WO2014002723A1 - Fluorescent material, light-emitting device, and lighting device - Google Patents

Fluorescent material, light-emitting device, and lighting device Download PDF

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Publication number
WO2014002723A1
WO2014002723A1 PCT/JP2013/065661 JP2013065661W WO2014002723A1 WO 2014002723 A1 WO2014002723 A1 WO 2014002723A1 JP 2013065661 W JP2013065661 W JP 2013065661W WO 2014002723 A1 WO2014002723 A1 WO 2014002723A1
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light
phosphor
mass
emitting device
light emitting
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PCT/JP2013/065661
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French (fr)
Japanese (ja)
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慶太 小林
康人 伏井
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電気化学工業株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • 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
    • C09K11/0883—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, 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
    • C09K11/77746—Aluminium Nitrides or Aluminium Oxynitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a phosphor, a light emitting device, and a lighting device.
  • Patent Document 1 discloses a light emitting device that emits white light using blue light emitted from a blue light emitting diode or laser diode chip and yellow light obtained by converting the blue light (wavelength: 420 nm to 470 nm) with a phosphor. Yes.
  • the phosphor is obtained by replacing part of Y of cerium activated YAG (yttrium, aluminum, garnet) with Lu, Sc, Gd, and La.
  • Patent Document 2 discloses YAG as a phosphor that converts blue light into yellow light.
  • yellow light emitted from cerium-activated YAG has a small red component (wavelength: 600 nm to 700 nm) and green component (wavelength: 510 nm to 550 nm), and therefore has a high color rendering property when combined with a blue light emitting diode. There was a problem that light could not be obtained.
  • Patent Document 3 green and red light emitting phosphors are used to secure a red component and a green component to enhance color rendering.
  • light emission of one phosphor is caused to occur on the other.
  • An object of the present invention is to provide a phosphor having a large amount of red and green components while being yellow light, and to provide a light emitting device and a lighting device having high color rendering properties using the phosphor.
  • the present inventors have specified the composition of the phosphor represented by the general formula LuAlON: Ce, so that the phosphor has a large amount of red and green components while the emission color is yellow light.
  • the inventors have found that a light emitting device and a lighting device having high color rendering properties can be obtained by using this phosphor, and the present invention has been completed.
  • the present invention is represented by the general formula LuAlON: Ce, N is 0.010 mass% or more and 5.0 mass% or less, Ce and Lu are in a molar ratio Ce / Lu ⁇ 0.05, and Al is in a molar ratio. It is a phosphor with Al / (O + N)> 5/13 with respect to O and N.
  • Another invention is a light emitting device having the above-described phosphor and a light emitting element, and yet another invention is an illumination device using the light emitting device.
  • the phosphor of the present invention is efficiently excited by light in a wavelength range of 350 nm or more and 500 nm or less emitted from a blue light-emitting element, and has a large chromaticity X, peak wavelength, and full width at half maximum while the emission color is yellow, It contains a lot of red and green components. For this reason, by combining with a blue light emitting element, it is possible to obtain a light emitting device and a lighting device that realize white with high color rendering properties.
  • the phosphor of the present invention is an oxynitride phosphor which is represented by the general formula LuAlON: Ce, contains a predetermined amount of nitrogen element, and contains a large amount of cerium.
  • N is 0.010 mass% or more and 5.0 mass% or less
  • Ce and Lu are molar ratios of Ce / Lu ⁇ 0.05
  • Al is molar ratio of O / N with respect to Al / Al. It is a phosphor with (O + N)> 5/13.
  • Lu is lutetium, and part or all of lutetium can be substituted with one or more elements selected from the group consisting of Y, Sc, La, Gd, and Sm.
  • Ce is cerium, and part or all of cerium may be substituted with one or more elements selected from the group consisting of Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Mn.
  • Al is aluminum, and a part or all of aluminum can be replaced with either one or both of Ga and In.
  • O oxygen and N is nitrogen.
  • N is 0.010% by mass or more and 5.0% by mass or less
  • Ce / Lu is in a molar ratio of Ce / Lu ⁇ 0.05
  • Al is in a molar ratio of Al / (O + N)> 5 /
  • the chromaticity X increases remarkably, the peak wavelength increases, the half-value width increases, the ratio of red (wavelength 600 nm to 700 nm) fluorescent components increases, and the wavelength tends to increase. is there. This is mainly because the ratio of the red component (wavelength: 600 nm to 700 nm) in the emission color of the phosphor increases when Ce / Lu is increased in molar ratio and the nitrogen content is increased.
  • the proportion of the green component (wavelength of 510 nm or more and 550 nm or less) in the emission color also increases.
  • the proportion of the green component (wavelength of 510 nm or more and 550 nm or less) in the emission color
  • the nitrogen atom in the phosphor of the present invention exists in the crystal lattice and / or between crystal lattices of the phosphor itself.
  • the nitrogen content in the obtained phosphor can be measured with an oxygen-nitrogen measuring machine (for example, EMGA-920 manufactured by Horiba, Ltd.).
  • an inert gas melting-non-dispersive infrared absorption method can be used for oxygen
  • an inert gas melting-thermal conductivity method TCD
  • the increase in the nitrogen content is related to the increase in the red component in the emission color of the phosphor, but if the nitrogen content is too large, the emission intensity tends to decrease.
  • the phosphor of the present invention has a light emission peak wavelength shifted to the long wavelength side, and in addition to a large amount of red component, there is also a large amount of green component. Indicates. Since the peak wavelength of the excitation spectrum is in the range of 350 to 500 nm, it is efficiently excited by light in that wavelength range and emits deep yellow light, which is suitable for white LEDs with high color rendering properties.
  • the phosphor production method of the present invention includes a mixing step of mixing a plurality of raw materials made of a compound containing Lu, Al, O and Ce, and a raw material mixed powder after the mixing step in a nitrogen atmosphere between 0.001 MPa and 100 MPa. It is preferable that it is comprised by the baking process hold
  • hydroxides, carbonates, nitrates, halides, oxalates with a purity of 99% or more which can be decomposed at high temperatures into oxides, oxides with a purity of 99.9% or more, purity It is preferable to use 99.9% or more of nitride.
  • the nitride include AlN and azide, and those having a purity of 99.9% or more are preferable.
  • a ball mill for mixing the starting materials, a ball mill, a V-type mixer or a stirring device can be used.
  • the firing step is preferably held for 1 hour to 100 hours in a temperature range of 1000 ° C. to 2400 ° C. and a pressure range of 0.001 MPa to 100 MPa, for example.
  • the firing temperature is more preferably 1500 ° C. or higher and 2200 ° C. or lower.
  • As for the pressure of the atmosphere in a baking process 0.7 MPa or more and 70 MPa or less are more preferable.
  • the nitrogen element-containing atmosphere includes an atmosphere containing nitrogen and / or ammonia, and may contain an inert gas such as argon or helium.
  • the content of nitrogen and / or ammonia is preferably 10% by volume or more, more preferably 50% by volume or more, still more preferably 100% by volume, and the nitrogen element-containing atmosphere is high purity nitrogen (purity 99.99% or more) and / or The case where it consists of high purity ammonia (purity 99.99% or more) is the most preferable.
  • the calcination atmosphere may be any of an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, and a nitrogen element-containing gas atmosphere.
  • the inert gas in the inert atmosphere include nitrogen and argon.
  • the gas in the oxidizing atmosphere include air, oxygen, oxygen-containing nitrogen, and oxygen-containing argon.
  • the gas in the reducing atmosphere include hydrogen-containing nitrogen and hydrogen-containing argon. An appropriate amount of flux may be added to these gases in order to promote the reaction.
  • the metal resistance heating method or the graphite resistance heating method is preferable, and an electric furnace using carbon as the material of the high temperature part of the furnace is used. preferable.
  • the phosphor obtained by the above method may be pulverized using a pulverizer that is usually used industrially, such as a ball mill, a vibration mill, an attritor, or a jet mill.
  • a pulverizer that is usually used industrially, such as a ball mill, a vibration mill, an attritor, or a jet mill.
  • re-firing may be performed.
  • re-baking may be performed in order to promote crystal growth or advance a synthesis reaction.
  • the phosphor is dispersed in the form of particles in an acidic aqueous solution and then washed with water.
  • inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and hydrochloric acid is preferred.
  • a known surface treatment can be applied as necessary in order to improve moisture resistance and dispersibility.
  • the phosphor of the present invention can be combined with a light emitting element to form a light emitting device.
  • the phosphor of the present invention is dispersed in a translucent resin such as epoxy resin, polycarbonate, silicon rubber, and the resin in which the phosphor is dispersed is used as a light emitting element on the stem (compound semiconductor). It can manufacture by shape
  • a blue light emitting nitride semiconductor is preferable as the light emitting element, and a compound semiconductor that emits light from ultraviolet to blue can also be used.
  • a light-emitting element made of a nitride semiconductor that emits light having a wavelength of 350 nm to 500 nm that excites the phosphor is preferable.
  • the emission wavelength of a nitride semiconductor can be changed depending on the ratio of constituent elements.
  • the peak of emission wavelength can be controlled from 320 nm to 450 nm in the Ga—N system and from 300 nm to 500 nm in the In—Al—Ga—N system.
  • the light-emitting layer is made of a compound represented by the composition formula In x Al y Ga 1-xy N (0 ⁇ x, 0 ⁇ y, x + y ⁇ 1), and has a heterostructure or a double structure. There is a light-emitting element having a heterostructure.
  • the phosphor of the present invention can be used alone, and it is also possible to produce a light emitting device with higher whiteness by using in combination with other phosphors such as a red light emitting phosphor and a green light emitting phosphor. Further, by applying such a light-emitting device, it is possible to obtain a lighting device that emits white light with high color rendering properties.
  • Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 32.7 mass%, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 28.3 mass%, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 39.0% by mass was blended to obtain 1 kg of a raw material mixture.
  • the raw material mixture was mixed with a super mixer manufactured by Kawata Co., Ltd., and passed through a nylon sieve having an opening of 850 ⁇ m to obtain a raw material powder for phosphor synthesis.
  • a container was placed inside a graphite box with an upper lid.
  • This graphite box has four long-side holes and four short-side holes each having a diameter of 20 mm. Further, a hole with a diameter of 50 mm was opened in the center of the bottom, and an exhaust gas pipe was installed under this hole, and atmospheric gas was exhausted from the exhaust gas pipe during firing. After heat treatment at 1700 ° C.
  • the obtained powder was gradually cooled to room temperature.
  • the fired product was crushed in a mortar and passed through a sieve having an opening of 250 ⁇ m to obtain a synthetic powder.
  • Table 1 shows the results of the external quantum efficiency, chromaticity X, peak wavelength, half-value width, color rendering index, and nitrogen content of the phosphor manufactured in Example 1.
  • the external quantum efficiency in Table 1 was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). A concave cell was filled with phosphor so that the cell surface was smooth, and an integrating sphere was attached. Monochromatic light separated into a wavelength of 455 nm from a light emitting light source (Xe lamp) was introduced into the integrating sphere using an optical fiber. The phosphor sample was irradiated with this monochromatic light as an excitation source, and the fluorescence spectrum of the sample was measured. Luminous efficiency was determined as follows.
  • a standard reflector (Spectralon, manufactured by Labsphere) having a reflectance of 99% was set on the sample portion, and the spectrum of excitation light having a wavelength of 455 nm was measured. At that time, the number of excitation light photons (Qex) was calculated from the spectrum in the wavelength range of 450 to 465 nm. Next, a sample was set in the sample portion, and the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) were calculated from the obtained spectrum data. The number of excited reflected light photons was calculated in the same wavelength range as the number of excited light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm.
  • External quantum efficiency Qem / Qex ⁇ 100
  • Internal quantum efficiency Qem / (Qex ⁇ Qref) ⁇ 100
  • the passed external quantum efficiency is 40% or more.
  • the chromaticity X in Table 1 is a value of CIE1931, and was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). As an example, the acceptable chromaticity X is 0.385 or more.
  • the peak wavelengths in Table 1 were measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.).
  • the acceptable peak wavelength is 544.0 nm or more.
  • the half width in Table 1 was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). As an example, the half width of the pass is 103.0 nm or more.
  • the nitrogen content in Table 1 was measured with an oxygen-nitrogen measuring machine (EMGA-920 manufactured by HORIBA Corporation).
  • EMGA-920 manufactured by HORIBA Corporation.
  • the acceptable nitrogen content is 0.010% by mass or more.
  • the color rendering index was measured by the following method. 10 g of the phosphor was added to 100 g of water together with 1.0 g of an epoxysilane coupling agent (KBE402 manufactured by Shin-Etsu Silicone Co., Ltd.) and left overnight with stirring. Thereafter, an appropriate amount of the phosphor treated with the filtered and dried silane coupling agent was kneaded with 10 g of an epoxy resin (NLD-SL-2101 manufactured by Sanyu Rec Co., Ltd.) and potted on a blue LED element having an emission wavelength of 460 nm. The resin was heat-cured at 110 ° C. by vacuum degassing, and a surface-mounted LED was produced. The light generated by passing a current of 10 mA was measured, and the color rendering index (Ra) was measured. As an example, a color rendering index (Ra) that is acceptable is 70.0 or more.
  • Example 1 As shown in Table 1, the external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra) of Example 1 all showed excellent values.
  • Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 50.9 mass%, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 11.0 mass%, Al 2 O 3 (TM-DAR grade, manufactured by Daimei Chemical Co., Ltd.) 38.1% by mass was blended to obtain 1 kg of a raw material mixture.
  • the subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
  • Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 59.1% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 3.3% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 37.6% by mass was blended to obtain 1 kg of a raw material mixture.
  • the subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
  • Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 36.8% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 31.8% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 31.4% by mass was blended to obtain 1 kg of a raw material mixture.
  • the subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
  • Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 57.1% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 12.4% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 30.5% by mass was blended to obtain 1 kg of a raw material mixture.
  • the subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
  • a phosphor was manufactured under the same conditions as in Example 1 except that the raw material mixing step was performed with the raw material compositions shown in Table 1. As shown in Table 1, it can be seen that the chromaticity X is low, the peak wavelength and the half-value width are small values, and the intensity of the red component is reduced as compared with the examples.
  • the color rendering index (Ra) was also below 70.0. In addition, the nitrogen content was reduced as compared with the examples.
  • a phosphor was manufactured under the same conditions as in Example 1 except that the raw material mixing step was performed with the raw material compositions shown in Table 1. As shown in Table 1, these comparative examples 5 to 7 having an Al / (O + N) molar ratio of 5/13 or less showed a particularly low value of the external quantum efficiency as compared with the examples.
  • the raw material mixture was mixed with a super mixer of Kawata Co., Ltd., and passed through a nylon sieve having an opening of 850 ⁇ m to obtain a raw material powder for phosphor synthesis.
  • 50 g of the raw material powder is filled into a cylindrical boron nitride container (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid having an internal size of 8 cm in diameter and 8 cm in height, and the internal size is 100 cm ⁇ 50 cm ⁇
  • a container was placed inside a graphite box with an upper lid having a height of 13 cm.
  • This graphite box has four long-side holes and four short-side holes each having a diameter of 20 mm.
  • the obtained powder was gradually cooled to room temperature.
  • the subsequent steps are the same as in Example 1.
  • the chromaticity X is low, the peak wavelength and the full width at half maximum are small, and it can be seen that the intensity of the red component is reduced.
  • the nitrogen content was significantly lower than that of other production examples.
  • the color rendering index (Ra) was also below 70.0.
  • the invention of Example 7 is a light emitting device having the above-described phosphor and a light emitting element.
  • the structure of the light-emitting device of Example 7 is shown in FIG.
  • the light emitting device emits white light
  • the blue LED chip 1 is connected to the conductive terminal 6 and installed at the bottom of the container 5, and the blue LED chip 1 is connected to the other conductive terminal 7 with the wire 3.
  • the phosphor 2 and the epoxy resin as the sealing resin 4 are heat-cured.
  • Example 8 is a lighting device, and although not shown, is a light bulb type lighting device having the light emitting device of Example 7. This lighting device exhibited good color rendering properties as shown in Table 1 when Examples 1 to 6 were used as phosphors.

Abstract

The purpose of the present invention is: to provide a fluorescent material that, while being a yellow light, also has a high amount of a red component and a green component; and to provide a light-emitting device and a lighting device that employ said fluorescent material and have good color rendering characteristics. The fluorescent material of the present invention is represented by the formula LuAlON:Ce, and the content of N is 0.010-5.0 mass%, Ce and Lu satisfy Ce/Lu ≥ 0.05 when expressed as mole ratios, and Al with respect to O and N satisfies Al/(O+N) > 5/13 when expressed as a mole ratio. Also provided are a light-emitting device comprising the fluorescent material and a light-emitting element, and a lighting device comprising the light-emitting device.

Description

蛍光体、発光装置及び照明装置Phosphor, light emitting device and lighting device
　本願発明は、蛍光体、発光装置及び照明装置に関する。 The present invention relates to a phosphor, a light emitting device, and a lighting device.
　特許文献１には、青色発光ダイオード又はレーザーダイオードチップで発光する青色光と、この青色光（波長：４２０ｎｍから４７０ｎｍ）を蛍光体で変換した黄色光とで白色を発光する発光装置が示されている。ここでの蛍光体は、セリウム付活ＹＡＧ（イットリウム・アルミニウム・ガーネット）のＹの一部をＬｕ、Ｓｃ、Ｇｄ、Ｌａで置換したものである。
　特許文献２には、青色光を黄色光に変換する蛍光体として、ＹＡＧが示されている。 Patent Document 1 discloses a light emitting device that emits white light using blue light emitted from a blue light emitting diode or laser diode chip and yellow light obtained by converting the blue light (wavelength: 420 nm to 470 nm) with a phosphor. Yes. Here, the phosphor is obtained by replacing part of Y of cerium activated YAG (yttrium, aluminum, garnet) with Lu, Sc, Gd, and La.
Patent Document 2 discloses YAG as a phosphor that converts blue light into yellow light.
　しかし、セリウム付活ＹＡＧが発する黄色光には、赤色成分（波長：６００ｎｍから７００ｎｍ）や緑色成分（波長：５１０ｎｍから５５０ｎｍ）が少ないため、青色発光ダイオードと組み合わせた場合に、演色性の高い白色光が得られないという課題があった。 However, yellow light emitted from cerium-activated YAG has a small red component (wavelength: 600 nm to 700 nm) and green component (wavelength: 510 nm to 550 nm), and therefore has a high color rendering property when combined with a blue light emitting diode. There was a problem that light could not be obtained.
　特許文献３では、赤色成分や緑色成分を確保して演色性を高めるために、緑色及び赤色発光の蛍光体を用いているが、異なる蛍光体を混合すると、一方の蛍光体の発光を他方の蛍光体が吸収して発光効率が低下するという新たな課題があった。 In Patent Document 3, green and red light emitting phosphors are used to secure a red component and a green component to enhance color rendering. However, when different phosphors are mixed, light emission of one phosphor is caused to occur on the other. There has been a new problem that the phosphor absorbs and the luminous efficiency decreases.
特開平１０－１９００６６号公報Japanese Patent Laid-Open No. 10-190066 特開２００３－８０８２号公報JP 2003-8082 A 国際公開第０６／０９３２９８号パンフレットInternational Publication No. 06/093298 Pamphlet
　本発明の目的は、黄色光でありながら赤色成分や緑色成分が多い蛍光体を提供すること、及び、この蛍光体を用いて演色性の高い発光装置及び照明装置を提供することにある。 An object of the present invention is to provide a phosphor having a large amount of red and green components while being yellow light, and to provide a light emitting device and a lighting device having high color rendering properties using the phosphor.
　本発明者らは、鋭意検討した結果、一般式ＬｕＡｌＯＮ：Ｃｅで表される蛍光体の組成を特定することにより、発光色が黄色光でありながら赤色成分や緑色成分が多い蛍光体となること、及び、この蛍光体を用いることにより演色性の高い発光装置及び照明装置が得られることを見出し、本発明を完成した。 As a result of intensive studies, the present inventors have specified the composition of the phosphor represented by the general formula LuAlON: Ce, so that the phosphor has a large amount of red and green components while the emission color is yellow light. The inventors have found that a light emitting device and a lighting device having high color rendering properties can be obtained by using this phosphor, and the present invention has been completed.
　本発明は、一般式ＬｕＡｌＯＮ：Ｃｅで表され、Ｎが０．０１０質量％以上５．０質量％以下、ＣｅとＬｕがモル比でＣｅ／Ｌｕ≧０．０５、及び、Ａｌがモル比でＯとＮに対してＡｌ／（Ｏ＋Ｎ）＞５／１３である蛍光体である。 The present invention is represented by the general formula LuAlON: Ce, N is 0.010 mass% or more and 5.0 mass% or less, Ce and Lu are in a molar ratio Ce / Lu ≧ 0.05, and Al is in a molar ratio. It is a phosphor with Al / (O + N)> 5/13 with respect to O and N.
　他の発明は、上述の蛍光体と発光素子とを有する発光装置であり、さらに他の発明は、この発光装置を用いた照明装置である。 Another invention is a light emitting device having the above-described phosphor and a light emitting element, and yet another invention is an illumination device using the light emitting device.
　本発明の蛍光体は、青色の発光素子が発する３５０ｎｍ以上５００ｎｍ以下の波長範囲の光により効率良く励起され、発光色が黄色でありながら、色度Ｘ、ピーク波長及び半値幅の値が大きく、赤色成分と緑色成分とを多く含む。このため、青色発光素子と組合せることにより、演色性の高い白色を実現する発光装置及び照明装置を得ることができる。 The phosphor of the present invention is efficiently excited by light in a wavelength range of 350 nm or more and 500 nm or less emitted from a blue light-emitting element, and has a large chromaticity X, peak wavelength, and full width at half maximum while the emission color is yellow, It contains a lot of red and green components. For this reason, by combining with a blue light emitting element, it is possible to obtain a light emitting device and a lighting device that realize white with high color rendering properties.
本発明に係る実施例７の発光装置を模式的に示した説明図。Explanatory drawing which showed typically the light-emitting device of Example 7 which concerns on this invention.
　以下に本発明の実施の形態を説明する。 Embodiments of the present invention will be described below.
　本発明の蛍光体は、一般式ＬｕＡｌＯＮ：Ｃｅで表され、所定量の窒素元素を含有し、多量のセリウムを含有する酸窒化物の蛍光体である。その組成比として、Ｎが０．０１０質量％以上５．０質量％以下、ＣｅとＬｕがモル比でＣｅ／Ｌｕ≧０．０５、及び、Ａｌがモル比でＯとＮに対してＡｌ／（Ｏ＋Ｎ）＞５／１３である蛍光体である。 The phosphor of the present invention is an oxynitride phosphor which is represented by the general formula LuAlON: Ce, contains a predetermined amount of nitrogen element, and contains a large amount of cerium. As the composition ratio, N is 0.010 mass% or more and 5.0 mass% or less, Ce and Lu are molar ratios of Ce / Lu ≧ 0.05, and Al is molar ratio of O / N with respect to Al / Al. It is a phosphor with (O + N)> 5/13.
　上記一般式において、Ｌｕはルテチウムであり、ルテチウムの一部又は全部はＹ、Ｓｃ、Ｌａ、Ｇｄ及びＳｍよりなる群から選ばれる１種以上の元素で置換することもできる。
　Ｃｅはセリウムであり、セリウムの一部又は全部はＰｒ、Ｎｄ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＭｎよりなる群から選ばれる１種以上の元素で置換することもできる。
　Ａｌはアルミニウムであり、アルミニウムの一部又は全部はＧａ及びＩｎのいずれか一方又は双方で置換することもできる。Ｏは酸素であり、Ｎは窒素である。 In the above general formula, Lu is lutetium, and part or all of lutetium can be substituted with one or more elements selected from the group consisting of Y, Sc, La, Gd, and Sm.
Ce is cerium, and part or all of cerium may be substituted with one or more elements selected from the group consisting of Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Mn.
Al is aluminum, and a part or all of aluminum can be replaced with either one or both of Ga and In. O is oxygen and N is nitrogen.
　Ｎが０．０１０質量％以上５．０質量％以下、ＣｅとＬｕがモル比でＣｅ／Ｌｕ≧０．０５、並びにＡｌがモル比でＯとＮに対してＡｌ／（Ｏ＋Ｎ）＞５／１３とすることで、色度Ｘが顕著に上昇し、ピーク波長が上昇し、半値幅が大きくなり、赤色（波長６００ｎｍ以上７００ｎｍ以下）の蛍光成分の割合が増大し、長波長化する傾向にある。これは主に、モル比でＣｅ／Ｌｕを高め、窒素含有量を多くすると、蛍光体の発光色における赤色成分（波長６００ｎｍ以上７００ｎｍ以下）の割合が増大するためである。また、半値幅が大きくなることによって、発光色における緑色成分（波長５１０ｎｍ以上５５０ｎｍ以下）の割合も増大する。かくして、赤色成分と緑色成分とを多く含む黄色光の蛍光体を得ることが可能となる。 N is 0.010% by mass or more and 5.0% by mass or less, Ce / Lu is in a molar ratio of Ce / Lu ≧ 0.05, and Al is in a molar ratio of Al / (O + N)> 5 / By setting the number to 13, the chromaticity X increases remarkably, the peak wavelength increases, the half-value width increases, the ratio of red (wavelength 600 nm to 700 nm) fluorescent components increases, and the wavelength tends to increase. is there. This is mainly because the ratio of the red component (wavelength: 600 nm to 700 nm) in the emission color of the phosphor increases when Ce / Lu is increased in molar ratio and the nitrogen content is increased. Further, as the half width increases, the proportion of the green component (wavelength of 510 nm or more and 550 nm or less) in the emission color also increases. Thus, it is possible to obtain a yellow light phosphor containing a large amount of red and green components.
　本発明の蛍光体における窒素原子は、蛍光体自体の結晶格子内及び／又は結晶格子間に存在する。得られた蛍光体中の窒素含有量は、酸素―窒素測定機（例えば株式会社堀場製作所製ＥＭＧＡ―９２０）で測定することができる。測定法については、酸素は不活性ガス融解－非分散型赤外線吸収法（ＮＤＩＲ）、窒素は不活性ガス融解－熱伝導度法（ＴＣＤ）を用いることができる。上述のように、窒素含有量の増加は蛍光体の発光色における赤色成分の増加に関与するが、窒素含有量があまりに多いと発光強度が低下する傾向がある。 The nitrogen atom in the phosphor of the present invention exists in the crystal lattice and / or between crystal lattices of the phosphor itself. The nitrogen content in the obtained phosphor can be measured with an oxygen-nitrogen measuring machine (for example, EMGA-920 manufactured by Horiba, Ltd.). Regarding the measurement method, an inert gas melting-non-dispersive infrared absorption method (NDIR) can be used for oxygen, and an inert gas melting-thermal conductivity method (TCD) can be used for nitrogen. As described above, the increase in the nitrogen content is related to the increase in the red component in the emission color of the phosphor, but if the nitrogen content is too large, the emission intensity tends to decrease.
　本発明の蛍光体は、特許文献２の従来の蛍光体と比較して、発光ピーク波長が長波長側にシフトしており、赤色成分が多いことに加え、緑色成分も多いことから、濃い黄色を示す。励起スペクトルのピーク波長が３５０から５００ｎｍの範囲にあるので、その波長範囲の光で効率良く励起され、濃い黄色に発光するため、演色性の高い白色ＬＥＤ用に好適である。 Compared with the conventional phosphor of Patent Document 2, the phosphor of the present invention has a light emission peak wavelength shifted to the long wavelength side, and in addition to a large amount of red component, there is also a large amount of green component. Indicates. Since the peak wavelength of the excitation spectrum is in the range of 350 to 500 nm, it is efficiently excited by light in that wavelength range and emits deep yellow light, which is suitable for white LEDs with high color rendering properties.
　本発明の蛍光体の製造方法は、Ｌｕ、Ａｌ、Ｏ及びＣｅを含んだ化合物からなる複数の原料を混合する混合工程と、混合工程後の原料混合粉を窒素雰囲気で０．００１ＭＰａ以上１００ＭＰａ以下のゲージ圧力、１０００℃以上２４００℃以下の温度範囲で保持する焼成工程で構成されるのが好ましい。 The phosphor production method of the present invention includes a mixing step of mixing a plurality of raw materials made of a compound containing Lu, Al, O and Ce, and a raw material mixed powder after the mixing step in a nitrogen atmosphere between 0.001 MPa and 100 MPa. It is preferable that it is comprised by the baking process hold | maintained in the temperature range of 1000 gauge or more and 2400 degrees C or less.
　混合工程での原料として、純度９９％以上の水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解し酸化物になりうるもの、純度９９．９％以上の酸化物、純度９９．９％以上の窒化物を使用することが好ましい。窒化物としてＡｌＮ、アジ化物があり、純度９９．９％以上のものが好ましい。 As raw materials in the mixing process, hydroxides, carbonates, nitrates, halides, oxalates with a purity of 99% or more, which can be decomposed at high temperatures into oxides, oxides with a purity of 99.9% or more, purity It is preferable to use 99.9% or more of nitride. Examples of the nitride include AlN and azide, and those having a purity of 99.9% or more are preferable.
　出発原料の混合にはボールミル、Ｖ型混合機又は攪拌装置等を用いることができる。 For mixing the starting materials, a ball mill, a V-type mixer or a stirring device can be used.
　焼成工程は、例えば１０００℃以上２４００℃以下の温度範囲と０．００１ＭＰａ以上１００ＭＰａ以下の圧力範囲において、１時間以上１００時間以下保持することが好ましい。焼成温度は１５００℃以上２２００℃以下がより好ましい。焼成工程での雰囲気の圧力は、０．７ＭＰａ以上７０ＭＰａ以下がより好ましい。 The firing step is preferably held for 1 hour to 100 hours in a temperature range of 1000 ° C. to 2400 ° C. and a pressure range of 0.001 MPa to 100 MPa, for example. The firing temperature is more preferably 1500 ° C. or higher and 2200 ° C. or lower. As for the pressure of the atmosphere in a baking process, 0.7 MPa or more and 70 MPa or less are more preferable.
　焼成の雰囲気としては、窒素元素含有雰囲気を用いる。窒素元素含有雰囲気としては、具体的には、窒素及び／又はアンモニアを含有する雰囲気があり、アルゴン、ヘリウム等の不活性ガスを含有してもよい。窒素及び／又はアンモニアの含有量は１０体積％以上が好ましく、５０体積％以上がより好ましく、１００体積％がさらに好ましく、窒素元素含有雰囲気が高純度窒素（純度９９．９９％以上）及び／又は高純度アンモニア（純度９９．９９％以上）からなる場合が最も好ましい。 As the firing atmosphere, a nitrogen element-containing atmosphere is used. Specifically, the nitrogen element-containing atmosphere includes an atmosphere containing nitrogen and / or ammonia, and may contain an inert gas such as argon or helium. The content of nitrogen and / or ammonia is preferably 10% by volume or more, more preferably 50% by volume or more, still more preferably 100% by volume, and the nitrogen element-containing atmosphere is high purity nitrogen (purity 99.99% or more) and / or The case where it consists of high purity ammonia (purity 99.99% or more) is the most preferable.
　焼成の前に仮焼を行う場合、仮焼の雰囲気は、不活性雰囲気、酸化性雰囲気、還元性雰囲気、窒素元素含有ガス雰囲気のいずれでもよい。不活性雰囲気での不活性ガスとしては、窒素、アルゴンがある。酸化性雰囲気でのガスとしては、空気、酸素、酸素含有窒素、酸素含有アルゴンがある。還元性雰囲気でのガスとしては、水素含有窒素、水素含有アルゴンがある。これらガスには、反応を促進するために、適量のフラックスを添加してもよい。 When calcination is performed before calcination, the calcination atmosphere may be any of an inert atmosphere, an oxidizing atmosphere, a reducing atmosphere, and a nitrogen element-containing gas atmosphere. Examples of the inert gas in the inert atmosphere include nitrogen and argon. Examples of the gas in the oxidizing atmosphere include air, oxygen, oxygen-containing nitrogen, and oxygen-containing argon. Examples of the gas in the reducing atmosphere include hydrogen-containing nitrogen and hydrogen-containing argon. An appropriate amount of flux may be added to these gases in order to promote the reaction.
　焼成用の炉は、焼成温度が高温であり焼成雰囲気が窒素元素含有雰囲気であることから、金属抵抗加熱方式又は黒鉛抵抗加熱方式が好ましく、炉の高温部の材料として炭素を用いた電気炉が好ましい。 Since the firing temperature is high and the firing atmosphere is a nitrogen element-containing atmosphere, the metal resistance heating method or the graphite resistance heating method is preferable, and an electric furnace using carbon as the material of the high temperature part of the furnace is used. preferable.
　上記方法にて得られる蛍光体を、ボールミル、振動ミル、アトライター、ジェットミル等の工業的に通常用いられている粉砕装置を用いて粉砕してもよい。得られる蛍光体の結晶性を高めるために、再焼成を行ってもよい。また、結晶成長の促進や合成反応を進行させるために再焼成を行ってもよい。 The phosphor obtained by the above method may be pulverized using a pulverizer that is usually used industrially, such as a ball mill, a vibration mill, an attritor, or a jet mill. In order to improve the crystallinity of the obtained phosphor, re-firing may be performed. Further, re-baking may be performed in order to promote crystal growth or advance a synthesis reaction.
　さらに、後処理として、上述の工程後、洗浄、分散処理、乾燥、分級等を行うことができる。なかでも、酸による洗浄工程を設けることが好ましい。酸洗浄を行うには、酸性の水溶液中に蛍光体を粒子状に分散させた後、水洗する。具体的には、塩酸、硫酸、硝酸等の無機酸の１種又は２種以上があり、塩酸が好ましい。酸洗浄を行うことにより未反応物、副成物、融剤を溶解し、分別除去できる。また、得られた蛍光体を後述するように透光性樹脂中に分散させて用いる場合には、耐湿性や分散性を高めるために、必要に応じて公知の表面処理を施すこともできる。 Furthermore, as post-treatment, washing, dispersion treatment, drying, classification and the like can be performed after the above-described steps. Especially, it is preferable to provide the washing process by an acid. In order to perform acid cleaning, the phosphor is dispersed in the form of particles in an acidic aqueous solution and then washed with water. Specifically, there are one or more inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and hydrochloric acid is preferred. By performing the acid cleaning, unreacted substances, by-products and fluxes can be dissolved and separated and removed. In addition, when the obtained phosphor is used by being dispersed in a light-transmitting resin as described later, a known surface treatment can be applied as necessary in order to improve moisture resistance and dispersibility.
　本発明の蛍光体は、発光素子と組み合わせることにより発光装置とすることができる。本発明の発光装置は、本発明の蛍光体をエポキシ樹脂、ポリカーボネート、シリコンゴムなどの透光性樹脂中に分散させ、この蛍光体を分散させた樹脂を、ステム上の発光素子（化合物半導体）を取り囲むように成形することにより製造することができる。本発明の発光装置においては、白色発光を実現するために、発光素子としては青色発光窒化物半導体が好ましく、紫外から青色に発光する化合物半導体を用いることも可能である。 The phosphor of the present invention can be combined with a light emitting element to form a light emitting device. In the light emitting device of the present invention, the phosphor of the present invention is dispersed in a translucent resin such as epoxy resin, polycarbonate, silicon rubber, and the resin in which the phosphor is dispersed is used as a light emitting element on the stem (compound semiconductor). It can manufacture by shape | molding so that it may surround. In the light emitting device of the present invention, in order to realize white light emission, a blue light emitting nitride semiconductor is preferable as the light emitting element, and a compound semiconductor that emits light from ultraviolet to blue can also be used.
　具体的には、蛍光体を励起する３５０ｎｍから５００ｎｍの波長の光を発する窒化物半導体からなる発光素子が好ましい。窒化物半導体は構成元素の比率により発光波長を変えることができ、例えば、Ｇａ－Ｎ系では３２０ｎｍから４５０ｎｍ、Ｉｎ－Ａｌ－Ｇａ－Ｎ系では３００ｎｍから５００ｎｍで発光の波長のピークを制御できる。窒化物半導体からなる発光素子としては、発光層が組成式ＩｎｘＡｌｙＧａ１－ｘ－ｙＮ（０＜ｘ、０＜ｙ、ｘ＋ｙ＜１）で表わされる化合物からなり、ヘテロ構造又はダブルヘテロ構造を有する発光素子がある。 Specifically, a light-emitting element made of a nitride semiconductor that emits light having a wavelength of 350 nm to 500 nm that excites the phosphor is preferable. The emission wavelength of a nitride semiconductor can be changed depending on the ratio of constituent elements. For example, the peak of emission wavelength can be controlled from 320 nm to 450 nm in the Ga—N system and from 300 nm to 500 nm in the In—Al—Ga—N system. In a light-emitting element made of a nitride semiconductor, the light-emitting layer is made of a compound represented by the composition formula In x Al y Ga 1-xy N (0 <x, 0 <y, x + y <1), and has a heterostructure or a double structure. There is a light-emitting element having a heterostructure.
　本発明の蛍光体は単独で使用でき、さらに赤色発光の蛍光体や緑色発光の蛍光体など他の蛍光体と併用して、白色度のより高い発光装置を製造することも可能である。
　また、かかる発光装置を応用することにより、演色性の高い白色を発光する照明装置を得ることも可能である。 The phosphor of the present invention can be used alone, and it is also possible to produce a light emitting device with higher whiteness by using in combination with other phosphors such as a red light emitting phosphor and a green light emitting phosphor.
Further, by applying such a light-emitting device, it is possible to obtain a lighting device that emits white light with high color rendering properties.
　本発明の実施例を説明する。実施例１の蛍光体は、表１に示されるように、一般式ＬｕＡｌＯＮ：Ｃｅで表される蛍光体であり、窒素含有量が０．０６６質量％、ＣｅとＬｕがモル比でＣｅ／Ｌｕ＝１．０００、及び、Ａｌがモル比でＯとＮに対してＡｌ／（Ｏ＋Ｎ）＝０．４４３であった。 Embodiments of the present invention will be described. As shown in Table 1, the phosphor of Example 1 is a phosphor represented by the general formula LuAlON: Ce, the nitrogen content is 0.066 mass%, and Ce and Lu are Ce / Lu in molar ratio. = 1.000, and Al was Al / (O + N) = 0.443 relative to O and N in a molar ratio.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜混合工程＞
　混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）３２．７質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）２８．３質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３９．０質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝１．５：１．５：７である。 <Mixing process>
In the mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 32.7 mass%, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 28.3 mass%, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 39.0% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of the charged Lu, Ce, and Al is Lu: Ce: Al = 1.5: 1.5: 7.
　原料混合物を、カワタ株式会社のスーパーミキサーにて混合し、目開き８５０μｍのナイロン製篩を全通させ、蛍光体合成用の原料粉末を得た。 The raw material mixture was mixed with a super mixer manufactured by Kawata Co., Ltd., and passed through a nylon sieve having an opening of 850 μm to obtain a raw material powder for phosphor synthesis.
＜焼成工程＞
　原料粉末を、内寸で直径８ｃｍ×高さ８ｃｍの蓋付きの円筒型窒化ホウ素製容器（電気化学工業株式会社製Ｎ－１グレード）に５０ｇ充填し、内寸で１００ｃｍ×５０ｃｍ×高さ１３ｃｍの上蓋付き黒鉛ボックス内部に容器を配置した。この黒鉛ボックスは側面に直径２０ｍｍの穴が長辺４個、短辺４個開いている。さらに底の中央に直径５０ｍｍの穴が開いており、この穴の下に排ガス管が設置されており、焼成中に排ガス管から雰囲気ガスの排気を行った。カーボンヒーターの電気炉で０．７ＭＰａの加圧窒素雰囲気中、１７００℃で１５時間の加熱処理を行った後、得られた粉末を室温まで徐冷した。この焼成物を乳鉢で解砕し、目開き２５０μｍの篩を通し、合成粉末にした。 <Baking process>
50 g of a raw material powder is filled into a cylindrical boron nitride container (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid having an internal size of 8 cm in diameter and 8 cm in height, and the internal size is 100 cm × 50 cm × 13 cm in height. A container was placed inside a graphite box with an upper lid. This graphite box has four long-side holes and four short-side holes each having a diameter of 20 mm. Further, a hole with a diameter of 50 mm was opened in the center of the bottom, and an exhaust gas pipe was installed under this hole, and atmospheric gas was exhausted from the exhaust gas pipe during firing. After heat treatment at 1700 ° C. for 15 hours in a 0.7 MPa pressurized nitrogen atmosphere with an electric furnace of a carbon heater, the obtained powder was gradually cooled to room temperature. The fired product was crushed in a mortar and passed through a sieve having an opening of 250 μm to obtain a synthetic powder.
　実施例１で製造された蛍光体の外部量子効率、色度Ｘ、ピーク波長、半値幅、演色性指数、窒素含有量の結果を表１に示す。 Table 1 shows the results of the external quantum efficiency, chromaticity X, peak wavelength, half-value width, color rendering index, and nitrogen content of the phosphor manufactured in Example 1.
　表１の外部量子効率は分光光度計（大塚電子株式会社製ＭＣＰＤ－７０００）により測定した。凹型のセルに蛍光体をセル表面が平滑になるように充填し、積分球を取り付けた。この積分球に、発光光源（Ｘｅランプ）から４５５ｎｍの波長に分光した単色光を、光ファイバーを用いて導入した。この単色光を励起源として、蛍光体試料に照射し、試料の蛍光スペクトル測定を行った。発光効率は次のように求めた。試料部に反射率が９９％の標準反射板（Ｌａｂｓｐｈｅｒｅ社製、スペクトラロン）をセットし、波長４５５ｎｍの励起光のスペクトルを測定した。その際、４５０～４６５ｎｍの波長範囲のスペクトルから励起光フォトン数（Ｑｅｘ）を算出した。次いで、試料部にサンプルをセットし、得られたスペクトルデータから励起反射光フォトン数（Ｑｒｅｆ）及び蛍光フォトン数（Ｑｅｍ）を算出した。励起反射光フォトン数は励起光フォトン数と同じ波長範囲で、蛍光フォトン数は４６５～８００ｎｍの範囲で算出した。得られた三種類のフォトン数から
外部量子効率（＝Ｑｅｍ／Ｑｅｘ×１００）、
吸収率（＝（Ｑｅｘ－Ｑｒｅｆ）×１００）、
内部量子効率（＝Ｑｅｍ／（Ｑｅｘ－Ｑｒｅｆ）×１００）
を求めた。
　実施例として合格の外部量子効率は４０％以上である。 The external quantum efficiency in Table 1 was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). A concave cell was filled with phosphor so that the cell surface was smooth, and an integrating sphere was attached. Monochromatic light separated into a wavelength of 455 nm from a light emitting light source (Xe lamp) was introduced into the integrating sphere using an optical fiber. The phosphor sample was irradiated with this monochromatic light as an excitation source, and the fluorescence spectrum of the sample was measured. Luminous efficiency was determined as follows. A standard reflector (Spectralon, manufactured by Labsphere) having a reflectance of 99% was set on the sample portion, and the spectrum of excitation light having a wavelength of 455 nm was measured. At that time, the number of excitation light photons (Qex) was calculated from the spectrum in the wavelength range of 450 to 465 nm. Next, a sample was set in the sample portion, and the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) were calculated from the obtained spectrum data. The number of excited reflected light photons was calculated in the same wavelength range as the number of excited light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm. External quantum efficiency (= Qem / Qex × 100) from the obtained three types of photons,
Absorption rate (= (Qex−Qref) × 100),
Internal quantum efficiency (= Qem / (Qex−Qref) × 100)
Asked.
As an example, the passed external quantum efficiency is 40% or more.
　表１の色度Ｘは、ＣＩＥ１９３１の値であり、分光光度計（大塚電子株式会社製ＭＣＰＤ－７０００）により測定した。実施例として合格の色度Ｘは０．３８５以上である。 The chromaticity X in Table 1 is a value of CIE1931, and was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). As an example, the acceptable chromaticity X is 0.385 or more.
　表１のピーク波長は、分光光度計（大塚電子株式会社製ＭＣＰＤ－７０００）により測定した。実施例として合格のピーク波長は５４４．０ｎｍ以上である。 The peak wavelengths in Table 1 were measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). As an example, the acceptable peak wavelength is 544.0 nm or more.
　表１の半値幅は、分光光度計（大塚電子株式会社製ＭＣＰＤ－７０００）により測定した。実施例として合格の半値幅は１０３．０ｎｍ以上である。 The half width in Table 1 was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). As an example, the half width of the pass is 103.0 nm or more.
　表１の窒素含有量は酸素―窒素測定機（ＨＯＲＩＢＡ株式会社製ＥＭＧＡ―９２０）により測定した。実施例として合格の窒素含有量は０．０１０質量％以上である。 The nitrogen content in Table 1 was measured with an oxygen-nitrogen measuring machine (EMGA-920 manufactured by HORIBA Corporation). As an example, the acceptable nitrogen content is 0.010% by mass or more.
　演色性指数は次の方法で測定した。蛍光体１０ｇを水１００ｇにエポキシシランカップリング剤（信越シリコーン株式会社製ＫＢＥ４０２）１．０ｇと共に加え、撹拌しながら一晩放置した。その後、ろ過乾燥したシランカップリング剤で処理された前記蛍光体の適量をエポキシ樹脂（サンユレック株式会社製ＮＬＤ－ＳＬ－２１０１）１０ｇに混練し、発光波長４６０ｎｍの青色ＬＥＤ素子の上にポッティングし、真空脱気し、１１０℃で前記樹脂を加熱硬化し、表面実装型ＬＥＤを作製した。これに１０ｍＡの電流を流して発生する光を測定し、演色性指数（Ｒａ）を測定した。実施例として合格の演色性指数（Ｒａ）は７０．０以上である。 The color rendering index was measured by the following method. 10 g of the phosphor was added to 100 g of water together with 1.0 g of an epoxysilane coupling agent (KBE402 manufactured by Shin-Etsu Silicone Co., Ltd.) and left overnight with stirring. Thereafter, an appropriate amount of the phosphor treated with the filtered and dried silane coupling agent was kneaded with 10 g of an epoxy resin (NLD-SL-2101 manufactured by Sanyu Rec Co., Ltd.) and potted on a blue LED element having an emission wavelength of 460 nm. The resin was heat-cured at 110 ° C. by vacuum degassing, and a surface-mounted LED was produced. The light generated by passing a current of 10 mA was measured, and the color rendering index (Ra) was measured. As an example, a color rendering index (Ra) that is acceptable is 70.0 or more.
　表１に示すように、実施例１の外部量子効率、色度Ｘ、ピーク波長、半値幅、窒素含有量、演色性指数（Ｒａ）はいずれも優秀な値を示した。 As shown in Table 1, the external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra) of Example 1 all showed excellent values.
　原料混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）５０．９質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）１１．０質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３８．１質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝２．４：０．６：７である。後の工程は実施例１と同様である。表１に示すように、外部量子効率、色度Ｘ、ピーク波長、半値幅、窒素含有量、演色性指数（Ｒａ）において、優秀な値を有していた。 In the raw material mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 50.9 mass%, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 11.0 mass%, Al 2 O 3 (TM-DAR grade, manufactured by Daimei Chemical Co., Ltd.) 38.1% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of the charged Lu, Ce, and Al is Lu: Ce: Al = 2.4: 0.6: 7. The subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
　原料混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）５９．１質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）３．３質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３７．６質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝２．８２：０．１８：７である。後の工程は実施例１と同様である。表１に示すように、外部量子効率、色度Ｘ、ピーク波長、半値幅、窒素含有量、演色性指数（Ｒａ）において、優秀な値を有していた。 In the raw material mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 59.1% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 3.3% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 37.6% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of the charged Lu, Ce, and Al is Lu: Ce: Al = 2.82: 0.18: 7. The subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
　原料混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）３６．８質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）３１．８質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３１．４質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝１．５：１．５：５である。後の工程は実施例１と同様である。表１に示すように、外部量子効率、色度Ｘ、ピーク波長、半値幅、窒素含有量、演色性指数（Ｒａ）において、優秀な値を有していた。 In the raw material mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 36.8% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 31.8% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 31.4% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of charged Lu, Ce, and Al is Lu: Ce: Al = 1.5: 1.5: 5. The subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
　原料混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）５７．１質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）１２．４質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３０．５質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝２．４：０．６：５である。後の工程は実施例１と同様である。表１に示すように、外部量子効率、色度Ｘ、ピーク波長、半値幅、窒素含有量、演色性指数（Ｒａ）において、優秀な値を有していた。 In the raw material mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 57.1% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 12.4% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 30.5% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of the charged Lu, Ce, and Al is Lu: Ce: Al = 2.4: 0.6: 5. The subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
　原料混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）６６．２質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）３．７質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３０．１質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝２．８２：０．１８：５である。後の工程は実施例１と同様である。表１に示すように、外部量子効率、色度Ｘ、ピーク波長、半値幅、窒素含有量、演色性指数（Ｒａ）において、優秀な値を有していた。
＜比較例１＞ In the raw material mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 66.2% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 3.7% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 30.1% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of the charged Lu, Ce, and Al is Lu: Ce: Al = 2.82: 0.18: 5. The subsequent steps are the same as in Example 1. As shown in Table 1, it had excellent values in external quantum efficiency, chromaticity X, peak wavelength, half width, nitrogen content, and color rendering index (Ra).
<Comparative Example 1>
　原料混合工程にあっては、Ｌｕ２Ｏ３（和光純薬工業株式会社製）６９．２質量％、ＣｅＯ２（和光純薬工業株式会社製、和光特級）０．８質量％、Ａｌ２Ｏ３（大明化学株式会社製ＴＭ－ＤＡＲグレード）３０．０質量％を配合し、原料混合物１ｋｇを得た。仕込みのＬｕ、Ｃｅ、Ａｌのモル比はＬｕ：Ｃｅ：Ａｌ＝２．９６：０．０４：５である。後の工程は実施例１と同様である。表１に示すように実施例と比較し、色度Ｘは低く、ピーク波長、半値幅は小さい値となり、赤色成分の強度が低下していることがわかる。演色性指数（Ｒａ）も７０．０を下回った。また、窒素含有量も実施例と比較し、低下した。
＜比較例２＞ In the raw material mixing step, Lu 2 O 3 (Wako Pure Chemical Industries, Ltd.) 69.2% by mass, CeO 2 (Wako Pure Chemical Industries, Ltd., Wako Special Grade) 0.8% by mass, Al 2 O 3 (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 30.0% by mass was blended to obtain 1 kg of a raw material mixture. The molar ratio of the charged Lu, Ce, and Al is Lu: Ce: Al = 2.96: 0.04: 5. The subsequent steps are the same as in Example 1. As shown in Table 1, it can be seen that the chromaticity X is low, the peak wavelength and the half-value width are small values, and the intensity of the red component is reduced as compared with the examples. The color rendering index (Ra) was also below 70.0. In addition, the nitrogen content was reduced as compared with the examples.
<Comparative Example 2>
　表１記載の原料組成で原料混合工程を行ったこと以外は、実施例１と同じ条件で蛍光体を製造した。表１に示すように実施例と比較し、色度Ｘは低く、ピーク波長、半値幅は小さい値となり、赤色成分の強度が低下していることがわかる。演色性指数（Ｒａ）も７０．０を下回った。また、窒素含有量も実施例と比較し、低下した。
＜比較例５～７＞ A phosphor was manufactured under the same conditions as in Example 1 except that the raw material mixing step was performed with the raw material compositions shown in Table 1. As shown in Table 1, it can be seen that the chromaticity X is low, the peak wavelength and the half-value width are small values, and the intensity of the red component is reduced as compared with the examples. The color rendering index (Ra) was also below 70.0. In addition, the nitrogen content was reduced as compared with the examples.
<Comparative Examples 5-7>
　表１記載の原料組成で原料混合工程を行ったこと以外は、実施例１と同じ条件で蛍光体を製造した。Ａｌ／（Ｏ＋Ｎ）のモル比が５／１３以下であるこれらの比較例５～７は、表１に示すように実施例と比較して特に外部量子効率が著しく低い値を示した。 A phosphor was manufactured under the same conditions as in Example 1 except that the raw material mixing step was performed with the raw material compositions shown in Table 1. As shown in Table 1, these comparative examples 5 to 7 having an Al / (O + N) molar ratio of 5/13 or less showed a particularly low value of the external quantum efficiency as compared with the examples.
＜比較例３及び４＞
　原料混合物を、カワタ株式会社のスーパーミキサーにて混合し、目開き８５０μｍのナイロン製篩を全通させ、蛍光体合成用の原料粉末を得た。焼成工程は原料粉末を、内寸で直径８ｃｍ×高さ８ｃｍの蓋付きの円筒型窒化ホウ素製容器（電気化学工業株式会社製Ｎ－１グレード）に５０ｇ充填し、内寸で１００ｃｍ×５０ｃｍ×高さ１３ｃｍの上蓋付き黒鉛ボックス内部に容器を配置した。この黒鉛ボックスは側面に直径２０ｍｍの穴が長辺４個、短辺４個開いている。カーボンヒーターの電気炉で絶対圧力で５．０Ｐａの真空雰囲気中、１７００℃で１５時間の加熱処理を行った後、得られた粉末を室温まで徐冷した。後の工程は実施例１と同様である。
　比較例３及び４のいずれも、表１に示すように色度Ｘは低く、ピーク波長、半値幅は小さい値となり、赤色成分の強度が低下していることがわかる。窒素含有量は他の製造例と比較しても著しく低くなった。演色性指数（Ｒａ）も７０．０を下回った。 <Comparative Examples 3 and 4>
The raw material mixture was mixed with a super mixer of Kawata Co., Ltd., and passed through a nylon sieve having an opening of 850 μm to obtain a raw material powder for phosphor synthesis. In the firing step, 50 g of the raw material powder is filled into a cylindrical boron nitride container (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid having an internal size of 8 cm in diameter and 8 cm in height, and the internal size is 100 cm × 50 cm × A container was placed inside a graphite box with an upper lid having a height of 13 cm. This graphite box has four long-side holes and four short-side holes each having a diameter of 20 mm. After heat treatment at 1700 ° C. for 15 hours in a vacuum atmosphere of 5.0 Pa in absolute pressure with an electric furnace of a carbon heater, the obtained powder was gradually cooled to room temperature. The subsequent steps are the same as in Example 1.
In both Comparative Examples 3 and 4, as shown in Table 1, the chromaticity X is low, the peak wavelength and the full width at half maximum are small, and it can be seen that the intensity of the red component is reduced. The nitrogen content was significantly lower than that of other production examples. The color rendering index (Ra) was also below 70.0.
　特に表１の比較例２、実施例１～３を見ると、酸化セリウムを増量させることで窒素含有量が増え、色度Ｘが高くなり、ピーク波長、半値幅が大きくなり、赤色成分の強度が増大していることがわかる。 In particular, looking at Comparative Example 2 and Examples 1 to 3 in Table 1, increasing the amount of cerium oxide increases the nitrogen content, increases the chromaticity X, increases the peak wavelength and the half-value width, and increases the intensity of the red component. It can be seen that increases.
　実施例７の発明は、上述の蛍光体と、発光素子とを有する発光装置である。実施例７の発光装置の構造を図１に示す。当該発光装置は、白色を発光するものであり、青色ＬＥＤチップ１を導電性端子６に接続させて容器５の底部に設置し、青色ＬＥＤチップ１をワイヤー３で他の導電性端子７に接続した後、蛍光体２と封止樹脂４としてのエポキシ樹脂を加熱硬化したものである。
　この表面実装型ＬＥＤに１０ｍＡの電流を流して発生する光の発光スペクトルを測定したところ、蛍光体として実施例１乃至６を用いた場合に、表１に示すような良好な演色性を発揮した。 The invention of Example 7 is a light emitting device having the above-described phosphor and a light emitting element. The structure of the light-emitting device of Example 7 is shown in FIG. The light emitting device emits white light, and the blue LED chip 1 is connected to the conductive terminal 6 and installed at the bottom of the container 5, and the blue LED chip 1 is connected to the other conductive terminal 7 with the wire 3. Then, the phosphor 2 and the epoxy resin as the sealing resin 4 are heat-cured.
When an emission spectrum of light generated by applying a current of 10 mA to this surface-mount type LED was measured, when Examples 1 to 6 were used as phosphors, good color rendering properties as shown in Table 1 were exhibited. .
　実施例８の発明は、照明装置であり、図示は省略したが、実施例７の発光装置を有する電球型の照明装置である。この照明装置は、蛍光体として実施例１乃至６を用いると、表１に示すような良好な演色性を発揮した。 The invention of Example 8 is a lighting device, and although not shown, is a light bulb type lighting device having the light emitting device of Example 7. This lighting device exhibited good color rendering properties as shown in Table 1 when Examples 1 to 6 were used as phosphors.
　１　青色ＬＥＤチップ
　２　蛍光体
　３　ワイヤー
　４　封止樹脂
　５　容器
　６　導電性端子
　７　他の導電性端子 DESCRIPTION OF SYMBOLS 1 Blue LED chip 2 Phosphor 3 Wire 4 Sealing resin 5 Container 6 Conductive terminal 7 Other conductive terminals

Claims (3)

  1. 一般式ＬｕＡｌＯＮ：Ｃｅで表され、Ｎが０．０１０質量％以上５．０質量％以下、ＣｅとＬｕがモル比でＣｅ／Ｌｕ≧０．０５、及び、Ａｌがモル比でＯとＮに対してＡｌ／（Ｏ＋Ｎ）＞５／１３である蛍光体。 General formula LuAlON: represented by Ce, N is 0.010 mass% or more and 5.0 mass% or less, Ce and Lu are in molar ratio Ce / Lu ≧ 0.05, and Al is molar ratio in O and N In contrast, a phosphor having Al / (O + N)> 5/13.
  2. 発光素子と、請求項１に記載の蛍光体とを有する発光装置。 The light-emitting device which has a light emitting element and the fluorescent substance of Claim 1.
  3. 請求項２記載の発光装置を有する照明装置。 A lighting device comprising the light emitting device according to claim 2.
PCT/JP2013/065661 2012-06-26 2013-06-06 Fluorescent material, light-emitting device, and lighting device WO2014002723A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005008844A (en) * 2003-02-26 2005-01-13 Nichia Chem Ind Ltd Phosphor, and light emitter using the same
JP2008533233A (en) * 2005-03-08 2008-08-21 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ Illumination system including a radiation source and a luminescent material
WO2012046642A1 (en) * 2010-10-05 2012-04-12 株式会社ネモト・ルミマテリアル Green light-emitting phosphor and light-emitting device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005008844A (en) * 2003-02-26 2005-01-13 Nichia Chem Ind Ltd Phosphor, and light emitter using the same
JP2008533233A (en) * 2005-03-08 2008-08-21 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ Illumination system including a radiation source and a luminescent material
WO2012046642A1 (en) * 2010-10-05 2012-04-12 株式会社ネモト・ルミマテリアル Green light-emitting phosphor and light-emitting device

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