CN103469306A - Method for growing Ce: YAG monocrystal fluorescent material - Google Patents
Method for growing Ce: YAG monocrystal fluorescent material Download PDFInfo
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- CN103469306A CN103469306A CN2013103698241A CN201310369824A CN103469306A CN 103469306 A CN103469306 A CN 103469306A CN 2013103698241 A CN2013103698241 A CN 2013103698241A CN 201310369824 A CN201310369824 A CN 201310369824A CN 103469306 A CN103469306 A CN 103469306A
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Abstract
The invention discloses a method for growing a Ce: YAG monocrystal fluorescent material. The chemical formula of the Ce: YAG monocrystal fluorescent material is (Y<1-x-m>AxCem)3(Al<1-y>By)5O12, wherein x is not less than 0 and not greater than 1, y is not less than 0 and not greater than 1, m is not less than 0 and not greater than 0.05, A is one type from Lu, Tb, Pr, La and Gd, and B is one type from Ga, Ti, Mn, Cr and Zr. The furnace temperature range for crystal growth is 1900 to 2000 DEG C, the temperature gradient of a solid liquid interface in the descending direction of a crucible is 10-50 DEG C/cm, the descending speed of the crucible is 0.1-5mm/h, the directions of (111), (100) and (001) can be adopted for seed crystals, the diameter of the crucible is 30-120 mm, and the height of the crucible is 50-200mm. Through adoption of the Bridgman-Stockbarger method, the method for growing the Ce: YAG monocrystal fluorescent material has the advantages of simplicity in operation, low cost, large size of grown Ce: YAG crystals, less internal defects, high doping concentration and the like.
Description
Technical field
The present invention relates to LED and manufacture field, relate in particular to a kind of method of Bridgman-Stockbarge method for growing Ce:YAG single crystal fluorescent material.
Background technology
LED is a kind of solid-state semiconducter device, and it can be electric energy conversion directly luminous energy.With traditional incandescent light, luminescent lamp, compare, white light LEDs has the advantages such as current consumption is little, luminous efficiency is high, long service life, energy-conserving and environment-protective, so it not only is widely used in the normal lighting field, and enters field of display devices.At present, the technology of obtaining white light LEDs can be divided into two large classes: (1) adopts three kinds of LED chips of emission red, green, blue coloured light line to mix; (2) adopt blue light or ultraviolet LED chip to excite suitable fluorescent material.White light LEDs is mainly to utilize blue-light LED chip and fluorescent material Ce that can effectively be excited by blue light, Yellow light-emitting low temperature at present
3+: the YAG combination, the recycling lens principle is mixed complementary gold-tinted and blue light, thereby obtains white light.
For the structure that adopts fluorescent powder packaging, phosphor material powder is close to the chip pyrotoxin, chip temperature raises and causes the fluorescent material performance degradation, and the heat that chip distributes simultaneously and short-wave radiation can make the packaged material accelerated deterioration cause transmitance to descend, white light LEDs shortening in work-ing life.In addition, due to fluorescent material skewness in colloid, the inconsistent problem of white light quality between different white light LED parts easily appears.Ce
3+: the YAG crystal compare fluorescent material have excitation-emission efficiency high, be subject to the advantages such as thermally-stabilised, that thermal conductivity is high, physical strength is good, be suitable as very much the equivalent material of conventional fluorescent powder.
Traditional Ce:YAG crystal production technique is mainly crystal pulling method and temperature gradient method.Wherein crystal pulling method is the method be most widely used in current Ce:YAG crystal growth, yet there are the following problems in actual applications for the method: 1) matter crystal internal defect of Czochralski grown is more, and dislocation desity is large; 2) in the Czochralski grown process, there is forced convection in melt, and the segregation coefficient of Ce ion in the YAG crystal little (0.2 left and right), so in crystal, the doping content of Ce is difficult to improve; 3) crystal pulling method adopts the iridium pot usually, and cost drops into too high; 4) crystalline size of Czochralski grown is restricted.The Ce:YAG crystalline size of Growth by Temperature Gradient Technique is larger, and more than diameter can reach 100mm, dislocation desity is little, but the temperature gradient method processing requirement is high, and usually adopts graphite heater, easily causes Prevent Carbon Contamination.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of the Ce:YAG of growth single crystal fluorescent material, comprises the following steps:
1) raw material is carried out to the weighing proportioning according to the mol ratio in following chemical formula, mix, be pressed into cake, high temperature sintering;
Chemical formula: (Y
1-x-ma
xce
m)
3(Al
1-yb
y)
5o
12
0≤x≤1，0≤y≤1，0≤m≤0.05
Wherein A is a kind of in Lu, Tb, Pr, La, Gd, Sm; B is a kind of in Ga, Ti, Mn, Cr, Zr;
2) seed crystal is put into to crucible bottom, crucible is put into to the decline stove, put into the material piece, be warming up to 1900～2000 ℃, constant temperature 3～5 hours;
3) decline crucible, fall off rate is 0.1～5mm/h, the thermograde of crucible descending direction solid-liquid interface is 10～50 ℃/cm;
4) after the crystal growth, control furnace temperature and descend, initially cooling rate, in 0.1～3 ℃/h scope, is lowered the temperature to fast the acceleration by slow, and the end of a period cooling rate is 30-50 ℃/h, and whole temperature-fall period is 50～180h;
5) make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible.
In described step 1, the temperature that sinters piece into is 1200 ℃, and sintering time is 12h.
Described crucible diameter is 30～120mm, is highly 50～220mm.
Described crucible is tungsten or miramint material.
Described heating element is heating element of tungsten, and volatilization is few.
Described seed crystal adopts<111 >,<100 or<001 > direction.
The method of descent method for growing Ce:YAG single crystal fluorescent material of the present invention compared with prior art has the following advantages:
1) crystalline size of growth is large, and matter crystal internal defect is few, and contaminating impurity is few.
2) owing to being the quasistatic growth, can realize the cerium ion-doped of high density, the actual doping content of cerium ion in the Ce:YAG crystal can approach 1%;
3) growth method is simple, and cost is low.
The accompanying drawing explanation
The structural representation that Fig. 1 is crystal growing apparatus of the present invention;
Relative energy distribution curve when the crystal that Fig. 2 is embodiment 3 growths excites with blue-ray LED.
Embodiment
In order to make those skilled in the art person understand better technical solution of the present invention, below in conjunction with drawings and embodiments, the present invention is described in further detail.
The method of a kind of growth crucible descent method for growing Ce:YAG single crystal fluorescent material of the present invention, the growing apparatus of employing, as shown in Figure 1, comprise heating element 1, crucible 2 is positioned at heating element 1.
Described crucible 2 is tungsten or miramint material, and its diameter is 30～120mm, is highly 50～220mm; Take up melt 5 in crucible 2, by descent method, generated crystal 6.
Simultaneously, described heating element is heating element of tungsten, and volatilization is few, is difficult for crystal is polluted.
Described heating element 1 outer setting has radiation shield 3, and thermal insulation layer 4 is positioned at outside radiation shield 3.
Embodiment mono-:
According to chemical formula (Y
1-mce
m)
3al
5o
12(m=0.01) Raw Y
2o
3, Al
2o
3, CeO
2the mol ratio of powder is carried out the weighing proportioning, and gross weight 2.7Kg mixes, briquetting, and 1200 ℃ of sintering, the time is 12h; Put into crucible after sintering; Crucible diameter is 80mm, length 150mm; By seed orientation<111>put into crucible bottom, crucible is put into to the decline stove, keep furnace temperature at 1950 ℃, keep constant temperature 5 hours; With constant speed decline crucible, fall off rate 0.4mm/h, the thermograde of crucible descending direction solid-liquid interface is 25 ℃/cm; After the crystal growth, control furnace temperature and descend, initially cooling rate is 1 ℃/h, by slow, to fast the acceleration, is lowered the temperature, and the end of a period cooling rate is 50 ℃/h, and temperature-fall period is 80h; Make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible, obtain the crystal yellow transparent complete, diameter 78mm, length 120mm.
Embodiment bis-:
According to chemical formula (Y
1-mce
m)
3al
5o
12(m=0.008) Raw Y
2o
3, Al
2o
3, CeO
2the mol ratio of powder is carried out the weighing proportioning, and gross weight 7.5Kg mixes, briquetting, and 1200 ℃ of sintering, the time is 12h; Put into crucible after sintering; Crucible diameter is 120mm, length 220mm; By seed orientation<111>put into crucible bottom, crucible is put into to the decline stove, keep furnace temperature at 1950 ℃, keep constant temperature 5 hours; With constant speed decline crucible, fall off rate 0.2mm/h, the thermograde of crucible descending direction solid-liquid interface is 25 ℃/cm; The control furnace temperature descends, and initial cooling rate is 0.2 ℃/h, and by the slow extremely fast cooling of accelerating, the end of a period cooling rate is 30 ℃/h, and temperature-fall period is 180h; After the crystal growth, make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible, obtain the crystal yellow transparent complete, diameter 118.5mm, length 160mm.
Embodiment tri-:
According to chemical formula (Y
0.99ce
0.01)
3(Al
0.998mn
0.002)
5o
12carry out the weighing proportioning, gross weight 5Kg, mix, briquetting, and 1200 ℃ of sintering, the time is 12h; Put into crucible after sintering; Crucible diameter is 100mm, length 200mm; By seed orientation<111>put into crucible bottom, crucible is put into to the decline stove, keep furnace temperature at 1950 ℃, keep constant temperature 5 hours; With constant speed decline crucible, fall off rate 0.3mm/h, the thermograde of crucible descending direction solid-liquid interface is 25 ℃/cm; The control furnace temperature descends, and initial cooling rate is 0.5 ℃/h, and by the slow extremely fast cooling of accelerating, the end of a period cooling rate is 35 ℃/h, and temperature-fall period is 120h; After the crystal growth, make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible, obtain the crystal yellow-green colour transparent complete, diameter 99mm, length 140mm.
Claims (6)
1. the method for Ce:YAG single crystal fluorescent material of growing comprises the following steps:
1) raw material is carried out to the weighing proportioning according to the mol ratio in following chemical formula, mix, be pressed into cake, high temperature sintering;
Chemical formula: (Y
1-x-ma
xce
m)
3(Al
1-yb
y)
5o
12
0≤x≤1，0≤y≤1，0≤m≤0.05
Wherein A is a kind of in Lu, Tb, Pr, La, Gd, Sm; B is a kind of in Ga, Ti, Mn, Cr, Zr;
2) seed crystal is put into to crucible bottom, crucible is put into to the decline stove, put into the material piece, be warming up to 1900～2000 ℃, constant temperature 3～5 hours;
3) decline crucible, fall off rate is 0.1～5mm/h, the thermograde of crucible descending direction solid-liquid interface is 10～50 ℃/cm;
4) after the crystal growth, control furnace temperature and descend, initially cooling rate, in 0.1～3 ℃/h scope, is lowered the temperature to fast the acceleration by slow, and the end of a period cooling rate is 30～50 ℃/h, and whole temperature-fall period is 50～180h;
5) make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible.
2. the method for growth as claimed in claim 1 Ce:YAG single crystal fluorescent material, it is characterized in that: in described step 1, the temperature that sinters piece into is 1200 ℃, and sintering time is 12h.
3. the method for growth as claimed in claim 1 Ce:YAG single crystal fluorescent material, it is characterized in that: described crucible diameter is 30～120mm, is highly 50～220mm.
4. the method for growth as claimed in claim 1 Ce:YAG single crystal fluorescent material, it is characterized in that: described crucible is tungsten or miramint material.
5. the method for growth as claimed in claim 1 Ce:YAG single crystal fluorescent material, it is characterized in that: described heating element is heating element of tungsten.
6. the method for growth Ce:YAG single crystal fluorescent material as claimed in claim 1, is characterized in that: described seed crystal employing<111 >,<100 or<001 > direction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062481A (en) * | 2015-07-15 | 2015-11-18 | 昆山开威电子有限公司 | Red light-fluorescent light conversion material for plant lamp and preparation method of conversion material |
| CN108486647A (en) * | 2018-05-24 | 2018-09-04 | 蔡凡 | Czochralski method CeAlO3Crystal growing apparatus and its control method |
| CN108570324A (en) * | 2018-06-01 | 2018-09-25 | 南京永煦能源科技有限公司 | The preparation of fluorescent material for white light LED |
| CN111205081A (en) * | 2020-01-21 | 2020-05-29 | 徐州凹凸光电科技有限公司 | Single-structure type low-color-temperature high-color-rendering-index fluorescent ceramic and preparation method and application thereof |
| JPWO2019181618A1 (en) * | 2018-03-23 | 2021-03-25 | Tdk株式会社 | Fluorescent material and light source device |
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| CN102168307A (en) * | 2011-03-28 | 2011-08-31 | 蔡鸿 | Method for growing cerium-yttrium-aluminum garnet crystal |
| CN102560665A (en) * | 2012-01-18 | 2012-07-11 | 中国科学院上海光学精密机械研究所 | Method for growing cerium-doped alumina-yttrium aluminum garnet eutectic fluorescent material |
| CN103147121A (en) * | 2013-04-03 | 2013-06-12 | 中国科学院上海硅酸盐研究所 | Device for growing crystals by using lifting and Kyropoulos method |
-
2013
- 2013-08-22 CN CN2013103698241A patent/CN103469306A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168307A (en) * | 2011-03-28 | 2011-08-31 | 蔡鸿 | Method for growing cerium-yttrium-aluminum garnet crystal |
| CN102560665A (en) * | 2012-01-18 | 2012-07-11 | 中国科学院上海光学精密机械研究所 | Method for growing cerium-doped alumina-yttrium aluminum garnet eutectic fluorescent material |
| CN103147121A (en) * | 2013-04-03 | 2013-06-12 | 中国科学院上海硅酸盐研究所 | Device for growing crystals by using lifting and Kyropoulos method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062481A (en) * | 2015-07-15 | 2015-11-18 | 昆山开威电子有限公司 | Red light-fluorescent light conversion material for plant lamp and preparation method of conversion material |
| JPWO2019181618A1 (en) * | 2018-03-23 | 2021-03-25 | Tdk株式会社 | Fluorescent material and light source device |
| CN108486647A (en) * | 2018-05-24 | 2018-09-04 | 蔡凡 | Czochralski method CeAlO3Crystal growing apparatus and its control method |
| CN108570324A (en) * | 2018-06-01 | 2018-09-25 | 南京永煦能源科技有限公司 | The preparation of fluorescent material for white light LED |
| CN111205081A (en) * | 2020-01-21 | 2020-05-29 | 徐州凹凸光电科技有限公司 | Single-structure type low-color-temperature high-color-rendering-index fluorescent ceramic and preparation method and application thereof |
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