CN107384399A - YAG types fluorescent material and preparation method, its YAG type crystalline ceramics fluorophor prepared and application - Google Patents
YAG types fluorescent material and preparation method, its YAG type crystalline ceramics fluorophor prepared and application Download PDFInfo
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- CN107384399A CN107384399A CN201710609957.XA CN201710609957A CN107384399A CN 107384399 A CN107384399 A CN 107384399A CN 201710609957 A CN201710609957 A CN 201710609957A CN 107384399 A CN107384399 A CN 107384399A
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- 229910002106 crystalline ceramic Inorganic materials 0.000 title claims description 39
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- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
This application discloses a kind of YAG types fluorescent material and preparation method thereof, the composition of the YAG types fluorescent material is R(3‑x)Al(5‑2y)O12：xCe3+,yMn2+,yM4+；Wherein, R is selected from least one of rare earth element；M4+For valence state counterion；X=0.005~0.2, y=0.05~0.4；Its preparation method includes：Each raw material is mixed in organic solvent, calcined under reducing atmosphere, is produced.The YAG type fluorescent transparents ceramics that the YAG types fluorescent material is prepared can replace fluorescent material and organic resin or silica type encapsulating material in existing white light LEDs, the high-quality white light that colour temperature is soft, colour rendering index is high is produced, and realizes LED light source encapsulating structure, light efficiency, the global optimization of stability.
Description
Technical field
The application is related to a kind of YAG types fluorescent material and preparation method, its YAG type crystalline ceramics fluorophor prepared and answered
With belonging to ceramic material field.
Background technology
White light LEDs have energy-conserving and environment-protective, light efficiency height, long lifespan, response soon etc. excellent as a kind of new solid state light emitter
Point, it is the forth generation green light source after three big light source of incandescent lamp, fluorescent lamp and high-voltage gas discharging light.It is widely used in counting
The fields such as code product, family or outdoor lighting.From the point of view of the industrialization factor such as technical matters maturity, production cost, fluorescence
Powder transformant white light LEDs are current mainstream technologys, are achieved in that YAG:Ce fluorescent material is glued by organic resin or silica gel
Connect coated on blue-light LED chip, absorption some blue light produces gold-tinted, and produces white light with remaining blue light.But the structure
White light LED technology still existing two big defect：On the one hand, the resin or silica gel as bonding agent are macromolecule organics,
Heat ageing, which easily occurs, reduces transmitance, and heat dispersion is poor.Under the persistent fever of blue chip, the light of device is had a strong impact on
Effect with it is photochromic, cause white light LEDs light decay outstanding problem, service life decline；On the other hand, YAG:Ce light-emitting phosphors lack red
Light composition, the white light colour temperature for causing device to be launched is higher, and colour rendering index is too low, can not meet the requirement of human eye comfort level, uncomfortable
Close the room lighting of high-quality.
Based on it is above-mentioned the problem of, key be change fluorescent material packaged type and optimization widen its emission spectrum.Closely
Nian Lai, researcher are attempted using the crystalline ceramics with high stability as fluorophor and encapsulating material.Fluorescent transparent ceramics are high
It thermal conductivity, low light scattering, can be declined with anti-light, improve the stability of brightness and spectrum.In the world, NEC glass company is first
Prepare the YAG for white light LEDs:Ce devitrified glass ceramics, PHILIPS Co. are proposed to YAG:Mixed in Ce powders certain
Measure Gd3+To improve the colour rendering index of white light, the well-known mechanism such as Ou Silang companies and Kyoto Univ Japan also expands this respect
Research.
Chinese patent CN104449718A, CN102501478A disclose a kind of bilayer for white-light LED encapsulation thoroughly
Bright ceramics and preparation method thereof, composite transparent ceramic are bonded by upper and lower two layers of crystalline ceramics, and upper strata uses Gd3+, Pr3+Mix
Miscellaneous YAG crystalline ceramics, lower floor YAG:The blue light of feux rouges, gold-tinted and transmission forms white light caused by Ce crystalline ceramics difference,
Colour rendering index and colour temperature are carried to improve.The problem of such a method is present be：First, two-layer ceramic piece interface passes through silica gel or organic
Glue bond, equally exist high temperature deterioration defect；Secondly, above fluorescent transparent ceramics are directly existed after being mixed using oxide raw material
Sintered in vacuum, the Ce of high price in raw material4+,Pr4+Plasma can not be effectively reduced to Ce3+,Pr3+Launching centre, and remove Ce3+
The rare earth ion emission spectra of trivalent is sharp keen line spectrum in addition, and area coverage is small, with Ce3+Band spectrum matching degree it is poor so that
Device light efficiency is relatively low, and colour rendering index improves unobvious, and general effect is unsatisfactory.The problem of similar, exists in Chinese special
Sharp CN102173774A, the Tb disclosed in CN103964834A3-xCexAl5O12, (CexY1-xRek)3Al5O12Made pottery Deng fluorescent transparent
In ceramic material.
The content of the invention
The problem of present invention lacks for fluorophor red color light component in the prior art, and overall light efficiency is low, first and Primordial Qi
YAG is synthesized in atmosphere:Ce3+,Mn2+,M4+Fluorescent material, wherein Mn2+The red spectrum of banding can be produced by energy transmission.Again with
This powder is raw material, and sintering prepares corresponding fluorescent transparent ceramics in a vacuum.Encapsulating material of the fluorophor as white light LEDs,
Avoid traditional silica gel, light decay problem caused by resin is thermally decomposed, and improve that original fluorescent material colour rendering index is relatively low, colour temperature
The problem of higher.Furthermore, it is possible to by adjusting Mn2+Concentration and counterion M4+Type, colour temperature luminous regulation and control LED and light
The luminous parameters such as spectrum, so as to obtain high-quality warm white LED device.
According to the one side of the application, there is provided a kind of YAG type fluorescent material for warm white LED encapsulation, the YAG types
The alternative traditional organic resin of crystalline ceramics or silica type encapsulating material that fluorescent material is prepared, have good stability
With the anti-light performance that declines.The raw material of the crystalline ceramics fluorophor is the fluorescent powder synthesized in reducing atmosphere, and contains and can produce
The Mn of banding red emission2+Center and the M as charge compensation4+Ion, therefore it has soft colour temperature, higher colour developing
Index and luminous efficiency.
The YAG types fluorescent material, it is characterised in that the composition of the YAG types fluorescent material is R(3-x)Al(5-2y)O12:xCe3+,
yMn2+,yM4+；
Wherein, R is selected from least one of rare earth element；M4+For valence state counterion；
X=0.005~0.2, y=0.05~0.4.
Preferably, x=0.03~0.12, y=0.1~0.3.
Preferably, x=0.03~0.09, y=0.1~0.2.
Preferably, the R is selected from Y3+、Lu3+、Gd3+At least one of；
The M4+Selected from Si4+、Ti4+、Zr4+、Ge4+At least one of.
Preferably, the endpoint value of number range where x be selected from 0.01,0.02,0.04,0.05,0.06,0.07,0.08,
0.09、0.10、0.15；The endpoint value of number range is selected from 0.125,0.15,0.25,0.35 where y.
The YAG types fluorescent material has yttrium-aluminium-garnet structure.
According to the another aspect of the application, there is provided the preparation method of the YAG types fluorescent material, including at least following steps：
(1) after the raw material containing R sources, Al sources, Ce sources, Mn sources, M sources is mixed with organic solvent, through drying, mixed
Thing；
(2) mixture obtained by step (1) is calcined under the reducing atmosphere of flowing, obtains being used for warm light LED envelopes
The YAG type fluorescent material of dress.
Preferably, R sources described in step (1) be selected from R oxide, R hydroxide, R halide, R nitrate,
R acylate, R carbonate, R at least one of subcarbonate.
Preferably, Al sources described in step (1) are selected from Al oxide, Al hydroxide, Al halide, Al nitre
Hydrochlorate, Al acylate, Al carbonate, Al at least one of subcarbonate.
Preferably, Ce sources described in step (1) are selected from Ce oxide, Ce hydroxide, Ce halide, Ce nitre
Hydrochlorate, Ce acylate, Ce carbonate, Ce at least one of subcarbonate.
Preferably, Mn sources described in step (1) are selected from Mn oxide, Mn hydroxide, Mn halide, Mn nitre
Hydrochlorate, Mn acylate, Mn carbonate, Mn at least one of subcarbonate.
Preferably, M sources described in step (1) be selected from M oxide, M hydroxide, M halide, M nitrate,
M acylate, M carbonate, M at least one of subcarbonate.
Preferably, in the raw material, R sources, Al sources, Ce sources, Mn sources, the molar ratio in M sources are
R：Al：Ce：Mn：M=(3-x)：(5-2y)：x：y：y.
Preferably, the R sources, Al sources, Ce sources, Mn sources and M sources purity >=99.9%.
Preferably, the organic solvent is selected from least one of the solvent of boiling point no more than 100 DEG C under normal pressure.
Preferably, the mass ratio of the organic solvent and raw material is 0.5~2:1.
Preferably, the organic solvent is selected from least one of acetone, ether, petroleum ether, ethanol.
Preferably, dried described in step (1) first to boil off organic solvent in Rotary Evaporators, then move to 70~90 DEG C
Drying box in continue drying out 4~6 hours.
Preferably, reducing atmosphere described in step (2) is N2And H2Gaseous mixture.It is further preferred that H in the gaseous mixture2
Volumn concentration be 5~20%.It is further preferred that H in the gaseous mixture2Volumn concentration for 10~
15%.
Preferably, the temperature calcined described in step (2) is 1400~1650 DEG C, and calcination time is 1~6 hour.Enter one
Preferably, the temperature calcined described in step (2) is 1450~1600 DEG C to step, and calcination time is 4~5 hours.
According to the another aspect of the application, there is provided a kind of YAG types crystalline ceramics fluorophor, it is characterised in that the YAG types
Crystalline ceramics fluorophor is that the YAG type fluorescent material being prepared by described YAG types fluorescent material and/or methods described is prepared into
Arrive.
The constituent of the crystalline ceramics fluorophor is identical with fluorescent material used.
Preferably, the preparation method of the YAG types crystalline ceramics fluorophor comprises at least：
Ceramic body is made in mixed powder containing YAG types fluorescent material, sintering aid, dispersant, through pre-burning dumping, very
Sky sintering, annealing, polishing, obtains the YAG types crystalline ceramics fluorophor.
Preferably, the addition of the sintering aid for mixed powder the weight/mass percentage composition upper limit be selected from 1.2wt%,
1.4wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%, 2.5wt%, 2.8wt%, 3wt%；Lower limit be selected from 0.1wt%,
0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%.It is further preferred that the sintering
Weight percentage of the auxiliary agent in mixed powder is 0.1~3wt%.It is further preferred that the sintering aid is mixing
Weight percentage in powder is 0.3~2wt%.Again it is further preferred that the sintering aid is in mixed powder
Weight percentage is 0.5~1wt%.
Preferably, the addition of the dispersant for mixed powder the weight/mass percentage composition upper limit be selected from 0.8wt%,
1.0wt%, 1.2wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%；Lower limit be selected from 0.01wt%,
0.02wt%, 0.04wt%, 0.06wt%, 0.08wt%, 0.10wt%, 0.15wt%, 0.18wt%.It is further preferred that
Weight percentage of the dispersant in mixed powder is 0.01~2wt%.It is further preferred that the dispersant exists
Weight percentage in mixed powder is 0.05~1wt%.Again it is further preferred that the addition of the dispersant is mixed
Close 0.2~0.75wt% of powder.
Preferably, the sintering aid is selected from boric acid, lanthana, magnesia, magnesium fluoride, calcirm-fluoride, barium fluoride, aluminum fluoride
At least one of.
Preferably, the dispersant is selected from polyethylene glycol, polyvinyl alcohol, polyvinyl butyral resin, methylcellulose, poly- first
At least one of base ammonium acrylate.
Preferably, the preparation process of the mixed powder is：By YAG types fluorescent material, sintering aid, dispersant, warp
Wet ball grinding refinement is crossed, sieves, produces after drying.
Preferably, the preparation process of the ceramic body is：Mixed powder is obtained by dry-pressing tabletting, isostatic cool pressing.
Preferably, the condition of the dry-pressing tabletting is：More than 50MPa dry-pressing 1~15 minute；The isostatic cool pressing is
More than 150MPa isostatic cool pressings 1~10 minute.
It is further preferred that the condition of the dry-pressing tabletting is：80~100MPa dry-pressing 5~10 minutes；It is described cold etc. quiet
Press as 200~more than 300MPa isostatic cool pressings 5~8 minutes.
The pre-burning dumping is warming up to added organic matter for the biscuit of shaping is fitted into tube furnace or batch-type furnace
Decomposition temperature, soaking time is determined according to base substrate size and matter property, using oxygen or inert gas shielding dumping.
Preferably, the temperature of the pre-burning dumping is 500~1100 DEG C, and the time is 2~10 hours.
It is further preferred that the temperature of the pre-burning dumping is 600~900 DEG C, the time is 4~6 hours.
The temperature of the vacuum-sintering is 1680~1900 DEG C, and the time of vacuum-sintering is 1~50 hour.
Preferably, the temperature of vacuum-sintering is 1750~1850 DEG C, and the time of vacuum-sintering is 6~48 hours.
It is further preferred that the temperature of vacuum-sintering is 1800~1850 DEG C, the time of vacuum-sintering is 8~36 hours.
The above-mentioned process for being related to heating can use stage heating schedule.
According to the another aspect of the application, there is provided a kind of light emitting diode, contain any YAG type crystalline ceramics
At least one of fluorophor.That is, described YAG types crystalline ceramics fluorophor is used for the application of warm white LED encapsulation.
Preferably, the light emitting diode includes blue-light LED chip.
Preferably, the light emitting diode launches white light in 480~800nm.
As a preferred embodiment, the light emitting diode is using the YAG types crystalline ceramics fluorophor and indigo plant
After the encapsulation of light LED chip, low colour temperature, the high white light emission for showing finger, specular removal are produced in 480~800nm.
Ce in the application3+、Mn2+Two aspect factors are considered in the selection of content：On the one hand need enough gold-tinteds with it is red
Light is launched, and on the other hand to avoid the concentration quenching of launching centre, ensures high-luminous-efficiency.
The YAG type crystalline ceramics fluorophor of the application introduces Mn2+Center, emission spectrum are widened to red light district, mutually and are passed through
It is co-doped with Si4+、Ti4+、Zr4+Or Ge4+As valence state counterion, strengthen luminous efficiency.The fluorescent transparent ceramics of the present invention can replace
Fluorescent material and organic resin or silica type encapsulating material in existing white light LEDs, produce the height that colour temperature is soft, colour rendering index is high
Quality white light, and realize LED light source encapsulating structure, light efficiency, the global optimization of stability.
Beneficial effect caused by the application energy includes but is not limited to：
1) YAG type crystalline ceramics fluorophor provided herein, avoids conventional LED package resin or silica gel material dissipates
Heat differential, it is easy to aging caused by light decay phenomenon, there is longer service life.
2) YAG type crystalline ceramics fluorophor provided herein uses the fluorescent powder synthesized in reducing atmosphere as original
Expect, contain efficient red color light component in emission spectra, colour temperature is low, and colour rendering index is high, and light efficiency is high, available for high-quality warm white LED
Encapsulation.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrum of sample P 01 in embodiment 1；
Fig. 2 is the X-ray diffraction spectrum of sample C1 in embodiment 1；
Fig. 3 is emission spectrum of the sample C1 in the case where 460nm blue lights excite in embodiment 1；
Fig. 4 is the X-ray diffraction spectrum of sample DC1 in embodiment 5；
Fig. 5 is emission spectrum of the sample DC1 in the case where 460nm blue lights excite in embodiment 5.
Embodiment
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and catalyst are bought by commercial sources.
Analysis method is as follows in embodiments herein：
XRD analysis are carried out using X-ray diffractometer (Miniflex-600, Rigaku Japan).
Emission spectrum, colour temperature, colour rendering index analysis are carried out using spectroscopic analysis system (PMS-80, Hangzhou distant place photoelectricity).
Luminous efficiency analysis is carried out using spectral radiometer (HAAS-3000, Hangzhou distant place photoelectricity).
The preparation of the YAG type fluorescent material sample P 01 of embodiment 1 and YAG type crystalline ceramics fluorophor C1
Use purity for 99.9% yittrium oxide (Y2O3), aluminum oxide (Al2O3), cerium oxide (CeO2), manganese monoxide
(MnO), silica (SiO2) powder, by Y2.97Al4.85O12:0.03Ce3+,0.075Mn2+,0.075Si4+The good original of composition configuration
The common 50g of material, powder is placed in same container；25g acetone is added into the container equipped with powder, it is mixed by mechanical agitation
Close powder to be sufficiently mixed, mixed slurry is placed in Rotary Evaporators and quickly boils off acetone, it is small that 5 are dried in 80 DEG C of drying box
When after sieve；Mixture loads crucible after sieving, in flowing N2/H2(volume ratio 90:10) in atmosphere, in tube furnace first
1000 DEG C are warming up to 10 DEG C/min heating rate, then 1450 DEG C are warming up to 5 DEG C/min heating rate, is reacted 5 hours
Natural cooling afterwards, that is, obtain the YAG fluorescent powder body P01.
The YAG fluorescent powder body P01 and sintering aid calcirm-fluoride (CaF2), dispersant polyethylene glycol mixing, mixed
Thing；Wherein, CaF in mixture2Content be 0.5wt%, the content of polyethylene glycol is 0.2wt%.Then mixture is passed through
High purity aluminium oxide abrading-ball carries out ball milling, ratio of grinding media to material 10:1, absolute ethyl alcohol is medium, ball milling mixing refinement in 12 hours, is dried, mistake
Fluorescent powder P1 is obtained after sieve；Using P1 as raw material, dry-pressing 5 minutes under 80MPa, then through isostatic cool pressing under 250MPa 5 minutes
Shaping, obtains YAG biscuit of ceramics；The YAG biscuit of ceramics is placed in Muffle furnace 700 DEG C of dumpings 5 hours, is placed in vacuum drying oven afterwards
In, 1800 DEG C are warming up to 5 DEG C/min heating rate, vacuum-sintering 8 hours, obtains YAG types ceramics；Alternatively it is carried out
Sanding and polishing, diameter about 10mm, thickness about 0.2-0.5mm crystalline ceramics fluorophor are obtained, is designated as ceramic C1.
The preparation of the YAG type fluorescent material sample P 02 of embodiment 2 and YAG type crystalline ceramics fluorophor C2
Use purity for 99.9% yittrium oxide (Y2O3), aluminium hydroxide (Al (OH)3), cerium oxide (CeO2), manganese acetate
(Mn(C2H3O2)2), zirconium dioxide (ZrO2) powder, by Y2.94Al4.8O12：0.06Ce3+,0.1Mn2+,0.1Zr4+Composition configures
The common 50g of raw material, powder is placed in same container；50g ethanol is added into the container equipped with powder, passes through mechanical agitation
Mixed powder is sufficiently mixed, and mixed slurry is placed in Rotary Evaporators and quickly boils off solvent, and 5 are dried in 80 DEG C of drying box
Sieved after hour；Mixture loads crucible after sieving, in flowing N2/H2(volume ratio 85:15) in atmosphere, in tube furnace
1000 DEG C first are warming up to 10 DEG C/min heating rate, then 1500 DEG C are warming up to 5 DEG C/min heating rate, reaction 4 is small
When after natural cooling, that is, obtain the YAG fluorescent powder body P02.
The YAG fluorescent powder body P02 and sintering aid barium fluoride (BaF2), polyethylene of dispersing agent butyral mixing, obtain
To mixture；Wherein, BaF in mixture2Content be 0.75wt%, the content of polyvinyl butyral resin is 0.3wt%.Then
Mixture is subjected to ball milling, ratio of grinding media to material 10 by high purity aluminium oxide abrading-ball:1, absolute ethyl alcohol is medium, and ball milling mixes for 12 hours
Refinement, drying, obtains fluorescent powder P2 after sieving；Using P2 as raw material, dry-pressing 5 minutes under 80MPa, through cold etc. under 250MPa
Static pressure is molded for 5 minutes, obtains YAG biscuit of ceramics；YAG biscuit of ceramics is placed in Muffle furnace 600 DEG C of dumpings 5 hours, is placed in afterwards
In vacuum drying oven, 1850 DEG C are warming up to 5 DEG C/min heating rate, vacuum-sintering 16 hours, other conditions obtain with embodiment 1
To YAG type crystalline ceramics fluorophor, ceramic C2 is designated as.
The preparation of the YAG type fluorescent material sample P 03 of embodiment 3 and YAG type crystalline ceramics fluorophor C3
Use purity for 99.9% lutecium nitrate (Lu (NO3)3), aluminum nitrate (Al (NO3)3), cerium oxide (CeO2), manganese carbonate
(MnCO3), titanium dioxide (TiO2) powder, by Y2.91Al4.7O12：0.09Ce3+,0.15Mn2+,0.15Ti4+Composition has configured raw material
Common 50g, powder is placed in same container；50g ether is added into the container equipped with powder, is mixed by mechanical agitation
Powder is sufficiently mixed, and mixed slurry is placed in Rotary Evaporators and quickly boils off solvent, is dried 5 hours in 80 DEG C of drying box
After sieve；Mixture loads crucible after sieving, in flowing N2/H2(volume ratio 85:15) in atmosphere, in tube furnace first with
10 DEG C/min heating rate is warming up to 1000 DEG C, then is warming up to 1550 DEG C with 5 DEG C/min heating rate, after reacting 4 hours
Natural cooling, that is, obtain the YAG fluorescent powder body P03.
The YAG fluorescent powder body P03 and sintering aid boric acid (H3BO3), polyethylene of dispersing agent alcohol mixing, obtain mixture；
Wherein, H in mixture3BO3Content be 1wt%, the content of polyvinyl alcohol is 0.5wt%.Then mixture is passed through into high pure oxygen
Change aluminium abrading-ball and carry out ball milling, ratio of grinding media to material 10:1, absolute ethyl alcohol is medium, ball milling mixing refinement in 12 hours, drying, is obtained after sieving
To fluorescent powder P3；Using P3 as raw material, dry-pressing 5 minutes under 80MPa, then be molded within 5 minutes through isostatic cool pressing under 250MPa, obtain
To YAG biscuit of ceramics；YAG biscuit of ceramics is placed in Muffle furnace 900 DEG C of dumpings 5 hours, is placed in afterwards in vacuum drying oven, with 5 DEG C/
Min heating rate is warming up to 1850 DEG C, and vacuum-sintering 24 hours, other conditions obtain YAG type crystalline ceramics with embodiment 1
Fluorophor, it is designated as ceramic C3.
The preparation of the YAG type fluorescent material sample P 04 of embodiment 4 and YAG type crystalline ceramics fluorophor C4
Use purity for 99.9% gadolinium acetate (Gd (C2H3O2)3), aluminium chloride (AlCl3), cerium oxide (CeO2), hydroxide
Manganese (Mn (OH)2), germanium dioxide (GeO2) powder, by Y2.91Al4.6O12：0.09Ce3+,0.2Mn2+,0.2Ge4+The good original of composition configuration
The common 50g of material, powder is placed in same container；75g ethanol is added into the container equipped with powder, it is mixed by mechanical agitation
Close powder to be sufficiently mixed, mixed slurry is placed in Rotary Evaporators and quickly boils off solvent, it is small that 5 are dried in 80 DEG C of drying box
When after sieve；Mixture loads crucible after sieving, in flowing N2/H2(volume ratio 85:15) in atmosphere, in tube furnace first
1000 DEG C are warming up to 10 DEG C/min heating rate, then 1600 DEG C are warming up to 5 DEG C/min heating rate, is reacted 4 hours
Natural cooling afterwards, that is, obtain the YAG fluorescent powder body P04.
The YAG fluorescent powder body P04 and sintering aid aluminum fluoride (AlF3), dispersant methylcellulose mixing, mixed
Compound；Wherein, AlF in mixture3Content be 1wt%, the content of methylcellulose is 0.75wt%.Then mixture is passed through
Cross high purity aluminium oxide abrading-ball and carry out ball milling, ratio of grinding media to material 10:1, absolute ethyl alcohol is medium, ball milling mixing refinement in 12 hours, is dried,
Fluorescent powder P4 is obtained after sieving；Using P4 as raw material, dry-pressing 5 minutes under 80MPa, then divide through isostatic cool pressing under 250MPa 5
Clock is molded, and obtains YAG biscuit of ceramics；Base substrate is placed in Muffle furnace 750 DEG C of dumpings 5 hours, is placed in afterwards in vacuum drying oven, with 5 DEG C/
Min heating rate is warming up to 1850 DEG C, and vacuum-sintering 36 hours, other conditions obtain YAG type crystalline ceramics with embodiment 1
Fluorophor, it is designated as ceramic C4.
The crystalline ceramics fluorophor sample DC1 of embodiment 5 preparation
Except being added without manganese monoxide (MnO) and silica (SiO2) outside, other conditions are prepared with embodiment 1
And it is Y to test constituent2.97Al5O12：0.03Ce3+Transparent fluorescent ceramic, be designated as ceramic DC1.
The thing of the sample of embodiment 6 mutually characterizes
01~P04 of gained sample P, C1~C4 and DC1 thing are mutually analyzed using XRD, the results showed that, powder P01-
P04 and ceramics sample, for C1~C4 things mutually without significant change, it is respectively provided with YAG types structure composition (Fig. 1 XRD counter samples P01；
Fig. 2 XRD counter sample C1).DC1 analysis result also indicates that DC1 has YAG structures (Fig. 4).
Sample C1~the C4 of embodiment 7 and sample DC1 optical property
The blue light for being respectively 460nm with wavelength excites crystalline ceramics fluorophor C1~C4 and DC1, the results showed that, C1~C4
Emission spectrum in 500nm~800nm regions, cover feux rouges and green Region, and substantially widened to red light district；Typical Representative is such as
C1, its emission spectrum are as shown in Figure 3.DC1 emission spectrum is as shown in Figure 5, it can be seen that and it is wider in green-yellow light area, and
Red light district deficiency.
The preparation of the light emitting diode of embodiment 8 and sign
C1~C4, DC1 and blue-light LED chip (purchased from three peace Photoelectric Co., Ltd.) encapsulation is respectively adopted, is prepared into
It is measured to light emitting diode, and to preparation-obtained light emitting diode.As a result show, what C1~C4 encapsulated to obtain lights
Diode colour temperature is soft, and colour rendering index is higher, belongs to high-quality warm white.Using C1 as Typical Representative, its colour temperature is 3256K,
Colour rendering index is 84.5, luminous efficiency 132lm/W.
And the white light colour temperature that the light emitting diode that DC1 encapsulates to obtain is sent is higher (5363K), colour rendering index is relatively low
(72.1), luminous efficiency is relatively low (114lm/W).
It should be noted that by the other conditions stated in claims of the present invention, respective sets can be equally obtained
The YAG type crystalline ceramics fluorophor divided, numerous to list herein, this has no effect on the protection domain of the claims in the present invention.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (10)
1. a kind of YAG types fluorescent material, it is characterised in that the composition of the YAG types fluorescent material is R(3-x)Al(5-2y)O12：xCe3+,
yMn2+,yM4+；
Wherein, R is selected from least one of rare earth element；M4+For valence state counterion；
X=0.005~0.2, y=0.05~0.4；Preferably, x=0.03~0.12, y=0.1~0.3.
2. YAG types fluorescent material according to claim 1, it is characterised in that the R is selected from Y3+、Lu3+、Gd3+In at least
It is a kind of；
The M4+Selected from Si4+、Ti4+、Zr4+、Ge4+At least one of.
A kind of 3. preparation method of YAG type fluorescent material as claimed in claim 1 or 2, including at least following steps：
(1) after the raw material containing R sources, Al sources, Ce sources, Mn sources, M sources is mixed with organic solvent, through drying, mixture is obtained；
(2) mixture obtained by step (1) is calcined under the reducing atmosphere of flowing, obtains YAG type fluorescent material.
4. the preparation method of YAG types fluorescent material according to claim 3, it is characterised in that select in R sources described in step (1)
The hydroxide of oxide, R, R halide, R nitrate, R acylate, R carbonate, R basic carbonate from R
At least one of salt；
The Al sources are selected from Al oxide, Al hydroxide, Al halide, Al nitrate, Al acylate, Al
Carbonate, Al at least one of subcarbonate；
The Ce sources are selected from Ce oxide, Ce hydroxide, Ce halide, Ce nitrate, Ce acylate, Ce
Carbonate, Ce at least one of subcarbonate；
The Mn sources are selected from Mn oxide, Mn hydroxide, Mn halide, Mn nitrate, Mn acylate, Mn
Carbonate, Mn at least one of subcarbonate；
The M sources are selected from M oxide, M hydroxide, M halide, M nitrate, M acylate, M carbonic acid
At least one of the subcarbonate of salt, M；
In the raw material, R sources, Al sources, Ce sources, Mn sources, the molar ratio in M sources are
R：Al：Ce：Mn：M=(3-x)：(5-2y)：x：y：y；
The organic solvent is selected from least one of the solvent of boiling point no more than 100 DEG C under normal pressure.
5. the preparation method of YAG types fluorescent material according to claim 3, it is characterised in that Primordial Qi is gone back described in step (2)
Atmosphere is N2And H2Gaseous mixture；
Preferably, H in the gaseous mixture2Volumn concentration be 5~20%；
The temperature of the calcining is 1400~1650 DEG C, and calcination time is 1~6 hour.
6. a kind of YAG types crystalline ceramics fluorophor, it is characterised in that the YAG types crystalline ceramics fluorophor is by claim 1
Or prepared by the YAG types fluorescent material that any one of YAG types fluorescent material described in 2 and/or claim 3~5 methods described are prepared
Obtain.
7. YAG types crystalline ceramics fluorophor according to claim 6, it is characterised in that the YAG types crystalline ceramics fluorescence
The preparation method of body comprises at least：
Ceramic body is made in mixed powder containing YAG types fluorescent material, sintering aid, dispersant, through pre-burning dumping, vacuum is burnt
Knot, annealing, polishing, obtains the YAG types crystalline ceramics fluorophor.
8. YAG types crystalline ceramics fluorophor according to claim 7, it is characterised in that the addition of the sintering aid
For 0.1~3wt% of mixed powder；
The addition of the dispersant is 0.01~2wt% of mixed powder；
The temperature of the vacuum-sintering is 1680~1900 DEG C, and the time of vacuum-sintering is 1~50 hour.
9. the YAG type crystalline ceramics fluorophor according to claim 7 or 8, it is characterised in that the sintering aid is selected from boron
At least one of acid, lanthana, magnesia, magnesium fluoride, calcirm-fluoride, barium fluoride, aluminum fluoride；
The dispersant is selected from polyethylene glycol, polyvinyl alcohol, polyvinyl butyral resin, methylcellulose, ammonium polymethacrylate
At least one of.
10. a kind of light emitting diode, it is characterised in that contain the YAG type crystalline ceramics as described in any one of claim 6~9
At least one of fluorophor；
Preferably, the light emitting diode contains blue-light LED chip；
Preferably, the light emitting diode launches white light in 480~800nm.
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| CN108281535A (en) * | 2018-02-02 | 2018-07-13 | 温州大学 | Composite fluorescence laminated glass and preparation method thereof and the application on white light LEDs |
| CN108484168A (en) * | 2018-03-27 | 2018-09-04 | 中国科学院上海硅酸盐研究所 | A kind of red, transparent fluorescence ceramics and preparation method thereof |
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