CN112239352A - Complex phase fluorescent ceramic material and preparation method thereof - Google Patents
Complex phase fluorescent ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 239000000919 ceramic Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 235000015895 biscuits Nutrition 0.000 claims abstract description 12
- 239000011812 mixed powder Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910017878 a-Si3N4 Inorganic materials 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 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
- 239000000126 substance Substances 0.000 claims abstract description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 238000001513 hot isostatic pressing Methods 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 abstract 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000009877 rendering Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002457 bidirectional effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 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
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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Abstract
The invention discloses a complex phase fluorescent ceramic material and a preparation method thereof. The chemical general formula of the multiphase fluorescent ceramic material is Al2O3‑(Y1‑xCex)3(Al1‑ySiy)5(O1‑yNy)12Wherein x is more than or equal to 0.001 and less than or equal to 0.01 and 0<y<0.3，Al2O3And (Y)1‑xCex)3(Al1‑ySiy)5(O1‑yNy)12The mass ratio of (A) to (B) is 0.5-50: 50 to 99.5. According to the mass ratio and the chemistryStoichiometric balance of Al2O3，Y2O3，CeO2And a-Si3N4Adding sintering aid and solvent into the raw material powder; ball milling, drying and sieving to obtain mixed powder; then carrying out dry pressing and cold isostatic pressing to obtain a biscuit; sintering at high temperature and polishing on both sides to obtain Al2O3‑(Y1‑xCex)3(Al1‑ySiy)5(O1‑yNy)12Complex phase fluorescent ceramic.
Description
Technical Field
The invention belongs to the field of electrodeless luminescent materials, relates to a fluorescent ceramic material, and particularly relates to a complex-phase fluorescent ceramic material and a preparation method thereof.
Background
The white light LED 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, and has wide application in the fields of solid-state illumination, projection display and the like. Currently, the most widespread and mature technical solution of white light LED is phosphor-converted white LED (phosphor-converted LED), also commonly referred to as PC-LED, i.e. Ce: YAG (Ce: Y)3Al5O12) Organic matters such as resin and silica gel are packaged with the blue light chip, and the white light effect is formed by mixing the blue light and the converted yellow light. However, the organic encapsulating material has the disadvantages of poor heat resistance, easy aging and the like, and is difficult to satisfy the application of the white light LED in high-power application occasions. The Ce: YAG fluorescent ceramic has high heat conductivity, low light decay and strong thermal shock resistanceThe method has the remarkable advantages of effectively replacing the traditional technical scheme of Ce: YAG fluorescent powder and resin, avoiding the processes of glue mixing and dispensing and becoming the current mainstream product.
However, the Ce: YAG fluorescent ceramic still has the problems of low color rendering index, poor light color quality and the like caused by lack of red light components in the spectrum. By introducing Al in comparison with the substitution of the Y site and the Al site by cations having larger ionic radii3+Anions having greater covalency, e.g. N3-Ions to form Al3+-N3-Substituted for Al3+-O2-On the basis of improving the crystal field strength, the position of the excited d-level can be further compressed by the enhanced electron cloud expansion effect, so that the emission spectrum is shifted to a long wavelength (a.a. setlru et al chem. mater. 20: 6722 (2008), US Pat. 197, 433). However, during the sintering of the fluorescent ceramic, due to Si3N4The introduction of (1) will generate a certain amount of impurity phase of Yttrium Aluminate (YAP) (Liuwenbin et al, silicate science 34: 1 (2015)) which can not reach Si3N433% of the theoretical solid solubility in the YAG lattice (D. Pasinski et al. J. Alloys Compd. 668: 194 (2016)). The experimental process shows that Si in the ceramic3N4Has a solid solubility of less than 10%, and thus cannot generate a sufficient red light component.
Al2O3Optical properties of high thermal conductivity, wide band gap and translucency per se are widely used for the preparation of complex phase ceramics for solid state lighting, but most of the published reports show that Al is a rare earth metal2O3Are present independently and do not react with the matrix phase (Tang et al Opt. Express 23: 17923 (2015), CN109678475A, CN110386822A, CN 109896852A). In the present invention, however, Al2O3After being introduced as a second phase, the YAP phase reacts to generate a YAG phase (3 YAlO)3（YAP）+Al2O3→Y3Al5O12(YAG)), Si is increased3N4Solid solubility in the matrix, thereby improving the splitting energy of a crystal field, enhancing the expansion effect of electron cloud and increasing the red light component. Al remaining after completion of the reaction2O3The second phase exists independently, and the thermal conductivity of the complex phase ceramic can be effectively improved.
Disclosure of Invention
The invention aims to provide a complex phase fluorescent ceramic material which has high thermal conductivity and high color rendering index, meets the application under high-power excitation and is prepared by a second phase Al2O3The nitrogen oxide matrix is introduced, so that the thermal conductivity of the ceramic material is improved while the red light component in the spectrum is supplemented, and the ceramic material can better meet the application under high-power excitation.
The second purpose of the invention is to provide a preparation method of the complex phase fluorescent ceramic material, and the material passes through the second phase Al2O3The nitrogen oxide matrix is introduced, so that the thermal conductivity of the ceramic material is improved while the red light component in the spectrum is supplemented, and the ceramic material can better meet the application under high-power excitation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a complex phase fluorescent ceramic material with a chemical formula of Al2O3-(Y1-xCex)3(Al1-ySiy)5(O1-yNy)12Wherein x is more than or equal to 0.001 and less than or equal to 0.01 and 0<y<0.3，Al2O3And (Y)1-xCex)3(Al1-ySiy)5(O1-yNy)12The mass ratio of (A) to (B) is 0.5-50: 50 to 99.5.
The preparation method of the complex phase fluorescent ceramic material comprises the following steps:
step 1, weighing Al according to mass ratio and stoichiometric ratio2O3，Y2O3，CeO2And a-Si3N4Adding 0.1-0.5 wt.% of Tetraethoxysilane (TEOS) into raw material powder to serve as a sintering aid, and adding alcohol to serve as a solvent;
step 2, placing the raw material powder raw material weighed in the step 1 into a ball milling tank, performing planetary ball milling while adding grinding balls for ball milling and mixing, wherein the ball milling rotation speed is 120-180 r/min, and the ball milling time is 12-24 h;
step 3, drying the slurry subjected to ball milling in the step 2 at the temperature of 40-60 ℃ for 10-24h, then crushing the dried slurry, and sieving the crushed slurry with a 100-200-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial two-way pressure molding on the mixed powder in the step 3 at the pressure of 2-5 MPa, and then carrying out cold isostatic pressing at the pressure of 200-300 MPa for the pressure maintaining time of 200-400 s to obtain a ceramic biscuit;
and 5, sintering the ceramic biscuit without annealing, and then performing double-sided polishing treatment to obtain Al2O3-(Y1-xCex)3(Al1-ySiy)5(O1-yNy)12 Complex phase fluorescent ceramic.
The improvement is that the sintering mode in the step 5 is any one of vacuum sintering, hot pressing sintering or hot isostatic pressing sintering.
The improvement is that the sintering temperature in the step 5 is 1500-1700 ℃, and the temperature is kept for 5-24 h.
Has the advantages that:
compared with the prior art, the complex phase fluorescent ceramic material and the preparation method thereof have the following advantages:
1. the thermal conductivity of the fluorescent ceramic material at room temperature can reach 9-20 Wm-1K-1The fluorescent powder is more than 10 times of the traditional fluorescent powder material, has good thermal stability, can ensure the stable output of various photoelectric properties, and has good prospect in the application field of high-power solid-state lighting.
2. The fluorescent ceramic material is excited by a blue light LED chip with the light-emitting wavelength of 400-500 nm, the obtained white light has the color temperature of 2000-3500K and the color rendering index of 70-95, and has larger promotion compared with the traditional Ce-YAG fluorescent powder and fluorescent ceramic, and the color temperature is similar to that of an incandescent lamp.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the complex phase fluorescent ceramic material prepared in example 1, wherein the abscissa is the incident angle of X-rays and the ordinate is the diffraction intensity;
FIG. 2 is a Scanning Electron Microscope (SEM) image and a micro-domain EDS element content distribution diagram of the multiphase fluorescent ceramic material prepared in example 1, wherein (a) is the SEM image of the ceramic surface after thermal etching, (b) is the EDS element content distribution diagram of "selected domain 1" in the diagram (a), and (c) is the EDS element content distribution diagram of "selected domain 2" in the diagram (a);
FIG. 3 is an electroluminescence spectrum of the complex phase fluorescent ceramic material prepared in example 1.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
60 g of target product is prepared, and raw material powder ingredients are weighed respectively and shown in table 1. The measurement methods in the following examples are conventional in the art, and the materials are all commercial finished products, which are not described herein again.
Table 1 ingredient table of the examples
Example 1
A complex phase fluorescent ceramic material with a chemical formula of Al2O3-(Y0.998Ce0.002)3(Al0.99Si0.01)5(O0.99N0.01)12Wherein Al is2O3And (Y)0.998xCe0.002)3(Al0.99ySi0.01)5(O0.99yN0.01)12The mass ratio of (A) to (B) is 5: 95.
the preparation method of the complex phase fluorescent ceramic material comprises the following steps:
step 1, weighing Al according to the mass ratio and stoichiometric ratio shown in # 1 in Table 12O3，Y2O3，CeO2，a-Si3N4Raw material powder, sintering aid tetraethyl orthosilicate (TEOS), and alcoholAs a solvent;
step 2, placing the raw material powder weighed in the step 1 into a ball milling tank, performing planetary ball milling, and simultaneously adding grinding balls for ball milling and mixing, wherein the ball milling rotation speed is 130 r/min, and the ball milling time is 15 hours;
step 3, drying the slurry subjected to ball milling in the step 2 at the drying temperature of 40 ℃ for 20 hours, crushing the dried slurry, and sieving the crushed slurry with a 100-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional pressure forming on the mixed powder in the step 3 at the pressure of 2 MPa, and then carrying out cold isostatic pressing at the pressure of 200 MPa for 200 s to obtain a ceramic biscuit;
Referring to FIG. 1, the X-ray diffraction pattern of the sample prepared in this example shows that the XRD test result shows that the prepared Al2O3-(Y1-xCex)3(Al1-ySiy)5(O1-yNy)12 X-ray diffraction peak of complex phase fluorescent ceramic, YAG (JCPDS (# 34-0379)) and Al2O3(JCPDS (# 046-2O3A complex phase structure of (1).
Referring to FIG. 2, this example produced 5:95 mass ratio Al2O3-(Y0.998Ce0.002)3(Al0.99Si0.01)5(O0.99-yN0.01)12 Scanning electron microscope images of the cross section of the complex phase fluorescent ceramic, and SEM test results show that the conditions of different contrasts exist. By EDS elemental analysis, the "selection zone 1" is YAG phase, and the "selection zone 2" is Al2O3And (4) phase(s).
Referring to FIG. 3, this example produced 5:95 mass ratio Al2O3-(Y0.998Ce0.002)3(Al0.99Si0.01)5(O0.99N0.01)12 And the complex phase fluorescent ceramic has electroluminescence spectrum under the excitation of a 460 nm blue light LED chip. The graph shows that the luminescence center wavelength of the fluorescence region is 580 nm, compared with the traditional Ce: YAG fluorescent powder and the fluorescent ceramic, the red shift is nearly 30 nm, and the red light component is effectively compensated. The color temperature was 3000K and the color rendering index was 90.
Example 2
A complex phase fluorescent ceramic material with a chemical formula of Al2O3-(Y0.995xCe0.005)3(Al0.9Si0.1)5(O0.9yN0.1)12Wherein Al is2O3And (Y)0.995Ce0.005)3(Al0.9Si0.1)5(O0.9N0.1)12The mass ratio of (A) to (B) is 1: 9.
The preparation method of the complex phase fluorescent ceramic material comprises the following steps:
step 1, weighing Al according to the mass ratio and stoichiometric ratio shown in # 2 in Table 12O3，Y2O3，CeO2，a-Si3N4Raw material powder, a sintering aid, namely tetraethyl orthosilicate (TEOS), and alcohol are used as solvents;
step 2, placing the raw material powder weighed in the step 1 into a ball milling tank, performing planetary ball milling while adding grinding balls for ball milling and mixing, wherein the ball milling rotation speed is 140 r/min, and the ball milling time is 20 hours;
step 3, drying the slurry subjected to ball milling in the step 2 at the drying temperature of 50 ℃ for 15 hours, crushing the dried slurry, and sieving the crushed slurry with a 150-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional pressure forming on the mixed powder in the step 3 at the pressure of 3 MPa, and then carrying out cold isostatic pressing at the pressure of 250 MPa for 250 s to obtain a ceramic biscuit;
Through observation, the main structural properties of the fluorescent ceramic material with high thermal conductivity and high color rendering index prepared in the embodiment 2 are similar to those of the embodiment 1 in the light emission spectrum.
Example 3
A complex phase fluorescent ceramic material with a chemical formula of Al2O3-(Y0.99Ce0.01)3(Al0.8Si0.2)5(O0.8N0.2)12，Al2O3And (Y)0.99Ce0.01)3(Al0.8Si0.2)5(O0.8N0.2)12The mass ratio of (A) to (B) is 3: 7.
the preparation method of the complex phase fluorescent ceramic material comprises the following steps:
step 1, weighing Al according to the mass ratio and stoichiometric ratio shown in #3 in Table 12O3，Y2O3，CeO2，a-Si3N4Raw material powder, sintering aid and alcohol are used as solvents;
step 2, placing the powder raw materials weighed in the step 1 into a ball milling tank, performing planetary ball milling, and simultaneously adding grinding balls for ball milling and mixing, wherein the ball milling rotation speed is 150 r/min, and the ball milling time is 18 h;
step 3, drying the slurry subjected to ball milling in the step 2 at the drying temperature of 60 ℃ for 12 hours, crushing the dried slurry, and sieving the crushed slurry with a 200-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial bidirectional pressure molding on the mixed powder in the step 3 at the pressure of 4 MPa, and then carrying out cold isostatic pressing at the pressure of 300 MPa for 300 s to obtain a ceramic biscuit;
Through observation, the main structural properties and the luminescence spectrum of the complex phase fluorescent ceramic material with high thermal conductivity and high color rendering index prepared in the embodiment 3 are similar to those of the embodiment 1.
In conclusion, the thermal conductivity of the fluorescent ceramic material at room temperature can reach 9-20 Wm-1K-1The fluorescent powder is more than 10 times of the traditional fluorescent powder material, has good thermal stability, can ensure the stable output of various photoelectric properties, and has good prospect in the application field of high-power solid-state lighting.
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 (4)
1. The complex phase fluorescent ceramic material is characterized in that the chemical general formula is Al2O3-(Y1-xCex)3(Al1-ySiy)5(O1- yNy)12Wherein x is more than or equal to 0.001 and less than or equal to 0.01 and 0<y<0.3，Al2O3And (Y)1-xCex)3(Al1-ySiy)5(O1-yNy)12The mass ratio of (A) to (B) is 0.5-50: 50 to 99.5.
2. The preparation method of the complex phase fluorescent ceramic material based on claim 1, which is characterized by comprising the following steps:
step 1, mixing according to mass ratioStoichiometric weighing of Al2O3，Y2O3，CeO2And a-Si3N4Adding 0.1-0.5 wt.% of Tetraethoxysilane (TEOS) into raw material powder to serve as a sintering aid, and adding alcohol to serve as a solvent;
step 2, placing the raw material powder raw material weighed in the step 1 into a ball milling tank, performing planetary ball milling while adding grinding balls for ball milling and mixing, wherein the ball milling rotation speed is 120-180 r/min, and the ball milling time is 12-24 h;
step 3, drying the slurry subjected to ball milling in the step 2 at the temperature of 40-60 ℃ for 10-24h, then crushing the dried slurry, and sieving the crushed slurry through a 100-200-mesh sieve to obtain mixed powder;
step 4, carrying out equiaxial two-way pressure molding on the mixed powder in the step 3 at the pressure of 2-5 MPa, and then carrying out cold isostatic pressing at the pressure of 200-300 MPa for the pressure maintaining time of 200-400 s to obtain a ceramic biscuit;
and 5, sintering the ceramic biscuit without annealing, and then performing double-sided polishing treatment to obtain Al2O3-(Y1-xCex)3(Al1-ySiy)5(O1-yNy)12 Complex phase fluorescent ceramic.
3. The method for preparing a complex phase fluorescent ceramic material as claimed in claim 2, wherein the sintering manner in step 5 is any one of vacuum sintering, hot pressing sintering or hot isostatic pressing sintering.
4. The method for preparing a complex phase fluorescent ceramic material as claimed in claim 2, wherein the sintering temperature in step 5 is 1500-.
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