WO2020015422A1 - Poudre fluorescente de nitrure pour l'émission de lumière à semi-conducteur et son procédé de préparation, et appareil électroluminescent - Google Patents

Poudre fluorescente de nitrure pour l'émission de lumière à semi-conducteur et son procédé de préparation, et appareil électroluminescent Download PDF

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WO2020015422A1
WO2020015422A1 PCT/CN2019/084587 CN2019084587W WO2020015422A1 WO 2020015422 A1 WO2020015422 A1 WO 2020015422A1 CN 2019084587 W CN2019084587 W CN 2019084587W WO 2020015422 A1 WO2020015422 A1 WO 2020015422A1
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nitride
phosphor
fluorescent material
chemical formula
preparing
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Chinese (zh)
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林金填
陈磊
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旭宇光电（深圳）股份有限公司
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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
    • C09K11/7766—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

Definitions

  • the invention belongs to the technical field of light-emitting materials, and particularly relates to a nitride phosphor for semiconductor light-emitting, a preparation method thereof and a light-emitting device.
  • High power light emitting diode (Light Emitting Diode, LED) has small volume, long life, high electro-optical conversion efficiency, fast response speed, energy saving, environmental protection and other excellent characteristics, is widely used in commercial lighting, street lights, automotive lights, searchlights and other fields.
  • white light LEDs have gained widespread popularity in the field of low-power lighting, and both technology and application areas have reached a relatively mature stage.
  • high-power technology and applications it is still in its infancy and development stage. The main reason is that under high-energy excitation, high thermal radiation and strong ray radiation cause large irreversible damage to the phosphor, which reduces the life and stability of the device. Sex and light effects. Therefore, the development of LED phosphors resistant to high energy density is the key to achieving high light efficiency, high stability and high power LED devices.
  • La 3 Si 6 N 11 : Ce 3+ phosphors have obvious advantages in high-power LED applications due to their high thermal stability. However, due to the relatively harsh preparation conditions, and the thermal stability and external quantum efficiency still need to be further improved, it has not yet been widely used in high-power LEDs. Therefore, it is critical to develop nitride phosphors with simple preparation methods, high thermal stability, and high external quantum efficiency that can be applied to high-power LED devices.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, to provide a nitride phosphor for semiconductor light emission, a preparation method and a light emitting device thereof, and to solve the existing technology of low phosphor efficiency and resistance to high energy density difference of the existing phosphor. problem.
  • One aspect of the present invention provides a nitride phosphor, wherein the chemical formula of the nitride phosphor is A 3-xyz M x D 6 (N 11-x C x ): (yCe, zR); 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, and R is selected from Pr At least one of Tb, Tb, Nd, and Dy, and 0.001 ⁇ x ⁇ 2, 0.005 ⁇ y ⁇ 0.2, 0.001 ⁇ z ⁇ 0.1.
  • the nitride phosphor In the nitride phosphor provided by the present invention, A 3+ and N 3- are replaced by appropriate amounts of M 2+ and C 4- ions, respectively, thereby improving the lattice stability and the crystal field environment around the phosphor's luminous center, so that the fluorescence
  • the light and color properties of the powder are controllable and adjustable, and the thermal stability is greatly improved; at the same time, R 3+ is introduced into the nitride phosphor of the present invention, and the luminous efficiency (external quantum efficiency) of the phosphor is further improved through the energy transfer method.
  • the nitride phosphor has high light efficiency and good thermal stability, which is very suitable for high-power LED devices.
  • Another aspect of the present invention provides a method for preparing the above-mentioned nitride phosphor, including the following steps:
  • the second A nitride, the second D carbide, the M nitride, and the R nitride or fluoride are added to the intermediate, and a second sintering treatment is performed in a C reducing atmosphere to obtain the nitrogen.
  • 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 formula of the nitride phosphor.
  • the nitride phosphor provided by the present invention is made by a two-step method.
  • the preparation method is simple in process and low in cost.
  • First, the nitride of the first A, the nitride of the first D and CeN are mixed to make an intermediate, and then the intermediate is prepared. It is mixed with the nitride of the second A, the carbide of the second D, the nitride of the M, and the nitride or fluoride of the R to make a final nitride phosphor.
  • the nitride phosphor produced in two steps is not only Higher light efficiency, better thermal stability, and better crystallization effect.
  • the present invention provides a light emitting device including an excitation light source and a fluorescent substance excited by the excitation light source, the fluorescent substance is the nitride phosphor according to the present invention or the nitride obtained by the preparation method according to the present invention. Phosphor.
  • the fluorescent substance excited by the excitation light source is a nitride phosphor unique to the present invention.
  • the nitride has high light efficiency and good thermal stability, and finally improves the light efficiency and stability of the light-emitting device. .
  • FIG. 1 is an excitation spectrum diagram (detection wavelength of 540 nm) in Example 40 of the present invention
  • FIG. 2 is an emission spectrum chart (excitation wavelength of 450 nm) of Example 40 of the present invention
  • FIG. 4 is a comparison chart of thermal stability between Example 40 and Comparative Example 1 of the present invention.
  • first and second are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as “first” and “second” may explicitly or implicitly include one or more of the features.
  • an embodiment of the present invention provides a nitride phosphor, and the chemical formula of the nitride phosphor is A 3-xyz M x D 6 (N 11-x C x ): (yCe, zR); Among them, A is selected from at least one of La (lanthanum), Y (yttrium), Lu (rhenium), and Gd (rhenium), and M is selected from at least 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 ( ⁇ )
  • R is selected from Pr ( ⁇ ), Tb ( ⁇ ), Nd (Neodymium) and Dy ( ⁇ ) at least one of 0.001 ⁇ x ⁇ 2, 0.005 ⁇ y ⁇ 0.2, 0.001 ⁇ z ⁇ 0.1.
  • the nitride phosphor provided by the embodiment of the present invention, A 3+ and N 3- are replaced by appropriate amounts of M 2+ and C 4- ions, respectively, thereby improving the lattice stability and the crystal field environment around the phosphor emitting center.
  • the light and color performance of the phosphor is controllable and adjustable, and the thermal stability is greatly improved; at the same time, R 3+ is introduced into the nitride phosphor of the present invention, and the luminous efficiency of the phosphor is further improved through the energy transfer method (external Quantum efficiency).
  • the nitride phosphor has higher light efficiency and better thermal stability, which is very suitable for high-power LED devices.
  • M is Ca. This is because the Ca 2+ radius is smaller than the La 3+ radius, and the C 4- ion radius is larger than the N 3- radius.
  • A is La and / or Lu.
  • A is La or Lu
  • the prepared phosphor phase has higher purity and higher luminous efficiency; when the appropriate amount of Lu replaces La element, that is, it contains both La and Lu, the phosphor has better crystallization performance, higher luminous efficiency, and its structure The compactness is enhanced and the stability is improved.
  • R is Pr and / or Tb. When Pr and / or Tb is selected, energy transfer will occur, which further improves the luminous efficiency of the phosphor.
  • D is selected from at least one of Si, Ge, Ti, and Se, and D includes Si. That is, D must contain Si, preferably, D is Si and Ge, or D is Si and Se. Based on the molar percentage of D being 100%, the molar content of Si is 80-90%. When the molar content of Si is 100%, that is, D is only Si, nitride phosphors have better luminous intensity; but when the Si content is too high, the amount of Se or Ge substitution is too small, which is not conducive to the appearance of the phosphor. The improvement of the phosphor color performance is not obvious.
  • the molar content of Si needs to be appropriately reduced.
  • the Si content is too low, the phosphor structure will be distorted and the luminous efficiency will be reduced. And stability will decrease; therefore, the molar content of Si is chosen to be between 80-90%, so that the phosphor not only improves the light color performance but also the luminous efficiency.
  • the nitride phosphor in the chemical formula of the nitride phosphor, A is La and Lu, and the molar ratio of La and Lu is (4-10): 1.
  • the nitride phosphor with composition A in this ratio range has the best thermal stability; when the La / Lu ratio is too low, the phosphor structure When the change occurs, the luminous efficiency of the phosphor will decrease.
  • the molar ratio of La and Lu is between (4-10) : In the range of 1, the phosphor improves both light color performance and luminous efficiency.
  • the concentration of the luminous center in the phosphor Too low the concentration of the luminous center in the phosphor Too low, the luminous efficiency is relatively low, so the effect is best in the range of 0.01 ⁇ y ⁇ 0.1;
  • the z value is too large to cause no radiant energy transfer between activators, concentration quenching, and more blue light absorption , Will cause Ce 3+ emission intensity to decrease, z value is too small, the energy transmission effect of R ions to Ce ions is not obvious, the improvement of luminous efficiency is not obvious, so the effect is best in the range of 0.005 ⁇ z ⁇ 0.05.
  • an embodiment of the present invention also provides a method for preparing the foregoing nitride phosphor, including the following steps:
  • 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 formula of the nitride phosphor.
  • the method for preparing a nitride phosphor provided by the embodiment of the present invention is simple in process and low in cost.
  • the preparation method is a two-step process, that is, the nitride of the raw material A is first divided into two parts: the nitride of the first A and the first The nitride of two A; the nitride of raw material D is divided into two parts: the nitride of the first D and the nitride of the second D; and then the nitride of the first A, the nitride of the first D and CeN are mixed to make Intermediate, and then mix 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 make the final nitride phosphor, which is made in two steps
  • the nitride phosphor not only has higher light efficiency and better thermal stability, but also has better crystallization
  • the sum of the molar amount of the A element in the first A nitride and the Ce element in the CeN and the molar amount of the D element in the first D nitride is 1: 3. Within this range, intermediates can be made better, which is conducive to the subsequent production of nitride phosphors.
  • the temperature of the first sintering process is 1300-1500 ° C and the time is 5-7h; the temperature of the second sintering process is 1500-1700 ° C and the time is 7-9h.
  • the intermediate and the final nitride phosphor can be better sintered.
  • a method for preparing the nitride phosphor includes:
  • a certain proportion of nitrides of A, nitrides of D, and CeN powder are uniformly mixed according to a certain stoichiometric ratio, and placed in a tungsten crucible, and maintained at 1400 ° C under the reduction of a N 2 / H 2 mixed gas. 6h sintering to obtain intermediates after crushing; where A is any one or more of La, Y, Lu, Gd, and D is any one or more of Si, Ge, Ti, Se, Hf;
  • an embodiment of the present invention provides a light emitting device including an excitation light source and a fluorescent substance excited by the excitation light source, the fluorescent substance is the nitride phosphor according to the embodiment of the present invention or the phosphor according to the embodiment of the present invention.
  • the fluorescent substance excited by the excitation light source is a nitride phosphor unique to the embodiment of the present invention.
  • the nitride has high light efficiency and good thermal stability, and finally improves the light of the light-emitting device. Efficiency and stability.
  • the excitation light source is a semiconductor chip having an emission wavelength range of 330 to 480 nm.
  • the method for preparing a nitride fluorescent material includes the following steps: a certain proportion of LaN, Si 3 N 4 and CeN are uniformly mixed according to a certain molar ratio, and placed in a tungsten crucible, and reduced in a N 2 / H 2 mixed gas Sintering at 1400 ° C for 6h, then the intermediate is obtained after crushing; then the obtained intermediate is uniformly mixed with LaN, Ba 3 N 2 , Si 3 N 4 , TbN, SiC in a certain molar ratio, and reduced in a C atmosphere The sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to obtain La 2.445 Ba 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb) phosphor.
  • the method for preparing a nitride fluorescent material includes the following steps: a certain proportion of LaN, Si 3 N 4 and CeN are uniformly mixed according to a certain molar ratio, and placed in a tungsten crucible, and reduced in a N 2 / H 2 mixed gas Sintering at 1400 ° C for 6h, and the intermediate obtained after crushing; then the obtained intermediate is uniformly mixed with LaN, Sr 3 N 2 , Si 3 N 4 , TbN, and SiC in a certain molar ratio, and reduced in a C atmosphere The sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to obtain La 2.445 Sr 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb) phosphor.
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: a certain proportion of LaN, Si 3 N 4 and CeN are uniformly mixed according to a certain molar ratio, and placed in a tungsten crucible, and mixed with N 2 / H 2 gas Under the reduction of sintering at 1400 ° C for 6h, the intermediates are obtained after crushing; then the obtained intermediates are uniformly mixed with LaN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC at a certain molar ratio, and mixed at C In a reducing atmosphere, sintered at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried, and finally La 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005T
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: uniformly mixing a certain proportion of YN, Si 3 N 4 and CeN in a certain molar ratio, putting the same into a tungsten crucible, and mixing the gas in N 2 / H 2 Under the reduction, sintered at 1400 ° C for 6 hours, and then obtained the intermediate after crushing; then the obtained intermediate was uniformly mixed with YN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and mixed at C Under a reducing atmosphere, sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to finally obtain Y 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: uniformly mixing a certain proportion of LuN, Si 3 N 4 and CeN according to a certain molar ratio, putting the same into a tungsten crucible, and mixing in a N 2 / H 2 gas Under the reduction, sintering was maintained at 1400 ° C for 6 hours, and the intermediate was obtained after crushing.
  • the obtained intermediate was uniformly mixed with LuN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC according to a certain molar ratio, and then mixed at C In a reducing atmosphere, sintering was performed at 1600 ° C for 8 hours.
  • the obtained fluorescent substance was crushed, washed, and dried to finally obtain Lu 2.445 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb) phosphor.
  • the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: uniformly mixing a certain proportion of GdN, Si 3 N 4 and CeN in a certain molar ratio, putting the same into a tungsten crucible, and mixing in a N 2 / H 2 gas Under the reduction of sintering at 1400 ° C for 6 hours, the intermediates are obtained after crushing; then the obtained intermediates are uniformly mixed with GdN, Ca 3 N 2 , Si 3 N 4 , TbN, and SiC at a certain molar ratio, and mixed at C In a reducing atmosphere, sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to finally obtain Gd 2.445 Ca 0.5 Si 6 N 10.5 C 0.5
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: uniformly mixing a certain proportion of LaN, Ge 3 N 4 and CeN in a certain molar ratio, putting the same into a tungsten crucible, and mixing the gas in N 2 / H 2 Under the reduction of sintering at 1400 ° C for 6h, the intermediates are obtained after crushing; then the obtained intermediates are uniformly mixed with LaN, Ca 3 N 2 , Ge 3 N 4 , TbN, and SiC at a certain molar ratio, and mixed at C Under a reducing atmosphere, sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to obtain La 2.445 Ca 0.5 Ge 6 N 10.5 C 0.5 : (0.05Ce,
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 2.145 Lu 0.3 Ca 0.5 Si 6 N 10.5 C 0.5 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of LaCa 2 Si 6 N 9 C 2 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a nitride fluorescent material for high power the chemical formula is La 1.9305 Y 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material the chemical formula is La 1.9305 Gd 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 TiN 10.2 C 0.8 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9305 Lu 0.2145 Ca 0.8 Si 5 HfN 10.2 C 0.8 : (0.05Ce, 0.005Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9795 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.005Ce, 0.001Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9545 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.03Ce, 0.001Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9045 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.08Ce, 0.001Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.8345 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : (0.15Ce, 0.001Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9255 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.01Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9055 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.03Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that of Examples 1-7; the fluorescence emission characteristics of the obtained phosphor are shown in Table 1, the excitation spectrum is shown in FIG. 1, and the emission spectrum is shown in FIG. The scanning electron microscope image of the phosphor is shown in Fig. 3 (a).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.8555 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.08Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.8355 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.1Tb).
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9055 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.03Tb).
  • the method for preparing the nitride near-infrared fluorescent material includes the following steps:
  • LaN, Si 3 N 4 , CeN, LuN, Ca 3 N 2 , Ge 3 N 4 , TbN, and SiC are uniformly mixed according to the stoichiometric ratio, and put into a tungsten crucible and mixed in N 2 / H 2 Under the reduction of gas, sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to obtain La 1.9055 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : (0.05Ce, 0.03Tb) phosphor.
  • the scanning electron microscope image of the finally obtained nitride phosphor is shown in FIG. 3 (b), and the light emission characteristics are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9355 Lu 0.2145 Ca 0.8 Si 5 GeN 10.2 C 0.8 : 0.05Ce.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9355 Lu 0.2145 Ca 0.8 Si 5 SeN 10.2 C 0.8 : 0.05Ce.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula of La 1.9355 Lu 0.2145 Ca 0.8 Si 6 N 10.2 C 0.8 : 0.05Ce.
  • the method for preparing the nitride near-infrared fluorescent material is basically the same as that in Examples 1-7; the fluorescence emission characteristics of the obtained phosphor powder are shown in Table 1.
  • a nitride fluorescent material for high power the formula is: La 2.95 Si 6 N 11 : 0.05Ce.
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: uniformly mixing a certain proportion of LaN, Si 3 N 4 and CeN according to a stoichiometric ratio, putting the same into a tungsten crucible, and mixing in N 2 / H 2 Under the reduction of gas, sintering was performed at 1600 ° C for 8 hours, and the obtained fluorescent substance was crushed, washed, and dried to obtain La 2.95 Si 6 N 11 : 0.05Ce phosphor. The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
  • a high-power nitride fluorescent material has a chemical formula: La 2.95 Si 6 N 11 : 0.05Ce.
  • the method for preparing a nitride near-infrared fluorescent material includes the following steps: a certain proportion of LaN, Si 3 N 4 and CeN are uniformly mixed according to a certain molar ratio, and placed in a tungsten crucible, and mixed with N 2 / H 2 gas Under the reduction, the sintering was maintained at 1400 ° C for 6h, and the intermediate was obtained after crushing. Then the obtained intermediate was uniformly mixed with LaN and Si 3 N 4 according to a certain molar ratio, and sintered at 1600 ° C for 8h in a C reducing atmosphere. After the obtained fluorescent substance is crushed, washed, and dried, La 2.95 Si 6 N 11 : 0.05Ce phosphor is finally obtained. The fluorescence emission characteristics of the obtained phosphor are shown in Table 1.
  • Example 1 La2.445Ba0.5Si6N10.5C0.5: 0.05Ce, 0.005Tb 104 101
  • Example 2 La2.445Sr0.5Si6N10.5C0.5: 0.05Ce, 0.005Tb 105 102
  • Example 3 La2.445Ca0.5Si6N10.5C0.5: 0.05Ce, 0.005Tb 108 104
  • Example 5 Lu2.445Ca0.5Si6N10.5C0.5: 0.05Ce, 0.005Tb 107 105
  • Example 6 Gd2.445Ca0.5Si6N10.5C0.5: 0.05Ce, 0.005Tb 104 99
  • Example 7 La2.445Ca0.5Ge6N10.5C0.5: 0.05Ce, 0.005Tb 107 104
  • Example 8 La2.445Ca
  • Figure 1 and Figure 2 are the excitation and emission spectra of Example 40. It can be seen from the figure that the nitride phosphor of this example can be effectively excited in the ultraviolet and blue light regions, and the emission peak wavelength is at 540 nm. Wide, with a shoulder peak around 580nm. According to Comparative Example 1 and Comparative Example 2, it can be known that the initial strength and thermal stability of the sample prepared by the two-step method of the embodiment of the present invention have obvious advantages over the traditional method of preparing the sample.
  • Figure 3 (a) is a two-step method according to Example 40. Scanning electron microscope image of the nitride phosphor obtained by the method.
  • FIG. 4 is a comparison chart of the thermal stability of Comparative Example 1 and Example 40. It can be seen that the thermal stability of Example 40 of the present invention has a significant improvement.
  • Example 30 and Example 31 it can be known from Example 30 and Example 31 that when the molar content of Si is 80% or more, the phosphor has better luminous intensity. It can be known from Example 13 and Example 14 that when the molar ratio of La and Lu is greater than 4: 1, the phosphor increases the light emission intensity. From Examples 33-37 or 38-43, it can be known that The effect is best when the ratio is between (4:10) -1.

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Abstract

La présente invention appartient au domaine technique des matériaux électroluminescents, et concerne plus particulièrement une poudre fluorescente de nitrure pour l'émission de lumière à semi-conducteur et son procédé de préparation, et un appareil électroluminescent. La formule chimique générale de la poudre fluorescente de nitrure est A3-x-y-zMxD6(N11-xCx):(yCe,zR), dans laquelle A est choisi parmi au moins un des La, Y, Lu et Gd, M est choisi parmi au moins un des Ca, Sr et Ba, D est choisi parmi au moins un des Si, Ge, Ti, Se et Hf, R est choisi parmi au moins un des Pr, Tb, Nd et Dy, 0,001≤x≤2, 0,005≤y≤0,2, et 0,001≤z≤0,1. La poudre fluorescente de nitrure présente une efficacité lumineuse élevée et une bonne stabilité thermique et est tout à fait appropriée pour être appliquée à des dispositifs de DEL haute puissance.
PCT/CN2019/084587 2018-10-23 2019-04-26 Poudre fluorescente de nitrure pour l'émission de lumière à semi-conducteur et son procédé de préparation, et appareil électroluminescent WO2020015422A1 (fr)

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CN101663372A (zh) * 2007-04-18 2010-03-03 三菱化学株式会社 荧光体及其制造方法、含荧光体组合物、发光装置、照明装置、图像显示装置以及含氮化合物
CN102939355A (zh) * 2010-05-14 2013-02-20 渲染材料公司 氧碳氮化物磷光体和使用该材料的发光器件
CN109370588A (zh) * 2018-10-23 2019-02-22 旭宇光电（深圳）股份有限公司 半导体发光用的氮化物荧光粉及其制备方法和发光装置

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CN101663372A (zh) * 2007-04-18 2010-03-03 三菱化学株式会社 荧光体及其制造方法、含荧光体组合物、发光装置、照明装置、图像显示装置以及含氮化合物
CN102939355A (zh) * 2010-05-14 2013-02-20 渲染材料公司 氧碳氮化物磷光体和使用该材料的发光器件
CN109370588A (zh) * 2018-10-23 2019-02-22 旭宇光电（深圳）股份有限公司 半导体发光用的氮化物荧光粉及其制备方法和发光装置

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