CN108753296B - Red light luminescent material capable of being excited by near ultraviolet or blue light chip and preparation method and application thereof - Google Patents

Red light luminescent material capable of being excited by near ultraviolet or blue light chip and preparation method and application thereof Download PDF

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CN108753296B
CN108753296B CN201810796604.XA CN201810796604A CN108753296B CN 108753296 B CN108753296 B CN 108753296B CN 201810796604 A CN201810796604 A CN 201810796604A CN 108753296 B CN108753296 B CN 108753296B
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red light
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transparent ceramic
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ceramic
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CN108753296A (en
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李晓东
马畅
任轶
孙旭东
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Northeastern University China
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Abstract

The invention relates to a red light luminescent material capable of being excited by a near ultraviolet or blue light chip, which has the chemical composition general formula: (RE)1‑x‑y‑z‑mLamZryMgz)2O3X is more than or equal to 0.01 and less than or equal to 0.2, y is more than or equal to 0.001 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.1, and m is more than or equal to 0 and less than or equal to 0.2, wherein RE is Lu1‑p‑rYpGdr，0≤p<1，0≤r<1. The red light luminescent material has wide excitation spectrum coverage range and can be matched with a near ultraviolet or blue light LED chip. The red light luminescent material product comprises a red light rubber powder material, a red light transparent ceramic material and a red light transparent film material. In addition, the red light luminescent material can be combined with blue, green and yellow fluorescent materials (YAG: Ce) for use, and can be packaged with near ultraviolet or blue light chips in different forms for manufacturing white light LED lighting sources.

Description

Red light luminescent material capable of being excited by near ultraviolet or blue light chip and preparation method and application thereof
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a red luminescent material excited by a near ultraviolet or blue light chip, and a preparation method and application thereof.
Background
The white light diode (WLED) is used as a novel solid light source, has the obvious advantages of high luminous efficiency, small volume, long service life, low power consumption, quick response, environmental protection, safety, reliability and the like, and is expected to be widely applied to the fields of indoor illumination, liquid crystal display backlight sources, aviation navigation, identification mark illumination, outdoor illumination, medical treatment, communication and the like in the future. Thus, the market economic benefit of the white light LED is quite considerable.
At present, the most common and commercialized white LED is prepared by using InGaN/GaN blue LED chip with Ce doped3+Y of (A) is3Al5O12The yellow phosphor powder of Ce (YAG: Ce), namely, the InGaN/GaN chip emits blue light to excite the YAG: Ce phosphor powder, and the generated yellow light is mixed with the transmitted blue light to realize white light emission. However, the method has the defects of high color temperature, soft light and low color rendering index of the generated white light due to the lack of red light components in the emission spectrum, and cannot meet the requirements of high-performance devices. By co-doping Tb in YAG to Ce powder3+，Gd3+The rare earth ions can make Ce3+The peak position of the emission peak of (1) is red-shifted, but the shift range thereof is very limited, so that the effect of improving the color temperature is not significant.
Another commonly used white LED is a near-ultraviolet LED chip with three primary colors (red, green, and blue) phosphor, i.e., a white light is formed by mixing red, green, and blue light. The method is easier to realize white light with stable light emitting color, and the color rendering index and the light output efficiency of the method are superior to those of a blue light LED chip and yellow fluorescent powder. However, among the three primary colors of phosphors currently used for near-ultraviolet LED chips, red phosphor has a technical challenge to blue phosphor and green phosphor. For example, sulfide Y has been commercialized2O2S:Eu3+The red fluorescent powder can not be effectively absorbed in a near ultraviolet band, so that the luminous intensity of the red fluorescent powder is far lower than that of commercial efficient green fluorescent powder and blue fluorescent powder. And, under excitation of near ultraviolet light, Y2O2S:Eu3+Has poor chemical stability and thermal stability, and is easy to release H harmful to human health2S gas, which is not friendly to the surrounding environment; nitrogen is present inAlthough the red fluorescent powder of the compound and the nitrogen oxide has good physicochemical properties and higher luminous efficiency, the preparation conditions are very harsh, and the red fluorescent powder can be prepared only by keeping the temperature for a long time at high temperature (1400-2000 ℃) in a nitrogen atmosphere. As can be seen, these deficiencies of red light emitting materials have been barriers to further development of white LEDs.
As one of the red fluorescent powder materials which are most widely applied in the fields of illumination and display at present, Y2O3The Eu fluorescent powder has excellent red light emission, high luminous efficiency, high color purity, stable physical and chemical properties and good light attenuation characteristics. Albeit Y2O3The Eu fluorescent powder has excellent red fluorescence performance under the excitation of cathode ray or short ultraviolet band (210-250nm), but has poor absorption to near ultraviolet and blue light, and can not be effectively matched with near ultraviolet and blue light LED chips.
Therefore, a red light material capable of being efficiently excited by a blue light LED chip or a near ultraviolet LED chip is developed, so that the red light material can be combined with the existing commercial fluorescent material to be applied to a white light LED, the deficiency of red light components is made up, the emission of warm white light is realized, and the red light material has very important significance and wide market economic application value.
On the other hand, in the conventional white LED packaging technology, phosphor is uniformly dispersed in an epoxy resin or silica gel layer to form phosphor gel to fix an LED chip, but these organic polymer packaging materials have low thermal conductivity and poor heat dissipation performance, and increase the temperature of a packaging layer during continuous lighting of an LED causes reduction in the luminous efficiency of the phosphor, and the organic polymer packaging materials undergo chemical reaction at high temperature, so that they age and deteriorate, and greatly affect the light output of an LED device. Especially in the application of high-power LED devices, the service life and the quality of the device can be directly influenced by the packaging scheme. Meanwhile, the packaging process is complicated, the coating thickness of the mixed layer of the fluorescent powder and the packaging material on the surface of the chip is difficult to control, uneven emission light is easy to cause, and the wide application of the fluorescent powder and the packaging material is limited to a certain extent.
In order to solve such problems, in recent years, fluorescent transparent ceramics and fluorescent transparent films have come into the field of vision as novel optically functional materials. Compared with epoxy resin and silica gel, the fluorescent transparent ceramic and the fluorescent transparent film have good thermal conductivity and thermal stability, can resist light decay, reduce scattering loss and are beneficial to obtaining high-quality fluorescence. The size and thickness of the fluorescent transparent ceramic and the fluorescent transparent film sample are adjustable, and the fluorescent transparent ceramic and the fluorescent transparent film sample are directly combined with the LED chip, so that the packaging process is simplified, and the service life and the stability of the device can be effectively prolonged.
Therefore, a red light transparent ceramic material and a red light transparent film material which are effectively matched with a blue light LED chip or a near ultraviolet LED chip and can efficiently emit light are developed to replace the conventional fluorescent powder material to construct a novel LED device, and the novel LED device has high economic benefit.
Disclosure of Invention
Technical problem to be solved
To solve the above technical problems, the present invention is widely applicable to Y2O3Based on Eu red-light fluorescent powder, the optical parameters of the luminescent material are adjusted by regulating and controlling components and introducing Zr, La and Mg elements in proper amount, and a high-efficiency red-light luminescent material RE excited by a near ultraviolet or blue light LED chip is provided2O3Eu (RE is Y, Lu, Gd), can be used for preparing high-quality red light luminescent materials meeting different application requirements.
(II) technical scheme
To achieve the above object, the technical solution of the present invention includes:
in a first aspect, the present invention provides a red light emitting material excited by a near ultraviolet or blue light chip, wherein the chemical composition general formula of the red light emitting material is:
(RE1-x-y-z-mLamZryMgz)2O3x is more than or equal to 0.01 and less than or equal to 0.2, y is more than or equal to 0.001 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.1, and m is more than or equal to 0 and less than or equal to 0.2, wherein RE is Lu1-p-rYpGdr，0≤p<1，0≤r<1。
In a second aspect, the invention provides a red light luminescent material product, wherein the red light luminescent material product contains the red light luminescent material, and the red light luminescent material product is fluorescent transparent ceramic, a fluorescent transparent film or fluorescent glue powder.
In a third aspect, the present invention provides a method for preparing the red light emitting material, comprising:
step S1, preparing a metal powder mixture according to the molar ratio of each metal element in the chemical composition of the red light luminescent material;
and step S2, calcining the metal powder mixture to obtain the red light emitting material.
When preparing the metal powder mixture in the step S1, the method comprises the following steps
Taking a Y raw material with the purity of more than 99.99%, a Lu raw material, a Gd raw material, a La raw material, a Eu raw material, a Zr raw material and a Mg raw material as raw materials;
wherein: the raw material of Y adopts Y2O3And Y (NO)3)3·6H2One of O;
the Lu raw material adopts Lu2O3And Lu (NO)3)3·6H2One of O;
gd is adopted as the raw material of Gd2O3And Gd (NO)3)3·6H2One of O;
the La raw material adopts La2O3And La (NO)3)3·6H2One of O;
the Eu raw material adopts Eu2O3And Eu (NO)3)3·6H2One of O;
the Zr raw material adopts ZrO2And Zr (NO)3)4·5H2One of O;
the Mg raw material adopts MgO and Mg (NO)3)2·6H2And O is one of the compounds.
In step S2, the calcination method includes:
firstly, calcining a metal powder mixture to be calcined in the air or oxygen atmosphere, wherein the calcining temperature is 700-1300 ℃, the heating rate is 2-5 ℃/min, and the calcining time is 0.5-6 h;
and calcining the obtained powder in vacuum or inert gas atmosphere to obtain the red light luminescent material, wherein the calcining temperature is 1000-1700 ℃, the heating rate is 2-10 ℃/min, and the calcining time is 0.5-10 h.
Optionally, a method of preparing the red light emitting material comprises:
step 101: obtaining a precursor precipitate: preparing metal salt mixed solution according to the molar ratio of each metal element in the red light luminescent material, and obtaining precursor precipitates containing the metal elements by adopting a precipitation method;
step 102: and calcining the precursor precipitate to obtain the red light luminescent material.
The step 101 comprises: adding a precipitant into the metal salt mixed solution by adopting a coprecipitation method, and continuously stirring for several hours until the metal salt mixed solution and the precipitant completely react to obtain a precursor precipitate; alternatively, the first and second electrodes may be,
adding a precipitator into the metal salt mixed solution by adopting a uniform precipitation method, heating the metal salt mixed solution to 80-98 ℃, and preserving heat for 60-240min to obtain a precursor precipitate; alternatively, the first and second electrodes may be,
adding a precipitator into the metal salt mixed solution by a hydrothermal method until the pH value of the metal salt mixed solution reaches a preset value, uniformly stirring the metal salt mixed solution to obtain a suspension, placing the suspension into a hydrothermal kettle, and carrying out hydrothermal reaction in an oven at a preset temperature to obtain a precursor precipitate.
Optionally, a method of preparing the red light emitting material comprises:
step 201, preparing a metal salt mixed solution according to the molar ratio of each metal element in the chemical composition of the red light luminescent material;
202, adding a complexing agent into the metal salt mixed solution to obtain sol;
step 203, volatilizing the solvent, and processing the sol to obtain gel;
step 204, drying and calcining the gel to obtain the red light emitting material.
Optionally, a method of preparing the red light emitting material comprises:
301, preparing a metal salt mixed solution according to the molar ratio of each metal element in the chemical composition of the red light luminescent material;
and 302, mixing a combustion agent with the metal salt mixed solution, and carrying out combustion reaction at high temperature to obtain the red light luminescent material.
In a fourth aspect, the invention provides a preparation method of a red light transparent ceramic, which comprises the following steps:
step 401, performing dry pressing molding on the red light luminescent material under a certain pressure in an axial pressurization mode to obtain a biscuit, and performing cold isostatic pressing molding on the biscuit under a certain pressure;
step 402, sintering the biscuit obtained in the step 401 to obtain ceramic;
and 403, annealing the ceramic processed in the step 402 to obtain the red transparent ceramic.
Said step 401 comprises the steps of,
step 401a, performing dry pressing molding on the red light emitting material under a certain pressure by adopting an axial pressing mode to prepare a biscuit, wherein the pressing pressure is 50-100 MPa, and the pressure maintaining time is 1-5 min;
and step 401b, carrying out cold isostatic pressing on the biscuit under a certain pressure, wherein the pressure is 180-400 MPa, and the pressure maintaining time is 1-5 min.
The step 402 comprises:
carrying out vacuum sintering on the biscuit obtained in the step 401 in a vacuum sintering furnace, wherein the vacuum degree is 10-3～10-4Pa, the sintering temperature is 1500-1850 ℃, and the heat preservation time is 0-15 h; alternatively, the first and second electrodes may be,
placing the biscuit obtained in the step 401 into a vacuum hot-pressing sintering furnace for sintering, wherein the sintering temperature is 1300-1800 ℃, the applied pressure is 10-70 MPa, the heat preservation time is 2-10 h, and the vacuum degree is 10-3Pa; alternatively, the first and second electrodes may be,
placing the biscuit obtained in the step 401 into a hot-pressing sintering furnace for sintering, wherein the applied pressure is 10-70 MPa, the sintering temperature is 1300-1700 ℃, and the heat preservation time is 1-10 hours; alternatively, the first and second electrodes may be,
and (3) sintering the biscuit obtained in the step (401) in an SPS sintering furnace, wherein the applied pressure is 10-70 MPa, the sintering temperature is 1300-1700 ℃, and the heat preservation time is 2-60 min.
The step 403 includes a step 403 a: and (3) annealing the ceramic treated in the step (402) in air or oxygen atmosphere, wherein the annealing temperature is 1100-1500 ℃, and the heat preservation time is 0.5-20 h.
Optionally, the step 403 further includes:
step 403b, placing the annealed ceramic sintered body into a hot isostatic pressing sintering furnace for sintering, wherein the sintering temperature is 1500-1850 ℃, the applied pressure is 150-200 MPa, and the heat preservation time is 0.5-10 h;
and 403c, annealing the ceramic subjected to hot isostatic pressing sintering in air or oxygen atmosphere to obtain the red-light transparent ceramic, wherein the annealing temperature is 1100-1500 ℃, and the heat preservation time is 0.5-20 h.
In a fifth aspect, the present invention provides a method for preparing a red light transparent film, comprising:
501, preparing a metal salt mixed solution according to the molar ratio of each metal element in the chemical composition of the red light emitting material according to claim 1;
502, adding ethylene glycol EG into the metal salt mixed solution, and heating while stirring to obtain a colloid;
503, dripping the colloid on the film forming template to obtain a film forming template with the surface covered with the red light luminescent material adhesive film;
504, sintering the film-forming template in the step 503 at 700-1100 ℃;
505, repeating the steps 503 and 504 until the target film thickness is reached, and obtaining the red light transparent film.
In a sixth aspect, the present invention provides an application of a red light emitting material in the manufacture of a white light lamp.
The application comprises the following steps:
combining the red light luminescent material with blue fluorescent powder and green fluorescent powder to prepare a white light LED; alternatively, the first and second electrodes may be,
and combining the red light luminescent material with yellow fluorescent powder to prepare the white light LED.
Optionally, the applying comprises:
coating yellow fluorescent powder on the red light transparent ceramic, and directly combining the red light transparent ceramic with a blue light LED chip to package the red light transparent ceramic into a white light LED; alternatively, the first and second electrodes may be,
mixing and coating blue and green fluorescent powder on the red light transparent ceramic, and directly combining the red light transparent ceramic with a near ultraviolet LED chip to package the red light transparent ceramic into a white light LED; alternatively, the first and second electrodes may be,
combining the red light transparent ceramic and the yellow light transparent ceramic to manufacture a composite structure transparent ceramic, and directly combining the composite structure transparent ceramic and a blue light LED chip to package into a white light LED; alternatively, the first and second electrodes may be,
combining the red light transparent ceramic with the blue light and green light transparent ceramic to manufacture composite structure transparent ceramic, and directly combining the composite structure transparent ceramic with a near ultraviolet LED chip to package into a white light LED; alternatively, the first and second electrodes may be,
combining the red light transparent film with the yellow light transparent ceramic, and directly combining with a blue light LED chip to package into a white light LED; alternatively, the first and second electrodes may be,
and combining the red light transparent film with the blue light and green light transparent ceramics, and directly combining the red light transparent film with the near ultraviolet LED chip to package the white light LED.
(III) advantageous effects
By adopting the design scheme, the red light luminescent material has the beneficial effects of wide excitation spectrum coverage range, stable physical and chemical properties, excellent thermal stability, high luminous intensity and high luminous efficiency, and can be matched with a near ultraviolet or blue light LED chip. The red light luminescent material product comprises a red light rubber powder material, a red light transparent ceramic material and a red light transparent film material, can be packaged with a near ultraviolet chip or a blue light chip in different forms, and is applied to a white light LED lighting source.
(1) The excitation peak of the red light luminescent material covers the near ultraviolet and blue light wave bands of 350-480nm and is matched with the emission peak positions of the near ultraviolet and blue light LED chips.
(2) The red light luminescent material has bright red light emission under the excitation of 360-400nm near ultraviolet and 465nm blue light, has high color purity, can meet the requirements of white light LED packaging with high brightness and high color rendering performance, and has very wide market application prospect.
(3) The red light luminescent material has simple preparation process and environment friendliness, and the prepared red light transparent ceramic material and the red light transparent film material have controllable sizes and thicknesses, can be made into different shapes, and are suitable for industrial batch production.
(4) The red light transparent ceramic material and the red light transparent film material have the advantages of good light transmittance, high density, good uniformity, high thermal quenching temperature and stable physical and chemical properties, are favorable for improving the luminous intensity and luminous efficiency, and are also favorable for processing products and packaging devices.
Drawings
FIG. 1 is a simplified structural diagram of a white LED packaged by the red transparent ceramic and commercial fluorescent powder;
FIG. 2 is a simplified diagram of a structure of a red transparent ceramic and a commercial fluorescent transparent ceramic combined for packaging a white LED according to the present invention;
FIG. 3 is an XRD spectrum of the red-light transparent ceramic obtained in example 2 of the present invention;
FIG. 4 shows a red-emitting transparent ceramic obtained in example 3 of the present invention and commercial Y2O3An excitation spectrum contrast chart of transparent ceramics prepared by Eu fluorescent powder under 612nm monitoring;
FIG. 5 shows the linear transmittance of the red-light transparent ceramic obtained in example 5 of the present invention;
FIG. 6 shows an emission spectrum of a red phosphor obtained in example 7 of the present invention under 395nm excitation;
FIG. 7 shows an emission spectrum of a red-light phosphor obtained in example 9 of the present invention under excitation at 465 nm;
FIG. 8 shows the emission spectrum of the red transparent ceramic obtained in example 13 of the present invention under 465nm excitation;
FIG. 9 shows an emission spectrum of a red-light transparent ceramic obtained in example 14 of the present invention under 395nm excitation;
FIG. 10 shows the emission spectra of the red-light transparent ceramic obtained in example 17 of the present invention at different temperatures, with the excitation wavelength of 465 nm;
FIG. 11 is a color coordinate diagram of a red light transparent film obtained in example 19 of the present invention.
Detailed Description
In order to better explain the present invention, the following detailed description of the embodiments of the present invention is provided in conjunction with the drawings.
The preparation method of the red-light fluorescent powder comprises the following steps: solid phase method, coprecipitation method, uniform precipitation method, hydrothermal method, sol-gel method, combustion method.
The preparation process of the red light transparent ceramic comprises the following steps: vacuum sintering, hot-pressing sintering, Spark Plasma (SPS) sintering, vacuum hot-pressing sintering, and hot isostatic pressing sintering.
The red light transparent film adopts a sol-gel spin coating method.
Example 1
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.68La0.2Zr0.04Mg0.01)2O3:0.07Eu。
The red-light fluorescent powder is prepared by a solid-phase method and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、La2O3(99.99％)、Eu2O3(99.99％)、 Zr(NO3)4·5H2O (99.0%) and Mg (NO)3)2·6H2O (99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O37at.％， La2O320at.％，Zr(NO3)4·5H2O 4at.％，Mg(NO3)2·6H2O 1at.％，Lu2O368 at.%; ball milling and mixing the raw materials prepared according to the formula;
(2) drying, grinding and sieving the slurry after ball milling and mixing to obtain a required powder mixture;
(3) calcining the obtained powder in an air atmosphere at the calcining temperature of 700 ℃, the heating rate of 2 ℃/min and the calcining time of 6h, and calcining the obtained powder in a vacuum atmosphere at the calcining temperature of 1000 ℃, the heating rate of 10 ℃/min and the calcining time of 6h to obtain the red-light fluorescent powder.
Example 2
The embodiment provides a red transparent ceramic capable of being excited by a near ultraviolet chip or a blue chip, and the chemical composition general formula of the red transparent ceramic is as follows: (Lu)0.68La0.2Zr0.04Mg0.01)2O3:0.07Eu。
The red light transparent ceramic is prepared by adopting a vacuum sintering process, and comprises the following steps:
(1) carrying out dry pressing molding on the red fluorescent powder obtained in the embodiment 1 under the pressure of 50MPa in an axial one-way pressurizing mode, wherein the pressure maintaining time is 2 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 180MPa, and keeping the pressure for 5 min;
(2) placing the formed biscuit into a vacuum sintering furnace for vacuum sintering at 1850 deg.C for 0h under 1 × 10 vacuum degree-3Pa。
(3) And (3) annealing the vacuum sintered ceramic in an air atmosphere at 1500 ℃, and keeping the temperature for 10 hours to obtain the compact and transparent red transparent ceramic.
The XRD spectrogram of the high-efficiency red transparent ceramic prepared in the embodiment is shown in figure 3, and as can be seen from figure 3, the diffraction peak and the cubic phase Lu of the red transparent ceramic2O3The standard cards are consistent, no diffraction peaks of other impurity phases appear, and the prepared efficient red light transparent ceramic is pure phase Lu2O3And (5) structure.
Example 3
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.41Y0.1Gd0.25Zr0.2)2O3:0.04Eu。
The red light transparent ceramic is prepared by adopting powder synthesized by coprecipitation and combining a vacuum sintering process, and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、Y2O3(99.99％)、Gd2O3(99.99％)、Eu2O3(99.99%) and Zr (NO)3)4·5H2O (99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O34at.％，Gd2O325at.％， Zr(NO3)4·5H2O 20at.％，Y2O310at.％，Lu2O341 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) slowly adding the mixed solution of ammonia water and ammonium bicarbonate into the raw material mixed solution under the condition of stirring, and continuously stirring for a plurality of hours after the dropwise addition is finished, so that the reaction is complete;
(3) centrifugally separating, washing and drying the obtained white precipitate to obtain precursor powder;
(4) calcining the obtained precursor in an air atmosphere at 700 ℃, at a heating rate of 3 ℃/min for 4h, calcining the obtained powder in a vacuum atmosphere at 1100 ℃, at a heating rate of 10 ℃/min for 0.5h to obtain the red-light fluorescent powder;
(5) dry pressing the calcined powder under 100MPa for 1min in an axial one-way pressurizing mode; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 400MPa, and keeping the pressure for 1 min;
(6) placing the formed biscuit into a vacuum sintering furnace for vacuum sintering, wherein the sintering temperature is 1500 ℃, the heat preservation time is 15h, and the vacuum degree is 10-4Pa。
(7) And annealing the vacuum sintered ceramic in an oxygen atmosphere at 1250 ℃ for 10h to obtain the compact and transparent red-light transparent ceramic.
The high efficiency red transparent ceramic and commercial Y made in this example2O3FIG. 4 shows a comparison of excitation spectra of transparent ceramics prepared from Eu phosphor, as monitored at 612nm, and Y is shown in FIG. 42O3The Eu transparent ceramic has weak excitation peaks in near ultraviolet and blue light wave bands, and the red light transparent ceramic prepared by the invention has strong excitation peaks in near ultraviolet and blue light wave bands, which shows that the red light transparent ceramic prepared by the invention can be effectively matched with near ultraviolet and blue light LED chips.
Example 4
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.71Zr0.07Mg0.02)2O3:0.2Eu。
The red-light fluorescent powder is prepared by adopting a uniform precipitation method, and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、Eu2O3(99.99％)、ZrO299.0 percent and 99.0 percent of MgO are taken as raw materials. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O320at.％，ZrO27at.％，MgO 2at.％，Lu2O371 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) adding a precipitant (actually a precipitant precursor which can generate precipitant after being added into the solution) into the raw material mixed solution, and uniformly stirring to obtain a uniform mixed solution;
the precipitant is a substance that can react with other components in the solution or water to generate a precipitant, and may be, for example, urea, ammonia water, or the like.
(3) Heating the mixed solution to 80 ℃, and preserving the temperature for 240min after white precipitates appear in the solution to obtain a suspension;
(4) after the suspension is cooled, centrifugally separating, washing and drying the obtained white precipitate to obtain precursor powder;
(5) calcining the obtained precursor in an oxygen atmosphere at 800 ℃, at a temperature rise rate of 5 ℃/min for 0.5h, and calcining the obtained powder in a vacuum atmosphere at 1100 ℃, at a temperature rise rate of 10 ℃/min for 4h to obtain the red-light fluorescent powder;
example 5
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.71Zr0.07Mg0.02)2O3:0.2Eu。
The red light transparent ceramic is prepared by adopting a vacuum hot-pressing sintering process, and comprises the following steps:
(1) dry pressing the red fluorescent powder obtained in the embodiment 4 under the pressure of 100MPa in an axial one-way pressurizing mode for 1 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 300MPa, and keeping the pressure for 2 min;
(2) sintering the formed biscuit in a vacuum hot-pressing sintering furnace at 1700 ℃ for 2h under 10MPa and 10 vacuum degree-3Pa。
(3) And annealing the ceramic subjected to vacuum hot pressing sintering in an oxygen atmosphere at 1400 ℃, and keeping the temperature for 0.5h to obtain the compact and transparent red-light transparent ceramic.
The linear transmittance of the high-efficiency red-light transparent ceramic prepared by the embodiment is shown in fig. 5, and as can be seen from fig. 5, the highest linear transmittance of the red-light transparent ceramic in the range of 600-800nm (visible light) is as high as 80.2%, which indicates that the red-light transparent ceramic prepared by the invention has high light transmittance.
Example 6
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.68La0.2Zr0.04Mg0.01)2O3:0.07Eu。
The red light transparent ceramic is prepared by adopting a vacuum hot-pressing sintering process, and comprises the following steps:
(1) carrying out dry pressing molding on the red fluorescent powder obtained in the embodiment 1 under the pressure of 100MPa in an axial one-way pressurizing mode, wherein the pressure maintaining time is 1 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 300MPa, and keeping the pressure for 2 min;
(2) sintering the formed biscuit in a vacuum hot-pressing sintering furnace at 1300 deg.C for 10h under 70MPa and 10 vacuum degree-3Pa。
(3) And annealing the ceramic subjected to vacuum hot pressing sintering in an oxygen atmosphere at the annealing temperature of 1100 ℃ for 20 hours to obtain the compact and transparent red-light transparent ceramic.
Example 7
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Y)0.56Lu0.2Zr0.08Mg0.1)2O3:0.06Eu。
The red-light fluorescent powder is prepared by adopting a uniform precipitation method, and comprises the following steps:
(1) using high purity Y2O3(99.99％)、Lu2O3(99.99％)、Eu2O3(99.99％)、 ZrO299.0 percent and 99.0 percent of MgO are taken as raw materials. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O36at.％，ZrO28at.％，MgO 10at.％，Lu2O320at.％，Y2O356 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) adding urea into the raw material mixed solution, and uniformly stirring to obtain a uniform mixed solution;
(3) heating the mixed solution to 98 ℃, and preserving the temperature for 60min after white precipitates appear in the solution to obtain a suspension;
(4) after the suspension is cooled, centrifugally separating, washing and drying the obtained white precipitate to obtain precursor powder;
(5) and calcining the obtained precursor in an oxygen atmosphere at the temperature of 900 ℃, at the temperature rise rate of 2 ℃/min and for 4h, and calcining the obtained powder in a vacuum atmosphere at the temperature of 1300 ℃, at the temperature rise rate of 5 ℃/min and for 4h to obtain the red-light fluorescent powder.
The emission spectrum of the high efficiency red phosphor prepared in this example is shown in FIG. 6. As can be seen from FIG. 6, at 396nm excitation, Eu appears3+Is/are as follows5D0-7F2Bright red emission (center wavelength 612nm) of the electric dipole transition.
Example 8
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.739Y0.25Zr0.001)2O3:0.01Eu。
The red-light fluorescent powder is prepared by a hydrothermal method and comprises the following steps:
(1) using high purity Lu (NO)3)3·6H2O(99.99％)、Y(NO3)3·6H2O(99.99％)、 Eu(NO3)3·6H2O (99.99%) and Zr (NO)3)4·5H2O (99.0%) nano powder is used as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (NO)3)3·6H2O 1at.％，Zr(NO3)4·5H2O 0.1at.％，Y(NO3)3·6H2O 25at.％，Lu(NO3)3·6H2O73.9 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) dropwise adding ammonia water into the raw material mixed solution until the pH value reaches a preset value, uniformly stirring, transferring the obtained suspension into a hydrothermal kettle, and carrying out hydrothermal reaction in an oven at a preset temperature;
(3) naturally cooling the reaction product, and then performing centrifugal separation, washing and drying to obtain precursor powder;
(4) and calcining the obtained precursor in an air atmosphere at the calcining temperature of 1100 ℃, at the heating rate of 3 ℃/min and for 0.5h, and calcining the obtained powder in a vacuum atmosphere at the calcining temperature of 1500 ℃, at the heating rate of 2 ℃/min and for 3h to obtain the red-light fluorescent powder.
Example 9
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.71Y0.05La0.05Zr0.05Mg0.05)2O3:0.09Eu。
The red-light fluorescent powder is prepared by adopting a sol-gel method, and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、Y2O3(99.99％)、La2O3(99.99％)、 Eu2O3(99.99％)、ZrO2(99.0%) and Mg (NO)3)2·6H2O (99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O39at.％， ZrO25at.％，Mg(NO3)2·6H2O 5at.％，Y2O35at.％，La2O35at.％，Lu2O371 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) adding a certain amount of citric acid into the raw material mixed solution, heating and stirring at a certain temperature, gradually forming sol along with the evaporation of water, and continuously evaporating to form gel;
(3) drying the gel in an oven to obtain dry gel;
(4) and calcining the xerogel in an air atmosphere at the calcining temperature of 700 ℃, at the heating rate of 5 ℃/min for 6h, calcining the obtained powder in a vacuum atmosphere at the calcining temperature of 1000 ℃, at the heating rate of 10 ℃/min for 4h to obtain the red-light fluorescent powder.
The emission spectrum of the high efficiency red phosphor prepared in this example is shown in FIG. 7. As can be seen from FIG. 7, the emission spectrum corresponding to Eu appears under 465nm excitation3+Is/are as follows5D0-7F2Bright red emission (center wavelength 612nm) of the electric dipole transition.
Example 10
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.71Y0.05La0.05Zr0.05Mg0.05)2O3:0.09Eu。
The red light transparent ceramic is prepared by adopting a hot-pressing sintering process, and comprises the following steps:
(1) dry pressing the red fluorescent powder obtained in the embodiment 9 under the pressure of 50MPa in an axial one-way pressurizing mode for 5 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 200MPa, and keeping the pressure for 1 min;
(2) placing the formed biscuit into a hot-pressing sintering furnace for sintering, wherein the sintering temperature is 1300 ℃, the heat preservation time is 10 hours, and the applied pressure is 70 MPa;
(3) and annealing the hot-pressed and sintered ceramic in an air atmosphere at the annealing temperature of 1100 ℃ for 20h to obtain the compact and transparent red transparent ceramic.
Example 11
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.71Y0.05La0.05Zr0.05Mg0.05)2O3:0.09Eu。
The red transparent ceramic is prepared by adopting an SPS sintering process, and comprises the following steps:
(1) dry pressing the red fluorescent powder obtained in the embodiment 9 under the pressure of 50MPa in an axial one-way pressurizing mode for 5 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 180MPa, and keeping the pressure for 1 min;
(2) placing the molded biscuit into an SPS sintering furnace for sintering, wherein the sintering temperature is 1300 ℃, the heat preservation time is 60min, and the applied pressure is 70 MPa;
(3) and (3) annealing the SPS sintered ceramic in an air atmosphere at the annealing temperature of 1100 ℃ for 15h to obtain the compact and transparent red transparent ceramic.
Example 12
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.765Gd0.05La0.05Zr0.1Mg0.005)2O3:0.03Eu。
The red-light fluorescent powder is prepared by adopting a sol-gel method, and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、Gd2O3(99.99％)、La2O3(99.99％)、 Eu2O3(99.99％)、ZrO299.0 percent and 99.0 percent of MgO are taken as raw materials. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O33at.％，MgO 0.5at.％，ZrO210at.％，La2O35at.％，Gd2O35at.％，Lu2O376.5 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) adding a certain amount of citric acid into the raw material mixed solution, heating and stirring at a certain temperature, gradually forming sol along with the evaporation of water, and continuously evaporating to form gel;
(3) drying the gel in an oven to obtain dry gel;
(4) and calcining the xerogel in an air atmosphere at the calcining temperature of 800 ℃, at the heating rate of 3 ℃/min and for 4h, calcining the obtained powder in a vacuum atmosphere at the calcining temperature of 1000 ℃, at the heating rate of 10 ℃/min and for 10h to obtain the red-light fluorescent powder.
Example 13
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.765Gd0.05La0.05Zr0.1Mg0.005)2O3:0.03Eu。
The red transparent ceramic is prepared by adopting an SPS sintering process, and comprises the following steps:
(1) dry pressing the red fluorescent powder obtained in the embodiment 12 under the pressure of 50MPa in an axial one-way pressurizing mode for 5 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 180MPa, and keeping the pressure for 1 min;
(2) sintering the formed biscuit in an SPS sintering furnace at 1700 ℃ for 2min under 10 MPa;
(3) and (3) annealing the SPS sintered ceramic in an air atmosphere at 1400 ℃ for 10h to obtain the compact and transparent red transparent ceramic.
The emission spectrum of the high-efficiency red transparent ceramic prepared in the embodiment is shown in FIG. 8, and as can be seen from FIG. 8, under the excitation of 465nm, the emission spectrum corresponding to Eu appears3+Is/are as follows5D0-7F2Bright red emission (center wavelength 612nm) of the electric dipole transition. The red light component is added into the yellow light spectrum of YAG: Ce, the display index of the device can be effectively improved, and the color temperature of the light source can be conveniently adjusted through adjusting the relative intensity of red, yellow and blue.
Example 14
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.765Gd0.05La0.05Zr0.1Mg0.005)2O3:0.03Eu。
The red light transparent ceramic is prepared by adopting a hot-pressing sintering process, and comprises the following steps:
(1) dry pressing the red fluorescent powder obtained in the embodiment 12 under the pressure of 50MPa in an axial one-way pressurizing mode for 3 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 200MPa, and keeping the pressure for 1 min;
(2) placing the formed biscuit into a hot-pressing sintering furnace for sintering, wherein the sintering temperature is 1700 ℃, the heat preservation time is 1h, and the applied pressure is 10 MPa;
(3) and (3) annealing the hot-pressed and sintered ceramic in an air atmosphere at 1400 ℃ for 10h to obtain the compact and transparent red transparent ceramic.
The emission spectrum of the high-efficiency red transparent ceramic prepared in this example is shown in FIG. 9, and it can be seen from FIG. 9 that under 395nm excitation, Eu is shown3+Is/are as follows5D0-7F2Bright red emission (center wavelength 612nm) of the electric dipole transition.
Example 15
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.64Gd0.15La0.03Zr0.08)2O3:0.1Eu。
The red-light fluorescent powder is prepared by adopting a combustion method and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、Gd2O3(99.99％)、La2O3(99.99％)、 Eu2O3(99.99%), and ZrO2(99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O310at.％，Gd2O315at.％，La2O33at.％， ZrO28at.％，Lu2O364 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) mixing a combustion agent with the raw materials, heating to raise the temperature, and generating a violent combustion reaction when the reaction liquid reaches a certain temperature;
(3) and after the reaction is finished, naturally cooling the reaction product to obtain the red fluorescent powder.
Example 16
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.739Y0.25Zr0.001)2O3:0.01Eu。
The red light transparent ceramic is prepared by adopting a process of firstly vacuum sintering and then hot isostatic pressing sintering, and comprises the following steps:
(1) carrying out dry pressing molding on the red fluorescent powder obtained in the embodiment 8 under the pressure of 50MPa in an axial one-way pressurizing mode, wherein the pressure maintaining time is 2 min; then carrying out cold isostatic pressing on the formed biscuit under the pressure of 200MPa, and keeping the pressure for 2 min;
(2) placing the formed biscuit into a vacuum sintering furnace for vacuum sintering, wherein the sintering temperature is 1700 ℃, the heat preservation time is 6h, and the vacuum degree is 10-3Pa。
(3) And (3) annealing the vacuum sintered ceramic in an air atmosphere at 1400 ℃ for 10h to obtain a ceramic sintered body.
(4) And placing the annealed ceramic sintered body into a hot isostatic pressing sintering furnace for sintering, wherein the sintering temperature is 1850 ℃, the heat preservation time is 0.5h, and the applied pressure is 150 MPa.
(5) And annealing the hot isostatic pressing sintered ceramic in an air atmosphere at 1300 ℃ for 10h to obtain the red light transparent ceramic.
Example 17
A red light transparent ceramic which can be excited by a near ultraviolet chip or a blue light chip, wherein the chemical composition general formula of the red light transparent ceramic is as follows: (Lu)0.71Gd0.05La0.05Zr0.05Mg0.05)2O3:0.09Eu。
The red light transparent ceramic is prepared by adopting a process of SPS sintering and then hot isostatic pressing sintering, and comprises the following steps:
(1) the sintered ceramic body obtained in example 11 and annealed by SPS was sintered at 1500 deg.c for 10 hours in a hot isostatic pressing sintering furnace under 200 MPa.
(2) And annealing the hot isostatic pressing sintered ceramic in an air atmosphere at the annealing temperature of 1200 ℃ for 15h to obtain the red light transparent ceramic.
The emission spectra of the high-efficiency red transparent ceramic prepared by the embodiment at different temperatures (298-573K) are shown in FIG. 10, and as can be seen from FIG. 10, under the excitation of 465nm, the luminous intensity of the transparent ceramic is gradually reduced along with the increase of the temperature, but the peak shape of the emission spectrum is unchanged. At 423K, the fluorescence intensity of the transparent ceramic was 88% at room temperature. When the temperature is increased to 573K, the fluorescence intensity is still 67% of room temperature, which indicates that the red transparent ceramic has very excellent thermal stability.
Example 18
A red light fluorescent powder which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Lu)0.6La0.2Zr0.08Mg0.04)2O3:0.08Eu。
The red-light fluorescent powder is prepared by a solid-phase method and comprises the following steps:
(1) adopts high-purity Lu2O3(99.99％)、La2O3(99.99％)、Eu2O3(99.99％)、 Zr(NO3)4·5H2O (99.0%) and Mg (NO)3)2·6H2O (99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (Eu)2O38at.％，La2O320at.％，Zr(NO3)4·5H2O 8at.％，Mg(NO3)2·6H2O4at.％，Lu2O360 at.%; ball milling and mixing the raw materials prepared according to the formula;
(2) drying, grinding and sieving the slurry after ball milling and mixing to obtain a required powder mixture;
(3) calcining the obtained powder in an air atmosphere at 1300 ℃, at a temperature rise rate of 5 ℃/min for 2h, and calcining the obtained powder in an inert gas atmosphere at 1700 ℃, at a temperature rise rate of 2 ℃/min for 2h to obtain the red-light fluorescent powder.
Example 19
A red light transparent film which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Y)0.45Lu0.25Gd0.2Zr0.06)2O3:0.04Eu。
The red light transparent film adopts a sol-gel spin coating method and comprises the following steps:
(1) using high purity Y (NO)3)3·6H2O(99.99％)、Lu(NO3)3·6H2O(99.99％)、 Gd(NO3)3·6H2O(99.99％)、Eu(NO3)3·6H2O (99.99%) and Zr (NO)3)4·5H2O (99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (NO)3)3·6H2O 4at.％，Zr(NO3)4·5H2O 6at.％，Gd(NO3)3·6H2O 20at.％， Lu(NO3)3·6H2O 25at.％，Y(NO3)3·6H2O45 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) a certain amount of Ethylene Glycol (EG) was added as a solvent to the raw material mixed solution, and the mixed solution was heated with stirring to remove water.
(3) Stirring for several hours, fixing the cleaned quartz substrate on a spin coater, dripping colloid on the quartz substrate for spin coating, and drying in a drying oven;
(4) then sintering treatment is carried out in a tube furnace at 700 ℃.
(5) And (5) repeating the steps (3) and (4) until the target film thickness is reached, so as to obtain the red light transparent film.
The color coordinate graph of the red transparent film prepared in this example is shown in fig. 11, and as can be seen from fig. 11, the chromaticity coordinates of the red transparent film of this example are (0.66, 0.34), which are close to the standard chromaticity coordinates of red light.
Example 20
A red light transparent film which can be excited by a near ultraviolet chip or a blue light chip has a chemical composition general formula as follows: (Y)0.64Lu0.25Zr0.06)2O3:0.05Eu。
The red light transparent film adopts a sol-gel spin coating method and comprises the following steps:
(1) using high purity Y (NO)3)3·6H2O(99.99％)、Lu(NO3)3·6H2O(99.99％)、 Eu(NO3)3·6H2O (99.99%) and Zr (NO)3)4·5H2O (99.0%) as raw material. The doping amount of each component is calculated by mole percentage, and the molar ratio of each raw material component is as follows: eu (NO)3)3·6H2O 5at.％，Zr(NO3)4·5H2O 6at.％，Lu(NO3)3·6H2O 25at.％， Y(NO3)3·6H2O64 at.%; mixing the raw materials prepared according to the formula, adding nitric acid to fully dissolve the raw materials to prepare a raw material mixed solution;
(2) a certain amount of Ethylene Glycol (EG) was added as a solvent to the raw material mixed solution, and the mixed solution was heated with stirring to remove water.
(3) Stirring for several hours, fixing the cleaned quartz substrate on a spin coater, dripping colloid on the quartz substrate for spin coating, and drying in a drying oven;
(4) then sintering treatment is carried out in a tube furnace at 1100 ℃.
(5) And (5) repeating the steps (3) and (4) until the target film thickness is reached, so as to obtain the red light fluorescent transparent film.
Example 21
In this embodiment, the application of the red light emitting material excited by the near ultraviolet chip in the white LED will be described.
The red fluorescent powder capable of being excited by the near ultraviolet chip can be used as the red fluorescent powder in a tricolor white light LED, namely, the red fluorescent powder is uniformly mixed with commercial blue fluorescent powder and green fluorescent powder by epoxy resin, coated on the near ultraviolet LED chip, packaged and cured to obtain the white light LED.
The red fluorescent powder capable of being excited by the blue light chip can be mixed with commercial YAG (yttrium aluminum garnet) Ce yellow fluorescent powder, coated on a blue InGaN chip, packaged and cured to prepare a white light LED, and warm white light emission is realized.
At present, patent CN 102620167B discloses a transparent ceramic white light LED and a preparation method thereof, and the invention utilizes (Y)1-xCex)3Al5O12(x is more than or equal to 0.0005 and less than or equal to 0.005) the transparent ceramic and the blue LED chip are packaged into a white LED, and the luminous efficiency can be improved to 99.48 lm/W; the patent CN 104177078B discloses a Lu-containing Ce: YAG-based transparent ceramic for white light LED fluorescence conversion and a preparation method thereof, when the ceramic is used as a white light LED packaging material, the luminous efficiency is 45.32-168.78lm/W, the color rendering index is 80.1-92.3, the color temperature is low, but the peak wave band is 500-600nm, the red wave band is absent, and the effect of warm white light is not achieved.
The high-efficiency red light transparent ceramic capable of being excited by the blue light chip can be used for coating commercial YAG (yttrium aluminum garnet): Ce fluorescent powder on the red light transparent ceramic and directly combining with the blue light LED chip as a packaging material to be packaged into a white light LED (as shown in figure 1). Under the excitation of blue light, the red light generated by the lower-layer red transparent ceramic is mixed with the yellow light generated by the upper-layer YAG, Ce fluorescent powder and the transmitted blue light to form high-quality white light, and the white light has the characteristics of mild color temperature and high display index; in addition, the packaging process is simplified, the light emitting is uniform, and the heat dissipation performance is good.
The high-efficiency red light transparent ceramic capable of being excited by blue light can be combined with commercial YAG (yttrium aluminum garnet): Ce (cerium oxide) transparent ceramic to manufacture composite structure transparent ceramic, and can be directly combined with a blue light LED chip as a packaging material to be packaged into a white light LED, namely, the two transparent ceramics are directly covered on the blue light LED chip (as shown in figure 2). Under the excitation of blue light, the red light generated by the lower-layer red transparent ceramic is mixed with the yellow light generated by the upper-layer YAG, Ce transparent ceramic and the transmitted blue light to form high-quality white light, and the white light has the characteristics of mild color temperature and high display index; in addition, the packaging process is simplified, the light emitting is uniform, and the heat dissipation performance is good.
The high-efficiency red light transparent ceramic capable of being excited by the near ultraviolet chip can be used for red light in a tricolor white light LED, and the application mode is the same as that of the red light transparent ceramic excited by the blue light;
the application of the high-efficiency red light transparent film capable of being excited by blue light is the same as the application principle of the red light transparent ceramic.
The starting materials used in the above examples were all commercially available and, unless otherwise specified, were analytical reagents.
It should be understood that the above description of specific embodiments of the present invention is only for the purpose of illustrating the technical lines and features of the present invention, and is intended to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, but the present invention is not limited to the above specific embodiments. It is intended that all such changes and modifications as fall within the scope of the appended claims be embraced therein.

Claims (18)

1. A red light luminescent material capable of being excited by a near ultraviolet or blue light chip is characterized in that the chemical composition general formula of the red light luminescent material is as follows:
(RE1-x-y-z-mLamZryMgz)2O3x is more than or equal to 0.01 and less than or equal to 0.2, y is more than or equal to 0.001 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.1, and m is more than or equal to 0 and less than or equal to 0.2, wherein RE is Lu1-p-rYpGdr，0≤p<1，0≤r<1；
The excitation peak of the red light luminescent material covers the near ultraviolet and blue light wave bands of 350-480nm and is matched with the emission peak positions of the near ultraviolet and blue light LED chips.
2. A red light luminescent material product, characterized in that the red light luminescent material product contains the red light luminescent material of claim 1, and the red light luminescent material product is fluorescent transparent ceramic, fluorescent transparent film or fluorescent glue powder.
3. A method of making the red light emitting material of claim 1, comprising:
step S1, preparing a metal powder mixture according to the molar ratio of each metal element in the chemical composition of the red light emitting material according to claim 1;
and step S2, calcining the metal powder mixture to obtain the red light emitting material.
4. The method of claim 3, wherein the step S1 is performed by mixing metal powders
Taking a Y raw material with the purity of more than 99.99%, a Lu raw material, a Gd raw material, a La raw material, a Eu raw material, a Zr raw material and a Mg raw material as raw materials;
wherein: the raw material Y adopts Y2O3And Y (NO)3)3·6H2One of O;
the Lu raw material adopts Lu2O3And Lu (NO)3)3·6H2One of O;
gd is adopted as the raw material of Gd2O3And Gd (NO)3)3·6H2One of O;
the La raw material adopts La2O3And La (NO)3)3·6H2One of O;
the Eu raw material adopts Eu2O3And Eu (NO)3)3·6H2One of O;
the Zr raw material adopts ZrO2And Zr (NO)3)4·5H2One of O;
the Mg raw material adopts MgO and Mg (NO)3)2·6H2And O is one of the compounds.
5. The method of claim 3, wherein in step S2, the calcining is performed by:
firstly, calcining a metal powder mixture to be calcined in the air or oxygen atmosphere, wherein the calcining temperature is 700-1300 ℃, the heating rate is 2-5 ℃/min, and the calcining time is 0.5-6 h;
and calcining the obtained powder in vacuum or inert gas atmosphere to obtain the red light luminescent material, wherein the calcining temperature is 1000-1700 ℃, the heating rate is 2-10 ℃/min, and the calcining time is 0.5-10 h.
6. A method of making the red light emitting material of claim 1, comprising:
step 101: obtaining a precursor precipitate: according to the molar ratio of each metal element in the chemical composition of the red light emitting material of claim 1, preparing a metal salt mixed solution, and obtaining a precursor precipitate containing the metal elements by a precipitation method;
step 102: and calcining the precursor precipitate to obtain the red light luminescent material.
7. The method of claim 6, wherein the step 101 comprises:
adding a precipitant into the metal salt mixed solution by adopting a coprecipitation method, and continuously stirring for several hours until the metal salt mixed solution and the precipitant completely react to obtain a precursor precipitate; alternatively, the first and second electrodes may be,
adding a precipitator into the metal salt mixed solution by adopting a uniform precipitation method, heating the metal salt mixed solution to 80-98 ℃, and preserving heat for 60-240min to obtain a precursor precipitate; alternatively, the first and second electrodes may be,
adding a precipitator into the metal salt mixed solution by a hydrothermal method until the pH value of the metal salt mixed solution reaches a preset value, uniformly stirring the metal salt mixed solution to obtain a suspension, placing the suspension into a hydrothermal kettle, and carrying out hydrothermal reaction in an oven at a preset temperature to obtain a precursor precipitate.
8. A method of making the red light emitting material of claim 1, comprising:
step 201, preparing a metal salt mixed solution according to the molar ratio of each metal element in the chemical composition of the red light luminescent material according to claim 1;
202, adding a complexing agent into the metal salt mixed solution to obtain sol;
step 203, volatilizing the solvent, and processing the sol to obtain gel;
step 204, drying and calcining the gel to obtain the red light emitting material.
9. A method of making the red light emitting material of claim 1, comprising:
step 301, preparing a metal salt mixed solution according to the molar ratio of each metal element in the chemical composition of the red light emitting material according to claim 1;
and 302, mixing a combustion agent with the metal salt mixed solution, and carrying out combustion reaction at high temperature to obtain the red light luminescent material.
10. A preparation method of a red transparent ceramic is characterized by comprising the following steps:
step 401, performing dry pressing molding on the red light emitting material according to claim 1 under a certain pressure by adopting an axial pressurization mode to obtain a biscuit, and performing cold isostatic pressing molding on the biscuit under a certain pressure;
step 402, sintering the biscuit obtained in the step 401 to obtain ceramic;
and 403, annealing the ceramic processed in the step 402 to obtain the red transparent ceramic.
11. The method of claim 10, wherein the step 401 comprises:
step 401a, performing dry pressing molding on the red light emitting material according to claim 1 under a certain pressure by adopting an axial pressing mode to obtain a biscuit, wherein the pressing pressure is 50-100 MPa, and the pressure maintaining time is 1-5 min;
and step 401b, carrying out cold isostatic pressing on the biscuit under a certain pressure, wherein the pressure is 180-400 MPa, and the pressure maintaining time is 1-5 min.
12. The production method according to claim 10,
the step 402 comprises:
carrying out vacuum sintering on the biscuit obtained in the step 401 in a vacuum sintering furnace, wherein the vacuum degree is 10-3～10-4Pa, the sintering temperature is 1500-1850 ℃, and the heat preservation time is 0-15 h; alternatively, the first and second electrodes may be,
placing the biscuit obtained in the step 401 into a vacuum hot-pressing sintering furnace for sintering, wherein the sintering temperature is 1300-1800 ℃, the applied pressure is 10-70 MPa, the heat preservation time is 2-10 h, and the vacuum degree is 10-3Pa; alternatively, the first and second electrodes may be,
placing the biscuit obtained in the step 401 into a hot-pressing sintering furnace for sintering, wherein the applied pressure is 10-70 MPa, the sintering temperature is 1300-1700 ℃, and the heat preservation time is 1-10 hours; alternatively, the first and second electrodes may be,
and (3) sintering the biscuit obtained in the step (401) in an SPS sintering furnace, wherein the applied pressure is 10-70 MPa, the sintering temperature is 1300-1700 ℃, and the heat preservation time is 2-60 min.
13. The production method according to claim 10,
the step 403 includes a step 403 a: and (3) annealing the ceramic treated in the step (402) in air or oxygen atmosphere, wherein the annealing temperature is 1100-1500 ℃, and the heat preservation time is 0.5-20 h.
14. The method of claim 13, wherein the step 403 further comprises:
step 403b, placing the annealed ceramic sintered body into a hot isostatic pressing sintering furnace for sintering, wherein the sintering temperature is 1500-1850 ℃, the applied pressure is 150-200 MPa, and the heat preservation time is 0.5-10 h;
and 403c, annealing the ceramic subjected to hot isostatic pressing sintering in air or oxygen atmosphere to obtain the red-light transparent ceramic, wherein the annealing temperature is 1100-1500 ℃, and the heat preservation time is 0.5-20 h.
15. A preparation method of a red light transparent film is characterized by comprising the following steps:
501, preparing a metal salt mixed solution according to the molar ratio of each metal element in the chemical composition of the red light emitting material according to claim 1;
502, adding ethylene glycol EG into the metal salt mixed solution, and heating while stirring to obtain a colloid;
503, dripping the colloid on the film forming template to obtain a film forming template with the surface covered with the red light luminescent material adhesive film;
504, sintering the film-forming template in the step 503 at 700-1100 ℃;
505, repeating the steps 503 and 504 until the target film thickness is reached, and obtaining the red light transparent film.
16. Use of the red light emitting material of claim 1 in the manufacture of a white light lamp.
17. The use according to claim 16, comprising:
combining the red light emitting material of claim 1 with blue phosphor and green phosphor to make a white LED; alternatively, the first and second electrodes may be,
the red light-emitting material of claim 1 is combined with yellow phosphor powder to prepare a white light LED.
18. The use according to claim 17, comprising:
coating yellow fluorescent powder on the red light transparent ceramic prepared by the preparation method of any one of claims 10 to 14, and directly combining with a blue light LED chip to package the red light transparent ceramic into a white light LED; alternatively, the first and second electrodes may be,
mixing and coating blue and green fluorescent powder on the red transparent ceramic prepared by the preparation method of any one of claims 10 to 14, and directly combining the red transparent ceramic with a near ultraviolet LED chip to package the red transparent ceramic into a white LED; alternatively, the first and second electrodes may be,
combining the red transparent ceramic and the yellow transparent ceramic prepared by the preparation method of any one of claims 10 to 14 to prepare a composite structure transparent ceramic, and directly combining the composite structure transparent ceramic with a blue LED chip to package the white LED; alternatively, the first and second electrodes may be,
combining the red transparent ceramic and the blue transparent ceramic prepared by the preparation method of any one of claims 10 to 14 and the green transparent ceramic to prepare a composite structure transparent ceramic, and directly combining the composite structure transparent ceramic with a near ultraviolet LED chip to package the white LED; alternatively, the first and second electrodes may be,
combining the red light transparent film prepared by the preparation method of claim 15 with yellow light transparent ceramic to prepare a composite transparent film, and directly combining the composite transparent film with a blue light LED chip to package the composite transparent film into a white light LED; alternatively, the first and second electrodes may be,
the red light transparent film prepared by the preparation method of claim 15 is combined with blue light transparent ceramic and green light transparent ceramic to prepare composite structure transparent ceramic, and the composite structure transparent ceramic is directly combined with a near ultraviolet LED chip to be packaged into a white light LED.
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