JP4535236B2 - Fluorescent member, fluorescent member manufacturing method, and semiconductor light emitting device - Google Patents
Fluorescent member, fluorescent member manufacturing method, and semiconductor light emitting device Download PDFInfo
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- JP4535236B2 JP4535236B2 JP2004066572A JP2004066572A JP4535236B2 JP 4535236 B2 JP4535236 B2 JP 4535236B2 JP 2004066572 A JP2004066572 A JP 2004066572A JP 2004066572 A JP2004066572 A JP 2004066572A JP 4535236 B2 JP4535236 B2 JP 4535236B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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Description
本発明は、半導体発光素子から発光した光により蛍光体を発光させる半導体発光装置用の蛍光部材、蛍光部材の製造方法及びこれを用いた半導体発光装置に関する。 The present invention relates to a fluorescent member for a semiconductor light emitting device that emits a phosphor by light emitted from a semiconductor light emitting element, a method for manufacturing the fluorescent member , and a semiconductor light emitting device using the same.
発光ダイオード(LED:Light Emitting Diode)は、光を放射する半導体発光素子であり、電気エネルギーを紫外光、可視光、赤外光などに変換するものである。例えば、可視光を利用するものとしては、GaP、GaAsP、GaAlAs、InGaN等の発光材料で形成した半導体発光素子があり、これらを透明樹脂等で封止したLEDランプが広く使用されている。また、発光材料をプリント基板や金属リードの上面に固定し、数字や文字をかたどった透明樹脂ケースで封止したディスプレイ型のLEDランプなども多用されている。 A light emitting diode (LED: Light Emitting Diode) is a semiconductor light emitting element that emits light, and converts electrical energy into ultraviolet light, visible light, infrared light, and the like. For example, as a device using visible light, there is a semiconductor light emitting element formed of a light emitting material such as GaP, GaAsP, GaAlAs, InGaN, etc., and LED lamps in which these are sealed with a transparent resin or the like are widely used. In addition, a display-type LED lamp in which a light emitting material is fixed on the upper surface of a printed circuit board or a metal lead and sealed with a transparent resin case shaped like a number or letter is also frequently used.
また、発光ダイオードは半導体発光素子であるため、寿命が長く、信頼性も高く、光源として用いた場合には、その交換作業も軽減できることから、携帯通信機器、パーソナルコンピュータ周辺機器、OA機器、家庭用電気機器、オーディオ機器、各種スイッチ、バックライト用光源、掲示板等の各種表示装置などの構成部品として広く使用されている。 In addition, since the light emitting diode is a semiconductor light emitting element, it has a long lifetime, high reliability, and when used as a light source, the replacement work can be reduced. Therefore, portable communication devices, personal computer peripheral devices, OA devices, homes It is widely used as a component part for various display devices such as electrical equipment, audio equipment, various switches, light sources for backlights, and bulletin boards.
LEDランプは、各種の蛍光体粒子を、半導体発光素子を封止する透明樹脂中に含有させることにより、LEDランプから放射される光の色を変化させることが可能であり、使用用途に応じて青色から赤色まで可視光領域の広い範囲の色を得ることが可能である。 The LED lamp can change the color of the light emitted from the LED lamp by including various phosphor particles in the transparent resin that seals the semiconductor light emitting element. It is possible to obtain a wide range of colors in the visible light region from blue to red.
特に、最近では、上記各種表示装置の色彩に対する需要者の要求が高まり、表示装置に微妙な色合いをより精密に再現できる性能が要求されていると共に、1個のLEDランプにより白色や各種の中間色を発光させることができることが強く求められている。 In particular, recently, demands from consumers for the colors of the above various display devices have increased, and the display device has been required to have a performance capable of reproducing subtle hues more precisely, and white and various intermediate colors can be achieved with a single LED lamp. There is a strong demand to be able to emit light.
そのため、LEDランプの半導体発光素子の表面に、赤色、緑色、青色の各種蛍光体を塗布したり、LEDランプの封止材、コーティング材等に上記各種蛍光体を含有させたりすることにより、1個のLEDランプで白色や各種の中間色を表示できるように構成することも試行されている。 Therefore, by applying various phosphors of red, green, and blue to the surface of the semiconductor light emitting element of the LED lamp, or by incorporating the various phosphors into the sealing material, coating material, etc. of the LED lamp, 1 Attempts have also been made to configure white LED and various intermediate colors with a single LED lamp.
このような蛍光体の中で、長波長紫外線又は短波長可視光線(350〜420nm)で励起する蛍光体として、現在、主に使用されているものとしては、発光色が青色のBaMg2Al16O27:Eu、(Sr,Ca,Ba)5(PO4)3Cl:Eu、発光色が緑色のBaMg2Al16O27:Eu,Mn、Zn2GeO4:Mn、発光色が赤色のY2O2S:Eu、La2O2S:Eu、3.5MgO・0.5MgF2・GeO2:Mnなどがあり、これらの発光蛍光体を適宜用いることにより広い範囲の発光色を得ることができる。 Among such phosphors, currently used as a phosphor excited by long-wavelength ultraviolet light or short-wavelength visible light (350 to 420 nm) is a BaMg 2 Al 16 whose emission color is blue. O 27 : Eu, (Sr, Ca, Ba) 5 (PO 4 ) 3 Cl: Eu, emission color of green BaMg 2 Al 16 O 27 : Eu, Mn, Zn 2 GeO 4 : Mn, emission color of red Y 2 O 2 S: Eu, La 2 O 2 S: Eu, 3.5MgO.0.5MgF 2 .GeO 2 : Mn, and the like, and a wide range of emission colors can be obtained by appropriately using these light emitting phosphors. be able to.
しかし、このような蛍光体を利用するLEDランプは、白色や中間色の光を自在に作り出すことができるものの、例えば、照明用として用いるには、従来型のいわゆる蛍光灯などに比べて十分な明るさが確保できておらず、発光強度の更なる向上が必要とされている。 However, although LED lamps using such phosphors can freely produce white or intermediate-color light, for example, they are sufficiently brighter than conventional so-called fluorescent lamps to be used for illumination. Therefore, further improvement in emission intensity is required.
特に、上記赤色発光蛍光体には、青色発光蛍光体、緑色発光蛍光体と比較して長波長紫外線及び短波長可視光線(350〜420nm)に対する発光が弱いという問題がある。 In particular, the red light-emitting phosphor has a problem that light emission with respect to long-wavelength ultraviolet light and short-wavelength visible light (350 to 420 nm) is weaker than blue light-emitting phosphor and green light-emitting phosphor.
そのため、これらの波長の光を用いて白色系の発光色を得る場合、赤色発光蛍光体の割合を多くしなければならず、コストが高くなること、白色系の発光色は、赤色、緑色、青色の発光量のバランスを合わせることにより白色を得ることができるものであるから、白色系の発光色を得るためには、赤色の発光量に合わせて緑色及び青色の発光量を減らさざるを得ず、また、蛍光体の使用量にも上限があるため、得られる白色光の発光量が少なくなってしまい、高輝度の白色が得られないことなどが問題となっている。 Therefore, when obtaining a white emission color using light of these wavelengths, the proportion of the red light emitting phosphor must be increased, the cost is increased, and the white emission color is red, green, Since white can be obtained by adjusting the balance of the blue light emission amount, in order to obtain a white light emission color, the green and blue light emission amounts must be reduced in accordance with the red light emission amount. In addition, since there is an upper limit to the amount of phosphor used, there is a problem in that the amount of white light obtained is reduced, and high brightness white cannot be obtained.
また、近年、長波長紫外線及び短波長可視光線領域の光を発光し、高輝度発光を可能とするLED素子として注目されているInGaN系素子(非特許文献1参照)は、外部量子効率が最も高い値を示す発光波長が400nm前後、特に400〜410nm程度の波長にあることが報告されており、この範囲の波長において赤色光を高強度で発光できる赤色発光蛍光体が求められている。しかしながら、酸化物系化合物の電子対の励起エネルギーに対応する波長は紫外領域にあり、長波長紫外線及び短波長可視光線(350〜420nm)の波長は蛍光体の吸収端と重なるため、これらの赤色発光蛍光体の350nmより長波長側での吸収強度は、波長が長くなるに従って急激に低下し、400nm以上の範囲ではかなり低くなってしまう。 In recent years, InGaN-based devices (see Non-Patent Document 1), which are attracting attention as LED devices that emit light in the long-wavelength ultraviolet and short-wavelength visible light regions and enable high-intensity light emission, have the highest external quantum efficiency. It has been reported that an emission wavelength exhibiting a high value is around 400 nm, particularly about 400 to 410 nm, and a red light emitting phosphor capable of emitting red light with high intensity at a wavelength in this range is desired. However, the wavelength corresponding to the excitation energy of the electron pair of the oxide compound is in the ultraviolet region, and the wavelengths of long-wavelength ultraviolet light and short-wavelength visible light (350 to 420 nm) overlap with the absorption edge of the phosphor. The absorption intensity of the light emitting phosphor on the longer wavelength side than 350 nm rapidly decreases as the wavelength becomes longer, and becomes considerably low in the range of 400 nm or more.
励起波長を長波長側へシフトさせた赤色発光蛍光体としては、例えば、ユーロピウムで付活された希土類酸硫化物蛍光体が特開平11−246857号公報(特許文献1)や特開2000−144130号公報(特許文献2)などにおいて提案されているが、これらの蛍光体の400nm以上の励起波長に対する発光強度は十分なものとはなっていなかった。また、本発明者は、特開2003−41252号公報(特許文献3)において、Euと、Y,La,Gd及びLuからなる群より選ばれた少なくとも1種とを含む金属酸化物系の赤色発光蛍光体について報告しているが、これらの蛍光体の400nm以上の励起波長に対する発光強度について更なる向上が求められていた。 As red light emitting phosphors whose excitation wavelength is shifted to the longer wavelength side, for example, rare earth oxysulfide phosphors activated by europium are disclosed in JP-A-11-246857 (Patent Document 1) and JP-A-2000-144130. However, the emission intensity of these phosphors with respect to the excitation wavelength of 400 nm or more has not been sufficient. In addition, the present inventor disclosed in Japanese Patent Application Laid-Open No. 2003-41252 (Patent Document 3) that a metal oxide red containing Eu and at least one selected from the group consisting of Y, La, Gd and Lu. Although the luminescent phosphors have been reported, further improvement has been required for the luminescence intensity of these phosphors with respect to the excitation wavelength of 400 nm or more.
一方、従来、蛍光灯(3波長型蛍光ランプ)等に用いられている蛍光体、例えば、LaPO4:Ce3+,Tb3+やCeMgAl11O19:Tb3+等に代表されるTb3+イオンの5D4→7F5遷移により発光する緑色発光蛍光体は、蛍光灯で利用される短波長の紫外線領域においては良好な発光を与えるものの、高輝度LEDランプで利用する波長350〜500nmの長波長紫外線又は可視光線に対しては、十分な発光が得られないものであった。 On the other hand, phosphors conventionally used in fluorescent lamps (three-wavelength fluorescent lamps) and the like, for example, Tb 3 represented by LaPO 4 : Ce 3+ , Tb 3+ , CeMgAl 11 O 19 : Tb 3+ and the like. + green-emitting phosphor which emits light by 5 D 4 → 7 F 5 transition ions, although giving good luminous in the ultraviolet region of the short wavelength is used in fluorescent lamps, the wavelength utilized in the high-intensity LED lamps 350 Sufficient light emission was not obtained with respect to 500 nm long wavelength ultraviolet rays or visible rays.
また、波長350〜500nmの長波長紫外線又は可視光線を用いて白色系の発光色を得る場合、例えば、緑色発光蛍光体として上記した緑色発光蛍光体を用いても、得られる緑色光の視感度がずれているため、高輝度の白色光が得られない。 Further, when a white emission color is obtained using long-wavelength ultraviolet light or visible light having a wavelength of 350 to 500 nm, for example, even when the above-described green light emitting phosphor is used as the green light emitting phosphor, the obtained green light visibility is obtained. Therefore, white light with high luminance cannot be obtained.
上述したような長波長紫外線又は可視光線により励起されて発光する蛍光体が種々検討され、これらの蛍光体を適宜用いることにより広い範囲の発光色を得ることができるようになりつつあるが、高輝度白色光を与えるLEDランプの実用化のためには、更に発光強度が高く、視感度が良好な光を発光する蛍光体を開発することが必要である。特に、視感度の点では、上記した緑色発光蛍光体で得られる緑色光は、視感度が良好とされる555nmからかなりずれており、これが高輝度化を妨げる要因となっていた。 Various phosphors that emit light when excited by long-wavelength ultraviolet light or visible light as described above have been studied, and a wide range of emission colors can be obtained by appropriately using these phosphors. In order to put the LED lamp that gives luminance white light into practical use, it is necessary to develop a phosphor that emits light with higher luminous intensity and good visibility. In particular, in terms of visibility, the green light obtained with the above-described green light-emitting phosphor is considerably deviated from 555 nm, which is considered to have good visibility, and this has been a factor that hinders high brightness.
一方、青色乃至青緑色の可視光(430〜500nm)を発光するLEDと、この波長で黄色を発光する蛍光体YAG:Ce3+等の蛍光体とを用いれば、白色光を発光するLEDランプを得ることができるが、この波長領域で有効な緑色発光を与える蛍光体がなかったため、自由に発光色を変化させることができなかった。 On the other hand, if an LED that emits blue to blue-green visible light (430 to 500 nm) and a phosphor such as YAG: Ce 3+ that emits yellow light at this wavelength are used, an LED lamp that emits white light. However, since there was no phosphor that gave effective green emission in this wavelength region, the emission color could not be changed freely.
なお、この発明に関する先行技術文献情報としては以下のものがある。 The prior art document information relating to the present invention includes the following.
本発明は、上記事情に鑑みなされたものであり、高輝度の発光光が得られる蛍光部材及び半導体発光装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorescent member and a semiconductor light emitting device capable of obtaining high-luminance emitted light.
本発明者は、上記問題を解決するため鋭意検討を重ねた結果、半導体発光素子から発光した光により励起されて発光する蛍光部材を、無機蛍光体粒子を焼結してなる焼結体とし、この焼結体からなる蛍光部材を半導体発光素子からの光の光路上に位置するように設けた半導体発光装置が、無機蛍光体を粒子状で用いた場合に比べて輝度が格段に向上し、特に、波長350〜500nmの長波長紫外線から短波長可視光線の領域の広い範囲の波長に対して安定して高い強度の発光が得られることを見出し、本発明をなすに至った。 As a result of intensive studies to solve the above problems, the present inventor made a fluorescent member excited by light emitted from a semiconductor light emitting element to emit light, a sintered body formed by sintering inorganic phosphor particles, The semiconductor light emitting device in which the fluorescent member made of this sintered body is provided so as to be positioned on the optical path of light from the semiconductor light emitting element, the luminance is remarkably improved as compared with the case where the inorganic fluorescent material is used in the form of particles, In particular, the inventors have found that stable and high-intensity light emission can be obtained with respect to a wide range of wavelengths ranging from a long-wavelength ultraviolet ray having a wavelength of 350 to 500 nm to a short-wavelength visible light region, and have led to the present invention.
即ち、本発明は、以下の蛍光部材、蛍光部材の製造方法及び半導体発光装置を提供する。
[1]半導体発光素子から発光した光により蛍光体を発光させる半導体発光装置の蛍光部材であって、上記蛍光体が、原料混合物を焼成し、粉砕した無機蛍光体粒子を成形容器内で圧縮成形し、該圧縮成形体を更に800〜1000℃の焼成温度にて焼成して得られた焼結体であり、且つ下記組成式(1)
LiyA1 (1-y)EuxLn1 (1-x)M1 2O8…(1)
(式中、A1はNa及びKから選ばれる少なくとも1種、Ln1はYを含む希土類元素(Euを除く)から選ばれる少なくとも1種、M1はMo及びWから選ばれる少なくとも1種であり、xは0.8≦x≦1を満たす正数、yは0.4≦y≦1を満たす正数である。)
で表される赤色発光蛍光体であることを特徴とする蛍光部材。
[2]半導体発光素子と、これを封止する封止材とを備える半導体発光装置であって、[1]記載の蛍光部材が、上記光の光路上に位置するように設けられていることを特徴とする半導体発光装置。
[3]上記蛍光部材が上記封止材内に封止されていることを特徴とする[2]記載の半導体発光装置。
[4]上記蛍光部材が上記封止材上に載置されていることを特徴とする[2]記載の半導体発光装置。
[5]半導体発光素子と、上記半導体発光素子から発光した光が照射されるように設けられた反射部材とを備える半導体発光装置であって、[1]記載の蛍光部材が、上記反射部材上に設けられていることを特徴とする半導体発光装置。
[6]上記半導体発光素子が波長350〜500nmの光を発光するものであることを特徴とする[2]乃至[5]のいずれか1項記載の半導体発光装置。
[7]半導体発光素子から発光した光により蛍光体を発光させる半導体発光装置の蛍光部材の製造方法であって、上記蛍光体が、下記組成式(1)
LiyA1 (1-y)EuxLn1 (1-x)M1 2O8…(1)
(式中、A1はNa及びKから選ばれる少なくとも1種、Ln1はYを含む希土類元素(Euを除く)から選ばれる少なくとも1種、M1はMo及びWから選ばれる少なくとも1種であり、xは0.8≦x≦1を満たす正数、yは0.4≦y≦1を満たす正数である。)
で表される赤色発光蛍光体であり、原料混合物を焼成し、粉砕した無機蛍光体粒子を成形容器内で圧縮成形し、該圧縮成形体を更に800〜1000℃の焼成温度にて焼成することにより、上記赤色発光蛍光体を得ることを特徴とする蛍光部材の製造方法。
That is, the present invention provides the following fluorescent member, method for manufacturing the fluorescent member, and semiconductor light emitting device.
[1] A fluorescent member of a semiconductor light-emitting device that emits a phosphor by light emitted from a semiconductor light-emitting element, wherein the phosphor is formed by compression-molding a pulverized inorganic phosphor particle by firing a raw material mixture And a sintered body obtained by further firing the compression-molded body at a firing temperature of 800 to 1000 ° C., and the following composition formula (1)
Li y A 1 (1-y) Eu x Ln 1 (1-x) M 1 2 O 8 (1)
(Wherein at least one A 1 is selected from Na and K, Ln 1 is at least one kind of element selected from rare earth elements including Y (other than Eu), M 1 is at least one selected from Mo and W X is a positive number satisfying 0.8 ≦ x ≦ 1, and y is a positive number satisfying 0.4 ≦ y ≦ 1.)
A fluorescent member characterized by being a red light emitting phosphor represented by the formula:
[2] A semiconductor light-emitting device including a semiconductor light-emitting element and a sealing material for sealing the semiconductor light-emitting element, wherein the fluorescent member according to [1] is provided so as to be positioned on the optical path of the light. A semiconductor light-emitting device.
[3] The semiconductor light emitting device according to [2], wherein the fluorescent member is sealed in the sealing material.
[4] The semiconductor light emitting device according to [2], wherein the fluorescent member is placed on the sealing material.
[5] A semiconductor light-emitting device comprising a semiconductor light-emitting element and a reflecting member provided so as to be irradiated with light emitted from the semiconductor light-emitting element, wherein the fluorescent member according to [1] is on the reflecting member A semiconductor light-emitting device provided in
[6] The semiconductor light-emitting device according to any one of [2] to [5], wherein the semiconductor light-emitting element emits light having a wavelength of 350 to 500 nm.
[7] A method of manufacturing a fluorescent member of a semiconductor light emitting device that emits a phosphor by light emitted from a semiconductor light emitting element, wherein the phosphor is represented by the following composition formula (1):
Li y A 1 (1-y) Eu x Ln 1 (1-x) M 1 2 O 8 (1)
(In the formula, A 1 is at least one selected from Na and K , Ln 1 is at least one selected from rare earth elements including Y (excluding Eu), and M 1 is at least one selected from Mo and W. X is a positive number satisfying 0.8 ≦ x ≦ 1, and y is a positive number satisfying 0.4 ≦ y ≦ 1.)
The raw material mixture is fired, the pulverized inorganic phosphor particles are compression molded in a molding container, and the compression molded body is further fired at a firing temperature of 800 to 1000 ° C. To obtain the red light-emitting phosphor.
本発明の蛍光部材は、無機蛍光体粒子を焼結してなる焼結体であることから、これを半導体発光素子から発光した光、特に、波長350〜500nmの光により蛍光体を発光させる半導体発光装置に用いれば、従来にない高い発光強度を得ることができる。 Since the fluorescent member of the present invention is a sintered body obtained by sintering inorganic phosphor particles, the semiconductor emits the phosphor with light emitted from the semiconductor light emitting element, particularly light with a wavelength of 350 to 500 nm. When used in a light emitting device, it is possible to obtain an unprecedented high emission intensity.
特に、上記無機蛍光体として、下記組成式(1)
LiyA1 (1-y)EuxLn1 (1-x)M1 2O8…(1)
(式中、A1はNa及びKから選ばれる少なくとも1種、Ln1はYを含む希土類元素(Euを除く)から選ばれる少なくとも1種、M1はMo及びWから選ばれる少なくとも1種であり、xは0.8≦x≦1を満たす正数、yは0.4≦y≦1を満たす正数である。)
で表される赤色発光蛍光体を用いれば、特に、InGaN系素子等の外部量子効率が最も高い値を示す発光波長が400〜410nm、特に405nm前後にある素子を用いた半導体発光装置において、この赤色発光蛍光体のみを用いれば、高輝度で赤色を発光する半導体発光装置、更には、緑色発光蛍光体、青色発光蛍光体と併用すれば、高輝度で白色若しくは中間色を発光する半導体発光装置を得ることができる。
In particular, as the inorganic phosphor, the following composition formula (1)
Li y A 1 (1-y) Eu x Ln 1 (1-x) M 1 2 O 8 (1)
(In the formula, A 1 is at least one selected from Na and K , Ln 1 is at least one selected from rare earth elements including Y (excluding Eu), and M 1 is at least one selected from Mo and W. X is a positive number satisfying 0.8 ≦ x ≦ 1, and y is a positive number satisfying 0.4 ≦ y ≦ 1.)
In particular, in a semiconductor light emitting device using an element having an emission wavelength of 400 to 410 nm, particularly around 405 nm, which exhibits the highest external quantum efficiency, such as an InGaN-based element. A semiconductor light-emitting device that emits red light with high luminance if only a red light-emitting phosphor is used, and a semiconductor light-emitting device that emits white or intermediate color with high luminance when used in combination with a green light-emitting phosphor and a blue light-emitting phosphor. Obtainable.
以下、本発明について更に詳述する。
本発明の蛍光部材は、半導体発光素子から発光した光により蛍光体を発光させる半導体発光装置の蛍光部材であり、この蛍光部材は、無機蛍光体粒子を焼結してなる焼結体である。このような半導体発光装置の蛍光部材として無機蛍光体粒子を焼結してなる焼結体を用いることにより、無機蛍光体を粒子状で用いた場合に比べて輝度が格段に向上し、特に、波長350〜500nmの長波長紫外線から短波長可視光線の領域の広い範囲の波長に対して安定して高い強度の発光が得られる。
The present invention will be described in detail below.
The fluorescent member of the present invention is a fluorescent member of a semiconductor light emitting device that emits a phosphor by light emitted from a semiconductor light emitting element, and this fluorescent member is a sintered body formed by sintering inorganic phosphor particles. By using a sintered body obtained by sintering inorganic phosphor particles as a fluorescent member of such a semiconductor light emitting device, the luminance is remarkably improved as compared with the case where the inorganic phosphor is used in the form of particles. High intensity light emission can be stably obtained with respect to a wide range of wavelengths in the range from long-wavelength ultraviolet light having a wavelength of 350 to 500 nm to short-wavelength visible light.
本発明において、蛍光部材は焼結体であるが、このような焼結体は、従来公知の無機蛍光体粒子を焼結することにより得ることができる。 In the present invention, the fluorescent member is a sintered body, but such a sintered body can be obtained by sintering conventionally known inorganic phosphor particles.
焼結体を得るためには、まず、粒子状の無機蛍光体を作製する。粒子状の無機蛍光体は、従来公知の方法で製造することができ、例えば、原料として、無機蛍光体を構成する元素を含む酸化物、炭酸塩などを、焼成後に所定の組成となるように化学量論比で配合し、ボールミル等で混合して得た原料混合物を焼成し、必要に応じて水洗、粉砕、篩分けして得ることができる。 In order to obtain a sintered body, first, a particulate inorganic phosphor is prepared. The particulate inorganic phosphor can be produced by a conventionally known method. For example, an oxide or carbonate containing an element constituting the inorganic phosphor as a raw material has a predetermined composition after firing. The raw material mixture obtained by blending at a stoichiometric ratio and mixing with a ball mill or the like is fired, and can be obtained by washing, pulverizing, and sieving as necessary.
粒子状の無機蛍光体を得る場合の焼成の方法は、蛍光体として用いられる金属酸化物の製造に用いられる従来公知の方法を適用することが可能であり、特に限定されないが、例えばアルミナ製坩堝中に上記原料混合物を入れて、電気炉等の焼成炉で焼成して製造する方法が採用し得る。この場合、焼成温度は800〜1,000℃、特に850〜900℃であることが好ましく、また、焼成時間は30分〜48時間、特に2〜12時間であることが好ましい。 The firing method for obtaining the particulate inorganic phosphor can be a conventionally known method used for producing a metal oxide used as the phosphor, and is not particularly limited. For example, an alumina crucible is used. A method can be adopted in which the raw material mixture is put in and fired in a firing furnace such as an electric furnace. In this case, the firing temperature is preferably 800 to 1,000 ° C., particularly preferably 850 to 900 ° C., and the firing time is preferably 30 minutes to 48 hours, particularly preferably 2 to 12 hours.
次に、上記粒子状の無機蛍光体を、焼結させて焼結体を作製するが、この場合、焼結体の製造方法は、原料混合物を焼成し、粉砕した無機蛍光体粒子を成形容器内で圧縮成形し、該圧縮成形体を更に焼成する方法を採用し得る。この場合、焼成温度は800〜1,000℃、特に850〜900℃であることが好ましく、また、焼成時間は30分〜48時間、特に2〜12時間であることが好ましい。得られた焼結体は必要に応じ、所定の厚さ、表面精度、平坦度を得るために機械加工することも可能である。 Next, the particulate inorganic phosphor is sintered to produce a sintered body. In this case, the sintered body is produced by firing the raw material mixture and pulverizing the inorganic phosphor particles into a molded container. It is possible to employ a method in which the compression molding is further performed and the compression molding is further fired . In this case, the firing temperature is preferably 800 to 1,000 ° C., particularly preferably 850 to 900 ° C., and the firing time is preferably 30 minutes to 48 hours, particularly preferably 2 to 12 hours. The obtained sintered body can be machined to obtain a predetermined thickness, surface accuracy, and flatness, if necessary.
この場合、焼結させる無機蛍光体粒子の平均粒径は3〜100μm、特に5〜20μmであることが好ましい。粒径があまり大きいと所望の形状に圧縮成形することが困難となり、さらに焼結時により高温にする必要があるおそれがあり、粒径があまり小さいと大型形状の焼結体の作製が困難となるおそれがある。 In this case, the average particle diameter of the inorganic phosphor particles to be sintered is preferably 3 to 100 μm, particularly 5 to 20 μm. If the particle size is too large, it will be difficult to compression-mold into the desired shape, and it may be necessary to increase the temperature during sintering. If the particle size is too small, it will be difficult to produce a large-sized sintered body. There is a risk.
また、焼結体を作製する際、無機蛍光体粒子と共に、気孔形成材料として、樹脂、ゴム、エラストマー等の常温で固体状の有機材料、好ましくは粒子状の有機材料を混合して成形し、これを焼成することにより、所望のサイズの気孔を有する焼結体を得ることも可能であり、本発明の蛍光部材としては、このようなものを用いることも可能である。気孔形成材料としては、焼成温度以下で分解、気化する材料であれば問題ないが、組成に影響を与える金属イオンを含まないものが望ましい。また、無機蛍光体の焼結の際に、気孔形成材料は分解、気化するが、その際にカーボン、無機物質等の残査が残らない材料が望ましい。 Further, when producing a sintered body, together with inorganic phosphor particles, as a pore forming material, resin, rubber, elastomer and the like solid organic material at room temperature, preferably mixed with a particulate organic material, By firing this, it is also possible to obtain a sintered body having pores of a desired size, and it is also possible to use such a fluorescent member of the present invention. As the pore forming material, there is no problem as long as it is a material that decomposes and vaporizes below the firing temperature, but a material that does not contain metal ions that affect the composition is desirable. Further, when the inorganic phosphor is sintered, the pore-forming material is decomposed and vaporized, but at this time, a material that does not leave a residue such as carbon or an inorganic substance is desirable.
本発明の蛍光部材は、シート状、キャップ状など、適宜な形状のものを用い得るが、その厚さは、0.1〜10mm、特に0.3〜0.4mmのものが好ましい。 The fluorescent member of the present invention may have a suitable shape such as a sheet shape or a cap shape, but the thickness is preferably 0.1 to 10 mm, particularly preferably 0.3 to 0.4 mm.
本発明において、無機蛍光体としては、下記組成式(1)
LiyA1 (1-y)EuxLn1 (1-x)M1 2O8…(1)
(式中、A1はNa及びKから選ばれる少なくとも1種、Ln1はYを含む希土類元素(Euを除く)から選ばれる少なくとも1種、好ましくはSm、M1はMo及びWから選ばれる少なくとも1種であり、xは0.8≦x≦1、好ましくは0.8≦x<1を満たす正数、yは0.4≦y≦1を満たす正数である。)
で表される赤色発光蛍光体を採用し得る。
In the present invention, as the inorganic phosphor, the following composition formula (1)
Li y A 1 (1-y) Eu x Ln 1 (1-x) M 1 2 O 8 (1)
( Wherein A 1 is at least one selected from Na and K , Ln 1 is at least one selected from rare earth elements including Y (excluding Eu), preferably Sm, M 1 is selected from Mo and W At least one kind, x is 0.8 ≦ x ≦ 1, preferably 0.8 ≦ x <1, and y is a positive number satisfying 0.4 ≦ y ≦ 1.)
The red light-emitting phosphor represented by
このような蛍光体は、原料として、蛍光体を構成する元素を含む酸化物、炭酸塩など、例えば、Li2CO3、Na2CO3、Eu2O3、Sm2O3、Tb4O7、W2O3、Mo2O3等を、焼成後に上記組成式(1)で示される所定の組成となるように化学量論比で配合し、ボールミル等で混合して得た原料混合物を焼成し、必要に応じて水洗、粉砕、篩分けして得ることができる。 Such phosphors are used as raw materials such as oxides and carbonates containing elements constituting the phosphor, such as Li 2 CO 3 , Na 2 CO 3 , Eu 2 O 3 , Sm 2 O 3 , Tb 4 O. 7 , W 2 O 3 , Mo 2 O 3 and the like are mixed in a stoichiometric ratio so as to have a predetermined composition represented by the above composition formula (1) after firing, and mixed with a ball mill or the like to obtain a raw material mixture Can be obtained by firing, washing, pulverizing, and sieving as necessary.
また、無機蛍光体としては、上記組成式(1)で示される赤色発光蛍光体に、例えば、Y2O2S:Eu、La2O2S:Eu、3.5MgO・0.5MgF2・GeO2:Mn等の赤色発光蛍光体を添加したものを用いることも可能である。 Further, as the inorganic phosphor, for example, Y 2 O 2 S: Eu, La 2 O 2 S: Eu, 3.5MgO.0.5MgF 2 .multidot. It is also possible to use a material to which a red light emitting phosphor such as GeO 2 : Mn is added.
更に、焼結体と焼結体を構成する無機蛍光体とは異なる他の蛍光体とを組み合わせることも可能である。この場合、例えば、焼結体の少なくとも1面に上記他の蛍光体を塗布することができる。他の蛍光体を塗布する場合、この他の蛍光体と共に、従来使用されているバインダーを含む塗布液を使用できる。バインダーとしては、ニトロセルロース、酢酸セルロース、エチルセルロース、ポリビニルブチラール、ポリエステル、塩化ビニル、酢酸ビニル、アクリル樹脂、ポリウレタン等の従来公知の樹脂などを使用できる。また、ゴム、樹脂、エラストマーなどの材料、好ましくは透明な材料に上記他の蛍光体を分散させ硬化させてもよい。 Furthermore, it is also possible to combine the sintered body and another phosphor different from the inorganic phosphor constituting the sintered body. In this case, for example, the other phosphor can be applied to at least one surface of the sintered body. When other phosphors are applied, a coating solution containing a conventionally used binder can be used together with the other phosphors. As the binder, conventionally known resins such as nitrocellulose, cellulose acetate, ethyl cellulose, polyvinyl butyral, polyester, vinyl chloride, vinyl acetate, acrylic resin, and polyurethane can be used. Further, the other phosphor may be dispersed and cured in a material such as rubber, resin, or elastomer, preferably a transparent material.
次に、本発明の半導体発光装置について説明する。
まず、本発明の半導体発光装置の第1の態様について説明する。この第1の態様の半導体発光装置は、半導体発光素子と、これを封止する封止材とを備える半導体発光装置であり、上述した蛍光部材が、上記光の光路上に位置するように設けられているものである。
Next, the semiconductor light emitting device of the present invention will be described.
First, a first aspect of the semiconductor light emitting device of the present invention will be described. The semiconductor light-emitting device according to the first aspect is a semiconductor light-emitting device including a semiconductor light-emitting element and a sealing material that seals the semiconductor light-emitting element, and is provided so that the fluorescent member described above is positioned on the optical path of the light. It is what has been.
第1の態様の半導体発光装置としては、特に、上記焼結体が上記封止材内に封止されているものを好ましく挙げることができる。このようなものとしては、例えば、図1に示されるような、リード1,2、半導体発光素子3、半導体発光素子3とリード2とを電気的に接続するリード細線4を、封止材5で砲弾型に封止した構造の、いわゆる砲弾タイプの発光ダイオードや、図2に示されるような、上面が開口した箱形の発光体収容部材6の内底から一対のリード1,2を発光体収容部材6の外部へ延出し、この発光体収容部材6の内部に半導体発光素子3やリード細線4,4を収容し、これらを接続して発光体収容部材6内部を封止材5で封止した構造の、いわゆるチップ型の発光ダイオードなどの封止材中に本発明の蛍光部材10を封止したものが挙げられる。
As the semiconductor light emitting device according to the first aspect, a semiconductor light emitting device in which the sintered body is sealed in the sealing material can be preferably exemplified. As such, for example, as shown in FIG. 1, the
また、半導体発光素子上に焼結体と焼結体を構成する無機蛍光体とは異なる他の蛍光体を含む蛍光層を設け、その発光方向前方に焼結体を設けたものも好適である。具体的には、図3に示されるような、リード1,2、半導体発光素子3、半導体発光素子3とリード2とを電気的に接続するリード細線4を、封止材5で砲弾型に封止した構造の、いわゆる砲弾タイプの発光ダイオードの半導体発光素子3上に蛍光層7を設けると共に、その発光方向前方に本発明の蛍光部材10を設けて半導体発光素子3等と共に封止したもの、図4に示されるような上面が開口した箱形の発光体収容部材6の内底から一対のリード1,2を発光体収容部材6の外部へ延出し、この発光体収容部材6の内部に半導体発光素子3やリード細線4,4を収容し、これらを接続して、発光体収容部材6内部を封止材5で封止した構造の、いわゆるチップ型の発光ダイオードの半導体発光素子3上に蛍光層7を設けると共に、その発光方向前方に本発明の蛍光部材10を設けて半導体発光素子3等と共に封止したものが挙げられる。
Further, it is also preferable to provide a sintered body and a fluorescent layer containing another phosphor different from the inorganic phosphor constituting the sintered body on the semiconductor light emitting element, and a sintered body provided in front of the light emitting direction. . Specifically, as shown in FIG. 3, the
また、この第1の態様の半導体発光装置としては、上記焼結体が上記封止材上に載置されているものも好適である。このようなものとしては、図5に示されるようなリード1,2、半導体発光素子3、半導体発光素子3とリード2とを電気的に接続するリード細線4を、封止材5で砲弾型に封止した構造の、いわゆる砲弾タイプの発光ダイオードや、図6に示されるような、上面が開口した箱形の発光体収容部材6の内底から一対のリード1,2を発光体収容部材6の外部へ延出し、この発光体収容部材6の内部に半導体発光素子3やリード細線4,4を収容し、これらを接続して発光体収容部材6内部を封止材5で封止した構造の、いわゆるチップ型の発光ダイオードの封止材5上に本発明の蛍光部材10を載置したものが挙げられる。
Moreover, as the semiconductor light emitting device of the first aspect, one in which the sintered body is placed on the sealing material is also suitable. As such, the
なお、第1の態様の半導体発光装置においては、樹脂、ゴム、エラストマー、ガラスなどの封止材材料に、焼結体である本発明の蛍光部材を構成する蛍光体とは異なる他の蛍光体を混合して封止してもよい。また、封止材中には色調変換材料として上述した蛍光体の他に、顔料、染料、擬似顔料などを添加してもよい。 In the semiconductor light emitting device of the first aspect, other phosphors different from the phosphor constituting the phosphor member of the present invention which is a sintered body are used as a sealing material such as resin, rubber, elastomer, glass, etc. May be mixed and sealed. In addition to the phosphor described above as a color tone conversion material, pigments, dyes, pseudo pigments, and the like may be added to the sealing material.
また、上記他の蛍光体を樹脂、ゴム、エラストマーなどに混合して成形した成形体を、焼結体と共に半導体発光素子の発光方向前方に設置してもよい。この場合、他の蛍光体を透光性の樹脂、ゴム、エラストマー又はガラス、特にシリコーン樹脂又はシリコーンゴムに分散させた成形体を用いることが好ましい。特に、複数種の蛍光体を分散させる場合、チキソトロピー調整剤で粘度を調整したシリコーンゴム組成物、シリコーン樹脂組成物などに混合し、これを硬化させる方法で分散させることが好ましい。また、成形体は、蛍光体を混合して分散させて1層としたものでも、蛍光体をいくつかの層にわけて分散させたものを積層したものでもよい。また、成形体には色調変換材料として上述した蛍光体の他に、顔料、染料、擬似顔料などを添加してもよい。 Moreover, you may install the molded object which mixed the said other fluorescent substance with resin, rubber | gum, an elastomer, etc. and was set in the light emission direction front direction of the semiconductor light-emitting element with the sintered compact. In this case, it is preferable to use a molded body in which another phosphor is dispersed in a translucent resin, rubber, elastomer, or glass, particularly silicone resin or silicone rubber. In particular, when a plurality of types of phosphors are dispersed, it is preferable to disperse the phosphors by mixing them with a silicone rubber composition or a silicone resin composition whose viscosity is adjusted with a thixotropy adjusting agent and curing the mixture. The molded body may be a single layer obtained by mixing and dispersing phosphors, or a laminate in which phosphors are dispersed in several layers. In addition to the phosphor described above as a color tone conversion material, pigments, dyes, pseudo pigments, and the like may be added to the molded body.
次に、本発明の半導体発光装置の第2の態様について説明する。この第2の態様の半導体発光装置は、半導体発光素子と、上記半導体発光素子から発光した光が照射されるように設けられた反射部材とを備える半導体発光装置であり、上述した蛍光部材が、上記反射部材上に設けられているものである。このようなものとしては、図7に示されるように、蛍光部材10を発光ダイオード8から離間する位置に設けると共に、この発光ダイオード8から発光した光を反射部材9で反射させる半導体発光装置が挙げられる。
Next, a second aspect of the semiconductor light emitting device of the present invention will be described. The semiconductor light-emitting device of this second aspect is a semiconductor light-emitting device comprising a semiconductor light-emitting element and a reflecting member provided so as to be irradiated with light emitted from the semiconductor light-emitting element. It is provided on the reflection member. As such a semiconductor light emitting device, as shown in FIG. 7, the
本発明の半導体発光装置においては、蛍光部材を1種の無機蛍光体からなる焼結体とすれば、その無機蛍光体の発光色に対応する色の光を発光させることができ、発光色の異なる複数種の無機蛍光体からなる焼結体とすれば、白色又は中間色を発光させることができる。また、焼結体を構成する無機蛍光体とは異なる他の蛍光体を焼結体の少なくとも1面に塗布したものを蛍光部材として用いることにより、白色又は中間色を発光させることも可能である。なお、焼結体からなる蛍光部材を複数用いることも可能である。更に、各無機蛍光体の焼結体を所定の位置に配列させ、発光方向前方に乱反射をおこさせる混合層を設置することで各蛍光体からの発光を混合してもよい。 In the semiconductor light emitting device of the present invention, if the fluorescent member is a sintered body made of one kind of inorganic phosphor, light of a color corresponding to the emission color of the inorganic phosphor can be emitted, If a sintered body made of a plurality of different inorganic phosphors is used, white or an intermediate color can be emitted. Moreover, it is also possible to emit white or intermediate colors by using as a fluorescent member a phosphor obtained by applying another phosphor different from the inorganic phosphor constituting the sintered body on at least one surface of the sintered body. A plurality of fluorescent members made of a sintered body can be used. Furthermore, the light emission from each phosphor may be mixed by arranging a sintered body of each inorganic phosphor at a predetermined position and installing a mixed layer that causes irregular reflection in front of the light emission direction.
なお、本発明の半導体発光装置は、特に、半導体発光素子の発光波長が波長350〜500nmである半導体発光装置として好適である。 The semiconductor light-emitting device of the present invention is particularly suitable as a semiconductor light-emitting device in which the emission wavelength of the semiconductor light-emitting element is 350 to 500 nm.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to the following Example.
[実施例1]
蛍光体の原料として、WO3粉末を156.22質量部、Eu2O3粉末を56.91質量部、Sm2O3粉末を2.35質量部、Li2CO3粉末を12.45質量部となるように各々秤量し、これらをボールミルで均一に混合して原料混合物とした。
[Example 1]
As a raw material of the phosphor, WO 3 powder 156.22 parts by mass 56.91 parts by mass of Eu 2 O 3 powder, 2.35 parts by mass of Sm 2 O 3 powder, Li 2 CO 3 powder 12.45 mass These were weighed so as to form parts, and these were uniformly mixed by a ball mill to obtain a raw material mixture.
次に、得られた原料混合物を、アルミナ製坩堝に入れ900℃の温度で6時間焼成した。得られた焼成物を純水にて十分洗浄して不要な可溶成分を除去し、その後、ボールミルにより細かく粉砕し、篩分け(目開き106μm)してLiEu0.96Sm0.04W2O8で示される組成の粒子状の赤色発光蛍光体を得た。 Next, the obtained raw material mixture was put in an alumina crucible and fired at a temperature of 900 ° C. for 6 hours. The obtained fired product is sufficiently washed with pure water to remove unnecessary soluble components, and then finely pulverized by a ball mill, sieved (mesh 106 μm), and indicated by LiEu 0.96 Sm 0.04 W 2 O 8 . A particulate red light-emitting phosphor having the composition described above was obtained.
得られた蛍光体を金型に10g入れ、油圧ポンプを用いて15MPaの圧力で圧縮成形し、更に、アルミナ製容器上に置き、900℃の温度で12時間焼成し、3×9×45mmの焼結体を得た。 10 g of the obtained phosphor is put into a mold, compression-molded at a pressure of 15 MPa using a hydraulic pump, further placed on an alumina container, fired at a temperature of 900 ° C. for 12 hours, and 3 × 9 × 45 mm A sintered body was obtained.
この粒子状の赤色発光蛍光体、及び焼結体について、小型分光蛍光光度計FP−750(日本分光製)を用いて、励起波長400nmの場合の発光強度を測定した。結果を図8に示す。なお、図8中、太線は焼結体の結果、細線は粒子状の蛍光体の結果を示す。 About the particulate red light-emitting phosphor and the sintered body, the emission intensity at an excitation wavelength of 400 nm was measured using a small spectrofluorometer FP-750 (manufactured by JASCO). The results are shown in FIG. In FIG. 8, the thick line indicates the result of the sintered body, and the thin line indicates the result of the particulate phosphor.
波長400nmにおいて、粒子状のLiEu0.96Sm0.04W2O8の発光強度を100とした場合、焼結体のLiEu0.96Sm0.04W2O8の発光強度は212となり、粒子状のものと比較して高い発光強度が得られることがわかる。 When the emission intensity of particulate LiEu 0.96 Sm 0.04 W 2 O 8 is set at 100 at a wavelength of 400 nm, the emission intensity of sintered LiEu 0.96 Sm 0.04 W 2 O 8 is 212, which is compared with that of particulate. It can be seen that high emission intensity can be obtained.
[実施例2]
実施例1と同様の方法で赤色発光蛍光体LiEu0.96Sm0.04W2O8の焼結体を作製し、得られた焼結体を、マルチブレードマシンを用いて0.4mmの厚さに切断し、更に、切断して得られた焼結体をLEDの発光が均一に照射される大きさに加工(約5mmφ)し、これを発光ピーク386nmのLEDの発光方向前方に設置し、LEDに電流を20mA印加した。
[Example 2]
A sintered body of red light emitting phosphor LiEu 0.96 Sm 0.04 W 2 O 8 was prepared in the same manner as in Example 1, and the obtained sintered body was cut into a thickness of 0.4 mm using a multi-blade machine. Furthermore, the sintered body obtained by cutting is processed into a size that allows the light emission of the LED to be uniformly irradiated (about 5 mmφ), and this is placed in front of the light emission direction of the LED having a light emission peak of 386 nm. A current of 20 mA was applied.
この焼結体を透過した発光を分光放射輝度計PR−704(Photo Research製)を用いて測定した。結果を図9に示す。 Luminescence transmitted through the sintered body was measured using a spectral radiance meter PR-704 (manufactured by Photo Research). The results are shown in FIG.
一方、比較用として、実施例1と同様の方法で粒子状の赤色発光蛍光体LiEu0.96Sm0.04W2O8を作製し、この粒子状の赤色発光蛍光体LiEu0.96Sm0.04W2O8200質量部を未硬化のシリコーンゴム100質量部に添加し、金型と加熱プレスを用いて厚さ0.5mmのゴム成形体を作製し、得られたゴム成形体をLEDの発光が均一に照射される大きさ(約5mmφ)に加工し、これを焼結体の代わりに発光ピーク386nmのLEDの発光方向前方に設置し、LEDに電流を20mA印加した。 On the other hand, for comparison, a particulate red light-emitting phosphor LiEu 0.96 Sm 0.04 W 2 O 8 was prepared in the same manner as in Example 1, and this particulate red light-emitting phosphor LiEu 0.96 Sm 0.04 W 2 O 8 200 Add a mass part to 100 parts by mass of uncured silicone rubber, make a rubber molded body with a thickness of 0.5 mm using a mold and a heat press, and irradiate the emitted light of the obtained rubber molded body uniformly with LED This was processed into a size (about 5 mmφ), and this was placed in front of the light emission direction of the LED having an emission peak of 386 nm instead of the sintered body, and a current of 20 mA was applied to the LED.
このゴム成形体を透過した発光を分光放射輝度計PR−704(Photo Research製)を用いて測定した。結果を図9に示す。なお、図9中、太線は焼結体の結果、細線はゴム成形体の結果を示す。 Luminescence transmitted through the rubber molded body was measured using a spectral radiance meter PR-704 (manufactured by Photo Research). The results are shown in FIG. In FIG. 9, the thick line indicates the result of the sintered body, and the thin line indicates the result of the rubber molded body.
粒子状のLiEu0.96Sm0.04W2O8を分散させたゴム成形体を用いた半導体発光装置の発光強度を100とした場合、LiEu0.96Sm0.04W2O8の焼結体を用いた半導体発光装置の発光強度は166となり、粒子状のものと比較して高い発光強度が得られることがわかる。 Semiconductor light emission using a sintered body of LiEu 0.96 Sm 0.04 W 2 O 8 when the emission intensity of a semiconductor light emitting device using a rubber molded body in which particulate LiEu 0.96 Sm 0.04 W 2 O 8 is dispersed is 100 The light emission intensity of the device is 166, and it can be seen that a higher light emission intensity can be obtained compared to the particulate form.
[実施例3]
実施例1と同様の方法で31×31×5mmの赤色発光蛍光体LiEu0.96Sm0.04W2O8の焼結体を作製した。次に、粒子状の緑色発光蛍光体ZnS:Cu,Alを8.2g、粒子状の青色発光蛍光体(Sr,Ca,Ba)5(PO4)3Cl:Euを6.2g、未硬化の液状シリコーンゴム50g中に分散させ、これを、得られた焼結体の厚さ方向の一方の端面に塗布して硬化させた。このシリコーンゴムと共に緑色発光蛍光体と青色発光蛍光体とが積層された面に対して発光ピークが396nmのLED(SANDER製3DL−5N3CUV−A)を両者が接するように配置し、LEDに電流を20mA印加した。
[Example 3]
A sintered body of 31 × 31 × 5 mm red light emitting phosphor LiEu 0.96 Sm 0.04 W 2 O 8 was produced in the same manner as in Example 1. Next, 8.2 g of the particulate green light emitting phosphor ZnS: Cu, Al, 6.2 g of the particulate blue light emitting phosphor (Sr, Ca, Ba) 5 (PO 4 ) 3 Cl: Eu, uncured Was dispersed in 50 g of the liquid silicone rubber, and applied to one end face in the thickness direction of the obtained sintered body and cured. An LED (SANDER 3DL-5N3CUV-A) having an emission peak of 396 nm is disposed on the surface where the green light emitting phosphor and the blue light emitting phosphor are laminated together with the silicone rubber so that the two are in contact with each other. 20 mA was applied.
この焼結体を反射した発光を分光放射輝度計PR−704(Photo Research製)を用いて測定した。結果を表1及び図10に示す。 Luminescence reflected from the sintered body was measured using a spectral radiance meter PR-704 (manufactured by Photo Research). The results are shown in Table 1 and FIG.
一方、比較用として、実施例1と同様の方法で粒子状の赤色発光蛍光体LiEu0.96Sm0.04W2O8を作製し、この粒子状の赤色発光蛍光体LiEu0.96Sm0.04W2O8と緑色発光蛍光体ZnS:Cu,Alと青色発光蛍光体(Sr,Ca,Ba)5(PO4)3Cl:Euとを体積比10:1:1で含まれるように、これらの総量を30質量部として未硬化のシリコーンゴム100質量部に添加し、金型と加熱プレスを用いて厚さ0.5mmのゴム成形体を作製し、得られたゴム成形体をLEDの発光が均一に照射される大きさ(約5mmφ)に加工し、これを焼結体の代わりに発光ピーク386nmのLEDの発光方向前方に設置し、LEDに電流を20mA印加した。 On the other hand, for comparison, a particulate red light-emitting phosphor LiEu 0.96 Sm 0.04 W 2 O 8 was prepared in the same manner as in Example 1, and this particulate red light-emitting phosphor LiEu 0.96 Sm 0.04 W 2 O 8 The total amount of the green light-emitting phosphor ZnS: Cu, Al and the blue light-emitting phosphor (Sr, Ca, Ba) 5 (PO 4 ) 3Cl: Eu is 30 mass so that the volume ratio is 10: 1: 1. As a part, 100 parts by weight of uncured silicone rubber was added, and a rubber molded body having a thickness of 0.5 mm was prepared using a mold and a heat press. The resulting rubber molded body was irradiated with light emitted from the LED uniformly. This was processed into a size (about 5 mmφ), placed in front of the light emission direction of the LED having an emission peak of 386 nm instead of the sintered body, and a current of 20 mA was applied to the LED.
このゴム成形体を反射した発光を分光放射輝度計PR−704(Photo Research製)を用いて測定した。結果を表1及び図10に示す。なお、図10中、太線は焼結体の結果、細線はゴム成形体の結果を示す。 The light emission reflected from the rubber molded body was measured using a spectral radiance meter PR-704 (manufactured by Photo Research). The results are shown in Table 1 and FIG. In FIG. 10, the thick line indicates the result of the sintered body, and the thin line indicates the result of the rubber molded body.
表1及び図10から、粒子状の蛍光体を用いるより焼結体を用いた方が、発光強度が高く、高輝度な白色発光を示すことがわかる。 From Table 1 and FIG. 10, it can be seen that the use of the sintered body has a higher emission intensity and emits bright white light than the use of the particulate phosphor.
1,2 リード
3 半導体発光素子
4 リード細線
5 封止材
6 発光体収容部材
7 蛍光層
8 発光ダイオード
9 反射部材
10 蛍光部材
DESCRIPTION OF
Claims (7)
LiyA1 (1-y)EuxLn1 (1-x)M1 2O8…(1)
(式中、A1はNa及びKから選ばれる少なくとも1種、Ln1はYを含む希土類元素(Euを除く)から選ばれる少なくとも1種、M1はMo及びWから選ばれる少なくとも1種であり、xは0.8≦x≦1を満たす正数、yは0.4≦y≦1を満たす正数である。)
で表される赤色発光蛍光体であることを特徴とする蛍光部材。 A fluorescent member of a semiconductor light-emitting device that emits a phosphor by light emitted from a semiconductor light-emitting element, wherein the phosphor is fired from a raw material mixture, and pulverized inorganic phosphor particles are compression-molded in a molding container, It is a sintered body obtained by further firing the compression-molded body at a firing temperature of 800 to 1000 ° C., and the following composition formula (1)
Li y A 1 (1-y) Eu x Ln 1 (1-x) M 1 2 O 8 (1)
(In the formula, A 1 is at least one selected from Na and K , Ln 1 is at least one selected from rare earth elements including Y (excluding Eu), and M 1 is at least one selected from Mo and W. X is a positive number satisfying 0.8 ≦ x ≦ 1, and y is a positive number satisfying 0.4 ≦ y ≦ 1.)
A fluorescent member characterized by being a red light emitting phosphor represented by the formula:
LiyA1 (1-y)EuxLn1 (1-x)M1 2O8…(1)
(式中、A1はNa及びKから選ばれる少なくとも1種、Ln1はYを含む希土類元素(Euを除く)から選ばれる少なくとも1種、M1はMo及びWから選ばれる少なくとも1種であり、xは0.8≦x≦1を満たす正数、yは0.4≦y≦1を満たす正数である。)
で表される赤色発光蛍光体であり、原料混合物を焼成し、粉砕した無機蛍光体粒子を成形容器内で圧縮成形し、該圧縮成形体を更に800〜1000℃の焼成温度にて焼成することにより、上記赤色発光蛍光体を得ることを特徴とする蛍光部材の製造方法。 A method of manufacturing a fluorescent member of a semiconductor light emitting device that emits a phosphor by light emitted from a semiconductor light emitting element, wherein the phosphor is represented by the following composition formula (1):
Li y A 1 (1-y) Eu x Ln 1 (1-x) M 1 2 O 8 (1)
(In the formula, A 1 is at least one selected from Na and K , Ln 1 is at least one selected from rare earth elements including Y (excluding Eu), and M 1 is at least one selected from Mo and W. X is a positive number satisfying 0.8 ≦ x ≦ 1, and y is a positive number satisfying 0.4 ≦ y ≦ 1.)
The raw material mixture is fired, the pulverized inorganic phosphor particles are compression molded in a molding container, and the compression molded body is further fired at a firing temperature of 800 to 1000 ° C. To obtain the red light-emitting phosphor.
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