CN112209710A - Method for preparing Ce: YAG fluorescent ceramic by laser sintering - Google Patents

Method for preparing Ce: YAG fluorescent ceramic by laser sintering Download PDF

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CN112209710A
CN112209710A CN202011113147.3A CN202011113147A CN112209710A CN 112209710 A CN112209710 A CN 112209710A CN 202011113147 A CN202011113147 A CN 202011113147A CN 112209710 A CN112209710 A CN 112209710A
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yag fluorescent
fluorescent ceramic
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张乐
孙炳恒
马跃龙
王蕊
邵岑
康健
周天元
蔡宏兵
李延彬
陈浩
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Jiangsu Normal University
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Abstract

The invention discloses a method for preparing Ce: YAG fluorescent ceramic by laser sintering. Firstly according to the chemical structural formula (Ce)xY1‑x)3Al5O12The stoichiometric ratio of each element in the raw material is measured, x is the atomic percentage of Ce doped into Y lattice position, and is 0.01<x<0.1; mixing the reaction raw materials with ethanol and then carrying out ball milling; drying, cooling, mixing with plasticizer: mixing and grinding polyvinyl alcohol solution to obtain precursor powder; drying the precursor powder at high temperature; pressing into sheet biscuit by dry pressing method; and then placing the sample on a YAG ceramic gasket, sintering two sides of the biscuit by using a laser to obtain a Ce: YAG fluorescent ceramic sample, and polishing one side of the Ce: YAG fluorescent ceramic sample without annealing to obtain the Ce: YAG fluorescent ceramic. The method effectively inhibits luminescent ion Ce3+The light effect is improved by the oxidation; the sintering time is shortened, the production cost is reduced, and energy conservation and emission reduction are realized.

Description

Method for preparing Ce: YAG fluorescent ceramic by laser sintering
Technical Field
The invention belongs to the technical field of preparation of inorganic luminescent materials, and relates to a method for preparing Ce by laser sintering: YAG fluorescent ceramic.
Background
White light emitting diode (white light emitting diode) is used as a fourth generation illumination light source, and has the remarkable advantages of energy conservation, environmental protection, long service life, small size and the like. The most traditional and most efficient realization mode of the current white light LED is blue light InGaN chip combined with rare earth ion cerium-doped yttrium aluminum garnet (Ce: Y)3Al5O12) Yellow phosphor, which emits white light after being encapsulated by organic substances such as epoxy resin, silica gel and the like (US Pat. 5998929, 6069440, 7071616). However, as the excitation power of the blue light chip is continuously increased, especially under the excitation of the blue light LD with higher energy density, the defects of poor heat resistance, easy aging and the like of epoxy resin, silica gel and the like are revealed, which causes serious consequences such as reduced light efficiency, color temperature drift, shortened service life and the like.
The Ce: YAG fluorescent ceramic has the advantages of high thermal conductivity, good thermal shock resistance, small light decay and the like, and can effectively replace the traditional technical scheme of 'Ce: YAG fluorescent powder + organic resin' (S. Nishiura et al).Opt. Mater.,33: 688 (2011) and avoids the processes of glue dispensing and mixing. In the preparation process of fluorescent ceramic, vacuum sintering, hot-press sintering and hot isostatic pressing are generally adopted to ensure the compactness of the ceramic and the necessary optical propertiesThe sintering technology such as pressure sintering and the like is used for preserving the heat of the ceramic for a long time under the action of high-temperature thermal driving force, and atomic diffusion is used for discharging pores among crystal grains so as to densify the ceramic. However, the above method requires higher sintering temperature and longer holding time, which leads to general increase of ceramic grain size and poor mechanical properties. In addition, the heat preservation time of several hours or even several days is a huge consumption for energy sources, and is not beneficial to industrial production. In addition, a large number of oxygen vacancies are generated in the interior of the ceramic due to the oxygen partial pressure caused by the vacuum environment in the furnace chamber, and the oxygen vacancies need to be compensated for by long-term air annealing. However, in the air annealing for a long time, a large amount of Ce is contained3+Will be oxidized into Ce4+And Ce4+Non-luminescent, reduced luminescent ion Ce3+The luminescence property of the Ce: YAG is obviously reduced.
In addition, to suppress abnormal grain growth, a divalent sintering aid is usually introduced into the formulation, and Ce is present due to charge compensation effect3+Also want Ce4+And (4) transformation. In addition, the light efficiency of the Ce: YAG fluorescent ceramic is low due to the low utilization rate of blue light. Therefore, the current Ce: YAG fluorescent ceramic can not meet the market demand.
CN201710523795.8 discloses a ceramic material consisting of Y2O3、Al2O3、CeO2And M oxide; and M is selected from one or more of Si, Ge, Ga, Sc and V. The ceramic material provided by the invention can generate green light with the peak wavelength less than or equal to 525nm and the half width of the luminous peak less than or equal to 70nm under the excitation of blue laser, the transparency of the ceramic material can be adjusted through the porosity, and the ceramic material has good thermal conductivity and thermal stability, so that the ceramic material can be prepared into a fluorescent ceramic device, can replace fluorescent powder to be used for a projection system, effectively avoids the thermal decline of the luminous brightness when the fluorescent powder is adopted, enables the projection system to have good color performance, ultra-long service life and good stability, and improves the output brightness of the system to the maximum extent. However, the sintering method adopted by the method is vacuum sintering or oxygen sintering, and when the vacuum sintering is adopted, although the valence state of Ce can be stabilized in the vacuum state+3, but oxygen vacancy defect is inevitably introduced in the sintering process, and the nonradiative transition probability of electrons is increased, so that the luminescent performance of the ceramic material at high temperature is weakened; if oxygen annealing is used, the valence state of Ce is inevitably oxidized to +4, thereby reducing the light emitting efficiency. In addition, both the sintering modes require high-temperature sintering at over 1600 ℃, and the heat preservation time is longer than 10 hours, thereby causing huge energy consumption.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing Ce: YAG fluorescent ceramic by laser sintering, which can effectively inhibit luminescent ions Ce3+The blue light utilization rate is improved, and the light efficiency is improved; meanwhile, the time in the sintering process is reduced, the production cost is reduced, and energy conservation and emission reduction are realized.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a method for preparing Ce: YAG fluorescent ceramic by laser sintering comprises the following steps:
step 1, according to the chemical structural formula (Ce)xY1-x)3Al5O12The stoichiometric ratio of each element in the formula (I) is determined by weighing Y3+Compound of (2) and containing Al3+And containing Ce3+The compound powder of (1) is used as a reaction raw material, wherein x is the atomic percentage of Ce doped into the lattice position of Y, and is 0.01<x<0.1；
Step 2, adding Y3+Compound of (2) and containing Al3+Compound of (2) and containing Ce3+Mixing the compound (A) with an ethanol solvent, and then carrying out ball milling;
and 3, drying the slurry obtained in the step 2, cooling to room temperature, and mixing with a plasticizer: grinding the polyvinyl alcohol solution to obtain precursor powder; the addition amount of the polyvinyl alcohol is 0.5-2 wt.% of the whole reaction system; then, carrying out secondary high-temperature drying to remove redundant water;
step 4, pressing the mixture into a sheet biscuit by adopting a dry pressing method, wherein the pressure is 700-1300 MPa, and the pressure maintaining time is 10-15 min;
and 5, placing the ceramic biscuit on a YAG ceramic gasket, sintering two sides of the biscuit by using a laser to obtain a Ce: YAG fluorescent ceramic sample, and polishing one side of the Ce: YAG fluorescent ceramic sample without annealing to obtain the Ce: YAG fluorescent ceramic.
Preferably, the Al is contained in the step 13+The compound of (A) is aluminum nitrate or aluminum oxide, and the compound contains Ce3+The compound of (2) is cerium oxide or cerium nitrate.
Preferably, the temperature of the secondary high temperature in the step 3 is 70-90 ℃.
Preferably, the plasticizer in the step 3 is diluted by distilled water, and the concentration of the plasticizer is 0.1-0.2 g/ml.
Preferably, the pressure when the ceramic sheet biscuit is pressed in the step 4 is 700-1300 MPa.
Preferably, in the step 5, the laser output power of the laser is 10-20W, the diameter of a light spot is 0.3-0.7 mm, the scanning speed is 10-30 mm/s, and the distance between the laser output end and the ceramic biscuit is 0.3-0.7 mm.
Has the advantages that:
compared with the prior art, the method for preparing the Ce: YAG fluorescent ceramic by laser sintering has the following advantages:
1. the laser sintering technology adopted by the invention can not generate oxygen vacancy and corresponding color center defects in the ceramic, weaken the non-radiative transition effect of fluorescence and ensure the light conversion efficiency of the ceramic. In addition, an annealing process is not needed in the subsequent process, so that Ce is effectively inhibited3+To Ce4+Transformation;
2. according to the invention, in the laser sintering process, the distance between the laser output point and the ceramic biscuit is controlled, and micron-sized gravure is formed on the lower surface of the ceramic, namely the blue light incident surface, the gravure can change the propagation path of a light path, the utilization rate of blue light is improved, the luminous efficiency is improved by 10-30%, and the process and the ceramic sintering are carried out synchronously, so that the later processing steps are avoided;
3. the grain size range of the Ce: YAG fluorescent ceramic prepared by the method provided by the invention is 2-5 μm, so that the Ce: YAG fluorescent ceramic has good mechanical properties, can meet the requirements of high-power blue light LED excitation, and has the advantages of short preparation time, energy saving and environmental protection.
Drawings
FIG. 1 is an XRD pattern of the Ce: YAG fluorescent ceramic prepared in example 1;
FIG. 2 is an electroluminescence spectrum of the Ce: YAG fluorescent ceramic material prepared in example 1;
fig. 3 is a schematic diagram illustrating the optical path propagation after the lower surface (blue light incident surface) of the ceramic material of example 1 is roughened.
Detailed Description
Example 1 (Ce)0.0005Y0.998)3Al5O12Fluorescent ceramic
A method for preparing Ce: YAG fluorescent ceramic by laser sintering comprises the following steps:
(1) according to (Ce)0.002Y0.998)3Al5O12Respectively weighing Al according to the stoichiometric ratio of each element2O3，Y2O3，Ce(NO3)3·5H2O is taken as a reaction raw material;
(2) will contain Y3+Compound of (2) and containing Al3+Compound of (2) and containing Ce3+Mixing the compound (A) with an ethanol solvent, and then carrying out ball milling;
(3) drying the slurry obtained in the step (2), cooling to room temperature, mixing with a mixed solution of a plasticizer and polyvinyl alcohol, grinding to obtain precursor powder, performing secondary drying, and removing excessive water to obtain a mixture, wherein the plasticizer is diluted by distilled water and has a concentration of 0.15g/ml, the purity of the polyvinyl alcohol is 98-99%, and the addition amount of the polyvinyl alcohol is 0.8% of the total mass of the mixture;
(4) pressing the mixture into sheet biscuit by dry pressing method under 700 MPa for 10 min;
(5) placing the ceramic biscuit on a YAG gasket and using CO with the power of 10W2The laser device emits laser with the laser spot diameter of 0.3 mm to sinter two surfaces of the biscuit, the scanning speed is 10 mm/s, and the distance between the ceramic biscuit and the laser output endThe distance is 0.3 mm, so that a Ce: YAG fluorescent ceramic sample is obtained, annealing is not needed, and finally the ceramic sample is subjected to single-side polishing to obtain the Ce: YAG fluorescent ceramic.
FIG. 1 is an XRD pattern of the above-mentioned Ce: YAG fluorescent ceramic, and it can be seen that the ceramic is a pure YAG phase, no other impurity phase appears, and the grain size of the obtained ceramic is 2.3 μm.
FIG. 2 is an electroluminescence spectrum of a Ce: YAG fluorescent ceramic with 450nm blue light as an excitation source, and it can be seen that the intensity of blue light (450nm) is significantly reduced, the intensity of yellow light (547nm) is significantly enhanced, the blue-yellow ratio is 0.47, and the light-to-light conversion efficiency is 230 lm/W, compared with the prior art.
FIG. 3 is the influence of the gravure that leads to because laser sintering to arousing blue light propagation path, because the existence of gravure, can effectively avoid because the reflection of the blue light that the polished surface leads to, has promoted the utilization ratio of blue light. And the process and the ceramic sintering are carried out synchronously, so that the later processing step is avoided.
Example 2 (Ce)0.001Y0.998)3Al5O12Fluorescent ceramic
(1) According to (Ce)0.01Y0.998)3Al5O12Respectively weighing Al according to the stoichiometric ratio of each element2O3，Y2O3，Ce(NO3)3·5H2O is taken as a reaction raw material;
(2) containing Y3+Compound of (2) and containing Al3+Compound of (2) and containing Ce3+Mixing the compound (A) with an ethanol solvent, and then carrying out ball milling;
(3) drying the slurry obtained in the step (2), cooling to room temperature, mixing with a mixed solution of a plasticizer and polyvinyl alcohol, grinding to obtain precursor powder, performing secondary drying, and removing excessive water to obtain a mixture, wherein the plasticizer is diluted by distilled water and has a concentration of 0.1g/ml, the purity of the polyvinyl alcohol is 98-99%, and the addition amount of the polyvinyl alcohol is 0.8% of the total mass of the mixture;
(4) pressing the mixture into a sheet ceramic biscuit by a dry pressing method, wherein the pressure is 1000MPa, and the pressure maintaining time is 12 min;
(5) placing the ceramic biscuit on a YAG gasket and using 15W CO2The laser device emits laser with the laser spot diameter of 0.5 mm to sinter two sides of the biscuit, the scanning speed is 15 mm/s, the distance between the ceramic biscuit and the laser output end is 0.5 mm, so that a Ce: YAG fluorescent ceramic sample is obtained, annealing is not needed, and finally the ceramic sample is subjected to single-side polishing to obtain the Ce: YAG fluorescent ceramic.
The Ce: YAG fluorescent ceramic prepared by the embodiment is a pure YAG phase, and other impure phases do not appear. The obtained ceramic grain size was 3.6 μm. When 460 nm blue light is used as an excitation source, the blue-yellow ratio is 0.65, and the light conversion efficiency is 239 lm/W.
Example 3 (Ce)0.005Y0.998)3Al5O12Fluorescent ceramic
(1) According to (Ce)0.01Y0.998)3Al5O12Respectively weighing Al according to the stoichiometric ratio of each element2O3，Y2O3，Ce(NO3)3·5H2O is taken as a reaction raw material;
(2) containing Y3+Compound of (2) and containing Al3+Compound of (2) and containing Ce3+Mixing the compound (A) with an ethanol solvent, and then carrying out ball milling;
(3) drying the slurry obtained in the step (2), cooling to room temperature, mixing with a mixed solution of a plasticizer and polyvinyl alcohol, grinding to obtain precursor powder, performing secondary drying, and removing excessive water to obtain a mixture, wherein the plasticizer is diluted by distilled water and has a concentration of 0.2g/ml, the purity of the polyvinyl alcohol is 98-99%, and the addition amount of the polyvinyl alcohol is 0.8% of the total mass of the mixture;
(4) pressing the mixture into a sheet ceramic biscuit by adopting a dry pressing method, wherein the pressure is 1300MPa, and the pressure maintaining time is 15 min;
(5) placing the ceramic biscuit on a YAG gasket and using CO with the power of 20W2The laser with the laser spot diameter of 0.5 mm is emitted by the laser to sinter the two surfaces of the biscuit, and the scanning speed is 20 mm/sAnd the distance between the ceramic biscuit and the laser output end is 0.7mm, so that a Ce: YAG fluorescent ceramic sample is obtained without annealing. And finally, polishing the single surface of the ceramic sample to obtain the Ce: YAG fluorescent ceramic.
The Ce: YAG fluorescent ceramic prepared by the embodiment is a pure YAG phase, and other impure phases do not appear. The obtained ceramic grain size was 4.7 μm. When 470nm blue light is used as the excitation source, the blue-yellow ratio is 0.8, and the light conversion efficiency is 250 lm/W.
It should be noted that the raw materials mentioned in the above examples are all commercialized and all available, and the measurement method is performed according to the conventional technical means, and will not be described herein again.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications 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 are within the scope of the present invention.

Claims (6)

1. A method for preparing Ce: YAG fluorescent ceramic by laser sintering is characterized by comprising the following steps:
step 1, according to the chemical structural formula (Ce)xY1-x)3Al5O12The stoichiometric ratio of each element in the formula (I) is determined by weighing Y3+Compound of (2) and containing Al3+And containing Ce3+The compound powder of (1) is used as a reaction raw material, wherein x is the atomic percentage of Ce doped into the lattice position of Y, and is 0.01<x<0.1；
Step 2, adding Y3+Compound of (2) and containing Al3+Compound of (2) and containing Ce3+Mixing the compound (A) with an ethanol solvent, and then carrying out ball milling;
step 3, drying the slurry obtained in the step 2, cooling to room temperature, mixing with a mixed solution of a plasticizer and polyvinyl alcohol, and grinding to obtain precursor powder; the addition amount of the polyvinyl alcohol is 0.5-2 wt.% of the whole reaction system; then, carrying out secondary high-temperature drying to remove redundant water;
step 4, pressing the mixture into a sheet ceramic biscuit by adopting a dry pressing method, wherein the pressure is 700-1300 MPa, and the pressure maintaining time is 10-15 min;
and 5, placing the ceramic biscuit on a YAG ceramic gasket, sintering two sides of the biscuit by using a laser to obtain a Ce: YAG fluorescent ceramic sample, and polishing one side of the Ce: YAG fluorescent ceramic sample without annealing to obtain the Ce: YAG fluorescent ceramic.
2. The method for preparing Ce: YAG fluorescent ceramic by laser sintering as claimed in claim 1, wherein the Al is contained in step 13+The compound of (A) is aluminum nitrate or aluminum oxide, and the compound contains Ce3+The compound of (2) is cerium oxide or cerium nitrate.
3. The method for preparing Ce: YAG fluorescent ceramic by laser sintering as claimed in claim 1, wherein the temperature of the secondary high temperature in step 3 is 70-90 ℃.
4. The method for preparing Ce: YAG fluorescent ceramic by laser sintering as claimed in claim 1, wherein the plasticizer is diluted by distilled water in the step 3, and the concentration is 0.1-0.2 g/ml.
5. The method for preparing Ce: YAG fluorescent ceramic by laser sintering as claimed in claim 1, wherein the pressure when pressing into the sheet ceramic biscuit in step 4 is 700-1300 MPa.
6. The method for preparing Ce: YAG fluorescent ceramic by laser sintering as claimed in claim 1, wherein in step 5, the laser output power of the laser is 10-20W, the spot diameter is 0.3-0.7 mm, the scanning speed is 10-30 mm/s, and the distance between the laser output end and the ceramic biscuit is 0.3-0.7 mm.
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CN108751991A (en) * 2018-08-17 2018-11-06 徐州市江苏师范大学激光科技有限公司 A kind of laser sintered preparation Tb:Lu2O3The method of ceramics

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Application publication date: 20210112