CN106929011B - A kind of white emitting fluorescent powder and preparation method thereof of ultraviolet LED excitation - Google Patents
A kind of white emitting fluorescent powder and preparation method thereof of ultraviolet LED excitation Download PDFInfo
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Abstract
The invention discloses a kind of white emitting fluorescent powder and preparation method thereof of ultraviolet LED excitation, the chemical general formula of the fluorescent powder is M1‑x‑y‑zSmxTbyTmzAlSiN3-2(x+y+z)/3O3(x+y+z)/2, wherein at least one of M Ca, Sr, Ba, 0.001≤x≤0.2,0.001≤y≤0.1,0.001≤z≤0.2.White emitting fluorescent powder provided by the invention can be excited by the shorter ultraviolet LED of wavelength；Preparation method are as follows: weigh raw material and fluxing agent according to the molar ratio of each element in chemical general formula, the fluorescent powder for emitting white light in single-matrix is made by segmented high-temperature solid phase calcination method, overcomes defect brought by fluorescent powder mixing preparation.The emission spectrum continuity of white emitting fluorescent powder of the present invention is good, colour rendering is high, photochromic decaying is consistent, stability is good, and product yield is higher, can be widely applied to the places such as plant growth lighting, mobile phone LED light compensating lamp, film studio decoration.
Description
Technical field
The present invention relates to a kind of white emitting fluorescent powder, the specifically a kind of white emitting fluorescent powder and its system of ultraviolet LED excitation
Preparation Method.
Background technique
In recent years, with the luminous efficiency of light emitting diode (Light Emitting Diode, LED) be gradually increased with
And cost is gradually reduced, semiconductor lighting is increasingly becoming the development trend of modern illumination, white light LEDs be known as after incandescent lamp,
Forth generation lighting electric light source after fluorescent lamp and energy-saving lamp, referred to as " 21 century green light source ".
Currently, preparing white light LEDs, there are mainly three types of methods, the first is obtained using LED red-green-blue chip portfolio
To white light；Second is using LED blue chip excitation yellow fluorescent powder or LED blue chip while excitated red fluorescent powder
White light is synthesized with green emitting phosphor；The third is to issue three primary colours synthesis white light using UV LED chip excitation RGB fluorescent powder.
Although first two prepares the methods of white light LEDs relative maturity, there is also very big disadvantages.First method is due to three
Primary colours light decay difference causes colour temperature unstable, and control circuit is more complex, higher cost.There are consistency for second method
The shortcomings that difference, colour temperature are with angle change forces people to seek efficient, high color rendering index (CRI) Ra, stability preferably ultraviolet+RGB three
Color fluorescent powder scheme.
The most nitride found in the recent period, nitric oxide fluorescent powder are all burst of ultraviolel, and show good calorifics, change
Learn stability.And from the comfort level of illumination and for being conducive to the angle of plant growth, there is the light close to daylight to be only most
Good selection.When preparing white light LEDs as excitaton source cooperation RGB fluorescent powder using ultraviolet LED, due to the fluorescence of different substrates
There is radiation to reabsorb between powder, will increase energy loss, reduces luminous efficiency.Therefore the excitation of exploitation ultraviolet LED is single-phase
Fluorescent powder becomes mainstream development trend.
Summary of the invention
One of the objects of the present invention is to provide a kind of white emitting fluorescent powders of ultraviolet LED excitation, to solve existing white light LEDs
Light-emitting phosphor low efficiency used, the problem that thermal stability is poor, light decay is inconsistent.
The second object of the present invention is to provide the preparation method of the white emitting fluorescent powder of above-mentioned ultraviolet LED excitation.
The present invention is that technical solution used by realizing object above is as follows:
The present invention provides a kind of white emitting fluorescent powder of ultraviolet LED excitation, chemical general formula M1-x-y- zSmxTbyTmzAlSiN3-2(x+y+z)/3O3(x+y+z)/2, in which: at least one of M Ca, Sr, Ba, 0.001≤x≤0.2,
0.001≤y≤0.1,0.001≤z≤0.2.
The white emitting fluorescent powder can launch white light, exciting light under the excitation for the ultraviolet light that wavelength is 250~390nm
Wavelength is shorter, and excitation spectrum range is wide.
The present invention also provides the preparation methods of the white emitting fluorescent powder of above-mentioned ultraviolet LED excitation, comprising the following steps:
(a) according to the chemical general formula M of fluorescent powder1-x-y-zSmxTbyTmzAlSiN3-2(x+y+z)/3O3(x+y+z)/2Middle each element is rubbed
You weigh the nitride containing M, Al, Si and the nitride or oxide of Sm, Tb, Tm by ratio, and the purity of weighed raw material is
99.99wt%, at 3~5 μm, and by weighed raw material and fluxing agent, dry-mixed grinding is made raw material particle size under inert gas protection
Mixture.
(b) it is sintered: mixture made from step (a) is subjected to multi-steps sintering under reducing atmosphere, wherein
Stage one: first under normal pressure, it is warming up to 1400-1550 DEG C with the rate of 150-300 DEG C/h, reducing gas flow is
0.5-1.2L/min, heat preservation sintering 5-8h；
Stage two: rising to 1-5MPa for pressure again, while being warming up to 1700-1850 DEG C with the rate of 100-250 DEG C/h, and
Heat preservation sintering 4-6h；
(c) it anneals: after (b) step, starting to be cooled to 900-1000 DEG C, then Temperature fall with the rate of 300-500 DEG C/h
It is taken out after to room temperature；
(d) products therefrom is ground, crosses 200 meshes, and pickling is glimmering to get the white light of ultraviolet LED excitation after washing and drying
Light powder.
In step (a), the fluxing agent is NH4Cl, NaF and H3BO3Mixture, the mass ratio of three is NH4Cl:
NaF:H3BO3=1:a:b, wherein 0.5≤a≤2,0.5≤b≤2；It is preferred that fluxing agent additional amount account for total mass of raw material 3%~
8%.
In step (a), raw material weigh with it is dry-mixed grinding carry out under inert gas protection, inert gas be nitrogen,
One of argon gas or helium, dry-mixed milling time is in 40min or more.
In step (b), reducibility gas is the mixed gas of nitrogen and hydrogen, the ratio of nitrogen and hydrogen be 80:20~
95:5。
In step (d), pickling processes are carried out with 10-25% hydrochloric acid, and revolving speed is 300r/min, time 30- when pickling
55min is washed to conductivity less than 20 μ s/cm with deionized water after pickling.
The present invention passes through doping Sm3+、Tb3+、Dy3+Equal elements, have obtained to be emitted white by shorter wavelength ultraviolet excitation
The single-phase phosphor of light, and the luminous intensity of fluorescent powder is high, overcomes defect brought by fluorescent powder mixing preparation and shows
The problem for having single-phase white-emitting phosphor light efficiency low.By change element doping concentration, the chromaticity coordinates of adjustable fluorescent powder,
The white light for emitting it is more suitable for the fields such as plant growth lighting, mobile phone LED light compensating lamp, film studio decoration closer to daylight
Institute.In addition, fluorescent powder of the invention has preferable chemical stability and moisture resistance, and there is preferable light decay consistency, energy
Meet the requirement of LED well.
Preparation method of the present invention is simple, and sintering time is short, using NH4Cl, NaF and H3BO3The mixture of composition is as fluxing
Agent obtains pure single-phase, has so that raw material preferably mixes in the molten state, while by the way of baking inphases
Effect improves the luminous intensity and finished product material yield of fluorescent powder, and gained finished product has preferable granule-morphology and the uniformity.
Detailed description of the invention
Fig. 1 is the SEM figure of 1 gained fluorescent powder of embodiment.
Fig. 2 is the exciting light spectrogram of embodiment 1.
Fig. 3 is the launching light spectrogram of embodiment 1.
Fig. 4 is the thermal quenching intensity variation curve figure of embodiment 1, embodiment 11 and comparative example 1.
Fig. 5 is the relative luminance change curve of comparative example 1 and embodiment 1 in double 85 experiments.
Fig. 6 is the x chromaticity coordinates change curve of comparative example 1 and embodiment 1 in double 85 experiments.
Specific embodiment
The present invention provides a kind of white emitting fluorescent powder of ultraviolet LED excitation, chemical general formula M1-x-y- zSmxTbyTmzAlSiN3-2(x+y+z)/3O3(x+y+z)/2, in which: at least one of M Ca, Sr, Ba, 0.001≤x≤0.2,
0.001≤y≤0.1,0.001≤z≤0.2.
The white emitting fluorescent powder can launch white light under the excitation for the ultraviolet light that wavelength is 250~390nm.
Illustrate the preparation method of fluorescent powder of the present invention combined with specific embodiments below, and to the correlation of prepared fluorescent powder
Performance is evaluated.
Pressure mentioned in the present invention is absolute pressure, and testing graininess is to utilize laser particle analyzer LS-C in the present invention
(I) it tests, relative luminance is tested using high-precision fast spectrum radiometer, and K=(D90-D10)/D50 is for measuring particle
Uniformity coefficient is spent, the quality after yield=post-processing before the quality (fluorescent powder finished product) × 100% of resulting materials/post-processing is (glimmering
Light powder crude product).
Embodiment 1
(1) according to chemical formula Sr0.6Ca0.25Sm0.04Tb0.06Tm0.05AlSiN2.9O0.225Stoichiometric ratio weigh respectively
0.02molSr3N2、0.0083mol Ca3N2、0.1mol AlN、0.033mol Si3N4、0.002mol Sm2O3、0.0015mol
Tb4O7、0.0025mol Tm2O3, the purity of raw material is 99.99%, and raw material particle size is at 3~5 μm；
Note: all of above raw material is weighed in glove box N2It is carried out under atmosphere
(2) it weighs by NH4Cl、NaF、H3BO3The mixed flux of composition, the gross mass of the mixed flux are step
(1) the 4% of total mass of raw material is weighed in, and three's mass ratio is NH4Cl:NaF:H3BO3=2:3:2；
(3) by step (1) and (two) weighed all raw materials and fluxing agent in N2It is ground in agate mortar under atmosphere
Mill 40min or more is uniformly mixed it, is then transferred in molybdenum crucible and covers crucible cover for raw material, crucible is put into air pressure furnace
In, after carrying out 4 vacuum pumpings by vacuum pump, reducing gas that nitrogen/hydrogen ratio is 90:10 is filled with to normal pressure, gas
Body flow is 1L/min；
(4) under normal pressure, 1450 DEG C first are warming up to the rate of 240 DEG C/h and keep the temperature 6h, then boost to air pressure furnace
2.5MPa is warming up to 1820 DEG C with the rate of 180 DEG C/h with this, and keeps the temperature 5h, is cooled to later with the rate of 360 DEG C/h
1000 DEG C, it is finally naturally cooling to room temperature, obtains fluorescent powder crude product；
(5) gained crude product is ground, crosses 200 meshes, be then stirred pickling with the hydrochloric acid that concentration is 18%
35min is washed to conductivity less than 20 μ s/cm with deionized water later, and finally at 80 DEG C, baking 4h obtains finished product Sr0.6
Ca0.25Sm0.04Tb0.06Tm0.05AlSiN2.9O0.225Fluorescent powder.Products obtained therefrom is characterized, as a result as shown in figs. 1 to 6.
The excitation spectrum and emission spectrum of above-mentioned fluorescent powder are shown in Fig. 2 and Fig. 3 respectively.It can be seen that being 310nm in wavelength
Ultraviolet light excitation under, fluorescent powder can launch simultaneously peak wavelength be respectively the feux rouges of 656nm, 550nm green light and
The blue light of 468nm, final three coloured light are mixed into white light.
Comparative example 1
It is as follows that repeated experiment is carried out according to the embodiment 1 of patent CN 105623660A:
Weigh 0.9701g Nb2O5, 0.9869g In2O3, 0.0136g Dy2O3, 0.0141g Tm2O3With 0.0077g Eu,
15min is ground in agate mortar, is uniformly mixed raw material.The raw material of mixing is placed in corundum crucible, with 5 in resistance furnace
DEG C/speed of min is warming up to 1000 DEG C of progress first stage sintering, sintering time 12h.Then furnace cooling produces sintering
Object grinds 10min, then is warming up to 1250 DEG C of progress second stage sintering with the speed of 5 DEG C/min, and sintering time is for 24 hours.With furnace
It is ground after cooling, it is In that ingredient, which can be obtained,0.974Dy0.01Tm0.01Eu0.006NbO4Fluorescent powder.This fluorescent powder is in ultraviolet region
Excitation band be 355-365nm, products obtained therefrom is characterized, as a result as shown in figures 4-6.
Embodiment 2-11
Change the doping (being specifically shown in Table 1) of Sm, Tb, Tm element, other process conditions are same as Example 1, by institute
It obtains dependence test result to be compared with embodiment 1 and comparative example 1, as shown in table 1.
Table 1:
As shown in Table 1, the relative luminance of the embodiment of the present invention will be substantially better than comparative example 1, and chromaticity coordinates is closer to pure
Positive white light chromaticity coordinates (0.33,0.33).
Choose embodiment 1, embodiment 11 and 1 gained fluorescent powder of comparative example carry out temperature quenching test, detection temperature from
300K is increased to 500K, and when temperature every variation 50K carries out one-time detection to it, and the results are shown in Table 2 for record, while by three samples
It is as shown in Figure 4 that product variation with temperature rule draws curve graph.
Table 2:
By table 2 and Fig. 4 it is found that when temperature rises to 500K, the relative luminance of comparative example 1 is down to former relative luminance
80%, the relative luminance of embodiment 1 and embodiment 11 is down to the 95% and 92% of former relative luminance respectively, illustrates 1 He of embodiment
The thermal stability of embodiment 11 is better than comparative example 1.
Double 85 experiment tests are carried out to embodiment 1 and comparative example 1, i.e., weigh 15g fluorescent powder respectively, in temperature be 85 DEG C,
Humidity is tested in the environment of being 85%, time 1000h, detects the change of primary its relative luminance and chromaticity coordinates every 200h
Change, and record sheet 3, the Testing index in table 3 is charted respectively, the changing rule of Testing index is as shown in Figure 5 and Figure 6.By
Test result is it is found that the stability of 1 gained fluorescent powder of embodiment is more preferable.
Table 3:
Embodiment 12-19
Change the additive amount of fluxing agent and changes the ratio (being specifically shown in Table 4) of each ingredient in fluxing agent, other technique items
Part and material rate are same as Example 1, gained dependence test result and embodiment 1 and comparative example 1 are compared, such as table
Shown in 4.
Table 4:
As shown in Table 4,1 gained fluorescent powder relative luminance of comparative example is lower, and particle is larger, needs break process, and finished product is received
Rate is relatively low, and addition known to embodiment 12-13 and embodiment 18-19 is a small amount of or excessive fluxing agent so that fluorescent powder grain compared with
It is small or larger, it is unfavorable for encapsulating, yield is also undesirable；When fluxing agent additional amount is 4%, NH4Cl:NaF:H3BO3When=2:3:2,
The comprehensive performance of the fluorescent powder of acquisition is best, present invention provide that fluorescent powder prepared after adding fluxing agent in range, grain
Diameter changes with the difference of fluxing agent additional amount, and product yield maintains preferable range, and product comprehensive performance is also preferable.
Claims (4)
1. a kind of white emitting fluorescent powder of ultraviolet LED excitation, it is characterised in that: the chemical general formula of the fluorescent powder is
M1-x-y-zSmxTbyTmzAlSiN3-2(x+y+z)/3O3(x+y+z)/2, in which: at least one of M Ca, Sr, Ba, 0.001≤x
≤ 0.2,0.001≤y≤0.1,0.001≤z≤0.2.
2. a kind of preparation method of the white emitting fluorescent powder of ultraviolet LED described in claim 1 excitation, which is characterized in that including with
Lower step:
(a) according to claim 1 chemical general formula M1-x-y-zSmxTbyTmzAlSiN3-2(x+y+z)/3O3(x+y+z)/2Mole of middle each element
Than the oxide for weighing the nitride of the nitride containing M, Al, the nitride of Si, the oxide of Sm, the oxide of Tb, Tm, and
By weighed raw material and fluxing agent, mixture is made in dry-mixed grinding under inert gas protection；
(b) it is sintered: mixture made from step (a) is subjected to multi-steps sintering under reducing atmosphere, wherein
Stage one: first under normal pressure, it is warming up to 1400-1550 DEG C with the rate of 150-300 DEG C/h, heat preservation sintering 5-8h；
Stage two: pressure is risen into 1-5MPa again, while being warming up to 1700-1850 DEG C with the rate of 100-250 DEG C/h, and keep the temperature
It is sintered 4-6h；
(c) it anneals: after (b) step, starting to be cooled to 900-1000 DEG C with the rate of 300-500 DEG C/h, then be naturally cooling to room
It is taken out after temperature；
(d) products therefrom is ground, sieving, pickling, to get the white emitting fluorescent powder of ultraviolet LED excitation after washing and drying.
3. the preparation method of the white emitting fluorescent powder of ultraviolet LED excitation according to claim 2, which is characterized in that step (a)
In, the fluxing agent is NH4Cl, NaF and H3BO3Mixture, the mass ratio of three is NH4Cl:NaF:H3BO3=1:a:b,
In, 0.5≤a≤2,0.5≤b≤2；The additional amount of fluxing agent is the 3% ~ 8% of total mass of raw material.
4. the preparation method of the white emitting fluorescent powder of ultraviolet LED excitation according to claim 2, which is characterized in that step (d)
In, revolving speed is 300r/min, time 30-55min when pickling, is washed to conductivity less than 20 μ s/ with deionized water after pickling
cm。
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| CN103525409A (en) * | 2013-10-09 | 2014-01-22 | 张书生 | A high-luminous-efficiency high-stability nitride luminescent material and a manufacture method thereof |
| CN105462588A (en) * | 2015-12-03 | 2016-04-06 | 河北利福光电技术有限公司 | Nitrogen oxide red fluorescence powder as well as preparation method and application thereof |
| CN105969356A (en) * | 2016-05-30 | 2016-09-28 | 江苏博睿光电有限公司 | Nitrogen oxide phosphor with anti-static function, preparation method thereof and light-emitting device |
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- 2017-03-14 CN CN201710150299.2A patent/CN106929011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525409A (en) * | 2013-10-09 | 2014-01-22 | 张书生 | A high-luminous-efficiency high-stability nitride luminescent material and a manufacture method thereof |
| CN105462588A (en) * | 2015-12-03 | 2016-04-06 | 河北利福光电技术有限公司 | Nitrogen oxide red fluorescence powder as well as preparation method and application thereof |
| CN105969356A (en) * | 2016-05-30 | 2016-09-28 | 江苏博睿光电有限公司 | Nitrogen oxide phosphor with anti-static function, preparation method thereof and light-emitting device |
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