1
2.98(Al, Ga)
0.1si
0.9o
5: Sm
0.01, Tm
0.01the emmission spectrum comparison diagram of fluorescent material crystal and commercially available yttrium aluminium garnet fluorescent powder.As shown in Figure 1, in figure, 1 is the emmission spectrum of the fluorescent material crystal prepared of the embodiment of the present invention 1, the 2nd, and the emmission spectrum of commercially available yttrium aluminium garnet fluorescent powder.The fluorescent material crystal that can find out the embodiment of the present invention 1 by contrast is compared with yttrium aluminium garnet fluorescent powder, and luminous intensity is approximately 2.3 times of the latter.
Claims (2)
1. a fluorescent material crystal, is characterized in that its chemical constitution expression is: Sr
2.98(Al, Ga)
0.1si
0.9o
5: Sm
0.01, Tm
0.01, it has 2 θ at approximately 6.0,9.1,18.8 and 23.3 X-ray powder diffraction figure.
2. a light-emitting device, comprises fluorescent material crystal claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210479616.2A CN103834392A (en) | 2012-11-23 | 2012-11-23 | Fluorescent material crystal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210479616.2A CN103834392A (en) | 2012-11-23 | 2012-11-23 | Fluorescent material crystal and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103834392A true CN103834392A (en) | 2014-06-04 |
Family
ID=50798294
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|---|---|---|---|
| CN201210479616.2A Pending CN103834392A (en) | 2012-11-23 | 2012-11-23 | Fluorescent material crystal and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7487815B2 (en) | 2017-01-31 | 2024-05-21 | 三菱ケミカル株式会社 | Light-emitting device and phosphor |
-
2012
- 2012-11-23 CN CN201210479616.2A patent/CN103834392A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7487815B2 (en) | 2017-01-31 | 2024-05-21 | 三菱ケミカル株式会社 | Light-emitting device and phosphor |
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Application publication date: 20140604 |