CN109370588B - Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device - Google Patents

Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device Download PDF

Info

Publication number
CN109370588B
CN109370588B CN201811236895.3A CN201811236895A CN109370588B CN 109370588 B CN109370588 B CN 109370588B CN 201811236895 A CN201811236895 A CN 201811236895A CN 109370588 B CN109370588 B CN 109370588B
Authority
CN
China
Prior art keywords
nitride
fluorescent material
fluorescent powder
phosphor
equal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811236895.3A
Other languages
Chinese (zh)
Other versions
CN109370588A (en
Inventor
林金填
陈磊
蔡金兰
李超
邱镇民
罗伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xuyu Photoelectric (shenzhen) Co Ltd
Original Assignee
Xuyu Photoelectric (shenzhen) Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xuyu Photoelectric (shenzhen) Co Ltd filed Critical Xuyu Photoelectric (shenzhen) Co Ltd
Priority to CN201811236895.3A priority Critical patent/CN109370588B/en
Publication of CN109370588A publication Critical patent/CN109370588A/en
Priority to PCT/CN2019/084587 priority patent/WO2020015422A1/en
Application granted granted Critical
Publication of CN109370588B publication Critical patent/CN109370588B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention belongs to the technical field of luminescent materials, and particularly relates to a semiconductor luminescent materialThe nitride fluorescent powder, a preparation method thereof and a light-emitting device. The chemical general formula of the nitride fluorescent powder is A3‑x‑y‑zMxD6(N11‑xCx) (yCe, zR); wherein, A is selected from at least one of La, Y, Lu and Gd, M is selected from at least one of Ca, Sr and Ba, D is selected from at least one of Si, Ge, Ti, Se and Hf, R is selected from at least one of Pr, Tb, Nd and Dy, and x is more than or equal to 0.001 and less than or equal to 2, Y is more than or equal to 0.005 and less than or equal to 0.2, and z is more than or equal to 0.001 and less than or equal to 0.1. The nitride fluorescent powder has high luminous efficiency and good thermal stability, and is very suitable for being applied to high-power LED devices.

Description

Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to nitride fluorescent powder for semiconductor luminescence, a preparation method thereof and a luminescent device.
Background
A high-power Light Emitting Diode (LED) has the excellent characteristics of small size, long service life, high electro-optical conversion efficiency, high response speed, energy saving, environmental protection, and the like, and is widely applied to the fields of commercial illumination, street lamps, automobile lamps, searchlights, and the like. In recent years, white light LEDs have become widely popular in the field of low power lighting, and both the technology and the application fields have reached a relatively mature stage. However, the high-power technology and application field are still in the starting and development stages, mainly because under the excitation of high energy, high thermal radiation and strong ray radiation cause great irreversible damage to the fluorescent powder, and the service life, stability and light efficiency of the device are reduced. Therefore, the development of the high-energy density resistant LED fluorescent powder is the key for realizing a high-light-efficiency and high-stability high-power LED device.
La3Si6N11：Ce3+Fluorescent powder is highly stable due to its high heatThe performance is clearly advantageous in high power LED applications. However, the preparation conditions are relatively harsh, and the thermal stability and external quantum efficiency still need to be further improved, so that the preparation method is not widely applied to high-power LEDs at present. Therefore, the development and preparation method is simple, and the nitride fluorescent powder with high thermal stability and external quantum efficiency can be applied to high-power LED devices.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides nitride fluorescent powder for semiconductor light emitting, a preparation method thereof and a light emitting device, and aims to solve the technical problems of low light efficiency and poor high-energy-resistant density of the conventional fluorescent powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a nitride fluorescent powder, wherein the chemical general formula of the nitride fluorescent powder is A3-x-y- zMxD6(N11-xCx) (yCe, zR); wherein, A is selected from at least one of La, Y, Lu and Gd, M is selected from at least one of Ca, Sr and Ba, D is selected from at least one of Si, Ge, Ti, Se and Hf, R is selected from at least one of Pr, Tb, Nd and Dy, and x is more than or equal to 0.001 and less than or equal to 2, Y is more than or equal to 0.005 and less than or equal to 0.2, and z is more than or equal to 0.001 and less than or equal to 0.1.
In the nitride fluorescent powder provided by the invention, a proper amount of M is used2+And C4-Ion substitution of A3+And N3-Therefore, the lattice stability and the crystal field environment around the luminescent center of the fluorescent powder are improved, the photochromic performance of the fluorescent powder is controllable and adjustable, and the thermal stability is greatly improved; simultaneously, R is introduced into the nitride fluorescent powder3+The luminous efficiency (external quantum efficiency) of the fluorescent powder is further improved through an energy transfer mode, and finally, the luminous efficiency and the thermal stability of the nitride fluorescent powder are higher and better based on the synergistic effect of all elements in the chemical general formula, so that the nitride fluorescent powder is very suitable for being applied to a high-power LED device.
The invention also provides a preparation method of the nitride fluorescent powder, which comprises the following steps:
mixing nitride of first A, nitride of first D and CeN at N2And H2Performing a first sintering treatment under the reduction of (1) to obtain an intermediate;
adding a nitride of a second A, a carbide of a second D, a nitride of M and a nitride or fluoride of R into the intermediate, and performing second sintering treatment in a reducing atmosphere of C to obtain the nitride fluorescent powder;
wherein, the total molar amount of A of the nitride of the first A and the nitride of the second A, and the total molar amount of D of the nitride of the first D and the nitride of the second D are respectively the molar amounts of A and D in the chemical general formula of the nitride fluorescent powder.
The nitride fluorescent powder provided by the invention is prepared by a two-step method, the preparation method is simple in process and low in cost, the nitride of the first A, the nitride of the first D and CeN are mixed to prepare an intermediate, and then the intermediate is mixed with the nitride of the second A, the carbide of the second D, the nitride of M and the nitride or fluoride of R to prepare the final nitride fluorescent powder.
Finally, the invention provides a light-emitting device, which comprises an excitation light source and a fluorescent substance excited by the excitation light source, wherein the fluorescent substance is the nitride fluorescent powder or the nitride fluorescent powder prepared by the preparation method.
In the light-emitting device, the fluorescent substance excited by the excitation light source is the special nitride fluorescent powder, and the nitride has high luminous efficiency and good thermal stability, so that the luminous efficiency and the stability of the light-emitting device are improved finally.
Drawings
FIG. 1 is a graph showing an excitation spectrum (detection wavelength 540nm) of example 40 of the present invention;
FIG. 2 is a graph showing an emission spectrum (excitation wavelength 450nm) of example 40 of the present invention
FIG. 3(a) is a scanning electron microscope image of nitride phosphor obtained by the two-step method in example 40 of the present invention;
FIG. 3(b) is a scanning electron micrograph of a nitride phosphor obtained by a one-step method according to example 44 of the present invention;
FIG. 4 is a graph comparing the thermal stability of example 40 of the present invention and comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In one aspect, embodiments of the present invention provide a nitride phosphor, where a chemical general formula of the nitride phosphor is a3-x-y-zMxD6(N11-xCx) (yCe, zR); wherein A is selected from at least one of La (lanthanum), Y (yttrium), Lu (lutetium) and Gd (gadolinium), M is selected from at least one of Ca (calcium), Sr (strontium) and Ba (barium), D is selected from at least one of Si (silicon), Ge (germanium), Ti (titanium), Se (selenium) and Hf (hafnium), R is selected from at least one of Pr (praseodymium), Tb (terbium), Nd (neodymium) and Dy (dysprosium), x is more than or equal to 0.001 and less than or equal to 2, Y is more than or equal to 0.005 and less than or equal to 0.2, and z is more than or equal to 0.001 and less than or equal to 0.1.
In the nitride fluorescent powder provided by the embodiment of the invention, a proper amount of M is used2+And C4-Ion substitution of A3+And N3-Therefore, the lattice stability and the crystal field environment around the luminescent center of the fluorescent powder are improved, the photochromic performance of the fluorescent powder is controllable and adjustable, and the thermal stability is greatly improved; simultaneously, R is introduced into the nitride fluorescent powder3+The luminous efficiency (external quantum efficiency) of the phosphor is further improved through an energy transfer mode, and finally, based on the synergistic effect of all elements in the chemical general formula, the nitride phosphor has high luminous efficiency and good thermal stability, and is very goodThe method is suitable for being applied to high-power LED devices.
Further, in the chemical general formula of the nitride phosphor, M is Ca, which is because of Ca2+Radius less than La3+Radius, C4-The ionic radius is larger than N3-The radius, when Ca-C replaces La-N element at the same time, the stability of the crystal structure is higher, the crystal field emission around the luminescence center is changed, the light color performance is easy to regulate and control, and the thermal stability is greatly improved; furthermore, A is La and/or Lu, and when A is La or Lu, the phase purity of the prepared fluorescent powder is higher, and the luminous efficiency is higher; when a proper amount of Lu replaces La element, namely La and Lu are simultaneously contained, the fluorescent powder has better crystallization performance and higher luminous efficiency, the structural compactness of the fluorescent powder is enhanced, and the stability is improved; furthermore, R is Pr and/or Tb, and when Pr and/or Tb is selected, energy transfer can be generated, and the luminous efficiency of the fluorescent powder is further improved.
Further, in the chemical general formula of the nitride fluorescent powder, D is selected from at least one of Si, Ge, Ti and Se, and D comprises Si. I.e. D must contain Si, preferably D is Si and Ge, or D is Si and Se. Based on the mole percentage content of D as 100%, wherein, the mole content of Si is 80-90%. When the molar content of Si is 100 percent, namely D is only Si, the nitride fluorescent powder has better luminous intensity; however, when the Si content is too high, the substitution amount of Se or Ge is too small, which is not favorable for improving the morphology and the crystallization performance of the phosphor, and the improvement of the photochromic performance of the phosphor is not obvious, so that in order to improve the comprehensive performance of the phosphor, the molar content of Si needs to be properly reduced, but when the Si content is too low, the structure of the phosphor is distorted, and the luminous efficiency and the stability are reduced; therefore, the molar content of Si is selected to be 80-90%, so that the fluorescent powder improves the light color performance and the luminous efficiency.
Further, in the chemical formula of the nitride phosphor, A is La and Lu, and the molar ratio of La to Lu is (4-10): 1. the lattice stability of the phosphor is better improved by regulating and controlling the ratio of La to Lu, and the thermal stability of the nitride phosphor consisting of A in the ratio range is optimal; when the La/Lu ratio is too low, the structure of the phosphor is changed, the luminous efficiency of the phosphor is reduced, and when the La/Lu ratio is too high, the crystallization and structural stability of the phosphor are not obviously improved, and the light color performance is not obviously improved, so that the molar ratio of La to Lu is (4-10): 1, the phosphor not only improves the light color performance but also improves the light emitting efficiency.
Furthermore, in the chemical general formula of the nitride fluorescent powder, x is more than or equal to 0.01 and less than or equal to 1.5, y is more than or equal to 0.01 and less than or equal to 0.1, and z is more than or equal to 0.005 and less than or equal to 0.05; when the value of x is too high, the phase purity of the fluorescent powder is reduced, the luminous efficiency and the stability are in a descending trend, when the value of x is too low, the microstructure change of the fluorescent powder is not obvious enough, the light color performance is not obvious, and the luminous efficiency and the thermal stability are improved by small effects, so that the effect is optimal in the range that x is more than or equal to 0.01 and less than or equal to 1.5; when the value of y is too high, Ce3+And Ce3+Non-radiative energy transfer can be generated between the fluorescent powder and the substrate, so that the luminous efficiency and stability of the fluorescent powder are reduced, when the value of y is too low, the concentration of luminous centers in the fluorescent powder is too low, the luminous efficiency is relatively low, and therefore, the effect is optimal within the range that y is more than or equal to 0.01 and less than or equal to 0.1; in addition, the large z value can cause nonradiative energy transfer between activators, concentration quenching and more blue light absorption, and can cause Ce3+When the z value is smaller, the energy transmission effect of the R ions to the Ce ions is not obvious, and the luminous efficiency is not obviously improved, so the effect is optimal within the range that z is more than or equal to 0.005 and less than or equal to 0.05.
On the other hand, the embodiment of the invention also provides a preparation method of the nitride fluorescent powder, which comprises the following steps:
s01: mixing nitride of first A, nitride of first D and CeN at N2And H2Performing a first sintering treatment under the reduction of (1) to obtain an intermediate;
s02: adding a nitride of a second A, a carbide of a second D, a nitride of M and a nitride or fluoride of R into the intermediate, and performing second sintering treatment in a reducing atmosphere of C to obtain the nitride fluorescent powder;
wherein, the total molar amount of A of the nitride of the first A and the nitride of the second A, and the total molar amount of D of the nitride of the first D and the nitride of the second D are respectively the molar amounts of A and D in the chemical general formula of the nitride fluorescent powder.
The preparation method of the nitride fluorescent powder provided by the embodiment of the invention has simple process and low cost, and the preparation method is a two-step process, namely, the nitride of the raw material A is divided into two parts: a nitride of a first a and a nitride of the second a; the nitride of the raw material D is divided into two parts: a nitride of the first D and a nitride of the second D; and then mixing the nitride of the first A, the nitride of the first D and CeN to prepare an intermediate, and mixing the intermediate with the nitride of the second A, the carbide of the second D, the nitride of M and the nitride or fluoride of R to prepare the final nitride fluorescent powder.
Further, in the above step S01, the ratio of the sum of the molar amounts of the a element in the nitride of the first a and the Ce element in the CeN to the molar amount of the D element in the nitride of the first D is 1: 3. In the proportion range, the intermediate can be better prepared, thereby being beneficial to preparing the nitride fluorescent powder subsequently.
Furthermore, the temperature of the first sintering treatment is 1300-1500 ℃, and the time is 5-7 h; the temperature of the second sintering treatment is 1500-. In the temperature and time ranges, the intermediate and the final nitride phosphor can be obtained by better sintering.
In a specific embodiment, the preparation method of the nitride phosphor comprises the following steps:
firstly, uniformly mixing a certain proportion of nitride of A, nitride of D and CeN powder according to a certain stoichiometric ratio, placing them into a tungsten crucible, adding N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; wherein A is any one or more of La, Y, Lu and Gd, and D is any one or more of Si, Ge, Ti, Se and Hf;
and (II) adding nitride of A, nitride of M, carbide of D and nitride or fluoride of R into the obtained intermediate, mixing according to a certain proportion, preserving heat for 8 hours at 1600 ℃ in a C reducing atmosphere, sintering, crushing, washing and drying the obtained fluorescent material, and finally obtaining the target nitride fluorescent powder.
Finally, an embodiment of the present invention provides a light emitting device, which includes an excitation light source and a fluorescent substance excited by the excitation light source, where the fluorescent substance is the nitride fluorescent powder according to the embodiment of the present invention or the nitride fluorescent powder obtained by the preparation method according to the embodiment of the present invention.
In the light-emitting device of the embodiment of the invention, the fluorescent substance excited by the excitation light source is the nitride fluorescent powder special for the embodiment of the invention, and the nitride has high luminous efficiency and good thermal stability, so that the luminous efficiency and the stability of the light-emitting device are finally improved.
Furthermore, the excitation light source is a semiconductor chip with the emission wavelength range of 330-480 nm.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A nitride fluorescent material for high power has a chemical formula of La2.445Ba0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride fluorescent material comprises the following steps: mixing a certain proportion of LaN and Si3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with Lan and Ba3N2、Si3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, the obtained fluorescent substance is crushed, washed and dried, and finally La is obtained2.445Ba0.5Si6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 2
A nitride fluorescent material for high power has a chemical formula of La2.445Sr0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride fluorescent material comprises the following steps: mixing a certain proportion of LaN and Si3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with Lan and Sr3N2、Si3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, the obtained fluorescent substance is crushed, washed and dried, and finally La is obtained2.445Sr0.5Si6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 3
A nitride fluorescent material for high power has a chemical formula of La2.445Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: mixing a certain proportion of LaN and Si3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with Lan and Ca3N2、Si3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, the obtained fluorescent substance is crushed, washed and dried, and finally La is obtained2.445Ca0.5Si6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 4
A high-power nitride fluorescent material with chemical formula of Y2.445Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: mixing YN and Si in a certain proportion3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is homoYN and Ca3N2、Si3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, the obtained fluorescent substance is crushed, washed and dried, and Y is finally obtained2.445Ca0.5Si6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 5
A high-power nitride fluorescent material with the chemical formula of Lu2.445Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: mixing LuN and Si in a certain proportion3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with LuN and Ca3N2、Si3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, the obtained fluorescent substance is crushed, washed and dried, and Lu is finally obtained2.445Ca0.5Si6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 6
A nitride fluorescent material for high power has a chemical formula of Gd2.445Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: will be oneGdN, Si in fixed proportion3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with GdN and Ca3N2、Si3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, and the obtained fluorescent substance is crushed, washed and dried to finally obtain Gd2.445Ca0.5Si6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 7
A nitride fluorescent material for high power has a chemical formula of La2.445Ca0.5Ge6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps: mixing a certain proportion of Lan and Ge3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with Lan and Ca3N2、Ge3N4TbN and SiC are uniformly mixed according to a certain molar ratio, and are sintered at 1600 ℃ for 8 hours in a C reducing atmosphere, the obtained fluorescent substance is crushed, washed and dried, and finally La is obtained2.445Ca0.5Ge6N10.5C0.5Fluorescent powder (0.05Ce,0.005 Tb). The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 8
A nitride fluorescent material for high power has a chemical formula of La2.445Ca0.5Ti6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 9
A nitride fluorescent material for high power has a chemical formula of La2.445Ca0.5Se6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 10
A nitride fluorescent material for high power has a chemical formula of La2.445Ca0.5Hf6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 11
A nitride fluorescent material for high power has a chemical formula of La1.956Lu0.489Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 12
A nitride fluorescent material for high power has a chemical formula of La2.2005Lu0.2445Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 13
A nitride fluorescent material for high power has a chemical formula of La2.145Lu0.3Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 14
A nitride fluorescent material for high power has a chemical formula of La1.845Lu0.6Ca0.5Si6N10.5C0.5:(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 15
A nitride fluorescent material for high power has a chemical formula of La2.345Lu0.1Ca0.5Si6N10.5C0.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 16
A nitride fluorescent material for high power has a chemical formula of La2.935Ca0.01Si6N10.99C0.01(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 17
A nitride fluorescent material for high power has a chemical formula of La2.845Ca0.1Si6N10.9C0.1(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 18
A nitride fluorescent material for high power has a chemical formula of La2.645Ca0.3Si6N10.7C0.3(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 19
A nitride fluorescent material for high power has a chemical formula of La2.145Ca0.8Si6N10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 20
A nitride fluorescent material for high power has a chemical formula of La1.945CaSi6N10C (0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 21
A nitride fluorescent material for high power has a chemical formula of La1.445Ca1.5Si6N9.5C1.5(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 22
A high-power nitride fluorescent material with chemical formula of LaCa2Si6N9C2(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 23
A nitride fluorescent material for high power has a chemical formula of La1.9305Y0.2145Ca0.8Si6N10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 24
A nitride fluorescent material for high power has a chemical formula of La1.9305Gd0.2145Ca0.8Si6N10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 25
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si6N10.2C0.8(0.05Ce,0.005 Tb). Near infrared fluorescence of the nitrideThe materials were prepared in essentially the same manner as in examples 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 26
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 27
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si5SeN10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 28
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si5TiN10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 29
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si5HfN10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 30
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si4.8Se1.2N10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the obtained phosphor has fluorescence characteristics as shown inTable 1.
Example 31
A nitride fluorescent material for high power has a chemical formula of La1.9305Lu0.2145Ca0.8Si4.5Se1.5N10.2C0.8(0.05Ce,0.005 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 32
A nitride fluorescent material for high power has a chemical formula of La1.9795Lu0.2145Ca0.8Si5SeN10.2C0.8(0.005Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 33
A nitride fluorescent material for high power has a chemical formula of La1.9545Lu0.2145Ca0.8Si5SeN10.2C0.8(0.03Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 34
A nitride fluorescent material for high power has a chemical formula of La1.9045Lu0.2145Ca0.8Si5SeN10.2C0.8(0.08Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 35
A nitride fluorescent material for high power has a chemical formula of La1.8845Lu0.2145Ca0.8Si5SeN10.2C0.8(0.1Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 36
A nitride fluorescent material for high power has a chemical formula of La1.8345Lu0.2145Ca0.8Si5SeN10.2C0.8(0.15Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 37
A nitride fluorescent material for high power has a chemical formula of La1.7845Lu0.2145Ca0.8Si5SeN10.2C0.8(0.2Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 38
A nitride fluorescent material for high power has a chemical formula of La1.9345Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.001 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 39
A nitride fluorescent material for high power has a chemical formula of La1.9255Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.01 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 40
A nitride fluorescent material for high power has a chemical formula of La1.9055Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.03 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in table 1, the excitation spectrum is shown in fig. 1, the emission spectrum is shown in fig. 2, and the scanning electron micrograph of the phosphor is shown in fig. 3 (a).
EXAMPLE 41
A kind ofThe chemical formula of the nitride fluorescent material for high power is La1.8855Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.05 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 42
A nitride fluorescent material for high power has a chemical formula of La1.8555Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.08 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 43
A nitride fluorescent material for high power has a chemical formula of La1.8355Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.1 Tb). The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Example 44
A nitride fluorescent material for high power has a chemical formula of La1.9055Lu0.2145Ca0.8Si5GeN10.2C0.8(0.05Ce,0.03 Tb). The preparation method of the nitride near-infrared fluorescent material comprises the following steps:
mixing a certain proportion of LaN and Si3N4、CeN、LuN、Ca3N2、Ge3N4TbN and SiC are uniformly mixed according to the stoichiometric ratio and put into a tungsten crucible, and N is added2/H2Under the reduction of the mixed gas, the mixed gas is subjected to heat preservation at 1600 ℃ for 8h for sintering, the obtained fluorescent substance is crushed, washed and dried, and finally the La is obtained1.9055Lu0.2145Ca0.8Si5GeN10.2C0.8Fluorescent powder (0.05Ce,0.03 Tb). The scanning electron micrograph of the finally obtained nitride phosphor is shown in fig. 3(b), and the emission characteristics are shown in table 1.
Comparative example 5
A nitride fluorescent material for high power has a chemical formula of La1.9355Lu0.2145Ca0.8Si5GeN10.2C0.80.05 Ce. The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Comparative example 4
A nitride fluorescent material for high power has a chemical formula of La1.9355Lu0.2145Ca0.8Si5SeN10.2C0.80.05 Ce. The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Comparative example 3
A nitride fluorescent material for high power has a chemical formula of La1.9355Lu0.2145Ca0.8Si6N10.2C0.80.05 Ce. The preparation method of the nitride near-infrared fluorescent material is basically the same as that of the embodiment 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Comparative example 2
A nitride fluorescent material for high power has a chemical formula as follows: la2.95Si6N110.05 Ce. The preparation method of the nitride near-infrared fluorescent material comprises the following steps: mixing a certain proportion of LaN and Si3N4CeN were mixed homogeneously in stoichiometric proportions and placed in a tungsten crucible under N2/H2Under the reduction of the mixed gas, the mixed gas is subjected to heat preservation at 1600 ℃ for 8h for sintering, the obtained fluorescent substance is crushed, washed and dried, and finally the La is obtained2.95Si6N110.05Ce fluorescent powder. The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
Comparative example 1
A nitride fluorescent material for high power has a chemical formula as follows: la2.95Si6N110.05 Ce. The preparation method of the nitride near-infrared fluorescent material comprises the following steps: mixing a certain proportion of LaN and Si3N4CeN are mixed evenly according to a certain molar ratio and put into a tungsten crucible in N2/H2Under the reduction of the mixed gas, preserving heat for 6h at 1400 ℃, sintering, and crushing to obtain an intermediate; then the obtained intermediate is mixed with Lan and Si3N4Uniformly mixing according to a certain molar ratio, preserving heat for 8h at 1600 ℃ in a C reducing atmosphere, crushing, washing and drying the obtained fluorescent substance to finally obtain La2.95Si6N110.05Ce fluorescent powder. The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
TABLE 1
Fig. 1 and 2 show excitation and emission spectra of example 40, and it can be seen that the nitride phosphor of this example can be excited effectively in both ultraviolet and blue regions, and has an emission peak wavelength of 540nm, a wide half-width, and a shoulder around 580 nm. As can be seen from comparative examples 1 and 2, the samples prepared by the two-step method according to the embodiment of the present invention have significant advantages in initial strength and thermal stability compared to the samples prepared by the conventional method, in which FIG. 3(a) is a scanning electron micrograph of the nitride phosphor obtained by the two-step method according to example 40, FIG. 3(b) is a scanning electron micrograph of the nitride phosphor obtained by the one-step method according to example 44, and it can be seen from comparison between (a) and (b) in FIG. 3 that the crystallinity of the two-step method is better. FIG. 4 is a graph comparing the thermal stability of comparative example 1 and example 40, and it can be seen that the thermal stability of example 40 of the present invention is significantly improved.
From example 30 and example 31, it can be seen that: when the molar content of Si is more than or equal to 80 percent, the fluorescent powder has better luminous intensity. From example 13 and example 14, it can be seen that: when the molar ratio of La to Lu is more than 4:1, the phosphor improved the luminous intensity, and as is clear from examples 33 to 37 or examples 38 to 43, the effect was best when the molar ratio of La to Lu was between (4:10) -1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. The nitride fluorescent powder is applied to a high-power LED device and is characterized in that the chemical general formula of the nitride fluorescent powder is A3-x-y-zMxD6(N11-xCx/2) (yCe, zR); wherein,
a is La and Lu, and the molar ratio of La to Lu is (4-10): 1,
m is at least one selected from Ca, Sr and Ba,
d is selected from at least one of Si, Ge, Ti, Se and Hf, and D includes Si; based on the mol percentage content of D as 100 percent, the mol content of Si is 80 to 90 percent,
r is at least one of Pr, Tb, Nd and Dy,
x is more than or equal to 0.001 and less than or equal to 2, y is more than or equal to 0.005 and less than or equal to 0.2, and z is more than or equal to 0.001 and less than or equal to 0.1.
2. The nitride phosphor according to claim 1, wherein in the chemical formula of the nitride phosphor, M is Ca; and/or
R is Pr and/or Tb.
3. The nitride phosphor of claim 1, wherein in the chemical formula of the nitride phosphor, D is at least one selected from the group consisting of Si, Ge, Ti, and Se, and D comprises Si.
4. The nitride phosphor of claim 3, wherein D is Si and Ge or D is Si and Se.
5. A method of preparing a nitride phosphor according to any of claims 1 to 4, comprising the steps of:
mixing nitride of first A, nitride of first D and CeN at N2And H2Performing a first sintering treatment under the reduction of (1) to obtain an intermediate;
adding a nitride of a second A, a carbide of a second D, a nitride of M and a nitride or fluoride of R into the intermediate, and performing second sintering treatment in a reducing atmosphere of C to obtain the nitride fluorescent powder;
wherein, the total molar amount of A of the nitride of the first A and the nitride of the second A, and the total molar amount of D of the nitride of the first D and the nitride of the second D are respectively the molar amounts of A and D in the chemical general formula of the nitride fluorescent powder.
6. The production method according to claim 5, wherein a ratio of a sum of a molar amount of the element A in the nitride of the first A and the element Ce in the CeN to a molar amount of the element D in the nitride of the first D is 1: 3; and/or
The temperature of the first sintering treatment is 1300-1500 ℃, and the time is 5-7 h; and/or
The temperature of the second sintering treatment is 1500-1700 ℃, and the time is 7-9 h.
7. A light-emitting device comprising an excitation light source and a fluorescent substance excited by the excitation light source, wherein the fluorescent substance is the nitride phosphor according to any one of claims 1 to 4 or the nitride phosphor obtained by the production method according to claim 5 or 6.
8. The light-emitting device according to claim 7, wherein the excitation light source is a semiconductor chip having an emission wavelength range of 330 to 480 nm.
CN201811236895.3A 2018-10-23 2018-10-23 Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device Active CN109370588B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201811236895.3A CN109370588B (en) 2018-10-23 2018-10-23 Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device
PCT/CN2019/084587 WO2020015422A1 (en) 2018-10-23 2019-04-26 Nitride fluorescent powder for semiconductor light emission and preparation method therefor, and light-emitting apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811236895.3A CN109370588B (en) 2018-10-23 2018-10-23 Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device

Publications (2)

Publication Number Publication Date
CN109370588A CN109370588A (en) 2019-02-22
CN109370588B true CN109370588B (en) 2019-12-24

Family

ID=65401390

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811236895.3A Active CN109370588B (en) 2018-10-23 2018-10-23 Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device

Country Status (2)

Country Link
CN (1) CN109370588B (en)
WO (1) WO2020015422A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109370588B (en) * 2018-10-23 2019-12-24 旭宇光电（深圳）股份有限公司 Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device
EP4194528A4 (en) * 2020-08-06 2024-08-14 Nichia Corp Nitride phosphor and manufacturing method therefor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4466757B2 (en) * 2007-04-18 2010-05-26 三菱化学株式会社 Phosphor, phosphor-containing composition, light emitting device, lighting device, image display device, and nitrogen-containing compound
US8551361B2 (en) * 2010-05-14 2013-10-08 Lightscape Materials, Inc. Oxycarbonitride phosphors and light emitting devices using the same
CN109370588B (en) * 2018-10-23 2019-12-24 旭宇光电（深圳）股份有限公司 Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device

Also Published As

Publication number Publication date
CN109370588A (en) 2019-02-22
WO2020015422A1 (en) 2020-01-23

Similar Documents

Publication Publication Date Title
KR101475497B1 (en) Aluminum-silicate based orange-red phosphors with mixed divalent and trivalent cations
JP4617323B2 (en) Yellow light emitting Ce3 + activated silicate-based yellow phosphor having a new composition, method for producing the same, and white light emitting diode including the phosphor
US9153754B2 (en) Light emitting diode (LED) red fluorescent material and lighting device having the same
CN112457848B (en) Narrow-band blue light fluorescent powder and preparation method and application thereof
CN108753296B (en) Red light luminescent material capable of being excited by near ultraviolet or blue light chip and preparation method and application thereof
WO2020015412A1 (en) Near infrared fluorescent nitride material and light-emitting device containing near infrared fluorescent nitride material
CN113249125B (en) Ce 3+ Doped silicate-based green fluorescent powder and preparation method and application thereof
KR101484428B1 (en) Light-emitting material of nitrogen compound, preparation process thereof and illumination source manufactured therefrom
CN114686225A (en) Near-infrared fluorescent powder and preparation method and application thereof
CN109370588B (en) Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device
CN111187622A (en) Single-matrix phosphate fluorescent powder for white light LED and preparation method thereof
CN112625683A (en) Germanate type red fluorescent powder and preparation method thereof
CN114907841B (en) Sm (Sm) 2+ Activated near infrared luminescent material, preparation method and application thereof
CN113999671B (en) Fluorescent powder for illumination display white light LED, and preparation and application thereof
Akhmadullina et al. Synthesis and Luminescence Properties of Tb 3+-Doped Aluminum Oxynitride
CN110272740B (en) Zero-doped rare earth borate red fluorescent powder, preparation and application thereof in L ED field
CN112940724A (en) Eu (Eu)3+Ion activated borate red fluorescent material and preparation method thereof
Fengyang et al. Orange-red emitting Eu2+-activated (Sr0. 883Ba0. 1Lu0. 0.17) 3 (Si0. 95Al0. 05) O5 phosphor: structure, photoluminescence, and application in white LEDs
Chen et al. TAG: Ce3+ phosphors prepared by a novel sol-combustion method for application in InGaN-based white LEDs
CN101619211B (en) A Ca1-x-yTiO3: eu3+x, sm3+yphosphor and its preparation method
CN112300799B (en) Nitrogen oxide fluorescent powder and light-emitting device containing same
CN114806559B (en) Eu (Eu) 2+ Activated ultra-wideband visible-near infrared luminescent material, preparation method and application
CN101619213A (en) Red light La(1-x)TiO(7/2):Eu<3+>x fluorescent powder and preparation method thereof
KR20120072547A (en) Green emitting calcium borate silicate based phosphor
CN110846032A (en) Rare earth ion and metal ion double-doped calcium tungstate luminescent material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant