CN118324529A - Full-spectrum complex-phase fluorescent ceramic and preparation method and application thereof - Google Patents
Full-spectrum complex-phase fluorescent ceramic and preparation method and application thereof Download PDFInfo
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- CN118324529A CN118324529A CN202410464029.9A CN202410464029A CN118324529A CN 118324529 A CN118324529 A CN 118324529A CN 202410464029 A CN202410464029 A CN 202410464029A CN 118324529 A CN118324529 A CN 118324529A
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- 238000001228 spectrum Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 83
- 238000005245 sintering Methods 0.000 claims abstract description 79
- 150000004767 nitrides Chemical class 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 10
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- 239000002994 raw material Substances 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
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- 229910052582 BN Inorganic materials 0.000 claims description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
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- 238000003825 pressing Methods 0.000 claims description 4
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- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention provides a full spectrum complex phase fluorescent ceramic, a preparation method and application thereof, wherein the complex phase fluorescent ceramic consists of a nitride phase and an oxide phase, the chemical composition of the nitride phase is Ca 1‑x‑ySryAlSiN3 xEu (x is more than 0 and less than or equal to 0.03, y is more than 0 and less than or equal to 1), and the crystal structure is the same as CaAlSiN 3; the oxide phase has a chemical composition (Lu1‑x‑a‑bYaGdb)3(Al1‑cGac)5O12:xCe(0<x≤0.06,0≤a<1,0≤b<1,0≤c<1,0≤a+b<1), and its crystal structure is identical to Lu 3Al5O12. According to the invention, the ceramic sintering in a short time and the rapid temperature rise and drop rate are used for effectively slowing down the grain growth in the ceramic sintering process, and the nitride powder is enabled not to be decomposed greatly or sintered so as to be disabled while forming an oxide phase in situ in the short-time sintering process. In short, by the short-time high-temperature pulse sintering, the sintering densification of the complex phase ceramic is promoted, and the sudden drop of luminous efficiency caused by the oxidation of the nitride phase in the long-time high-temperature process is avoided.
Description
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to full-spectrum complex-phase fluorescent ceramic, and a preparation method and application thereof.
Background
In 2022, the total yield of semiconductor lighting and display industry in China is about 14000 hundred million Yuan people's coins, which makes a great contribution to realizing the double-carbon strategic goal in China. With the development of economy and society, ultra-high brightness light sources are needed in military fields such as fighter formation lights, air refueling guide lights of a conveyor and deep sea searchlights of a submarine, and in civil fields such as illumination lights of a cargo area of a passenger plane, landing skid lights, intelligent projection headlamps of an automobile and the like. The white light source constructed by taking the ultra-high brightness laser as the excitation light source has good light emitting directivity and more compact structure, and causes the wide attention of the industry personnel and the rapid development of the related technology. Village two among the nobel physical prize acquirer, blue LED inventor, states "in the future, laser illumination or will replace LED illumination". High energy density lasers are used as excitation light sources to impose stringent requirements on structural stability, thermal conductivity, irradiation resistance and the like of fluorescent conversion materials. The traditional technology of adopting organic silica gel to encapsulate fluorescent powder is eliminated (the organic silica gel is easy to be carbonized under high-energy-density laser irradiation), and the development of all-inorganic fluorescent block materials is not two choices.
As shown in the schematic diagram 3, the conventional technology of encapsulating fluorescent powder with organic silica gel is easy to generate carbonization failure under the irradiation of a high-power density light source, and development of a new generation of all-inorganic fluorescent conversion material is urgently needed. By sintering the fluorescent powder into fluorescent ceramic at high temperature, the fluorescent ceramic has the advantages of high temperature resistance, high reliability and the like, so that the all-inorganic fluorescent ceramic becomes an ideal new generation light conversion material and is also a new research direction in the field of matched materials in the semiconductor lighting and display industry.
If garnet structural compound ((Lu1-x-a-bYaGdb)3(Al1-cGac)5O12:xCe(0<x≤0.06,0≤a<1,0≤b<1,0≤c<1,0≤a+b<1)) and nitride (Ca 1-x-ySryAlSiN3: xEu (0 < x is less than or equal to 0.03,0< y is less than or equal to 1)) realize the sintering preparation of integrated complex-phase fluorescent ceramic, the full-spectrum fluorescent ceramic with high reliability is obtained, and then the development requirement of the new-generation semiconductor lighting and display industry is met. However, in the conventional sintering method, the nitride is severely oxidized during the sintering process at high temperature and for a long time, and thus the luminous efficiency is drastically reduced, and even if the rapid spark plasma sintering is used, the sintering time is sufficient for the reaction between the nitride and the oxide, so that a more rapid sintering method is required to avoid the reaction between the two.
Patent document CN115490508a discloses a composite fluorescent ceramic for white light LD lighting, which is formed by a layer-by-layer casting method and further sintered by an oxide ceramic layer ((Y 3-□xCex)3Al5O12, 0.001. Ltoreq.x.ltoreq.0.01), a oxynitride ceramic layer (Si 6-yAlyOyN8-y:Eu2+, 0.2. Ltoreq.y.ltoreq.2) and a nitride ceramic layer (CaAlSiN 3:Eu2+) from bottom to top.
Patent document CN111285682a discloses a full spectrum complex phase fluorescent ceramic for laser illumination and display and a preparation method, and adopts a scheme of preparing full spectrum complex phase fluorescent ceramic by combining two phases. In the scheme, both phases are oxides with garnet structures, and the spectrum of the composite fluorescent ceramic is not completely covered to a full spectrum band due to the limitation of the spectrum of the phases of the components.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides full-spectrum complex-phase fluorescent ceramic as well as a preparation method and application thereof.
In order to achieve the above object, in a first aspect, the present invention provides a full spectrum complex phase fluorescent ceramic, which is composed of two phases of a nitride phase and an oxide phase, wherein the chemical composition of the nitride phase is Ca 1-x- ySryAlSiN3 xEu (0 < x.ltoreq.0.03, 0< y.ltoreq.1), and the crystal structure is the same as CaAlSiN 3; the oxide phase has a chemical composition (Lu1-x-a-bYaGdb)3(Al1-cGac)5O12:xCe(0<x≤0.06,0≤a<1,0≤b<1,0≤c<1,0≤a+b<1), and its crystal structure is identical to Lu 3Al5O12.
In one embodiment, the weight ratio of nitride phase to oxide phase in the complex phase fluorescent ceramic is 1:5 to 1:15.
In one embodiment, x=0.008 and y=0 in the nitride phase; x=0.01 in the oxide phase, a=b=c=0.
In one embodiment, the complex phase fluorescent ceramic emits fluorescence with a wavelength in the range of 480-780 nanometers when excited by a blue light source.
In a second aspect, the invention provides a method for preparing full spectrum complex phase fluorescent ceramics, comprising the following steps:
Preparing nitride phase powder;
Weighing and mixing high-purity Lu 2O3 powder, Y 2O3 powder, gd 2O3 powder, al 2O3 powder, ga 2O3 powder, ceO 2 powder and nitride phase powder according to the weight ratio of different nitride phases to different oxide phases to obtain a raw material mixture; putting the raw material mixture into a mortar, sequentially adding a dispersing agent, a fluxing agent and alcohol into the mortar, and grinding the raw material mixture to uniformly mix the raw materials to obtain the raw material mixture;
Carrying out dry press molding on the raw material mixture to obtain a complex-phase fluorescent ceramic block ceramic green body;
and (3) placing the obtained complex-phase fluorescent ceramic block ceramic green body into a muffle furnace for glue discharging, and performing in-situ rapid sintering in a vacuum Joule furnace after cold isostatic pressing to obtain the full-spectrum complex-phase fluorescent ceramic.
In one embodiment, preparing nitride phase powder includes:
Weighing and mixing high-purity Ca 3N2、Sr3N2、AlN、Si3N4 and EuN serving as raw material powder in a glove box according to a composition general formula Ca 1-x-ySryAlSiN3:xEu (x is more than 0 and less than or equal to 0.03, y is more than 0 and less than or equal to 1) to obtain raw material mixed powder, putting the obtained raw material mixed powder into a high-purity boron nitride crucible, then putting the high-purity boron nitride crucible into a pneumatic furnace, sintering at 1600-1800 ℃ and nitrogen pressure of 0.9 MPa, keeping the temperature for 4-10 hours, and cooling to obtain Ca 1-x-ySryAlSiN3:xEu red fluorescent powder, namely nitride phase powder.
In one embodiment, the method of preparing Lu 2O3 powder includes:
Dissolving 6-10 g of Lu 2O3 micro powder in 20ml of nitric acid, reacting for 24 hours in a reaction kettle at 80 ℃, adding 8-12 ml of supersaturated ammonium bicarbonate solution, reacting for 4 hours, stirring, taking out, centrifuging for 3-5 times by using ionized water or ethanol, putting into an 80 ℃ oven for drying, taking out, grinding, moving into a muffle furnace, and roasting for 2 hours at 900 ℃ to obtain Lu 2O3 powder.
In one embodiment, the dispersing agent is ammonium citrate, the additive amount is 1-5 wt%, the fluxing agent is ethyl orthosilicate, the additive amount is 0.1-1 wt%, and the alcohol addition amount is 5-6 ml; the pressurizing pressure of the dry-pressing molding is 20-60 kilonewtons, and the pressure maintaining time is 2-6 minutes.
In one embodiment, the glue discharging condition in the muffle furnace is 550 ℃ and the glue discharging time is 12-16 hours; the cold isostatic pressure is 250 megapascals, and the dwell time is 180 seconds; and (3) in-situ rapid sintering, wherein a ceramic green body is fixed through a sintering medium, the sintering temperature is 1500-1700 ℃, the sintering time is 8-20 seconds, and the nitrogen protection atmosphere or the vacuum environment with the vacuum degree not higher than 0.001 Pa.
In a third aspect, the invention provides an application of full-spectrum complex-phase fluorescent ceramics in the field of laser illumination.
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the ceramic sintering in a short time and the rapid temperature rise and drop rate are used for effectively slowing down the grain growth in the ceramic sintering process, and the nitride powder is enabled not to be decomposed greatly or sintered so as to be disabled while forming an oxide phase in situ in the short-time sintering process. In short, by the short-time high-temperature pulse sintering, the sintering densification of the complex phase ceramic is promoted, and the sudden drop of luminous efficiency caused by the oxidation of the nitride phase in the long-time high-temperature process is avoided.
(2) By adjusting the proportion of the red luminescent material and the green luminescent material, the full spectrum adjustable complex-phase fluorescent ceramic capable of fluorescence in the range of 480-780 nanometers is realized, and the complex-phase fluorescent ceramic with high color rendering index is realized, the maximum color rendering index is higher than 90, and the maximum color rendering index can reach 92. The prepared nano fluorescent ceramic can be effectively excited by an ultraviolet light or blue light source, has the advantages of adjustable color, long service life and the like, and can be expected to be widely applied and developed in the field of laser illumination.
(3) In the invention, the full spectrum complex phase fluorescent ceramic is prepared by adopting the Joule heating equipment, and the oxide phase of the part is sintered in situ, so that the operation is simple and the preparation speed is high. The sintering method is shortened from tens of hours to seconds, so that the energy consumption in the preparation process is successfully saved, and the time cost and the energy cost for producing the complex-phase fluorescent ceramics are reduced.
Drawings
FIG. 1 is a schematic view of the principle of the Joule-thermal-sintered ceramic of the present invention;
FIG. 2 is a schematic illustration of a Ca 0.992AlSiN3:0.008 Eu powder coating;
FIG. 3 is a schematic diagram of the package of a conventional light conversion material and a schematic diagram of the structure and light path of the prepared complex-phase fluorescent ceramic;
FIG. 4 is a spectrum of the complex phase fluorescent ceramics prepared at different sintering temperatures in example 1;
FIG. 5 is an electron microscope image of the complex phase fluorescent ceramics prepared in example 2 under the conditions of a sintering temperature of 1625 ℃ and a time of 9-13 seconds;
FIG. 6 is an XRD pattern of a complex phase fluorescent ceramic prepared in example 3 under conditions of a sintering temperature of 1625 degrees Celsius, a sintering time of 10 seconds, and a weight ratio of nitride phase to oxide phase of 1:5 to 1:15;
FIG. 7 is a spectrum diagram of a complex phase fluorescent ceramic prepared in example 3 under conditions that the sintering temperature is 1625 ℃, the sintering time is 10 seconds, and the weight ratio of nitride phase to oxide phase is 1:5-1:15;
FIG. 8 is a graph showing the color of the complex phase fluorescent ceramics prepared in example 3 under the conditions of a sintering temperature of 1625 degrees Celsius, a sintering time of 10 seconds, and a weight ratio of nitride phase to oxide phase of 1:5 to 1:15.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, the invention provides a full spectrum complex phase fluorescent ceramic, which consists of two phases of nitride phase and oxide phase, wherein the chemical composition of the nitride phase is Ca 1-x-ySryAlSiN3 xEu (x is more than 0 and less than or equal to 0.03, y is more than 0 and less than or equal to 1), and the crystal structure of the complex phase fluorescent ceramic is the same as that of CaAlSiN 3; the oxide phase has a chemical composition (Lu1-x-a-bYaGdb)3(Al1-cGac)5O12:xCe(0<x≤0.06,0≤a<1,0≤b<1,0≤c<1,0≤a+b<1), and its crystal structure is identical to Lu 3Al5O12.
In these numerical ranges, red and green fluorescent materials that perform well and meet the emission band can be prepared.
When the oxide phase is Lu 3Al5O12:Ce3+, lu 3Al5O12:Ce3+ is formed in situ, and Ce 3+ in Lu 3Al5O12:Ce3+ is used as a luminescence center and an activator, and the doping ratio is 0.6at.%. The crystal of Lu 3Al5O12:Ce3+ is formed in a pure phase, the crystal phase thereof is formed in a compact block manner, and in the structure of the complex phase fluorescent ceramic, when the nitride phase is CaAlSiN 3:Eu2 +, the formed Lu 3Al5O12:Ce3+ and CaAlSiN 3:Eu2+ powder are contacted with each other, so that a relatively compact structure can be formed.
Wherein the prepared nitride phase is fired at high temperature under high nitrogen pressure in an air pressure furnace. The oxide phase is formed in situ during the ceramic sintering process, and after crystallization, it can form a pure phase and be formed in the form of a dense block. The luminescent center and the activator in the luminescent phase are cerium ions (Ce 3+), and the doping proportion is 0-0.06 (at.).
Further, x=0.008 in the nitride phase and y=0; x=0.01 in the oxide phase, a=b=c=0. I.e. the preferred value in nitride x=0.008, y=0. The preferred value in the oxide is x=0.01, a=b=c=0. The complex-phase fluorescent ceramic prepared at the moment can cover a wider emission band, has high efficiency, and can have a color rendering index of more than 90 and up to 92, and under the preferable conditions:
when the weight ratio of the nitride phase to the oxide phase is 1:3-1:5 and above 1:15, the sintering temperature is 1500-1700 ℃, and when the sintering time is 8-20 seconds, the color rendering index is less than or equal to 70.
When the weight ratio of the nitride phase to the oxide phase is 1:7 and 1:13, the sintering temperature is 1500-1700 ℃, and when the sintering time is 8-20 seconds, the obtained color rendering index is 75-78.
When the weight ratio of the nitride phase to the oxide phase is 1:9-1:11, the sintering temperature is 1500-1700 ℃, and when the sintering time is 8-20 seconds, the obtained color rendering index is more than or equal to 88.
Further, the weight ratio of the nitride phase to the oxide phase in the complex-phase fluorescent ceramic is 1:5-1:15. The weight ratio can be used for preparing the complex-phase fluorescent ceramics with adjustable emission color from red to yellow-green. Preferably, when the weight ratio of the nitride phase to the oxide phase is 1:9-1:11, the color rendering index of the obtained complex-phase fluorescent ceramic reaches the highest value, and the color rendering index of the complex-phase fluorescent ceramic prepared by the ratio in the interval is more than or equal to 88.
Further, the complex-phase fluorescent ceramic can emit fluorescence with the wavelength covering 480-780 nm under the excitation of a blue light source (with the wavelength of 440-470 nm).
By adjusting the proportion of the nitride phase (red fluorescent phase) to the oxide phase (green fluorescent phase), the full-spectrum adjustable fluorescent ceramic capable of fluorescence in the range of 480-780 nanometers is realized, the wide regulation and control of the emission spectrum in the visible light region can be realized, and further the complex-phase fluorescent ceramic with high color rendering index can be realized.
In a second aspect, the invention also provides a preparation method of the full-spectrum complex-phase fluorescent ceramic, which can synthesize the complex-phase fluorescent ceramic in situ. The joule heat pulse joule heat apparatus is used to raise the temperature to 1500-1700 deg.c in short time by joule effect, and the schematic diagram is shown in fig. 1. The complex-phase fluorescent ceramic prepared by the method does not need to be subjected to heat treatment and other processes. The full spectrum complex phase fluorescent ceramics mixed with nitride and oxide can be directly synthesized at one time under the conditions of heating rate of 10 5 ℃ per second and pulse heating rate of 1500-1700 ℃ within 20 seconds and nitrogen protection atmosphere or vacuum environment with vacuum degree not higher than 0.001 Pa, and the specific steps comprise:
S1, preparing nitride phase powder;
S2, weighing and mixing high-purity Lu 2O3 powder, Y 2O3 powder, gd 2O3 powder, al 2O3 powder, ga 2O3 powder, ceO 2 powder and nitride phase powder according to different weight ratios of nitride phase to oxide phase to obtain a raw material mixture; putting the raw material mixture into a mortar, sequentially adding a dispersing agent, a fluxing agent and alcohol into the mortar, and grinding the raw material mixture to uniformly mix the raw materials to obtain the raw material mixture;
Wherein, the purity is high, namely, the purity is more than 99.99 percent; meanwhile, lu 2O3 powder is prepared by oneself, and besides Y 2O3 powder, gd 2O3 powder, al 2O3 powder, ga 2O3 powder and CeO 2 powder are all commercial powder;
S3, carrying out dry press molding on the raw material mixture to obtain a complex-phase fluorescent ceramic block ceramic green body;
And S4, placing the obtained green compact of the complex-phase fluorescent ceramic block into a muffle furnace for glue discharging, and performing in-situ rapid sintering in a vacuum Joule furnace after cold isostatic pressing to obtain the complex-phase fluorescent ceramic with full spectrum.
Further, preparing nitride phase powder, including:
Weighing and mixing high-purity Ca 3N2、Sr3N2、AlN、Si3N4 and EuN serving as raw material powder in a glove box according to a composition general formula Ca 1-x-ySryAlSiN3:xEu (x is more than 0 and less than or equal to 0.03, y is more than 0 and less than or equal to 1) to obtain raw material mixed powder, putting the obtained raw material mixed powder into a high-purity boron nitride crucible, then putting the high-purity boron nitride crucible into a pneumatic furnace, sintering at 1600-1800 ℃ and nitrogen pressure of 0.9 MPa, keeping the temperature for 4-10 hours, and cooling to obtain Ca 1-x-ySryAlSiN3:xEu red fluorescent powder, namely nitride phase powder.
Further, the preparation method of the Lu 2O3 powder comprises the following steps:
Dissolving 6-10 g of Lu 2O3 micro powder in 20 ml of nitric acid, reacting for 24 hours in a reaction kettle at 80 ℃, adding 8-12 ml of supersaturated ammonium bicarbonate solution, reacting for 4 hours, stirring, taking out, centrifuging for 3-5 times by using ionized water or ethanol, putting into an 80 ℃ oven for drying, taking out, grinding, moving into a muffle furnace, and roasting for 2 hours at 900 ℃ to obtain Lu 2O3 powder. Wherein, the addition amount of Lu 2O3 is preferably 8 g, and the addition amount of supersaturated ammonium bicarbonate solution is preferably 10 ml.
Further, the dispersing agent is ammonium citrate, the additive amount is 1-5 wt%, the fluxing agent is ethyl orthosilicate, the additive amount is 0.1-1 wt%, and the alcohol addition amount is 5-6 ml; the pressurizing pressure of the dry-pressing molding is 20-60 kilonewtons, and the pressure maintaining time is 2-6 minutes.
Furthermore, the glue discharging condition in the muffle furnace is 550 ℃, and the glue discharging time is 12-16 hours; the cold isostatic pressure is 250 megapascals, and the dwell time is 180 seconds; and (3) in-situ rapid sintering, namely fixing the ceramic green body by using a sintering medium carbon cloth, wherein the sintering temperature is 1500-1700 ℃, the sintering time is 8-20 seconds, and the nitrogen protection atmosphere or the vacuum degree is not higher than 0.001 Pa. Under the condition, the ceramic with good density and good luminous efficiency can be synthesized.
Preferably, the dispersant additive amount is 2wt.%, the flux additive amount is 1wt.%; the pressurizing pressure of the dry-pressing forming is 40 kilonewtons, and the pressure maintaining time is 3 minutes; the glue discharging time is 12 hours; the sintering temperature was 1650 degrees celsius and the sintering time was 10 seconds under nitrogen atmosphere.
In a third aspect, the invention provides an application of full-spectrum complex-phase fluorescent ceramics in the field of laser illumination.
The invention has been tested several times in succession, and the invention will now be described in further detail with reference to a few test results, which are described in detail below in connection with specific examples.
Example 1
A preparation method of full spectrum complex phase fluorescent ceramics comprises the following steps:
Step one, preparing nitride phase powder
Weighing and mixing high-purity Ca 3N2、AlN、Si3N4 and EuN serving as raw material powder in a glove box according to a general formula Ca 0.992AlSiN3:0.008 Eu to obtain raw material mixed powder, putting the obtained raw material mixed powder into a high-purity boron nitride crucible, then putting the crucible into a pneumatic furnace, sintering at 1750 ℃ under nitrogen pressure of 0.9 MPa for 8 hours, and cooling to obtain Ca 0.992AlSiN3:0.008 Eu red fluorescent powder, namely nitride phase powder;
Step two, preparing Lu 2O3 powder
Dissolving 8 g of Lu 2O3 micro-powder in 20 ml of nitric acid, reacting for 24 hours in a reaction kettle at 80 ℃, adding 10 ml of supersaturated ammonium bicarbonate solution, reacting for 4 hours, stirring, taking out, centrifuging for 5 times by using ionized water, putting into an 80 ℃ oven for drying, taking out, grinding, moving into a muffle furnace, and roasting for 2 hours at 900 ℃ to obtain Lu 2O3 powder;
Step three, preparing a raw material mixture
Weighing and mixing high-purity Lu 2O3 powder, Y 2O3 powder, gd 2O3 powder, al 2O3 powder, ga 2O3 powder, ceO 2 powder and nitride phase powder with the weight ratio of nitride phase to oxide phase being 1:9 to obtain a raw material mixture; putting the raw material mixture into a mortar, sequentially adding 2wt.% of ammonium citrate, 1wt.% of tetraethoxysilane and 6ml of alcohol into the mortar, and grinding the mixture to uniformly mix the raw materials to obtain the raw material mixture;
step four, preparing a complex-phase fluorescent ceramic block ceramic green body
Weighing 0.16 g of raw material mixture, placing the raw material mixture into a die with the diameter of 10 mm, maintaining the pressure for 3 minutes under the pressure of 40 kilonewtons to obtain a fluorescent ceramic green body, then moving the fluorescent ceramic green body into a muffle furnace, discharging glue for 12 hours under the temperature of 550 ℃, and after the glue discharge is completed, performing cold isostatic pressing under the pressure of 250 megapascals, and maintaining the pressure for 3 minutes to finally obtain a complex-phase fluorescent ceramic blocky ceramic green body;
Step five, sintering
And sintering the complex-phase fluorescent ceramic block ceramic green body in a nitrogen atmosphere by using a pulse Joule heat sintering method, wherein the sintering temperature is 1600-1675 ℃, the sintering time is 10 seconds, and the complex-phase fluorescent ceramic is prepared by sintering.
The spectrum is shown in fig. 4, and it can be seen that the spectrum can better cover the range of 480-780 nm and the green spectrum part is better at the sintering temperature of 1650 ℃.
Example 2
The difference from example 1 is that the sintering temperature is 1625 degrees celsius and the time is 9 to 13 seconds.
The electron micrograph is shown in FIG. 5, which shows that the porosity in the ceramic is minimal at a firing time of 10 seconds. In all sintered complex-phase fluorescent ceramics, the red-emitting nitride phase is distributed very uniformly therein.
Example 3
The difference from example 1 is that the sintering temperature is 1625 degrees celsius, the sintering time is 10 seconds, and the weight ratio of red-emitting nitride to green-emitting oxide is 1:5 to 1:15.
As can be seen in the X-ray diffraction pattern of FIG. 6, these proportions of the complex phase fluorescent ceramic all form a pure Lu 3Al5O12 phase, and the presence of peaks of the CaAlSiN 3 phase can be seen therein. It can be seen from the emission spectrum of fig. 7 that the complex-phase fluorescent ceramics with the weight ratio of 1:9 to 1:11 can cover a more complete spectrum band of 480 to 780 nm, and the color coordinates of the complex-phase fluorescent ceramics can be seen from the color coordinates of the color coordinates to move from yellow to red along with the increase of the weight ratio of the red-emitting nitride phase to the green-emitting oxide phase in fig. 8.
Example 4:
The difference from example 1 is that the spark plasma sintering method is used, the sintering temperature is 1625 ℃, and the sintering heat preservation time is 5 minutes.
The efficiency of the obtained complex-phase fluorescent ceramic is shown in Table 1, and the internal quantum efficiency is 25% and the absorptivity is 0.68.
Example 5:
the difference from example 1 is that the pulsed joule heating sintering method was used, the sintering temperature was 1625 degrees celsius and the sintering time was 10 seconds.
The efficiency of the obtained complex-phase fluorescent ceramic is shown in Table 1, and the internal quantum efficiency is 38% and the absorptivity is 0.78.
Example 6:
Step one, preparing nitride phase powder
Weighing and mixing high-purity Ca 3N2、AlN、Si3N4 and EuN serving as raw material powder in a glove box according to a general formula Ca 0.992AlSiN3:0.008 Eu to obtain raw material mixed powder, putting the obtained raw material mixed powder into a high-purity boron nitride crucible, then putting the crucible into a pneumatic furnace, sintering at 1750 ℃ under nitrogen pressure of 0.9 MPa for 8 hours, and cooling to obtain Ca 0.992AlSiN3:0.008 Eu red fluorescent powder, namely nitride phase powder; coating the prepared nitride phase powder by using an atomic layer deposition device, and coating an AlN layer with the thickness of 15 nanometers on the nitride phase powder to obtain coated nitride phase powder, wherein the schematic diagram is shown in figure 2;
Step two, preparing Lu 2O3 powder
Preparation of Lu 2O3 powder was consistent with example 1;
Step three, preparing a raw material mixture
The raw material mixture was prepared in accordance with example 1;
step four, preparing a complex-phase fluorescent ceramic block ceramic green body
Preparing a green compact of the complex-phase fluorescent ceramic block ceramic in accordance with example 1;
Step five, sintering
Sintering the complex-phase fluorescent ceramic block ceramic green body in a nitrogen atmosphere by using a pulse Joule heat sintering method, wherein the sintering temperature is 1625 ℃, the sintering time is 10 seconds, and the complex-phase fluorescent ceramic block ceramic green body is sintered into full spectrum complex-phase fluorescent ceramic;
The efficiency of the obtained complex-phase fluorescent ceramic is shown in Table 1, the internal quantum efficiency is 60%, the absorptivity is 0.81, and the color rendering index is 92.
The full spectrum complex phase fluorescent ceramics prepared in examples 4-6 are detected, and the detection results are shown in table 1;
table 1:
| Example 4 | Example 5 | Example 6 | |
| Internal quantum efficiency | 25％ | 38％ | 60％ |
| Absorption rate | 0.68 | 0.78 | 0.81 |
In example 6, comparative example 5, after coating, the prepared complex-phase fluorescent ceramic has higher efficiency because the red-emitting nitride phase can be effectively protected from reaction during high-temperature sintering after coating, thereby making the sintered complex-phase fluorescent ceramic have higher efficiency.
According to the preparation method disclosed by the invention, the grain growth in the ceramic sintering process is effectively slowed down in the short-time ceramic sintering and faster temperature rising and falling rate, and the nitride powder is enabled not to be greatly decomposed or sintered so as to be disabled while being in-situ to form an oxide phase in the short-time sintering process. Not only promotes the sintering densification of the two types of ceramics, but also avoids the reduction of luminous efficiency caused by oxidation of nitride phases in the long-time high-temperature process.
The full-spectrum complex-phase fluorescent ceramic prepared by the method has application prospect in the field of laser illumination, has higher internal quantum efficiency by optimizing the preparation process and sintering conditions, and has a maximum color rendering index higher than 90. The integrated full-spectrum complex-phase fluorescent ceramic has great advantages under the excitation of heat dissipation and high-power blue laser, and has great application potential in the field of full-spectrum laser illumination.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A full spectrum complex phase fluorescent ceramic is characterized in that the complex phase fluorescent ceramic consists of a nitride phase and an oxide phase, wherein the chemical composition of the nitride phase is Ca 1-x-ySryAlSiN3 xEu (x is more than or equal to 0.03 and y is more than or equal to 0 and less than or equal to 1), and the crystal structure of the complex phase fluorescent ceramic is the same as that of CaAlSiN 3; the oxide phase has a chemical composition (Lu1-x-a-bYaGdb)3(Al1-cGac)5O12:xCe(0<x≤0.06,0≤a<1,0≤b<1,0≤c<1,0≤a+b<1), and its crystal structure is identical to Lu 3Al5O12.
2. The full spectrum complex phase fluorescent ceramic of claim 1, wherein the weight ratio of nitride phase to oxide phase in the complex phase fluorescent ceramic is 1:5-1:15.
3. A full spectrum complex phase fluorescent ceramic according to claim 1, wherein x = 0.008 and y = 0 in the nitride phase; x=0.01 in the oxide phase, a=b=c=0.
4. The full spectrum complex phase fluorescent ceramic of claim 1, wherein the complex phase fluorescent ceramic emits fluorescent light with a wavelength in the range of 480-780 nm under excitation of a blue light source.
5. A method of preparing a full spectrum, complex phase fluorescent ceramic according to any one of claims 1 to 4, comprising:
Preparing nitride phase powder;
Weighing and mixing high-purity Lu 2O3 powder, Y 2O3 powder, gd 2O3 powder, al 2O3 powder, ga 2O3 powder, ceO 2 powder and nitride phase powder according to the weight ratio of different nitride phases to different oxide phases to obtain a raw material mixture; putting the raw material mixture into a mortar, sequentially adding a dispersing agent, a fluxing agent and alcohol into the mortar, and grinding the raw material mixture to uniformly mix the raw materials to obtain the raw material mixture;
Carrying out dry press molding on the raw material mixture to obtain a complex-phase fluorescent ceramic block ceramic green body;
and (3) placing the obtained complex-phase fluorescent ceramic block ceramic green body into a muffle furnace for glue discharging, and performing in-situ rapid sintering in a vacuum Joule furnace after cold isostatic pressing to obtain the full-spectrum complex-phase fluorescent ceramic.
6. The method for preparing full spectrum complex phase fluorescent ceramic according to claim 5, wherein preparing nitride phase powder comprises:
Weighing and mixing high-purity Ca 3N2、Sr3N2、AlN、Si3N4 and EuN serving as raw material powder in a glove box according to a composition general formula Ca 1-x-ySryAlSiN3:xEu (x is more than 0 and less than or equal to 0.03, y is more than 0 and less than or equal to 1) to obtain raw material mixed powder, putting the obtained raw material mixed powder into a high-purity boron nitride crucible, then putting the high-purity boron nitride crucible into a pneumatic furnace, sintering at 1600-1800 ℃ and nitrogen pressure of 0.9 MPa, keeping the temperature for 4-10 hours, and cooling to obtain Ca 1-x-ySryAlSiN3:xEu red fluorescent powder, namely nitride phase powder.
7. The method for preparing full spectrum complex phase fluorescent ceramic according to claim 5, wherein the method for preparing Lu 2O3 powder comprises:
Dissolving 6-10 g of Lu 2O3 micro powder in 20ml of nitric acid, reacting for 24 hours in a reaction kettle at 80 ℃, adding 8-12 ml of supersaturated ammonium bicarbonate solution, reacting for 4 hours, stirring, taking out, centrifuging for 3-5 times by using ionized water or ethanol, putting into an 80 ℃ oven for drying, taking out, grinding, moving into a muffle furnace, and roasting for 2 hours at 900 ℃ to obtain Lu 2O3 powder.
8. The preparation method of full spectrum complex phase fluorescent ceramic according to claim 5, wherein the dispersant is ammonium citrate, the additive amount is 1-5 wt%, the fluxing agent is ethyl orthosilicate, the additive amount is 0.1-1 wt%, and the alcohol addition amount is 5-6 ml; the pressurizing pressure of the dry-pressing molding is 20-60 kilonewtons, and the pressure maintaining time is 2-6 minutes.
9. The preparation method of full spectrum complex phase fluorescent ceramics according to claim 5, which is characterized in that the glue discharging condition in a muffle furnace is 550 ℃ and the glue discharging time is 12-16 hours; the cold isostatic pressure is 250 megapascals, and the dwell time is 180 seconds; and (3) in-situ rapid sintering, wherein a ceramic green body is fixed through a sintering medium, the sintering temperature is 1500-1700 ℃, the sintering time is 8-20 seconds, and the nitrogen protection atmosphere or the vacuum environment with the vacuum degree not higher than 0.001 Pa.
10. Use of the full spectrum complex phase fluorescent ceramic according to claims 1-4 in the field of laser illumination.
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