CN115650725B - Fluorescent ceramic material with multiband fluorescence emission and preparation method thereof - Google Patents
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 235000015895 biscuits Nutrition 0.000 claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910020203 CeO Inorganic materials 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 230000002457 bidirectional effect Effects 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002223 garnet Substances 0.000 description 7
- 238000009877 rendering Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BEZBEMZKLAZARX-UHFFFAOYSA-N alumane;gadolinium Chemical compound [AlH3].[Gd] BEZBEMZKLAZARX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a fluorescent ceramic material with multiband emission, which is characterized in that the chemical general formula is (Gd 1‑ x Ce x ) 3 (Al 0.5‑y Ga 0.5 Mn y ) 2 Al 3 O 12 Wherein x is more than or equal to 0.002 and less than or equal to 0.005, and y is more than or equal to 0.001 and less than or equal to 0.004. Gd is weighed according to the stoichiometric ratio 2 O 3 ，Al 2 O 3 ，Ga 2 O 3 ，CeO 2 And MnCO 3 Raw material powder and solvent; ball milling, drying and sieving to obtain mixed powder, and then carrying out dry pressing and cold isostatic pressing to obtain a biscuit; finally, the (Gd) is obtained after high-temperature oxygen sintering and double-sided polishing 1‑x Ce x ) 3 (Al 0.5‑ y Ga 0.5 Mn y ) 2 Al 3 O 12 Fluorescent ceramics.
Description
Technical Field
The invention belongs to the field of inorganic luminescent materials, relates to a fluorescent ceramic material, and in particular relates to a fluorescent ceramic material with multiband emission and a preparation method thereof.
Background
The white light LED is used as a fourth-generation illumination light source, has the remarkable advantages of low energy consumption, high efficiency, long service life, no pollution and the like, is currently the most widely realized, and the most mature technical scheme is to package yellow-green luminous YAG-Ce fluorescent powder with a blue light chip through resin, silica gel and other organic matters, and form a white light effect through mixing blue light with fluorescence. However, the thermal conductivity of the organic encapsulating material is only 0.1 to 0.5Wm -1 K -1 Resulting in a large amount of the whole fluorescence conversion moduleHeat build-up causes a series of problems such as reduced efficiency, color temperature drift, etc. The fluorescent ceramic material has the remarkable advantages of high heat conductivity, strong thermal shock resistance and the like. Therefore, the fully inorganic fluorescent ceramic scheme based on remote excitation can effectively replace the traditional technical scheme of Ce: YAG fluorescent powder and resin.
However, the above-described scheme has mainly the following problems: the emission spectrum of the Ce:YAG fluorescent ceramic still faces the problems of low color rendering index, poor light color quality and the like caused by the lack of red light components in the spectrum. At present rare earth ion Eu 2+ Doped CaAlSiN 3 :Eu 2+ The red fluorescent material is limited by complex preparation process and low preparation efficiency; 2. in the production process of the fluorescent ceramics of the oxide garnet system, a vacuum sintering method is often adopted, and the cost and the energy consumption of the method are relatively high, so that the commercial application of the fluorescent ceramics is limited. In order to solve the above problems, it is needed to find a fluorescent ceramic material which has a wider emission peak in the red light region and is simple in preparation method.
The transition metal Mn ion has the advantages of good spectral performance, easily available raw materials and easy synthesis. Mn ions mainly have trivalent valence and tetravalent valence, emission peaks of the Mn ions are respectively positioned in orange red light and red light areas, and the Mn ions have strong application potential in improving the light color quality. Typically in garnet structures, mn ions exhibit different valence states depending on the radius of the polyhedral center they occupy in the crystal field. Although researchers have prepared Mn ion doped gadolinium aluminum gallium garnet phosphors, mn 2+ The luminescence of the material belongs to spin forbidden transition, and is difficult to be effectively excited by blue light, so that the quantum efficiency of the material is low. In addition, the phosphor needs to be mixed with an organic resin during the packaging process of the whole light source, so that the phosphor is difficult to meet the requirement of the use under the excitation of high-power density blue light. Due to Ce 3+ Has stronger absorption at 460nm, and researchers prepare Ce by oxygen sintering 3+ And Mn of 2+ Co-doped garnet fluorescent ceramics utilizing Ce 3+ To Mn of 2+ Energy transfer enhanced Mn of (2) 2+ Is a red light emission of (c). The method is to obtain Mn 2+ Ions, need to be added with fourCharge compensators of valence, e.g. SiO 2 So that Mn ions are completely converted into bivalent Mn ions which are ignored 4+ The light emission in the red light area limits the improvement of the light color quality.
Disclosure of Invention
One of the purposes of the present invention is to provide a fluorescent ceramic material with multiband fluorescence emission, comprising Ce with a dominant wavelength of 520-550nm 3+ Mn with dominant wavelength of 580-630nm 2+ Orange fluorescence of (C) and Mn having a dominant wavelength of 670-710nm 4+ Red fluorescence of (2).
The second purpose of the invention is to provide the preparation method of the fluorescent ceramic material with multiband fluorescence emission, which can effectively reduce energy consumption and realize industrialized production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a fluorescent ceramic material with multiband fluorescence emission has a chemical general formula of (Gd 1-x Ce x ) 3 (Al 0.5- y Ga 0.5 Mn y ) 2 Al 3 O 12 Wherein x is more than or equal to 0.002 and less than or equal to 0.005, y is more than or equal to 0.001 and less than or equal to 0.004,1<x/y≤2。
In the solid-phase sintering process, ce is adopted in the fluorescence ceramic material with multiband fluorescence emission 3+ Occupying the central position of the dodecahedron position, mn 2+ And Mn of 4+ Occupying the central position of the octahedral site. The fluorescent ceramic emits Ce with the dominant wavelength of 520-550nm under the excitation of 440-460nm blue light 3+ Mn with dominant wavelength of 580-630nm 2+ Orange fluorescence of (C) and Mn having a dominant wavelength of 670-710nm 4+ Red fluorescence of (2).
Preferably, x is less than 0.0025 and less than 0.0035,0.0015 and y is less than 0.0025.
The invention also provides a preparation method of the fluorescent ceramic material with wide spectrum red light emission, which comprises the following steps:
step 1, according to the stoichiometric ratio (Gd 1-x Ce x ) 3 (Al 0.5-y Ga 0.5 Mn y ) 2 Al 3 O 12 Wherein x is more than or equal to 0.002 and less than or equal to 0.005, y is more than or equal to 0.001 and less than or equal to 0.004, and Gd is weighed 2 O 3 ，Al 2 O 3 ，Ga 2 O 3 ，CeO 2 ，MnCO 3 Raw material powder, and adding alcohol as a solvent;
step 2, placing the raw material powder weighed in the step 1 into a ball milling tank, and simultaneously adding grinding balls for planetary ball milling, wherein the ball milling speed is 150-250r/min, and the ball milling time is 18-24h;
step 3, drying the slurry subjected to ball milling in the step 2 at 50-80 ℃ for 6-24 hours, crushing the dried slurry, and sieving with a 100-200 mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional compression molding on the mixed powder in the step 3, wherein the pressure is 3-6MPa, then carrying out cold isostatic pressing molding, the pressure is 200-300MPa, and the pressure maintaining time is 200-300s, so as to obtain a ceramic biscuit;
step 5, sintering the ceramic biscuit with high temperature oxygen without annealing, and then performing double-sided polishing treatment to obtain (Gd) 1-x Ce x ) 3 (Al 0.5-y Ga 0.5 Mn y ) 2 Al 3 O 12 Fluorescent ceramics.
Preferably, the oxygen sintering temperature in the step 5 is 1550-1680 ℃, the temperature is kept for 5-24 hours, and the flow rate of oxygen is 0.5-2 ml/min.
Compared with the prior art, the invention has the following beneficial effects:
1. the fluorescent ceramic material with multiband fluorescence emission provided by the invention is prepared from Gd 3 (Al,Ga) 3 O 12 Mn ions of transition group metal ions at the central lattice position of octahedron in solid solution lattice, and Ga is utilized without introducing charge compensation agent 3+ With Mn 2+ Al and 3+ and Mn of 4+ Ion radius matching effect between Gd 3 (Al,Ga) 3 O 12 Mn is realized in the solid solution matrix 2+ And Mn of 4+ Is controlled by the control program.
2. The fluorescent ceramic material with multiband fluorescence emission provided by the invention is prepared from Gd 3 (Al,Ga) 3 O 12 Ce is introduced into the dodecahedron central lattice site in the solid solution lattice 3+ The energy transfer among Ce-Mn ions is utilized to improve the luminous efficiency of Mn ions, and meanwhile, the multiband luminescence of yellow-green light, orange-red light and red light is realized.
3. The fluorescent ceramic with multiband fluorescence emission is prepared by sintering in flowing oxygen atmosphere, and the valence state of Mn is convenient to control by controlling the sintering temperature and the oxygen flow rate, so that the fluorescent ceramic has better thermal stability and physicochemical property compared with a fluorescent powder material, and has the advantages of simple preparation process, lower energy consumption and the like.
Drawings
FIG. 1 is an XRD pattern of a fluorescent ceramic material with multiband fluorescence emission prepared in examples 1 to 3 of the present invention;
FIG. 2 is an SEM image of a fluorescent ceramic material with multi-band fluorescence emission prepared in example 1 of the present invention;
FIG. 3 is a graph showing photoluminescence quantum efficiency (PLQE) of the fluorescent ceramic materials with multiband fluorescence emission prepared in examples 1 to 3 according to the present invention under excitation at different 460nm blue light power densities;
FIG. 4 is an electroluminescent spectrum diagram of the fluorescent ceramic material with multi-band fluorescence emission prepared in example 2 according to the present invention under 460nm blue excitation.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
The raw material powder formulation for preparing 60g of the target product is respectively weighed in Table 1. The measurement modes involved in the following examples are all conventional in the art, and the materials are all commercial products, and are not described herein.
Table 1 example dosage form
Example 1
A fluorescent ceramic material with multiband fluorescent light emission has a chemical formula of (Gd 0.998 Ce 0.002 ) 3 (Al 0.499 Ga 0.5 Mn 0.001 ) 2 Al 3 O 12
The preparation method of the fluorescent ceramic material comprises the following steps:
step 1, gd is weighed according to the mass ratio and the stoichiometric ratio shown in 1# in Table 1 2 O 3 ，Al 2 O 3 ，CeO 2 ，MnCO 3 Ga 2 O 3 Raw material powder and alcohol as solvent;
step 2, placing the raw material powder weighed in the step 1 into a ball milling tank, and simultaneously adding grinding balls for planetary ball milling, wherein the ball milling speed is 150r/min, and the ball milling time is 18h;
step 3, drying the slurry subjected to ball milling in the step 2 at 50 ℃ for 6 hours, crushing the dried slurry, and sieving with a 100-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional compression molding on the mixed powder in the step 3, wherein the pressure is 3MPa, then carrying out cold isostatic pressing molding, the pressure is 200MPa, and the pressure maintaining time is 200s, so as to obtain a ceramic biscuit;
and 5, performing oxygen sintering on the ceramic biscuit obtained in the step 4, wherein the sintering temperature is 1550 ℃, the temperature is kept for 5 hours, and the flow rate of oxygen is 0.5ml/min. Then annealing is not needed, and finally double-sided polishing treatment is carried out, thus obtaining (Gd 0.998 Ce 0.002 ) 3 (Al 0.499 Ga 0.5 Mn 0.001 ) 2 Al 3 O 12 Fluorescent ceramics.
The XRD pattern of the sample prepared in this example, as shown in FIG. 1, shows that the prepared (Gd 0.997 Ce 0.003 ) 3 (Al 0.499y Ga 0.5 Mn 0.002 ) 2 Al 3 O 12 X-ray diffraction peak of fluorescent ceramic and Gd 3 Al 5 O 12 The standard card of (JCPLDS (# 73-1371)) is identical, and is garnet phase.
See FIG. 2, the (Gd) 0.998 Ce 0.002 ) 3 (Al 0.499 Ga 0.5 Mn 0.001 ) 2 Al 3 O 12 The breaking mode of the fluorescent ceramic belongs to through-crystal breaking, which shows that the prepared fluorescent ceramic has better mechanical property, uniform grain size distribution and compactness.
See FIG. 3, the (Gd) 0.998 Ce 0.002 ) 3 (Al 0.499y Ga 0.5 Mn 0.001 ) 2 Al 3 O 12 Fluorescent ceramic at 8.4mW/cm 2 PLQE at blue light power density of 70.9%, which is significantly higher than that of Mn ion singly doped fluorescent materials.
Prepared in this example (Gd 0.998 Ce 0.002 ) 3 (Al 0.499y Ga 0.5 Mn 0.001 ) 2 Al 3 O 12 After the fluorescent ceramic and the 20W blue light COB chip are packaged, ce is simultaneously presented in an electroluminescent spectrum through an integrating sphere test 3+ ，Mn 2+ Mn and 4+ is characterized by an emission peak having a color rendering index of 85 and a color temperature of 5500K.
Example 2
A fluorescent ceramic material with broad spectrum red light emission has a chemical formula of (Gd 0.997 Ce 0.003 ) 3 (Al 0.498 Ga 0.5 Mn 0.002 ) 2 Al 3 O 12
The preparation method of the fluorescent ceramic material with multiband fluorescence emission comprises the following steps:
step 1, gd is weighed according to the mass ratio and the stoichiometric ratio shown in the 2# in the table 1 2 O 3 ，Al 2 O 3 ，CeO 2 ，MnCO 3 Ga 2 O 3 Raw material powder and alcohol as solvent;
step 2, placing the raw material powder weighed in the step 1 into a ball milling tank, and simultaneously adding grinding balls for planetary ball milling, wherein the ball milling speed is 200r/min, and the ball milling time is 20h;
step 3, drying the slurry subjected to ball milling in the step 2 at a drying temperature of 60 ℃ for 18 hours, crushing the dried slurry, and sieving with a 150-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional compression molding on the mixed powder in the step 3, wherein the pressure is 5MPa, then carrying out cold isostatic pressing molding, the pressure is 250MPa, and the pressure maintaining time is 250s, so as to obtain a ceramic biscuit;
step 5, performing oxygen sintering on the ceramic biscuit obtained in the step 4, wherein the sintering temperature is 1640 ℃, the temperature is kept for 10 hours, the flow rate of oxygen is 1.0ml/min, then annealing is not needed, and finally double-sided polishing treatment is performed, thus obtaining the (Gd) 0.997 Ce 0.003 ) 3 (Al 0.498 Ga 0.5 Mn 0.002 ) 2 Al 3 O 12 Fluorescent ceramics.
The XRD pattern of the sample prepared in this example, as shown in FIG. 1, shows that the prepared (Gd 0.997 Ce 0.003 ) 3 (Al 0.498 Ga 0.5 Mn 0.002 ) 2 Al 3 O 12 X-ray diffraction peak of fluorescent ceramic and Gd 3 Al 5 O 12 The standard card of (JCPLDS (# 73-1371)) is identical, and is garnet phase.
See FIG. 3, the (Gd) 0.997 Ce 0.003 ) 3 (Al 0.498 Ga 0.5 Mn 0.002 ) 2 Al 3 O 12 The fluorescent ceramic material is 8.4mW/cm 2 PLQE at blue optical power density of 74.6%.
See FIG. 4, the preparation of the present example ((Gd) 0.997 Ce 0.003 ) 3 (Al 0.498 Ga 0.5 Mn 0.002 ) 2 Al 3 O 12 After the fluorescent ceramic is packaged with a 20W blue light COB chip, the color rendering index is 93 and the color temperature is 5200K through integrating sphere test.
Example 3
A fluorescent ceramic material with multiband fluorescence emission has a chemical general formula of (Gd 0.995 Ce 0.005 ) 3 (Al 0.496 Ga 0.5 Mn 0.004 ) 2 Al 3 O 12 The preparation method of the fluorescent ceramic material with wide spectrum red light emission comprises the following steps:
step 1, gd is weighed according to the mass ratio and the stoichiometric ratio shown in 3# in Table 1 2 O 3 ，Al 2 O 3 ，CeO 2 ，MnCO 3 Ga 2 O 3 Raw material powder and alcohol as solvent;
step 2, placing the powder raw materials weighed in the step 1 into a ball milling tank, and simultaneously adding grinding balls for planetary ball milling, wherein the ball milling speed is 250r/min, and the ball milling time is 24 hours;
step 3, drying the slurry subjected to ball milling in the step 2 at 80 ℃ for 24 hours, crushing the dried slurry, and sieving with a 200-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional compression molding on the mixed powder in the step 3, wherein the pressure is 6MPa, then carrying out cold isostatic pressing molding, the pressure is 300MPa, and the pressure maintaining time is 300s, so as to obtain a ceramic biscuit;
step 5, sintering the ceramic biscuit obtained in the step 4 by oxygen at 1680 ℃ for 24 hours at an oxygen flow rate of 2ml/min, then carrying out double-sided polishing treatment without annealing, and obtaining (Gd) 0.995 Ce 0.002 ) 3 (Al 0.496 Ga 0.5 Mn 0.004 ) 2 Al 3 O 12 Fluorescent ceramics.
The XRD pattern of the sample prepared in this example, as shown in FIG. 1, shows that the prepared (Gd 0.995 Ce 0.002 ) 3 (Al 0.496 Ga 0.5 Mn 0.004 ) 2 Al 3 O 12 X-ray diffraction peak of fluorescent ceramic and Gd 3 Al 5 O 12 The standard card of (JCPLDS (# 73-1371)) is identical, and is garnet phase.
See FIG. 3, the (Gd) 0.995 Ce 0.005 ) 3 (Al 0.496 Ga 0.5 Mn 0.004 ) 2 Al 3 O 12 Fluorescent ceramic at 8.4mW/cm 2 PLQE at blue optical power density of 53.4%.
Prepared in this example (Gd 0.995 Ce 0.005 ) 3 (Al 0.496 Ga 0.5 Mn 0.004 ) 2 Al 3 O 12 After the fluorescent ceramic and the 20W blue light COB chip are packaged, the color rendering index is 89 and the color temperature is 5900K through integrating sphere test.
The color temperature, color rendering index, and the like in the examples were measured by an ATA 1000 type integrating sphere spectrometer system produced by remote photovoltaics in hangzhou.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed in the present invention fall within the protection scope of the present invention.
Claims (4)
1. A preparation method of a fluorescent ceramic material with multiband fluorescence emission, wherein the chemical general formula of the fluorescent ceramic material is (Gd 1-x Ce x ) 3 (Al 0.5-y Ga 0.5 Mn y ) 2 Al 3 O 12 Wherein x is more than or equal to 0.002 and less than or equal to 0.005, y is more than or equal to 0.001 and less than or equal to 0.004,1<x/y is less than or equal to 2, and is characterized in that,
step 1, weighing Gd according to a chemical formula 2 O 3 ，Al 2 O 3 ，Ga 2 O 3 ，CeO 2 MnCO 3 Raw material powder, and adding alcohol as a solvent;
step 2, placing the raw material powder weighed in the step 1 into a ball milling tank, and simultaneously adding grinding balls for planetary ball milling, wherein the ball milling speed is 150-250r/min, and the ball milling time is 18-24h;
step 3, drying the slurry subjected to ball milling in the step 2 at 50-80 ℃ for 6-24 hours, crushing the dried slurry, and sieving with a 100-200 mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional compression molding on the mixed powder in the step 3, wherein the pressure is 3-6MPa, then carrying out cold isostatic pressing molding, the pressure is 200-300MPa, and the pressure maintaining time is 200-300s, so as to obtain a ceramic biscuit;
step 5, sintering the ceramic biscuit with high temperature oxygen without annealing, and then performing double-sided polishing treatment to obtain (Gd) 1- x Ce x ) 3 (Al 0.5-y Ga 0.5 Mn y ) 2 Al 3 O 12 Fluorescent ceramics.
2. The method for preparing a fluorescent ceramic material with multi-band fluorescent emission according to claim 1, wherein the oxygen sintering temperature in the step 5 is 1550-1680 ℃, the temperature is kept for 5-24 hours, and the flow rate of oxygen is 0.5-2.0ml/min.
3. The method for preparing a fluorescent ceramic material with multiband fluorescence emission according to claim 1, wherein the fluorescent ceramic emits Ce with dominant wavelength of 520-550nm under excitation of blue light of 440-460nm 3+ Mn with dominant wavelength of 580-630nm 2+ Orange fluorescence of (C) and Mn having a dominant wavelength of 670-710nm 4+ Red fluorescence of (2).
4. The method for preparing a fluorescent ceramic material with multiband fluorescence emission according to claim 1, wherein Ce during solid phase sintering 3+ Occupying the central position of the dodecahedron position, mn 2+ And Mn of 4+ Occupying the central position of the octahedral site.
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