WO2006117984A1 - Luminophore a base de nitrure et dispositif electroluminescent l'utilisant - Google Patents

Luminophore a base de nitrure et dispositif electroluminescent l'utilisant Download PDF

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Publication number
WO2006117984A1
WO2006117984A1 PCT/JP2006/307672 JP2006307672W WO2006117984A1 WO 2006117984 A1 WO2006117984 A1 WO 2006117984A1 JP 2006307672 W JP2006307672 W JP 2006307672W WO 2006117984 A1 WO2006117984 A1 WO 2006117984A1
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Prior art keywords
phosphor
light
nitride
nitride phosphor
light emitting
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PCT/JP2006/307672
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English (en)
Japanese (ja)
Inventor
Shoji Hosokawa
Takayuki Shinohara
Masatoshi Kameshima
Yoshinori Murazaki
Suguru Takashima
Hiroto Tamaki
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Nichia Corporation
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Priority claimed from JP2005130566A external-priority patent/JP4892861B2/ja
Priority claimed from JP2005130565A external-priority patent/JP5066786B2/ja
Application filed by Nichia Corporation filed Critical Nichia Corporation
Publication of WO2006117984A1 publication Critical patent/WO2006117984A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—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
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • 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
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    • 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
    • H01L2224/48257—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 die pad of the item
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    • 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
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48464—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area also being a ball bond, i.e. ball-to-ball
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • 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
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
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    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
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    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
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    • 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

Definitions

  • the present invention relates to a nitride phosphor used for lighting such as a light emitting diode and a fluorescent lamp, a display, a backlight for liquid crystal, and the like, and in particular, a nitride that emits red light when excited by blue light from near ultraviolet light. It relates to a phosphor.
  • Light emitting diodes are small in size, have high power efficiency, and emit bright colors. In addition, the light emitting diode does not have to worry about running out of a bulb because it is not a light bulb that heats the filament to emit light. In addition, the response speed is extremely fast and it is strong against vibration and repeated on / off lighting. Because of such excellent characteristics, light emitting diodes are used as various light sources.
  • a light emitting diode emits light in a specific wavelength region. Therefore, a light source has been developed in which a part of the emitted light is wavelength-converted by a phosphor and light that has been wavelength-converted by the phosphor and light from a light-emitting diode are mixed and emitted.
  • This light source can be made various emission colors different from the light emitting diode by selecting the emission color of the phosphor.
  • light sources that emit white light are used in a wide range of fields such as general illumination, displays, and backlights for liquid crystals. For this reason, there is a demand for a phosphor that can be used in a white light emitting device, particularly in combination with a light emitting diode.
  • the white light source composed of light emitting diodes is white due to the light emission of the blue light emitting diode and the phosphor, based on the principle of light color mixing.
  • This white light source excites the phosphor with blue light emitted from the light emitting element of the light emitting diode.
  • the phosphor absorbs blue light of the light emitting element and emits yellow fluorescence.
  • the yellow light of the phosphor and the blue light of the light-emitting element have a complementary color relationship, and the human eye sees the mixed light as white. Based on this principle, a white light source of a light emitting diode combining a blue light emitting element and a phosphor is manufactured.
  • Patent Document 1 Pamphlet of International Publication No. 01Z40403
  • Y O S: Eu oxysulfide phosphors have a sufficient red light emission spectrum.
  • the above-described light emitting device that emits white light is difficult to obtain light on the long wavelength side in the visible light region, and thus has become a slightly pale white light emitting device that lacks a red component.
  • warm red light emitting devices with a slightly reddish color are required for store display lighting and medical site lighting.
  • light emitting elements generally have a longer life than human light bulbs and are therefore easier on the eyes of humans. Therefore, there is a strong demand for white light emitting devices that are close to the light bulb color.
  • the light emission characteristics of the light emitting device deteriorate.
  • the color that the human eye perceives has a wavelength of 380 ⁇ ! ⁇
  • a brightness sensation is generated in the electromagnetic wave of 780nm region.
  • One of the indicators for this is the visibility characteristic.
  • the visibility characteristics are mountain-shaped, with a peak at 550 ⁇ m. 580 ⁇ which is the wavelength range of the red component!
  • the red component wavelength region feels darker. Therefore, in order to feel the same level of brightness as the green and blue regions, the red region requires high-density electromagnetic waves.
  • a first object of the present invention is to provide a nitride phosphor that further improves the luminance of a nitride phosphor that is excited by blue light from near ultraviolet light and emits red light, and a light emitting device using the same. is there.
  • the afterglow characteristics of the phosphor are determined by the basic composition of the phosphor generally used.
  • preferable afterglow characteristics are desired depending on the application in which the phosphor is used. For example, in applications such as general lighting LEDs and displays, phosphors with a short afterglow time are desired. Ma ⁇ .
  • a printing information selection phosphor for detecting printed matter such as stamps can be used for specific printing parts to identify specific printing parts by detecting high persistence in a very short time after 10 ms. The position of the stamp is identified and postmarked, and the stamp type and authenticity are determined. For this reason, these phosphors are also required to have high luminance and short afterglow.
  • a long afterglow phosphor having a relatively long afterglow time is also used.
  • Fritzka is most noticeable in green with high visibility, so use a mixed phosphor of long afterglow and short afterglow phosphors for green light emitting elements, and use short afterglow phosphors for red and blue light emitting elements. It is also made. However, it was easy to adjust the afterglow time of a phosphor having a certain basic yarn composition.
  • conventional phosphors having long afterglow often store energy by radiation excitation such as ⁇ -rays, X-rays, and ultraviolet rays, and emit light for a long time after the excitation is stopped.
  • radiation excitation such as ⁇ -rays, X-rays, and ultraviolet rays
  • visible light there are few phosphors excited by visible light, and in particular, phosphors excited by blue light and emitting red light in this way. There was no phosphor that could adjust the brightness.
  • phosphors that can adjust the afterglow time are also required for illumination phosphors combined with LEDs.
  • a second object of the present invention is to provide a nitride phosphor capable of selecting the afterglow characteristics of a phosphor excited by visible light according to the application, and a light emitting device using the nitride phosphor.
  • one nitride phosphor according to the present invention is a nitride phosphor activated by europium, and is represented by the following general formula: w, x, y, z is within the following range, and further contains any one of Y, Ga, and In or one of Ge and Zr.
  • another nitride phosphor according to the present invention is a nitride phosphor activated by europium, and is represented by the following general formula, and w, x, y, and z are in the following ranges.
  • at least one selected from the group forces of La, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu, or any one of Sc, Y, Ga, and In, or Ge, Zr One of these strengths is contained.
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba,
  • nitride phosphor is a nitride phosphor activated by europium, represented by the following general formula, wherein w, x, y, z are in the following ranges, Furthermore, any one of Y, Ga, and In, or one of the tetravalent elements Ge and Zr, is contained.
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba,
  • another nitride phosphor according to the present invention is a nitride phosphor activated by europium, which is represented by the following general formula, and w, x, y, z are in the following ranges, Furthermore, at least one selected from the group consisting of La, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu, or any one of Sc, Y, Ga, and In, or the tetravalent element Ge, Zr One kind of power is contained.
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba,
  • the nitride phosphor absorbs near ultraviolet or blue light and emits light having a longer wavelength than the light (for example, yellow-red light or red light).
  • Yellow-red light is 584 ⁇ ! ⁇ 610nm
  • red light has a wavelength range of 610 ⁇ m ⁇ 780nm.
  • the spectrum of the phosphor is broad, the boundary between yellow-red and red is not always clear.
  • the nitride phosphor is a nitride phosphor activated with europium, which is represented by the following general formula, and further adjusts afterglow, yttrium, trivalent element and tetravalent for adjusting afterglow. Contains at least one element selected. [0020] M Al Si N: Eu
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba
  • the afterglow characteristics of the phosphor excited by visible light can be adjusted.
  • the trivalent element may be Ga, In !, or one of them, and the tetravalent element may be at least one selected from the group of Ge, Zr, and Hf.
  • the rare earth element is added, a long afterglow can be obtained compared to the case.
  • the nitride phosphor according to the present invention is a nitride phosphor activated with europium.
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba
  • the afterglow characteristics of the phosphor excited by visible light can be adjusted.
  • the tetravalent element can be either Ge or Zr. As a result, when the rare earth element is added, the afterglow can be shortened compared to the case.
  • the trivalent element may be Ga, In !, or one of them, and the tetravalent element may be Hf.
  • the rare earth element can be added to provide a long afterglow compared to the case.
  • the nitride phosphor is composed of Fe, Ni, Cr, Ti, Nb, Yb, and Sm. , Not more than 0.01 or not in molar ratio to molar concentration 1 of M. Some of these elements have an effect such as a short afterglow, but if they are contained in an amount of more than 0.01, the emission luminance is greatly reduced.
  • the nitride phosphor may contain O in the composition.
  • the light-emitting device absorbs at least a part of the first emission spectrum by using an excitation light source having a first emission vector that emits near-ultraviolet or blue light, and a second emission spectrum.
  • the nitride phosphor of the present invention and the light-emitting device using the same can shift the peak wavelength to a long wavelength by containing A1, so that even if the activation amount of europium, which is an expensive rare earth element, is reduced, it can be further increased. Can emit deep red light. In general, the emission characteristics tend to decrease when the red component is increased, but the addition of certain rare earth elements, trivalent elements, and tetravalent elements to the nitride phosphor suppresses the decrease in emission luminance. And high brightness can be maintained.
  • the afterglow characteristic of the phosphor excited by visible light can be adjusted by selecting an additive element, and the nitride phosphor can be used depending on the application. Further, a nitride phosphor having an afterglow time and a light emitting device using the same can be obtained.
  • each element constituting the present invention may be configured such that a plurality of elements are configured by the same member and the plurality of elements are shared by one member, and conversely the function of one member is a plurality of functions. This is achieved by sharing the materials.
  • the light-emitting device in FIG. 1 includes a light-emitting element having a first emission spectrum, a phosphor that absorbs at least part of the first emission spectrum, converts the wavelength, and emits light of the second emission spectrum.
  • the light emitting device 1 in FIG. 1 includes a lead frame conductively connected by a semiconductor layer 2 stacked on an upper part of a sapphire substrate 1 and a conductive wire 14 extending from positive and negative electrodes 3 formed on the semiconductor layer 2. 13, the phosphor 11 and the coating member 12 provided in the cup of the lead frame 13a so as to cover the outer periphery of the light emitting element 10 composed of the sapphire substrate 1 and the semiconductor layer 2, and the phosphor 11 and the lead frame 13 And a mold member 15 covering the outer peripheral surface of the mold member 15.
  • a semiconductor layer 2 is formed on the sapphire substrate 1, and positive and negative electrodes 3 are formed on the same plane side of the semiconductor layer 2.
  • the semiconductor layer 2 is provided with a light emitting layer (not shown), and the peak wavelength output from this light emitting layer has a light emission spectrum in the vicinity of 500 nm or less in the blue region of the ultraviolet power.
  • the light-emitting element 10 is set on a die bonder, face-up to a lead frame 13a provided with a cup, and die-bonded (adhered).
  • face-up refers to mounting the light-emitting element so that the semiconductor layer side is disposed on the viewer side and the emitted light is extracted from the semiconductor layer side.
  • face-down mounting there is a face-down mounting in which the substrate side of the light emitting element is arranged on the viewer side and the emitted light is taken out from the substrate side, and flip chip mounting is also possible.
  • the lead frame 13 is transferred to a wire bonder, the negative electrode 3 of the light emitting element is wire-bonded to the lead frame 13a provided with the cup with a gold wire, and the positive electrode 3 is wire-bonded to the other lead frame 13b.
  • the force that uses two wires to obtain electrical connection with the positive and negative electrodes is not limited to this configuration.
  • only one wire is bonded to make electrical contact with one electrode.
  • the other electrical contact can be obtained at the contact surface between the light emitting element and the substrate.
  • the phosphor 11 and the coating member 12 are injected into the cup of the lead frame 13 using a dispenser of the molding apparatus.
  • the phosphor 11 and the coating member 12 are uniformly mixed in advance at a desired ratio.
  • the lead frame 13 is immersed in a mold mold in which the mold member 15 has been injected in advance, and then the mold is removed to cure the grease, and a bullet-shaped mold as shown in FIG.
  • Light-emitting device 1 the phosphor is a YAG phosphor and a nitride phosphor. The phosphor absorbs part of the light in the near ultraviolet to blue region emitted from the light emitting element and emits light in the yellow to red region.
  • a light emitting device that emits a warm white light by mixing the blue light emitted from the light emitting element 10 and the yellow light to red light of the phosphor I will provide a.
  • the light-emitting device can be a light-emitting device that emits light of a light bulb color so as to comply with the JIS standard.
  • the light bulb color is a white range according to the JIS standard (JIS Z8110), centering on a point of 2700-2800K on the locus of black body radiation, and having a yellow to red color. ! /, The color! Specifically, it has a luminescent color in the (light) yellow-red, (orange) pink, pink, (light) pink, and (yellowish) white areas in the chromaticity locus.
  • the light emitting device 1 in FIG. 2 forms a surface mount type light emitting device.
  • an ultraviolet light-excited nitride semiconductor light-emitting element can be used.
  • the light-emitting element 101 can also be a blue-light-excited nitride semiconductor light-emitting element.
  • the light-emitting element 101 excited by ultraviolet light will be described as an example.
  • the LED chip that is the light emitting element 101 uses a nitride semiconductor light emitting element having an InGaN semiconductor having a peak wavelength of about 370 nm as a light emitting layer.
  • the n-type GaN layer, the n-type AlGaN layer that is a nitride semiconductor, and the InGaN layer that constitutes the light-emitting layer are formed as a single quantum well structure.
  • the light-emitting layer has a structure in which an AlGaN layer as a p-type cladding layer doped with Mg and a GaN layer as a p-type contact layer doped with Mg are stacked in sequence.
  • the p-type semiconductor is annealed at 400 ° C or higher after the film formation.
  • Etching exposes the surface of each pn contact layer on the same side of the nitride semiconductor on the sapphire substrate.
  • An n-electrode is formed in a strip shape on the exposed n-type contact layer, and a light-transmitting P-electrode made of a metal thin film is formed on almost the entire surface of the p-type contact layer that remains without being excised.
  • a pedestal electrode is formed on the optical p-electrode in parallel with the n-electrode by sputtering.
  • a Kovar package 105 that has a recess in the central portion and a base portion in which Kovar lead electrodes 102 are inserted and fixed in an airtight manner on both sides of the recess is used.
  • NiZAg layers are provided on the surfaces of the package 105 and the lead electrode 102.
  • an LED chip which is the above-described light emitting element is die-bonded with an Ag—Sn alloy.
  • all the components of the light-emitting device can be made of an inorganic material, and even if the light emitted from the light-emitting element 101 is in the ultraviolet region or the short wavelength region of visible light, the reliability is dramatically improved. A light emitting device with high brightness can be obtained.
  • the respective electrodes of the light-emitting element 101 that are die-bonded and the respective lead electrodes 102 that are also exposed to the package bottom surface force are electrically connected by Ag wires 104.
  • sealing is performed with a Kovar lid 106 having a glass window 107 at the center, and seam welding is performed.
  • phosphor 108 is contained in a slurry having a force of 90% by weight of trocellulose and 10% by weight of ⁇ -alumina, and is applied to the rear surface of the transparent window part 107 of the lid 106.
  • the color conversion member is constructed by heating and curing at 220 ° C for 30 minutes.
  • the light emitting device formed in this manner emits light
  • a light emitting diode capable of emitting white light with high luminance can be obtained.
  • One phosphor according to the present embodiment is activated by Eu, and is a nitride phosphor containing Group II elements M, Si, A1, and N, and absorbs ultraviolet light or blue light. Lights from yellow red to red.
  • This nitride phosphor has the general formula M Al Si N: Eu,
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba.
  • the nitride phosphor can be represented by the general formula M Al Si BN: Eu and w X yz ((2/3) w + x + (4/3) y + z) to which boron B is added.
  • the molar concentration z is set to 0.5 or less as described above, preferably 0.3 or less, and further set to more than 0.0005. More preferably, the molar concentration of boron is set to 0.001 or more and 0.2 or less.
  • these nitride phosphors further include at least one selected from the group force of La, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu, or any force of Sc, Y, Ga, and In. Contains 1 type, or 1 type of Ge or Zr. By containing these, it is possible to output luminance, quantum efficiency or peak intensity equal to or higher than those of Gd, Nd, and Tm.
  • the nitride phosphor according to the embodiment of the present invention is manufactured by mixing various phosphor raw materials in a wet type and a dry type.
  • Raw materials such as CaN, SiN, A1N, BN, and HBO as phosphor materials
  • Boron, boride, boron nitride, boron oxide, borate and the like can be used as the boron raw material of the phosphor. Specifically, boron, B, BN, H BO added to the phosphor material
  • Ca in the phosphor composition is preferably used alone. However, a part of Ca can be substituted with Sr, Mg, Ba, Sr and Ba, etc. By substituting part of Ca with Sr, the emission wavelength peak of the nitride phosphor can be adjusted.
  • Si is also preferably used alone, but a part of it can be substituted with C of Group IV element.
  • the nitride phosphor is inexpensive and has good crystallinity.
  • the nitride phosphor is further at least one selected from the group consisting of La, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu, or any one of Sc, Y, Ga, and In Or any one of Ge and Zr.
  • some of the activator Eu may be replaced by La, Ce, Pr, Gd, Tb, Dy, Ho, Er, Lu, etc.
  • Sc, Y, Ge, and Zr may be substituted for some of Al and Si. These elements increase the particle size, adjust the color tone, increase the emission peak intensity, It has an effect such as.
  • Eu as an activator is preferably used alone. As described above, a part of Eu can be replaced as described above.
  • Nitto-pium has mainly divalent and trivalent energy levels.
  • the nitride phosphor according to the embodiment of the present invention uses Eu 2+ as an activator for the base Ca.
  • Eu 2+ is commercially available as a trivalent Eu O yarn after being acidified. In the case of commercially available Eu O,
  • the nitride phosphor further includes a group I element including Cu, Ag, and Au forces, a group II element including Al, Ga, and In forces, and a group IV including Ti, Zr, Hf, Sn, and Pb. It can also contain at least one element selected from Group V element consisting of element, P, Sb, Bi, and Group VI element force consisting of S. Luminous efficiency can be adjusted by adding these elements.
  • the element added to the above-described nitride phosphor is usually a force that can be generated by an oxide or an oxyhydroxide, but is not limited to this metal, nitride, imide, amide, Alternatively, other inorganic salts may be used. Alternatively, it may be contained in other raw materials in advance.
  • the composition of the nitride phosphor contains oxygen. It is conceivable that oxygen is introduced from various oxides as raw materials or oxygen is mixed during firing. This oxygen is thought to promote the effects of Eu diffusion, grain growth, and crystallinity improvement. In other words, the same effect can be obtained even if one compound used as a raw material is replaced with metal, nitride, or oxide, but the effect when using an oxide is rather large. .
  • Another phosphor is activated by Eu, and is a nitride phosphor containing a group II element M, Si, A1, and N, and absorbs ultraviolet light or blue light and emits red light.
  • This nitride phosphor has a general formula of M Al Si N: Eu, and a rare earth element as an additive element
  • the nitride phosphor may also contain at least one selected from the group consisting of rare earth elements Ce, Pr, Nd, Sm, Tb, Dy, Tm, and Yb. This makes it possible to have a short afterglow compared to V, which does not contain rare earth elements.
  • this nitride phosphor is at least one selected from the group of rare earth elements La, Gd, Ho, Er, Lu, one of trivalent elements Sc and Y, one of tetravalent elements, and tetravalent element Ge Or at least one selected from the group consisting of Zr and Hf.
  • the nitride phosphor may be represented by the general formula M Al Si B N added with boron B: Eu and w X yz ((2/3) w + x + (4/3) y + z).
  • the molar concentration z is set to 0.5 or less as described above, preferably 0.3 or less, and further set to more than 0.0005. More preferably, the molar concentration of boron is set to 0.001 or more and 0.2 or less.
  • This nitride phosphor is composed of rare earth elements Ce, Pr, Nd, Sm, Gd, Tb, Dy, Tm, and Yb. It can also contain seeds. As a result, the afterglow can be reduced compared with the case where rare earth elements are added.
  • this nitride phosphor is at least one selected from the group of rare earth elements Sc, Y, La, Ho, Er, Lu, trivalent element Ga, In any one type, tetravalent
  • the element Hf can also be contained. As a result, a long afterglow can be achieved compared with the case where rare earth elements are added.
  • the nitride phosphor according to the embodiment of the present invention is manufactured by mixing various phosphor raw materials in a wet type and a dry type.
  • Raw materials such as CaN, SiN, A1N, BN, and HBO as phosphor materials
  • Boron, boride, boron nitride, boron oxide, borate and the like can be used as the boron raw material of the phosphor. Specifically, boron, B, BN, H BO added to the phosphor material
  • Ca in the phosphor composition is preferably used alone. However, a part of Ca can be substituted with Sr, Mg, Ba, Sr and Ba, etc. By substituting part of Ca with Sr, the emission wavelength peak of the nitride phosphor can be adjusted.
  • Si is also preferably used alone, but a part thereof can be substituted with C of the group IV element.
  • the nitride phosphor is inexpensive and has good crystallinity.
  • Rare earth elements Ce, Pr, Nd, Sm, Tb, Dy, Tm, Yb, La, Gd, Ho, Er, Lu, trivalent element Sc, Y, tetravalent element Ge, Zr, Hf Contains at least one species. Although it is not certain, it is considered that some activators act by co-activating by replacing rare earth elements with a part of Eu. In addition, although it is not certain, some trivalent and tetravalent elements may be substituted for some of A1 and Si. These elements have actions such as increasing the particle size, adjusting the color tone, and increasing the emission peak intensity. The afterglow time can also be controlled by the element to be added.
  • the activator Eu is preferably used alone. It is also conceivable that a part of Eu is substituted as described above. When using a mixture that requires Eu, the mixing ratio can be changed as desired.
  • Europium mainly has bivalent and trivalent energy levels, but the nitride phosphor according to the embodiment of the present invention uses Eu 2+ as an activator for the base Ca.
  • Eu 2+ is commercially available in the form of trivalent Eu O as soon as it is oxidized.
  • Eu 2+ is commercially available in the form of trivalent Eu O as soon as it is oxidized.
  • Nitride phosphors are also Group I elements that have Cu, Ag, and Au forces, and Group I elements that also have Al, Ga, and In forces. Includes Group II elements, Group IV elements composed of Ti, Zr, Hf, Sn, and Pb, Group V elements composed of P, Sb, and Bi, and Group VI element forces composed of S. You can also. Luminous efficiency can be adjusted by adding these elements.
  • the element added to the above-described nitride phosphor is usually a force that can be generated by an oxide or an oxyhydroxide, but is not limited to this metal, nitride, imide, amide, Alternatively, other inorganic salts may be used. Alternatively, it may be contained in other raw materials in advance.
  • Oxygen is contained in the composition of the nitride phosphor. It is conceivable that oxygen is introduced from various oxides as raw materials or oxygen is mixed during firing. This oxygen is thought to promote the effects of Eu diffusion, grain growth, and crystallinity improvement. In other words, the same effect can be obtained even if one compound used as a raw material is replaced with metal, nitride, or oxide, but the effect when using an oxide is rather large. .
  • a nitride phosphor activated by europium represented by the following general formula, wherein w, x, y, z are in the following ranges, and La, Ce, Pr, Gd, Tb, Dy, It contains at least one selected from the group of Ho, Er, and Lu, or one of Sc, Y, Ga, and In, or one of Ge and Zr.
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba,
  • M is at least one selected from the group consisting of Mg, Ca, Sr and Ba,
  • the color tone can be slightly changed.
  • a phosphor containing at least one element selected from rare earth elements, trivalent elements, and tetravalent elements Ca Al Si BN: Made of Eu
  • a manufacturing method is demonstrated, it is not limited to this manufacturing method.
  • a nitride phosphor CaAlSiN: Eu containing at least one element selected from rare earth elements, trivalent elements, and tetravalent element forces can be produced in substantially the same manner.
  • the raw material Ca is pulverized (Pl).
  • the raw material Ca is preferably a simple substance, but a compound such as an imido compound or an amide compound can also be used. Further, the raw material Ca may contain Li, Na, K, soot, Al and the like.
  • the raw material is preferably purified. Thereby, since a purification process is not required, the manufacturing process of the phosphor can be simplified, and an inexpensive nitride phosphor can be provided.
  • the raw material Ca is pulverized in a glove box in an argon atmosphere.
  • the average particle size should be in the range of about 0 .: L m or more and 15 m or less in terms of reactivity with other raw materials, particle size control during and after firing, etc. Although it is preferable, it is not limited to this range.
  • the purity of Ca is preferably 2N or higher, but is not limited thereto.
  • Ca can be nitrided in a nitrogen atmosphere at 600 ° C. to 900 ° C. for about 5 hours to obtain a Ca nitride.
  • the Ca nitride is preferably of high purity.
  • the Ca nitride is pulverized (P3). Ca nitride in an argon atmosphere, or
  • the raw material Si is pulverized (P4).
  • the raw material Si is preferably a simple substance, but a nitride compound, an imido compound, an amido compound, or the like can also be used.
  • Si silicon
  • the purity of the raw material Si is preferably 3N or higher
  • Si is pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere, as is the case with Ca.
  • the average particle size of the Si compound is preferably in the range of about 0.1 ⁇ m to 15 ⁇ m from the viewpoints of reactivity with other raw materials, particle size control during and after firing, and the like.
  • the silicon Si is also nitrided in a nitrogen atmosphere at 800 ° C to 1200 ° C for about 5 hours to obtain a nitrided silicon.
  • the silicon nitride used in the present invention preferably has a high purity.
  • Si nitride is pulverized (P6).
  • A1N is synthesized by the direct nitridation method of A1 or the like. However, you can use A1N powder that is already on the market.
  • BN is synthesized by direct nitridation of B or the like. However, you can use BN powder that is already on the market.
  • an additive element compound at least one selected from the group consisting of La, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu, or any of Sc, Y, Ga, and In One oxide or one of Ge or Zr is synthesized.
  • commercially available oxide or nitride powders can also be used.
  • the rare earth element is at least one selected from the group of Ce, Pr, Nd, Sm, Gd, Tb, Dy, Tm, and Yb
  • the tetravalent element is Ge
  • oxide or nitride of Zr is commercially available oxide or nitride powders.
  • the rare earth element is at least one selected from the group of Sc, Y, La, Ho, Er, and Lu
  • the trivalent element is any one of Ga and In.
  • Tetravalent elements synthesize oxides or nitrides of Hf. However, commercially available oxide or nitride powders can also be used.
  • the average particle size after crushing is preferably about 0.1 ⁇ m force and 15 ⁇ m.
  • Ca nitride, A1 nitride, Si nitride, B nitride, additive element compound, Eu compound Eu O can also be mixed in a dry manner.
  • nitride phosphors of Examples 1 to 77 are obtained by changing the blending ratio of each raw material.
  • a tubular furnace, a small furnace, a high-frequency furnace, a metal furnace, or the like can be used.
  • the firing temperature is preferably a force capable of firing in the range of 1200 ° C to 2000 ° C and a firing temperature of 1400 ° C to 1800 ° C.
  • a one-step firing in which the temperature is gradually raised and the firing is performed at 1200 ° C to 1500 ° C for several hours, but the first-step firing is performed at 800 ° C to 1000 ° C and gradually.
  • a two-stage firing multi-stage firing
  • the second stage firing is carried out at 1200 ° C to 1500 ° C by heating to 200 ° C.
  • the reducing atmosphere is an atmosphere containing at least one of nitrogen, hydrogen, argon, carbon dioxide, carbon monoxide, and ammonia.
  • firing can be performed in a reducing atmosphere other than these.
  • the nitride phosphor according to the embodiment of the present invention is used by being mixed with other phosphors to make the light emission of the blue light emitting element a white light source with high color rendering properties.
  • the phosphor mixed with the nitride phosphor according to the embodiment of the present invention includes a phosphor emitting blue light, a phosphor emitting green light, and a phosphor emitting yellow light.
  • phosphors that emit blue light there are various types of phosphors that emit blue light, phosphors that emit green light, and phosphors that emit yellow light.
  • Phosphor, at least cerium activated yttrium 'gadolinium' aluminum oxide phosphor, and at least cerium activated yttrium 'gallium' aluminum It is preferable that at least one of the phosphoric acid phosphors. Thereby, a light emitting device having a desired emission color can be realized.
  • the phosphor according to the present invention and the yttrium-aluminum oxide phosphor or the like activated with cerium are used, light can be extracted efficiently.
  • Ln MO R (Ln is a small amount selected from Y, Gd, Lu, La)
  • M includes at least one of Al and Ga.
  • R is a lanthanide type. ;), (Y Gd) (Al Ga) O: Rz (R is Ce ⁇ Tb, Pr ⁇ Sm, Eu ⁇ Dy, l-x x 3 1-y y 5 12
  • At least one selected from Ho. 0 ⁇ z ⁇ 0.5. ) Can be used.
  • the phosphor is 270 ⁇ from the near ultraviolet to the short wavelength side of visible light! It is excited by light in the wavelength range of ⁇ 500nm and has a peak wavelength at 500nm ⁇ 600nm.
  • the phosphor having the third emission spectrum is not limited to the above phosphor, and various phosphors can be used.
  • the desired chromaticity can be adjusted.
  • the yttrium-aluminum oxide phosphor or the like activated with cerium absorbs part of the blue light emitted by the light emitting element 10 and emits light in the yellow region.
  • the blue light emitted by the light emitting element 10 and the yellow light of the yttrium / aluminum oxide phosphor emit light in white by mixing colors. Therefore, the phosphor 11 obtained by mixing the yttrium / aluminum oxide phosphor and the nitride phosphor together with the translucent coating member is combined with the blue light emitted by the light emitting element 10.
  • a warm white light emitting device can be provided.
  • a white light-emitting device with excellent color rendering can be provided.
  • the phosphor used in combination with the nitride phosphor according to the embodiment of the present invention is not limited to the yttrium aluminum oxide phosphor etc., and has the same purpose as the phosphor.
  • Phosphors having at least one second emission spectrum from the blue region having green to the green region, yellow region, and red region can also be used in combination with the nitride phosphor.
  • a light emitting device that emits white light based on the principle of color mixing of light can be provided.
  • Phosphors used in combination with nitride phosphors are green light emitting phosphors SrAlO: Eu, YSiO: Ce, Tb, MgAlO: Ce, Tb, SrAlO: EuM (Mg
  • a desired emission spectrum can be obtained by doping S 2: Eu or the like.
  • the light emitting phosphors such as green, blue, and red are not limited to the above phosphors, and various phosphors can be used.
  • Excitation light sources include semiconductor light emitting devices, laser diodes, ultraviolet radiation generated in the positive column of arc discharge, and ultraviolet radiation generated in the positive column of glow discharge.
  • semiconductor light-emitting elements and laser diodes that emit light in the near ultraviolet region
  • semiconductor light-emitting elements and laser diodes that emit blue light semiconductor light-emitting elements and laser diodes that emit blue-green light are preferred.
  • Light in the short wavelength region from near ultraviolet to visible light refers to the wavelength region from 270 nm to around 500 nm.
  • the light-emitting element is preferably a semiconductor light-emitting element having a light-emitting layer capable of emitting an emission wavelength capable of efficiently exciting the phosphor.
  • materials for such semiconductor light emitting devices include various semiconductors such as BN, SiC, ZnSe, GaN, InGaN, InAlGaN, AlGaN, BAlGaN, and BlnAlGaN.
  • these elements can contain Si, Zn, etc. as impurity elements to be the emission center.
  • nitride semiconductors for example, nitride semiconductors containing A1 and Ga, nitrides containing In and Ga, etc.
  • materials for light emitting layers capable of efficiently emitting short wavelengths of visible light from the ultraviolet region that can excite phosphors efficiently In Al Ga N as a semiconductor
  • a homostructure having a MIS junction, a PIN junction, a pn junction, or the like, a heterostructure, or a double heterostructure can be preferably cited.
  • Various emission wavelengths can be selected depending on the material of the semiconductor layer and the mixed crystal ratio.
  • the output can be further improved by adopting a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated.
  • a nitride semiconductor When a nitride semiconductor is used, sapphire, spinel, SiC, Si, A material such as ZnO, GaAs, or GaN is preferably used. In order to form a nitride semiconductor having good crystallinity with high productivity, it is preferable to use a sapphire substrate. Nitride semiconductors can be formed on this sapphire substrate using HVPE or MOCVD. A GaN, A1N, GaAIN or other non-single crystal nofer layer is formed on a sapphire substrate and a nitride semiconductor having a pn junction is formed thereon.
  • SiO stripes are formed on the notch layer approximately perpendicularly to the orientation flat surface of the sapphire substrate.
  • GaN is grown on the stripe using EHV (Epitaxial Lateral Grows GaN) by HVPE method.
  • the first contact layer formed of n-type gallium nitride, the first cladding layer formed of n-type aluminum nitride 'gallium, the indium nitride' aluminum 'well layer of gallium and the aluminum nitride by MOCVD 'A multi-quantum well structure active layer with multiple gallium barrier layers, a second cladding layer made of p-type aluminum nitride and gallium, and a second contact layer made of p-type gallium nitride.
  • the configuration such as the double hetero configuration.
  • the active layer is formed into a ridge stripe shape, sandwiched between guide layers, and provided with a cavity end face to obtain a semiconductor laser device usable in the present invention.
  • a nitride semiconductor exhibits n-type conductivity without being doped with impurities.
  • a desired n-type nitride semiconductor such as improving luminous efficiency, it is preferable to appropriately introduce Si, Ge, Se, Te, C, etc. as an n-type dopant.
  • p-type nitride semiconductor it is preferable to dope p-type dopants such as Zn, Mg, Be, Ca, Sr, and Ba.
  • nitride semiconductors are not easily converted to p-type by simply doping with p-type dopants, it is preferable to reduce the resistance by heating in a furnace or plasma irradiation after introduction of p-type dopants. If a sapphire substrate is not used, the contact layer is exposed by etching from the p-type side to the surface of the first contact layer. After forming the electrodes on each contact layer, a light emitting element having a nitride semiconductor power can be formed by cutting the semiconductor wafer into chips.
  • the light emitting device In order to form the light emitting device with high mass productivity, it is preferable to form the light emitting device using a translucent sealing member.
  • a translucent sealing member In particular, since the phosphor 11 is mixed and sealed, I prefer fat.
  • the light emitting element has an emission spectrum in the ultraviolet region, and the main emission wavelength is from 360 nm to 420 nm, or from 450 nm to 470 nm. The following can also be used.
  • the sheet resistance of the n-type contact layer formed at an impurity concentration of 10 17 to 10 2 cm 3 and the sheet resistance of the light-transmitting p-electrode satisfy Rp ⁇ Rn. It is preferable that the relationship is adjusted.
  • the n-type contact layer has a film thickness of 3 to: LO / zm, preferably 4 to 6 ⁇ m.
  • the sheet resistance is estimated to be 10 to 15 ⁇ .
  • Rp is preferably formed in a thin film so as to have a sheet resistance value equal to or higher than the sheet resistance value.
  • the translucent p-electrode may be formed of a thin film having a thickness of 150 m or less.
  • ITO other than metal and ⁇ can be used for the p electrode.
  • an electrode having a plurality of light extraction openings such as a mesh electrode can also be used.
  • the translucent rho electrode is formed of a multilayer film or alloy composed of one kind selected from the group of gold and platinum group elements and at least one other element, it is contained. Therefore, stability and reproducibility are improved by adjusting the sheet resistance of the translucent rho electrode depending on the content of the gold or platinum group element. Since gold or a metal element has a high absorption coefficient in the wavelength region of the semiconductor light emitting device used in the present invention, the smaller the amount of gold or platinum group element contained in the translucent ⁇ electrode, the better the transparency. In the conventional semiconductor light emitting device, the force of the sheet resistance is Rp ⁇ Rn. In the present invention, Rp ⁇ Rn. Therefore, the translucent p-electrode is formed in a thin film as compared with the conventional one. However, thinning can be easily achieved by reducing the content of gold or platinum group elements.
  • the semiconductor light emitting device used in the present invention has a relationship between the sheet resistance RnQ Z port of the n-type contact layer, the sheet resistance Rp QZ port of the translucent p electrode, and the force Rp ⁇ Rn.
  • RnQ Z port of the n-type contact layer the sheet resistance Rp QZ port of the translucent p electrode
  • Rp ⁇ Rn the force required to measure Rn after forming it as a semiconductor light emitting device. It is practically impossible to know the relationship between Rp and Rn. From the state of the light intensity distribution during light emission, what kind of Rp and Rn You can know if they are in a relationship.
  • the translucent p-electrode and the n-type contact layer have a relationship of Rp ⁇ Rn
  • a P-side pedestal electrode having an extended conduction portion is provided on the translucent p-electrode
  • further external quantum can be provided.
  • the extended conductive portion that is not limited in the shape and direction of the extended conductive portion is on the satellite, it is preferable because the area for blocking light is reduced, but a mesh shape may be used. Further, the shape may be a curved line shape, a lattice shape, a branch shape, or a saddle shape in addition to the straight line shape.
  • the line width and length of the extended conductive part should be designed so that the light shielding effect does not exceed the light emission enhancing effect.
  • a blue-light-excited light-emitting element different from the above-described ultraviolet-light-excited light-emitting element can also be used.
  • the blue light-excited light emitting element 10 is preferably a metal nitride compound light emitting element.
  • the light-emitting element 10 includes, for example, an n-type GaN layer in which Si is undoped, an n-type contact layer having an n-type GaN force doped with Si, an and GaN layer, and a multiple quantum layer on a sapphire substrate 1 via a GaN buffer layer.
  • Light emitting layer with well structure GaN barrier layer, quantum well structure of ZlnGaN well layer
  • p-type GaN layer made of p-type GaN doped with Mg
  • p-type GaN layer doped with Mg p-type GaN layer doped with Mg
  • the electrodes are formed as follows.
  • a light emitting element 10 different from this configuration can also be used.
  • the p-form electrode is formed on almost the entire surface of the p-type contact layer, and the p-pad electrode 3 is formed on a part of the p-form electrode.
  • the n-electrode is formed in the exposed portion by removing the undoped GaN layer from the p-type contact layer by etching to expose a part of the n-type contact layer.
  • the present invention is not limited to this.
  • a single quantum well structure using InGaN may be used.
  • GaN doped with n-type and p-type impurities such as Si and Zn may be used.
  • the light-emitting layer of the light-emitting element 10 has a 420 nm force by changing the In content.
  • the main emission peak can be changed in the range of 90 nm.
  • the emission wavelength is not limited to the above range, and those having an emission wavelength of 360 nm to 550 nm can be used.
  • the coating member 12 (light transmissive material) is provided in the cup of the lead frame 13.
  • the phosphor 11 that converts the light emission of the light emitting element 10 is used in combination.
  • Specific materials for the coating member 12 include transparent resins, silica sol, glass, inorganic noinders, etc., which have excellent temperature characteristics and weather resistance, such as epoxy resin, urea resin, and silicone resin.
  • a diffusing agent, barium titanate, titanium oxide, aluminum oxide, or the like may be contained.
  • you may contain a light stabilizer and a coloring agent.
  • the lead frame 13 includes a mount lead 13a and an inner lead 13b.
  • the mount lead 13a is for arranging the light emitting element 10.
  • the upper part of the mount lead 13a has a cup shape.
  • the light emitting element 10 is die-bonded in the cup, and the outer peripheral surface of the light emitting element 10 is covered with the phosphor 11 and the coating member 12 inside the cup.
  • a plurality of light emitting elements 10 can be arranged in the cup, and the mount lead 13a can be used as a common electrode of the light emitting element 10. In this case, sufficient electrical conductivity and connectivity with the conductive wire 14 are required.
  • the die bonding (adhesion) between the light emitting element 10 and the cup of the mount lead 13a can be performed by a thermosetting resin or the like.
  • thermosetting resins examples include epoxy resins, acrylic resins, and imide resins.
  • Ag paste, carbon paste, metal bumps, or the like can be used for die-bonding and electrical connection with the mount lead 13a using the face-down light emitting element 10 or the like.
  • An inorganic binder can also be used.
  • the inner lead 13b is intended to be electrically connected to the conductive wire 14 extending from the electrode 3 of the light emitting element 10 disposed on the mount lead 13a.
  • the inner lead 13b is preferably arranged at a position away from the mount lead 13a in order to avoid a short circuit due to electrical contact with the mount lead 13a.
  • the conductive wires be arranged so as not to contact each other.
  • the inner lead 13b can be made of iron, copper, iron-containing copper, gold, platinum, silver, or the like, which is preferably the same material as the mount lead 13a.
  • the conductive wire 14 is for electrically connecting the electrode 3 of the light emitting element 10 and the lead frame 13.
  • the conductive wire 14 preferably has good ohmic properties, mechanical connectivity, electrical conductivity, and thermal conductivity with the electrode 3.
  • Specific materials for the conductive wire 14 include gold, Metals such as copper, platinum, and aluminum, and alloys thereof are preferable.
  • the mold member 15 is provided to protect the light emitting element 10, the phosphor 11, the coating member 12, the lead frame 13, the conductive wire 14, and the like from external force. In addition to the purpose of protection from the outside, the mold member 15 also has the purposes of widening the viewing angle, relaxing the directivity from the light emitting element 10, and converging and diffusing the emitted light. In order to achieve these objects, the mold member can have a desired shape. Further, the mold member 15 may have a structure in which a plurality of layers are laminated in addition to the convex lens shape and the concave lens shape.
  • the mold member 15 As a specific material of the mold member 15, a material excellent in translucency, weather resistance, and temperature characteristics such as epoxy resin, urea resin, silicone resin, silica sol, and glass can be used.
  • the mold member 15 may contain a diffusing agent, a colorant, an ultraviolet absorber, and a phosphor.
  • the diffusing agent barium titanate, titanium oxide, aluminum oxide or the like is preferable. In order to reduce the resilience of the material with the coating member 12 and to take into account the refractive index, it is preferable to use the same material.
  • the particle diameter in the examples is a value measured by an air permeation method called F.S.S.S.No. (Fisher Sub Sieve Sizer's No-).
  • the nitride phosphors of Examples 1 to 10 were manufactured by the above-described method, and the characteristics of the nitride phosphors according to the respective examples were measured. The results are shown in Table 1.
  • the nitride phosphors of Comparative Examples 1 to 3 were also manufactured by the same method as described above, and the characteristics of the nitride phosphors according to each Comparative Example were measured.
  • the brightness, quantum efficiency and peak intensity of the Gd-containing nitride phosphor of Comparative Example 1 are used as the reference (100%).
  • FIG. 5 shows the excitation spectra of the nitride phosphors of Example 1 and Comparative Example 1
  • FIG. 6 shows the reflection spectra of the nitride phosphors of Example 1 and Comparative Example 1, respectively.
  • an SEM photograph of the nitride phosphor of Example 1 was taken.
  • Figure 7 shows.
  • Fig. 7 (a) shows the image taken at 1000x
  • Fig. 7 (b) shows the image taken at 5000x.
  • the nitride phosphors of Examples 1 to 10 are represented by Ca Eu AlSiN.
  • Ca, A1 and Si are represented by Ca Eu AlSiN.
  • the Eu concentration is 0.01.
  • Eu concentration is the molar ratio to the molar concentration of Ca.
  • the additive element concentration is 0.01.
  • the additive element concentration is a molar ratio with respect to the molar concentration of Ca.
  • the above phosphors are manufactured as follows. First, the raw material Ca is ground to 1 to 15 m and nitrided in a nitrogen atmosphere. Thereafter, the Ca nitride is pulverized to 0.1 ⁇ to 10 / ⁇ m. Weigh 20g of raw material Ca and perform nitriding. Similarly, the raw material Si is pulverized to 1 to 15 m and nitrided in a nitrogen atmosphere. After that, the Si nitride is ground to 0. m. Weigh 20g of raw material Si and perform nitriding. Next, the compound A1N of A1, Eu compound EuO is pulverized to 0.1 m to 10 ⁇ m. Ca nitride, A1 nitride, Si nitride
  • Example 1 Eu acid mixture is mixed in a nitrogen atmosphere.
  • raw materials calcium nitride Ca N, aluminum nitride A1N, silicon nitride Si N, Eu oxide Pio Eu,
  • N (Molecular weight 140. 31 Eu O is weighed and mixed. The above compounds are mixed and calcined. I got it. Firing conditions are as follows: In an ammonia atmosphere, the above compound is put into a crucible, gradually heated from room temperature, fired at about 1600 ° C for about 5 hours, and slowly cooled to room temperature.
  • nitride phosphors of Examples 1 to 10 have slightly different color tones depending on the additive elements.
  • the average particle diameter of each phosphor is 5. O ⁇ m-lO.O / zm. Further, the phosphors in the examples contain oxygen.
  • Comparative Examples 1 to 3 were prepared using substantially the same manufacturing method except that Example 1 was different from LO and the additive element. The same applies to the concentration of addition. Comparative Example 1 uses Gd as the additive element. Comparative Example 2 uses Nd as the additive element, and Comparative Example 3 uses Tm as the additive element. These showed low emission and emission luminance. In Examples 1 to 77, values are shown based on Comparative Example 1.
  • a rare earth element Lu which shows an increase in quantum efficiency is selected, and a nitride phosphor in which the composition ratio of Ca, Al, and Si is adjusted is the same as in the above-described embodiment. It was produced as ⁇ 25.
  • Table 2 shows the results of measuring the characteristics of the nitride phosphor according to each example. 8 is a graph showing the emission spectrum of the phosphor of Example 11 of the present invention, FIG. 9 is a graph showing the excitation spectrum of the phosphor of Example 11 of the present invention, and FIG. 10 is an example of the present invention. 11 is a graph showing the reflection spectrum of 11 phosphors.
  • Example 11 25 The nitride phosphor of Example 11 25 is represented by CaAlSiN: Eu.
  • Example 11 25 is represented by CaAlSiN: Eu.
  • the Eu concentration is a molar ratio with respect to 1 mol of the phosphor.
  • the average particle diameter of the nitride phosphor of Example 17 3 1 is 5. O ⁇ m ⁇ lO. ⁇ m. From these results, the quantum efficiency and the peak intensity with almost no decrease in luminance even when the molar concentration of Ca A 1 Si is increased or decreased are generally high.
  • Example 26 37 a nitride phosphor in which Y having a high peak intensity was selected and the composition ratio of Ca 2 Al and Si was adjusted was produced as Example 26 37 in the same manner as in the above Example.
  • Table 3 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • a graph of the emission spectrum of the phosphor of Example 26 of the present invention is shown by a wavy line in FIG.
  • the wavy line in FIG. 9 is a graph showing the excitation spectrum of the phosphor of Example 26 of the present invention
  • the wavy line in FIG. 10 is a graph showing the reflection spectrum of the phosphor of Example 26 of the present invention.
  • Example 26 0.9875 1 1 0.01 Y 0.0025 0.653 0.339 132.6 181.8 652 185.9
  • Example 27 0.985 1 1 0.01 Y 0.005 0.657 0.335 126.3 184.7 655 189.1
  • Example 28 0.98 1 1 0.01 Y 0.01 0.652 0.341 1 16.4 1 71.4 651 175.5
  • Example 29 0.97 1 1 0.01 Y 0.02 0.656 0.337 102.9 163.3 653 166.6
  • Example 30 0.96 1 1 0.01 Y 0.03 0.657 0.337 94.8 152.8 655 155.2
  • Example 31 0.95 1 1 0.01 Y 0.04 0.657 0.336 84.0 138.9 655 140.3
  • Example 32 0.99 0.9975 1 0.01 Y 0.0025 0.656 0.336 129.9 1 77.6 652 180.9
  • Example 33 0.99 0.995 1 0.01 Y 0.005 0.660 0.332 1 14.6 165.8 653 168.9
  • Example 34 0.
  • nitride phosphor in which Sc is selected as the rare earth element and the composition ratio of Si is fixed and the composition ratio of Ca and A1 is adjusted is obtained in the same manner as in the above embodiment. It was made as.
  • Table 4 shows the results of measuring the characteristics of the nitride phosphor according to each example.
  • Example 43 46 was produced.
  • Table 5 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • FIG. 11 is a graph showing the emission spectrum of the phosphor of Example 44 of the present invention
  • FIG. 13 is a graph showing the reflection spectrum of the phosphor of Example 44 of the present invention
  • FIG. 13 is a graph showing the reflection spectrum of the phosphor of Example 44 of the present invention.
  • Table 6 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • a graph showing the emission spectrum of the phosphor of Example 48 of the present invention is shown by a wavy line in FIG.
  • the wavy line in FIG. 12 is a graph showing the excitation spectrum of the phosphor of Example 48 of the present invention
  • the wavy line in FIG. 13 is a graph showing the reflection spectrum of the phosphor of Example 48 of the present invention.
  • nitride phosphor in which Ge or Zr is added as a tetravalent element, the composition ratio of Ca and Al is fixed to 0.999: 1, and the composition ratio of Si is adjusted is described above. It produced as Examples 51-58 by the method similar to an Example.
  • Table 7 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • 14 is a graph showing the emission spectra of the phosphors of Examples 51 and 55 of the present invention
  • FIG. 15 is a graph showing the excitation spectrum of the phosphors of Examples 51 and 55 of the present invention
  • FIG. It is a graph which shows the reflection spectrum of the fluorescent substance of Example 51, 55 of this invention. In these graphs, the solid line shows Example 51, and the wavy line shows Example 55.
  • the resultant force also showed a low peak intensity when the Hf concentration was 0.01.
  • the nitride phosphor of the general formula M Al Si N: Eu is described w x y ((2/3) w + x + (4/3) y)
  • Examples 59 to 70 were prepared and examined for changes in characteristics when boron was further added to the phosphor.
  • Table 8 shows the measurement results of the characteristics of the nitride phosphors according to these examples.
  • rare earth elements are added as elemental calories, and the concentration is 0.01 as the molar ratio to the molar concentration of Ca.
  • the concentration is set to 0.0025.
  • the Eu concentration is 0.01. Eu concentration is the molar ratio to the molar concentration of Ca.
  • the nitride phosphors doped with boron in Examples 59 to 70 showed higher values than Comparative Example 1 in any of luminance, quantum efficiency, and peak intensity.
  • Y in Examples 59 and 60 and Lu in Examples 69 and 70 have particularly high peak intensities.
  • Examples 71 to 77 in which tetravalent elements were added in place of rare earth elements to nitride phosphors containing B were prepared, and the characteristics were measured. Table 9 shows the results. As shown in this table, Examples 71 to 73 include Ge as a tetravalent element, and Examples 74 to 77 include Zr. In each example, the composition ratio of Ca and A1 is both 0.99, that is, 1: 1. The Eu concentration is 0.01 as a molar ratio to the Ca molar concentration. Furthermore, the molar concentration of B is 0.01.
  • the resultant force also showed a low peak intensity when the Hf concentration was 0.01.
  • the nitride phosphors of Examples 1 to 77 show a color tone different from that of the nitride phosphor of Comparative Example 1. Accordingly, a light emitting device adjusted to a desired color tone can be obtained by adding an element such as rare earth.
  • the nitride phosphor according to Examples 78 to 173 will be described.
  • afterglow is irradiated with 253.7 nm of light for a certain period of time at room temperature, and then the excitation light source lamp is turned off.
  • the standard for time is defined as 0 when the excitation light source lamp is turned off. If the luminance during excitation light source irradiation is 100%, measure the time (msec) required for the luminance to decay to 1/10 or 1/100. Afterglow characteristics are determined based on the result of this measurement.
  • FIG. 19 shows the excitation spectra of the nitride phosphors of Comparative Example 9 and Example 78
  • FIG. 20 shows the reflection spectra of the nitride phosphors of Comparative Example 9 and Example 78, respectively.
  • FIG. 21 shows an SEM photograph of the nitride phosphor of Example 78.
  • Fig. 21 (a) shows the image taken at 1000x
  • Fig. 21 (b) shows the image taken at 5000x.
  • Comparative Example 9 is substantially the same as Examples 78 to 92 except that it contains a predetermined element.
  • Example 9 0.99 1 1 0.01 None None 0.649 0.344 100 100 650 100 35 460
  • Example 78 0.98 1 1 0.01 Y 0.01 0.652 0.341 83.4 97.0 651 97.3 40 4360
  • Example 79 0.98 1 1 0.01 Sc 0.01 0.639 0.354 77.7 67.1 647 65.5 35 835
  • Example 80 0.98 1 1 0.01 La 0.01 0.643 0.349 80.7 76.9 649 75.8 35 530
  • Example 81 0.98 1 1 0.01 Ce 0.01 0.644 0.348 84.5 83.1 649 81.6 35
  • Example 82 0.98 1 1 0.01 Pr 0.01 0.648 0.345 63.5 62.5 649 62.5 35 60
  • Example 83 0.98 1 1 0.01 Nd 0.01 0.647 0.345 39.1 37.1 651 36.7
  • Example 84 0.98 1 1 0.01 Sm 0.01 0.636 0.354 18.9 15.3 642 14.9 30 50
  • Example 85 0.98 1 1 0.01 Gd
  • the nitride phosphor of Comparative Example 9 is represented by Ca Eu AlSiN. Ca, Al and Si are 0.99
  • Example 78 92 Rare earth elements were added as element additions, and Ca, A1 and Si were set to 0.98: 1: 1.
  • the Eu concentration is 0.01 and the rare earth element concentration is 0.01.
  • the concentration is 0.01 as the molar ratio to the molar concentration of Ca.
  • the phosphor described above is manufactured as follows. First, the raw material Ca is ground to 1 ⁇ m and 15 ⁇ m and nitrided in a nitrogen atmosphere. Thereafter, the Ca nitride is pulverized to 0.1 ⁇ 10 / ⁇ m. Weigh 20g of raw material Ca and perform nitriding. Similarly, the raw material Si is pulverized to 1 m 15 m and nitrided in a nitrogen atmosphere. After that, the Si nitride is ground to 0. m. Weigh 20g of raw material Si and perform nitriding. Next, the compound A1N Eu of compound A1 EuO is pulverized to 0.1 m 10 ⁇ m. Ca nitride, A1 nitride, Si nitride
  • Eu oxides are mixed in a nitrogen atmosphere.
  • the raw materials were calcium nitride Ca N, aluminum nitride A1N, silicon nitride Si N, and Eu oxide Pio O
  • the firing conditions are as follows. The above compound is put into a crucible in an ammonia atmosphere, and gradually from room temperature. The temperature is raised gradually, firing is performed at about 1600 ° C for about 5 hours, and then slowly cooled to room temperature.
  • Y in Example 78, Sc in Example 79, La in Example 80, Gd in Example 85, and Lu in Example 92 have long afterglow and high luminance.
  • a nitride phosphor having a predetermined afterglow according to the application can be provided.
  • nitride phosphors of Examples 78 to 92 have slightly different color tones depending on the additive elements.
  • the average particle size of each phosphor is 5. O ⁇ m-10.O / zm. Further, the phosphors in the examples contain oxygen.
  • Lu is selected as a rare earth element, which shows an increase in luminance and quantum efficiency, and a nitride phosphor in which the composition ratio of Ca, Al, and Si is adjusted is performed in the same manner as in the above-described example.
  • Example 9 Prepared as 3-107.
  • Table 11 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • FIG. 22 is a graph showing the emission spectrum of the phosphor of Example 93 of the present invention
  • FIG. 23 is a graph showing the excitation spectrum of the phosphor of Example 93 of the present invention
  • FIG. 42 is a graph showing the reflection spectrum of the phosphor of Example 93.
  • the horizontal bars indicate that they are measured.
  • nitride phosphors of Examples 93 to 107 are represented by CaAlSiN: Eu.
  • the Eu concentration is a molar ratio relative to 1 mol of the phosphor.
  • the light emission luminance and energy efficiency of the phosphors of Examples 93 to 107 are also expressed as relative values with Comparative Example 9 as 100%.
  • the average particle diameters of the nitride phosphors of Examples 93 to 107 are 5. ⁇ m to 10. O / z m. From the results in Table 11, even if the molar concentration of Ca, Al, and Si is increased or decreased, it shows long afterglow, high brightness, and high quantum efficiency and peak intensity. The peak wavelength also became longer. This reveals that Lu is a suitable additive element in order to obtain a long-afterglow and high-brightness nitride phosphor.
  • a nitride phosphor in which Y showing long afterglow and high luminance was selected as the rare earth element, and the composition ratio of Ca, Al, and Si was adjusted was used in the same manner as in the above examples. 108 to 119 were prepared.
  • Table 12 shows the measurement results of the characteristics of the nitride phosphor according to each example. Further, the graph of the emission spectrum of the phosphor of Example 108 of the present invention is shown by the wavy line in FIG. Similarly, the wavy line in FIG. 23 is a graph showing the excitation spectrum of the phosphor of Example 108 of the present invention, and the wavy line in FIG. 24 is a graph showing the reflection spectrum of the phosphor of Example 108 of the present invention.
  • the light emission luminance and quantum efficiency of the nitride phosphors of Examples 108 to 119 are expressed as relative values with Comparative Example 9 as 100%.
  • nitride phosphor in which Sc is selected as the rare earth element, and the composition ratio of Ca and A1 is adjusted by fixing the composition ratio of Si is obtained in the same manner as in the above-described embodiment.
  • Table 13 shows the measurement results of the characteristics of the nitride phosphor according to each example. The light emission luminance and quantum efficiency of the nitride phosphors of Examples 120 to 124 are set to 100% in Comparative Example 9, and are expressed as relative values based on this.
  • a nitride phosphor in which Ga is added as a trivalent element and the composition ratio of Ca and the composition ratio of Ca and A1 are adjusted in the same manner is adjusted in the same manner as in the above example.
  • Table 14 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • FIG. 25 is a graph showing the emission spectrum of the phosphor of Example 126 of the present invention
  • FIG. 26 is a graph showing the excitation spectrum of the phosphor of Example 126 of the present invention
  • FIG. 14 is a graph showing the reflection spectrum of the phosphor of Example 126.
  • the light emission luminance and quantum efficiency of the nitride phosphors of Examples 125 to 128 are expressed as relative values with Comparative Example 9 as 100%.
  • the emission spectrum of the phosphor of Example 130 of the present invention is shown by the wavy line in the graph of FIG.
  • the wavy line in FIG. 26 is a graph showing the excitation spectrum of the phosphor of Example 130 of the present invention
  • the wavy line in FIG. 27 is a graph showing the reflection spectrum of the phosphor of Example 130 of the present invention.
  • the light emission luminance and quantum efficiency of the nitride phosphors of Examples 129 to 132 are expressed as relative values with Comparative Example 9 as 100%.
  • Example 133 136 a nitride phosphor in which Ge is added as a tetravalent element, the composition ratio of Ca and A1 is fixed at 0.99: 1, and the composition ratio of Si is adjusted, is compared with the above examples. It produced as Example 133 136 by the same method.
  • Table 16 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • FIG. 28 is a graph showing the emission spectrum of the phosphor of Example 133 of the present invention
  • FIG. 29 is a graph showing the excitation spectrum of the phosphor of Example 133 of the present invention
  • FIG. 30 is an example of the present invention. It is a graph which shows the reflection spectrum of 133 fluorescent substance.
  • the light emission luminance and quantum efficiency of the nitride phosphor of Example 133 136 are expressed as relative values with Comparative Example 9 as 100%.
  • Example 137 140 A nitride phosphor fixed at 99: 1 and adjusting the composition ratio of Si was produced as Example 137 140 by the same method as in the above example.
  • Table 17 shows the measurement results of the characteristics of the nitride phosphor according to each example.
  • a graph showing the emission spectrum of the phosphor of Example 137 of the present invention is shown by the wavy line in FIG.
  • the wavy line in FIG. 29 is a graph showing the excitation spectrum of the phosphor of Example 137 of the present invention
  • the wavy line in FIG. 30 is a graph showing the reflection spectrum of the phosphor of Example 137 of the present invention.
  • Example 137 Luminous luminance of 140 nitride phosphors The quantum efficiency is expressed as a relative value with reference to Comparative Example 9 as 100%.
  • Example 141 144 A nitride phosphor in which Hf was added as a tetravalent element, and the composition ratio of Ca and A1 was fixed at 0.99: 1 and the composition ratio of Si was adjusted, was compared with the above examples. It produced as Example 141 144 by the same method. Table 18 shows the measurement results of the characteristics of the nitride phosphor according to each example. The light emission luminance and quantum efficiency of the nitride phosphor of Example 141 144 are expressed as relative values with reference to Comparative Example 9 as 100%.
  • Example 78 144 the nitride phosphor w X y ((2/3) w + x + (4/3) y) of the general formula M AI Si N: Eu
  • Examples 145 to 161 a rare earth element was added to the nitride phosphor.
  • the light emission luminance and quantum efficiency of the nitride phosphors of Examples 145 to 173 are expressed as relative values with Comparative Example 9 as 100%.
  • Comparative Example 10 0.01% of boron B was added to Comparative Example 9.
  • the composition ratio of Ca, Al, and Si in these phosphors was set to 0.999: 1: 1.
  • rare earth elements were added as element additions, and the concentrations were 0.01 as the molar ratio of Ca to the molar concentration.
  • Ca, A1, and Si are set to 0.98: 1: 1.
  • the Eu concentration is 0.01.
  • Eu concentration is the molar ratio to the molar concentration of Ca
  • Example 162 173 in which a tetravalent element was added in place of a rare earth element to a nitride phosphor containing B was prepared, and the characteristics were measured.
  • Example 162 165 includes Ge as a tetravalent element
  • Example 166 169 adds Zr
  • Example 17 0 173 adds Hf.
  • the composition ratios of Ca and A1 are both 0.99, that is, 1: 1.
  • the Eu concentration is 0.0 1 in terms of molar ratio to the Ca molar concentration.
  • the molar concentration of B is 0.01.
  • FIG. 31 shows a graph showing the change in peak intensity in the case where boron is added to the above results.
  • Comparative Example 9 is taken as 100%.
  • the peak intensity in Comparative Example 10 is increased by adding boron to Comparative Example 9 compared to the reference example !, but the nitride phosphor has rare earth elements and trivalent elements.
  • the peak intensity also changes depending on the added element.
  • the peak intensity is increased by La Pr Nd Gd Dy Ho Er Lu Sc Zr and the like.
  • the graph of Fig. 32 shows how the afterglow of 1Z100 changes with and without the addition of boron.
  • Example 78 which is a reference, a long afterglow due to the addition of boron, a rare earth element, a trivalent element, and a tetravalent element are added to the nitride phosphor.
  • the afterglow characteristics change depending on the added element.
  • Gd of Example 85 when Gd of Example 85 is used V, long afterglow is obtained, and when Gd of Example 153 is used V, short afterglow is obtained. Even when the same Gd is added, afterglow characteristics are caused by the difference in composition. A difference occurs.
  • Example 135 examples include Ge in Example 135 and Example 145.
  • the afterglow is relatively short, but when La in Example 148 is used, the afterglow is significantly long. Even when the same La is added, the afterglow is caused by the difference in composition. Differences in characteristics occur. From this, it was confirmed that the addition of boron is effective in adjusting the afterglow of the phosphor.
  • the nitride phosphors of Examples 78 to 173 exhibit a color tone different from that of the nitride phosphor of Comparative Example 9.
  • a light emitting device adjusted to a desired color tone and afterglow characteristics can be obtained by adding an element such as rare earth.
  • FIG. 33 shows emission spectra of the phosphor of the example of the present invention and the YAG phosphor. Further, FIG. 34 shows an emission spectrum of a white light source using the phosphor of the example of the present invention.
  • an n-type and p-type GaN semiconductor layer 2 is formed on a sapphire substrate 1
  • an electrode 3 is provided on the n-type and p-type semiconductor layer 2
  • an electrode 3 Is electrically connected to the lead frame 13 by a conductive wire 14.
  • the upper part of the light emitting element 10 is covered with the phosphor 11 and the coating member 12, and the outer periphery of the lead frame 13, the phosphor 11, the coating member 12 and the like is covered with the mold member 15.
  • the semiconductor layer 2 is stacked on the sapphire substrate 1 in the order of n + GaN: Si ⁇ n—AlGaN: Si ⁇ n_GaN, GalnN QWs ⁇ p "GaN: Mg ⁇ p" AlGaN: Mg, p_GaN: Mg.
  • a part of the n + GaN: Si layer is etched to form an n-type electrode.
  • a p-type electrode is formed on the p_GaN: Mg layer.
  • the lead frame 13 uses iron-containing copper.
  • a cup for mounting the light emitting element 10 is provided on the upper portion of the mount lead 13a, and the light emitting element 10 is die-bonded to the bottom surface of the substantially central portion of the cup.
  • the phosphor 11 is mixed with the phosphor of the example and the YAG phosphor.
  • Coating member 12 includes epoxy resin and diffusing agent In addition, a mixture of barium titanate, titanium oxide and phosphor 11 in a predetermined ratio is used.
  • the mold member 15 uses epoxy resin.
  • This bullet-type light emitting device 1 is a cylindrical shape in which the upper part of the mold member 15 having a radius of 2 mm to 4 mm and a height of about 7 mm to 10 mm is a hemisphere.
  • blue light-emitting element 10 having a first emission spectrum having an emission peak at approximately 450 nm emits light, and this first emission spectrum is converted to phosphor 11 covering semiconductor layer 2.
  • the nitride phosphor in the light absorbs and performs color tone conversion, and emits light in a second emission spectrum different from the first emission spectrum.
  • the YAG phosphor contained in the phosphor 11 absorbs the first emission spectrum and is excited by this to emit light in the third emission spectrum.
  • the first, second, and third emission spectra are mixed with each other to emit white light.
  • the phosphor 11 of the light-emitting device 1 includes a phosphor according to an embodiment of the present invention, a coating member 12, and a YAG-based phosphor that is a yttrium-gadolinium'aluminum oxide phosphor activated with cerium. Is used.
  • the solid line in FIG. 33 shows the emission spectrum of the phosphor according to the example of the present invention, and the chain line in the figure shows the emission spectrum of the YAG phosphor.
  • the phosphor of the embodiment of the present invention is used in combination with a YAG-based phosphor whose emission spectrum of the red component is strong, and realizes a white light source that does not lack the red region, that is, has excellent color rendering properties. it can.
  • Table 21 shows the light emission characteristics of the white light emitting device 1 for reference.
  • the emission spectrum is shown in Fig. 34.
  • the phosphor used in the light-emitting device 1 is represented by Ca Eu AlSiN which does not contain an additive element as compared with the nitride phosphor containing the rare earth element according to the present invention.
  • nitride phosphor is used, it is sufficiently possible to use the nitride phosphor according to the present invention in place of the phosphor described above.
  • the white light emitting device 1 uses a light emitting element having an emission peak at 450 nm, and uses a YAG phosphor and a nitride phosphor.
  • YAG phosphors are (Y, Gd) AI O: Ce is used.
  • the nitride phosphor is CaAlSiB N of Example 1: 0.01.
  • the phosphor of the present invention can also be used in the light-emitting device 2 shown in FIG.
  • This figure shows a surface-mount type light-emitting device.
  • the light emitting element 101 used in the light emitting device 2 uses a blue light excited light emitting element, but 380 ⁇ !
  • a light emitting element excited by ultraviolet light with a wavelength of up to 400 nm can also be used, and the light emitting element 101 is not limited to this.
  • the light-emitting element 101 having an InGaN-based semiconductor layer with a 460 nm peak wavelength in the blue region is used as the light-emitting layer.
  • the light-emitting element 101 includes a p-type semiconductor layer and an n-type semiconductor layer (not shown).
  • the p-type semiconductor layer and the n-type semiconductor layer have conductive wires 104 connected to the lead electrode 102. Is formed.
  • An insulating sealing material 103 is formed so as to cover the outer periphery of the lead electrode 102 to prevent a short circuit.
  • a translucent window 107 extending from a lid 106 at the top of the knocker 105 is provided above the light emitting element 101.
  • a uniform mixture of the phosphor 108 and the coating member 109 according to the present invention is applied to the entire inner surface of the translucent window 107.
  • the phosphor of Example 1 is used.
  • the package 105 is a square having a side with a corner of 8 mm to 12 mm.
  • the blue light emitted from the light emitting element 101 is irradiated on the phosphor 108 according to the embodiment of the present invention by indirect light reflected by the reflecting plate and light directly emitted from the light emitting element 101.
  • the phosphor emits yellow light and red light when excited by blue light emission. Both the yellow light and red light of the phosphor and the blue light of the light emitting element are emitted to the outside and become a light source of white light emission by mixing yellow light, red light and blue light.
  • FIG. 35 is a diagram showing a cap-type light-emitting device 3 manufactured using the phosphor according to the example of the present invention.
  • the light emitting device 3 is configured by covering the surface of the mold member 15 of the light emitting device 1 with a cap 16 made of a light transmissive resin in which a phosphor (not shown) is dispersed. Cap 16 uniformly distributes the phosphor in the light-transmitting resin.
  • the light transmissive resin containing the phosphor is molded into a shape that fits into the shape of the mold member 15 of the light emitting device 1.
  • a manufacturing method is also possible in which a light-transmitting resin containing a phosphor is placed in a predetermined mold and then the light-emitting device 1 is pushed into the mold and molded.
  • the resin include transparent resin, silica sol, glass, inorganic binder, etc. with excellent temperature characteristics and weather resistance, such as epoxy resin, urea resin, and silicone resin. It is.
  • thermosetting resin such as melamine resin and phenol resin can be used.
  • thermoplastic resins such as polyethylene, polypropylene, polychlorinated butyl and polystyrene, thermoplastic rubbers such as styrene butadiene block copolymer and segmented polyurethane can also be used.
  • a diffusing agent, barium titanate, titanium oxide, aluminum oxide, etc. may be contained. Further, a light stabilizer or a colorant may be contained.
  • the phosphor mixed in the cap 16 and the phosphor 11 mixed in the cup of the mount lead 13a are the phosphor used in the embodiment of the present invention, or the phosphor of the embodiment and the YAG-based fluorescence. Use the body mixed. Also, the phosphor of the embodiment of the present invention is mixed with the cap, the YAG phosphor is mixed with the cup, or the YAG phosphor is mixed with the cap, and the embodiment of the present invention is intensively added. These phosphors can also be mixed.
  • the phosphor of the embodiment of the present invention and the YAG phosphor are mixed in the cap, and the phosphor is not mixed in the cup, or the phosphor is not mixed in the cap, and the present invention is added to the cup.
  • These phosphors can be mixed with YAG phosphors.
  • the light emitting device configured as described above excites the phosphor of the cup or cap 16 with a part of the light emitted from the light emitting element 10, and emits red light. It also excites YAG phosphors to emit light. Furthermore, a part of the blue light of the light emitting element is emitted outside without being absorbed by the phosphor.
  • the red light of the phosphor of the embodiment radiated to the outside, the light emission of the YAG phosphor, and the blue light of the light emitting element are mixed to form white light.
  • the nitride phosphor of the present invention and a light-emitting device using the same can be used together with a blue light-emitting element and another phosphor to provide a white light source with high color rendering properties.
  • FIG. 1 is a cross-sectional view of a white light source using a phosphor according to an embodiment of the present invention.
  • FIG. 2 is a plan view and a cross-sectional view of a white light source having another structure using the phosphor according to the embodiment of the present invention.
  • FIG. 3 is a block diagram showing a method for producing the phosphor of the present invention.
  • FIG. 4 is a graph showing emission spectra of phosphors according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 5 is a graph showing excitation spectra of phosphors according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 6 is a graph showing reflection spectra of phosphors according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 7 is an electron micrograph of the phosphor according to Example 1 of the present invention.
  • FIG. 8 is a graph showing emission spectra of the phosphors according to Example 11 and Example 26 of the present invention.
  • FIG. 9 is a graph showing excitation spectra of phosphors according to Example 11 and Example 26 of the present invention.
  • FIG. 10 is a graph showing reflection spectra of phosphors according to Example 11 and Example 26 of the present invention.
  • FIG. 11 is a graph showing emission spectra of the phosphors according to Example 44 and Example 48 of the present invention.
  • FIG. 12 is a graph showing excitation spectra of phosphors according to Example 44 and Example 48 of the present invention.
  • FIG. 13 is a graph showing the reflection spectra of the phosphors according to Example 44 and Example 48 of the present invention.
  • FIG. 14 is a graph showing emission spectra of phosphors according to Example 51 and Example 55 of the present invention. It is fu.
  • FIG. 15 is a graph showing excitation spectra of phosphors according to Example 51 and Example 55 of the present invention.
  • FIG. 16 is a graph showing reflection spectra of phosphors according to Example 51 and Example 55 of the present invention.
  • FIG. 17 is a graph showing changes in peak intensity.
  • FIG. 18 is a graph showing emission spectra of the phosphors according to Example 78 and Comparative Example 9 of the present invention.
  • FIG. 19 is a graph showing excitation spectra of phosphors according to Example 78 and Comparative Example 9 of the present invention.
  • FIG. 20 is a graph showing reflection spectra of phosphors according to Example 78 and Comparative Example 9 of the present invention.
  • FIG. 22 is a graph showing emission spectra of the phosphors according to Example 93 and Example 108 of the present invention.
  • FIG. 23 is a graph showing excitation spectra of the phosphors according to Example 93 and Example 108 of the present invention.
  • FIG. 24 is a graph showing reflection spectra of phosphors according to Example 93 and Example 108 of the present invention.
  • FIG. 25 is a graph showing an emission spectrum of the phosphor according to Example 126 and Example 130 of the present invention.
  • FIG. 26 is a graph showing excitation spectra of phosphors according to Example 126 and Example 130 of the present invention.
  • FIG. 27 is a graph showing reflection spectra of phosphors according to Example 126 and Example 130 of the present invention.
  • FIG. 28 is a graph showing emission spectra of the phosphors according to Example 133 and Example 137 of the present invention.
  • FIG. 29 is a graph showing excitation spectra of phosphors according to Example 133 and Example 137 of the present invention. It is rough.
  • FIG. 30 is a graph showing reflection spectra of phosphors according to Example 133 and Example 137 of the present invention.
  • FIG. 31 is a graph showing changes in peak intensity with and without boron added.
  • FIG. 32 is a graph showing changes in 1Z100 afterglow with and without boron.
  • FIG. 33 is a diagram showing an emission spectrum of the phosphor according to Example 1 of the present invention and a YAG phosphor.
  • FIG. 34 is a diagram showing an emission spectrum of white light-emitting device 1.
  • FIG. 35 is a cross-sectional view of another white light source using the phosphor according to the example of the present invention. Explanation of symbols

Abstract

L'invention concerne un luminophore rouge présentant d'excellentes caractéristiques d'émission, et un dispositif électroluminescent utilisant un tel luminophore rouge. L'invention concerne spécifiquement un luminophore à base de nitrure activé à l'europium, absorbant la lumière ultraviolette à bleue et émettant de la lumière rouge. Ce luminophore à base de nitrure est représenté par la formule générale ci-dessous, w, x, y et z étant compris dans les plages ci-dessous, et comprend en outre au moins un élément de terre rare, des éléments tétravalents et des éléments trivalents, en tant qu'éléments additionnels. MwAlxSiyN((2/3)w + x + (4/3)y):Eu2+ (Dans la formule, M représente au moins un élément choisi parmi Mg, Ca, Sr et Ba ; et 0,04 ≤ w ≤ 9, x = 1, 0,056 ≤ y ≤ 18.) La longueur d'onde de pic pouvant être déplacée vers une longueur d'onde plus grande, ce luminophore à base de nitrure est capable d'émettre une lumière rouge plus profonde, même quand la quantité d'élément activateur europium, qui est un élément de terre rare coûteux, est réduite.
PCT/JP2006/307672 2005-04-27 2006-04-11 Luminophore a base de nitrure et dispositif electroluminescent l'utilisant WO2006117984A1 (fr)

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JP2005130566A JP4892861B2 (ja) 2005-04-27 2005-04-27 窒化物蛍光体及びそれを用いた発光装置
JP2005130565A JP5066786B2 (ja) 2005-04-27 2005-04-27 窒化物蛍光体及びそれを用いた発光装置
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US7262439B2 (en) 2005-11-22 2007-08-28 Lumination Llc Charge compensated nitride phosphors for use in lighting applications
JP2010217310A (ja) * 2009-03-13 2010-09-30 Sony Corp 画像表示装置、画像表示観察システム及び画像表示方法
US7859182B2 (en) 2005-08-31 2010-12-28 Lumination Llc Warm white LED-based lamp incoporating divalent EU-activated silicate yellow emitting phosphor
US8441026B2 (en) 2007-12-19 2013-05-14 Koninklijke Philips Electronics N.V. Red emitting SiAlON-based material
CN106520120A (zh) * 2016-11-08 2017-03-22 河北利福光电技术有限公司 一种led氮化物红色荧光粉及其制备方法
JP2017149963A (ja) * 2013-04-26 2017-08-31 日亜化学工業株式会社 蛍光体及びそれを用いた発光装置
EP2109652B1 (fr) 2007-02-06 2017-10-04 Philips Intellectual Property & Standards GmbH Matière électroluminescente rouge
CN109054817A (zh) * 2017-09-30 2018-12-21 有研稀土新材料股份有限公司 一种氮化物荧光物质及含有该荧光物质的发光装置
WO2023123386A1 (fr) * 2021-12-31 2023-07-06 苏州君诺新材科技有限公司 Matériau de lumière rouge profond à base de nitrure, procédé de préparation et dispositif

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JP2003336059A (ja) * 2002-05-23 2003-11-28 National Institute For Materials Science サイアロン系蛍光体
JP2004186278A (ja) * 2002-11-29 2004-07-02 Toyoda Gosei Co Ltd 発光装置及び発光方法
JP2004238505A (ja) * 2003-02-06 2004-08-26 Ube Ind Ltd サイアロン系酸窒化物蛍光体およびその製造方法
JP2005048105A (ja) * 2003-07-30 2005-02-24 Matsushita Electric Ind Co Ltd 蛍光体組成物およびそれを用いた発光装置
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7859182B2 (en) 2005-08-31 2010-12-28 Lumination Llc Warm white LED-based lamp incoporating divalent EU-activated silicate yellow emitting phosphor
US7262439B2 (en) 2005-11-22 2007-08-28 Lumination Llc Charge compensated nitride phosphors for use in lighting applications
EP2109652B1 (fr) 2007-02-06 2017-10-04 Philips Intellectual Property & Standards GmbH Matière électroluminescente rouge
US8441026B2 (en) 2007-12-19 2013-05-14 Koninklijke Philips Electronics N.V. Red emitting SiAlON-based material
JP2010217310A (ja) * 2009-03-13 2010-09-30 Sony Corp 画像表示装置、画像表示観察システム及び画像表示方法
JP2017149963A (ja) * 2013-04-26 2017-08-31 日亜化学工業株式会社 蛍光体及びそれを用いた発光装置
CN106520120A (zh) * 2016-11-08 2017-03-22 河北利福光电技术有限公司 一种led氮化物红色荧光粉及其制备方法
CN109054817A (zh) * 2017-09-30 2018-12-21 有研稀土新材料股份有限公司 一种氮化物荧光物质及含有该荧光物质的发光装置
KR20190120819A (ko) * 2017-09-30 2019-10-24 그리렘 어드밴스드 머티리얼스 캄파니 리미티드 질화물 형광 물질 및 상기 형광 물질을 함유하는 발광 장치
JP2020517790A (ja) * 2017-09-30 2020-06-18 有研稀土新材料股▲フン▼有限公司 窒化物蛍光物質および当該蛍光物質を含む発光装置
JP6997799B2 (ja) 2017-09-30 2022-01-18 有研稀土新材料股▲フン▼有限公司 窒化物蛍光物質および当該蛍光物質を含む発光装置
KR102391156B1 (ko) 2017-09-30 2022-05-04 그리렘 어드밴스드 머티리얼스 캄파니 리미티드 질화물 형광 물질 및 상기 형광 물질을 함유하는 발광 장치
JP6997799B6 (ja) 2017-09-30 2022-06-07 有研稀土新材料股▲フン▼有限公司 窒化物蛍光物質および当該蛍光物質を含む発光装置
WO2023123386A1 (fr) * 2021-12-31 2023-07-06 苏州君诺新材科技有限公司 Matériau de lumière rouge profond à base de nitrure, procédé de préparation et dispositif

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