CN103590111B - A kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer - Google Patents
A kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer Download PDFInfo
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- CN103590111B CN103590111B CN201310460006.2A CN201310460006A CN103590111B CN 103590111 B CN103590111 B CN 103590111B CN 201310460006 A CN201310460006 A CN 201310460006A CN 103590111 B CN103590111 B CN 103590111B
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Abstract
The invention discloses a kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer, described method for annealing comprises the steps: that cerium dropped yttrium aluminum garnet wafer is put into porcelain boat and sent into tubular annealing stove by (1), passes into annealing atmosphere, airtight; Described annealing atmosphere is mixed gas A or oxygen, and described mixed gas A is: iH
2+ kL, L represent inert protective gas, and i, k represent H respectively
2the volume parts shared in mixed gas A with L, and 25%≤i/i+k≤75%; (2) from the ramp to 300 DEG C of room temperature according to 100 ~ 150 DEG C/h, 3 ~ 8 hours are incubated; Again according to the ramp to 900 DEG C of 150 ~ 200 DEG C/h, be incubated 3 ~ 8 hours; Then according to 100 ~ 150 DEG C/h ramp to 1100 ~ 1500 DEG C between cycle annealing 30 ~ 72 hours; Be cooled to 1100 DEG C with the speed being not more than 50 DEG C/h after annealing, then be cooled to 900 DEG C with the speed of 100 DEG C/h, be finally down to room temperature with the speed of 150 ~ 200 DEG C/h, total temperature-fall period required time is about 6.5 ~ 16h, takes out and obtain the wafer after annealing.
Description
[technical field]
The present invention relates to a kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer, belong to LED fluorescent material technical field.
[background technology]
LED is acknowledged as 21 century " green illumination ".In the preparation of white light LEDs, the performance of fluorescent material directly affects the luminous efficiency of white light LEDs, efficiency of conversion, chromaticity coordinates, colour temperature and color developing.At present, white-light LED fluorescence material is mainly based on amorphous fluorescent material, and commercialization white light LEDs product forms white light for Developing mainstream with blue chip and phosphor combination.But, present stage phosphor for white light LED there is following outstanding problem: launching efficiency and light conversion efficiency lower; The lack of homogeneity of granular size and dispersion, apply uneven, color uniformity is undesirable; Light decay is large, has a strong impact on white light LEDs work-ing life; Physical and chemical performance is poor, and thermal conductance is low, unstable, easily aging under hot conditions, is not suitable with great power LED growth requirement.Just due to these problems, so various countries all drop into the novel fluorescent material that a large amount of man power and materials seeks to surmount existing fluorescent material.
Part work is from seeking breakthrough current fluorescent material composition.Patent CN102079977A adopts (∑ Ln)
3(Al
1-xa
x/2b
x/2)
2[AlO
4-yf
y/2n
y/2]
3fluorescent material, wherein Ln=Gd, Y, Lu, Tb, Ce, Pr, Sm, A are IA race element, and B is VB race element, 0.001<x<0.1,0.001<y<0.05, it is the optical excitation of 430nm-490nm that such fluorescent material is applicable to by wavelength, and colour rendering index is between 74.3-80.1; Patent CN102071024A adopts
fluorescent material, wherein ∑ Ln=Ln, Gd, La, Ce, Dy, Sm, Yb, Tb, Pr, Me
2+=Zn
2+and Cd
2+, A
3-=N
3-or P
3-, 0.001≤x≤0.05,0≤y≤0.06,0.001≤Z≤0.06,0≤p≤0.1, the colour rendering index of such fluorescent material is between 71.3-75.3; Patent CN102120932A adopts
fluorescent material, wherein Me
2+=∑ (Mg
2+, Ca
2+, Sr
2+, Ba
2+), Me
3+=∑ (Ce
3+, Tb
3+, Lu
3+, Yb
3+, Pr
3+), Me
4+=∑ (Si
4+, Sn
4+), 0.001<x<0.05, the colour rendering index of such fluorescent material is between 78-84; Patent CN101838536A adopts and introduce sensitizing agent Sb, Bi in the fluorescent material of routine, thus enhances exciting and luminous intensity of Ce.A part is operated in existing fluorescent material preparation technology and makes improvement.Patent CN1818016A first with oxidizing atmosphere calcining, then uses nitric acid acidwashing, finally with the method preparation (Y of reducing atmosphere calcining
1-x-ym
yce
x)
3al
5o
12fluorescent material, wherein M=∑ (Gd, Tb, Pr, Si, Mg); Patent CN102367383A then according to
stoichiometric make metallic nitrate mixed solution, add soluble salt, organic-fuel and ammonium nitrate again, heating for dissolving, microwave exposure causes self-propagating combustion, washing, dry, grind, sieve, obtain size tunable and the yellow fluorescent powder of rule.Some work concentrates on searching novel fluorescent material, and have bibliographical information crystallofluorescence material at present, such as patent CN102061169A discloses white light LEDs Garnet single crystal fluorescent material and preparation method thereof, points out that this type oxide has A
3b
5o
12structure formation, wherein A comprises yttrium (Y) and rare earth (RE) ... at interior many elements, B comprises aluminium (Al), gallium (Ga) ... at interior many elements.Crystallofluorescence material has following particular advantages compared with fluorescent material: excitation-emission efficiency is high; The intrinsic property of crystal determines its high homogeneity, and physical and chemical performance is stablized, and thermal conductivity is high, and the life-span is long.
For crystallofluorescence material, its in process of growth because some uncertain factors in the links such as material purity, growing environment and growth technique can cause crystal to have some defects, these defects often affect final lasing efficiency, and severe patient directly can cause crystal self major injury.Wherein common several defects are as cloud layer, colour center, cracking, dislocation, twin and little etc.Due to the element such as zirconium (Zr), iron (Fe) can be mixed in the Feedstock treating process of growing crystal fluorescent material unavoidably, and part material can because the physical and chemical performance of self loses certain amount in the case of a high temperature, so the crystal formed has colour center substantially, colour center number be directly connected to the luminous efficiency of the white light LEDs finally made with crystallofluorescence material, and due to the impact of surrounding environment during crystal pulling, the crystal grown out has serious thermal stresses, and the lasting of thermal stresses piles up the work-ing life significantly reducing crystallofluorescence material.
In addition, for the internal composition of crystallofluorescence material, the valence state of rare earth ion is a kind of admixture, i.e.+3 valencys ,+4 valency equivalent states situation about coexisting, but effective excitation center is generally valence state+3 valency determined, so be necessary to regulate the valence state of rare earth ion, make the rare earth ion of as far as possible many high prices change the rare earth ion of+3 valencys into, finally reach the double effects improving luminous efficiency and can reduce costs again simultaneously.
Therefore the crystal grown must carry out annealing to get rid of colour center, abatement stress and adjustment valence state.Select suitable Annealing Scheme both effectively can to reduce intracrystalline colour center, crystal stress and improve light efficiency etc., can increase the service life again, reduce production cost, overall efficiency is improved.The Ce:YAG crystal grown by graphite heating method is annealed with high-temperature hydrogen annealing and cryogenic oxygen by patent CN101545143A respectively, the luminous efficiency of Ce:YAG crystal is made to have larger lifting, but it has some weak point: (1) growing method is single, only for graphite heating body method; (2) single utilization oxygen and hydrogen annealing process, do not consider both advantages to get up; (3) object of annealing is single, is only conceived to crystal transmitance and photoluminescence spectrum intensity, does not consider the application prospect that Ce:YAG crystal is more wide.
[summary of the invention]
The object of the present invention is to provide a kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer, under the prerequisite that the method can make the white light LEDs of cerium dropped yttrium aluminum garnet wafer configuration substantially remain unchanged at colour temperature and development index, light efficiency has obvious lifting.
For achieving the above object, the present invention adopts following technical scheme:
A method for annealing for white light LEDs cerium dropped yttrium aluminum garnet wafer, the thickness of described white light LEDs cerium dropped yttrium aluminum garnet wafer is 0.3 ~ 1.5mm, and its chemical formula is: (Y
1-xce
x)
3(Al
1-yga
y)
5o
12, wherein 0<x≤0.022,0≤y≤0.022; Described method for annealing comprises the steps:
(1) cerium dropped yttrium aluminum garnet wafer is put into porcelain boat and send into tubular annealing stove, pass into annealing atmosphere, airtight; Described annealing atmosphere is mixed gas A or oxygen, and described mixed gas A is: iH
2+ kL, L represent inert protective gas, and i, k represent H respectively
2the volume parts shared in mixed gas A with L, and 25%≤i/i+k≤75%;
(2) from the ramp to 300 DEG C of room temperature according to 100 ~ 150 DEG C/h, 3 ~ 8 hours are incubated; Again according to the ramp to 900 DEG C of 150 ~ 200 DEG C/h, be incubated 3 ~ 8 hours; Then according to 100 ~ 150 DEG C/h ramp to 1100 ~ 1500 DEG C between cycle annealing 30 ~ 72 hours; Be cooled to 1100 DEG C with the speed being not more than 50 DEG C/h after annealing, then be cooled to 900 DEG C with the speed of 100 DEG C/h, finally with 150 ~ 200 DEG C/h
Speed be down to room temperature, total temperature-fall period required time is about 6.5 ~ 16h, takes out and obtain the wafer after annealing.
In the present invention, cerium dropped yttrium aluminum garnet crystallofluorescence material (Y
1-xce
x)
3(Al
1-yga
y)
5o
12preparation adopt crystal growth from melt method, such as crystal pulling method, descent method, crucible Mobile Method, zone melting method, gradient method,
Heat-exchanging method etc.Raw materials adopts the oxide form of required metallic element, generally has A
2b
3, AB
2these 2 kinds of forms, guarantee the raw material Y forming yag crystal
2o
3, Al
2o
3and Ga
2o
3purity>=99.99%, CeO
2purity>=99.9%.The present invention specifically recommends described cerium dropped yttrium aluminum garnet crystallofluorescence material to be prepared by following method:
A) raw material is according to stoichiometric equation (Y
1-xce
x)
3(Al
1-yga
y)
5o
12calculate processing compound, wherein 0<x≤0.022,0≤
y≤ 0.022; By raw material precise, mix rear briquetting, in 1100-1300 DEG C of pre-burning 12-24h;
B) product after pre-burning and seed crystal are transferred in crystal furnace, after sealing, are evacuated to 10
-2-10
-4pa, pass into inert protective gas when furnace temperature arrives 1000-1300 DEG C, continue to be warming up to design temperature, described design temperature is in the scope of 1800-1900 DEG C; After the furnace temperature of crystal furnace reaches design temperature, insulation 1-3 hour, makes melting sources by regulating stove bore temperature, roasting seed crystal, through processes such as inoculation, shouldering, isometrical, endings, the direction of growth is <111> direction, pulling growth (Y
1-xce
x)
3(Al
1-yga
y)
5o
12crystallofluorescence material;
C), after growth terminates in crystal furnace, with the speed slow cooling of 20-80 DEG C/h, after being down to room temperature, take out crystal, obtain cerium dropped yttrium aluminum garnet crystallofluorescence material (Y
1-xce
x)
3(Al
1-yga
y)
5o
12.
Further, step B) described in inert protective gas be preferably Ar or N that purity is greater than 99%
2, special, in order to protect Ga
2o
3certain O can be passed into
2to keep the weak oxide atmosphere in stove.
Before annealing, need to process up-to-standard cerium dropped yttrium aluminum garnet crystallofluorescence material, complete processing mainly comprises corase grind, cutting, if necessary also uses polishing.Cutting profile is according to the size design of LED blue chip support, and can be different shape, the most frequently used shape be sheet, and its thickness is generally between 0.3mm to 1.5mm.According to white light LEDs to the absorption of chip light emitting and luminescent designs, wafer process finished product can be cutting corase grind sheet, single-sided polishing sheet and twin polishing sheet.
The annealing atmosphere that the present invention adopts has two classes, and wherein mixed gas A is valence state adjustment atmosphere, is again structural adjustment atmosphere, and oxygen mainly structural adjustment atmosphere.So-called valence state adjustment atmosphere main component is reducing atmosphere H
2, the rare earth ion of the high-valence state in crystallofluorescence material can be reduced to the ion of 3 valence states by it, the effective luminous efficiency improving wafer, but pure H
2danger close in operation and gas can be caused to waste, the present invention is by inert protective gas L and H
2mixing passes into.Described inert protective gas L can be nitrogen or rare gas element (such as Ar, N
2, Ne etc.), preferred nitrogen or argon gas, more preferably the gas purity nitrogen or the argon gas that are greater than 99%.Structural adjustment atmosphere then can eliminate colour center, crystals stress etc.The cerium dropped yttrium aluminum garnet wafer of the present invention after step (1) and step (2) process the annealing obtained can use another annealing atmosphere again to carry out anneal according to the operation of step (1) and step (2), namely mixed atmosphere A first can be used to carry out anneal, then carry out anneal with oxygen; Also first oxygen treatments applied can be used, then with mixed gas A process, to obtain the better cerium dropped yttrium aluminum garnet wafer of performance.
In the present invention, the pressure gauge reading of the atmosphere valve of tubular annealing stove be applicable to scope for (0.025MPa, 0.05MPa].
Compared with prior art, beneficial effect of the present invention is:
(1) method for annealing of the present invention not only eliminates (Y
1-xce
x)
3(Al
1-yga
y)
5o
12the subsurface defect of crystal, improves transmitance, and eliminates the Lacking oxygen in crystal, especially, also causes crystals and divide the valence state of Ce ion to be changing into 3+ from 4+ after hydrogen annealing, these all result in (Y
1-xce
x)
3(Al
1-yga
y)
5o
12under the prerequisite that the white light LEDs of crystal configuration remains unchanged substantially at colour temperature and development index, light efficiency has the obvious lifting of about 10lm/W.
(2) method for annealing of the present invention is applied widely, is applicable to stepping back of YAG crystal prepared by multiple method, specifically comprises crystal pulling method, descent method, crucible Mobile Method, zone melting method, gradient method, heat-exchanging method etc.
[embodiment]
Below by embodiment, the present invention is described in further detail, but limits the present invention absolutely not.
Embodiment 1.
According to stoichiometric equation (Y
1-xce
x)
3(Al
1-yga
y)
5o
12(x=0.04/3, y=0) takes the Y of purity>=99.99%
2o
3, Al
2o
3, CeO
2raw material, grinds and mixes, briquetting, and be transferred to together with seed crystal after 1200 DEG C of pre-burning 24h in Medium frequency induction single crystal growing furnace, after shove charge completes, tightness system is evacuated to 10
-4p
a, pass into the nitrogen that purity is greater than 99% when furnace temperature arrives 1400 DEG C, be warming up to 1900 DEG C this atmosphere relaying is continuous, be incubated 2 hours, by regulating stove bore temperature until raw materials melt, then the process pulling growth Y such as process inoculation, shouldering, isometrical, ending
2.96al
5o
12: Ce
0.04crystal.Crystal growth direction is <111> direction, and after growth terminates, with the speed slow cooling of 25 DEG C/h to room temperature, cooling end obtains Y
2.96al
5o
12: Ce
0.04crystal.Crystal entire body is in yellow, and transparent complete flawless, quality is better.With slicing machine by Y
2.96al
5o
12: Ce
0.04crystal-cut becomes the sheet of 4mm*4mm*0.5mm, sends in tubular annealing stove, pass into 0.25H after vacuumizing after polished finish
2+ 0.75N
2mixed gas, stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 120 DEG C/h and be incubated 3h, rise to 900 DEG C with 150 DEG C/h again and be incubated 3h, finally rising to 1500 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1500 DEG C that heat up continue process 24h, speed again through 50 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, obtains the Y after annealing
2.96al
5o
12: Ce
0.04wafer, this wafer can be used to encapsulation high-performance white light LEDs.
Embodiment 2.
With the 4mm*4mm*0.5mmY obtained according to embodiment 1 method
2.96al
5o
12: Ce
0.04send into after wafer polishing process in tubular annealing stove, after vacuumizing, pass into O
2stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 120 DEG C/h and be incubated 3h, rise to 900 DEG C with 150 DEG C/h again and be incubated 3h, finally rising to 1500 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1500 DEG C that heat up continue process 24h, speed again through 50 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, obtains the Y after annealing
2.96al
5o
12: Ce
0.04wafer, this wafer can be used to encapsulation high-performance white light LEDs.
Embodiment 3.
According to stoichiometric equation (Y
1-xce
x)
3(Al
1-yga
y)
5o
12(x=0.03/3, y=0) takes the Y of purity>=99.99%
2o
3, Al
2o
3, CeO
2raw material, grinds and mixes, briquetting, and be transferred to together with seed crystal after 1200 DEG C of pre-burning 12h in Medium frequency induction single crystal growing furnace, after shove charge completes, tightness system is evacuated to 10
-4pa, passes into the nitrogen that purity is greater than 99% when furnace temperature arrives 1400 DEG C, be warming up to 1850 DEG C this atmosphere relaying is continuous, be incubated 2 hours, by regulating stove bore temperature until raw materials melt, then the process pulling growth Y such as process inoculation, shouldering, isometrical, ending
2.97al
5o
12: Ce
0.03crystal.Crystal growth direction is <111> direction, and after growth terminates, with the speed slow cooling of 20 DEG C/h to room temperature, cooling end obtains Y
2.97al
5o
12: Ce
0.03crystal.Crystal entire body is light yellow, and transparent complete flawless, quality is better.With slicing machine by Y
2.97al
5o
12: Ce
0.03crystal-cut becomes the sheet of 4mm*4mm*0.5mm, sends in tubular annealing stove, pass into O after vacuumizing after polished finish
2stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 100 DEG C/h and be incubated 3h, rise to 900 DEG C with 150 DEG C/h again and be incubated 3h, finally rising to 1500 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1500 DEG C that heat up continue process 18h, speed again through 40 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, obtains the Y after annealing
2.97al
5o
12: Ce
0.03wafer, this wafer can be used to encapsulation high-performance white light LEDs.
Embodiment 4.
According to stoichiometric equation (Y
1-xce
x)
3(Al
1-yga
y)
5o
12(x=0.04/3, y=0.04/5) takes the Y of purity>=99.99%
2o
3, Al
2o
3, CeO
2, Ga
2o
3raw material, grinds and mixes, briquetting, and be transferred to together with seed crystal after 1200 DEG C of pre-burning 12h in Medium frequency induction single crystal growing furnace, after shove charge completes, tightness system is evacuated to 10
-4pa, passes into O
2the vacuum tightness in stove is made to reach 10
-2pa, passes into the nitrogen that purity is greater than 99% when furnace temperature arrives 1400 DEG C, be warming up to 1800 DEG C this atmosphere relaying is continuous, be incubated 2 hours, by regulating stove bore temperature until raw materials melt, then the process pulling growth Y such as process inoculation, shouldering, isometrical, ending
2.96al
4.96o
12: Ce
0.04ga
0.04crystal.Crystal growth direction is <111> direction, and after growth terminates, with the speed slow cooling of 25 DEG C/h to room temperature, cooling end obtains Y
2.96al
4.96o
12: Ce
0.04ga
0.04crystal.With slicing machine by Y
2.96al
4.96o
12: Ce
0.04ga
0.04crystal-cut becomes the sheet of 4mm*4mm*0.5mm, sends in tubular annealing stove, pass into 0.30H after vacuumizing after polished finish
2+ 0.70N
2stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 110 DEG C/h and be incubated 3h, rise to 900 DEG C with 140 DEG C/h again and be incubated 3h, finally rising to 1300 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1300 DEG C that heat up continue process 30h, speed again through 50 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, obtains the Y after annealing
2.96al
4.96o
12: Ce
0.04ga
0.04wafer, this wafer can be used to encapsulation high-performance white light LEDs.
Embodiment 5.
With the 4mm*4mm*0.5mmY that embodiment 4 obtains
2.96al
4.96o
12: Ce
0.04ga
0.04send into after wafer polishing process in tubular annealing stove, after vacuumizing, pass into O
2stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 110 DEG C/h and be incubated 3h, rise to 900 DEG C with 140 DEG C/h again and be incubated 3h, finally rising to 1300 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1300 DEG C that heat up continue process 30h, speed again through 50 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, obtains the Y after annealing
2.96al
4.96o
12: Ce
0.04ga
0.04wafer, this wafer can be used to encapsulation high-performance white light LEDs.
Embodiment 6.
According to stoichiometric equation (Y
1-xce
x)
3(Al
1-yga
y)
5o
12(x=0.04/3, y=0) takes the Y of purity>=99.99%
2o
3, Al
2o
3, CeO
2raw material, grinds and mixes, briquetting, and be transferred to together with seed crystal after 1200 DEG C of pre-burning 10h in Medium frequency induction single crystal growing furnace, after shove charge completes, tightness system is evacuated to 10
-4p
a, pass into the nitrogen that purity is greater than 99% when furnace temperature arrives 1400 DEG C, be warming up to 1900 DEG C this atmosphere relaying is continuous, be incubated 2 hours, by regulating stove bore temperature until raw materials melt, then the process pulling growth Y such as process inoculation, shouldering, isometrical, ending
2.96al
5o
12: Ce
0.04crystal.Crystal growth direction is <111> direction, and after growth terminates, with the speed slow cooling of 22 DEG C/h to room temperature, cooling end obtains Y
2.96al
5o
12: Ce
0.04crystal.Crystal entire body is in yellow, and transparent complete flawless, quality is better.With slicing machine by Y
2.96al
5o
12: Ce
0.04crystal-cut becomes the sheet of 4mm*4mm*0.5mm, sends in tubular annealing stove, pass into O after vacuumizing after polished finish
2stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 120 DEG C/h and be incubated 3h, rise to 900 DEG C with 150 DEG C/h again and be incubated 4h, finally rising to 1300 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1300 DEG C that heat up continue process 30h, speed again through 50 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, passes into 0.75H after vacuumizing
2+ 0.25N
2stove internal gas pressure is adjusted to 0.05MPa, rise to 300 DEG C from room temperature with 120 DEG C/h and be incubated 3h, rise to 900 DEG C with 150 DEG C/h again and be incubated 4h, finally rising to 1500 DEG C with 100 DEG C/h, 3 sections of rear maintenances 1500 DEG C that heat up continue process 12h, speed again through 40 DEG C/h is cooled to 1100 DEG C, the speed of 100 DEG C/h is cooled to 900 DEG C, and the speed of 200 DEG C/h is down to room temperature, finally obtains the Y after annealing
2.96al
5o
12: Ce
0.04wafer, this wafer can be used to encapsulation high-performance white light LEDs.
Comparative example 1.
With the 4mm*4mm*0.5mmY that embodiment 1 method obtains
2.96al
5o
12: Ce
0.04according to O described in patent CN101545143A after wafer polishing process
2method for annealing process is as follows: crystal is loaded in porcelain boat tubular annealing stove of making a gift to someone, pass into O after vacuumizing
2, start heating schedule, with the ramp to 1000 DEG C of 100 DEG C/h, then with the ramp to 1400 DEG C of 50 DEG C/h, 2 sections of rear maintenances 1400 DEG C that heat up continue process 20h, then are cooled to 1000 DEG C through the speed of 50 DEG C/h from 1400 DEG C, and the speed of 100 DEG C/h is cooled to room temperature.Finally take out Y
2.96al
5o
12: Ce
0.04wafer package white light LEDs.
The comparison of white light LEDs photoelectric properties obtained before and after table 1 the present invention anneals
1
a: (Y
1-xce
x)
3(Al
1-yga
y)
5o
12crystal, x=0.04/3, y=0;
1
b: (Y
1-xce
x)
3(Al
1-yga
y)
5o
12crystal, x=0.03/3, y=0;
1
c: (Y
1-xce
x)
3(Al
1-yga
y)
5o
12crystal, x=0.04/3, y=0.04/5.
Claims (5)
1. a white light LEDs method for annealing for cerium dropped yttrium aluminum garnet wafer, the thickness of described white light LEDs cerium dropped yttrium aluminum garnet wafer is 0.3 ~ 1.5mm, and its chemical formula is: (Y
1-xce
x)
3(Al
1-yga
y)
5o
12, wherein 0 < x≤0.022,0≤y≤0.022; It is characterized in that described method for annealing comprises the steps:
(1) cerium dropped yttrium aluminum garnet wafer is put into porcelain boat and send into tubular annealing stove, pass into annealing atmosphere, airtight; Described annealing atmosphere is mixed gas A or oxygen, and described mixed gas A is: iH
2+ kL, L represent inert protective gas, and i, k represent H respectively
2the volume parts shared in mixed gas A with L, and 25%≤i/ (i+k)≤75%;
(2) from the ramp to 300 DEG C of room temperature according to 100 ~ 150 DEG C/h, 3 ~ 8 hours are incubated; Again according to the ramp to 900 DEG C of 150 ~ 200 DEG C/h, be incubated 3 ~ 8 hours; Then according to 100 ~ 150 DEG C/h ramp to 1100 ~ 1500 DEG C between cycle annealing 30 ~ 72 hours; Be cooled to 1100 DEG C with the speed being not more than 50 DEG C/h after annealing, then be cooled to 900 DEG C with the speed of 100 DEG C/h, be finally down to room temperature with the speed of 150 ~ 200 DEG C/h, total temperature-fall period required time is 6.5 ~ 16h, takes out and obtain the wafer after annealing.
2. the white light LEDs method for annealing of cerium dropped yttrium aluminum garnet wafer as claimed in claim 1, is characterized in that described inert protective gas L is nitrogen or rare gas element.
3. the white light LEDs method for annealing of cerium dropped yttrium aluminum garnet wafer as claimed in claim 1, is characterized in that described inert protective gas L is nitrogen or argon gas.
4. the white light LEDs method for annealing of cerium dropped yttrium aluminum garnet wafer as claimed in claim 1, is characterized in that described inert protective gas L is nitrogen or the argon gas that purity is greater than 99%.
5. the method for annealing of cerium dropped yttrium aluminum garnet wafer of the white light LEDs as described in one of Claims 1 to 4, is characterized in that: the cerium dropped yttrium aluminum garnet wafer after step (1) and step (2) process the annealing obtained uses another kind of annealing atmosphere again to carry out anneal according to the operation of step (1) and step (2).
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|---|---|---|---|
| CN201310460006.2A CN103590111B (en) | 2013-09-29 | 2013-09-29 | A kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer |
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