CN117945751A - Broadband green luminous fluorescent ceramic and preparation method thereof - Google Patents
Broadband green luminous fluorescent ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000004090 dissolution Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 235000015895 biscuits Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000000462 isostatic pressing Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000005286 illumination Methods 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000009877 rendering Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a broadband green luminescent fluorescent ceramic and a preparation method thereof, wherein the fluorescent chemical formula is Ca (Y 1‑xCex)2HfAl4O12, wherein x is Ce 3+ doped to replace Y 3+ with a mole percentage coefficient of 0.01-0.03, the white mixed powder is obtained by calcining by adopting a mixed solution method, and the fluorescent ceramic is prepared by solid phase sintering.
Description
Technical Field
The invention relates to the technical field of fluorescent ceramics, in particular to a broadband green luminous fluorescent ceramic and a preparation method thereof.
Background
White light LEDs have the advantages of high integration level, small volume, low heat value, low power consumption and the like, and have been paid attention to worldwide. Currently, there are three main ways of generating white light, respectively: the blue light LED chip excites the yellow fluorescent powder, the plurality of monochromatic LED chips are mixed to generate white light, and the ultraviolet LED chip excites the multicolor fluorescent powder. Compared with other two white light generating modes, the white light generating mode of exciting yellow fluorescence by the blue light LED has the advantages of high luminous efficiency, high color rendering index, low preparation cost, long service life and the like, and has become the main white light generating mode on the market. However, with the continuous improvement of the living standard of people, the way of generating white light by mixing blue light and yellow light cannot meet the needs of people for healthy illumination. In addition, as the white light generation mode needs the organic packaging material to directly coat the yellow fluorescent powder on the blue light LED chip, the organic packaging material is easy to age and can cause the problems of decay, color change, shortened service life and the like of the light emitting device, and the white light generation mode is insufficient for meeting the application requirements of white light illumination with high lumen density in the future.
In order to solve the problems, the scholars at home and abroad use Ce: YAG fluorescent ceramics with high optical quality and good heat conduction performance as a substitute material. However, since the luminescence center of Ce 3+ ions belongs to the yellow light emission band near 525nm, the lack of red light component in the spectrum results in lower Color Rendering Index (CRI) of the ceramic-based white LED device, which restricts the development of the ceramic-based white LED device in the field of white light illumination sources. For this reason, researchers replaced the Y 3+ position with Gd 3+ ions in the Ce-YAG lattice, causing the emission spectrum of the Ce 3+ ion to be red shifted, enhancing the red emission of the Ce 3+ ion. Nishioura et al red shifted the photoluminescence spectrum of Ce 3+ ions by 10-30nm using the Ce 3+ ion substitution scheme; cao Yongge et al obtain a white light output with a luminous efficacy of 128lm/W and a color rendering index of 78. CN110003908a proposes a modification technology for silicate system red fluorescent powder to realize high-quality white light output; CN106367062A prepares a full spectrum fluorescent powder to obtain high-efficiency white light which can meet the application requirements of different illumination fields. Although these approaches achieve high quality white light output, the white LED devices fabricated by this approach cannot make efficient use of blue light.
Disclosure of Invention
The invention provides a broadband green luminescent fluorescent ceramic and a preparation method thereof, which aim to solve the application problem of low color rendering index of a blue light LED excited fluorescent material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In one aspect, the invention provides a broadband green luminescent fluorescent ceramic, which has a chemical formula of Ca (Y 1-xCex)2HfAl4O12, wherein x is a mole percentage coefficient of Ce 3+ doped substituted Y 3+, and x is more than or equal to 0.01 and less than or equal to 0.03.
On the other hand, the invention also provides a preparation method of the broadband green luminescent fluorescent ceramic, which comprises the following steps:
(1) Adding high-purity 99.99% HfO 2 into hydrofluoric acid for dissolution, adding deionized water, and adjusting the concentration of Hf 4+ to 0.1-2 mol/L; adding commercial Y 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Y 3+ to be 0.1-2 mol/L; adding commercial Al 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Al 3+ to be 0.1-2 mol/L; adding commercial H 12CeNO9 with high-grade purity into deionized water for dissolution, and adjusting the concentration of Ce 4+ to be 0.1-2 mol/L; adding commercial CaCl 2 with high purity into deionized water for dissolution, and adjusting the concentration of Ca 2+ to be 0.1-2 mol/L;
(2) Proportioning the solution obtained in the step (1) according to the stoichiometric ratio of each element in Ca (Y 1-xCex)2HfAl4O12, wherein x is more than or equal to 0.01 and less than or equal to 0.03, heating, keeping the temperature of the solution at 55-65 ℃, and stopping heating when the pH value is adjusted to 3.5-3.8;
(3) Adding Ca (OH) 2 into the solution obtained in the step (2) to adjust the pH value to 4.5-4.8, and then stirring at a stirring speed of 100-160 r/min for 2-6 h;
(4) Adding the solution obtained in the step (3) into a crucible, calcining the solution in an oxygen atmosphere by using a muffle furnace to obtain white mixed powder, adding commercial YAG powder with the mass of 0.1-0.5% and PEI with the mass of 0.1-1% into the white mixed powder, and adding absolute ethyl alcohol to perform ball milling;
(5) Drying and sieving the slurry obtained in the step (4) to obtain mixed powder, and performing isostatic compaction to obtain a fluorescent ceramic biscuit;
(6) Sintering the biscuit obtained in the step (5) in air atmosphere or oxygen atmosphere, wherein the sintering temperature is 1600-1700 ℃, and the heat preservation time is 6-12 h, so that the fluorescent ceramics with broad-band green luminescence can be obtained.
Preferably, the crucible in the step (4) is a quartz crucible, the calcination temperature is 600-800 ℃, the heating rate is 0.5-2 ℃/min, and the heat preservation time is 4-6 h.
Preferably, the addition amount of the absolute ethyl alcohol in the step (4) is 1.0-1.2 times of the mass of the white mixed powder, and then ball milling is carried out at a ball milling speed of 160-200 r/min for 4-6 h.
Preferably, the number of the screen meshes of the screen in the step (5) is 80-200 meshes.
Preferably, the isostatic compaction pressure in the step (5) is 200-250 Mpa, and the pressure maintaining time is 5-10 min.
Preferably, the oxygen sintering in the step (6) is performed, the temperature is raised to 1000 ℃, the temperature raising rate is 1.0-5.0 ℃/min, the temperature is raised to 1600-1700 ℃, and the temperature raising rate is 0.5-2.0 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional preparation process, the preparation method does not need annealing treatment, directly prepares the high-efficiency fluorescent material, and is beneficial to the blue light LED packaging yellow fluorescent material to realize white light illumination with high color rendering index.
(2) The preparation method has the advantages of short preparation period, energy saving, environmental protection and high efficiency in the preparation process; although hydrofluoric acid is used in the preparation process, the harmful atmosphere can be introduced into lime water to realize complete absorption, and no extra burden is caused to the environment.
(3) The product prepared by the method has no waste ions, high powder yield, high activity, uniform component distribution and high purity, and is suitable for industrial production; the preparation process is simple and easy to operate, and the cost is low.
Drawings
FIG. 1 is an excitation and emission spectrum of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramics) prepared in example 1;
FIG. 2 is a temperature-dependent emission spectrum of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramics (a) between 303K and 463K) prepared in example 1;
FIG. 3 is a plot of relative PL intensity of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent samples at various test temperatures) prepared in example 1;
FIG. 4 is an electroluminescence spectrum of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramic and commercial Ce: YAG ceramic under excitation of 450nm blue chip) sprayed with red phosphor;
fig. 5 shows the LED lighting effect Ca (Y 0.98Ce0.02)2HfAl4O12 at 60 mA.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
Example 1: preparation of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramics)
(1) Adding high-purity 99.99% HfO 2 into hydrofluoric acid for dissolution, adding deionized water, and adjusting the concentration of Hf 4+ to 0.5mol/L; adding commercial Y 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Y 3+ to 0.5mol/L; adding commercial Al 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Al 3+ to 0.5mol/L; adding commercial H 12CeNO9 with high-grade purity into deionized water for dissolution, and adjusting the concentration of Ce 4+ to 0.5mol/L; adding commercial CaCl 2 with high purity into deionized water for dissolution, and adjusting the concentration of Ca 2+ to 0.5mol/L;
(2) Proportioning the solution obtained in the step (1) according to a stoichiometric ratio Ca (Y 0.98Ce0.02)2HfAl4O12, then heating, keeping the temperature of the solution at 60 ℃, testing the pH value of the solution, adjusting the pH value to 3.5, and stopping heating;
(3) Adding Ca (OH) 2 into the solution obtained in the step (2) to adjust the pH to 4.5, and then stirring by using a magnetic stirrer at a stirring speed of 140r/min for 4 hours;
(4) Adding the solution obtained in the step (3) into a quartz crucible, calcining the solution in an oxygen atmosphere by using a muffle furnace, wherein the calcining temperature is 800 ℃, the heat preservation is carried out for 6 hours, the heating rate is 1 ℃/min, so as to obtain white mixed powder, then adding commercial YAG powder (serving as a heterogeneous doping ion for promoting the sintering densification of Ca (Y 1-xCex)2HfAl4O12)) with the mass of 0.1wt.% of PEI (serving as a dispersing agent) with the mass of 0.1wt.% of the white mixed powder, adding absolute ethyl alcohol (serving as a ball milling medium) with the mass of 1.2 times of the white mixed powder, and carrying out ball milling at the ball milling rotating speed of 180r/min for 5 hours;
(5) Drying the slurry obtained in the step (4), sieving with a 80-mesh sieve to obtain mixed powder, performing isostatic compaction, wherein the forming pressure is 200Mpa, and maintaining the pressure for 10min to obtain a fluorescent ceramic biscuit with green and luminous broadband;
(6) And (3) sintering the biscuit obtained in the step (5) in an oxygen atmosphere, heating to 1000 ℃ at a speed of 3.0 ℃/min, then sintering at a temperature of 1650 ℃ at a heating rate of 0.5 ℃/min, and preserving heat for 6 hours to obtain the broadband green luminescent fluorescent ceramic.
FIG. 1 is a graph showing the excitation and emission spectra of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramics) obtained in this example, from which it can be seen that Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramics have a spectral width of 120nm;
FIG. 2 is a graph showing the temperature-dependent emission spectrum of Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramic (a) prepared in this example between 303K and 463K, and it can be seen from the graph that Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramic has high temperature stability, and retains broad-band green luminescence at 423K;
FIG. 3 is a graph showing the relative PL intensity curves of the Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent sample at different test temperatures) prepared in this example, and it can be seen from the graph that Ca (Y 0.98Ce0.02)2HfAl4O12 fluorescent ceramic has higher temperature stability, and the luminous efficiency is still maintained at 68% at 423K;
FIG. 4 is an electroluminescence spectrum of CaAlSiN 3:Eu2+ red phosphor coated Ca (Y 0.98Ce0.02)2HfAl4O12 phosphor and commercial Ce: YAG ceramic excited by 450nm blue chip, from which the spectral curve of Ca (Y 0.98Ce0.02)2HfAl4O12 phosphor has no blue canyon;
Fig. 5 shows the LED lighting effect at 60mA, and it can be seen from the graph that Ca (color coordinates of Y 0.98Ce0.02)2HfAl4O12 illumination are 0.39,0.37), which indicates that the ceramic has a good illumination effect and can meet the future requirement for high color rendering index illumination.
Example 2: preparation of Ca (Y 0.99Ce0.01)2HfAl4O12 fluorescent ceramics)
(1) Adding high-purity 99.99% HfO 2 into hydrofluoric acid for dissolution, adding deionized water, and adjusting the concentration of Hf 4+ to 2.0mol/L; adding commercial Y 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Y 3+ to 2.0mol/L; adding commercial Al 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Al 3+ to 2.0mol/L; adding commercial H 12CeNO9 with high-grade purity into deionized water for dissolution, and adjusting the concentration of Ce 4+ to 2.0mol/L; adding commercial CaCl 2 with high purity into deionized water for dissolution, and adjusting the concentration of Ca 2+ to 2.0mol/L;
(2) Proportioning the solution obtained in the step (1) according to a stoichiometric ratio Ca (Y 0.99Ce0.01)2HfAl4O12, then heating, maintaining the temperature of the solution at 60 ℃, testing the pH value of the solution until the pH value is adjusted to 3.8, and stopping heating;
(3) Adding Ca (OH) 2 into the solution obtained in the step (2) to adjust the pH to 4.8, and then stirring by using a magnetic stirrer at a stirring speed of 120r/min for 6 hours;
(4) Adding the solution obtained in the step (3) into a quartz crucible, calcining the solution in an oxygen atmosphere by using a muffle furnace, wherein the calcining temperature is 600 ℃, the heat preservation is carried out for 4 hours, the heating rate is 2 ℃/min, so as to obtain white mixed powder, then adding commercial YAG powder (serving as a heterogeneous doping ion for promoting the sintering densification of Ca (Y 1-xCex)2HfAl4O12)) with the mass of 0.5wt.% of the white mixed powder, adding PEI (serving as a dispersing agent) with the mass of 0.1wt.% of the white mixed powder, adding absolute ethyl alcohol (serving as a ball milling medium) with the mass of 1.0 time of the white mixed powder, and carrying out ball milling at the ball milling rotating speed of 200r/min for 4 hours;
(5) Drying the slurry obtained in the step (4), sieving with a 100-mesh sieve to obtain mixed powder, performing isostatic compaction, wherein the forming pressure is 250Mpa, and maintaining the pressure for 5min to obtain a fluorescent ceramic biscuit with green and luminous broadband;
(6) And (3) sintering the biscuit obtained in the step (5), wherein the sintering environment is oxygen atmosphere, heating to 1000 ℃ at a speed of 3.0 ℃/min, then sintering at 1700 ℃ at a heating rate of 1.5 ℃/min, and preserving heat for 12 hours to obtain the broadband green luminescent fluorescent ceramic.
The excitation and emission spectra of the Ca (Y 0.99Ce0.01)2HfAl4O12 fluorescent ceramics) prepared in this example were similar to those of Ca (Y 0.98Ce0.02)2HfAl4O12) prepared in example 1.
Example 3: preparation of Ca (Y 0.97Ce0.03)2HfAl4O12 fluorescent ceramics)
(1) Adding high-purity 99.99% HfO 2 into hydrofluoric acid for dissolution, adding deionized water, and adjusting the concentration of Hf 4+ to 1.5mol/L; adding commercial Y 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Y 3+ to 1.5mol/L; adding commercial Al 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Al 3+ to 1.5mol/L; adding commercial H 12CeNO9 with high-grade purity into deionized water for dissolution, and adjusting the concentration of Ce 4+ to be 1.5mol/L; adding commercial CaCl 2 with high purity into deionized water for dissolution, and adjusting the concentration of Ca 2+ to 1.5mol/L;
(2) Proportioning the solution obtained in the step (1) according to a stoichiometric ratio Ca (Y 0.97Ce0.03)2HfAl4O12, then heating, maintaining the temperature of the solution at 60 ℃, testing the pH value of the solution until the pH value is adjusted to 3.7, and stopping heating;
(3) Adding Ca (OH) 2 into the solution obtained in the step (2) to adjust the pH to 4.5, and then stirring by using a magnetic stirrer at a stirring speed of 160r/min for 4 hours;
(4) Adding the solution obtained in the step (3) into a quartz crucible, calcining the solution in an oxygen atmosphere by using a muffle furnace, wherein the calcining temperature is 800 ℃, the heating rate is 1 ℃/min, obtaining white mixed powder, then adding commercial YAG powder (serving as a heterogeneous doping ion for promoting the sintering densification of Ca (Y 1-xCex)2HfAl4O12)) with the mass of 0.1wt.% of PEI (serving as a dispersing agent) with the mass of the white mixed powder, adding absolute ethyl alcohol (serving as a ball milling medium) with the mass of 1.2 times of the mass of the white mixed powder, and performing ball milling for 180r/min for 4h;
(5) Drying the slurry obtained in the step (4), sieving with a 200-mesh sieve to obtain mixed powder, performing isostatic compaction, wherein the forming pressure is 200Mpa, and maintaining the pressure for 5min to obtain a fluorescent ceramic biscuit with green and luminous broadband;
(6) And (3) sintering the biscuit obtained in the step (5), wherein the sintering environment is oxygen atmosphere, heating to 1000 ℃ at a speed of 5.0 ℃/min, then sintering at a temperature of 1650 ℃ at a heating rate of 1.5 ℃/min, and preserving heat for 6 hours to obtain the broadband green luminescent fluorescent ceramic.
The excitation and emission spectra of the Ca (Y 0.97Ce0.03)2HfAl4O12 fluorescent ceramics) prepared in this example were similar to those of Ca (Y 0.98Ce0.02)2HfAl4O12) prepared in example 1.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (7)
1. A broadband green luminescent fluorescent ceramic is characterized in that the chemical formula of the fluorescent ceramic is Ca (Y 1-xCex)2HfAl4O12, wherein x is the mole percentage coefficient of Ce 3+ doped substituted Y 3+, and x is more than or equal to 0.01 and less than or equal to 0.03.
2. A method for preparing the broadband green luminescent fluorescent ceramic according to claim 1, comprising the steps of:
(1) Adding high-purity 99.99% HfO 2 into hydrofluoric acid for dissolution, adding deionized water, and adjusting the concentration of Hf 4+ to 0.1-2 mol/L; adding commercial Y 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Y 3+ to be 0.1-2 mol/L; adding commercial Al 2O3 with high purity of 99.99% into nitric acid for dissolution, and adjusting the concentration of Al 3+ to be 0.1-2 mol/L; adding commercial H 12CeNO9 with high-grade purity into deionized water for dissolution, and adjusting the concentration of Ce 4+ to be 0.1-2 mol/L; adding commercial CaCl 2 with high purity into deionized water for dissolution, and adjusting the concentration of Ca 2+ to be 0.1-2 mol/L;
(2) Proportioning the solution obtained in the step (1) according to the stoichiometric ratio of each element in Ca (Y 1-xCex)2HfAl4O12, wherein x is more than or equal to 0.01 and less than or equal to 0.03, heating, keeping the temperature of the solution at 55-65 ℃, and stopping heating when the pH value is adjusted to 3.5-3.8;
(3) Adding Ca (OH) 2 into the solution obtained in the step (2) to adjust the pH value to 4.5-4.8, and then stirring at a stirring speed of 100-160 r/min for 2-6 h;
(4) Adding the solution obtained in the step (3) into a crucible, calcining the solution in an oxygen atmosphere by using a muffle furnace to obtain white mixed powder, adding commercial YAG powder with the mass of 0.1-0.5% and PEI with the mass of 0.1-1% into the white mixed powder, and adding absolute ethyl alcohol to perform ball milling;
(5) Drying and sieving the slurry obtained in the step (4) to obtain mixed powder, and performing isostatic compaction to obtain a fluorescent ceramic biscuit;
(6) Sintering the biscuit obtained in the step (5) in air atmosphere or oxygen atmosphere, wherein the sintering temperature is 1600-1700 ℃, and the heat preservation time is 6-12 h, so that the fluorescent ceramics with broad-band green luminescence can be obtained.
3. The method for preparing the broadband green luminescent fluorescent ceramic according to claim 2, wherein the crucible in the step (4) is a quartz crucible, the calcining temperature is 600-800 ℃, the heating rate is 0.5-2 ℃/min, and the heat preservation time is 4-6 h.
4. The method for preparing the broadband green luminescent fluorescent ceramic according to claim 2, wherein the addition amount of the absolute ethyl alcohol in the step (4) is 1.0-1.2 times of the mass of the white mixed powder, and then ball milling is carried out at a ball milling rotating speed of 160-200 r/min for 4-6 h.
5. The method for preparing a broad band green luminescent fluorescent ceramic as claimed in claim 2, wherein the number of the sieves screened in the step (5) is 80 to 200 mesh.
6. The method for preparing the broadband green luminescent fluorescent ceramic according to claim 2, wherein the isostatic pressing pressure in the step (5) is 200-250 Mpa, and the holding time is 5-10 min.
7. The method for preparing the broadband green luminescent fluorescent ceramic according to claim 2, wherein the oxygen sintering in the step (6) is performed, the temperature is raised to 1000 ℃, the temperature raising rate is 1.0-5.0 ℃/min, the temperature is raised to 1600-1700 ℃, and the temperature raising rate is 0.5-2.0 ℃/min.
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