CN108264899A - A kind of fluorescence ceramics applied to LED and preparation method thereof - Google Patents
A kind of fluorescence ceramics applied to LED and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of fluorescence ceramics applied to LED, chemical general formula is (A1‑xBx)m‑yCy(D1‑zEz)8‑mO12, wherein, at least one of A Y, Gd, Tb, Lu；B is at least one of La, Yb；C is at least one of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm, Ti, Cr, Mn；D is Ga；E is at least one of B, Al, In, Sc；Wherein, x, y, z, m represent the molar fraction of corresponding element, and 0≤x≤0.2,0.0001≤y≤0.2,0≤z≤0.8,2.5≤m≤3.5.The present invention also provides a kind of preparation methods of fluorescence ceramics, fluorescent powder is directly translated into the fluorescence block with light transmission features in this method, as remote phosphor i.e. in the form of transparent fluorescent ceramic, it is directly packaged in above LED chip, not only fluorescent material with heat source is detached and reduces hot light decay, also prevent the use of epoxy resin or silica gel simultaneously, extend the service life of LED component.
Description
Technical field
The present invention relates to field of light emitting materials, more particularly to a kind of fluorescence ceramics applied to LED and preparation method thereof.
Background technology
With the progress of light emitting diode (Light Emitting Diode, LED) technology, white light LEDs are from special light
Source application field gradually steps into general lighting field.White light LEDs with its high brightness, high color rendering index (CRI), energy-saving and environmental protection, long lifespan,
Small, high reliability, it is considered to be the forth generation after incandescent lamp, fluorescent lamp and high-intensity gas discharge lamp shines
Mingguang City source.
High performance white LED lamp price is relatively high, this is mainly caused by two aspect factors.On the one hand, it is existing white
Light LED product relies primarily on DC powered, this, which means that, needs additional electronic component.Pass through current/voltage rectifier
110V/220V cities AC mains are converted into direct current by (power switch) and constant-current source, to control the input of white light LEDs electric
Stream.On the other hand, it in traditional white-light LED encapsulation technique, is directly coated after epoxy resin or silica gel and fluorescent powder are mixed
White light is formed in chip surface.The heat generated during with chip operation constantly accumulates, it is easy to lead to epoxy resin or silicon
The aging of the encapsulating materials such as glue turns yellow, and therefore, it is necessary to carry out heat management using additional radiator.In addition, AC-DC
Converter and cooling system account for the 30%~50% of LED product expense, higher which results in cost.
AC LED device can directly be driven by urban electric power, not only eliminated a large amount of electronic component, reduced valency
Lattice, while also there is high energy utilization efficiency, overall compact volume and longer service life, corresponding product also obtains
Extensive use.In AC LED, when being only more than cut-in voltage by the voltage in circuit, device could shine.Due to alternating current frequency
The difference of rate and LED component design, usually there are the time difference of 5ms~20ms during entire AC cycles, human eye is to this
One time is although insensitive, but can also cause visual fatigue with eye for a long time.It can be with although capacitor is configured in AC LED
Solve the problems, such as this, but the service life of capacitor is much smaller than the service life of LED.And by the light-decay characteristic of fluorescence ceramics, it can solve
Certainly this problem.
At present, the mainstream scheme for obtaining white light LEDs is that YAG is applied on blue-light LED chip:Ce3+Yellow fluorescent powder passes through
The yellow light that the blue light and fluorescent powder that LED chip is sent out are sent out is mixed to get white light.But YAG:Ce3+It is special that bloom does not have long afterglow
Property.And the fluorescent powder with long afterglow property can only effectively be excited by ultraviolet light at present, such as SrSi2O2N2:Eu2+,Mn2+Green powder
(document Yeh, C.et al is referred to, " Appropriate green phosphor of SrSi2O2N2:Eu2+,Mn2+for AC
LEDs, Opt.Express, 2012,20,18031-18034. ") and SrAl2O4:Eu2+,R3+Green powder (document Chen is referred to,
L.et al,The green phosphor SrAl2O4:Eu2+,R3+(R=Y, Dy) and its applicationin
alternating current light-emitting diodes,Funct.Mater.Lett.,2013,6,1350047.)。
Therefore, the fluorescence ceramics that can be effectively excited by existing blue-light LED chip are urgently developed.
In addition, in traditional packaging technology, since the epoxy resin of use or the heat conductivility of silica gel are poor, and LED
Temperature during chip operation is up to 150 DEG C, this easilys lead to the heat fade of light-emitting phosphor and epoxy resin or silica gel
Aging, turn yellow.Especially in great power LED, chip surface can generate amount of heat, and cause seriously to reduce device performance
And service life.
Invention content
The present invention provides a kind of fluorescence ceramics that can be applied to LED, which has the advantages that luminous intensity is high, can expire
The requirement of foot exchange white light LEDs, can also be used as remote fluorescence block, in large power white light LED.The fluorescence ceramics
Preparation method have the advantages that it is at low cost, simple for process.
The present invention provides a kind of fluorescence ceramics applied to LED, and chemical general formula is (A1-xBx)m-yCy(D1-zEz)8-mO12,
Wherein,
A is at least one of Y, Gd, Tb, Lu；
B is at least one of La, Yb；
C is at least one of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm, Ti, Cr, Mn；
D is Ga；
E is at least one of B, Al, In, Sc；
Wherein, x, y, z, the molar fraction of m expression corresponding elements, and 0≤x≤0.2,0.0001≤y≤0.2,0≤z≤
0.8,2.5≤m≤3.5.
Wherein, the fluorescence ceramics are excited by wavelength for 420nm~480nm blue lights.
Wherein, x, y, z, the value range of m are：0≤x≤0.2,0.01≤y≤0.15,0≤z≤0.6,2.5≤m≤
3.5。
Wherein, the light transmittance of the fluorescence ceramics is 40%~80%.
The present invention also provides a kind of preparation methods of the fluorescence ceramics applied to LED, include the following steps：
(1) raw material is provided and carries out ball milling, drying, calcination successively, obtains powder；
(2) powder is ground successively, the processing of molding and isostatic cool pressing, obtains biscuit；
(3) in oxygen atmosphere, the biscuit is sintered to obtain prefabricated ceramics；
(4) in a reducing atmosphere, it anneals to the prefabricated ceramics, obtains fluorescence ceramics.
Wherein, raw material described in step (1) for the oxide containing corresponding A, B, C, D and E element, fluoride, chloride,
Carbonate, borate, oxalates or acetate.
Wherein, in step (1) during ball milling, ball grinder and abrading-ball are polytetrafluoroethylproducts products, abrading-ball size 5mm
~10mm, ball-milling medium are at least one of water, ethyl alcohol, acetone, glycerine, and rotational speed of ball-mill is 100rad/min~300rad/
Min, Ball-milling Time are 5 hours or more.
Wherein, the temperature of calcination is 600 DEG C~900 DEG C in step (1), and the time of calcination is 2 hours~10 hours.
Wherein, the temperature being sintered in step (2) is 1500 DEG C~1800 DEG C, and the time of sintering is 2 hours or more.
Wherein, reducing atmosphere described in step (3) is hydrogen atmosphere, ammonia atmosphere, carbon monoxide atmosphere or nitrogen hydrogen mix
Gas atmosphere, the temperature of annealing is 1000 DEG C~1600 DEG C, and the time of annealing is 2 hours~10 hours.
Fluorescence ceramics of the present invention have the following advantages：
First, compared with using epoxy resin or silica gel when existing LED is encapsulated, the fluorescence can be used directly in the present invention
Ceramics carry out the encapsulation of LED, and can avoid the use of epoxy resin or silica gel, and then improve the service life of LED component.Together
When, the fluorescence ceramics good heat conductivity, and far from chip heat source, and then the hot light decay of fluorescent material is reduced, improve LED
The luminous efficiency of device.
Second, with existing commercialization YAG:Ce3+Yellow fluorescent powder is compared, and shining for fluorescence ceramics provided by the invention has length
Light-decay characteristic can make up AC LED caused light loss during stroboscopic, meet the application requirement of AC LED.
Third, the fluorescence ceramics can effectively be excited by the blue light that wavelength is 420nm~480nm, and emission spectrum covers
480nm~750nm visible light wave ranges, transmitance is in 40%-80%.
Strong, transmitance is high, persistence is long with shining for the fluorescence ceramics, and heat conductivility is good, can be used as remotely glimmering
Body of light is used in great power LED, has actual application value and commercial promise..
The preparation method of fluorescence ceramics of the present invention has the following advantages：
It is needed with existing fluorescent glass using glass as carrier, then adds in phosphor process and compare, it is of the present invention glimmering
Light ceramic is not needed to using glass matrix, this was not only simple for process, but also avoided due to being directly prepared by single fluorescent components
Non-uniform problem during mixing.In addition, compared with existing glass, the fluorescence ceramics have better heat conductivility.
Preparation principle is as follows in this preparation method：
Containing Ga elements in the fluorescence ceramics, element highly volatile at high temperature, especially in a reducing atmosphere.Cause
And the present invention uses oxidizing atmosphere in first step sintering, can effectively control the volatilization of Ga elements in raw material, and make Ga elements
With forming stable crystal structure together with other elements, so as to play fixed function to Ga elements；It is used in the second step annealing
Reducing atmosphere makes the prefabricated ceramics with stable crystalline phase structure being sintered in the first step further be reduced, to promote hair
The concentration of light emitting ionic and the excellent fluorescence ceramics of luminescent properties are obtained in luminescent material.
It is all from commercially available in addition, raw materials used, raw material is easy to get, cost is relatively low, process is simple, the product quality that obtains is stablized
Reliably, and conducive to industrialized production.
Description of the drawings
Fig. 1 is the photo of fluorescence ceramics that the embodiment of the present invention 1 to 3 is prepared.
Fig. 2 is the light transmittance collection of illustrative plates of fluorescence ceramics that the embodiment of the present invention 1 to 3 is prepared.
Fig. 3 is the exciting light spectrogram of fluorescence ceramics that is prepared of the embodiment of the present invention 1 to 3, wherein, emit the wavelength of light
λem=570nm.
Fig. 4 is the launching light spectrogram of fluorescence ceramics that the embodiment of the present invention 1 to 3 is prepared, wherein, the wavelength of excitation wave
λex=460nm.
Fig. 5 is that the fluorescence ceramics that the embodiment of the present invention 2 is prepared excite after five minutes in the blue light that wavelength is 460nm
Twilight sunset launching light spectrogram.
Fig. 6 is that the fluorescence ceramics that the embodiment of the present invention 2 is prepared excite after five minutes in the blue light that wavelength is 460nm
Decay of afterglow curve graph.
Specific embodiment
In order to which the present invention is better described, the specific embodiment of the present invention is described in detail below in conjunction with attached drawing.
It will be appreciated by those skilled in the art that illustrated embodiment is served only for explaining the present invention, it is not intended to limit the scope of the present invention.
The present invention provides a kind of fluorescence ceramics applied to LED.The chemical general formula of the fluorescence ceramics is (A1-xBx)m- yCy(D1-zEz)8-mO12.Wherein,
A is at least one of Y, Gd, Tb, Lu；
B is at least one of La, Yb；
C is at least one of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm, Ti, Cr, Mn；
D is Ga；
E is at least one of B, Al, In, Sc；
Wherein, x, y, z, the molar fraction of m expression corresponding elements, and 0≤x≤0.2,0.0001≤y≤0.2,0≤z≤
0.8,2.5≤m≤3.5.
Preferably, x, y, z, the value range of m are：0≤x≤0.2,0.01≤y≤0.15,0≤z≤0.6,2.5≤m≤
3.5.It is preferred that the reasons why be：Within this range, the fluorescence ceramics performance of acquisition is more excellent.
The present invention also provides a kind of preparation methods of the fluorescence ceramics applied to LED.The preparation method includes following step
Suddenly：
S1 provides raw material and carries out ball milling, drying, calcination successively, obtains powder；
The powder is ground, the processing of molding and isostatic cool pressing, obtains the prefabricated ceramics preparative of biscuit by S2 successively
Ceramics；
S3 in oxygen atmosphere, the biscuit is sintered to obtain prefabricated ceramics；
S4 in a reducing atmosphere, anneals to the prefabricated ceramics, obtains the prefabricated ceramics of fluorescence ceramics.
In step sl, according to (A1-xBx)m-yCy(D1-zEz)8-mO12Stoichiometric ratio weigh reaction raw materials.City can be used
The micron order or nano level raw material that purity is more than 99% are sold, without carrying out reprocessing processing to raw material, this can be saved into
This, to realize industrialization.
Preferably, the raw material for the oxide containing corresponding A, B, C, D and E element, fluoride, chloride, carbonate,
Borate, oxalates or acetate.
It after prepared raw material is mixed, and is put into ball grinder and carries out ball milling in planetary ball mill, obtain slurry.In ball milling
During, ball grinder and abrading-ball are polytetrafluoroethylproducts products, abrading-ball size 5mm~10mm, ball-milling medium is water, ethyl alcohol,
At least one of acetone, glycerine, rotational speed of ball-mill are 100rad/min~300rad/min, and Ball-milling Time is 5 hours or more.
Slurry after grinding can be dried using microwave drying or air dry oven, what is had good uniformity is dry
Dry powder.
Dry powder is subjected to calcination, to remove some organic impurities introduced in mechanical milling process.The temperature of the calcination
It is 600 DEG C~900 DEG C to spend, and the time of calcination is 2 hours~10 hours.
In step s 2, the powder after calcination is ground, and crosses the mesh of 100 mesh~300 sieve.Again to the powder after sieving
By the way that powder is dry-pressing formed, injection forming or gel injection-moulding are molded, most after being carried out at isostatic cool pressing under 100-300MPa
Reason, obtains biscuit.
In step s3, the temperature of the sintering is 1500 DEG C~1800 DEG C, and the time of sintering is 2 hours or more.It is preferred that
, the temperature of the sintering is 1600 DEG C~1700 DEG C.
The purpose of the sintering is：The volatilization of Ga elements in raw material can be effectively controlled, and make Ga elements and other elements
Stable crystal structure is formed together, so as to play fixed function to Ga elements.
In step s 4, the reducing atmosphere is hydrogen atmosphere, ammonia atmosphere, carbon monoxide atmosphere or nitrogen and hydrogen mixture gas
Atmosphere or other atmosphere built with the gas compared with strong reducing property.
The temperature of the annealing is 1000 DEG C~1600 DEG C, and the time of annealing is 2 hours~10 hours.Preferably, it anneals
Temperature be 1200 DEG C~1400 DEG C.
The purpose of the annealing is：It is further reduced in the prefabricated ceramics with stable crystalline phase structure that sintering obtains,
To promote the concentration of light emitting ionic in luminescent material and obtain the excellent fluorescence ceramics of luminescent properties.
The fluorescence ceramics can effectively be excited by 420nm~480nm blue lights, and emission spectrum covers 480~750nm can
See optical band.Therefore, which can be combined with the blue-ray LED of business, to synthesize white light, while as remote fluorescence
Body meets the application requirement of great power LED.In addition, the fluorescence ceramics also have the advantages that luminous intensity is high, persistence is long,
AC LED caused light loss during stroboscopic can be made up, therefore, which can meet the application requirement of AC LED.
The preparation method processes of fluorescence ceramics of the present invention is simple, of low cost, obtained stable and reliable product quality,
Conducive to industrialized production.
For a better understanding of the present invention, below by fluorescence ceramics of the specific embodiment to the present invention and its preparation side
Method is further described.The raw material that fluorescent powder is used to prepare in following embodiment is all from commercially available (purity is more than 99%).This
The feature that the features described above or embodiment that invention is mentioned are mentioned can be in any combination.The revealed all features of this case specification
It can be used in combination with any composition form, each feature disclosed in specification, it can be identical, impartial or similar by any offer
The alternative characteristics substitution of purpose.Therefore, except there is special instruction, revealed feature is only impartial or similar features generality
Example.
Embodiment 1
The chemical general formula of the fluorescence ceramics is (Y0.5Gd0.5)2.9999Ce0.0001(Ga0.6Al0.4)5O12, i.e. x=0, y=
0.0001, z=0.4, m=3, A are Y and Gd, C Ce, D Ga, E Al.
The preparation method of the fluorescence ceramics is as follows：
With commercially available high-purity Y2O3、Gd2O3、Ce2(CO3)3、Ga2O3、Al2O3For starting material, respectively aoxidized by above formula precise
Object or carbonic acid salt quality.By the reaction raw materials weighed using 5mm polytetrafluoroethylene (PTFE) ball as abrading-ball, using absolute ethyl alcohol as ball-milling medium,
Ball in mass ratio：Material：Medium=7：1：The reaction raw materials weighed, abrading-ball and medium are put into polytetrafluoroethylene (PTFE) ball by 1.5 ratio
In grinding jar, slurry is obtained after 12 hours with the rotating speed ball milling of 300rad/min in planetary ball mill.Slurry is in air dry oven
In after 70 DEG C of dry 12h, in 600 DEG C of calcination 2h, obtain powder.
The powder in corundum crucible is ground, crosses 200 mesh sieve, the then dry-pressing in the steel die of diameter 25mm
After molding, isostatic cool pressing processing is carried out under 200MPa, obtains biscuit.
By the biscuit in oxygen atmosphere, 1300 DEG C are warming up to 5 DEG C/min rates, keeps the temperature 2h, then with 5 DEG C/min speed
Rate is warming up to 1600 DEG C, keeps the temperature 2h, after furnace cooling, obtains prefabricated ceramics.
By prefabricated ceramics in the H that volume fraction is 5%2With the N that volume fraction is 95%2Mixing reducing atmosphere under,
1200 DEG C are annealed 2 hours, obtain fluorescence ceramics.
Embodiment 2
The chemical general formula of the fluorescence ceramics is (Y0.5Gd0.5)2.99Ce0.01(Ga0.6Sc0.4)5O12, i.e. x=0, y=0.01, z
=0.4, m=3, A are Y and Gd, C Ce, D Ga, E Sc.
The preparation method of the fluorescence ceramics is as follows：
With commercially available high-purity Y2O3、Gd2O3、Ce2(CO3)3、Ga2O3、Sc2O3For starting material, respectively aoxidized by above formula precise
Object or carbonic acid salt quality.By the reaction raw materials weighed using 5mm polytetrafluoroethylene (PTFE) ball as abrading-ball, using absolute ethyl alcohol as ball-milling medium,
Ball in mass ratio：Material：Medium=7：1：The reaction raw materials weighed, abrading-ball and medium are put into polytetrafluoroethylene (PTFE) ball by 1.5 ratio
In grinding jar, slurry is obtained after 12 hours with the rotating speed ball milling of 300rad/min in planetary ball mill.Slurry is in air dry oven
In after 70 DEG C of dry 12h, in 900 DEG C of calcination 2h, obtain powder.
The powder in corundum crucible is ground, crosses 200 mesh sieve, the then dry-pressing in the steel die of diameter 25mm
After molding, isostatic cool pressing processing is carried out under 200MPa, obtains biscuit.
By the biscuit in oxygen atmosphere, 1400 DEG C are warming up to 5 DEG C/min rates, keeps the temperature 2h, then with 5 DEG C/min speed
Rate is warming up to 1650 DEG C, keeps the temperature 2h, after furnace cooling, obtains prefabricated ceramics.
By prefabricated ceramics in the H that volume fraction is 5%2With the N that volume fraction is 95%2Mixing reducing atmosphere under,
1400 DEG C are annealed 2 hours, obtain fluorescence ceramics.
Embodiment 3
The chemical general formula of the fluorescence ceramics is (Lu0.5Gd0.5)2.99Ce0.01(Ga0.4Al0.6)5O12, i.e. x=0, y=0.01, z
=0.6, m=3, A are Lu and Gd, C Ce, D Ga, E Al.
The preparation method of the fluorescence ceramics is as follows：
With commercially available high-purity Lu2O3、Gd2O3、Ce2(CO3)3、Ga2O3、Al2O3For starting material, by each oxygen of above formula precise
Compound or carbonic acid salt quality.By the reaction raw materials weighed using 5mm polytetrafluoroethylene (PTFE) ball as abrading-ball, it is situated between by ball milling of absolute ethyl alcohol
Matter, in mass ratio ball：Material：Medium=7：1：The reaction raw materials weighed, abrading-ball and medium are put into polytetrafluoroethyl-ne by 1.5 ratio
In alkene ball grinder, slurry is obtained after 12 hours with the rotating speed ball milling of 300rad/min in planetary ball mill.Slurry is done in air blast
In dry case after 70 DEG C of dry 12h, in 900 DEG C of calcination 2h, powder is obtained.
The powder in corundum crucible is ground, crosses 200 mesh sieve, the then dry-pressing in the steel die of diameter 25mm
After molding, isostatic cool pressing processing is carried out under 200MPa, obtains biscuit.
By the biscuit in oxygen atmosphere, 1400 DEG C are warming up to 5 DEG C/min rates, keeps the temperature 2h, then with 5 DEG C/min speed
Rate is warming up to 1800 DEG C, keeps the temperature 2h, after furnace cooling, obtains prefabricated ceramics.
By prefabricated ceramics in the H that volume fraction is 5%2With the N that volume fraction is 95%2Mixing reducing atmosphere under,
1600 DEG C are annealed 6 hours, obtain fluorescence ceramics.
Embodiment 4
The chemical general formula of the fluorescence ceramics is (Lu0.5Gd0.5)2.49Ce0.01Ga5.5O12, i.e. x=0, y=0.01, z=0, m
=2.5, A are Lu and Gd, C Ce, D Ga.
The preparation method of the fluorescence ceramics is as follows：
With commercially available high-purity Lu2O3、Gd2O3、Ce2(CO3)3、Ga2O3For starting material, by each oxide of above formula precise or
Carbonic acid salt quality.By the reaction raw materials weighed using 5mm polytetrafluoroethylene (PTFE) ball as abrading-ball, using absolute ethyl alcohol as ball-milling medium, by matter
Amount compares ball：Material：Medium=7：1：The reaction raw materials weighed, abrading-ball and medium are put into polytetrafluoroethylene (PTFE) ball grinder by 1.5 ratio
In, slurry is obtained after 12 hours with the rotating speed ball milling of 300rad/min in planetary ball mill.Slurry is 70 in air dry oven
After DEG C dry 12h, in 900 DEG C of calcination 2h, powder is obtained.
The powder in corundum crucible is ground, crosses 200 mesh sieve, the then dry-pressing in the steel die of diameter 25mm
After molding, isostatic cool pressing processing is carried out under 200MPa, obtains biscuit.
By the biscuit in oxygen atmosphere, 1400 DEG C are warming up to 5 DEG C/min rates, keeps the temperature 2h, then with 5 DEG C/min speed
Rate is warming up to 1600 DEG C, keeps the temperature 2h, after furnace cooling, obtains prefabricated ceramics.
By prefabricated ceramics in the H that volume fraction is 5%2With the N that volume fraction is 95%2Mixing reducing atmosphere under,
1000 DEG C are annealed 10 hours, obtain fluorescence ceramics.
Embodiment 5
The chemical general formula of the fluorescence ceramics is [(Y0.5Gd0.5)0.8La0.2]3.3(Ce0.5Mn0.5)0.2(Ga0.2Al0.8)4.5O12,
That is x=0.2, y=0.2, z=0.8, m=3.5, A are Ce and Mn, D Ga, E Al for Y and Gd, B La, C.
The preparation method of the fluorescence ceramics is as follows：
With commercially available high-purity Y2O3、Gd2O3、La2O3、Ce2(CO3)3、MnCO3、Ga2O3、Al2O3It is accurate by above formula for starting material
Really weigh each oxide or carbonic acid salt quality.By the reaction raw materials weighed using 5mm polytetrafluoroethylene (PTFE) ball as abrading-ball, with absolute ethyl alcohol
For ball-milling medium, in mass ratio ball：Material：Medium=7：1：The reaction raw materials weighed, abrading-ball and medium are put by 1.5 ratio
In polytetrafluoroethylene (PTFE) ball grinder, slurry is obtained after 12 hours with the rotating speed ball milling of 300rad/min in planetary ball mill.Slurry
In air dry oven after 70 DEG C of dry 12h, in 900 DEG C of calcination 2h, powder is obtained.
The powder in corundum crucible is ground, crosses 200 mesh sieve, the then dry-pressing in the steel die of diameter 25mm
After molding, isostatic cool pressing processing is carried out under 200MPa, obtains biscuit.
By the biscuit in oxygen atmosphere, 1450 DEG C are warming up to 5 DEG C/min rates, keeps the temperature 2h, then with 5 DEG C/min speed
Rate is warming up to 1700 DEG C, keeps the temperature 2h, after furnace cooling, obtains prefabricated ceramics.
By prefabricated ceramics in the H that volume fraction is 5%2With the N that volume fraction is 95%2Mixing reducing atmosphere under,
1600 DEG C are annealed 2 hours, obtain fluorescence ceramics.
The thickness for the fluorescence ceramics that embodiment 1 to 3 obtains is 1.5mm.The fluorescence ceramics that embodiment 1 to 3 is obtained carry out
Material object is taken pictures, and picture is shown in Fig. 1.
The fluorescence ceramics that embodiment 1 to 3 is obtained carry out light transmittance and luminescent properties test.As a result see Fig. 2 to Fig. 6.
By Fig. 1 and Fig. 2 as it can be seen that the fluorescence ceramics uniformity, has very high light transmission features.Under 1.5mm thickness,
The straight line transmittance of fluorescence ceramics is up to 72%.
As seen from Figure 3, the wavelength of fixed transmission light is 570nm, and the fluorescence ceramics in embodiment 1 to 3 are respectively provided with broad
Excitation band.Wherein best excites scope covers the blue region of 420nm~480nm, this transmitting with commercial blue-light LED chip
Spectrum is well matched with together.Therefore, fluorescence ceramics of the present invention can be combined with commercial blue-light LED chip, to
Prepare white light LEDs.
From fig. 4, it can be seen that in wavelength under the excitation of 460nm blue lights, the fluorescence ceramics in embodiment 1 to 3 are respectively provided with broad
Transmitting band.Emission spectrum covers the wave-length coverage of 480nm~750nm, and the highest peak of emission spectrum is located near 570nm, and
And emission spectrum peak shape has larger halfwidth, up to 130nm, covers the visible light wave range from green light to feux rouges.
Comparison diagram 4 and Fig. 5 it is found that the emission spectrum and twilight sunset spectrum shape of the fluorescence ceramics of embodiment 2 remain unchanged, because
This, though during AC LED stroboscopic without blue light excitation light source in the case of, the emission spectrum of fluorescence ceramics is still kept not
Become.
With reference to 5 and Fig. 6 it is found that the fluorescence ceramics of embodiment 2 then have very high afterglow intensity and very long persistence.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of fluorescence ceramics applied to LED, which is characterized in that the chemical general formula of the fluorescence ceramics is (A1-xBx)m-yCy
(D1-zEz)8-mO12, wherein,
A is at least one of Y, Gd, Tb, Lu；
B is at least one of La, Yb；
C is at least one of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm, Ti, Cr, Mn；
D is Ga；
E is at least one of B, Al, In, Sc；
Wherein, x, y, z, the molar fraction of m expression corresponding elements, and 0≤x≤0.2,0.0001≤y≤0.2,0≤z≤0.8,
2.5≤m≤3.5。
2. the fluorescence ceramics according to claim 1 applied to LED, which is characterized in that x, y, z, the value range of m are：0
≤ x≤0.2,0.01≤y≤0.15,0≤z≤0.6,2.5≤m≤3.5.
3. the fluorescence ceramics according to claim 1 applied to LED, which is characterized in that the fluorescence ceramics are by wavelength
420nm~480nm blue lights excite.
4. the fluorescence ceramics according to claim 1 applied to LED, which is characterized in that the light transmittance of the fluorescence ceramics
It is 40%~80%.
It is 5. a kind of such as preparation method of the Claims 1 to 4 any one of them applied to the fluorescence ceramics of LED, which is characterized in that
It includes the following steps：
(1) raw material is provided and carries out ball milling, drying, calcination successively, obtains powder；
(2) powder is ground successively, the processing of molding and isostatic cool pressing, obtains biscuit；
(3) in oxygen atmosphere, the biscuit is sintered to obtain prefabricated ceramics；
(4) in a reducing atmosphere, it anneals to the prefabricated ceramics, obtains fluorescence ceramics.
6. the preparation method of the fluorescence ceramics according to claim 5 applied to LED, which is characterized in that institute in step (1)
Raw material is stated as oxide, fluoride, chloride, carbonate, borate, oxalates or vinegar containing corresponding A, B, C, D and E element
Hydrochlorate.
7. the preparation method of the fluorescence ceramics according to claim 5 applied to LED, which is characterized in that in step (1)
During ball milling, ball grinder and abrading-ball are polytetrafluoroethylproducts products, and abrading-ball size 5mm~10mm, ball-milling medium is water, second
At least one of alcohol, acetone, glycerine, rotational speed of ball-mill be 100rad/min~300rad/min, Ball-milling Time for 5 hours with
On.
8. the preparation method of the fluorescence ceramics according to claim 5 applied to LED, which is characterized in that burn in step (1)
The temperature of burning is 600 DEG C~900 DEG C, and the time of calcination is 2 hours~10 hours.
9. the preparation method of the fluorescence ceramics according to claim 5 applied to LED, which is characterized in that burnt in step (2)
The temperature of knot is 1500 DEG C~1800 DEG C, and the time of sintering is 2 hours or more.
10. the preparation method of the fluorescence ceramics according to claim 5 applied to LED, which is characterized in that in step (3)
The reducing atmosphere is hydrogen atmosphere, ammonia atmosphere, carbon monoxide atmosphere or nitrogen and hydrogen mixture atmosphere, and the temperature of annealing is 1000
DEG C~1600 DEG C, the time of annealing is 2 hours~10 hours.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437900A (en) * | 2018-12-12 | 2019-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of fluorescence ceramics block, preparation method and its application in laser lighting |
| CN109592978A (en) * | 2018-12-03 | 2019-04-09 | 江苏师范大学 | High-capacity LED/LD illumination refers to fluorescence ceramics and the preparation method and application thereof with warm white height is aobvious |
| CN111116207A (en) * | 2019-12-19 | 2020-05-08 | 徐州凹凸光电科技有限公司 | Oxynitride fluorescent ceramic material with long-wave-band emission and high color rendering index and preparation method thereof |
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| CN115650725A (en) * | 2022-10-12 | 2023-01-31 | 中国科学院上海光学精密机械研究所 | Fluorescent ceramic material with multiband fluorescent emission and preparation method thereof |
| CN115677349A (en) * | 2022-10-12 | 2023-02-03 | 中国科学院上海光学精密机械研究所 | Fluorescent ceramic material with broad-spectrum red light emission and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601484A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院宁波材料技术与工程研究所 | Preparation method for lutetium-aluminum garnet-based transparent ceramic |
-
2016
- 2016-12-30 CN CN201611253876.2A patent/CN108264899A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601484A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院宁波材料技术与工程研究所 | Preparation method for lutetium-aluminum garnet-based transparent ceramic |
Non-Patent Citations (5)
| Title |
|---|
| JIAN XU等: "Design of deep-red persistent phosphors of Gd3Al5-xGaxO12:Cr3+ transparent ceramics sensitized by Eu3+ as an electron trap using conduction band engineering", 《OPTICAL MATERIALS EXPRESS》 * |
| JUMPEI UEDA等: "Bright persistent ceramic phosphors of Ce3+-Cr3+-codoped garnet able to store by blue light", 《APPLIED PHYSICS LETTERS》 * |
| YI LUO等: "Effect of Al/Ga Substitution on Photoluminescence and Phosphorescence Properties of Garnet-Type Y3Sc2Ga3−xAlxO12:Ce3+ Phosphor", 《J. PHYS. CHEM. C》 * |
| ZHAO-HUA LUO等: "Effect of Yb3+ on the Crystal Structural Modification and", 《INORGANIC CHEMISTRY》 * |
| 潘裕柏等: "《稀土陶瓷材料》", 31 May 2016 * |
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