WO2024247687A1 - Luminophore et dispositif luminescent - Google Patents

Luminophore et dispositif luminescent Download PDF

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WO2024247687A1
WO2024247687A1 PCT/JP2024/017603 JP2024017603W WO2024247687A1 WO 2024247687 A1 WO2024247687 A1 WO 2024247687A1 JP 2024017603 W JP2024017603 W JP 2024017603W WO 2024247687 A1 WO2024247687 A1 WO 2024247687A1
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phosphor
light
wavelength
light emitting
emitting device
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雄介 武田
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Denka Co Ltd
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Denka Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent 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
    • 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

Definitions

  • the present invention relates to a phosphor and a light-emitting device.
  • Phosphors are sometimes used industrially to form wavelength conversion members in light emitting devices, that is, members that convert light of a short wavelength into light of a long wavelength. With the recent widespread use of LEDs (light emitting diodes), phosphors have become increasingly important in industry.
  • Patent Document 2 as Example 11, a phosphor having a design composition represented by Ce0.05Sr0.95Al2Si3O4N4 is described. Patent Document 2 also describes that when this phosphor is irradiated with excitation light having a peak wavelength of 340 nm , emission having a peak wavelength of 411 nm is observed.
  • Patent Document 3 can be cited as a document that describes a phosphor having a chemical structure or chemical composition similar to the phosphors described in Patent Documents 1 and 2.
  • the present invention has been made in consideration of these circumstances.
  • One of the objects of the present invention is to provide a phosphor with good luminescence characteristics, such as external quantum efficiency.
  • a phosphor represented by the general formula Ba a1 Sr a2 Ce b Al c Si d O e N f, in which the composition ratios a1, a2, b, c, d, e, and f have the following relationship when c+d 5:
  • the phosphor according to any one of 1. to 9., The phosphor is a powder having a median diameter D50 of 10 to 50 ⁇ m. 11.
  • a light emitting device comprising a light emitting element and the phosphor according to any one of 1. to 11. 13.
  • the light-emitting device according to claim 12, The light emitting device, wherein the light emitting element is an LED element. 15. 12. The light emitting device according to any one of claims 12 to 14, A light-emitting device that is a lighting device or a signaling device.
  • the present invention provides a phosphor with good luminescence properties, such as external quantum efficiency.
  • FIG. 2 is a diagram showing X-ray diffraction spectra of phosphors of Examples and Comparative Examples.
  • the phosphor of this embodiment is a phosphor represented by the general formula Ba a1 Sr a2 Ce b Al c Si d O e N f .
  • the composition ratios a1, a2, b, c, d, e and f have the following relationship: a1>a2 0.70 ⁇ a1+a2+b ⁇ 1.20 0.001 ⁇ b ⁇ 0.20 1.50 ⁇ c ⁇ 2.50 2.50 ⁇ d ⁇ 3.50 3.05 ⁇ e ⁇ 6.50 2.75 ⁇ f ⁇ 4.40
  • the peak wavelength of the fluorescence emitted is 412 to 420 nm.
  • the inventors have found through their investigations that in the above composition and its neighboring compositions, the peak wavelength of the fluorescence emitted when irradiated with light having a wavelength of 350 nm seems to correlate with the magnitude of the external quantum efficiency. Based on this finding, the peak wavelength of the fluorescence emitted when irradiated with light having a wavelength of 350 nm was adopted as one of the design indicators. Specifically, the external quantum efficiency could be increased by designing a phosphor so that the peak wavelength of the fluorescence emitted when irradiated with light having a wavelength of 350 nm is 412 to 420 nm.
  • the phosphor contains a large amount of foreign phases, impurities, fine powder, etc., which hinder the improvement of the external quantum efficiency, the presence of these substances causes the peak wavelength of the fluorescence to be outside the range of 412 to 420 nm (often exceeding 420 nm).
  • the peak wavelength of the fluorescence is thought to be within the range of 412 to 420 nm.
  • the phosphor of this embodiment can be manufactured by using appropriate raw materials in an appropriate ratio and through an appropriate manufacturing process.
  • it is effective to optimize the selection and blending of raw materials, as well as the manufacturing conditions.
  • the luminescence characteristics may be further improved by performing an acid treatment or classification treatment, which will be described later.
  • the manufacturing conditions are inappropriate, a phosphor having the desired characteristics may not be obtained even if appropriate raw materials are used in the appropriate ratio.
  • a1 is preferably 0.50 ⁇ a1 ⁇ 0.99, more preferably 0.70 ⁇ a1 ⁇ 0.99, further preferably 0.85 ⁇ a1 ⁇ 0.97, and particularly preferably 0.90 ⁇ a1 ⁇ 0.96.
  • a2 is preferably 0 ⁇ a2 ⁇ 0.10, more preferably 0 ⁇ a2 ⁇ 0.05, and further preferably 0 ⁇ a2 ⁇ 0.02. a2 may be zero.
  • b is preferably 0.001 ⁇ b ⁇ 0.15, and more preferably 0.003 ⁇ b ⁇ 0.10.
  • a1+a2+b 0.80 ⁇ a1+a2+b ⁇ 1.10 is preferable, and 0.90 ⁇ a1+a2+b ⁇ 1.00 is more preferable.
  • c may be in the range of 1.50 ⁇ c ⁇ 2.50, but is preferably in the range of 1.70 ⁇ c ⁇ 2.30, more preferably 1.80 ⁇ c ⁇ 2.20, and even more preferably 1.90 ⁇ c ⁇ 2.10.
  • d may be in the range of 2.50 ⁇ d ⁇ 3.50, but is preferably in the range of 2.70 ⁇ d ⁇ 3.30, more preferably 2.80 ⁇ d ⁇ 3.20, and even more preferably 2.90 ⁇ d ⁇ 3.10.
  • e may be in the range of 3.05 ⁇ e ⁇ 6.50, but is preferably in the range of 4.00 ⁇ e ⁇ 6.50, more preferably 4.50 ⁇ e ⁇ 6.25, even more preferably 5.00 ⁇ e ⁇ 6.00, particularly preferably 5.00 ⁇ e ⁇ 5.80, and especially preferably 5.00 ⁇ e ⁇ 5.50.
  • f may be in the range of 2.75 ⁇ f ⁇ 4.40, but is preferably in the range of 3.00 ⁇ f ⁇ 4.30, more preferably 3.00 ⁇ f ⁇ 4.00, and even more preferably 3.20 ⁇ f ⁇ 3.80.
  • the relative magnitudes between the respective numerical values are preferably as follows: c/d: Preferably, 0.50 ⁇ c/d ⁇ 0.80, more preferably, 0.55 ⁇ c/d ⁇ 0.75, further preferably, 0.60 ⁇ c/d ⁇ 0.75, and particularly preferably, 0.62 ⁇ c/d ⁇ 0.73.
  • e/f Preferably, 0.90 ⁇ e/f ⁇ 2.00, more preferably, 1.00 ⁇ e/f ⁇ 1.90, and even more preferably, 1.20 ⁇ e/f ⁇ 1.80.
  • the phosphor of this embodiment generally does not substantially contain Eu, because, as described above, Ce is thought to act as the luminescence center in the phosphor of this embodiment.
  • the phosphor of the present embodiment does not contain Eu.
  • the phosphor of this embodiment may have a characteristic spectrum of emitted fluorescence due to its chemical composition, etc.
  • the half width (full width at half maximum) of the fluorescence spectrum emitted when the phosphor of this embodiment is irradiated with light having a wavelength of 350 nm is preferably 75 to 130 nm, more preferably 75 to 100 nm, even more preferably 80 to 95 nm, and particularly preferably 80 to 90 nm.
  • the internal quantum efficiency of the phosphor of this embodiment when irradiated with light having a wavelength of 350 nm is preferably 50 to 95%, more preferably 60 to 95%, and even more preferably 70 to 90%.
  • the chromaticity x of the fluorescence emitted when the phosphor of this embodiment is irradiated with light having a wavelength of 350 nm in the XYZ color system is preferably 0.168 to 0.182, more preferably 0.170 to 0.180, and the chromaticity y of the fluorescence is preferably 0.095 to 0.135, more preferably 0.100 to 0.130.
  • the phosphor of this embodiment Since the phosphor of this embodiment has an appropriate absorptance for light with a wavelength of 500 nm, the luminescence characteristics such as external quantum efficiency may be further improved.
  • the absorptance of the phosphor of this embodiment for light with a wavelength of 500 nm is preferably 1 to 10%, more preferably 3 to 9%, further preferably 4 to 8%, and particularly preferably 4 to 7%.
  • the phosphor of this embodiment generally has a crystal structure identical to or similar to that of a crystal of an inorganic compound represented by the general formula BaAl 2 Si 3 O 4 N 4.
  • the phosphor of this embodiment can be considered as a solid solution in which part of Ba in the general formula BaAl 2 Si 3 O 4 N 4 is substituted with Ce or Sr.
  • the X-ray diffraction spectrum of the phosphor of this embodiment has a peak at approximately the same position (2 ⁇ ) as the peak observed in the X-ray diffraction spectrum of a crystal of an inorganic compound represented by the general formula BaAl 2 Si 3 O 4 N 4 .
  • the peak positions in the X-ray diffraction spectrum of a crystal of an inorganic compound represented by the general formula BaAl 2 Si 3 O 4 N 4 based on simulation are shown at the bottom of FIG.
  • the ratio of the heterogeneous phase in the phosphor of this embodiment can be estimated.
  • the heterogeneous phase refers to a phase that has a crystal structure different from the crystal structure of the inorganic compound represented by the general formula BaAl 2 Si 3 O 4 N 4 and does not contribute to or may adversely affect the light emission characteristics of the phosphor of this embodiment.
  • the value of B/A is preferably 0.3 or less, more preferably 0.2 or less.
  • the value of B/A is zero, but considering the manufacturing cost and the like, in reality, 0.01 to 0.3 is preferable, and 0.03 to 0.2 is more preferable.
  • the phosphor of this embodiment has an appropriate diffuse reflectance for light with a wavelength of 700 nm or 800 nm, which may further improve the light emitting characteristics of the phosphor of this embodiment.
  • the diffuse reflectance of light with a wavelength of 700 nm or 800 nm may also be related to the surface condition of the phosphor and the amount of heterogeneous phases in the phosphor that do not contribute to or may have a negative effect on the luminescence characteristics of the phosphor (diffuse reflectance may also change depending on the conditions of acid treatment or elutriation treatment in the manufacture of the phosphor).
  • the diffuse reflectance of the phosphor of this embodiment for light with a wavelength of 700 nm is preferably 92 to 98%, and more preferably 93 to 97%.
  • the diffuse reflectance of the phosphor of this embodiment for light with a wavelength of 800 nm is preferably 92 to 98%, and more preferably 93 to 97%.
  • the phosphor of this embodiment is typically in a powder form, or in other words, an aggregate of phosphor particles.
  • the particle size distribution can be adjusted, for example, by changing the pulverization conditions or the elutriation conditions in the phosphor manufacturing process described below.
  • the powdered phosphor of this embodiment has a median diameter D 50 (cumulative 50% particle diameter on a volume basis determined by a laser diffraction/scattering method) of preferably 10 to 50 ⁇ m, and more preferably 10 to 40 nm.
  • the powdered phosphor of this embodiment has a volume-based cumulative 10% particle diameter D 10 determined by a laser diffraction/scattering method of preferably 3 to 25 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the powdered phosphor of this embodiment has a volume-based cumulative 90% particle diameter D 90 determined by a laser diffraction/scattering method of preferably 20 to 80 ⁇ m, and more preferably 25 to 70 ⁇ m.
  • the value of (D 90 -D 10 )/D 50 is preferably 1.20 to 1.90, more preferably 1.30 to 1.80. This value indicates that the particle size distribution of the powdered phosphor is relatively sharp. A sharp particle size distribution means that the phosphor particles in the powdered phosphor are homogeneous at least in terms of particle size. This is expected to lead to stable light emission and to reduce the variation in light emission characteristics between product lots.
  • the fact that the value of (D 90 -D 10 )/D 50 is not too large can also be said to represent that the ratio of coarse particles or phosphors with extremely small particle sizes (fine powder) in the powdered phosphor that do not contribute to improving the light emission characteristics or have a negative effect on the light emission characteristics is relatively small.
  • the phosphor of this embodiment can be manufactured by using appropriate raw materials in an appropriate ratio and through an appropriate manufacturing process. If the raw materials used or their blending are inappropriate, or if the manufacturing conditions are inappropriate, a phosphor having good luminescence characteristics may not be manufactured. An example of a preferred manufacturing process will now be described.
  • raw materials containing Ba, Eu, etc. are prepared.
  • the raw materials are usually in powder form.
  • raw materials containing Ba include BaAl 2 O 4 , BaCO 3 , BaO, Ba 2 N, and Ba 3 N 2.
  • BaAl 2 O 4 is preferred from the viewpoint of further improving the performance of the phosphor that is finally produced.
  • examples of raw materials containing Sr include SrAl2O4 , SrCO3 , SrO, Sr2N , and Sr3N2 .
  • An example of a raw material containing Ce is CeO.
  • An example of a raw material containing Si is Si 3 N 4 .
  • An example of a raw material containing Al is Al2O3 .
  • the prepared raw materials are weighed and thoroughly mixed to prepare a mixture.
  • the amount (molar ratio) of each raw material is an appropriate amount calculated backwards from the values of a1, a2, b, c, d, e, and f in the general formula described above. It is preferable to pass the mixture through a sieve to ensure uniform mixing and remove coarse particles.
  • the above mixture is filled into a heat-resistant container (preferably a boron nitride container) and heated to form a fired product.
  • the firing temperature is preferably 1500 to 1800°C, more preferably 1500 to 1700°C.
  • the firing time (the time for maintaining the above temperature) is preferably 1 to 12 hours, more preferably 2 to 8 hours.
  • the firing is preferably carried out in an atmosphere of an inert gas such as nitrogen gas, and the gas pressure is preferably about 0.01 to 0.1 MPa ⁇ G.
  • the phosphor (calcined product) obtained by firing is usually in a lump form. Therefore, it is preferable to crush it appropriately.
  • a pulverization process may be performed to adjust the particle size.
  • a jet mill can be used for pulverization.
  • annealing By heating (annealing) the phosphor obtained by firing (fired product) at the same heating temperature as the firing or at a lower temperature, it is possible to further improve the performance of the phosphor, such as its luminescence characteristics. Although the details are unknown, it is assumed that annealing homogenizes and reconstructs the crystal structure in the phosphor.
  • the annealing is preferably carried out by placing the phosphor (fired product) in a heat-resistant container, preferably a boron nitride container.
  • the annealing temperature is preferably 1400 to 1550°C, and more preferably 1450 to 1550°C.
  • the annealing time (the time for which the temperature is maintained) is preferably 2 to 24 hours, more preferably 4 to 12 hours.
  • the annealing is preferably carried out in an atmosphere of an inert gas such as nitrogen gas, with the gas pressure preferably being about 0.01 to 0.1 MPa ⁇ G.
  • the phosphor of this embodiment is preferably subjected to an acid treatment.
  • the acid treatment can be performed, for example, by immersing the phosphor in an acid aqueous solution and stirring appropriately.
  • the acid treatment may remove or reduce foreign matter on the phosphor surface or a different phase that does not contribute to fluorescence or has a negative effect on the light emission characteristics. In other words, the acid treatment may further improve the characteristics of the phosphor.
  • the light absorptance or diffuse reflectance of the phosphor may change.
  • the acid aqueous solution may be an aqueous solution containing one or more acids selected from hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid.
  • the acid treatment can be carried out by stirring the phosphor in an aqueous acid solution for a few minutes to a few hours (for example, 10 minutes to 6 hours).
  • a known stirrer or the like can be used for stirring.
  • a magnetic stirrer is preferably used.
  • the temperature during stirring is, for example, 50 to 100°C, preferably 65 to 85°C (the liquid is maintained at this temperature).
  • the stirring time is, for example, 1 minute to 2 hours, preferably about 10 minutes to 1 hour.
  • the stirring speed depends on the scale of the stirring device, but is, for example, 300 to 600 rpm, preferably 350 to 500 rpm on a laboratory scale. Stirring at a relatively high speed applies a strong shear force to the phosphor, making it possible to more effectively remove foreign matter and heterogeneous phases, and thus a further improvement in the performance of the phosphor can be expected.
  • After the acid treatment it is desirable to appropriately perform filtration, washing with water, drying, etc.
  • Classification (preferably by elutriation)
  • elutriation In order to reduce the amount of phosphors (fine powders) with extremely small particle sizes that do not contribute to improving the luminescence characteristics or that adversely affect the luminescence characteristics in the powdered phosphor, it is preferable to perform classification.
  • classification There are various specific methods for classification, but in this embodiment, it is preferable to perform classification by elutriation.
  • the classification point can be found by calculation based on Stokes' equation or by several trial experiments.
  • the elutriation treatment can be preferably carried out by dispersing the powdered phosphor in an aqueous solution of sodium hexametaphosphate or water to prepare a dispersion, allowing the dispersion to stand, and then removing the supernatant.
  • Other specific methods for classification can be appropriately applied by known methods.
  • a light emitting device can be configured by combining the above phosphor with a light emitting element. Specifically, the light emitting element emits light capable of exciting the phosphor, and the above phosphor emits fluorescence upon receiving the light emitted from the light emitting element.
  • the phosphor is usually encapsulated with an encapsulant and incorporated into the light emitting device in the form of a wavelength conversion member.
  • the light-emitting element is preferably a light-emitting element that emits light with a wavelength of 300 to 400 nm, and more preferably a light-emitting element that emits light with a wavelength of 345 to 385 nm.
  • the light emitting element is preferably an LED element.
  • the application of the light emitting device of this embodiment is not particularly limited.
  • the light emitting device of this embodiment can be applied, for example, to backlights for liquid crystal display devices, light source devices for projectors, lighting devices, traffic lights, and the like.
  • the light emitting device of this embodiment is considered to be preferable as a lamp for indicating autonomous driving (an indicator light for indicating to the outside of the vehicle that the vehicle is in autonomous driving). This is because the light emitted from the light emitting device of this embodiment can conform to the characteristics (chromaticity x, y, etc.) of lamps for indicating autonomous driving proposed by SAE International (Society of Automotive Engineers).
  • the light emitting device of this embodiment can be preferably applied to a light source for inspection.
  • halogen lamps with a broad emission spectrum have been used as light sources for industrial inspection.
  • an LED that includes a phosphor that emits fluorescence with a broad spectrum when excited as a wavelength conversion member.
  • the spectrum of the fluorescence emitted when the phosphor of this embodiment is excited with light having a wavelength of 300 to 400 nm is relatively broad and flat in the wavelength region of 400 nm or slightly longer. Therefore, a light-emitting device constructed by combining the phosphor of this embodiment with a light-emitting element meets the above-mentioned objectives.
  • the phosphor was produced as follows. (1) Weighing and mixing of raw materials Each raw material was weighed according to the mass ratio shown in Table 1 below. All of the weighed raw materials were placed in a polyethylene bag with a zipper, the zipper of the bag was closed, and the bag was shaken for 1 minute. In this way, a mixture of raw materials was obtained. The obtained mixture was sieved through a #100 sieve, and the mixture that passed through the sieve was used in the next step.
  • composition analysis was carried out on some of the phosphors of Examples 1 to 5.
  • the contents of Ba, Sr, Ce, Al and Si in the phosphor were quantitatively analyzed by dissolving the phosphor by a pressurized acid decomposition method and then using an ICP emission spectrometer (5110VDV manufactured by Agilent).
  • compositions of the phosphors of Examples 2 and 3 are considered to be similar to that of Example 4, considering that the raw material compositions of Examples 2 and 3 are the same as those of Example 4, and that the manufacturing processes of Examples 2 and 3 are similar to that of Example 4.
  • ⁇ Particle size distribution measurement> Using Microtrac SYNC (manufactured by Microtrac Bell Co., Ltd.), the measurement was performed by the laser diffraction scattering method in accordance with JIS R1629:1997. 0.2 g of phosphor powder was added to 80 mL of ion-exchanged water, and a dispersion process was performed for 90 seconds using a horn-type ultrasonic homogenizer (output 300 W, horn diameter 26 mm), and then the particle size distribution was measured using SYNC. From the obtained particle size distribution, the volume-based median diameter D50 and the like were obtained. The obtained values, such as D50, are shown in Table 4.
  • the X-ray diffraction spectrum of the obtained sample was measured using an Ultima IV-N device manufactured by Rigaku Corporation.
  • the peak intensity (maximum value) A in the range of 2 ⁇ from 25.0 to 26.0° and the peak intensity (maximum value) B in the range of 2 ⁇ from 29.0 to 30.0° were read, and the value of B/A was calculated.
  • Figure 1 The obtained X-ray diffraction spectrum is shown in Figure 1.
  • the lower part of Figure 1 also shows the positions of peaks in the X-ray diffraction spectrum of a crystal of an inorganic compound represented by the general formula BaAl 2 Si 3 O 4 N 4 based on simulation.
  • the B/A value is shown in Table 5.
  • the diffuse reflectance of light with a wavelength of 700 nm or 800 nm was measured using an integrating sphere device (ISV-469) attached to a JASCO UV-Visible Spectrophotometer (V-550). Specifically, baseline correction was first performed using a standard reflector (Spectralon). Then, a solid sample holder filled with phosphor powder was attached to a predetermined position, and the diffuse reflectance of light with wavelengths of 700 nm and 800 nm was measured.
  • the absorptance (%) of light with a wavelength of 500 nm was calculated in the same manner as the ⁇ Performance evaluation> shown below (absorptance, internal quantum efficiency, and external quantum efficiency when irradiated with light with a wavelength of 350 nm) except that the wavelength of the irradiated light was 500 nm instead of 350 nm, and Qex and Qref were calculated from the spectrum with a wavelength range of 495 nm to 510 nm.
  • the diffuse reflectance of light with a wavelength of 700 nm or 800 nm, and the absorptance of light with a wavelength of 500 nm are shown in Table 6.
  • Monochromatic light which was split into 350 nm wavelengths from a light emission source (Xe lamp), was introduced into the integrating sphere using an optical fiber. This monochromatic light was irradiated onto the phosphor, and the fluorescence spectrum was measured.
  • a standard reflector with a reflectance of 99% (Spectralon, manufactured by Labsphere) was attached to a predetermined position of the integrating sphere to measure the spectrum of excitation light with a wavelength of 350 nm. At that time, the number of excitation light photons (Qex) was calculated from the spectrum in the wavelength range of 345 nm to 360 nm.
  • a cell filled with powdered phosphor was attached to a predetermined position of the integrating sphere, and the number of reflected excitation light photons (Qref) and the number of fluorescent photons (Qem) were calculated from the obtained spectrum data.
  • the number of reflected excitation light photons was calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescent photons was calculated in the range of 360 nm to 700 nm.
  • the obtained Qex, Qref, and Qem were substituted into the following formula to determine the absorptance, internal quantum efficiency, and external quantum efficiency.
  • the peak wavelength, half width, chromaticity x value, and chromaticity y value were determined.
  • the chromaticity coordinates (x, y) were calculated according to the method in accordance with JIS Z 8724 (Method of measuring color-light source color-) and the calculation method in the XYZ color system defined in JIS Z 8701.
  • the external quantum efficiency of the phosphors of Examples 1 to 4 was better than that of Example 5. That is, the phosphors represented by the general formula Ba a1 Sr a2 Ce b Al c Si d O e N f , which satisfied a1>a2, 0.70 ⁇ a1+a2+b ⁇ 1.20, 0.001 ⁇ b ⁇ 0.20, 1.50 ⁇ c ⁇ 2.50, 2.50 ⁇ d ⁇ 3.50, 3.05 ⁇ e ⁇ 6.50, and 2.75 ⁇ f ⁇ 4.40, and which emitted fluorescence with a peak wavelength of 412 to 420 nm when irradiated with light having a wavelength of 350 nm, exhibited good light-emitting properties. From the viewpoint of composition, such favorable light emission characteristics are believed to be due to the fact that the phosphor contains a relatively small amount of Ce, and the Ba content is relatively large compared to Sr, and so on.
  • Example 5-1 A phosphor (Example 5-2) produced in the same manner as in Example 4, except that in the above ⁇ Production of phosphor>, (4) the annealing step, (5) the acid treatment and decantation, and (6) the elutriation classification were not carried out.
  • Example 4-1 and 4-2 which did not undergo an annealing process or acid treatment, the various properties were different from those of Example 4.
  • the peak wavelength of the fluorescence spectrum was over 520 nm.
  • the B/A value determined by X-ray diffraction in Example 4-1 was large. From these, it can be seen that the luminescence properties can be optimized by appropriately reducing foreign phases, impurities, etc. through appropriate treatment after firing.

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Abstract

La présente divulgation concerne un luminophore qui est représenté par la formule générale Baa1Sra2CebAlcSidOeNf. Dans la formule générale, lorsque c + d = 5, les rapports de composition a1, a2, b, c, d, e et f satisfont a1 > a2, 0,70 ≤ a1 + a2 + b ≤ 1,20, 0,001 ≤ b ≤ 0,20, 1,50 ≤ c ≤ 2,50, 2,50 ≤ d ≤ 3,50, 3,05 ≤ e ≤ 6,50, et 2,75 ≤ f ≤ 4,40. De plus, la longueur d'onde de pic de fluorescence émise lorsque le luminophore est irradié avec de la lumière ayant une longueur d'onde de 350 nm est de 412 à 420 nm.
PCT/JP2024/017603 2023-05-26 2024-05-13 Luminophore et dispositif luminescent Ceased WO2024247687A1 (fr)

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JP2011037913A (ja) * 2009-08-06 2011-02-24 Showa Denko Kk 蛍光体及びその製造方法、並びにそれを用いた発光装置
CN102181285A (zh) * 2011-03-08 2011-09-14 中国科学技术大学 一种硅氧氮化物荧光粉及其制备方法
WO2013069696A1 (fr) * 2011-11-07 2013-05-16 独立行政法人物質・材料研究機構 Phosphore, son procédé de production, dispositif d'émission de lumière et dispositif d'affichage d'images utilisant du phosphore
WO2015093429A1 (fr) * 2013-12-17 2015-06-25 電気化学工業株式会社 Luminophore, dispositif électroluminescent et leur procédé de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011037913A (ja) * 2009-08-06 2011-02-24 Showa Denko Kk 蛍光体及びその製造方法、並びにそれを用いた発光装置
CN102181285A (zh) * 2011-03-08 2011-09-14 中国科学技术大学 一种硅氧氮化物荧光粉及其制备方法
WO2013069696A1 (fr) * 2011-11-07 2013-05-16 独立行政法人物質・材料研究機構 Phosphore, son procédé de production, dispositif d'émission de lumière et dispositif d'affichage d'images utilisant du phosphore
WO2015093429A1 (fr) * 2013-12-17 2015-06-25 電気化学工業株式会社 Luminophore, dispositif électroluminescent et leur procédé de fabrication

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