JP2013179335A - White light emitting element - Google Patents

White light emitting element Download PDF

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JP2013179335A
JP2013179335A JP2013098041A JP2013098041A JP2013179335A JP 2013179335 A JP2013179335 A JP 2013179335A JP 2013098041 A JP2013098041 A JP 2013098041A JP 2013098041 A JP2013098041 A JP 2013098041A JP 2013179335 A JP2013179335 A JP 2013179335A
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phosphor
light
light emitting
white light
emitting element
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Takashi Hase
尭 長谷
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Mitsubishi Chemical Corp
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

PROBLEM TO BE SOLVED: To provide a compact white light emitting element which uses a blue or violet light emitting diode and has high luminance.SOLUTION: A white light emitting element comprises a combination of a blue or violet light emitting diode and one or more kinds of phosphor which absorb light emitted by the light emitting diode and emits light in a visible range. In the white light emitting element, the phosphor is selected so that light emission color of the light emitting diode and the light emission color of the phosphor have complementary color relation with each other, and white light having a light emission chromaticity point in a region shown by W on chromaticity coordinates in Fig.1 is emitted.

Description

本発明は、屋内、屋外、さらに水中などにおける表示や、光源またはディスプレイ用バックライトとして利用することができる、高輝度で耐候性及び寿命特性に優れた白色発光素子に関する。   The present invention relates to a white light-emitting element that can be used as an indoor, outdoor, or underwater display, or as a light source or a backlight for a display, and has high brightness and excellent weather resistance and life characteristics.

従来、可視発光ダイオードとしては緑色から赤色発光の素子しか実用化されていなかったが、近年、青色発光ダイオードが実用に供され始め、それに伴い、青色、緑色、赤色の各色発光素子を一つの画素として組み合わせたフルカラーの大型ディスプレイが実現している。   Conventionally, only green to red light emitting elements have been put into practical use as visible light emitting diodes, but in recent years blue light emitting diodes have begun to be put into practical use, and accordingly, blue, green and red light emitting elements are combined into one pixel. A large full-color display combined with the

これに対し、ダイオード単独で白色に発光する白色発光素子を得るためには、青色、緑色、赤色の各色発光素子を同時に発光させ、混色して白色化させることはできるが、小型の白色ディスプレイ、光源又は液晶ディスプレイ等のバックライト等を得るために、前記の各色発光素子を組み合わせると、画素自身が大きくなりすぎ、また、各色の駆動条件が異なると、駆動制御が煩雑になるという欠点があった。   On the other hand, in order to obtain a white light emitting element that emits white light with a diode alone, each light emitting element of blue, green, and red can emit light at the same time, and can be mixed to whiten, but a small white display, Combining the above-described light emitting elements to obtain a light source or a backlight such as a liquid crystal display has the disadvantage that the pixels themselves become too large, and that the driving control becomes complicated if the driving conditions for each color are different. It was.

他方、特許文献１、特許文献２等には、（Ｇａ，Ａｌ）Ｎ青色発光ダイオードと、蛍光顔料又は蛍光物質を組み合わせた発光素子が記載されているが、発光ダイオードと蛍光物質とを組み合わせ白色発光を得ることについては何も記載はされていない。   On the other hand, Patent Document 1, Patent Document 2, and the like describe a light emitting element in which a (Ga, Al) N blue light emitting diode and a fluorescent pigment or a fluorescent material are combined. There is no mention of obtaining luminescence.

特開平５−１５２６０９号公報JP-A-5-152609 特開平７−９９３４５号公報JP-A-7-99345

そこで、本発明では、青色又は青紫色発光ダイオードを用い、高輝度でコンパクトな白色発光素子を提供しようとするものである。   Therefore, the present invention intends to provide a high-intensity and compact white light-emitting element using a blue or blue-violet light-emitting diode.

本発明者等は、上記目的を達成するために鋭意検討した結果、青色又は青紫色発光の発光ダイオードが高輝度でバンド巾の狭いシャープな青色発光を呈することに着目し、この青色又は青紫色発光で励起され得る蛍光体を調べ、前記ダイオードの発光色と前記蛍光体の発光色を混色するときに、加色混合して白色光を呈する蛍光体を見出し、高輝度でコンパクトな白色発光素子の提供を可能にした。   As a result of intensive studies to achieve the above object, the present inventors have focused on the fact that blue or blue-violet light emitting diodes exhibit sharp blue light emission with high brightness and narrow bandwidth. Investigate phosphors that can be excited by light emission, and find a phosphor that emits white light by adding colors when mixing the light emission color of the diode and the light emission color of the phosphor. Made it possible to provide

即ち、本発明の構成は以下のとおりである。
（１）青色又は青紫色の発光ダイオードと、該発光ダイオードの発光を吸収して可視域に発光する１種又は２種類以上の蛍光体とを組み合わせた白色発光素子において、前記発光ダイオードと前記蛍光体の発光色が加色して互いに補色の関係になるように、前記蛍光体を選択したことを特徴とする白色発光素子。
（２）前記発光ダイオードと前記蛍光体の発光色を加色して、図１の色度座標中のＷで示した領域内の発光色度点を有する白色に発光するように、前記蛍光体を選択したことを特徴とする上記（１）に記載の白色発光素子。 That is, the configuration of the present invention is as follows.
(1) A white light-emitting element in which a blue or blue-violet light-emitting diode and one or more phosphors that absorb light emitted from the light-emitting diode and emit light in the visible range are combined. A white light-emitting element, wherein the phosphor is selected so that the luminescent color of the body is added to form a complementary color relationship.
(2) The phosphors so as to emit white light having emission chromaticity points in the region indicated by W in the chromaticity coordinates of FIG. The white light-emitting element according to (1) above, wherein

（３）前記白色発光素子の発光色の発光色度点（ｘ、ｙ）が０．２１≦ｘ≦０．４８、０．１９≦ｙ≦０．４５の範囲にあることを特徴とする上記（１）又は（２）に記載の白色発光素子。
（４）前記蛍光体の励起光として、前記発光ダイオードの４００〜５００ｎｍの波長の光を用いることを特徴とする上記（１）〜（３）のいずれかに記載の白色発光素子。 (3) The emission chromaticity point (x, y) of the emission color of the white light emitting element is in the range of 0.21 ≦ x ≦ 0.48, 0.19 ≦ y ≦ 0.45, The white light emitting element as described in (1) or (2).
(4) The white light-emitting element according to any one of (1) to (3), wherein light having a wavelength of 400 to 500 nm of the light-emitting diode is used as excitation light of the phosphor.

（５）前記蛍光体が（Ｚｎ，Ｃｄ）Ｓ：Ａｇ，Ｃｌ蛍光体、（Ｚｎ，Ｃｄ）Ｓ：Ａｇ，Ａｌ蛍光体、（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ａｌ蛍光体、（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ｃｌ蛍光体，（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ａｕ，Ａｌ蛍光体及び（Ｙ，Ｇｄ）3（Ａｌ，Ｇａ）5 Ｏ12
：Ｃｅ，Ｅｕ蛍光体の群から選択される少なくとも一種の蛍光体であることを特徴とする上記（１）〜（４）のいずれかに記載の白色発光素子。
（６）前記発光ダイオードが（Ｉｎx，Ａｌy，Ｇａ1-x-y） Ｎ（但し、０≦ｘ，０≦ｙ，ｘ＋ｙ≦１）、ＳｉＣ、ＢＮ及びＺｎ（Ｓ，Ｓｅ）の群から選択される少なくとも一種のものであることを特徴とする上記（１）〜（５）のいづれかに記載の白色発光素子。 (5) The phosphor is a (Zn, Cd) S: Ag, Cl phosphor, (Zn, Cd) S: Ag, Al phosphor, (Zn, Cd) S: Cu, Al phosphor, (Zn, Cd) ) S: Cu, Cl phosphor, (Zn, Cd) S: Cu, Au, Al phosphor and (Y, Gd) 3 (Al, Ga) 5 O 12
The white light-emitting element according to any one of (1) to (4) above, wherein the white light-emitting element is at least one phosphor selected from the group of Ce and Eu phosphors.
(6) selected from the group of the light emitting diode (In x, Al y, Ga 1-xy) N ( where, 0 ≦ x, 0 ≦ y , x + y ≦ 1), SiC, BN and Zn (S, Se) The white light-emitting element according to any one of (1) to (5) above, wherein the white light-emitting element is any one of the above-described (1) to (5).

本発明は、上記の構成を採用することにより、従来の青色、緑色及び赤色発光ダイオードの組み合わせや、青色及び黄色発光ダイオードの組み合わせでは得られなかった、コンパクトで安価で簡便な白色発光素子を得ることができ、表示の多色化多様化に大きく寄与するものである。   By adopting the above configuration, the present invention obtains a compact, inexpensive, and simple white light emitting element that cannot be obtained by a conventional combination of blue, green and red light emitting diodes or a combination of blue and yellow light emitting diodes. This greatly contributes to the diversification and diversification of the display.

本発明の白色発光素子の発光色の範囲Ｗを色度座標で示した図である。It is the figure which showed the range W of the luminescent color of the white light emitting element of this invention by the chromaticity coordinate. 本発明の白色発光素子の構造を例示した概略断面図である。It is the schematic sectional drawing which illustrated the structure of the white light emitting element of this invention. 本発明の白色発光素子に用いる青色発光ダイオードの１例であるＧａＮダイ オードの発光スペクトルである。2 is an emission spectrum of a GaN diode which is an example of a blue light emitting diode used in the white light emitting element of the present invention. 本発明で用いるＺｎＳ：Ａｇ，Ｃｌ蛍光体の励起スペクトルである。It is an excitation spectrum of the ZnS: Ag, Cl phosphor used in the present invention. 本発明で用いるＺｎＳ；Ｃｕ，Ａｌ蛍光体の励起スペクトルである。It is an excitation spectrum of ZnS; Cu, Al phosphor used in the present invention. 本発明で用いる（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ蛍光体の励起スペク トルである。This is an excitation spectrum of a (Zn 0.15 , Cd 0.85 ) S: Ag, Cl phosphor used in the present invention. 本発明で用いるＹ3Ａｌ5Ｏ12：Ｃｅ，Ｅｕ蛍光体の励起スペクトルである。It is an excitation spectrum of a Y 3 Al 5 O 12 : Ce, Eu phosphor used in the present invention. 本発明で用いる（Ｙ0.8，Ｇｄ0.2）3Ａｌ5Ｏ12：Ｃｅ蛍光体の励起スペクト ルである。It is an excitation spectrum of (Y 0.8 , Gd 0.2 ) 3 Al 5 O 12 : Ce phosphor used in the present invention. 本発明で用いるＺｎＳ：Ａｇ，Ｃｌ蛍光体を４５０ｎｍの光で励起するとき の発光スペクトルである。It is an emission spectrum when the ZnS: Ag, Cl phosphor used in the present invention is excited with 450 nm light. 本発明で用いるＺｎＳ：Ｃｕ，Ａｌ蛍光体を４５０ｎｍの光で励起すると きの発光スペクトルである。It is an emission spectrum when the ZnS: Cu, Al phosphor used in the present invention is excited with 450 nm light. 本発明で用いる（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ蛍光体を４５０ｎ ｍの光で励起するときの発光スペクトルである。It is an emission spectrum when the (Zn 0.15 , Cd 0.85 ) S: Ag, Cl phosphor used in the present invention is excited with 450 nm light. 本発明で用いるＹ3Ａｌ5Ｏ12：Ｃｅ，Ｅｕ蛍光体を４５０ｎｍの光で励起 するときの発光スペクトルである。It is an emission spectrum when the Y 3 Al 5 O 12 : Ce, Eu phosphor used in the present invention is excited with 450 nm light. 本発明で用いる（Ｙ0.8，Ｇｄ0.2）3Ａｌ5Ｏ12：Ｃｅ蛍光体を４５０ｎｍ の光で励起するときの発光スペクトルである。It is an emission spectrum when the (Y 0.8 , Gd 0.2 ) 3 Al 5 O 12 : Ce phosphor used in the present invention is excited with 450 nm light. 実施例において、ＧａＮ青色発光ダイオードと（Ｙ0.8，Ｇｄ0.2）3Ａｌ5 Ｏ12：Ｃｅ蛍光体を組み合わせた白色発光素子の発光スペクトルである。In embodiments, GaN blue light-emitting diodes and (Y 0.8, Gd 0.2) 3 Al 5 O 12: an emission spectrum of a white light emitting device that combines Ce phosphor. 実施例において、ＧａＮ青色発光ダイオードと、ＺｎＳ：Ｃｕ，Ａｌ蛍光 体及び（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ蛍光体とを組み合わせた白色発光 素子の発光スペクトルである。In an Example, it is an emission spectrum of the white light emitting element which combined the GaN blue light emitting diode, ZnS: Cu, Al fluorescent substance, and ( Zn0.15 , Cd0.85 ) S: Ag, Cl fluorescent substance. 実施例において、ＧａＮ青色発光ダイオードと、Ｙ3Ａｌ5Ｏ12：Ｃｅ，Ｅ ｕ蛍光体及び（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ蛍光体を組み合わせた白色発光素子の発光スペクトルである。In embodiments, a GaN blue light-emitting diodes, Y 3 Al 5 O 12: Ce, E u phosphor and (Zn 0.15, Cd 0.85) S : Ag, an emission spectrum of a white light emitting device that combines Cl phosphor.

本発明は、青色又は青紫色の発光ダイオードと１種又は２種類以上の蛍光体とを組み合わせた白色発光素子であって、発光ダイオードの発光を吸収して可視域に発光する蛍光体を選択し、かつ、発光ダイオードと蛍光体の発光色を加色するときに互いに補色の関係になるような蛍光体を選択することにより、高輝度の白色発光を可能にした。   The present invention is a white light-emitting element combining a blue or blue-violet light-emitting diode and one or more phosphors, and selects a phosphor that absorbs light emitted from the light-emitting diode and emits light in the visible region. In addition, by selecting phosphors that are complementary to each other when the emission colors of the light-emitting diode and the phosphor are added, high-luminance white light emission is made possible.

図２は、本発明の白色発光素子の１例である断面構造を示した模式図である。フレーム３の上に青色又は青紫色発光ダイオードチップ４をセットし、その上に蛍光体を塗布し、全体を透明樹脂モールドで被覆し、チップからの電極端子５、６を引き出して素子を形成したものである。   FIG. 2 is a schematic view showing a cross-sectional structure as an example of the white light emitting device of the present invention. A blue or blue-violet light emitting diode chip 4 is set on the frame 3, a phosphor is applied thereon, the whole is covered with a transparent resin mold, and electrode terminals 5 and 6 from the chip are drawn to form an element. Is.

本発明で使用する青色又は青紫色発光ダイオードとしては、（Ｉｎx，Ａｌy，Ｇａ1-x-y）Ｎ（但し、０≦ｘ，０≦ｙ，ｘ＋ｙ≦１）、ＳｉＣ、ＢＮ及びＺｎ（Ｓ，Ｓｅ）など
を挙げることができ、それらを組み合わせて用いることもできる。図３は、ＧａＮ発光ダイオードの発光スペクトル図を示したものである。この発光スペクトルの発光ピーク波長は、ほぼ４５０ｎｍ付近にある。本発明の蛍光体は、前記発光ダイオードの発光の一部を用いて励起される。その結果、発光ダイオードの発光色と励起された蛍光体の発光色が混色する。両者が補色の関係にあるときには、混色により白色発光を呈する。 Blue or blue-violet light emitting diodes used in the present invention include (In x , Al y , Ga 1-xy ) N (where 0 ≦ x, 0 ≦ y, x + y ≦ 1), SiC, BN and Zn (S , Se) and the like, and combinations thereof can also be used. FIG. 3 shows an emission spectrum of the GaN light emitting diode. The emission peak wavelength of this emission spectrum is about 450 nm. The phosphor of the present invention is excited by using a part of the light emitted from the light emitting diode. As a result, the emission color of the light emitting diode and the emission color of the excited phosphor are mixed. When the two are in a complementary color relationship, white light is emitted due to the mixed color.

本発明で使用する蛍光体は、青色又は青紫色発光ダイオードの発光の一部を励起光として発光する、ほぼ４００〜５００ｎｍの範囲に励起波長を有する蛍光体であって、発光ダイオードの発光色と蛍光体の発光色が補色の関係にあり、混色により白色を呈するような蛍光体が選択される。具体的には、発光ダイオードの発光を吸収して自ら青色ないし赤色の可視光に発光する、以下の組成式で表される蛍光体を挙げることがてきる。   The phosphor used in the present invention is a phosphor having an excitation wavelength in a range of approximately 400 to 500 nm, which emits a part of the light emission of a blue or blue-violet light emitting diode as excitation light, and the emission color of the light emitting diode A phosphor is selected such that the emission color of the phosphor has a complementary color relationship and white color is exhibited by color mixture. Specific examples include phosphors represented by the following composition formula that absorb light emitted from the light-emitting diode and emit blue to red visible light.

青色発光する（Ｚｎ1-x，Ｃｄx）Ｓ：Ａｇ，Ｃｌ蛍光体（但し０≦ｘ≦０．０７）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ａｇ，Ａｌ蛍光体（但し０≦ｘ≦０．０７）等。緑色発光する（Ｚｎ1-x，Ｃｄx）Ｓ：Ｃｕ，Ａｌ蛍光体（但し、０≦ｘ≦０．１５）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ｃｕ，Ｃｌ蛍光体（但し、０≦ｘ≦０．２０）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ａｇ，Ｃｌ蛍光体（但し、０．０７≦ｘ≦０．５０）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ａｇ，Ａｌ蛍光体（但し、０．０７≦ｘ≦０．５０）、ＺｎＳ：Ａｕ，Ｃｕ，Ａｌ蛍光体等。 Blue-emitting (Zn 1-x , Cd x ) S: Ag, Cl phosphor (where 0 ≦ x ≦ 0.07), (Zn 1-x , Cd x ) S: Ag, Al phosphor (where 0 ≦ x ≦ 0.07) and the like. (Zn 1-x , Cd x ) S: Cu, Al phosphor (provided that 0 ≦ x ≦ 0.15), (Zn 1-x , Cd x ) S: Cu, Cl phosphor (provided that 0 ≦ x ≦ 0.20), (Zn 1−x , Cd x ) S: Ag, Cl phosphor (where 0.07 ≦ x ≦ 0.50), (Zn 1−x , Cd x ) S: Ag, Al phosphor (however, 0.07 ≦ x ≦ 0.50), ZnS: Au, Cu, Al phosphor, etc.

黄色発光する（Ｙ1-u，Ｇｄu）3（Ａｌ1-v，Ｇａv）5Ｏ12：Ｃｅ，Ｅｕ蛍光体（但し、０≦ｕ≦０．３、０≦ｖ≦０．５）等。橙色又は赤色発光する（Ｚｎ1-x，Ｃｄx）Ｓ：Ｃｕ，Ａｌ蛍光体（但し、０．１５≦ｘ≦０．３０）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ｃｕ，Ｃｌ蛍光体（但し、０．２０≦ｘ≦０．３０）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ａｇ，Ｃｌ蛍光体（但し、０．５０≦ｘ≦０．９０）、（Ｚｎ1-x，Ｃｄx）Ｓ：Ａｇ，Ａｌ蛍光体（但し、０．５０≦ｘ≦０．９０）等。 Yellow-emitting (Y 1-u , Gd u ) 3 (Al 1-v , Ga v ) 5 O 12 : Ce, Eu phosphor (where 0 ≦ u ≦ 0.3, 0 ≦ v ≦ 0.5) etc. (Zn 1-x , Cd x ) S: Cu, Al phosphor (provided that 0.15 ≦ x ≦ 0.30), (Zn 1-x , Cd x ) S: Cu, Cl fluorescence emitting orange or red light Body (provided that 0.20 ≦ x ≦ 0.30), (Zn 1−x , Cd x ) S: Ag, Cl phosphor (provided that 0.50 ≦ x ≦ 0.90), (Zn 1−x , Cd x ) S: Ag, Al phosphor (provided that 0.50 ≦ x ≦ 0.90), etc.

本発明の蛍光体は、４００〜５００ｎｍの範囲に励起波長を有し、これらの蛍光体の１種もしくは２種以上の中から、同時に用いる青色又は青紫色発光ダイオードと組み合わせて使用した時、その発光色の発光色度点（ｘ、ｙ）が０．２１≦ｘ≦０．４８、０．１９≦ｙ≦０．４５の範囲に入り、図１の色度座標中の領域Ｗ内に入りほぼ白色の発光を呈するように蛍光体の組み合わせを選択したものである。   The phosphor of the present invention has an excitation wavelength in the range of 400 to 500 nm, and when used in combination with a blue or blue-violet light emitting diode used simultaneously from one or more of these phosphors, The emission chromaticity point (x, y) of the emission color falls within the range of 0.21 ≦ x ≦ 0.48 and 0.19 ≦ y ≦ 0.45, and enters the region W in the chromaticity coordinates of FIG. The combination of phosphors is selected so as to exhibit almost white light emission.

なお、発光ダイオードと組み合わせて用いる蛍光体の種類や混合蛍光体の混合比により、上記ｘ、ｙ、ｕ及びｖの値が上記範囲を外れると、得られる白色発光素子の色度及び輝度において本発明の特性が得られなくなる。   Note that when the values of x, y, u, and v are out of the above range depending on the type of phosphor used in combination with the light emitting diode and the mixing ratio of the mixed phosphor, the chromaticity and luminance of the white light emitting element obtained are The characteristics of the invention cannot be obtained.

本発明の白色発光素子の製造は、予め所定量秤取した蛍光体を、アセトンやトルエン等有機溶剤等に希釈したアクリル樹脂、エポキシ樹脂、ポリイミド樹脂等の透明な樹脂と混合し、例えば、注射器のような細いノズルから発光ダイオードチップ上に数十μｇ滴下して塗布する。また、上記の樹脂の代わりに水溶性樹脂を用いたり、アルカリ珪酸塩を用いても良い。   The production of the white light emitting device of the present invention is performed by mixing a predetermined amount of a phosphor, which is mixed with a transparent resin such as an acrylic resin, an epoxy resin, or a polyimide resin diluted in an organic solvent such as acetone or toluene. Apply several tens of micrograms on a light emitting diode chip from such a thin nozzle. Further, a water-soluble resin may be used instead of the above resin, or an alkali silicate may be used.

蛍光体を塗布した発光ダイオードチップは乾燥後、エポキシ樹脂等の透明樹脂又はガラス製キャップを発光チップの蛍光体塗布部分に取り付けて白色発光素子を完成する。本発明の発光素子には、最大５Ｖ、３０ｍＡまでの定格直流負荷を加え発光させて白色発光を得ることができる。   After the light emitting diode chip coated with the phosphor is dried, a transparent resin such as an epoxy resin or a glass cap is attached to the phosphor coated portion of the light emitting chip to complete a white light emitting element. The light emitting device of the present invention can emit white light by applying a rated DC load of up to 5 V and 30 mA to emit light.

図４〜８は、本発明で使用する蛍光体の主発光を与えるための励起スペクトルを例示したものであり、図４はＺｎＳ：Ａｇ，Ｃｌ蛍光体、図５はＺｎＳ；Ｃｕ，Ａｌ蛍光体、図６は（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ蛍光体、図７はＹ3Ａｌ5Ｏ12：Ｃｅ，Ｅｕ蛍光体、図８は（Ｙ0.8，Ｇｄ0.2）3Ａｌ5Ｏ12：Ｃｅ蛍光体の励起スペクトルを例示したものである。 4 to 8 illustrate the excitation spectrum for giving the main light emission of the phosphor used in the present invention, FIG. 4 is a ZnS: Ag, Cl phosphor, and FIG. 5 is a ZnS; Cu, Al phosphor. 6 shows (Zn 0.15 , Cd 0.85 ) S: Ag, Cl phosphor, FIG. 7 shows Y 3 Al 5 O 12 : Ce, Eu phosphor, and FIG. 8 shows (Y 0.8 , Gd 0.2 ) 3 Al 5 O 12. : Explains excitation spectrum of Ce phosphor.

図９〜１３は、市販のＧａＮ青色発光ダイオードの発光ピークである４５０ｎｍで、上記各蛍光体を励起した時の発光スペクトルを示したものであり、図９はＺｎＳ：Ａｇ，Ｃｌ蛍光体、図１０はＺｎＳ；Ｃｕ，Ａｌ蛍光体、図１１は（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ蛍光体、図１２はＹ3Ａｌ5Ｏ12：Ｃｅ，Ｅｕ蛍光体、図１３は（Ｙ0.8，Ｇｄ0.2）3Ａｌ5Ｏ12：Ｃｅ蛍光体の発光スペクトルを示したものである。 9 to 13 show emission spectra when the above phosphors are excited at 450 nm which is an emission peak of a commercially available GaN blue light emitting diode, and FIG. 9 shows ZnS: Ag, Cl phosphors, FIG. 10 is ZnS; Cu, Al phosphor, FIG. 11 is (Zn 0.15 , Cd 0.85 ) S: Ag, Cl phosphor, FIG. 12 is Y 3 Al 5 O 12 : Ce, Eu phosphor, and FIG. 13 is (Y 0.8 , Gd 0.2 ) 3 Al 5 O 12 : Ce emission spectrum.

図１４〜１６は、ＧａＮ青色発光ダイオードと組み合わせた本発明の白色発光素子の発光スペクトルを示したものであり、図１４で使用した蛍光体は（Ｙ0.8，Ｇｄ0.2）3Ａｌ5Ｏ12：Ｃｅ、図１５で使用した蛍光体はＺｎＳ：Ｃｕ，Ａｌ及び（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ、図１６で使用した蛍光体はＹ3Ａｌ5Ｏ12：Ｃｅ，Ｅｕ及び（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌである。 14 to 16 show the emission spectrum of the white light emitting device of the present invention combined with a GaN blue light emitting diode, and the phosphor used in FIG. 14 is (Y 0.8 , Gd 0.2 ) 3 Al 5 O 12 : The phosphors used in FIG. 15 are ZnS: Cu, Al and (Zn 0.15 , Cd 0.85 ) S: Ag, Cl, and the phosphors used in FIG. 16 are Y 3 Al 5 O 12 : Ce, Eu and (Zn 0.15 , Cd 0.85 ) S: Ag, Cl.

〔実施例１〕
エポキシ樹脂（日東電工社製、ＮＴ８０１４） １ｇｒ
酸無水物系硬化剤 １ｇｒ
蛍光体（Ｙ0.8，Ｇｄ0.2）3Ａｌ5Ｏ12：Ｃｅ ２ｍｇ
上記の蛍光体と樹脂との混合液を注射器を用いて、４５０ｎｍに発光ピークを有するＧａＮ青色発光ダイオードチップ（０．４ｍｍ角）上に５０μリットル滴下し、乾燥した後、更に半円形の透明なエポキシ樹脂キャップで被覆して白色発光素子を得た。
この白色発光素子は図１４の発光スペクトルを示し、その発光色度Ｗ3はｘ＝０．２７
５、ｙ＝０．３３５であった。なお、上記蛍光体の発光色度はＹ1であった。 [Example 1]
Epoxy resin (NT8014, manufactured by Nitto Denko Corporation) 1 gr
1g of acid anhydride curing agent
Phosphor (Y 0.8, Gd 0.2) 3 Al 5 O 12: Ce 2mg
Using a syringe, the mixture of the above phosphor and resin was dropped on a GaN blue light-emitting diode chip (0.4 mm square) having an emission peak at 450 nm, dried, and then further semicircular transparent A white light emitting device was obtained by covering with an epoxy resin cap.
This white light emitting element shows the emission spectrum of FIG. 14, and its emission chromaticity W 3 is x = 0.27.
5, y = 0.335. The emission chromaticity of the phosphor was Y 1.

〔実施例２〕
アクリル樹脂（日本カーバイト工業製、ニッカゾール、固形分５０％） １ｇｒ
脱イオン水 ５ｇｒ
蛍光体 ＺｎＳ：Ｃｕ，Ａｌ １ｍｇ
（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ ０．５ｍｇ
上記の蛍光体と樹脂との混合液を注射器を用いて、４５０ｎｍに発光ピークを有するＧａＮ青色発光ダイオードチップ（０．４ｍｍ角）上に５０μリットル滴下し、乾燥した後、更に半円形の透明なエポキシ樹脂キャップで被覆して白色発光素子を得た。この白色発光素子は図１５の発光スペクトルを示し、その発光色度Ｗ2はｘ＝０．２３７、ｙ＝０．
２７４であった。なお、上記蛍光体の発光色度はＧ2とＲであった。 [Example 2]
Acrylic resin (Nihon Carbite Industries, Nikkasol, solid content 50%) 1gr
Deionized water 5gr
Phosphor ZnS: Cu, Al 1 mg
(Zn 0.15 , Cd 0.85 ) S: Ag, Cl 0.5 mg
Using a syringe, the mixture of the above phosphor and resin was dropped on a GaN blue light-emitting diode chip (0.4 mm square) having an emission peak at 450 nm, dried, and then further semicircular transparent A white light emitting device was obtained by covering with an epoxy resin cap. This white light emitting element shows the emission spectrum of FIG. 15, and its emission chromaticity W 2 is x = 0.237, y = 0.
274. The emission chromaticity of the phosphor was G 2 and R.

〔実施例３〕
水ガラス（東京応化社製、オーカシールＡ） １ｇｒ
酢酸バリウム １０ｇｒ
蛍光体 Ｙ3Ａｌ5Ｏ12：Ｃｅ，Ｅｕ0.001 １ｍｇ
（Ｚｎ0.15，Ｃｄ0.85）Ｓ：Ａｇ，Ｃｌ ０．５ｍｇ
上記の蛍光体と水ガラスの混合液を注射器を用いて、４５０ｎｍに発光ピークを有するＧａＮ青色発光ダイオードチップ（４ｍｍ角）上に３０μリットル滴下し、乾燥した後、更に半円形の透明なエポキシ樹脂キャップで被覆して白色発光素子を得た。
この白色発光素子は図１６の発光スペクトルを示し、その発光色度Ｗ1はｘ＝０．２２
３、ｙ＝０．２５３であった。なお、上記蛍光体の発光色度はＹ2とＲであった。 Example 3
1 glass of water glass (Okaseal A, manufactured by Tokyo Ohkasha)
Barium acetate 10gr
Phosphor Y 3 Al 5 O 12 : Ce, Eu 0.001 1mg
(Zn 0.15 , Cd 0.85 ) S: Ag, Cl 0.5 mg
Using a syringe, the mixture of the above phosphor and water glass was dropped on a GaN blue light-emitting diode chip (4 mm square) having a light emission peak at 450 nm, dried, and then further semicircular transparent epoxy resin A white light emitting device was obtained by covering with a cap.
This white light emitting element shows the emission spectrum of FIG. 16, and its emission chromaticity W 1 is x = 0.22.
3, y = 0.253. The emission chromaticity of the phosphor was Y 2 and R.

１．樹脂モールド
２．蛍光体
３．フレーム
４．発光ダイオードチップ
５．電極端子 1. 1. Resin mold 2. Phosphor 3. Frame 4. 4. Light emitting diode chip Electrode terminal

Claims (6)

青色又は青紫色の発光ダイオードと、該発光ダイオードの発光を吸収して可視域に発光する１種又は２種類以上の蛍光体とを組み合わせた白色発光素子において、前記発光ダイオードと前記蛍光体の発光色が加色して互いに補色の関係になるように、前記蛍光体を選択したことを特徴とする白色発光素子。   In a white light-emitting element in which a blue or blue-violet light-emitting diode and one or more phosphors that absorb light emitted from the light-emitting diode and emit light in the visible region are combined, light emission of the light-emitting diode and the phosphor A white light-emitting element, wherein the phosphor is selected so that colors are added to form a complementary color relationship. 前記発光ダイオードと前記蛍光体の発光色を加色して、図１の色度座標中のＷで示した領域内の発光色度点を有する白色に発光するように、前記蛍光体を選択したことを特徴とする請求項１記載の白色発光素子。   The phosphors were selected so as to emit white light having an emission chromaticity point in the region indicated by W in the chromaticity coordinates of FIG. 1 by adding the emission colors of the light emitting diode and the phosphor. The white light-emitting element according to claim 1. 前記白色発光素子の発光色の発光色度点（ｘ、ｙ）が０．２１≦ｘ≦０．４８、０．１９≦ｙ≦０．４５の範囲にあることを特徴とする請求項１又は２記載の白色発光素子。   The emission chromaticity point (x, y) of the emission color of the white light emitting element is in the range of 0.21 ≦ x ≦ 0.48, 0.19 ≦ y ≦ 0.45. 2. The white light emitting device according to 2. 前記蛍光体の励起光として、前記発光ダイオードの４００〜５００ｎｍの波長の光を用いることを特徴とする請求項１〜３のいずれか１項に記載の白色発光素子。   The white light-emitting element according to claim 1, wherein light having a wavelength of 400 to 500 nm of the light emitting diode is used as excitation light of the phosphor. 前記蛍光体が（Ｚｎ，Ｃｄ）Ｓ：Ａｇ，Ｃｌ蛍光体、（Ｚｎ，Ｃｄ）Ｓ：Ａｇ，Ａｌ蛍光体、（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ａｌ蛍光体、（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ｃｌ蛍光体，（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ａｕ，Ａｌ蛍光体及び（Ｙ，Ｇｄ）3（Ａｌ，Ｇａ）5 Ｏ12：Ｃ
ｅ，Ｅｕ蛍光体の群から選択される少なくとも一種の蛍光体であることを特徴とする請求項１〜４のいずれか１項に記載の白色発光素子。 The phosphor is (Zn, Cd) S: Ag, Cl phosphor, (Zn, Cd) S: Ag, Al phosphor, (Zn, Cd) S: Cu, Al phosphor, (Zn, Cd) S: Cu, Cl phosphor, (Zn, Cd) S: Cu, Au, Al phosphor and (Y, Gd) 3 (Al, Ga) 5 O 12 : C
5. The white light-emitting element according to claim 1, wherein the white light-emitting element is at least one phosphor selected from the group of e and Eu phosphors. 前記発光ダイオードが（Ｉｎx，Ａｌy，Ｇａ1-x-y） Ｎ（但し、０≦ｘ，０≦ｙ，ｘ＋ｙ≦１）、ＳｉＣ、ＢＮ及びＺｎ（Ｓ，Ｓｅ）の群から選択される少なくとも一種のものであることを特徴とする請求項１〜５のいづれか１項に記載の白色発光素子。 The light emitting diode (In x, Al y, Ga 1-xy) N ( where, 0 ≦ x, 0 ≦ y , x + y ≦ 1), SiC, at least is selected from the group of BN and Zn (S, Se) The white light-emitting element according to claim 1, wherein the white light-emitting element is one type.
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