CN113416545A - Yellow fluorescent material, preparation method, light-emitting device and application - Google Patents

Yellow fluorescent material, preparation method, light-emitting device and application Download PDF

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CN113416545A
CN113416545A CN202110784657.1A CN202110784657A CN113416545A CN 113416545 A CN113416545 A CN 113416545A CN 202110784657 A CN202110784657 A CN 202110784657A CN 113416545 A CN113416545 A CN 113416545A
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fluorescent material
yellow fluorescent
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陈磊
李超
黎学文
林金填
蔡济隆
李凤
田琪
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Xuyu Optoelectronics Shenzhen Co ltd
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Xuyu Optoelectronics Shenzhen Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/77928—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements

Abstract

The invention provides a yellow fluorescent material, a preparation method, a luminescent device and application, and relates to the technical field of luminescent materials, wherein the yellow fluorescent material has a chemical general formula of Mz(La(x‑z)/3,A1‑x/3)3(Si(2x+z)/5Al1‑x/3‑z/5)5O12‑4xN11x/3yCe, mEu, wherein x is more than or equal to 0.3 and less than or equal to 0.7, Y is more than or equal to 0.03 and less than or equal to 0.09, z is more than or equal to 0.03 and less than or equal to 0.2, M is more than or equal to 0.005 and less than or equal to 0.02, M is selected from at least one of Ca, Sr or Ba, and A is selected from at least one of Y or Lu. The yellow fluorescent material provided by the invention has the advantages that through mutual synergy of all elements, the color rendering index is larger than or equal to 70, the light emission intensity is larger than or equal to 105, the light intensity attenuation is smaller than or equal to 3% under the high-temperature and high-humidity condition, meanwhile, the half-wave width is larger than or equal to 139nm, and the yellow fluorescent material has a wide application prospect in the field of outdoor lighting.

Description

Yellow fluorescent material, preparation method, light-emitting device and application
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a yellow fluorescent material, a preparation method, a luminescent device and application.
Background
White light LEDs (light emitting diodes) are widely used as novel solid light sources in the fields of illumination and display, due to their advantages of high luminous efficiency, low energy consumption, long life, no pollution, etc. The requirement on the color rendering index of a white light LED in the field of outdoor lighting application is not high and can reach more than 70, but the requirement on the luminous efficiency is higher, the current white light LED is realized by exciting a yellow fluorescent material and a short-wave red fluorescent powder through a blue light chip, and the luminous efficiency loss is larger due to certain difference between the quantum efficiency and the stability of the short-wave red fluorescent powder and the yellow fluorescent material.
In view of the above, there is a need for developing a novel fluorescent material that can satisfy both high luminous efficiency and the color rendering index requirement of the white LED in the field of outdoor lighting.
Disclosure of Invention
The invention aims to provide a yellow fluorescent material with high luminous efficiency, so as to solve the technical problem that the luminous efficiency loss is large due to certain difference between quantum efficiency and stability of short-wave red fluorescent powder and yellow fluorescent powder when a blue light chip excites the yellow fluorescent material and the short-wave red fluorescent powder in the conventional white light LED.
The chemical general formula of the yellow fluorescent material provided by the invention is Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/ 5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, wherein x is more than or equal to 0.3 and less than or equal to 0.7, Y is more than or equal to 0.03 and less than or equal to 0.09, z is more than or equal to 0.03 and less than or equal to 0.2, M is more than or equal to 0.005 and less than or equal to 0.02, M is selected from at least one of Ca, Sr and Ba, and A is selected from at least one of Y and Lu.
Furthermore, x is more than or equal to 0.5 and less than or equal to 0.7;
preferably, 0.05. ltoreq. y.ltoreq.0.07;
preferably, z is 0.08-0.1;
preferably, 0.005. ltoreq. m.ltoreq.0.02.
Further, M is Sr.
Further, A is a combination of Y and Lu.
Further, the molar ratio of Y to Lu is 1-4:1, preferably 1-2:1, more preferably 1-1.5: 1.
The second purpose of the present invention is to provide a method for preparing the yellow fluorescent material, which comprises the following steps:
mixing oxide or nitride of M, oxide or nitride of Eu, oxide or nitride of A, La-Si alloy, Al2O3And CeO2And uniformly mixing according to the metering ratio, and sintering to obtain the yellow fluorescent material.
Further, the sintering temperature is 1500-;
preferably, the sintering temperature is 1550-.
Further, sintering in N2And H2Under the mixed gas atmosphere;
preferably, in the mixed gas, N2And H2In a volume ratio of 90-95:10-5, preferably 95: 5.
the invention also aims to provide a light-emitting device, which comprises an excitation source and a luminescent material, wherein the excitation source is blue light, and the luminescent material comprises a yellow fluorescent material provided by one of the purposes of the invention;
preferably, the wavelength band of the blue light is 445-460 nm.
The fourth purpose of the present invention is to provide the application of the yellow fluorescent material or the light emitting device in the field of outdoor lighting.
The invention has at least the following beneficial effects:
(1) the yellow fluorescent material provided by the invention introduces M element and Eu in the structure, so that the yellow fluorescent material not only has a color rendering index of more than or equal to 70 and light emission intensity of more than or equal to 105 under the excitation of blue light, but also has light intensity attenuation of less than or equal to 3% under the humidity condition of 85 ℃ and 85%, and has half wave width of more than or equal to 139nm, thereby having wide application prospect in the field of outdoor lighting.
(2) The preparation method of the yellow fluorescent material provided by the invention is simple in process, convenient to operate, easy to realize large-scale production and low in production cost.
(3) The luminescent device provided by the invention adopts the yellow fluorescent material as the luminescent material, not only has the color rendering index of more than or equal to 70 and the light emission intensity of more than or equal to 105, but also has the light intensity attenuation of less than or equal to 3% under the humidity conditions of 85 ℃ and 85%, and simultaneously has the half-wave width of more than or equal to 139nm, thereby having wide application prospect in the field of outdoor lighting.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of a phosphor for example 8 of the present invention;
FIG. 2 shows the excitation spectrum of the phosphor used in example 8 of the present invention;
FIG. 3 is an emission spectrum of a phosphor used in example 8 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The chemical composition of the yellow fluorescent material adopted by the existing white light LED is Y2.95Al5O120.05Ce or La2.95Si6N110.05Ce, but the color rendering indexes of the two yellow fluorescent materials can not reach 70 under the excitation of a blue chip, and after the short-wave nitride red powder is added, the color rendering indexes can reach 70, but the light efficiency loss is large. Therefore, there is a great need forThe fluorescent material which can simultaneously meet the condition that the color rendering index is more than or equal to 70 and has high luminous efficiency is developed.
According to a first aspect of the present invention, there is provided a yellow fluorescent material having a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, wherein x is more than or equal to 0.3 and less than or equal to 0.7, Y is more than or equal to 0.03 and less than or equal to 0.09, z is more than or equal to 0.03 and less than or equal to 0.2, M is more than or equal to 0.005 and less than or equal to 0.02, M is selected from at least one of Ca, Sr and Ba, and A is selected from at least one of Y and Lu.
In the present invention, x is typically, but not limited to, 0.3, 0.4, 0.5, 0.6 or 0.7; y is, for example, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08 or 0.09; z is e.g. 0.03, 0.05, 0.08, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.2; m is selected from 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.02.
In the present invention, M is any one or a combination of two or more elements of Ca, Sr, or Ba, for example, M is a combination of Ca and Sr, a combination of Sr and Ba, a combination of Ca and Ba, or a combination of Ca, Sr, and Ba.
A is any one of Y or Lu or the combination of Y and Lu.
The invention introduces La and A elements into the matrix to form 2 Ce elements in the same matrix3+The light-emitting center forms 2 emission peaks on an emission spectrum, the half-peak width of the fluorescent powder is widened to a certain extent, the red and green parts of the spectrum are increased, and the color rendering index is obviously improved compared with that of the traditional yellow powder. In addition, divalent M element and Eu are simultaneously introduced into the system2+Element, proper amount of M element can promote the integrity of crystal lattice, contribute to the crystallinity of the fluorescent powder, and Eu2+The proper introduction of the fluorescent powder is beneficial to reducing the non-radiative transition of the luminescence center, improving the radiative transition probability and further improving the luminous efficiency of the fluorescent powder.
The yellow fluorescent material provided by the invention introduces M element and Eu in the structure, so that the yellow fluorescent material not only has a color rendering index of more than or equal to 70 and light emission intensity of more than or equal to 105 under the excitation of blue light, but also has light intensity attenuation of less than or equal to 3% under the humidity condition of 85 ℃ and 85%, and has half wave width of more than or equal to 139nm, thereby having wide application prospect in the field of outdoor lighting.
In a preferable scheme of the invention, when x is more than or equal to 0.5 and less than or equal to 0.7, y is more than or equal to 0.05 and less than or equal to 0.07, z is more than or equal to 0.08 and less than or equal to 0.1, or m is more than or equal to 0.005 and less than or equal to 0.02, the prepared yellow fluorescent material has higher luminous efficiency and more stable luminous intensity and smaller attenuation under the conditions of high temperature and high humidity. Particularly, when x, y, z and m simultaneously satisfy x is more than or equal to 0.5 and less than or equal to 0.7, y is more than or equal to 0.05 and less than or equal to 0.07, z is more than or equal to 0.08 and less than or equal to 0.1, and m is more than or equal to 0.005 and less than or equal to 0.02, the prepared yellow fluorescent powder simultaneously has stronger emission intensity, wider emission spectrum and lower light intensity attenuation under the high-temperature and high-humidity conditions.
The high temperature and high humidity conditions are 85 ℃ and 85% humidity conditions.
The specific principle analysis is as follows: firstly, the content (z value) of the M element is too high, so that the original crystal structure is damaged, and the crystallinity is poor; too low results in Eu2+The fluorescent powder can not completely enter the crystal lattice to influence the emission intensity of the fluorescent powder. The content (x value) of the La element directly affects the reliability, half-peak width and luminous intensity of the fluorescent powder, and if the content is too high, the crystallinity is deteriorated; if the value is too low, the luminescence center can not completely enter the crystal lattice, the luminescence brightness is poor, the half-peak width is narrowed, and the reliability is reduced; the appropriate La content can widen the half-peak width, promote the integrity of the crystal structure, improve the reliability and induce more Ce3+The luminous center enters the crystal lattice, and the luminous intensity of the system can be improved. Ce3+The content (y value) directly determines the emission intensity of the fluorescent powder, and too low causes too few luminescent centers and reduced luminescent intensity, and too high causes concentration quenching and increase of nonradiative transition and reduced luminescent intensity.
Preferably, when M is Sr, the yellow phosphor prepared has more stable light intensity and less light intensity attenuation under high temperature and high humidity conditions. The main reasons are that on one hand, the ionic radii of Sr2+ and Eu2+ are closer, and the stability of Eu2+ after doping is better; on the other hand, when Sr-Si replaces La/A-Al bond, the crystal lattice adaptation is small, and the crystal integrity and the crystallinity are better.
Preferably, when a is a combination of Y and Lu, the yellow fluorescent material prepared by the mutual cooperation of Y and Lu can effectively improve the light emission intensity under the excitation of a blue light source. The main reason is that the Lu particles have smaller radius, and the proper amount of Lu substituted for Y can adjust the crystal field around the rare earth particles, balance local lattice expansion caused by La substituted part of Y and maintain the integrity of the crystal structure.
Further preferably, A is a combination of Y and Lu, and the molar ratio of Y to Lu is 1-4:1, the prepared yellow fluorescent material has higher light emission intensity, especially when the molar ratio of Y to Lu is 1-2:1, the prepared yellow fluorescent material has higher light emission intensity, and especially when the molar ratio of Y to Lu is 1-1.5:1, the prepared yellow fluorescent material has higher light emission intensity.
Typically, but not by way of limitation, A is a combination of Y and Lu, and the molar ratio of Y to Lu is 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, or 4: 1.
According to a second aspect of the present invention, there is provided a method for preparing the above yellow fluorescent material, comprising the steps of mixing an oxide or nitride of M, an oxide or nitride of Eu, an oxide or nitride of A, La-Si alloy, Al2O3And CeO2And uniformly mixing according to the metering ratio, and sintering to obtain the yellow fluorescent material.
The preparation method of the yellow fluorescent material provided by the invention is simple in process, convenient to operate, easy to realize large-scale production and low in production cost.
Preferably, the sintering temperature is 1500-1700 ℃, and the sintering time is 3-5h, the stability of the yellow fluorescent material prepared by sintering is excellent, and especially, the stability of the yellow fluorescent material prepared by sintering is better when the sintering temperature is 1550-1650 ℃ and the sintering time is 3.5-4.5 h.
Typically, but not by way of limitation, the sintering temperature is, for example, 1500, 1550, 1600, 1650, 1700 ℃, and the sintering time is, for example, 3, 3.5, 4, 4.5, or 5 hours.
In a preferred embodiment of the invention, the sintering is carried out in N2And H2The method is carried out in the mixed gas atmosphere, so as to avoid the influence of the oxidation of the raw materials on the performance of the prepared yellow fluorescent material.
Preferably, in the mixed gas, N2And H2When the volume ratio of (A) to (B) is 90-95:10-5, the yellow fluorescent material with excellent performance can be prepared from various raw materials, especially when N is used2And H2The volume ratio of (A) to (B) is 95:5, and the performance of the prepared yellow fluorescent material is better.
Typically, but not by way of limitation, in a mixture of gases, N2And H2In a volume ratio of 90:10, 92:8, 93:97, 94:6 or 95: 5.
In a preferred embodiment of the present invention, in order to facilitate the preparation of the light emitting device, the yellow phosphor obtained by sintering is sequentially crushed, washed and dried to obtain the yellow phosphor.
According to a third aspect of the present invention, there is provided a light emitting device comprising an excitation source and a luminescent material, wherein the excitation source is blue light and the luminescent material comprises the yellow fluorescent material provided by the first aspect of the present invention.
The luminescent device provided by the invention adopts the yellow fluorescent material as the luminescent material, not only has the color rendering index of more than or equal to 70 and the light emission intensity of more than or equal to 105, but also has the light intensity attenuation of less than or equal to 3% under the humidity conditions of 85 ℃ and 85%, and simultaneously has the half-wave width of more than or equal to 139nm, thereby having wide application prospect in the field of outdoor lighting.
Preferably, the wavelength range of the blue light is 445-.
Typically, but not by way of limitation, blue light has a wavelength band of 445, 446, 448, 450, 452, 455, 456, 458, or 460nm, for example.
According to a fourth aspect of the present invention, the present invention provides an application of the yellow fluorescent material or the light emitting device in the field of outdoor lighting, so as to better save energy.
In order to facilitate understanding of those skilled in the art, the technical solutions provided by the present invention will be further described below with reference to examples and comparative examples.
Example 1
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is Y, x is 0.5, Y is 0.05, z is 0.08, and M is 0.02.
Example 2
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is Y, x is 0.3, Y is 0.03, z is 0.03, and M is 0.005.
Example 3
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is Y, x is 0.7, Y is 0.09, z is 0.2, and M is 0.02.
Example 4
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.2), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 5
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.4), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 6
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 7
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu is 4), x is 0.5, Y is 0.05, z is 0.08, and M is 0.015.
Example 8
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.5), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 9
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 2), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 10
This example provides a yellow phosphorThe chemical general formula of the color fluorescent powder is Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 2.5), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 11
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 3), x equals 0.5, Y equals 0.05, z equals 0.08, and M equals 0.015.
Example 12
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.5), x equals 0.7, Y equals 0.07, z equals 0.1, and M equals 0.02.
Example 13
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.5), x equals 0.6, Y equals 0.06, z equals 0.09, and M equals 0.018.
Example 14
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.5), x equals 0.4, Y equals 0.04, z equals 0.02, and M equals 0.004.
Example 15
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is a combination of Y and Lu (molar ratio Y/Lu equals 1.5), x equals 0.4, Y equals 0.08, z equals 0.15, and M equals 0.018.
Example 16
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Ca, a is a combination of Y and Lu (molar ratio Y/Lu equals 2.5), x equals 0.5, Y equals 0.05, z equals 0.18, and M equals 0.015.
Example 17
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Ba, a is a combination of Y and Lu (molar ratio Y/Lu equals 2.5), x equals 0.5, Y equals 0.05, z equals 0.18, and M equals 0.015.
Example 18
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, where M is Sr, a is Lu, x is 0.5, y is 0.05, z is 0.08, and M is 0.015.
Example 19
This example provides a yellow phosphor, which has a chemical formula of Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, wherein M isSr, a is Y, x is 0.5, Y is 0.05, z is 0.08, m is 0.015.
The yellow fluorescent powder is prepared according to the following steps:
mixing oxide or nitride of M, oxide or nitride of Eu, oxide or nitride of A, La-Si alloy, Al2O3And CeO2Uniformly mixing according to the metering ratio, sintering to obtain a yellow fluorescent material, and sequentially crushing, washing and drying the yellow fluorescent material to obtain the yellow fluorescent powder.
Comparative example 1
This comparative example provides a commercially available yellow phosphor having the chemical formula Y3-yAl5O12yCe, wherein y is 0.05.
Comparative example 2
The comparative example provides a commercially available yellow phosphor having the chemical formula La3-ySi6N11yCe, wherein y is 0.05.
Test example 1
The yellow phosphors provided in examples 1 to 19 and comparative examples 1 to 2, which have the same mass and the same particle size distribution range, were respectively packaged into light emitting devices, and the relative luminous intensity, half-wave width, high-temperature and high-humidity light decay, and color rendering index of the light emitting devices were respectively measured under excitation of blue chips, with the results shown in table 1 below.
Wherein, the relative luminous intensity refers to the emission intensity of the yellow fluorescent powder, the high-temperature high-humidity light decay refers to the attenuation of the emission intensity of the yellow fluorescent powder under the conditions of 85 ℃ and 85% relative humidity, and the color rendering index refers to the color rendering index after the yellow fluorescent powder is excited by adopting a blue chip with the wavelength of 450-452.5 nm.
TABLE 1
Figure BDA0003158746210000111
Figure BDA0003158746210000121
Test example 2
The yellow phosphor provided in example 8 was subjected to XRD, excitation spectrum and emission spectrum tests, and the results are shown in fig. 1, fig. 2 and fig. 3. FIG. 1 is an XRD pattern of a phosphor for example 8 of the present invention; FIG. 2 shows the excitation spectrum of the phosphor used in example 8 of the present invention; FIG. 3 is an emission spectrum of a phosphor used in example 8 of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The yellow fluorescent material is characterized in that the chemical general formula of the yellow fluorescent material is Mz(La(x-z)/3,A1-x/3)3(Si(2x+z)/5Al1-x/3-z/5)5O12-4xN11x/3yCe, mEu, wherein x is more than or equal to 0.3 and less than or equal to 0.7, Y is more than or equal to 0.03 and less than or equal to 0.09, z is more than or equal to 0.03 and less than or equal to 0.2, M is more than or equal to 0.005 and less than or equal to 0.02, M is selected from at least one of Ca, Sr and Ba, and A is selected from at least one of Y and Lu.
2. The yellow fluorescent material according to claim 1, wherein x is 0.5. ltoreq. x.ltoreq.0.7;
preferably; y is more than or equal to 0.05 and less than or equal to 0.07;
preferably, z is 0.08-0.1;
preferably, 0.005. ltoreq. m.ltoreq.0.02.
3. The yellow fluorescent material according to claim 1, wherein M is Sr.
4. The yellow phosphor according to claim 1, wherein a is a combination of Y and Lu.
5. The yellow fluorescent material according to claim 4, wherein the molar ratio of Y to Lu is 1-4:1, preferably 1-2:1, more preferably 1-1.5: 1.
6. The method for producing a yellow fluorescent material according to any one of claims 1 to 5, characterized by comprising the steps of: mixing oxide or nitride of M, oxide or nitride of Eu, oxide or nitride of A, La-Si alloy, Al2O3And CeO2And uniformly mixing according to the metering ratio, and sintering to obtain the yellow fluorescent material.
7. The method for preparing a yellow fluorescent material as claimed in claim 6, wherein the sintering temperature is 1500-;
preferably, the sintering temperature is 1550-.
8. The method of claim 6, wherein the sintering is performed on N2And H2Under the mixed gas atmosphere;
preferably, in the mixed gas, N2And H2In a volume ratio of 90-95:10-5, preferably 95: 5.
9. a light-emitting device comprising an excitation source and a light-emitting material, wherein the excitation source is blue light, and the light-emitting material comprises the yellow fluorescent material according to any one of claims 1 to 5;
preferably, the wavelength band of the blue light is 445-460 nm.
10. Use of the yellow fluorescent material according to any one of claims 1 to 5 or the light-emitting device according to claim 9 in the field of outdoor lighting.
CN202110784657.1A 2021-07-12 2021-07-12 Yellow fluorescent material, preparation method, light-emitting device and application Pending CN113416545A (en)

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