CN104046355B - A kind of preparation method of fluorescent material and made fluorescent material thereof - Google Patents

A kind of preparation method of fluorescent material and made fluorescent material thereof Download PDF

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CN104046355B
CN104046355B CN201310084071.XA CN201310084071A CN104046355B CN 104046355 B CN104046355 B CN 104046355B CN 201310084071 A CN201310084071 A CN 201310084071A CN 104046355 B CN104046355 B CN 104046355B
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fluorescent material
preparation
nitride phosphor
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CN104046355A (en
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刘荣辉
刘元红
周小芳
何华强
陈观通
张书生
庄卫东
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Grirem Advanced Materials Co Ltd
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Abstract

The present invention discloses a kind of preparation method of fluorescent material and made fluorescent material thereof. First this preparation method needs M3N2(M is Ca, at least one element in Sr and Ba) and Si3N4Mix by stoichiometric proportion, after calcining, obtain pre-burning product, then by obtained pre-burning product and required nitrogenize europium, the raw material such as aluminium nitride and alkaline-earth nitride mixes, heat preservation sintering 3-20 hour at 1200-1800 DEG C obtains fluorescent material by sintered product after the processing such as fragmentation, washing, classification. Compared with prior art, the fluorescent material that utilizes preparation method provided by the invention to obtain has that size of microcrystal is large, good crystallinity, and heat endurance is strong, brightness advantages of higher.

Description

A kind of preparation method of fluorescent material and made fluorescent material thereof
Technical field
The present invention relates to a kind of preparation method of fluorescent material and made fluorescent material thereof, belong to semiconductor technology neckTerritory.
Background technology
In recent years, the most noticeable at lighting field is exactly the rise of LED illuminating industry. In the nineties in 20th centuryPhase, Japanese Ya chemical company has broken through and has manufactured the key technology of blue-ray LED, and develops thus with blue-ray LEDThe technology of the compound generation white light source of excitated fluorescent powder. With conventional luminescence technology as compared with incandescent lamp or fluorescent lamp,LED solid-state illumination not only has low-voltage, high light efficiency, low energy consumption, long-life, the advantage such as pollution-free, also hasBrightness is high, volume is little, response is fast, heating less with reliability high. At present at semiconductor lighting and liquid crystalFPD field is successfully applied.
At present fluorescent material plays critical effect in white light LEDs technology, and its performance has determined white light LEDsLuminous efficiency, colour temperature, the critical technical parameters such as colour rendering and service life. Conventional fluorescent powder ubiquity effectively turnsChange the shortcomings such as the low or colour rendering of efficiency is poor, and higher redness and the green emitting phosphor of conversion efficiency mostly is sulfuration objectSystem, its stability of photoluminescence is poor, and light decay is larger. And industry has been carried out and has been permitted around the LED fluorescent material of high light efficiency in recent yearsMany creative work, wherein outstanding is exactly successfully opening first of Nitride phosphor at the end of last centurySend out. Nitride is as host material, the N that its anionic group contains high negative electrical charge3-, electron cloud bulking effect makesIts excitation spectrum moves to the long wave such as near ultraviolet, visible ray direction, can be by blue light within the scope of 200-500nm andBurst of ultraviolel is luminous, and utilizing emitted light covering scope is extremely wide, possesses the feature that colour rendering is good, luminous efficiency is high, securityCan good, nontoxic, environmental protection, and matrix has network structure closely, and physicochemical properties are stable.
And the means of preparing at present Nitride phosphor are many from preparing the technological evolution of nitride ceramics, asHTHP nitrogenize, vapour phase reduction nitrogenize, carbothermal reduction-nitridation (CRN) or self propagating high temperature synthesize (SHS)Deng; Wherein synthetic high temperature (1700-2200 DEG C), the high pressure (5-10atm) of all needing of HTHP nitrogenize and self propagating high temperatureEtc. condition, and vapour phase reduction nitrogenize need to be carried out long high-temperature ammonolysis reduction, and carbothermal reduction-nitridation also needsIntroduce the powder carbon black easily polluting, therefore, above method is not all desirable industrialized route. As can be seen here, prominentThe synthetic technology barrier of broken nitride, develops the efficient nitride technology of preparing with industrial prospect, for pushing awayThe development of moving China White LED Industry is significant. Therefore, the present invention proposes a kind of fluorescent material preparation methodAnd made fluorescent material.
Summary of the invention
The object of the invention is for the deficiency in existing Nitride phosphor technology of preparing, a kind of fluorescent material is providedPreparation method and made fluorescent material thereof.
Concrete technical scheme of the present invention is as follows:
A preparation method for fluorescent material, comprises the following steps:
1) will at least contain M3N2(M is Ca, at least one element in Sr and Ba) and Si3N4Raw material mixEvenly, wherein, M3N2And Si3N4Mol ratio be 0.35-0.45;
2) by the raw material mixing heat preservation sintering 3-20 hour at 1200-1800 DEG C, obtain pre-burning product;
3) by pre-burning product through broken, sieve, after drying and processing, then add EuN, M3N2(M is Ca, SrWith at least one element in Ba) and AlN, and mix;
4) by the material mixing heat preservation sintering 3-20 hour at 1200-1800 DEG C;
5) sintered product is obtained to Nitride phosphor after the processing such as fragmentation, washing, classification.
Above-mentioned fluorescent material preparation method's step 2) and 4) in sintering atmosphere can be N2。
Above-mentioned fluorescent material preparation method's step 2) and 4) in sintering atmosphere can be N2/H2Gaseous mixture, whereinH2Volume ratio is 0.5-5%.
Fluorescent material preparation method's of the present invention step 5) in the mol ratio of the Nitride phosphor that obtains consist of:M3N2∶AlN∶Si3N4: EuN=(0.8-1.2): 3: (0.8-1.5): (0.003-0.5), wherein M element is Ca, Sr and BaIn at least one element.
The sem test result demonstration of above-mentioned fluorescent material, single crystal grain length is greater than the distribution of the crystal grain of 15 μ mArea accounts for the more than 80% of whole crystal grain distribution areas.
The mol ratio of the Nitride phosphor that preferably, described fluorescent material preparation method obtains consists of:M3N2∶AlN∶Si3N4: EuN=1.1: 3: 1.25: 0.024, wherein M element was at least one in Ca, Sr and BaElement.
The mol ratio of the Nitride phosphor that more preferably, described fluorescent material preparation method obtains consists of:M3N2∶AlN∶Si3N4: EuN=1.1: 3: 1.25: 0.024, wherein M element was one or both elements in Ca and Sr.
As can be seen from the above technical solutions, the Nitride phosphor that preparation method provided by the invention obtains is currentBe used for white light LEDs, but along with scientific and technological development, the application of this Nitride phosphor has more than and is defined in white lightLED, any technological improvement or purposes change, and only otherwise depart from technical spirit of the present invention, all should drop on thisWithin bright protection domain.
Fluorescent material preparation method provided by the present invention easily becomes the nitride of phase effective as pre-burning product by preparationGround has relaxed harsh nitride synthesis condition, realizes and under condition of normal pressure, utilizes the pre-burning product of synthesized to prepare lightImitate the nitride high, heat endurance is strong. And, the nitrogenize using nitride substrate structure as pre-burning product synthesizedThe size of microcrystal size of thing is large, thereby significantly improves the luminosity of fluorescent material. And, the nitrogen that the method is preparedCompound fluorescent material has good crystallinity, and the regular and brightness advantages of higher of pattern, can be good at meeting white light LEDsPackage application requirement.
Brief description of the drawings
Fig. 1 is the excitation spectrum of the fluorescent material that relates to of the embodiment of the present invention 3.
Fig. 2 is the SEM figure of the fluorescent material that relates to of the embodiment of the present invention 9.
Detailed description of the invention
Be below embodiments of the invention, protection scope of the present invention is not limited to the examples, and it protects modelEnclose by claim and decide.
Embodiment 1
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molCa3N2Take raw material and mix, under nitrogen atmosphere, after being incubated 10 hours at 1500 DEG C, temperature being fallenTo below 100 DEG C, after taking-up, grind, sieve and the post processing such as oven dry. In the pre-burning product of preparation, press0.998molCa3N2, 5.0molAlN, 0.005molEuN take raw material and mix, under nitrogen atmosphere,After being incubated 10 hours at 1500 DEG C, cool the temperature to below 100 DEG C, after taking-up, grind, wash, dryThe post processing such as dry and sieve, the chromaticity coordinates of this fluorescent material, the photochromic data such as peak position and relative luminous brightness, asShown in table 1.
Embodiment 2
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molCa3N2Take raw material and mix, under nitrogen nitrogen atmosphere, wherein hydrogen volume ratio is to protect at 5%, 1500 DEG CAfter temperature 10 hours, cool the temperature to below 100 DEG C, after taking-up, grind, sieve and the post processing such as oven dry.In the pre-burning product of preparation, press 0.998molCa3N2, 5.0molAlN, 0.005molEuN take raw material mixedClose evenly, under nitrogen nitrogen atmosphere, wherein hydrogen volume ratio be at 5%, 1500 DEG C, be incubated 10 hours after, willTemperature is down to below 100 DEG C, post processings such as after taking-up, grinding, wash, dry and sieve, this fluorescent materialChromaticity coordinates, the photochromic data such as peak position and relative luminous brightness, as shown in table 1.
Embodiment 3
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molCa3N2Take raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2.In the pre-burning product of preparation, press 0.992molCa3N2, 5.0molAlN, 0.025molEuN take raw material mixedClose evenly, its preparation method and aftertreatment technology are substantially the same manner as Example 2. The chromaticity coordinates of gained fluorescent material, mainThe photochromic data such as peak position and relative luminous brightness, as shown in table 1. The excitation spectrum of gained fluorescent material is as Fig. 1 instituteShow, all there is stronger absorption to the light of 325-500nm in this fluorescent material as shown in Figure 1, is applicable to ultraviolet, closely purpleOuter and blue-ray LED.
Embodiment 4-5
The fluorescent material preparation method of embodiment 4-5 and the component of pre-burning product composition are substantially the same manner as Example 3,The component composition of different is prepared fluorescent material, as shown in table 1. By pre-burning product and required EuN, Ca3N2And AlN raw material is mixed with and obtains fluorescent material described in embodiment 4-5 by stoichiometric proportion.
Chromaticity coordinates and the relative luminous brightness etc. of the LED fluorescent material product of these embodiment are as shown in table 1.
Mol ratio composition and the photochromic data thereof of table 1 embodiment 1-5 gained fluorescent material component
Embodiment 6
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molCa3N2Take raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2.In the pre-burning product of preparation, press 0.167molSr3N2、0.820molCa3N2、5.0molAlN、0.040molEuNTake raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2. Gained fluorescent materialChromaticity coordinates, the photochromic data such as peak position and relative luminous brightness, as shown in table 2.
Embodiment 7-8
The fluorescent material preparation method of embodiment 7-8 and the component of pre-burning product composition are substantially the same manner as Example 6,The component composition of different is prepared fluorescent material, as shown in table 2. By pre-burning product and required EuN, Sr3N2、 Ca3N2And AlN raw material is mixed with and obtains fluorescent material described in embodiment 7-8 by stoichiometric proportion.
Chromaticity coordinates and the relative luminous brightness etc. of the LED fluorescent material product of these embodiment are as shown in table 2.
Embodiment 9
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molSr3N2Take raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2.In the pre-burning product of preparation, press 0.306molSr3N2、0.558molCa3N2、4.167molAlN、0.033molEuNTake raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2. Gained fluorescent materialThe photochromic data such as chromaticity coordinates and relative luminous brightness, as shown in table 2. The sem test knot of gained fluorescent materialAs shown in Figure 2, the single crystal grain length of this fluorescent material is greater than the distribution area of the crystal grain of 15 μ m to fruit as shown in Figure 2Account for the more than 80% of whole crystal grain distribution areas. The single crystalline substance of the fluorescent material that all embodiment in the present invention obtainThe distribution area that grain length is greater than the crystal grain of 15 μ m all accounts for the more than 80% of whole crystal grain distribution areas, is not listed as one by oneGo out.
Embodiment 10
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molSr3N2Take raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2.In the pre-burning product of preparation, press 0.333molSr3N2、0.336molCa3N2、3.333molAlN、0.027molEuNTake raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2. Gained fluorescent materialThe photochromic data such as chromaticity coordinates and relative luminous brightness, as shown in table 2.
Mol ratio composition and the photochromic data thereof of table 2 embodiment 6-10 gained fluorescent material component
Embodiment 11
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.67molSr3N2Take raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2.In the pre-burning product of preparation, press 0.820molSr3N2、0.167molBa3N2、5.0molAlN、0.040molEuNTake raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2. Gained fluorescent materialMol ratio consist of: Sr3N2∶Ba3N2∶AlN∶Si3N4: EuN=0.892: 0.1: 3: 1: 0.024. The chromaticity coordinates of this fluorescent material is(0.6224,0.3952), peak position is 617nm, relative luminous brightness is 82.8%.
Embodiment 12
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.583molSr3N2Take raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2.In the pre-burning product of preparation, press 0.750molSr3N2、0.123molCa3N2、4.0molAlN、0.032molEuNTake raw material and mix, its preparation method and aftertreatment technology are substantially the same manner as Example 2. Gained fluorescent materialChromaticity coordinates, the photochromic data such as peak position and relative luminous brightness, as shown in table 3.
Embodiment 13-16
The fluorescent material preparation method of embodiment 13-16 and the component of the fluorescent material that obtains composition thereof are basic with embodiment 12Identical, the component composition of different is prepared nitride pre-burning product, as shown in table 3. By pre-burning product withRequired EuN, Sr3N2、Ca3N2And AlN raw material is mixed with and obtains embodiment 13-16 by stoichiometric proportionDescribed fluorescent material, chromaticity coordinates and the relative luminous brightness etc. of the LED fluorescent material product of these embodiment are as shown in table 3.
Mol ratio composition and the photochromic data thereof of table 3 embodiment 12-16 gained fluorescent material and pre-burning product
Embodiment 17
The Nitride phosphor of the present embodiment, its pre-burning product preparation method is: by 1.67molSi3N4、0.663molSr3N2, 0.01EuN takes raw material and mixes, its preparation method and aftertreatment technology and embodiment2 is basic identical. In the pre-burning product of preparation, press 0.670molSr3N2、0.123molCa3N2、4.0molAlN、0.022molEuN takes raw material and mixes, and its preparation method and aftertreatment technology are substantially the same manner as Example 2.The mol ratio of gained fluorescent material consists of: Ca3N2∶Sr3N2∶AlN∶Si3N4: EuN=0.092: 1: 3: 1.25: 0.024. This fluorescent materialChromaticity coordinates be (0.6320,0.3674), peak position is 618.9nm, relative luminous brightness is 140.2%.

Claims (5)

1. a preparation method for fluorescent material, is characterized in that comprising the following steps:
1) will at least contain M3N2And Si3N4Raw material mix, wherein, M is Ca, in Sr and Ba at leastA kind of element, M3N2And Si3N4Mol ratio be 0.35-0.45;
2) by the raw material mixing heat preservation sintering 3-20 hour at 1200-1800 DEG C, obtain pre-burning product;
3) by pre-burning product through broken, sieve, after drying and processing, then add EuN, M3N2(M is Ca, Sr andAt least one element in Ba) and AlN, and mix;
4) by the material mixing heat preservation sintering 3-20 hour at 1200-1800 DEG C;
5) sintered product is obtained to Nitride phosphor through fragmentation, washing, classification after processing;
Described step 2) and 4) in sintering atmosphere be N2Or N2/H2Gaseous mixture; The Nitride phosphor obtainingMol ratio consists of: M3N2:AlN:Si3N4: EuN=(0.8-1.2): 3:(0.8-1.5): (0.003-0.5), wherein M elementFor at least one element in Ca, Sr and Ba.
2. the preparation method of fluorescent material according to claim 1, is characterized in that: described N2/H2H in gaseous mixture2Volume ratio is 0.5-5%.
3. fluorescent material preparation method according to claim 1, is characterized in that: the Nitride phosphor obtaining is sweptRetouch Electronic Speculum test result and show, the distribution area that single crystal grain length is greater than the crystal grain of 15 μ m accounts for whole crystal grain and distributesThe more than 80% of area.
4. fluorescent material preparation method according to claim 1, is characterized in that: the Nitride phosphor obtainingMol ratio consists of: M3N2:AlN:Si3N4: EuN=1.1:3:1.25:0.024, wherein M element is Ca, Sr and BaIn at least one element.
5. fluorescent material preparation method according to claim 4, is characterized in that: the Nitride phosphor obtainingMol ratio consists of: M3N2:AlN:Si3N4: EuN=1.1:3:1.25:0.024, wherein M element is in Ca and SrOne or both elements.
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CN102766455A (en) * 2012-06-30 2012-11-07 江苏博睿光电有限公司 Nitride fluorescent powder and preparation method thereof

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