JP2007131794A - Nitride-based phosphor and light emitting device using the same - Google Patents

Nitride-based phosphor and light emitting device using the same Download PDF

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JP2007131794A
JP2007131794A JP2005328214A JP2005328214A JP2007131794A JP 2007131794 A JP2007131794 A JP 2007131794A JP 2005328214 A JP2005328214 A JP 2005328214A JP 2005328214 A JP2005328214 A JP 2005328214A JP 2007131794 A JP2007131794 A JP 2007131794A
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nitride
phosphor
light
light emitting
emitting device
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JP4899431B2 (en
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Shoji Hosokawa
Masatoshi Kameshima
正敏 亀島
昌治 細川
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Nichia Chem Ind Ltd
日亜化学工業株式会社
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    • H01L2224/44Structure, shape, material or disposition of the wire connectors prior to the connecting process
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    • H01L2224/45138Material 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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    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/48151Connecting 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
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    • H01L2224/48247Connecting 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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    • H01L2224/48151Connecting 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
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    • H01L2224/48257Connecting 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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    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181Encapsulation

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a nitride-based phosphor that has a high luminous efficiency, excellent temperature properties and a luminescent color from blue to yellow. <P>SOLUTION: The nitride-based phosphor is activated by cerium, absorbs light from near ultraviolet to blue, emits a yellow light and is represented by general formula M<SB>w</SB>Al<SB>x</SB>Si<SB>y</SB>B<SB>z</SB>N<SB>((2/3)w+x+(4/3)y+z)</SB>:Ce (w, x, y and z are in the following ranges; M is at least one selected from the group consisting of Mg, Ca, Sr and Ba; w, x, y and z are in 0.04≤w≤9, x=1, 0.056≤y≤18 and 0≤z≤0.5). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a nitride-based phosphor that emits light when excited by electromagnetic waves such as light, electron beams, and X-rays, or heat, and a phosphor used in a light-emitting device, and more particularly to signal lamps, illumination, displays, indicators, and various types. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting device used for a light source or the like, and relates to a nitride-based phosphor that converts the wavelength of an excitation light source, and a light emitting device using the same for white and multicolor light emitting devices that use a semiconductor light emitting element as an excitation light source.

  A light-emitting device using a semiconductor light-emitting element as a light-emitting element emits light with a small size, high power efficiency, and vivid colors. In addition, since the light-emitting element is a semiconductor element, there is no worry about a broken ball. Furthermore, the initial drive characteristics are excellent, and it is characterized by being strong against vibration and ON / OFF lighting repetition. Because of such excellent characteristics, light emitting devices using semiconductor light emitting elements such as LEDs (Light Emitting Diodes) and LDs (Laser Diodes) are used as various light sources.

  A part or all of the light of such a light emitting element is wavelength-converted by a phosphor, and the light having the wavelength converted and the light of the light emitting element that is not wavelength-converted are mixed and emitted. Light emitting devices capable of emitting different emission colors have been developed.

  Among such light-emitting devices, a light-emitting device capable of emitting white light (hereinafter referred to as “white light-emitting device”) in a wide range of fields such as lighting such as fluorescent lamps, signal lights, in-vehicle lighting, displays, and backlights for liquid crystals. ) Is required. Further, there is a demand for light-emitting devices having a pastel color or the like by combining a semiconductor light-emitting element and a phosphor.

  The emission color of a light emitting device using a white semiconductor light emitting element is obtained by the principle of light color mixing. The blue light emitted from the light emitting element is incident on the phosphor layer arranged around the light emitting element, and after being repeatedly absorbed and scattered several times in the layer, is emitted to the outside. On the other hand, the blue light absorbed by the phosphor serves as an excitation light source and emits yellow fluorescence. This yellow light and blue light are mixed and appear as white to the human eye.

In the white light emitting device, for example, a light emitting element that emits blue light (hereinafter referred to as “blue light emitting element”) is used as the light emitting element, and a phosphor is thinly coated on the surface of the blue light emitting element. As the light emitting element, a blue light emitting element using an InGaN-based material can be used. As the phosphor, a YAG phosphor represented by a composition formula of (Y, Gd) 3 (Al, Ga) 5 O 12 : Ce is used.
JP 2002-322474 A

However, YAG phosphors have a problem that the excitation wavelength range is relatively narrow, and the half width of the emission spectrum is not sufficient. In particular, among phosphors that fluoresce from green to yellow, highly efficient phosphors that are well excited by light in the vicinity of 400 nm emitted by blue light-emitting elements are still in the development stage. Research and development of phosphors with improved brightness are underway. As such a phosphor, for example, a phosphor represented by Sr 2 Si 5 N 8 : Ce 3+ or SrSi 7 N 10 : Ce 3+ has been reported (see Patent Document 1).

However, the phosphor represented by Sr 2 Si 5 N 8 : Ce 3+ described above has low luminous efficiency and is still insufficient for practical use as a light emitting device. Also, the luminescent color does not sufficiently satisfy the luminescent characteristics in a desired color. In particular, in order to be used as a light source including displays and illumination, the characteristics of the luminous efficiency of the phosphor represented by Sr 2 Si 5 N 8 : Ce 3+ are not sufficient. Therefore, further improvement in light emission luminance and improvement in color tone are required. On the other hand, since the light emitting characteristics are not sufficient for the performance of the light emitting element, the blending ratio of the phosphor represented by Sr 2 Si 5 N 8 : Ce 3+ must be increased, and the relative luminance is lowered. There is also the problem of tending to.

  In addition, since the phosphor combined with such an excitation light source is disposed close to the excitation light source, it is exposed to heat generated by the excitation light source and becomes high temperature. If the fluorescent color changes at such a high temperature or the light emission luminance decreases, the color reproducibility deteriorates. Therefore, it is required that the phosphor does not change its characteristics depending on the temperature.

  The present invention has been made to solve such problems. The main object of the present invention is a nitride system which can be converted into a wavelength by being excited by an excitation light source in the ultraviolet to visible light region, has a high luminous efficiency, and has an emission color from blue to yellow having excellent temperature characteristics. The object is to provide a phosphor and a light-emitting device using the same.

  To achieve the above object, a first nitride-based phosphor of the present invention is a nitride-based phosphor activated with cerium that absorbs near-ultraviolet or blue light and emits yellow light. , A nitride-based phosphor having at least one selected from the group consisting of Ca, Sr, and Ba, Al, Si, and N. Thereby, a nitride-based phosphor capable of emitting yellow light can be obtained. In particular, the molar ratio of Al to Si is preferably Al: Si = 1: 0.056-8. In addition, the molar ratio of at least one selected from the group of Mg, Ca, Sr, and Ba to Al is (at least one selected from the group of Mg, Ca, Sr, Ba): Al = 0.04-9 : 1 is preferred.

The second nitride phosphor of the present invention is represented by the following general formula, and w, x, y, and z are in the following ranges.
M w Al x Si y B z N ((2/3) w + x + (4/3) y + z): Ce
M is at least one selected from the group consisting of Mg, Ca, Sr, and Ba.
0.04 ≦ w ≦ 9, x = 1, 0.056 ≦ y ≦ 18, 0 ≦ z ≦ 0.5

  As a result, it is possible to obtain a nitride-based phosphor that can be excited at a wide wavelength and can emit yellow light. In addition, a nitride-based phosphor having a wide half-value width of the emission spectrum and excellent temperature characteristics with less color shift and lowering of luminance at high temperatures can be obtained.

  The third nitride phosphor of the present invention further contains a rare earth element. Thereby, a nitride-based phosphor capable of emitting yellow to red light by being excited at a wide wavelength can be obtained.

  Furthermore, the fourth nitride-based phosphor of the present invention contains O in the composition. By including an oxide in addition to the nitride, oxidation resistance can be improved by oxidizing a part in advance.

  Furthermore, in the fifth nitride-based phosphor of the present invention, the average particle size of the phosphor is 2 μm to 15 μm. Thereby, the light absorption rate and the conversion efficiency can be increased.

  In the nitride-based phosphor, M is preferably Ca. Thereby, higher luminance and intensity can be obtained than in the case of M = Mg, Sr, Ba.

  Furthermore, the sixth light emitting device of the present invention absorbs at least part of the first emission spectrum of the excitation light source and the excitation light source having the first emission spectrum that emits near ultraviolet to blue light, A light-emitting device having one or more phosphors that emit an emission spectrum, and the phosphor includes the nitride-based phosphor described above. Thereby, a light emitting device with high luminous efficiency can be obtained. In particular, a part of the light from the excitation light source having an emission peak wavelength in the short wavelength region from near ultraviolet to blue light and a part of the light of the phosphor having an emission color different from the emission color of the excitation light source are mixed color light. A light emitting device having luminescent colors in various colors can be obtained.

  As described above, the nitride-based phosphor of the present invention is excited by light in the short wavelength region from near ultraviolet to visible light, and a phosphor having an emission peak wavelength in a longer wavelength region than the excitation light source can be obtained. Further, it is possible to emit fluorescence by being excited in a wider wavelength range than conventional phosphors such as YAG phosphors. In addition, it has an excellent feature that it has a wide half-value width of the emission spectrum, and exhibits good temperature characteristics with little color shift and luminance reduction even at high temperatures.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the embodiment described below exemplifies a nitride-based phosphor for embodying the technical idea of the present invention and a light-emitting device using the same, and the present invention includes a nitride-based phosphor, The light emitting device using the same is not specified as follows. Further, the present specification by no means specifies the members shown in the claims to the members of the embodiments. In particular, the dimensions, materials, shapes, relative arrangements, and the like of the component parts described in the embodiments are not intended to limit the scope of the present invention unless otherwise specified, and are merely explanations. It is just an example. Note that the size, positional relationship, and the like of the members shown in each drawing may be exaggerated for clarity of explanation. Furthermore, in the following description, the same name and symbol indicate the same or the same members, and detailed description thereof will be omitted as appropriate. Furthermore, each element constituting the present invention may be configured such that a plurality of elements are constituted by the same member and the plurality of elements are shared by one member, and conversely, the function of one member is constituted by a plurality of members. It can also be realized by sharing.

The nitride-based phosphor according to the present embodiment can be a phosphor having a higher luminance than the conventional phosphor. It is also possible to provide a phosphor having an emission color from blue to yellow by absorbing a part of light from an excitation light source having an emission peak wavelength in a short wavelength region from ultraviolet to visible light, performing wavelength conversion it can. The color tone that can be realized with this nitride-based phosphor can realize various colors compared with the conventional phosphor represented by Sr 2 Si 5 N 8 : Ce 3+ . Moreover, a phosphor having extremely high emission luminance can be provided by substituting a group III element together with an activator such as Ce into a nitride-based phosphor serving as a base. This is because when a group III element is mixed in the position of the group II element included in the composition of the nitride phosphor, the group III element is mixed in the position of the group IV element, and Ce 3+ Is stabilized in a chargeable manner. In addition, a nitride phosphor having a different color tone can be provided by mixing a Group III element.

  When the nitride phosphor containing the above elements is irradiated with light from an excitation light source having an emission peak wavelength in the short wavelength region of visible light from near ultraviolet (near ultraviolet light), the nitride phosphor is excited and excited. Absorbs part of the light from the light source and performs wavelength conversion. The wavelength-converted light has an emission peak wavelength from blue to yellow. Accordingly, a light emitting device that emits light in a predetermined color can be provided. This nitride-based phosphor is excited by light in the short wavelength region from ultraviolet to visible light, and has an emission peak wavelength in the long wavelength region of visible light. In addition, the nitride-based phosphor has a stability equal to or higher than that of the YAG-based phosphor.

  Here, the short wavelength region from near ultraviolet to visible light in this specification is not particularly limited, but refers to a region of 240 nm to 480 nm. As the excitation light source, one having an emission peak wavelength at 240 nm to 480 nm can be used. Among these, it is preferable to use an excitation light source having an emission peak wavelength at 360 nm to 470 nm. In particular, it is preferable to use an excitation light source having a wavelength of 380 nm to 420 nm or 450 nm to 470 nm used in a semiconductor light emitting device.

  The excitation light source is preferably a light emitting element. The light emitting element is small in size, has high power efficiency, and emits bright colors. In addition, since the light-emitting element is a semiconductor element, there is no worry about a broken ball. Further, it has excellent initial driving characteristics and is strong against vibration and repeated on / off lighting. Therefore, a light-emitting device that combines a light-emitting element and a nitride-based phosphor is preferable.

  The light emitting element is preferably a nitride semiconductor light emitting element containing In or Ga. Thereby, the light emitting element emits light having an emission peak wavelength in the vicinity of 360 nm to 410 nm, and the nitride-based phosphor is excited by the light from the light emitting element and exhibits a predetermined emission color. This is because the nitride-based phosphor emits light strongly in the vicinity of 360 nm to 410 nm, and thus a light emitting element in the wavelength region is required. In addition, since it is possible to narrow the emission spectrum width, it is possible to efficiently excite the nitride-based phosphor, and from the light emitting device, an emission spectrum that does not substantially affect the color tone change. Can be released.

  The phosphor may contain a second phosphor used together with the nitride-based phosphor. The second phosphor is preferably a light-emitting device that converts the wavelength of at least part of light from the excitation light source and light from the nitride-based phosphor and has an emission peak wavelength in the visible light region. Thereby, not only the mixed color light of the light from the excitation light source and the light of the nitride-based phosphor but also the second phosphor can be used to expand the range of the emission color that can be realized. The second phosphor has at least one emission peak wavelength from the blue region to the green, yellow, and red regions. Thereby, since the light emitting device in which the second phosphor is combined with the nitride phosphor can realize various colors, a desired emission color can be obtained. Two or more kinds of phosphors may be used as the second phosphor. For example, a light emitting device in which two or more kinds of phosphors such as green and red, green and yellow, blue, green and yellow red are combined may be used. The second phosphor is an alkaline earth halogen apatite phosphor, an alkaline earth metal borate phosphor, an alkaline earth metal aluminin mainly activated by a lanthanoid-based element such as Eu or a transition metal-based element such as Mn. Rare earth aluminates mainly activated by lanthanoid elements such as phosphate phosphors, alkaline earth silicates, alkaline earth sulfides, alkaline earth thiogallates, alkaline earth silicon nitrides, germanates, or Ce It is preferably at least one or more selected from a salt, a rare earth silicate, or an organic or organic complex mainly activated by a lanthanoid element such as Eu. This is because it is possible to provide a light emitting device having high light emission efficiency such as light emission luminance and quantum efficiency. In addition, a light-emitting device with favorable color rendering properties can be provided. However, the second phosphor is not limited to the above, and phosphors that emit light in various colors can be used.

  The emission spectrum of the excitation light source is on the shorter wavelength side than the nitride-based phosphor or the second phosphor, and has high energy. Since the light emitting device according to the present invention has a broad emission spectrum, it has high color rendering properties and is suitable for lighting applications. For example, when the emission peak wavelength of the light emitting element is in the blue region, the emission peak wavelength of the excited nitride-based phosphor is from green to yellow, and the emission peak wavelength of the excited second phosphor is in red It is possible to show a white emission color by mixing three colors. As a different example, the emission peak wavelength of the light emitting element is in the ultraviolet region, the emission peak wavelength of the excited nitride-based phosphor is green, and the emission peak wavelength of the excited second phosphor is from blue and yellow. When in red, it is possible to show white and multicolored emission colors. By changing the blending amount of the nitride phosphor and the second phosphor, light emission from a color close to the emission color of the nitride phosphor to a color close to the emission color of the second phosphor Can show the color. Furthermore, when the second phosphor has two or more emission peaks, the emission main wavelength of the excitation light source, the emission main wavelength of the nitride phosphor, and two or more of the second phosphor have It is a light-emitting device which shows the luminescent color between luminescence main wavelengths. The second phosphor can be used not only in one type but also in combination of two or more types. In addition to light emitting devices that emit white light, there is also a need for light emitting devices that emit light in various colors such as pastel colors. A light emitting device having a desired color can be provided by variously combining a nitride phosphor that emits light from green to yellow, a phosphor that emits red, and a phosphor that emits blue. . Light emitting devices with different colors are not only a method of changing the type of phosphor, but also a method of changing the blending ratio of the phosphors to be combined, a method of changing the coating method of applying the phosphor to the excitation light source, It can be realized by using a method of adjusting the lighting time of each.

The light emitting device has an emission spectrum having at least one emission peak wavelength at 360 nm to 485 nm, 485 nm to 548 nm, and 548 nm to 730 nm. In addition, color rendering can be improved by combining several phosphors. This is because even if the light emission is the same white, there is a yellowish white and a bluish white. The light emitting device preferably has an average color rendering index (Ra) of 80 or more. As a result, a light emitting device having excellent color rendering can be provided.
(Cannonball type light emitting device according to Embodiment 1)

Next, a bullet-type light-emitting device is shown in FIG. 1 as the light-emitting device according to Embodiment 1 of the present invention. The light-emitting device includes a light-emitting element and a nitride-based phosphor that converts the wavelength of at least part of light from the light-emitting element. In addition to this, a second phosphor can be contained. The relationship between the color name and chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, and the like comply with JIS Z8110. Specifically, 380 nm to 455 nm is blue purple, 455 nm to 485 nm is blue, 485 nm to 495 nm is blue green, 495 nm to 548 nm is green, 548 nm to 573 nm is yellow green, 573 nm to 584 nm is yellow, 584 nm to 610 nm is yellow red , 610 nm to 780 nm is red.
(Excitation light source)

  An excitation light source having an emission peak wavelength in the short wavelength region from ultraviolet to visible light is used. Any excitation light source having an emission peak wavelength in the range is not particularly limited. Examples of the excitation light source include a lamp and a semiconductor light emitting element, and it is preferable to use a semiconductor light emitting element.

  The light emitting device according to the first embodiment includes a semiconductor layer 2 stacked on an upper part of a sapphire substrate 1, and a lead frame 13 conductively connected by a conductive wire 14 extending from positive and negative electrodes 3 formed on the semiconductor layer 2. The phosphor 11 and the coating member 12 provided in the cup of the lead frame 13 a 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 outer periphery of the phosphor 11 and the lead frame 13. It is comprised with the mold member 15 which covers a surface. 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 an emission peak wavelength output from the light emitting layer has an emission spectrum in the vicinity of 500 nm or less from the ultraviolet to the blue region.

Hereinafter, a method for manufacturing the light-emitting device according to Embodiment 1 will be described. The light emitting element 10 is set in a die bonder, face-up to a lead frame 13a provided with a cup, and die bonded (adhered). After die bonding, 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 a cup with a gold wire, and the positive electrode 3 is wire bonded to the other lead frame 13b. . Next, 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. After the phosphor 11 is injected, the lead frame 13 is immersed in a mold mold in which a mold member 15 has been injected in advance, and then the mold is removed to cure the resin, and a bullet-type light emitting device as shown in FIG. To do.
(Light-emitting device according to Embodiment 2)

  Next, a configuration and a manufacturing method of the light emitting device according to Embodiment 2 of the present invention will be described with reference to FIG. The light-emitting device according to Embodiment 2 is a surface-mounted light-emitting device, in which FIG. 2A is a plan view and FIG. 2B is a cross-sectional view. As the light-emitting element 101, an ultraviolet-excited nitride semiconductor light-emitting element can be used. The light emitting element 101 may be a blue light-excited nitride semiconductor light emitting element. Here, the light emitting element 101 excited by ultraviolet light will be described as an example. The light emitting element 101 uses a nitride semiconductor light emitting element having an InGaN semiconductor with an emission peak wavelength of about 370 nm as a light emitting layer. The light-emitting element 101 includes a p-type semiconductor layer and an n-type semiconductor layer (not shown), and the p-type semiconductor layer and the n-type semiconductor layer have a conductive wire 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. Above the light emitting element 101, a translucent window 107 extending from a lid 106 at the top of the package 105 is provided. A uniform mixture of the phosphor 108 and the coating member 109 is applied to almost the entire inner surface of the translucent window 107. As a more specific LED element structure, an n-type GaN layer that is an undoped nitride semiconductor on a sapphire substrate, a GaN layer that is formed with an Si-doped n-type electrode and becomes an n-type contact layer, and an undoped nitride semiconductor A single quantum well structure includes an n-type GaN layer, an n-type AlGaN layer that is a nitride semiconductor, and then an InGaN layer that constitutes a light-emitting layer. On the light emitting layer, 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 sequentially laminated. (Note that a GaN layer is formed on the sapphire substrate at a low temperature to serve as a buffer layer. In addition, the p-type semiconductor is annealed at 400 ° C. or higher after film formation). Etching exposes the surface of each pn contact layer on the same side as 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 translucent 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 cut. A pedestal electrode is formed on the p-electrode in parallel with the n-electrode using a sputtering method.

  Next, a Kovar package 105 having a concave portion at the center and a base portion having Kovar lead electrodes 102 inserted and fixed in an airtight manner on both sides of the concave portion is used. Ni / Ag layers are provided on the surfaces of the package 105 and the lead electrode 102. The light emitting element 101 described above is die-bonded with an Ag—Sn alloy in the recess of the package 105. With this configuration, all components of the light-emitting device can be made of an inorganic material, and the reliability of the light-emitting device can be dramatically improved even if the light emitted from the light-emitting element 101 is in the ultraviolet region or the short wavelength region of visible light. A light emitting device with high brightness can be obtained.

Next, each electrode of the die-bonded light emitting element 101 and each lead electrode 102 exposed from the bottom of the package recess are electrically connected by an Ag wire 104. After sufficiently removing moisture in the recess of the package, sealing is performed with a Kovar lid 106 having a glass window 107 at the center, and seam welding is performed. In the glass window portion, CaAlSiN 3 : Ce, (Y 1−x Gd x ) 3 (Al 1−y Ga y ) 5 O 12 : Ce with respect to a slurry of 90 wt% nitrocellulose and 10 wt% γ-alumina in advance. (However, 0 <x <1, 0 <y <1) and the like are contained, applied to the back surface of the translucent window 107 of the lid 106, and cured by heating at 220 ° C. for 30 minutes. By doing so, a color conversion member is configured. When the light-emitting device thus formed emits light, a light-emitting diode capable of emitting white light with high luminance can be obtained. As a result, it is possible to obtain a light emitting device that is extremely easy to adjust the chromaticity and has excellent mass productivity and reliability.
(Phosphor 11, 108)

  Next, each member constituting the light emitting device will be described in detail. The phosphors 11 and 108 include nitride phosphors. In addition, the phosphors 11 and 108 may be a combination of a nitride phosphor and a second phosphor.

The nitride-based phosphor is a nitride-based phosphor that is activated by cerium and absorbs near-ultraviolet to blue light and emits yellow light, and has a general formula M w Al x Si y B z N ((2 / 3) w + x + (4/3) y + z) : represented by Ce, M is at least one selected from the group consisting of Mg, Ca, Sr, and Ba, and the range of w, x, y, and z 0.04 ≦ w ≦ 9, x = 1, 0.056 ≦ y ≦ 18, and 0 ≦ z ≦ 0.5. Nitride phosphors in this range exhibit high emission luminance. Preferably, the ranges of w, x, y, z are 0.05 ≦ w ≦ 3, x = 1, 0.15 ≦ y ≦ 9, 0.001 ≦ z ≦ 0.5, Better emission luminance is exhibited. Most preferably, y = 1. However, it is not limited to the said range, Arbitrary things can also be used. Further, other elements may be included to such an extent that the characteristics are not impaired. The composition when B is not included is as follows.

M w Al x Si y N ( (2/3) w + x + (4/3) y): Ce
M is at least one selected from the group consisting of Mg, Ca, Sr, and Ba.
0.04 ≦ w ≦ 9, x = 1, 0.056 ≦ y ≦ 18

Further, the nitride phosphor is a nitride-based phosphor activated with cerium that absorbs near-ultraviolet to blue light and emits yellow light, and has a general formula M w Al x Si y B z N ((2 / 3) w + x + (4/3) y + z) : represented by Ce, M is at least one selected from the group consisting of Mg, Ca, Sr, and Ba, and the range of w, x, y, and z It is also possible to use 0.04 ≦ w ≦ 9, x = 1, 0.056 ≦ y ≦ 18, 0 ≦ z ≦ 0.5, and further include a rare earth element as an additive element. As a result, a nitride-based phosphor that can emit light from yellow to red by being excited at a wide wavelength can be obtained. The rare earth elements are Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. For example, when only Eu is added, red light emission can be obtained.

  Further, these nitride phosphors may contain O in the composition.

For the emission center, cerium Ce, which is a rare earth element, is used. In this embodiment mode, description will be made using only Ce. However, the present invention is not limited to this, and a material co-activated with Ce can also be used. Cerium tends to generate +4 valence and easily separates other rare earth elements. Ce reacts with Cl 2 and Br 2 to give CeCl 3 and CeBr 3 . It is gradually oxidized in air and rapidly oxidized at high temperature to become CeO 2 . H 2 is generated and dissolved into Ce 3+ gradually with water and with acid aqueous solution. The stable oxidation number is + III like other rare earth elements, but + IV is easy to take. Cerium compounds are most stable in the + III oxidation state, but + IV is also fairly stable in solution. The phosphor of the present invention uses Ce 3+ as an activator with respect to the base alkaline earth metal silicon nitride.

M nitride, Al, and Si nitride are mixed as a base material. In the base material, an oxide of Ce is mixed as an activator. Weigh these in the desired amount and mix until uniform. These base materials, M w Al x Si y B z N ((2/3) w + x + (4/3) y + z): so that the composition ratio of Ce, weighing the predetermined amount mixed To do.
(Cap type light emitting device according to Embodiment 3)

  Next, as a light-emitting device according to Embodiment 3 of the present invention, a cap-type light-emitting device will be described with reference to FIG. In this light-emitting device, the same members as those in the light-emitting device according to Embodiment 1 are assigned the same reference numerals, and descriptions thereof are omitted. The light emitting element 10 uses a light emitting element having an emission peak wavelength at 400 nm. This light emitting device is configured by covering the surface of the mold member 15 of the light emitting device of Embodiment 1 with a cap 16 made of a light transmissive resin in which a phosphor (not shown) is dispersed.

  A cup for mounting the light emitting element 10 is provided on the top of the mount lead 13a, and the light emitting element 10 is die-bonded to the bottom surface of the substantially central part of the cup. In the light emitting device according to the first embodiment, the phosphor 11 is provided so as to cover the light emitting element 10 on the upper part of the cup. However, the light emitting device according to the third embodiment may not be provided. By not providing the phosphor 11 on the top of the light emitting element 10, there is an advantage that the phosphor is not directly affected by the heat generated from the light emitting element 10.

  The cap 16 has the phosphor uniformly dispersed in the light transmissive resin. The light-transmitting resin containing this phosphor is molded into a shape that fits into the shape of the mold member 15 of the light-emitting device. Alternatively, 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 is pushed into the mold and molded. Specific materials for the light transmissive resin of the cap 16 include transparent resins, silica sol, glass, inorganic binders, and the like that are excellent in temperature characteristics and weather resistance such as epoxy resins, urea resins, and silicone resins. In addition to the above, thermosetting resins such as melamine resins and phenol resins can be used. In addition, thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene, thermoplastic rubbers such as styrene-butadiene block copolymer, segmented polyurethane, and the like can also be used. Further, a diffusing agent, barium titanate, titanium oxide, aluminum oxide or the like may be contained together with the phosphor. Moreover, you may contain a light stabilizer and a coloring agent. The phosphor used for the cap 16 can be not only one type but also a mixture of a plurality of phosphors or a layered layer.

Only the coating member 12 is used in the cup of the mount lead 13a. This is because a phosphor is used for the cap 16. However, a mixture of one or a plurality of phosphors may be used in the cup of the mount lead 13a, and different phosphors may be used for the cap 16.
In the light emitting device configured as described above, the light emitted from the light emitting element 10 excites the phosphor 11 and emits light from blue green to green and from yellow red to red. A part of the light emitted from the phosphor 11 excites the phosphor of the cap 16 and emits light from green to yellow. Thereby, white light is emitted from the surface of the cap 16 to the outside by the mixed color light of these phosphors.
(Nitride-based phosphor manufacturing method)

Next, an example of a method for producing CaAlSiB 0.005 N 3.005 : Ce as a nitride-based phosphor will be described based on the process diagram of FIG.

  The raw material Ca is pulverized (P1). The raw material Ca is preferably a simple substance, but compounds such as an imide compound and an amide compound can also be used. The raw material Ca may contain Li, Na, K, B, Al, or 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. As a guide for Ca grinding, the average particle size is preferably in the range of about 0.1 μm or more and 15 μm or less from the viewpoint of reactivity with other raw materials, particle size control during and after firing, etc., It is not limited to this range. The purity of Ca is preferably 2N or higher, but is not limited thereto.

  The raw material Ca is nitrided in a nitrogen atmosphere (P2).

  Ca can be nitrided in a nitrogen atmosphere at 600 ° C. to 900 ° C. for about 5 hours to obtain a nitride of Ca. The Ca nitride is preferably of high purity.

  The nitride of Ca is pulverized (P3). Ca nitride is pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere.

The raw material Si is pulverized (P4). The raw material Si is preferably a simple substance, but a nitride compound, an imide compound, an amide compound, or the like can also be used. For example, Si 3 N 4 , Si (NH 2 ) 2 , Mg 2 Si, etc. The purity of the raw material Si is preferably 3N or more, but may contain different elements such as Li, Na, K, B, Al and Cu. Si is also pulverized in a glove box in an argon atmosphere or a nitrogen atmosphere in the same manner as the raw material Ca. The average particle size of the Si compound is preferably in the range of about 0.1 μm or more and 15 μm or less from the viewpoints of reactivity with other raw materials, particle size control during and after firing, and the like.

  Next, the raw material Si is nitrided in a nitrogen atmosphere (P5). Silicon Si is also nitrided in a nitrogen atmosphere at 800 ° C. to 1200 ° C. for about 5 hours to obtain silicon nitride. The silicon nitride used in the present invention is preferably highly pure.

  Similarly, Si nitride is pulverized (P6).

  AlN is synthesized by direct nitridation of Al or the like. However, AlN powder that is already available on the market can also be used.

  BN is synthesized by a direct nitridation method of B or the like. As the BN, commercially available BN powder can be used.

Next, the Ce compound CeO 2 is pulverized (P7). The average particle size after pulverization is preferably about 0.1 to 15 μm.

In step P8, Ca nitride, Al nitride, Si nitride, B nitride, and Ce compound CeO 2 are mixed in a dry manner.

Ca nitride, Al nitride, Si nitride, B nitride, and CeO 2 are fired in an ammonia atmosphere (P9). By calcination, a phosphor represented by CaAlSiB 0.005 N 3.005 : Ce can be obtained (P10).

  However, this composition is a representative composition estimated from the blending ratio, and has sufficient characteristics to withstand practical use in the vicinity of the ratio. Moreover, the composition of the target phosphor can be changed by changing the blending ratio of each raw material.

For firing, a tubular furnace, a small furnace, a high-frequency furnace, a metal furnace, or the like can be used. The firing temperature can be in the range of 1200 ° C to 2000 ° C, but the firing temperature of 1400 ° C to 1800 ° C is preferred. For firing, it is preferable to use one-stage firing in which the temperature is gradually raised and firing is performed at 1200 to 1500 ° C. for several hours, but the first-stage firing is performed at 800 to 1000 ° C. Two-stage baking (multi-stage baking) in which the second baking is performed at 1200 to 1500 ° C. can also be used. The raw material of the phosphor 11 is preferably fired using a crucible or boat made of boron nitride (BN). In addition to the boron nitride crucible, an alumina (Al 2 O 3 ) crucible can also be used. This is because these B, Al, and the like can improve the luminance more than Mo and can provide a phosphor having high luminous efficiency.

  The reducing atmosphere is an atmosphere containing at least one of nitrogen, hydrogen, argon, carbon dioxide, carbon monoxide, and ammonia. However, firing can be performed in a reducing atmosphere other than these.

The target nitride-based phosphor can be obtained by the above manufacturing method.
(Second phosphor 11, 108)

  The nitride-based phosphors 11 and 108 can include a second phosphor together with the nitride-based phosphor. Examples of the second phosphor include alkaline earth halogen apatite phosphors, alkaline earth metal borate phosphors, alkaline earth metals mainly activated by lanthanoid compounds such as Eu and transition metal elements such as Mn. Rare earth alumina mainly activated by aluminate phosphor, alkaline earth silicate, alkaline earth sulfide, alkaline earth thiogallate, alkaline earth silicon nitride, germanate, or lanthanoid elements such as Ce It is preferable that it is at least any one selected from an organic acid, an organic complex, or the like mainly activated with an acid salt, a rare earth silicate, or a lanthanoid element such as Eu. As specific examples, the following phosphors can be used, but are not limited thereto.

Alkaline earth halogen apatite phosphors mainly activated by lanthanoid compounds such as Eu and transition metal elements such as Mn include M 5 (PO 4 ) 3 X: R (M is Sr, Ca, Ba, X is at least one selected from F, Cl, Br, and I. R is any one or more of Eu, Mn, Eu and Mn. There is.)

The alkaline earth metal borate phosphor has M 2 B 5 O 9 X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F, Cl , Br, or I. R is Eu, Mn, or any one of Eu and Mn.).

Alkaline earth metal aluminate phosphors include SrAl 2 O 4 : R, Sr 4 Al 14 O 25 : R, CaAl 2 O 4 : R, BaMg 2 Al 16 O 27 : R, BaMgAl 10 O 17 : R (R is Eu, Mn, or any one of Eu and Mn).

As the rare earth oxysulfide phosphor, La 2 O 2 S: Eu, Y 2 O 2 S: Eu, Gd 2 O 2 S: Eu, or the like can be used.

As the alkaline earth metal sulfide phosphor, CaS: Ce 3+ , CaS: Eu 2+ , CaS: Mn 2+ and the like can be used.

Rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce include Y 3 Al 5 O 12 : Ce, (Y 0.8 Gd 0.2 ) 3 Al 5 O 12 : Ce, Y 3 (Al 0.8 Ga 0.2 ) 5 O 12 : Ce, (Y, Gd) 3 (Al, Ga) 5 O 12 and other YAG phosphors represented by the composition formula.

Other phosphors include ZnS: Mn, Zn 2 GeO 4 : Mn, MGa 2 S 4 : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn). is there. M 2 Si 5 N 8 : Eu, MSi 7 N 10 : Eu, M 1.8 Si 5 O 0.2 N 8 : Eu, M 0.9 Si 7 O 0.1 N 10 : Eu, MAlSiN 3 : Eu (M is Sr, And at least one selected from Ca, Ba, Mg, and Zn.

  The above-mentioned second phosphor may be one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti instead of Eu or in addition to Eu as desired. Can also be included.

  Moreover, it is fluorescent substance other than the said fluorescent substance, Comprising: The fluorescent substance which has the same performance and effect can also be used.

  As these second phosphors, phosphors having emission spectra in yellow, red, green, and blue can be used by the excitation light of the light-emitting elements 10 and 101, and yellow, blue-green, which are intermediate colors thereof, can be used. A phosphor having an emission spectrum in orange or the like can also be used. These second phosphors are not limited to one type, and by using them in combination with different types of phosphors, light emitting devices having various emission colors can be manufactured.

For example, CaSi 2 O 2 N 2 : Eu or SrSi 2 O 2 N 2 : Eu that emits green to yellow as the second phosphor emits blue light (Sr, Ca) 5 (PO 4 ) 3 Cl : Eu, which emits red light (Ca, Sr) 2 Si 5 N 8 : Eu, or CaAlSiN 3 : Eu, by using phosphors 11 and 108, light emission which emits white light with good color rendering properties An apparatus can be provided. Because this uses the three primary colors of light, red, blue, and green, the desired white light can be achieved simply by changing the blend ratio of the first phosphor and the second phosphor. Can do. In particular, when the nitride phosphor and the second phosphor are irradiated with light near 460 nm as the excitation light source, the nitride phosphor emits green to yellow-red light around 500 nm to 610 nm. . Thereby, a white light-emitting device excellent in color rendering can be provided.
(Particle size)

  The particle diameters of the nitride phosphors 11 and 108 are preferably in the range of 2 μm to 15 μm, more preferably 2 μm to 8 μm. Particularly, 5 μm to 8 μm is preferable. A phosphor having a particle size smaller than 2 μm tends to form an aggregate. On the other hand, a phosphor having a particle size range of 5 μm to 8 μm has high light absorptivity and conversion efficiency. In this manner, the mass productivity of the light-emitting device is improved by including a phosphor having a large particle diameter and having optically excellent characteristics.

Here, the particle size refers to the average particle size obtained by the air permeation method. Specifically, in an environment with an air temperature of 25 ° C. and a humidity of 70%, a sample of 1 cm 3 is weighed and packed in a special tubular container, and then a constant pressure of dry air is flowed to read the specific surface area from the differential pressure. It is a value converted into an average particle diameter. The average particle diameter of the phosphor used in the present embodiment is preferably in the range of 2 μm to 15 μm. Moreover, it is preferable that the phosphor having this average particle diameter value is contained frequently. In addition, it is preferable that the particle size distribution is distributed in a narrow range. As described above, by using a phosphor having a small variation in particle size and particle size distribution, color unevenness is further suppressed, and a light emitting device having a good color tone can be obtained.

The arrangement place of the phosphor 108 in the light emitting device 2 can be arranged at various places in the positional relationship with the light emitting element 101. For example, the phosphor 108 can be contained in the molding material that covers the light emitting element 101. Further, the light emitting element 101 and the phosphor 108 may be arranged with a gap therebetween, or the phosphor 108 may be directly placed on the light emitting element 101.
(Coating member 12, 109)

  The phosphors 11 and 108 can be attached using various coating members (binders) such as a resin that is an organic material and glass that is an inorganic material. The coating members 12 and 109 may have a role as a binder for fixing the phosphors 11 and 108 to the light emitting elements 10 and 101, the window portion 107, and the like. When an organic material is used as the coating member, a transparent resin excellent in weather resistance such as an epoxy resin, an acrylic resin, or silicone is suitably used as a specific material. In particular, it is preferable to use silicone because it is excellent in reliability and the dispersibility of the phosphors 11 and 108 can be improved.

In addition, it is preferable to use an inorganic material that approximates the thermal expansion coefficient of the window portion 107 as the coating members 12 and 109 because the phosphor 108 can be satisfactorily adhered to the window portion 107. As a specific method, a precipitation method, a sol-gel method, a spray method, or the like can be used. For example, the phosphors 11 and 108 are mixed with silanol (Si (OEt) 3 OH) and ethanol to form a slurry. After the slurry is discharged from the nozzle, the slurry is heated at 300 ° C. for 3 hours. Can be made SiO2, and the phosphor can be fixed to a desired place.

  In addition, an inorganic binder can be used as the coating members 12 and 109. The binder is so-called low-melting glass, is a fine particle, has little absorption with respect to radiation in the ultraviolet to visible region, and is preferably extremely stable in the coating members 12 and 109.

  In addition, when a phosphor having a large particle size is attached to the coating members 12 and 109, a fine particle size obtained by a binder, for example, silica, alumina, or a precipitation method, in which the particle is an ultrafine powder even if the melting point is high. The alkaline earth metal pyrophosphates and orthophosphates are preferably used. These binders can be used alone or mixed with each other.

  Here, a method for applying the binder will be described. In order to sufficiently enhance the binding effect, the binder is preferably wet pulverized in a vehicle to form a slurry and used as a binder slurry. A vehicle is a high viscosity solution obtained by dissolving a small amount of a binder in an organic solvent or deionized water. For example, an organic vehicle can be obtained by adding 1 wt% of nitrocellulose as a binder to butyl acetate as an organic solvent.

  The binder slurry thus obtained contains phosphors 11 and 108 to prepare a coating solution. The added amount of the slurry in the coating solution can be such that the total amount of the binder in the slurry is about 1 to 3% wt with respect to the amount of the phosphor in the coating solution. In order to suppress a decrease in the luminous flux maintenance factor, it is preferable that the amount of the binder added is small.

The coating liquid is applied to the back surface of the window portion 107. After that, hot air or hot air is blown to dry. Finally, baking is performed at a temperature of 400 ° C. to 700 ° C. to disperse the vehicle. As a result, the phosphor layer is adhered to the desired place with the binder.
(Light emitting element 10, 101)

The light emitting elements 10 and 101 are preferably semiconductor light emitting elements having a light emitting layer capable of emitting a light emission peak wavelength capable of efficiently exciting the phosphor. Examples of the material of such a semiconductor light emitting device include various semiconductors such as BN, SiC, ZnSe, GaN, InGaN, InAlGaN, AlGaN, BAlGaN, and BInAlGaN. Similarly, these elements may contain Si, Zn, or the like as an impurity element to serve as a light emission center. In particular, a nitride semiconductor (for example, a nitride semiconductor containing Al or Ga, In or Ga, for example) is used as a light emitting layer material that can efficiently emit short wavelengths of visible light from the ultraviolet region that can excite the phosphors 11 and 108 efficiently. As the nitride semiconductor to be included, In X Al Y Ga 1-XY N, 0 ≦ X, 0 ≦ Y, and X + Y ≦ 1) are more preferable.

  In order to form the light emitting device with high productivity, it is preferable to use a resin when the phosphors 11 and 108 are fixed to the light emitting elements 10 and 101. In this case, in consideration of the emission peak wavelength from the phosphors 11 and 108 and the deterioration of the translucent resin, the light emitting elements 10 and 101 have an emission spectrum in the ultraviolet region, and the emission peak wavelength is 360 nm or more and 420 nm. It is preferable to use the following, or 450 nm or more and 470 nm or less.

  As the light emitting elements 10 and 101, an ultraviolet light emitting element or a blue light emitting element can be used. The light emitting elements 10 and 101 that emit blue light are preferably group III nitride compound light emitting elements.

  In the present embodiment, the light emitting layer having a multiple quantum well structure is used. However, the present invention is not limited to this, and for example, a single quantum well structure using InGaN may be used. GaN doped with Zn may be used.

The light emitting layers of the light emitting elements 10 and 101 can change the main light emission peak wavelength in the range of 420 nm to 490 nm by changing the In content. The emission peak wavelength is not limited to the above range, and those having an emission peak wavelength in the range of 360 nm to 550 nm can be used.
(Coating member 12, 109)

The coating member 12 (light transmissive material) is provided in the cup of the lead frame 13 and is used by mixing with the phosphor 11 that converts the light emission of the light emitting element 10. Specific materials for the coating member 12 include transparent resins, silica sol, glass, inorganic binders, and the like that are excellent in temperature characteristics and weather resistance, such as epoxy resins, urea resins, and silicone resins. Further, a diffusing agent, barium titanate, titanium oxide, aluminum oxide or the like may be contained together with the phosphor. Moreover, you may contain a light stabilizer and a coloring agent.
(Lead frame 13)

  The lead frame 13 includes a mount lead 13a and an inner lead 13b. The mount lead 13a is for placing the light emitting element 10 thereon. 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 13 a can be used as a common electrode of the light emitting elements 10. In this case, sufficient electrical conductivity and connectivity with the conductive wire 14 are required. Die bonding (adhesion) between the light emitting element 10 and the cup of the mount lead 13a can be performed with a thermosetting resin or the like. Examples of the thermosetting resin include an epoxy resin, an acrylic resin, and an imide resin. In addition, Ag-ace, carbon paste, metal bumps, or the like can be used for die-bonding and electrical connection with the mount lead 13a by 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 disposed 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. In the case where the plurality of light emitting elements 10 are provided on the mount lead 13a, it is necessary that the conductive wires be arranged so as not to contact each other. The inner lead 13b is preferably made of the same material as the mount lead 13a, and iron, copper, iron-containing copper, gold, platinum, silver, or the like can be used.
(Conductive wire)

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 are preferably metals such as gold, copper, platinum, and aluminum, and alloys thereof.
(Mold member)

  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 the outside. 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 stacked in addition to the convex lens shape and the concave lens shape. 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 can contain a diffusing agent, a colorant, an ultraviolet absorber, and a phosphor. As 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, it is preferable to use the same material in consideration of the refractive index.

  Hereinafter, as examples of the present invention, the results of manufacturing a nitride-based phosphor and a light-emitting device using the same and measuring the light-emission characteristic temperature characteristics and the like will be described.

The temperature characteristics are shown as relative luminance with the emission luminance at 25 ° C. being 100%. The particle size indicates the average particle size described above. S. S. S. No. (Fisher Sub Sieve Sizer's No.) Value by air permeation method.
[Examples 1-2]

Examples of the present invention will be described in detail below. Here, for a nitride-based phosphor represented by the general formula Ca 0.990 Al 1.000 Si 1.000 B z N 3.000 + z : 0.010Ce, z = 0 in Example 1 and z = 0.005 in Example 2. The manufacturing method will be described. First, the raw material Ca is pulverized to 1 μm to 15 μm and nitrided in a nitrogen atmosphere. Thereafter, the Ca nitride is pulverized to 0.1 μm to 10 μm. Weigh 20g of raw material Ca and perform nitriding. Similarly, raw material Si is pulverized to 1 μm to 15 μm and nitrided in a nitrogen atmosphere. Thereafter, the Si nitride is pulverized to 0.1 μm to 10 μm. 20 g of raw material Si is weighed and nitriding is performed. Next, the Al compound AlN and the Ce compound CeO 2 are pulverized to 0.1 μm to 10 μm. Ca nitride, Al nitride, Si nitride, and Ce oxide are mixed in a nitrogen atmosphere.
The average particle diameter of the nitride phosphor of the example is in the range of 2 μm to 15 μm. Further, the phosphors in the examples contain oxygen.

In Example 1, the mixing ratio (molar ratio) of each element of calcium nitride Ca 3 N 2 , aluminum nitride AlN, silicon nitride Si 3 N 4 , and cerium oxide CeO 2 as raw materials was Ca: Al: Si: Ce = It adjusts so that it may become 0.99: 1.00: 1.00: 0.01. Ca 3 N 2 (molecular weight 148.26), AlN (molecular weight 40.99), Si 3 N 4 (molecular weight 140.31), and CeO 2 are weighed and mixed so that this mixing ratio is obtained. The above compounds were mixed and fired. As the firing conditions, the above compound is put into a crucible in an ammonia atmosphere, gradually heated from room temperature, fired at about 1600 ° C. for about 5 hours, and slowly cooled to room temperature.

  Emission characteristics and temperature characteristics when the nitride phosphor according to Example 1 obtained in this way and the Example 2 obtained in the same manner were excited with a blue LED having a peak at 460 nm as an excitation light source. Is shown in Table 1.

  FIG. 5 is a diagram showing an emission spectrum when the nitride phosphors of Example 1 and Example 2 are excited at Ex = 460 nm. FIG. 6 is a diagram showing a general excitation spectrum of YAG: Ce for comparison with the nitride phosphors of Example 1 and Example 2. FIG. FIG. 7 is a diagram showing the reflection spectra of the nitride phosphors of Example 1 and Example 2. In the graphs of FIGS. 5 to 7, Example 1 is a thick line, and Example 2 is a thin line, each showing a spectrum. In FIG. 4, the excitation spectrum of YAG: Ce is indicated by a broken line. Further, FIG. 8 is an SEM photograph of the nitride phosphor of Example 1 taken. FIG. 9 is a SEM photograph of the nitride phosphor of Example 2. 8A and 9A are taken at 1000 times. 8B and 9B are taken at a magnification of 5000 times.

Note that the luminance and the peak intensity represent relative values based on Example 1 with Example 1 being 100%. From the table, Example 2 including B 0.005 shows higher values of brightness and intensity than Example 1, and the peak wavelength is longer.

The temperature characteristics of Ca 0.990 Al 1.000 Si 1.000 B z N 3.000 + z : 0.010Ce nitride phosphor maintain about 80% luminance at 200 ° C., and maintain about 60% luminance at 300 ° C. It can be seen that the temperature characteristics are excellent. When the boron B of Example 2 is included, there is less decrease in luminance on the high temperature side, and the effect of including B can be confirmed.

In the YAG: Ce phosphor shown in FIG. 6, the peak of the excitation spectrum is around 470 nm and 340 nm, and the wavelength range of the excitation light is narrow. On the other hand, in the nitride phosphors according to Example 1 and Example 2, the wavelength range of the excitation light is broadened, and it can be confirmed that the excitation phosphor is efficiently excited regardless of the excitation light source.
[Examples 3 to 8]

Next, as Examples 3 to 8, for the nitride-based phosphor represented by the general formula Ca 1-a Al 1.000 Si 1.000 B z N 3.000 + z : aCe, the values of a and z were changed in the same manner. A nitride-based phosphor is produced. Here, the values of a and z in each example are as follows.
Example 3 ... a = 0.006, z = 0.000
Example 4 ... a = 0.020, z = 0.000
Example 5: a = 0.030, z = 0.000
Example 6: a = 0.006, z = 0.005
Example 7: a = 0.020, z = 0.005
Example 8: a = 0.006, z = 0.005
Table 2 shows the results of measuring the light emission characteristics of the nitride phosphor obtained by changing the amount of Ce to be activated in accordance with the above composition ratio.

  In Table 2, the results of Example 1 and Example 2 in Table 1 are also shown for comparison.

  FIG. 10 is a diagram showing an emission spectrum when the nitride phosphors of Examples 6, 7, and 8 are excited at Ex = 460 nm. FIG. 11 is a diagram showing excitation spectra of the nitride phosphors of Examples 6, 7, and 8. FIG. 12 is a diagram showing the reflection spectra of the nitride phosphors of Examples 6, 7, and 8. In the graphs of FIGS. 10 to 12, Example 6 is a thick line, Example 7 is a thin line, and Example 8 is a broken line, and each shows a spectrum.

In the nitride phosphors of Examples 3 to 8, the luminance and peak intensity are shown as relative values with Example 1 as 100%. Table 2 shows different color tones and peak wavelengths depending on the concentration of Ce as an activator, and can be adjusted to the desired color tones and peak wavelengths using this. When boron B is not included, the luminance and peak intensity are maximum when a = 0.006 and z = 0 in Example 3. When boron B is included, it can be seen that the peak intensity is the maximum in Example 2.
[Examples 9 to 15]

Next, as an embodiment 9-15 of the general formula Ca 0.99 Al y Si 1.000 B z N 3.000 + z: per nitride phosphor represented by 0.010Ce, similarly by changing the values of y and z A nitride-based phosphor is produced. Here, the values of y and z in each example are as follows.
Example 9: y = 1.000, z = 0.010
Example 10: y = 1.000, z = 0.050
Example 11: y = 1.000, z = 0.100
Example 12: y = 0.0.99, z = 0.005
Example 13: y = 0.990, z = 0.010
Example 14: y = 0.950, z = 0.050
Example 15... Y = 0.900, z = 0.100
Table 3 shows the results of measuring the light emission characteristics of the nitride-based phosphor obtained by changing the amount of boron B according to the above composition ratio.

In Examples 9 to 11, the B concentration of Example 2 was further increased, but it can be seen that the luminance and peak intensity were not significantly reduced. In Examples 12 to 15, the Al concentration was reduced when B was added. In this case, it can be seen that the luminance decreases to 90% or less when the B concentration is 0.05 or more.
[Examples 16 to 19]

Next, as Examples 16 to 19, a nitride system represented by the general formula (Ca, Sr, Ba) 0.99 Al 1.000 Si 1.000 B 0.01 N 3.01 : 0.010Ce in which a part of Ca is substituted with Sr and Ba Nitride phosphors are similarly produced by changing the ratio of Ca and Sr and Ca and Ba for the phosphor. Here, the values of Ca / Sr and Ca / Ba in each example are as follows.
Example 16 Ca / Sr = 0.5 / 0.5
Example 17 Ca / Sr = 0.0 / 1.0
Example 18: Ca / Ba = 0.5 / 0.5
Example 19 Ca / Ba = 0.0 / 1.0
Table 4 shows the results of measuring the light emission characteristics of the nitride-based phosphor obtained by changing the alkaline earth element according to the above composition ratio. For comparison, the results of Example 9 in Table 4 are also shown.

The nitride-based phosphors of Examples 16 to 19 exhibit a color tone different from that of Example 9. Thereby, a light emitting device having a desired color tone from yellow green to yellow can be manufactured.
[Examples 20 to 23]

Next, as Examples 20 to 23, the nitride phosphors represented by the general formula Ca 0.99-b Al 1.000 Si 1.000 B 0.01 N 3.01 : 0.010 Ce, bEu were similarly used by changing the value of b. A nitride-based phosphor is produced. Here, the value of b in each example is as follows.
Example 20... B = 0.002
Example 21... B = 0.004
Example 22... B = 0.006
Example 23... B = 0.008
Table 5 shows the results of measuring the emission characteristics of each nitride-based phosphor produced in order to investigate the effect of the amount of Eu in the nitride-based phosphor activated with Ce and Eu according to the above composition ratio. For comparison, the results of Example 2 in Table 1 are also shown.

In Examples 20 to 23, Eu is added in addition to Ce serving as the emission center. By adding Eu to Ce, the color tone was changed, and the peak wavelength was also greatly shifted to the long wavelength side. Further, it can be seen that although the luminance is lowered, the peak intensity is increased. A light emitting device having a desired color tone of yellow to red light emission can be manufactured.
[Examples 24-26]

Next, as Examples 24-26, for nitride-based phosphors represented by the general formula Ca 1.000-2c Al 1.000 Si 1.000 N 3.01 : cCe, cTb, the value of c is changed to similarly nitride-based fluorescence. Create a body. Here, the value of c in each example is as follows.
Example 24 c = 0.005
Example 25... C = 0.010
Example 26... C = 0.030
Table 6 shows the results of producing a nitride-based phosphor activated with Ce and Tb according to the above composition ratio and measuring the light emission characteristics.

In Examples 24 to 26, Tb was activated in addition to Ce, but it was found that even when Tb was added, it had high luminance and peak intensity.
[Examples 27 to 30]

Next, as Examples 27 to 30, the ratio of Ca / Si / Al is used for the nitride-based phosphor represented by the general formula Ca w (1-0.01) Al x Si y B z N 3.01 : 0.01 wCe. Table 7 shows the results of measuring the emission characteristics of nitride-based phosphors produced in the same manner by changing. For comparison, the results of Example 1 in Table 1 are also shown.

In Examples 27 to 30, Ca: Al: Si = 0.99: 1: 1 in Example 1 was slightly adjusted, but each had a color tone and peak intensity different from those in Example 1. By utilizing this, a light emitting device having a high luminance and a desired color tone can be manufactured.
[Examples 31 to 40]

Next, as Examples 31 to 40, nitride type phosphors represented by the general formula Ca w (1-0.01) Al x Si y B z N 3.01 : 0.01 wCe as in Examples 27 to 30 above. The nitride phosphors were similarly produced by changing the ratio of Ca / Si / Al, and the emission characteristics when excited with a blue LED having a peak at 400 nm and a blue LED having a peak at 460 nm as an excitation light source, respectively. Is shown in Table 8. For comparison, the results of Example 1 in Table 1 are also shown.

  Examples 31 to 40 show the light emission characteristics when Ca: Al: Si = 0.99: 1: 1 in Example 1 is significantly changed as compared with Table 7. Example 1 has high emission luminance even when excited at 400 nm or excited at 460 nm. On the other hand, the nitride-based phosphors of Examples 31 to 38 have a color tone different from that of Example 1, and the emission luminance at 460 nm excitation is low, but relatively high emission luminance and peak at 400 nm excitation. Has strength. By utilizing this, a light emitting device having a high luminance and a desired color tone can be manufactured.

  As described above, the light emitting device using the nitride-based phosphor according to the embodiment of the present invention absorbs light from an excitation light source having an emission peak wavelength in the short wavelength region from near ultraviolet to visible light, and has a wavelength By performing the conversion, it is possible to emit a light emission color different from the light emission color from the excitation light source. In particular, since the nitride-based phosphor has a light emission peak wavelength in a blue-green to yellow-green color region, it has extremely high light emission efficiency. Nitride-based phosphors are expected to be wavelength-converting phosphors for white light-emitting devices that are extremely excellent in light emission characteristics using blue light-emitting diodes or ultraviolet light-emitting diodes as light sources because of their high stability to heat.

  The nitride-based phosphor of the present invention and a light-emitting device using the same have a light emission characteristic using a fluorescent display tube, a display, a PDP, a CRT, a FL, a FED, a projection tube, etc., particularly a blue light-emitting diode or an ultraviolet light-emitting diode as a light source. It can be suitably used for an extremely excellent white illumination light source, LED display, backlight light source, traffic light, illumination switch, various sensors, various indicators, and the like.

1 is a schematic cross-sectional view showing a bullet-type light emitting device according to Embodiment 1 of the present invention. (A) is a top view which shows the surface mounted light-emitting device based on Embodiment 2 of this invention, (b) is the sectional drawing. It is a schematic cross section which shows the cap type light-emitting device which concerns on Embodiment 3 of this invention. It is process drawing which shows the manufacturing method of nitride type fluorescent substance. It is a graph which shows the emission spectrum of the fluorescent substance of Example 1,2. It is a graph which shows the excitation spectrum of the fluorescent substance of Example 1, 2, and the excitation spectrum of YAG: Ce. It is a graph which shows the reflection spectrum of the fluorescent substance of Example 1,2. 2 is an electron micrograph of the phosphor of Example 1. FIG. 4 is an electron micrograph of the phosphor of Example 2. It is a graph which shows the emission spectrum of the fluorescent substance of Example 6, 7, 8. It is a graph which shows the excitation spectrum of the fluorescent substance of Example 6, 7, 8. It is a graph which shows the reflection spectrum of the fluorescent substance of Example 6, 7, 8.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Package 2 ... Semiconductor light emitting element 3 ... Phosphor layer 4 ... Wire 10 ... Light emitting element 11 ... Fluorescent member 12 ... Coating member 13 ... Lead frame 13a ... Mount lead 13b ... Inner lead 14 ... Conductive wire 15 ... Mold member 16 ... cap 101 ... light emitting element 102 ... lead electrode 104 ... wire 103 ... insulating sealing material 105 ... package 106 ... lid 107 ... window 108 ... phosphor 109 ... coating member

Claims (6)

  1. A nitride-based phosphor activated with cerium that absorbs near ultraviolet or blue light and emits yellow light,
    At least one selected from the group consisting of Mg, Ca, Sr and Ba;
    Al and
    Si,
    N-based phosphor having at least N.
  2. The nitride-based phosphor according to claim 1,
    A nitride-based phosphor represented by the following general formula, wherein w, x, y, and z are in the following ranges.
    M w Al x Si y B z N ((2/3) w + x + (4/3) y + z): Ce
    M is at least one selected from the group consisting of Mg, Ca, Sr, and Ba.
    0.04 ≦ w ≦ 9, x = 1, 0.056 ≦ y ≦ 18, 0 ≦ z ≦ 0.5
  3. The nitride-based phosphor according to claim 1 or 2,
    Further, a nitride phosphor containing a rare earth element.
  4. The nitride phosphor according to any one of claims 1 to 3, wherein
    A nitride-based phosphor comprising O in the composition of the nitride-based phosphor.
  5. The nitride-based phosphor according to any one of claims 1 to 4,
    An average particle size of the nitride-based phosphor is 2 μm to 15 μm.
  6. An excitation light source having a first emission spectrum that emits near ultraviolet to blue light;
    One or more phosphors that absorb at least part of the first emission spectrum of the excitation light source and emit a second emission spectrum;
    A light emitting device comprising:
    The light emitting device, wherein the phosphor includes the nitride phosphor according to any one of claims 1 to 5.
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KR101639992B1 (en) 2015-06-04 2016-07-15 한국화학연구원 Manufacturing method of oxynitride phosphor using alkaline earth metal silicates

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