CN105385441A - Alkaline earth metal silicate green/yellowgreen fluorescent powder, and preparation method and application thereof - Google Patents
Alkaline earth metal silicate green/yellowgreen fluorescent powder, and preparation method and application thereof Download PDFInfo
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- CN105385441A CN105385441A CN201510881825.3A CN201510881825A CN105385441A CN 105385441 A CN105385441 A CN 105385441A CN 201510881825 A CN201510881825 A CN 201510881825A CN 105385441 A CN105385441 A CN 105385441A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
Abstract
The invention discloses an alkaline earth metal silicate green/yellowgreen fluorescent powder with a general chemical formula of (Sr,A<1>)<x>SiO<2+x>: <y>Eu<2+>, zA<2><3+>. In the general chemical formula, A<1> is not added, or is at least one selected from the group consisting of Ba, Mg and Ca; A2 is at least one selected from the group consisting of Y, La, Sc and Er; x is no less than 1.9 and no more than 2.1; y is no less than 0.05 and no more than 0.2; and z is no less than 0.01 and no more than 0.2. The preparation method comprises the following steps: weighing oxide or carbonate containing Sr, A<1>, Si, Eu and A<2> according to a mol ratio of all the elements described in the general formula and a proper amount of a fluxing agent, and carrying out mixing and grinding; subjecting the ground mixture to a reaction in a reducing atmosphere and then carrying out cooling; and carrying out post-treatment so as to obtain the fluorescent powder. The fluorescent powder provided by the invention can be effectively excited by light with a wavelength in a range of 300 to 470 nm, emits green or yellowgreen light with a peak wavelength in a range of 510 to 570 nm, has great luminous intensity, narrow half-peak width, a particle size of 13 to 16 [mu]m and no agglomeration, and is applicable to white light LED or LED display backlight in combination with a blue light chip and am ultraviolet light chip. The preparation method is simple, has low requirements on equipment, meets requirements of low-carbon environment-friendly modernization production and is applicable to large-scale industrial production.
Description
Technical field
The present invention relates to luminescent material and its production and use, specifically a kind of alkaline earth metal silicate green/yellowish green fluorescent powder and its preparation method and application.
Background technology
Photodiode (LED) has the plurality of advantages such as energy-saving and environmental protection, safety, broken colour, specular removal, long lifetime, driving voltage are low, anti-vibration, is subject to whole world extensive concern.Wherein with GaN blue-ray LED and Y
3al
5o
12: Ce
3+(YAG:Ce
3+) the yellow emission fluorescent material technical scheme that realizes white light as light-converting material become the current main flow realizing white light LEDs.Meanwhile, based on the feature of LED light source, LED is used to be applied on liquid crystal display as back light, also noticeable all the more.LED backlight light source is compared with traditional CCFL (cold-cathode tube) backlight, its not only volume little, low in energy consumption, generate heat little, and the life-span is longer, light efficiency is higher, for the application of ultra-thin display display screen in mobile phone, notebook computer, computer monitor, LCD TV provides maximum power, cater to current mainstream electronic commodity market consumer demand completely.
At present, the white light LEDs of main flow utilizes InGaN blue chip to excite YAG:Ce
3+fluorescent material produces and the gold-tinted of blue light complementation, and then mixing realizes.But, due to YAG:Ce
3+in fluorescent material, red-light spectrum energy accounts for 8 ~ 15% of total spectral energy, far below the ratio of yellow green light.Therefore, the product colour rendering index manufactured in this way is on the low side, generally about 70; And colour temperature is higher, substantially at more than 5500K, require that (3000 ~ 5000K) exists certain deviation with the optimum visual of human eye, therefore cannot be used for domestic lighting.For this reason, researchist passes through to YAG:Ce
3+middle interpolation rouge and powder is to reach lifting colour rendering index.But when realizing colour rendering index up to more than 90 target, the combination only by existing bloom+rouge and powder can not realize.Based on researching and analysing of colorimetry aspect, this mainly due to the intensity at green light band relatively weak caused by.Therefore, in industry, the green emitting phosphor of the more excellent performances of exploitation just becomes one of problem of technician's active research.As US Patent No. 2006/0027781 and US2006/0028122 etc. take the lead in disclosing a collection of with silicate be the modified version of matrix green-yellowish green fluorescent powder, wherein, the elements such as introducing Al, P, Ge, B of novelty are to M
2siO
4si in system anionic group replaces, and with F, Cl, Br, I, P, S, N replaces O, especially when replace O be F time, improve M
2siO
4the crystallinity of system, improves light efficiency; But activator only has Eu disclosed in it, do not relate to activator codope or adulterate more, the more doping of its luminous efficiency is on the low side.And CN101113330B discloses a kind of siliceous LED fluorescent powder and manufacture method thereof and made luminescent device, is for M
2siO
4system, make the improvement of oneself, introduce codope or many doping and change the modes such as matrix composition and significantly improve its luminous efficiency, improve the matching of it and ultraviolet, purple light or blue-light LED chip etc., boric acid and the oxide compound of what but its fusing assistant adopted is fluorochemical that corrodibility is stronger or less effective of fluxing, this causes stronger corrodibility to fluorescent material semi-finished granules, make the granule-morphology of final preparing product poor, the yield of aftertreatment gained finished product is low, and production cost and efficiency are subject to a definite limitation.For overcoming this defect, CN101851508B discloses a kind of europium-activated silicate green fluorescent powder and preparation method thereof, done correlative study on CN101113330B basis, namely the problem of finished particle pattern difference is affected for fluoride flux, certain not fusant is added when sintering, control semi-finished granules particle diameter, improve granule-morphology, thus promote M
2siO
4the final light efficiency of system, but its final sintering still uses fluoride flux, add not fusant and can only control fluoride particles particle diameter, be difficult to improve fluoride particles pattern poor, work in-process small-particle causes the shortcomings such as aftertreatment poor yields too much, meanwhile, in technique not fusant add the difficulty also exacerbating work in-process aftertreatment, reduce production efficiency.Visible, its improvement is unsatisfactory.
In addition, in LED-backlit field, current white light LED backlight mainly adopts the combination of blue chip+red fluorescence powder+Huang (green) look fluorescent material, wherein the wavelength of red fluorescence powder normally 620 ~ 630nm, the wavelength normally 520 ~ 545nm of yellow (green) look fluorescent material.But the selection of yellow (green) look fluorescent material is then different, due to YAG:Ce
3+the peak width at half height of system is wider, and colorimetric purity is lower, is difficult to the requirement reaching NTSC standard value, so first industry selects the Ca adopting narrow band
3sc
2si
3o
12: Ce
3+fluorescent material, but Ca
3sc
2si
3o
12: Ce
3+green emitting phosphor luminous efficiency is low, cost is high, and is all the beta-Sialon of narrow band: Eu
2+green emitting phosphor, synthesis condition is but quite harsh, and finished product is high.Therefore, the green phosphor for white light LED of the excellent combination properties such as how new matrix is stablized, synthesis condition is simple, cost is lower, yield is higher and half-peak width, crystal formation are good, good luminous performance is the base material of active demand in industry.
Summary of the invention
The object of this invention is to provide a kind of alkaline earth metal silicate green/yellowish green fluorescent powder and its preparation method and application, to solve the problem of the integrated application poor-performings such as existing silicate green fluorescent powder granule-morphology is poor, peak width at half height is wider, luminescent properties is poor and cost is high, yield is low.
The object of the invention is to be achieved through the following technical solutions: a kind of alkaline earth metal silicate is green/yellowish green fluorescent powder, the chemical general formula of this fluorescent material is (Sr, A
1)
xsiO
(2+x): yEu
2+, zA
2 3+; A is not added in formula
1or A
1for at least one in Ba, Mg, Ca, A
2for at least one in Y, La, Sc, Er, and 1.9≤x≤2.1,0.005≤y≤0.2,0.01≤z≤0.2.
Preferably, chemical general formula (Sr, A
1)
xsiO
(2+x): yEu
2+, zA
2 3+in, 1.9≤x≤2.1,0.01≤y≤0.16,0.01≤z≤0.2; And preferred 1.95≤x≤2.05 further, 0.02≤y≤0.16,0.02≤z≤0.1; And under optimum condition, prepared fluorescent material has that work in-process dephasign is few, and post-processing difficulty is low, yield high.
More preferably, chemical general formula (Sr, A
1)
xsiO
(2+x): yEu
2+, zA
2 3+in, 1.98≤x≤2.02,0.06≤y≤0.1,0.04≤z≤0.08.Under still more preferential conditions, it is few that prepared fluorescent material has work in-process small-particle, particle evenly, the features such as granule-morphology is good.
Present invention also offers a kind of alkaline earth metal silicate green/preparation method of yellowish green fluorescent powder, comprise the following steps:
A () is according to chemical general formula (Sr, A
1)
xsiO
(2+x): yEu
2+, zA
2 3+in the mol ratio of each element take containing Sr, A
1, Si, A
2, the oxide compound of Eu element or carbonate and mole number be the fusing assistant of described Si mole number 1-30%, mixing, grinding, obtains mixture;
B mixture is warming up to 1250-1450 DEG C by () under reducing atmosphere condition, insulation 3-12h, is cooled to room temperature, obtains fluorescent material crude product;
C () broken by described fluorescent material crude product, sieve, moisture, oven dry, obtain alkaline earth metal silicate green/yellowish green fluorescent powder.
Fusing assistant described in step (a) of the present invention is the mixture of one or more arbitrary proportions in bivalent metal halide, and bivalent metal halide does not comprise fluorochemical, preferably, the divalent metal in described bivalent metal halide is any one or a few in Sr, Ba, Mg or Ca; Described bivalent metal halide is the mixture of one or more arbitrary proportions in magnesium chloride, calcium chloride, strontium chloride or bariumchloride.
The mole number of the described fusing assistant of step (a) of the present invention is preferably the 1-20% of described Si mole number, and more preferably 5%.Under optimum condition, yield and relative brightness are significantly increased.
The mode of the grinding described in step (a) of the present invention is roller bottle formula ball milling, and milling time is 10h.
The preferred 1300-1450 DEG C of temperature described in step (b) of the present invention, the relative brightness of the fluorescent material prepared at such a temperature is higher.
Reducing atmosphere described in step (b) of the present invention refers to N
2, H
2the reducing atmosphere that mixed gas is formed; Preferably, N
2and H
2volume range be 75-95:25-5.
The temperature rise rate of the described intensification of step (b) of the present invention is 5-10 DEG C/min.
Mixture is put into crucible by described mixture temperature reaction under reducing atmosphere condition being referred to of step (b) of the present invention, is placed in high temperature Muffle furnace and carries out temperature reaction; Described crucible preferential oxidation aluminium crucible, does not add a cover during reaction.
The described grit number excessively of step (c) of the present invention is 200 orders, is milled to D
50for 13-16 μm.
The temperature of the described oven dry of step (c) of the present invention is 40-80 DEG C, and the time is 2-3h; Preferably 80 DEG C, 2h.
The described alcohol wash of step (c) of the present invention refers to washes moisture removal small-particle through ethanol.
Described alkaline earth metal silicate prepared by the present invention is green/and yellowish green fluorescent powder silicate green fluorescent powder stably can be launched green glow or the yellow green light of 510-570nm by blue light or ultraviolet excitation, and light conversion efficiency is high, half-peak width, luminous relative brightness are strong, can utilize by LED, illumination or indicating system in can be applied.
The present invention passes through to select specific raw material and formula rate, with Eu
2+while activator, be doped with Sc, Y, La or/and Er, with the addition of specific fusing assistant, adopt high temperature solid-state method one-step synthesis can effectively absorb the concurrent fluorescent material penetrating green glow or yellow green light of luminous energy at blue wave band under reducing atmosphere.The present invention, is regulated or/and the doping of Er fluorescent powder crystal field by micro-Sc, Y, La; By with the addition of specific fusing assistant, replace existing fluorochemical as M
2siO
4system fusing assistant, while guarantee light efficiency, can play the effect improving grain diameter and pattern, and improves M
2siO
4the yield of system aftertreatment.Prove by experiment, alkaline-earth metal silicate fluorescent powder provided by the present invention, can effectively be excited by 300nm-470nm wavelength, and adjust proportioning as required, launch green glow or yellow green light that peak wavelength is positioned at 510-570nm, luminous intensity is large, half-peak width, little and the soilless sticking of particle diameter, can mate with blue chip and UV chip and be applied in white light LEDs or LED display backlight field.And silicate fluorescent powder, preparation method thereof provided by the present invention, step is succinctly easy, low for equipment requirements, and easy handling is pollution-free, and cost is low, meets low-carbon environment-friendly modern production requirement, is applicable to large-scale industrial production.
Specifically, the fluorescent material prepared by the present invention has the following advantages:
(1) by coactivated mode, in original technical foundation, the rare earth elements such as doping Sc, Y, La and Er, enhance M
2siO
4system, to the assimilated efficiency of blue chip, improves the emissive porwer of this system;
(2) have selected the CaCl of applicable system
2, MgCl
2in halogenide as fusing assistant, this comparatively conventional fluoride fusing assistant compare, it is less that the present invention can obtain semi-finished granules particle diameter, crystal formation pattern is more mellow and fuller, the loss of aftertreatment emissive porwer and chromaticity coordinates drift about less, and yield is higher, the better product of packaging effect;
(3) CaCl is used
2do part calcium source, namely make fusing assistant, can peak wavelength be regulated again, more traditional CaCO
3+ fluoride flux, formula is simple, granule-morphology is better;
(4) take silicate as matrix, stable chemical nature, acid and alkali-resistance, and do not have obvious light efficiency to decay normal use temperature 30 DEG C to 80 DEG C;
(5) by adjustment strontium barium magnesium calcium, fusing assistant and europium content, can obtain launching under blue light and ultraviolet excitation 510nm-570nm all types of green-yellow-green colour product, there are market outlook widely;
(6) peak width at half height of green emitting phosphor that prepared by the present invention controls between 59nm-70nm, compares, can obtain the better backlight of purity of color in field of backlights compared with the green powder LuAG (peak width at half height 106nm) of main flow;
(7) present invention process equipment cheapness is easy to operate, and processing step is succinct, and whole process waste produces few, and products material is cheap and easy to get, relatively at present another novel narrow spectrum green powder beta-Sialon: the harsh synthetic environment condition of Eu, more universal and application.
Therefore, fluorescent material prepared by the present invention can coordinate other luminescent materials, white light is exported under blue light or ultraviolet excitation, luminescent device can be made into or be applied to indicating system, also can in field widespread uses such as Office lighting systems, factory illumination system, home lighting systems, roadway lighting system, decorative lightening system, automobile lighting system and telltale lighting systems.
Accompanying drawing explanation
Fig. 1 is the emmission spectrum of the fluorescent material that embodiment 56 obtains, and it is launched peak position and is about 525nm.
Fig. 2 is the utilizing emitted light collection of illustrative plates of the fluorescent material that embodiment 56 and comparative example 1 obtain, and as can be seen from the figure, the light-emitting phosphor intensity that this patent provides is better than comparative example.
Fig. 3 is that the fluorescent material SEM that embodiment 56 obtains schemes.
Fig. 4 is that the fluorescent material SEM that comparative example 1 obtains schemes; This figure can obviously show fluoride flux to M
2siO
4there is strong corrosive nature in system particle, and AlN etc. do not make to there is a large amount of broken small-particles in work in-process adding of fusant, these 2 raisings being all unfavorable for aftertreatment yield.
Embodiment
Embodiment is for further describing the present invention below, but does not limit the present invention in any form.
Comparative example 1
Repeated experiment is carried out as follows according to the embodiment 20 in patent CN101851508:
Concrete technology is as follows: take SrCO
367.91g, BaCO
3284.17g, Sc
2o
31.04g, Er
2o
31.91g, SiO
258.28g, Eu
2o
313.20g, KF2.77g, AlN4.52g, BN0.011g mixes in rear loading corundum crucible, at 950 DEG C of calcination 5h, then after being pulverized by firing product, adding mass percent after sieving is in the citric acid solution of 2.8%, be mixed with the suspension that mass percent is 20%, be heated to 85 DEG C, be incubated and stir 45min, after being washed till neutrality with deionized water, pigment are separated, and dry, namely obtaining chemical composition is Ba
1.44sr
0.46sc
0.015er
0.01si
0.97o
3.94: Eu
0.075green emitting phosphor.
Embodiment 1
According to (Ba, Sr)
2siO
4: 0.02Eu
2+, 0.04Y
3+in the carbonate of each element or oxide compound and fusing assistant stoichiometric ratio take raw material SrCO
3182.24g, BaCO
3243.60g, SiO
274.16g, Eu
2o
33.91g, Y
2o
35.57g, MgCl
25.9g (5% of Si mole number), mixing, after roller bottle ball mill grinding 10h; be placed in corundum crucible; uncapping, crucible is placed in tube furnace, is be warming up to 1350 DEG C with the speed of 10 DEG C/min in 3:1 at shielding gas nitrogen, hydrogen volume ratio; then room temperature is naturally cooled to after being incubated 4 hours; take out broken, cross 200 mesh sieves, ball milling, moisture (removing small-particle by washing with alcohol); at 60 DEG C, dry 2h, obtain alkaline earth metal silicate green/yellowish green fluorescent powder.
Comparative example 2
According to (Ba, Sr)
2siO
4: 0.02Eu
2+, 0.04Y
3+in the carbonate of each element or oxide compound and fusing assistant stoichiometric ratio take raw material SrCO
3182.24g, BaCO
3243.60g, SiO
274.16g, Eu
2o
33.91g, Y
2o
35.57g, MgF
23.69g (5% of Si mole number), mixing, after roller bottle ball mill grinding 10h; be placed in corundum crucible; uncapping, crucible is placed in tube furnace, is be warming up to 1350 DEG C with the speed of 10 DEG C/min in 3:1 at shielding gas nitrogen, hydrogen volume ratio; then room temperature is naturally cooled to after being incubated 4 hours; take out broken, cross 200 mesh sieves, ball milling, remove small-particle by washing with alcohol; at 60 DEG C, dry 2h, obtain alkaline earth metal silicate green/yellowish green fluorescent powder.
Embodiment 2-4 and comparative example 3-7
Comparative example 3-7 uses the structural formula raw material identical with comparative example 2 and technique, but use fusing assistant difference to some extent.Concrete fusing assistant service condition is as following table:
In conjunction with comparative example 2-7 and embodiment 1-4, can reflect to a certain extent, different flux is to M
2siO
4impact.In order to more significantly characterize these impacts, the Performance Detection of sample uses work in-process to measure, simultaneously, aftertreatment needs the number of times of moisture also can characterize the number of broken particle contained by work in-process, after yield=aftertreatment resulting materials quality (fluorescent material finished product)/aftertreatment before quality (fluorescent material crude product).
| Experiment sequence number | Peak wavelength/nm | Relative brightness/% | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Embodiment 1 | 522 | 90.7 | 16.7 | 1.35 | 61.2 | 0.875 | 2 |
| Comparative example 2 | 521 | 98.6 | 25.7 | 1.47 | 61.3 | 0.657 | 4 |
| Embodiment 2 | 524 | 76.3 | 18.2 | 1.36 | 64.6 | 0.832 | 2 |
| Comparative example 3 | 522 | 92.3 | 26.4 | 1.49 | 62.7 | 0.636 | 5 |
| Embodiment 3 | 523 | 88.4 | 17.6 | 1.31 | 61.7 | 0.889 | 1 |
| Comparative example 4 | 521 | 95.8 | 31.2 | 1.43 | 61.4 | 0.643 | 5 |
| Embodiment 4 | 531 | 62.3 | 19.2 | 1.28 | 72.3 | 0.867 | 2 |
| Comparative example 5 | 524 | 88.6 | 28.3 | 1.46 | 63.6 | 0.591 | 5 |
| Comparative example 6 | 522 | 70.3 | 16.2 | 1.31 | 61.2 | 0.885 | 1 |
| Comparative example 7 | 522 | 82.3 | 23.2 | 1.52 | 61.4 | 0.579 | 6 |
As seen from the above table, most of muriate fusing assistant is obvious not as fluorochemical for the lifting of particle or spectral intensity, and this also may be that current industry seldom adopts muriate fusing assistant as M
2siO
4the reason of system fusing assistant, but muriate also has its advantage clearly, and compared to fluorochemical, muriate integral particle homogeneity is far better, and aftertreatment yield wants high a lot, and needs moisture number of times also less.In the present invention, moisture refers to the small-particle removing fluorescent material by washing with alcohol, and moisture number of times is exactly the number of times by washing with alcohol.
Embodiment 5-7, comparative example 8-9
Embodiment 5-7, comparative example 8-9 use the structural formula raw material identical with embodiment 1 and technique, but its fusing assistant usage quantity difference to some extent.Concrete fusing assistant usage quantity situation is as following table:
This group laboratory test results is as following table:
| Experiment sequence number | Peak wavelength/nm | Relative brightness/% | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Comparative example 8 | 520 | 72.3 | 9.2 | 1.45 | 62.4 | 0.823 | 3 |
| Embodiment 5 | 521 | 86.4 | 12.7 | 1.35 | 61.3 | 0.857 | 2 |
| Embodiment 6 | 522 | 91.3 | 17.2 | 1.32 | 61.7 | 0.886 | 1 |
| Embodiment 7 | 522 | 87.5 | 23.2 | 1.21 | 62.2 | 0.833 | 3 |
| Comparative example 9 | 523 | 77.2 | 26.5 | 1.44 | 64.2 | 0.623 | 4 |
As seen from the above table, fusing assistant usage quantity too low or too high time, half-finished performance is all bad, too low, and core particle diameter is too little, and lattice defect is many, luminous intensity be difficult to ensure.Too high, based on fusing assistant mechanism, reactive center is too many, cause particle inter-adhesive, and macrobead part is etched into small-particle, and fusing assistant itself also affects material body luminescent properties, therefore effect bad.
Comprehensive Experiment result, muriate is to M
2siO
4system effect of fluxing can not show a candle to fluorochemical, especially for CaCl
2, SrCl
2deng two kinds of muriates, these two kinds of auxiliary agents help and melt effect not only not as fluorochemical, there is a large amount of dephasign in its semi-finished product material body.For M
2siO
4system, adjustment peak wavelength generally adopts two kinds of methods, one is Sr/Ba ratio in change system, two is introduce Ca in system, but no matter be the introducing of Ca or the change of Sr/Ba ratio, system quantum yield all can be made to change, therefore, in conjunction with human eye vision function, the final luminous light efficiency of its change process is a process first increasing rear reduction.
Embodiment 8-13 and comparative example 10
This group laboratory test results is as following table:
| Experiment sequence number | Peak wavelength/nm | Relative brightness | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Embodiment 8 | 522 | 91.1 | 16.4 | 1.37 | 61.5 | 0.865 | 2 |
| Embodiment 9 | 523 | 94.6 | 16.3 | 1.33 | 62.1 | 0.878 | 2 |
| Embodiment 10 | 526 | 98.9 | 17.1 | 1.36 | 63.4 | 0.869 | 2 |
| Embodiment 11 | 529 | 105.8 | 16.8 | 1.41 | 67.9 | 0.886 | 2 |
| Comparative example 10 | 528 | 64.3 | 16.2 | 1.31 | 69.2 | 0.889 | 1 |
| Embodiment 12 | 523 | 98.2 | 12.6 | 1.33 | 62.8 | 0.883 | 1 |
| Embodiment 13 | 526 | 108.6 | 19.2 | 1.28 | 65.9 | 0.877 | 1 |
| Embodiment 14 | 529 | 114.2 | 24.3 | 1.31 | 69.3 | 0.891 | 2 |
As shown above, CaCl
2make fusing assistant, effect is still very poor, but it should be noted that when in system, with part MgO as in magnesium source replacement system during Sr or Ba, still uses CaCl
2make fusing assistant, material body dephasign rapidly disappears, and system luminous intensity increases rapidly, and compared to traditional CaCO
3do calcium source, in same peak wavelength situation, its luminescence is not a halfpenny the worse, and there be limited evidence currently of has relevant report.
Embodiment 15-22, comparative example 11-14:
In high temperature solid-state method, sintering process is obvious equally for the impact of the spectral intensity of final sample.This group experiment major ingredient formula and heat preservation method as follows, rest part, with embodiment 1, repeats no more.
The experimental data detecting fluorescent material is as follows.
| Experiment sequence number | Peak wavelength/nm | Relative brightness/% | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Comparative example 11 | 524 | 81.2 | 12.2 | 1.47 | 64.6 | 0.804 | 2 |
| Embodiment 15 | 525 | 103.2 | 16.8 | 1.36 | 65.6 | 0.853 | 2 |
| Embodiment 16 | 526 | 105.1 | 18.2 | 1.31 | 66.0 | 0.872 | 2 |
| Embodiment 10 | 526 | 108.6 | 19.2 | 1.28 | 65.9 | 0.877 | 1 |
| Embodiment 17 | 527 | 107.5 | 20.2 | 1.26 | 66.2 | 0.881 | 2 |
| Embodiment 18 | 527 | 106.8 | 20.8 | 1.27 | 66.1 | 0.889 | 2 |
| Comparative example 12 | 529 | 98.2 | 26.5 | 1.26 | 68.2 | 0.725 | 3 |
| Comparative example 13 | 522 | 68.2 | 12.6 | 1.56 | 73.3 | 0.617 | 5 |
| Embodiment 19 | 526 | 105.7 | 18.9 | 1.33 | 66.2 | 0.856 | 2 |
| Embodiment 20 | 526 | 108.3 | 19.0 | 1.28 | 66.0 | 0.885 | 1 |
| Embodiment 21 | 526 | 108.5 | 19.6 | 1.30 | 66.1 | 0.879 | 2 |
| Embodiment 22 | 526 | 106.8 | 19.8 | 1.29 | 65.7 | 0.863 | 1 |
| Comparative example 14 | 526 | 101.2 | 19.6 | 1.37 | 67.3 | 0.796 | 3 |
Too low temperature and too short soaking time are unfavorable for M
2siO
4the generation of system, be also unfavorable for that fusing assistant plays a role, and namely too high temperature and long soaking time is unfavorable for Simplified flowsheet, save energy, dephasign content in resultant also can be made to increase, and increase the half-finished difficulty of process.
Embodiment 23-30 comparative example 15,16
For M
2siO
4system, M case is most important to final crystal structure quality, and simple large elements Sr or Ba add, and is difficult to the sample obtaining good crystallinity, and therefore, often adulterate some trace elements, adjusts M
2siO
4system crystallinity, reduces this system lattice imperfection, obtains luminous intensity or the higher fluorescent material of quantum yield.This group experiment major ingredient proportioning is as following table, and other experiment condition is with embodiment 1.
This group experimental test data is as follows, for convenience of analyzing, embodiment 10 data is inserted contrast.
| Experiment sequence number | Peak wavelength/nm | Relative brightness | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Embodiment 23 | 526 | 101.6 | 18.7 | 1.36 | 67.6 | 0.836 | 2 |
| Embodiment 10 | 526 | 108.6 | 19.2 | 1.28 | 65.9 | 0.877 | 1 |
| Embodiment 24 | 526 | 109.2 | 18.8 | 1.34 | 66.2 | 0.864 | 2 |
| Embodiment 25 | 525 | 104.2 | 18.1 | 1.41 | 66.8 | 0.822 | 3 |
| Comparative example 15 | 523 | 90.6 | 16.5 | 1.56 | 69.6 | 0.684 | 5 |
| Embodiment 26 | 528 | 110.2 | 19.0 | 1.33 | 67.2 | 0.847 | 2 |
| Embodiment 27 | 529 | 111.3 | 19.2 | 1.33 | 69.8 | 0.853 | 2 |
| Embodiment 28 | 530 | 112.6 | 19.5 | 1.37 | 70.2 | 0.862 | 2 |
| Embodiment 29 | 534 | 110.6 | 18.9 | 1.40 | 71.4 | 0.855 | 3 |
| Embodiment 30 | 540 | 108.6 | 17.6 | 1.39 | 73.9 | 0.824 | 3 |
| Comparative example 16 | 567 | 52.6 | 16.7 | 1.48 | 86.6 | 0.752 | 4 |
The introducing of magnesium, system brightness can be promoted, if under burst of ultraviolel, the blue-light emitting body that magnesium and system acting in conjunction generate can be found under the microscope, but introduce magnesium in a large number, the not luminous small-particle of system can be made to increase rapidly, and then affect sample crystallinity, cause lattice imperfection, reduction system luminous intensity, and introduce calcium, as mentioned before, be M
2siO
4one of system red shift method, red shift successful, also as mentioned before, auxiliary agent usage quantity is too much unsuitable, so use CaCl
2make the limitation that fusing assistant regulates chromaticity coordinates, if desired, in system, still will add CaCO
3do calcium source, to obtain the fluorescent material of required chromaticity coordinates, but a large amount of introducings of calcium, system luminous intensity can be made to reduce rapidly.
Embodiment 31-38, comparative example 17,18
Many doping are for M
2siO
4system also has greatly improved, and its mechanism may be, in many doping process, the doping agent of introducing reduces M
2siO
4the lattice imperfection of system, thus its luminous efficiency is improved.This group experiment major ingredient proportioning is as following table, and other conditions are with embodiment 1.
Experimental test data is as follows.
| Experiment sequence number | Peak wavelength/nm | Relative brightness/% | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Comparative example 17 | 525 | 82.6 | 18.6 | 1.30 | 66.1 | 0.876 | 2 |
| Embodiment 31 | 526 | 97.3 | 18.2 | 1.32 | 65.9 | 0.857 | 2 |
| Embodiment 10 | 526 | 108.6 | 19.2 | 1.28 | 65.9 | 0.877 | 1 |
| Embodiment 32 | 526 | 101.2 | 19.3 | 1.39 | 66.4 | 0.815 | 3 |
| Comparative example 18 | 528 | 65.3 | 15.2 | 1.64 | 70.2 | 0.522 | 6 |
| Embodiment 33 | 526 | 110.2 | 19.0 | 1.31 | 66.2 | 0.889 | 1 |
| Embodiment 34 | 526 | 106.3 | 18.6 | 1.33 | 65.9 | 0.876 | 2 |
| Embodiment 35 | 526 | 109.2 | 18.8 | 1.30 | 66.0 | 0.884 | 1 |
| Embodiment 36 | 526 | 104.3 | 19.1 | 1.29 | 66.0 | 0.879 | 2 |
| Embodiment 37 | 526 | 106.7 | 19.2 | 1.34 | 66.1 | 0.868 | 2 |
| Embodiment 38 | 526 | 108.6 | 18.9 | 1.32 | 65.8 | 0.877 | 2 |
When introducing the second hotchpotch in system, system bulk crystal defect is obvious, and luminous intensity is limited, and the many hotchpotchs of appropriate introducing, contribute to M
2siO
4system luminous intensity increases, but should not introduce too much hotchpotch.
Embodiment 39,40, comparative example 19,20
Eu is as M
2siO
4system activator, it is direct that to affect in system luminescence center how many, therefore, Eu doping number, on the impact of its luminous intensity the most directly and obviously.This group experiment major ingredient proportioning is as following table, and other conditions are with embodiment 1.
This group experimental test data is as follows, for convenience of analyzing, embodiment 10 data is inserted contrast.
When in system, luminescence center is very few, system luminous intensity is limited, and when in system, luminescence center is too much, transmission ofenergy each other between luminescence center and luminescence center, thus causes luminescence center cancellation, affects the luminous intensity of system.
Embodiment 43-47, comparative example 21,22:
Si is at M
2siO
4system plays the effect of nucleation, in whole split particle growth process, Si number be related to the final whether M generated
2siO
4, M
3siO
5and M
5si
2o
7also be common silicate fluorescent powder, final concrete generate which phase, and Si number relevant.This group experiment major ingredient proportioning is as following table, and other conditions are with embodiment 1.
This group experimental test data is as follows, for convenience of analyzing, embodiment 10 data is inserted contrast.
Have above data to find out, Si is very few, and system dephasign is too much, and sample brightness is difficult to ensure, aftertreatment yield is extremely low, and Si is too much, and sample small-particle increases obviously, even direct at high temperature vitrify.
Embodiment 48-53:
For M
2siO
4system, introduces Ba and can make system blue shift, therefore, changes Sr/Ba than one of main method being adjustment system peak wavelength and chromaticity coordinates.This group experiment major ingredient proportioning is as following table, and other conditions are with embodiment 1.
This group experimental test data is as follows.
| Numbering | Peak wavelength/nm | Relative brightness/% | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Embodiment 48 | 532 | 120.1 | 17.8 | 1.39 | 68.4 | 0.852 | 2 |
| Embodiment 49 | 540 | 112.2 | 16.7 | 1.34 | 69.6 | 0.868 | 2 |
| Embodiment 50 | 558 | 100.6 | 16.8 | 1.32 | 70.5 | 0.891 | 1 |
| Embodiment 51 | 520 | 102.1 | 18.1 | 1.34 | 64.7 | 0.864 | 2 |
| Embodiment 52 | 516 | 96.7 | 18.4 | 1.41 | 65.8 | 0.873 | 2 |
| Embodiment 53 | 510 | 87.2 | 18.5 | 1.43 | 65.6 | 0.864 | 2 |
Embodiment 54-60:
Comprehensive described various factors impact and the present invention's various trial in experimentation above, obtain the silicate fluorescent powder of a collection of excellent property, one of object of adjustment is exactly, obtain that particle diameter is little, uniform particles, the simple silicate fluorescent powder of aftertreatment, then an object uses the luminous intensity meeting or exceeding fluoride flux only for muriate fusing assistant.This group experiment major ingredient proportioning is as following table, and other conditions are with embodiment 1.
This group experimental test data is as follows, for convenience of analyzing, includes comparative example 1 in following table
| Numbering | Peak wavelength/nm | Relative brightness/% | D 50 | (D 90-D 10)/D 50 | Peak width at half height/nm | Yield | Moisture number of times |
| Comparative example 1 | 522 | 100 | 13.6 | 1.59 | 64.1 | 0.591 | 5 |
| Embodiment 54 | 521 | 110.7 | 16.0 | 1.24 | 62.7 | 0.901 | 1 |
| Embodiment 55 | 523 | 113.3 | 16.1 | 1.26 | 63.6 | 0.892 | 1 |
| Embodiment 56 | 525 | 114.7 | 15.6 | 1.20 | 66.0 | 0.904 | 1 |
| Embodiment 57 | 530 | 129.3 | 16.1 | 1.11 | 70.3 | 0.912 | 1 |
| Embodiment 58 | 540 | 125.3 | 16.0 | 1.14 | 73.4 | 0.907 | 1 |
| Embodiment 59 | 565 | 101.3 | 12.3 | 1.11 | 82.7 | 0.914 | 1 |
| Embodiment 60 | 570 | 100.5 | 14.9 | 1.06 | 92.9 | 0.926 | 1 |
As shown in allocation sheet, test the fusing assistant only used for these several groups, ensure that grain diameter growth is little, like this, can save in last handling process broken, then save production stage, reduce production cost; Used by multiple fusing assistant doping, ensure fluorescent material each temperature section in sintering process, have applicable fusing assistant effect, ensure that its particle growth homogeneity, ensure that powder light efficiency when particle is little; Pass through CaCl
2, CaCO
3, adjustment Sr/Ba than etc., have adjusted peak wavelength, obtain the fluorescent material of different peak wavelength excellent performance; And Comprehensive Correlation example 1, the present invention only uses muriate fusing assistant, obtains the light efficiency of fluoride flux in no way inferior.
Claims (9)
1. alkaline earth metal silicate green/yellowish green fluorescent powder, it is characterized in that, the chemical general formula of this fluorescent material is (Sr, A
1)
xsiO
(2+x): yEu
2+, zA
2 3+; A is not added in formula
1or A
1for at least one in Ba, Mg, Ca, A
2for at least one in Y, La, Sc, Er, and 1.9≤x≤2.1,0.005≤y≤0.2,0.01≤z≤0.2.
2. alkaline earth metal silicate green/preparation method of yellowish green fluorescent powder, it is characterized in that, comprise the following steps:
A () is according to claim 1 chemical general formula (Sr, A
1)
xsiO
(2+x): yEu
2+, zA
2 3+in the mol ratio of each element take containing Sr, A
1, Si, A
2, the oxide compound of Eu element or carbonate and mole number be the fusing assistant of described Si mole number 1-30%, mixing, grinding, obtains mixture;
B mixture is warming up to 1250-1450 DEG C by () under reducing atmosphere condition, insulation 3-12h, is cooled to room temperature, obtains fluorescent material crude product;
C () broken by described fluorescent material crude product, sieve, ball milling, alcohol wash, oven dry, obtain alkaline earth metal silicate green/yellowish green fluorescent powder.
3. alkaline earth metal silicate according to claim 2 green/preparation method of yellowish green fluorescent powder, it is characterized in that, fusing assistant described in step (a) is the mixture of one or more arbitrary proportions in bivalent metal halide, and bivalent metal halide is not fluorochemical.
4. alkaline earth metal silicate according to claim 3 green/preparation method of yellowish green fluorescent powder, it is characterized in that, the divalent metal in described bivalent metal halide is any one or a few in Sr, Ba, Mg or Ca.
5. alkaline earth metal silicate according to claim 4 green/preparation method of yellowish green fluorescent powder, it is characterized in that, described bivalent metal halide is the mixture of one or more arbitrary proportions in magnesium chloride, calcium chloride, strontium chloride or bariumchloride.
6. alkaline earth metal silicate according to claim 2 green/preparation method of yellowish green fluorescent powder, it is characterized in that, the reducing atmosphere described in step (b) refers to N
2, H
2the reducing atmosphere that mixed gas is formed.
7. alkaline earth metal silicate according to claim 2 green/preparation method of yellowish green fluorescent powder, it is characterized in that, the temperature rise rate of the described intensification of step (b) is 5-10 DEG C/min.
8. alkaline earth metal silicate according to claim 2 green/preparation method of yellowish green fluorescent powder, it is characterized in that, the temperature of the described oven dry of step (c) is 40-80 DEG C, and the time is 2-3h.
9. an alkaline earth metal silicate according to claim 1 green/yellow-green fluorescence pruinescence blue light or ultraviolet excitation under application in illumination or indicating system.
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