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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/64—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing aluminium
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/0883—Arsenides; Nitrides; Phosphides
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/64—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing aluminium
  • C09K11/644—Halogenides
  • C09K11/645—Halogenides with alkali or alkaline earth metals
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7715—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing cerium
  • C09K11/77217—Silicon Nitrides or Silicon Oxynitrides
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/77346—Aluminium Nitrides or Aluminium Oxynitrides
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/851—Wavelength conversion means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/851—Wavelength conversion means
  • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
  • H10H20/8512—Wavelength conversion materials

Definitions

• the present invention relates to surface-coated phosphor particles and a light emitting device.
• Patent Document 1 describes SrLiAl 3 N 4 : Eu, a so-called SLAN phosphor (claim 1, paragraph 0113, etc. of Patent Document 1).
• the present inventor has found that the emission intensity characteristics in a high temperature and high humidity environment can be enhanced by appropriately heat-treating the surface-coated phosphor particles. Although the detailed mechanism is not clear, it is considered that the surface layer of the phosphor particles is stabilized and the deterioration of the light emitting characteristics is suppressed even under high temperature and high humidity conditions.
• the phosphor is a general formula M 1 a M 2 b M 3 c Al 3 N 4-d Od (where M 1 is one or more elements selected from Sr, Mg, Ca and Ba, and M 2 Is one or more elements selected from Li, Na and K, and M 3 is one or more elements selected from Eu, Ce and Mn) and has a composition represented by the above a, b.
• the covering portion constitutes at least a part of the outermost surface of the particles and contains AlF 3 .
• a light emitting device having the above-mentioned surface-coated phosphor particles and a light emitting element is provided.
• a surface-coated phosphor particle having excellent emission intensity characteristics in a high-temperature and high-humidity environment, and a light-emitting device using the same are provided.
• the surface-coated phosphor particles of the present embodiment are phosphor particles containing particles containing a phosphor and a coating portion that covers the surface of the particles.
• the phosphor contained in the surface-coated phosphor particles has a composition represented by the general formula M 1 a M 2 b M 3 c Al 3 N 4-d Od .
• M 1 is one or more elements selected from Sr, Mg, Ca and Ba
• M 2 is one or more elements selected from Li, Na and K
• M 3 is Eu, Ce.
• Mn is Eu, Ce.
• a, b, c, 4-d, and d indicate the molar ratio of each element.
• A, b, c, and d in the general formula satisfy each of the following formulas. 0.850 ⁇ a ⁇ 1.150 0.850 ⁇ b ⁇ 1.150 0.001 ⁇ c ⁇ 0.015 0 ⁇ d ⁇ 0.40 0 ⁇ d / (a + d) ⁇ 0.30
• M 1 is one or more elements selected from Sr, Mg, Ca and Ba, and preferably contains at least Sr.
• the lower limit of the molar ratio a of M 1 is preferably 0.850 or more, more preferably 0.950 or more.
• the upper limit of the molar ratio a of M 1 is preferably 1.150 or less, more preferably 1.100 or less, and even more preferably 1.050 or less.
• M 2 is one or more elements selected from Li, Na and K, preferably containing at least Li.
• Molar ratio lower limit of b of M 2 is preferably not less than 0.850, more preferably not less than 0.950.
• the upper limit of the molar ratio b of M 2 is preferably 1.150 or less, more preferably 1.100 or less, more preferably 1.050 or less.
• the molar ratio a of M 2 is in the above range, it is possible to improve the crystal structure stability.
• M 3 is an activator added to the parent crystal, that is, an element constituting the emission center ion of the phosphor, and is one or more elements selected from Eu, Ce and Mn.
• M 3 can be selected according to the required emission wavelength, and preferably contains at least Eu.
• the lower limit of the molar ratio c of M 3 is preferably 0.001 or more, and more preferably 0.005 or more.
• the upper limit of the molar ratio c of M 3 is preferably 0.015 or less, more preferably 0.010 or less.
• the lower limit of the molar ratio d of oxygen (O) is preferably 0 or more, more preferably 0.05 or more.
• the upper limit of the molar ratio d of oxygen is preferably 0.40 or less, more preferably 0.35 or less.
• the lower limit of the molar ratio of M 1 and oxygen that is, the value of d / (a + d) calculated from a and d is preferably 0 or more, and more preferably 0.05 or more.
• the upper limit of the value of d / (a + d) is preferably less than 0.30, more preferably 0.25 or less.
• the coating portion constitutes at least a part of the outermost surface of the particles containing the above-mentioned phosphor.
• the coating contains a fluorine-containing compound containing a fluorine element and an aluminum element.
• the fluorine-containing compound it is preferable that the fluorine element and the aluminum element are directly covalently bonded, and more specifically, the fluorine-containing compound preferably contains AlF 3 .
• the fluorine-containing compound may be composed of a single compound containing a fluorine element and an aluminum element.
• the coating portion containing the fluorine-containing compound constitutes at least a part of the outermost surface of the particles containing the phosphor, the moisture resistance of the phosphor constituting the particles can be improved. From the viewpoint of further improving the moisture resistance of the phosphor, it is more preferable that the coating portion contains AlF 3 .
• the mode of the covering portion is not particularly limited.
• Examples of the mode of the coating portion include a mode in which a large number of particulate fluorine-containing compounds are distributed on the surface of the particles containing the phosphor, and a mode in which the fluorine-containing compound continuously covers the surface of the particles containing the phosphor. Can be mentioned.
• the coating may be configured to cover part or all of the particle surface.
• An X-ray diffraction pattern is obtained by X-ray diffraction using Cu—K ⁇ rays for the surface-coated phosphor particles.
• the emission intensity of the 2 [Theta] is the emission intensity of the maximum peak A in the range of 23 ° or more 26 ° or less and I A, the maximum peak B 2 [Theta] is in the range of 36 ° or more 39 ° or less
• IB the surface-coated phosphor particles of the present embodiment, I A, is I B, satisfies the I A / I B ⁇ 0.10.
• the diffraction pattern of the surface-coated phosphor particles is measured using an X-ray diffractometer based on the following measurement conditions.
• Sample preparation Place powdered surface-coated fluorophore particles on the sample holder. The peak intensity is a value obtained by performing background correction.
• the emission intensity characteristics in a high temperature and high humidity environment can be enhanced by appropriately heat-treating the surface-coated phosphor particles.
• the detailed mechanism is not clear, it is considered that the surface layer of the phosphor particles is stabilized and the deterioration of the light emitting characteristics is suppressed even under high temperature and high humidity conditions.
• the X-ray diffraction pattern obtained by X-ray diffraction method the light emission intensity of the maximum peak A 2 [Theta] is in the range of less than 26 ° 23 ° or more and I A, when 2 ⁇ is the emission intensity of the maximum peak B in the range of 36 ° or more 39 ° or less was I B, by an index I a / I B, the stabilization of the surface layer of the surface-coated phosphor particles the degree can be stably evaluated and, moreover, by a within a reasonable numerical range I a / I B, seen to produce excellent surface coverage phosphor particles emission intensity characteristics in a high-temperature and high-humidity environment It was issued.
• the upper limit of I A / I B is 0.10 or less, preferably 0.09 or less, more preferably 0.08 or less, more preferably 0.07 or less. Thereby, the emission intensity characteristic in a high temperature and high humidity environment can be improved.
• the lower limit of I A / I B is not particularly limited.
• the maximum peak A of luminous intensity I A comprises peaks derived SrAlF 5.
• Maximum peak B of the emission intensity I B comprises peaks from SLAN.
• the type and amount of raw material components for use in the surface-coated phosphor particles by appropriately selecting the method for producing such a surface-coated phosphor particles, and controls the I A, I A / I B It is possible.
• performing the acid treatment and the hydrofluoric acid treatment such as by the temperature of the heat treatment within the appropriate range, the I A, the desired numerical value range I A / I B It can be mentioned as an element for.
• the diffuse reflectance for light irradiation at a wavelength of 300 nm is, for example, 56% or more, preferably 65% or more, and more preferably 70% or more.
• the diffuse reflectance with respect to light irradiation at the peak wavelength of the fluorescence spectrum is, for example, 80% or more, preferably 83% or more, and more preferably 85% or more.
• the surface-coated phosphor particles When excited with blue light having a wavelength of 455 nm, the surface-coated phosphor particles are configured so that the peak wavelength is in the range of, for example, 640 nm or more and 670 nm or less, and the half width thereof satisfies, for example, 45 nm or more and 60 nm or less. Good. By providing such characteristics, excellent color rendering and color reproducibility can be expected.
• the surface-coated phosphor particles When excited with blue light having a wavelength of 455 nm, the surface-coated phosphor particles may be configured such that the x value in the CIE-xy chromaticity diagram satisfies, for example, 0.680 ⁇ x ⁇ 0.735. By having such characteristics, excellent color reproducibility can be expected. If the x value is 0.680 or more, red light emission with good color purity can be further expected, and if the x value is 0.735 or more, it exceeds the maximum value in the CIE-xy chromaticity diagram, so the above range is satisfied. Is preferable.
• the method for producing the surface-coated phosphor particles is a method of producing at least one element M 1 selected from the group consisting of Sr, Mg, Ca and Ba, and at least one element M selected from the group consisting of Li, Na and K. 2.
• a phosphor particle (surface-coated phosphor particle) having a composition containing a group consisting of at least one element M 3 , Al, and N selected from the group consisting of Eu, Ce, and Mn is produced. ..
• the method for producing the surface-coated phosphor particles can include a mixing step, a firing step, a pulverization step, an acid treatment step, a hydrofluoric acid treatment step, and a heat treatment step. Each step will be described in detail.
• each raw material weighed so as to obtain the desired surface-coated phosphor particles is mixed to obtain a powdery raw material mixture.
• the method of mixing the raw materials is not particularly limited, but for example, there is a method of sufficiently mixing using a mixing device such as a mortar, a ball mill, a V-type mixer, and a planetary mill. It is appropriate to handle strontium nitride, lithium nitride, etc., which react violently with moisture and oxygen in the air, in a glove box in which the inside is replaced with an inert atmosphere or by using a mixing device.
• a mixing device such as a mortar, a ball mill, a V-type mixer, and a planetary mill. It is appropriate to handle strontium nitride, lithium nitride, etc., which react violently with moisture and oxygen in the air, in a glove box in which the inside is replaced with an inert atmosphere or by using a mixing device.
• the amount of M 1 charged when the molar ratio of Al is 3 is 1.10 or more in terms of molar ratio.
• the amount of M 1 charged when the molar ratio of Al is 3 is 1.20 or less in terms of molar ratio.
• Each raw material used in the mixing step can include one or more selected from the group consisting of a simple substance of a metal element contained in the composition of a phosphor and a metal compound containing the metal element.
• the metal compound include nitrides, hydrides, fluorides, oxides, carbonates, chlorides and the like. Of these, nitrides are preferably used as the metal compound containing M 1 and M 2 from the viewpoint of improving the emission intensity of the phosphor.
• a metal compound containing M 1, Sr 3 N 2, Sr 2 N, SrN 2, etc. SrN the like.
• the metal compound containing M 2 include Li 3 N and Li N 3 .
• the metal compound containing M 3 include Eu 2 O 3 , Eu N, and Eu F 3 .
• the metal compound containing Al include AlN, AlH 3 , AlF 3 , LiAlH 4 and the like.
• flux may be added.
• the flux include LiF, SrF 2 , BaF 2 , AlF 3, and the like. These may be used alone or in combination of two or more.
• firing process for example, the above-mentioned raw material mixture is filled inside a firing container and fired.
• the firing container preferably has a structure that can improve airtightness.
• the firing vessel is preferably made of a material that is stable under high temperature atmospheric gas and does not easily react with the mixture of raw materials and its reaction products.
• a vessel made of boron nitride or carbon, molybdenum or tantalum It is preferable to use a container made of a refractory metal such as molybdenum or tungsten.
• an atmospheric gas of non-oxidizing gas such as argon, helium, hydrogen, and nitrogen.
• the lower limit of the firing temperature in the firing step is preferably 900 ° C. or higher, more preferably 1000 ° C. or higher, and even more preferably 1100 ° C. or higher.
• the upper limit of the firing temperature is preferably 1500 ° C. or lower, more preferably 1400 ° C. or lower, and even more preferably 1300 ° C. or lower.
• Type of firing atmosphere gas As the type of firing atmosphere gas in the firing step, for example, a gas containing nitrogen as an element can be preferably used. Specific examples include nitrogen and / or ammonia, with nitrogen being particularly preferred. Similarly, an inert gas such as argon or helium can also be preferably used.
• the firing atmosphere gas may be composed of one type of gas or may be a mixed gas of a plurality of types of gases.
• the pressure of the firing atmosphere gas is selected according to the firing temperature, but is usually in a pressurized state in the range of 0.1 MPa ⁇ G or more and 10 MPa ⁇ G or less.
• the firing time in the firing step a time range is selected in which a large amount of unreacted substances are not present, the phosphor particles are insufficiently grown, or the productivity is not lowered.
• the lower limit of the firing time is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more.
• the upper limit of the firing time is preferably 48 hours or less, more preferably 36 hours or less, and even more preferably 24 hours or less.
• the raw material mixture (calcined product) after the firing step is pulverized to obtain a pulverized product.
• the state of the fired product obtained by the firing process varies from powdery to lumpy depending on the raw material composition and firing conditions.
• the fired product can be made into a powder of a predetermined size.
• the member of the device that comes into contact with the fired product is made of silicon nitride, alumina, sialon or the like in order to prevent impurities derived from the treatment from being mixed.
• the average particle size of the pulverized product may be adjusted so that the average particle size of the surface-coated phosphor particles is 5 ⁇ m or more and 30 ⁇ m or less.
• the surface-coated phosphor particles are excellent in absorption efficiency and luminous efficiency of excitation light, and therefore can be suitably used for LEDs and the like.
• the ground product is acid-treated with a solution containing an acid.
• a mixed solution containing an acid and a solvent may be used, preferably a mixed solution of an acid and an organic solvent, and more preferably a mixed aqueous solution of an acid and an organic solvent.
• an inorganic acid for example, an inorganic acid may be used, and specific examples thereof include nitric acid, hydrochloric acid, acetic acid, sulfuric acid, formic acid, and phosphoric acid. These may be used alone or in combination of two or more.
• an aqueous solvent or an organic solvent is used as the solvent.
• organic solvent examples include alcohol, acetone and the like. Of these, alcohol is preferable.
• alcohol for example, methanol, ethanol, 2-propanol and the like are used.
• the mixing ratio of the organic solvent in the mixed solution may be adjusted so that the acid content is 0.1% by volume or more and 3% by volume or less with respect to 100% by volume of the mixed solution containing the acid and the solvent.
• impurity elements contained in the raw material, impurity elements derived from the firing container, different phases generated in the firing process, and impurity elements mixed in the crushing process can be dissolved and removed. Since it is possible to remove fine powder at the same time, light scattering can be suppressed and the light absorption rate of the phosphor can be improved. That is, the acid treatment can wash foreign substances and the like.
• cleaning may be performed with an organic solvent, or cleaning may be performed with a mixed solution containing an acid and an organic solvent.
• the pulverized product may be dispersed and immersed in a solution containing an acid for, for example, about 0.5 to 5 hours.
• hydrofluoric acid treatment process In the hydrofluoric acid treatment, the pulverized product after the acid treatment step is subjected to the hydrofluoric acid treatment.
• an aqueous hydrofluoric acid solution is preferably used as a compound containing a fluorine element.
• the lower limit of the concentration of the hydrofluoric acid aqueous solution is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more.
• the upper limit of the concentration of the hydrofluoric acid aqueous solution is preferably 40% by mass or less, more preferably 38% by mass or less, and further preferably 35% by mass or less.
• a coating portion containing (NH 4 ) 3 AlF 6 can be formed on at least a part of the outermost surface of the particles containing the phosphor.
• concentration of the hydrofluoric acid aqueous solution it is possible to prevent the reaction between the particles and hydrofluoric acid from becoming too violent.
• the pulverized product and the aqueous hydrofluoric acid solution can be mixed by a stirring means such as a stirrer.
• the lower limit of the mixing time of the pulverized product and the aqueous hydrofluoric acid solution is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more.
• the upper limit of the mixing time of the fired product and the hydrofluoric acid aqueous solution is preferably 30 minutes or less, more preferably 25 minutes or less, still more preferably 20 minutes or less.
• a coating portion containing (NH 4 ) 3 AlF 6 is stably formed on at least a part of the outermost surface of the particles containing the phosphor. Can be done.
• the type of acid and solvent in the acid treatment step, the acid concentration, the hydrofluoric acid concentration in the hydrofluoric acid treatment step, the hydrofluoric acid treatment time, the heating temperature and the heating time in the heat treatment step performed after the hydrofluoric acid treatment.
• Heat treatment process In the heat treatment, the pulverized product after the hydrofluoric acid treatment is heated in the air.
• the lower limit of the heating temperature in the heat treatment step is preferably 220 ° C. or higher, more preferably 250 ° C. or higher.
• the upper limit of the heating temperature is preferably 380 ° C. or lower, more preferably 350 ° C. or lower, and even more preferably 330 ° C. or lower.
• the heating temperature to the above upper limit or less, the crystal structure of the phosphor can be maintained well and the emission intensity can be increased.
• the lower limit of the heating time is preferably 1 hour or more, more preferably 1.5 hours or more, still more preferably 2 hours or more.
• the upper limit of the heating time is preferably 6 hours or less, more preferably 5.5 hours or less, and even more preferably 5 hours or less.
• the heat treatment step is preferably carried out in the air or in a nitrogen atmosphere. According to this, the target substance can be produced without the substance itself in the heating atmosphere hindering the above reaction formula (1).
• the light emitting device according to the present embodiment has surface-coated phosphor particles and a light emitting element.
• the light emitting element an ultraviolet LED, a blue LED, a fluorescent lamp alone, or a combination thereof can be used.
• the light emitting element is preferably one that emits light having a wavelength of 250 nm or more and 550 nm or less, and particularly preferably a blue LED light emitting element of 420 nm or more and 500 nm or less.
• fluorescent particles having other emission colors may be used in combination.
• Examples of phosphor particles having other emission colors include blue emission phosphor particles, green emission phosphor particles, yellow emission phosphor particles, orange emission phosphor particles, and red phosphor.
• Ca 3 Sc 2 Si 3 O 12 : Ce, CaSc 2 O 4 : Ce, ⁇ -SiAlON: Eu, Y 3 Al 5 O 12 : Ce, Tb 3 Al 5 O 12 : Ce, (Sr, Ca, Ba) 2 SiO 4 : Eu, La 3 Si 6 N 11 : Ce, ⁇ -SiAlON: Eu, Sr 2 Si 5 N 8 : Eu and the like can be mentioned.
• the other phosphor particles are not particularly limited, and can be appropriately selected according to the brightness, color rendering properties, etc. required for the light emitting device.
• the light emitting device include a lighting device, a backlight device, an image display device, a signal device, and the like.
• the raw material mixture was filled in a cylindrical BN container with a lid (manufactured by Denka Co., Ltd.).
• a firing step was carried out.
• the inside of the electric furnace was once degassed to a vacuum state, and then firing was started in a pressurized nitrogen atmosphere of 0.8 MPa ⁇ G from room temperature. After the temperature in the electric furnace reached 1100 ° C., firing was continued while maintaining the temperature for 8 hours, and then cooled to room temperature.
• Comparative Example 2 Except for the fact that the fluorescent powder, which had been subjected to hydrofluoric acid treatment and then passed through a sieve having a mesh size of 45 ⁇ m to disaggregate, was heat-treated at 200 ° C. for 4 hours in an air atmosphere.
• the phosphor particles of Comparative Example 2 were obtained by the same amount and procedure of charging raw materials as in Comparative Example 1.
• Example 1 Except for the fact that the fluorescent powder, which had been subjected to hydrofluoric acid treatment and then passed through a sieve having a mesh size of 45 ⁇ m to disaggregate, was heat-treated at 250 ° C. for 4 hours in an air atmosphere.
• the phosphor particles of Example 1 were obtained by the same amount and procedure of charging raw materials as in Comparative Example 1.
• Example 2 Except for the fact that the fluorescent powder, which had been subjected to hydrofluoric acid treatment and then passed through a sieve having a mesh size of 45 ⁇ m to disaggregate, was heat-treated at 300 ° C. for 4 hours in an air atmosphere.
• the phosphor particles of Example 2 were obtained by the same raw material charge amount and procedure as in Comparative Example 1.
• Comparative Example 3 Except for the fact that the fluorescent powder, which had been subjected to hydrofluoric acid treatment and then passed through a sieve having a mesh size of 45 ⁇ m to disaggregate, was heat-treated at 400 ° C. for 4 hours in an air atmosphere.
• the phosphor particles of Comparative Example 3 were obtained by the same amount and procedure of charging raw materials as in Comparative Example 1.
• the resulting phosphor particles the chemical composition which is the sum of all crystalline phases (i.e., Sr a Li b Eu c Al 3 N 4-d O d) was determined subscripts a ⁇ d of each element. Specifically, for Sr, Li, Al and Eu, an ICP emission spectrophotometer (CIROS-120, manufactured by SPECTRO) was used, and for O and N, an oxygen nitrogen analyzer (EMGA-920, manufactured by Horiba Seisakusho) was used. Subscripts a to d were calculated using the analysis results used. The numerical values of a to d of each phosphor particle are shown in Table 1.
• Sample preparation Powdered fluorophore particles were placed on the sample holder. The peak intensity was a value obtained by performing background correction.
• Examples 1 and 2 and Comparative Example 3 a peak (maximum peak A) corresponding to SrAlF 5 was confirmed in the range where 2 ⁇ was 24.5 ° or more and 25.5 ° or less. In Comparative Examples 1 and 2, no peak corresponding to SrAlF 5 was confirmed. In Examples 1 and 2 and Comparative Examples 1 to 3, a peak (maximum peak B) corresponding to SLAN was confirmed in the range where 2 ⁇ was 36.5 ° or more and 37.5 ° or less. The emission intensity of the maximum peak A and I A, the emission intensity of the maximum peak B of when the I B, was calculated I A / I B. The results are shown in Table 1.
• Examples 1 and 2 and Comparative Example 3 a peak corresponding to AlF 3 was confirmed in the range where 2 ⁇ was 14 ° or more and 15 ° or less.
• a peak corresponding to (NH 4 ) 3 AlF 6 was confirmed in the range where 2 ⁇ was 16.5 ° or more and 17.5 ° or less.
• a small peak corresponding to (NH 4 ) 3 AlF 6 was observed.
• Examples 1 and 2 were surface-coated phosphor particles in which at least a part of the outermost surface of the phosphor particles was composed of AlF 3 .
• Comparative Example 1 was a surface-coated fluorescent particle in which at least a part of the outermost surface of the fluorescent particle was composed of (NH 4 ) 3 AlF 6 .
• the obtained phosphor particles were evaluated based on the following evaluation items.
• the diffuse reflectance was measured by attaching an integrating sphere device (ISV-469) to an ultraviolet visible spectrophotometer (V-550) manufactured by JASCO Corporation. Baseline correction was performed with a standard reflector (Spectralon), and a solid sample holder filled with the obtained phosphor particles was attached, and the diffuse reflectance for light of 300 nm and peak wavelength was measured.
• the chromaticity x was measured by a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.) and calculated by the following procedure.
• the obtained phosphor particles were filled so that the surface of the concave cell was smooth, and an integrating sphere was attached.
• Blue monochromatic light dispersed at a wavelength of 455 nm from a light source (Xe lamp) was introduced into this integrating sphere using an optical fiber.
• Xe lamp blue monochromatic light as an excitation source
• the sample of the phosphor was irradiated, and the fluorescence spectrum of the sample was measured. The peak wavelength and the half width of the peak were obtained from the obtained fluorescence spectrum data.
• the chromaticity x is the CIE chromaticity coordinate x value in the XYZ color system defined by JIS Z 8781-3: 2016 according to JIS Z 8724: 2015 from the wavelength range data in the range of 465 nm to 780 nm of the fluorescence spectrum data. (Saturation x) was calculated.
• the emission intensity (I 0 ) before starting the high temperature and high humidity test was measured by the following procedure. Subsequently, it was placed in an environment of 60 ° C. and 90% RH for 100 hours or 200 hours (high temperature and high humidity test). The emission intensity (I 100 ) after the high temperature and high humidity test for 100 hours and the emission intensity (I 200 ) after the high temperature and high humidity test for 200 hours were measured by the following procedure. Using the obtained measured values, the emission intensity ratio was calculated from the following formulas: I 100 / I 0 (%) and I 200 / I 0 (%). The results of the emission intensity ratio are shown in Table 1.
• the emission intensity of phosphor particles was measured using a spectral fluorometer (F-7000 manufactured by Hitachi High-Technologies Corporation) corrected by Rhodamine B and a sub-standard light source.
• the solid sample holder attached to the spectrofluorometer was used, and the fluorescence spectrum at an excitation wavelength of 455 nm was used.
• the peak wavelength of the fluorescence spectrum of the phosphor particles of each Example and each Comparative Example was 656 nm.
• the intensity value at the peak wavelength of the fluorescence spectrum was defined as the emission intensity of the phosphor particles.
• the phosphor particles of Examples 1 and 2 suppressed the decrease in emission intensity after the high temperature and high humidity test as compared with Comparative Examples 1 to 3. Therefore, the phosphor particles of Examples 1 and 2 can realize surface-coated phosphor particles having excellent emission intensity characteristics in a high-temperature and high-humidity environment.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Luminescent Compositions (AREA)
• Led Device Packages (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=73552232

Family Applications (1)

Country Status (5)

Cited By (3)

Citations (3)

Family Cites Families (8)

• 2020
  • 2020-05-22 KR KR1020217041679A patent/KR102773226B1/ko active Active
  • 2020-05-22 WO PCT/JP2020/020273 patent/WO2020241482A1/ja not_active Ceased
  • 2020-05-22 CN CN202080039850.6A patent/CN113891926A/zh active Pending
  • 2020-05-22 JP JP2021522308A patent/JP7498171B2/ja active Active
  • 2020-05-26 TW TW109117463A patent/TWI844681B/zh active

Patent Citations (3)

Also Published As

Similar Documents

Legal Events