JP2003160785A - Red-light-emitting phosphor and light emitter using the same - Google Patents

Red-light-emitting phosphor and light emitter using the same

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Publication number
JP2003160785A
JP2003160785A JP2001360965A JP2001360965A JP2003160785A JP 2003160785 A JP2003160785 A JP 2003160785A JP 2001360965 A JP2001360965 A JP 2001360965A JP 2001360965 A JP2001360965 A JP 2001360965A JP 2003160785 A JP2003160785 A JP 2003160785A
Authority
JP
Japan
Prior art keywords
light
phosphor
light emitting
emitting device
red
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
JP2001360965A
Other languages
Japanese (ja)
Inventor
Kenji Terajima
賢二 寺島
Nobuyuki Yokozawa
信幸 横沢
Nobuyuki Sudo
伸行 須藤
Takeshi Iwasaki
剛 岩崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Toshiba Development and Engineering Corp
Original Assignee
Toshiba Corp
Toshiba Electronic Engineering Co Ltd
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Filing date
Publication date
Application filed by Toshiba Corp, Toshiba Electronic Engineering Co Ltd filed Critical Toshiba Corp
Priority to JP2001360965A priority Critical patent/JP2003160785A/en
Publication of JP2003160785A publication Critical patent/JP2003160785A/en
Withdrawn legal-status Critical Current

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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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/3201—Structure
    • H01L2224/32012—Structure relative to the bonding area, e.g. bond pad
    • H01L2224/32013—Structure relative to the bonding area, e.g. bond pad the layer connector being larger than the bonding area, e.g. bond pad
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    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector 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
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
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    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a red-light-emitting phosphor having the characteristics of an La<SB>2</SB>O<SB>2</SB>S: Eu, Sm phosphor (a red-light-emitting phosphor) capable of efficiently giving a red light when excited with a long-wavelength ultraviolet radiation and moreover improving temperature characteristics. <P>SOLUTION: The red-light-emitting phosphor comprises a trivalent-europium and samarium-activated lanthanum oxysulfide phosphor having a composition represented by (La<SB>1-x-y</SB>Eu<SB>x</SB>Sm<SB>y</SB>)<SB>2</SB>O<SB>2</SB>S.mM<SB>2</SB>O<SB>3</SB>(wherein M is at least one metal element selected from Ga and In; 0.01≤x≤0.15; 0.00005≤y≤0.05; and 0.00001≤m≤0.001). A light emitter is provided with a light-emitting part (16) that contains the red-light-emitting phosphor and emits a visible light when excited with an ultraviolet radiation from a light source 11. <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、ＬＥＤランプなど
の発光装置に用いられる赤色発光蛍光体とそれを用いた
発光装置に関する。TECHNICAL FIELD The present invention relates to a red light emitting phosphor used in a light emitting device such as an LED lamp and a light emitting device using the same.

【０００２】[0002]

【従来の技術】発光ダイオード（ＬＥＤ）を用いたＬＥ
Ｄランプは、携帯機器、ＰＣ周辺機器、ＯＡ機器、各種
スイッチ、バックライト用光源、表示板などの各種表示
装置に用いられている。ＬＥＤチップは半導体素子であ
るために、長寿命でかつ信頼性が高く、光源として用い
た場合にその交換作業が軽減されることから、種々の用
途への応用が試みられている。LE using a light emitting diode (LED)
D lamps are used in various display devices such as portable devices, PC peripheral devices, OA devices, various switches, light sources for backlights, and display boards. Since the LED chip is a semiconductor element, it has a long life and high reliability, and when it is used as a light source, the replacement work is reduced, so that application to various applications has been attempted.

【０００３】ＬＥＤランプを種々の用途に適用する場
合、特に1個のＬＥＤランプで白色発光を得ることが重
要となる。そこで、ＬＥＤチップの表面に青色、緑色お
よび赤色発光蛍光体を塗布したり、あるいはＬＥＤラン
プを構成する樹脂中に各色発光の蛍光体粉末を含有させ
ることによって、1個のＬＥＤランプから白色発光を取
り出すことが試みられている。また、最近では色彩感覚
が豊かになり、各種表示装置にも微妙な色合い（色再現
性）が要求されるようになってきたことから、1個のＬ
ＥＤランプから白色発光のみならず、任意の中間色の発
光を取り出すことが試みられている。When the LED lamp is applied to various uses, it is particularly important to obtain white light emission with one LED lamp. Therefore, by applying blue, green, and red light-emitting phosphors on the surface of the LED chip, or by containing phosphor powder of each color emission in the resin that constitutes the LED lamp, white light is emitted from one LED lamp. Attempting to take it out. In addition, recently, the color sense has become richer, and various display devices are now required to have a delicate hue (color reproducibility).
Attempts have been made to extract not only white light emission but also light emission of any intermediate color from the ED lamp.

【０００４】上記したようなＬＥＤランプにおいては、
光源として波長370nm前後の長波長紫外線を放射するＬ
ＥＤチップ（例えば発光層としてＧａＮ系化合物半導体
層を有するＬＥＤチップ）が用いられている。このた
め、ＬＥＤランプに用いられる蛍光体には、上記したよ
うな長波長の紫外線をよく吸収し、かつ効率よく可視光
を発光するものが求められている。さらに、ＬＥＤラン
プは動作時にチップ近傍の温度が80℃前後に達すること
があるため、ＬＥＤランプを構成している蛍光体の温度
もその温度近辺まで上昇する。従って、ＬＥＤランプに
用いられる蛍光体は、温度により輝度が大きく変動しな
い、すなわち良好な温度特性を有することが必要とされ
る。In the LED lamp as described above,
L that emits long-wavelength ultraviolet light with a wavelength of around 370 nm as a light source
ED chips (for example, LED chips having a GaN-based compound semiconductor layer as a light emitting layer) are used. For this reason, phosphors used in LED lamps are required to be those that absorb the above-mentioned long-wavelength ultraviolet light well and efficiently emit visible light. Furthermore, since the temperature of the LED lamp in the vicinity of the chip may reach around 80 ° C. during operation, the temperature of the phosphor forming the LED lamp also rises to around that temperature. Therefore, the phosphor used for the LED lamp is required to have a brightness that does not largely change depending on the temperature, that is, have good temperature characteristics.

【０００５】ところで、長波長紫外線で励起される各色
発光の蛍光体のうち、赤色発光蛍光体としては3価のユ
ーロピウム（Ｅｕ）およびサマリウム（Ｓｍ）で付活さ
れた希土類酸硫化物蛍光体（Ｌａ2Ｏ2Ｓ：Ｅｕ，Ｓｍな
ど）が知られている（例えば特開平11-246857号公報や
特開2000-73052号公報参照）。このような希土類酸硫化
物蛍光体は波長370nm前後の長波長紫外線を効率的に吸
収するため、ＬＥＤランプなどに用いた際に赤色発光を
効率よく得ることができる。By the way, among the phosphors of each color emission excited by long-wavelength ultraviolet light, the red-emitting phosphor is a rare earth oxysulfide phosphor activated by trivalent europium (Eu) and samarium (Sm) ( La 2 O 2 S: Eu, Sm, etc.) are known (see, for example, JP-A-11-246857 and JP-A-2000-73052). Since such a rare earth oxysulfide phosphor efficiently absorbs long-wavelength ultraviolet light having a wavelength of around 370 nm, red light emission can be efficiently obtained when used in an LED lamp or the like.

【０００６】[0006]

【発明が解決しようとする課題】しかしながら、上述し
た3価のＥｕおよびＳｍで付活された希土類酸硫化物蛍
光体（Ｌａ2Ｏ2Ｓ：Ｅｕ，Ｓｍなど）からなる赤色発光
蛍光体は、青色発光蛍光体や緑色発光蛍光体に比べて温
度特性に劣るという問題を有している。具体的には、青
色発光蛍光体や緑色発光蛍光体は30℃での輝度を100％
としたときの80℃における輝度が95〜99％であるのに対
して、上記した赤色発光蛍光体は80℃での輝度が90％程
度まで低下してしまう。However, a red light emitting phosphor made of the above-mentioned trivalent Eu and Sm-activated rare earth oxysulfide phosphor (La 2 O 2 S: Eu, Sm, etc.) is There is a problem that the temperature characteristics are inferior to those of the blue light emitting phosphor and the green light emitting phosphor. Specifically, the blue light emitting phosphor and the green light emitting phosphor have 100% brightness at 30 ° C.
In contrast, the brightness at 80 ° C. is 95 to 99%, whereas the above-mentioned red-emitting phosphor has a brightness of about 90% at 80 ° C.

【０００７】上述したように、従来の長波長紫外線励起
用の赤色発光蛍光体は、青色発光蛍光体や緑色発光蛍光
体に比べて温度特性に劣り、この赤色発光蛍光体の温度
特性に基づく輝度の低下によって、例えばＬＥＤランプ
から発光される白色光の色温度が変化してしまうという
ような問題を招いている。これはＬＥＤランプの品質低
下要因となっている。このようなことから、長波長紫外
線励起用の3価のＥｕおよびＳｍで付活された希土類酸
硫化物蛍光体からなる赤色発光蛍光体の温度特性を改善
することが強く望まれている。As described above, the conventional red light emitting phosphor for exciting long-wavelength ultraviolet light is inferior in temperature characteristics to the blue light emitting phosphor and the green light emitting phosphor, and the brightness based on the temperature characteristic of the red light emitting phosphor. As a result, the problem that the color temperature of white light emitted from an LED lamp changes, for example, is caused. This is a factor that deteriorates the quality of the LED lamp. Therefore, it is strongly desired to improve the temperature characteristics of the red light emitting phosphor made of a trivalent Eu and Sm activated rare earth oxysulfide phosphor for long wavelength ultraviolet excitation.

【０００８】なお、長波長の紫外線で励起して発光させ
る発光装置としては、上述したＬＥＤランプが代表例と
して挙げられるが、これに限られるものではなく、例え
ば蛍光体を含有させた塗料を所定の形状に塗付し、これ
にブラックライトなどの蛍光ランプから長波長の紫外線
を照射して、蛍光体を含有させた塗料を発光させること
により所定の表示を行う装置が、道路標識のような大型
の表示装置として用いられるようになってきている。こ
のような表示装置用の発光装置においても、ＬＥＤラン
プほどではないものの、温度特性の改善が求められてい
る。The above-mentioned LED lamp is mentioned as a typical example of the light-emitting device which is excited by long-wavelength ultraviolet light to emit light. However, the light-emitting device is not limited to this and, for example, a coating material containing a phosphor is predetermined. A device that displays a predetermined indication by applying a long-wavelength ultraviolet ray from a fluorescent lamp such as a black light to emit light of a phosphor-containing paint is applied to the shape of It has come to be used as a large-sized display device. Even in the light emitting device for such a display device, improvement in temperature characteristics is required, though not as much as the LED lamp.

【０００９】本発明はこのような課題に対処するために
なされたもので、例えば長波長紫外線で励起した際に赤
色光が効率よく得られるＬａ2Ｏ2Ｓ：Ｅｕ，Ｓｍ蛍光体
の温度特性を青色発光蛍光体や緑色発光蛍光体と同等の
レベルまで改善した赤色発光蛍光体を提供することを目
的としており、さらにそのような赤色発光蛍光体を用い
ることによって、種々の動作条件下で任意の色温度の白
色光や各種中間色光を効率および精度よく取り出すこと
を可能にした発光装置を提供することを目的としてい
る。The present invention has been made to solve such a problem. For example, the temperature characteristics of the La 2 O 2 S: Eu, Sm phosphor that can efficiently obtain red light when excited with long-wavelength ultraviolet light. It is an object of the present invention to provide a red light emitting phosphor improved to a level equivalent to that of a blue light emitting phosphor or a green light emitting phosphor, and by using such a red light emitting phosphor, it is possible to obtain a desired light emission under various operating conditions. It is an object of the present invention to provide a light emitting device capable of efficiently and accurately extracting white light of various color temperatures and various intermediate color lights.

【００１０】[0010]

【課題を解決するための手段】上記した目的を達成する
ために、本発明者らは赤色発光の希土類酸硫化物蛍光体
の組成などについて詳細に調査、実験、検討を重ねた結
果、3価のユーロピウム（Ｅｕ）およびサマリウム（Ｓ
ｍ）で付活された酸硫化ランタン蛍光体（Ｌａ 2Ｏ2Ｓ：
Ｅｕ，Ｓｍ）中に、3価の金属であるガリウムやインジ
ウムの酸化物（Ｇａ2Ｏ3やＩｎａ2Ｏ3）を固溶させるこ
とによって、温度特性を著しく改善することができ、こ
れにより実使用時の長波長紫外線などによる発光効率を
高めることが可能であることを見出した。[Means for Solving the Problems] To achieve the above object.
For this reason, the present inventors have developed a red-emitting rare earth oxysulfide phosphor.
The results of detailed investigations, experiments, and studies on the composition of
As a result, trivalent europium (Eu) and samarium (S
m) lanthanum oxysulfide phosphor (La) 2O2S:
Eu, Sm) in the trivalent metal gallium and indium
Umium oxide (Ga2O3And Ina2O3) As a solid solution
With, the temperature characteristics can be significantly improved.
As a result, the luminous efficiency due to long-wavelength ultraviolet light during actual use is improved.
It was found that it is possible to increase.

【００１１】本発明はこのような知見に基づいて成され
たもので、本発明の赤色発光蛍光体は請求項１に記載し
たように、 一般式：（Ｌａ1-x-yＥｕxＳｍy）2Ｏ2Ｓ・mＭ2Ｏ3 （式中、ＭはＧａおよびＩｎから選ばれる少なくとも1
種の元素を示し、ｘ、ｙおよびｍはそれぞれ0.01≦ｘ≦
0.15、0.00005≦ｙ≦0.05、0.00001≦ｍ≦0.001を満足
する数である）で実質的に表される組成を有する3価の
ユーロピウムおよびサマリウム付活酸硫化ランタン蛍光
体からなることを特徴としている。[0011] The present invention has been made based on these findings, the red-emitting phosphor of the present invention as described in claim 1, the general formula: (La 1-xy Eu x Sm y) 2 O 2 S · mM 2 O 3 (wherein M is at least 1 selected from Ga and In)
Indicates the element of the species, x, y and m are 0.01 ≦ x ≦
0.15, 0.00005 ≤ y ≤ 0.05, 0.00001 ≤ m ≤ 0.001), which is a trivalent europium- and samarium-activated lanthanum oxysulfide phosphor having a composition substantially represented by .

【００１２】本発明の発光装置は、請求項４に記載した
ように、紫外線を放射する光源と、上記した本発明の赤
色発光蛍光体を含み、かつ前記光源からの紫外線により
励起されて可視光を発光させる発光装置用蛍光体を有す
る発光部とを具備することを特徴としている。A light emitting device of the present invention comprises, as described in claim 4, a light source that emits ultraviolet light and the above-described red light emitting phosphor of the present invention, and is excited by the ultraviolet light from the light source to emit visible light. And a light emitting section having a phosphor for a light emitting device for emitting light.

【００１３】本発明の発光装置において。発光部は請求
項５に記載したように、上記した赤色発光蛍光体に加え
て、青色発光蛍光体や緑色発光蛍光体を含む発光装置用
蛍光体を用いることができる。また、本発明の発光装置
の具体例としては、請求項８に記載した光源として波長
350〜390nmの長波長紫外線を放射する窒化物系化合物半
導体層を有する発光チップを具備するＬＥＤランプや、
請求項９に記載した光源として波長330〜390nmの長波長
紫外線を放射するブラックライトを具備する表示装置な
どが挙げられる。In the light emitting device of the present invention. As described in claim 5, for the light emitting section, in addition to the above red light emitting phosphor, a light emitting device phosphor including a blue light emitting phosphor or a green light emitting phosphor can be used. In addition, as a specific example of the light emitting device of the present invention, the light source having the wavelength of
An LED lamp including a light emitting chip having a nitride-based compound semiconductor layer that emits long-wavelength ultraviolet light of 350 to 390 nm,
Examples of the light source described in claim 9 include a display device including a black light that emits long-wavelength ultraviolet light having a wavelength of 330 to 390 nm.

【００１４】[0014]

【発明の実施の形態】以下、本発明を実施するための形
態について説明する。本発明の赤色発光蛍光体は、 一般式：（Ｌａ1-x-yＥｕxＳｍy）2Ｏ2Ｓ・mＭ2Ｏ3 …
(1) （式中、ＭはＧａおよびＩｎから選ばれる少なくとも1
種の元素を示し、ｘ、ｙおよびｍはそれぞれ0.01≦ｘ≦
0.15、0.00005≦ｙ≦0.05、0.00001≦ｍ≦0.001を満足
する数である）で実質的に表される組成を有する3価の
ユーロピウムおよびサマリウム付活酸硫化ランタン蛍光
体からなるものである。BEST MODE FOR CARRYING OUT THE INVENTION Modes for carrying out the present invention will be described below. Red light-emitting phosphor of the present invention have the general formula: (La 1-xy Eu x Sm y) 2 O 2 S · mM 2 O 3 ...
(1) (wherein M is at least 1 selected from Ga and In)
Indicates the element of the species, x, y and m are 0.01 ≦ x ≦
0.15, 0.00005 ≤ y ≤ 0.05, 0.00001 ≤ m ≤ 0.001), which is a trivalent europium and samarium activated lanthanum oxysulfide phosphor.

【００１５】ここで、3価のユーロピウム（Ｅｕ）は、
蛍光体母体としての酸硫化ランタンの発光効率を高める
付活剤であり、上記(1)式のｘの値として0.01〜0.15の
範囲で含有させる。Ｅｕの含有量を示すｘの値が0.01未
満であると、発光効率の改善効果が少なく、十分な輝度
を得ることができない。一方、ｘの値が0.15を超えると
濃度消光などにより輝度が低下する。ｘの値は0.03〜0.
08の範囲とすることがより好ましい。Here, the trivalent europium (Eu) is
It is an activator that enhances the luminous efficiency of lanthanum oxysulfide as a phosphor matrix, and is contained in the range of 0.01 to 0.15 as the value of x in the above formula (1). When the value of x showing the content of Eu is less than 0.01, the effect of improving the luminous efficiency is small and sufficient luminance cannot be obtained. On the other hand, when the value of x exceeds 0.15, the brightness decreases due to density quenching. The value of x is 0.03 to 0.
The range of 08 is more preferable.

【００１６】サマリウム（Ｓｍ）は付活剤として機能す
る他に、酸硫化ランタンを母体とする蛍光体の励起スペ
クトルを長波長側にシフトさせる作用を有する。これに
よって、例えば波長330〜390nmの長波長紫外線の吸収効
率が改善され、そのような長波長紫外線で励起した際の
発光効率を向上させることができる。このようなＳｍは
(1)式のｙの値として0.00005〜0.05の範囲で含有させ
る。なお、本発明ではＬａ2Ｏ2Ｓ：Ｅｕ，Ｓｍ蛍光体に
特定の金属酸化物（Ｍ2Ｏ3）を固溶させているために、
Ｓｍの最適な範囲が従来のものに比べて拡大している。
ｙの値が0.00005未満であると、励起スペクトル波長を
長波長側にシフトさせる効果が不十分となる。一方、ｙ
の値が0.05を超えると蛍光体の発光効率がかえって低下
する。ｙの値は0.0005〜0.005の範囲とすることがより
好ましい。In addition to functioning as an activator, samarium (Sm) has a function of shifting the excitation spectrum of a phosphor having lanthanum oxysulfide as a base material to the longer wavelength side. Thereby, for example, the absorption efficiency of long-wavelength ultraviolet light having a wavelength of 330 to 390 nm is improved, and the emission efficiency when excited by such long-wavelength ultraviolet light can be improved. Such Sm
The value of y in the formula (1) is contained in the range of 0.00005 to 0.05. In the present invention, since the specific metal oxide (M 2 O 3 ) is solid-dissolved in the La 2 O 2 S: Eu, Sm phosphor,
The optimum range of Sm has expanded compared with the conventional one.
If the value of y is less than 0.00005, the effect of shifting the excitation spectrum wavelength to the long wavelength side becomes insufficient. On the other hand, y
When the value of exceeds 0.05, the luminous efficiency of the phosphor is rather lowered. The value of y is more preferably in the range of 0.0005 to 0.005.

【００１７】なお、蛍光体母体としての酸硫化ランタン
において、ランタン（Ｌａ）の一部はイットリウム
（Ｙ）およびガドリニウム（Ｇｄ）から選ばれる少なく
とも1種の元素、具体的にはＹ、Ｇｄ、Ｙ＋Ｇｄのいず
れかにより置換してもよい。ＹやＧｄは蛍光体中に固溶
することで、赤色領域における発光エネルギーを高める
効果を示す。ただし、ＹやＧｄによるＬａの置換量が多
すぎると、結晶の歪みが無視できなくなり、逆に発光強
度が低下するため、ＹやＧｄによる置換量はＬａの30モ
ル％以下とすることが好ましい。In lanthanum oxysulfide as a phosphor matrix, a part of lanthanum (La) is at least one element selected from yttrium (Y) and gadolinium (Gd), specifically, Y, Gd, Y + Gd. You may substitute by either. Y and Gd, when solid-dissolved in the phosphor, have the effect of increasing the emission energy in the red region. However, if the amount of substitution of La with Y or Gd is too large, the strain of the crystal cannot be ignored, and the emission intensity is reduced on the contrary. Therefore, the amount of substitution with Y or Gd is preferably 30 mol% or less of La. .

【００１８】本発明の赤色発光蛍光体においては、上述
したようなＬａ2Ｏ2Ｓ：Ｅｕ，Ｓｍ蛍光体に、Ｇａおよ
びＩｎから選ばれる少なくとも1種のＭ元素の酸化物
（Ｍ2Ｏ 3）を固溶させており、これにより酸硫化ランタ
ン系の赤色発光蛍光体の温度特性を改善することができ
る。すなわち、3価の金属であるＧａやＩｎは蛍光体母
体のＬａの位置に置換した形で固溶し、これにより酸硫
化ランタン系の赤色発光蛍光体の温度特性が改善され
る。酸化物として蛍光体母体に固溶させるＭ元素は、Ｇ
ａおよびＩｎをそれぞれ単独で使用してもよいし、Ｇａ
とＩｎの混合物で使用してもよい。In the red light emitting phosphor of the present invention,
La like2O2S: Eu, Sm phosphor, Ga and
And oxides of at least one M element selected from In
(M2O 3) As a solid solution, and
Can improve the temperature characteristics of red-emitting phosphors
It That is, Ga and In, which are trivalent metals, are phosphor matrix.
It forms a solid solution in the form of substitution at the La position of the body.
The temperature characteristics of the lanthanum bromide-based red-emitting phosphor are improved.
It The M element dissolved in the phosphor matrix as an oxide is G
a and In may be used alone or Ga
You may use with the mixture of In and In.

【００１９】このようなＭ元素の酸化物（Ｍ2Ｏ3）は、
上記(1)式のｍの値が0.00001〜0.001の範囲となるよう
に、Ｌａ2Ｏ2Ｓ：Ｅｕ，Ｓｍ蛍光体中に固溶させる。Ｍ
元素の酸化物の固溶量が0.00001モル未満の場合には、
Ｍ2Ｏ3による温度特性の改善効果が不十分であり、良好
な温度特性を得ることができない。一方、Ｍ元素の酸化
物の固溶量が0.001モルを超えると、蛍光体の発光を阻
害すると共に、温度特性の改善効果も逆に低下してしま
う。Ｍ元素の酸化物の固溶量は0.00005〜0.0005モルの
範囲とすることがより好ましい。Such an M element oxide (M 2 O 3 ) is
It is solid-dissolved in the La 2 O 2 S: Eu, Sm phosphor so that the value of m in the above formula (1) is in the range of 0.00001 to 0.001. M
When the solid solution amount of the oxide of the element is less than 0.00001 mol,
The effect of improving the temperature characteristics by M 2 O 3 is insufficient, and good temperature characteristics cannot be obtained. On the other hand, when the solid solution amount of the oxide of the M element exceeds 0.001 mol, the emission of the phosphor is inhibited and the effect of improving the temperature characteristics is also decreased. The solid solution amount of the oxide of the M element is more preferably in the range of 0.00005 to 0.0005 mol.

【００２０】上述した(1)式で表される3価のＥｕおよび
Ｓｍ付活酸硫化ランタン蛍光体は、波長270〜395nmの紫
外線、特に波長330〜390nmの長波長紫外線を効率よく吸
収する。従って、そのような紫外線（特に長波長紫外
線）で励起した際に、例えばピーク波長が625nm付近の
赤色光を効率よく得ることができることから、各種の紫
外線励起発光装置用の赤色発光蛍光体として有用なもの
である。その上で、本発明の赤色発光蛍光体は良好な温
度特性を有することから、実使用条件下での発光効率を
高めることができる。また、青色発光蛍光体や緑色発光
蛍光体と混合して使用する場合に、温度上昇が想定され
る実使用条件下での赤色発光蛍光体の発光効率の低下が
抑制されるため、任意の色温度の白色光や各種中間色光
を効率および精度よく得ることが可能となる。The trivalent Eu and Sm activated lanthanum oxysulfide phosphor represented by the above formula (1) efficiently absorbs ultraviolet rays having a wavelength of 270 to 395 nm, particularly long wavelength ultraviolet rays having a wavelength of 330 to 390 nm. Therefore, when excited by such ultraviolet rays (especially long-wavelength ultraviolet rays), it is possible to efficiently obtain red light with a peak wavelength of around 625 nm, and therefore useful as a red-emitting phosphor for various ultraviolet-excited light-emitting devices. It is something. In addition, since the red light emitting phosphor of the present invention has good temperature characteristics, it is possible to increase the light emission efficiency under actual use conditions. In addition, when used by mixing with a blue-emitting phosphor or a green-emitting phosphor, a decrease in the luminous efficiency of the red-emitting phosphor under actual use conditions in which a temperature rise is assumed is suppressed, so any color It is possible to efficiently and accurately obtain white light of various temperatures and various intermediate color lights.

【００２１】上述した本発明の赤色発光蛍光体、すなわ
ち3価のＥｕおよびＳｍ付活酸硫化ランタン（（Ｌａ
1-x-yＥｕxＳｍy）2Ｏ2Ｓ・mＭ2Ｏ3）蛍光体は、例えば
以下のようにして作製される。まず、Ｌａ2Ｏ3、Ｅｕ2
Ｏ3、Ｓｍ2Ｏ3、Ｓ、Ｍ2Ｏ3（Ｇｄ2Ｏ3やＩｎ2Ｏ3）な
どの各原料粉末を、上記した(1)式の組成となるように
所定量秤量し、これらをＮａ2ＣＯ3やＬｉ3ＰＯ4などの
融剤と共に、ボールミルなどを用いて十分に混合する。
このようにして得られた原料混合物をアルミナるつぼな
どに収容して、大気中にて1100〜1400℃程度の温度で 3
〜 6時間程度焼成する。The above-mentioned red light-emitting phosphor of the present invention, that is, trivalent Eu and Sm activated lanthanum oxysulfide ((La
1-xy Eu x Sm y) 2 O 2 S · mM 2 O 3) phosphor, for example, produced as follows. First, La 2 O 3 and Eu 2
Raw material powders such as O 3 , Sm 2 O 3 , S and M 2 O 3 (Gd 2 O 3 and In 2 O 3 ) were weighed in predetermined amounts so as to obtain the composition of the above formula (1), Is thoroughly mixed with a flux such as Na 2 CO 3 or Li 3 PO 4 using a ball mill or the like.
The raw material mixture thus obtained was placed in an alumina crucible or the like and heated at a temperature of about 1100 to 1400 ° C in the atmosphere.
Bake for about 6 hours.

【００２２】ここで、各原料粉末には酸化物に限らず、
加熱により容易に酸化物に分解し得る炭酸塩、硝酸塩、
蓚酸塩、水酸化物などを用いてもよい。また、各希土類
原料粉末としての酸化物を反応槽にて酸で溶解し、混合
蓚酸塩として沈殿させた後、この沈殿物を焼成して得ら
れる共沈酸化物を出発原料として用いてもよい。この場
合には10％前後の輝度の向上が期待できる。Here, each raw material powder is not limited to oxides,
Carbonates, nitrates that can be easily decomposed into oxides by heating,
You may use oxalate, a hydroxide, etc. Alternatively, a coprecipitated oxide obtained by dissolving the oxide as each rare earth raw material powder with an acid in a reaction tank and precipitating it as a mixed oxalate and then firing the precipitate may be used as a starting material. . In this case, a brightness improvement of about 10% can be expected.

【００２３】次に、得られた焼成物を純水にて洗浄し、
不要な可溶成分を除去する。さらに、例えばpH2以上の
酸性液で酸洗浄した後、純水で3〜5回程度洗浄し、ろ過
・乾燥させることにより、目的とする赤色発光蛍光体が
得られる。ここで、酸洗浄の際に、洗浄液のpHを2以上
に保つことによって、蛍光体粒子に混入した非発光成分
を効率よく除去することができると共に、蛍光体粒子の
製品歩留りを90％以上に高めることができる。酸洗浄時
の洗浄液のpHは2〜4の範囲に保つことがさらに好まし
い。Next, the fired product obtained is washed with pure water,
Remove unwanted soluble components. Further, for example, after acid washing with an acidic liquid having a pH of 2 or more, washing with pure water about 3 to 5 times, filtration and drying, the desired red-emitting phosphor can be obtained. Here, during the acid cleaning, by keeping the pH of the cleaning solution at 2 or more, it is possible to efficiently remove the non-luminescent component mixed in the phosphor particles, and the product yield of the phosphor particles is 90% or more. Can be increased. It is more preferable to maintain the pH of the cleaning liquid during the acid cleaning in the range of 2 to 4.

【００２４】本発明の赤色発光蛍光体は、例えば波長27
0〜395nmの紫外線、特に波長330〜390nmの長波長紫外線
で励起して可視光を得るような用途、例えば発光装置用
蛍光体として好適に用いられる。そして、本発明の発光
装置は、上述した本発明の赤色発光蛍光体を少なくとも
含む発光装置用蛍光体を有する発光部に、各種の光源か
ら長波長の紫外線などを照射し、これにより発光部から
可視光を得るように構成したものである。このような発
光装置の代表例としては、光源として波長350〜390nmの
長波長紫外線を放射する窒化物系化合物半導体層を有す
る発光チップを具備するＬＥＤランプが挙げられるが、
これ以外にも例えば標識用表示装置などに適用すること
ができる。The red light emitting phosphor of the present invention has a wavelength of 27
It is preferably used as a fluorescent substance for a light emitting device, for example, when it is excited by ultraviolet rays having a wavelength of 0 to 395 nm, particularly long wavelength ultraviolet rays having a wavelength of 330 to 390 nm to obtain visible light. Then, the light emitting device of the present invention, the light emitting unit having a phosphor for a light emitting device containing at least the above-described red light emitting phosphor of the present invention, irradiates long-wavelength ultraviolet light or the like from various light sources, thereby emitting light from the light emitting unit. It is configured to obtain visible light. A typical example of such a light emitting device is an LED lamp including a light emitting chip having a nitride-based compound semiconductor layer that emits long-wavelength ultraviolet light having a wavelength of 350 to 390 nm as a light source.
Besides this, it can be applied to, for example, a display device for a sign.

【００２５】図１は本発明の発光装置をＬＥＤランプに
適用した一実施形態の概略構成を示す断面図である。同
図において、１１は例えばＩｎＧａＮ活性層を有する中
心波長が370nm付近の紫外ＬＥＤチップであり、この紫
外ＬＥＤチップ１１はリードフレーム１２上に接着剤層
１３を介して固定されている。また、紫外ＬＥＤチップ
１１とリードフレーム１２とは、ボンディングワイヤ１
４により電気的に接続されている。紫外ＬＥＤチップ１
１は、ボンディングワイヤ１４などと共に樹脂層１５に
より覆われている。ここで、樹脂層１５は紫外ＬＥＤチ
ップ１１の周囲を覆うプレディップ材１６と、このプレ
ディップ材１６の周囲を覆うキャスティング材１７とを
有している。プレディップ材１６とキャスティング材１
７には、透明な樹脂などが用いられる。FIG. 1 is a sectional view showing a schematic structure of an embodiment in which the light emitting device of the present invention is applied to an LED lamp. In the figure, reference numeral 11 denotes an ultraviolet LED chip having an InGaN active layer and having a center wavelength of around 370 nm, and this ultraviolet LED chip 11 is fixed on a lead frame 12 via an adhesive layer 13. The ultraviolet LED chip 11 and the lead frame 12 are bonded to each other by the bonding wire 1.
4 electrically connected. UV LED chip 1
1 is covered with a resin layer 15 together with the bonding wires 14 and the like. Here, the resin layer 15 has a pre-dip material 16 that covers the periphery of the ultraviolet LED chip 11, and a casting material 17 that covers the periphery of the pre-dip material 16. Predip 16 and casting 1
A transparent resin or the like is used for 7.

【００２６】図１に示すＬＥＤランプにおいて、プレデ
ィップ材１６は前述した本発明の赤色発光蛍光体を少な
くとも含む発光装置用蛍光体を含有しており、紫外ＬＥ
Ｄチップ１１から放射された紫外線により励起され、発
光装置用蛍光体の種類や混合比率などに応じた可視光を
発光させる発光部として機能するものである。なお、発
光装置用蛍光体はプレディップ材１６中に含有させて使
用することに限られるものではなく、例えば紫外ＬＥＤ
チップ１１の発光面に蛍光体層を形成して用いるなど、
種々の形態で使用することができる。In the LED lamp shown in FIG. 1, the pre-dip material 16 contains a phosphor for a light emitting device containing at least the above-described red light emitting phosphor of the present invention, and the ultraviolet LE
It functions as a light emitting unit that is excited by the ultraviolet rays emitted from the D chip 11 and emits visible light according to the type and mixing ratio of the phosphor for the light emitting device. The phosphor for a light emitting device is not limited to being used by being contained in the pre-dip material 16, and may be, for example, an ultraviolet LED.
For example, by forming a phosphor layer on the light emitting surface of the chip 11,
It can be used in various forms.

【００２７】上記した発光装置用蛍光体は、目的とする
発光色に応じて、本発明の赤色発光蛍光体に加えて、青
色発光蛍光体や緑色発光蛍光体などを混合して用いるこ
とができる。ここで、青色発光成分および緑色発光成分
としての各蛍光体の種類は、特に限定されるものではな
いが、長波長の紫外線による発光効率に優れる蛍光体を
使用することが好ましい。The above-mentioned phosphor for a light emitting device can be used in combination with a blue light emitting phosphor, a green light emitting phosphor and the like in addition to the red light emitting phosphor of the present invention, depending on the intended emission color. . Here, the type of each phosphor as a blue light emitting component and a green light emitting component is not particularly limited, but it is preferable to use a phosphor having excellent emission efficiency by long-wavelength ultraviolet light.

【００２８】例えば、青色発光蛍光体としては、 一般式：（Ｍ1，Ｅｕ）10（ＰＯ4）6・Ｃｌ2 （式中、Ｍ1はＭｇ、Ｃａ、ＳｒおよびＢａから選ばれ
る少なくとも1種の元素を示す）で実質的に表される2価
のユーロピウム付活ハロ燐酸塩蛍光体、 一般式：ａ（Ｍ2，Ｅｕ）Ｏ・ｂＡｌ2Ｏ3 （式中、Ｍ2はＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｌｉ、
ＲｂおよびＣｓから選ばれる少なくとも1種の元素を示
し、ａおよびｂはａ＞0、ｂ＞0、0.1≦ａ／ｂ≦1.0を満
足する数である）で実質的に表される2価のユーロピウ
ム付活アルミン酸塩蛍光体、および 一般式：ａ（Ｍ2，Ｅｕv，Ｍｎw）Ｏ・ｂＡｌ2Ｏ3 （式中、Ｍ2はＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｌｉ、
ＲｂおよびＣｓから選ばれる少なくとも1種の元素を示
し、ａ、ｂ、ｖおよびｗはａ＞0、ｂ＞0、0.1≦ａ／ｂ
≦1.0、0.001≦ｗ／ｖ≦0.2を満足する数である）で実
質的に表される2価のユーロピウムおよびマンガン付活
アルミン酸塩蛍光体から選ばれる少なくとも1種を用い
ることが好ましい。For example, as the blue light emitting phosphor, a general formula: (M1, Eu) 10 (PO 4 ) 6 .Cl 2 (wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba) divalent europium-activated halophosphate phosphor substantially represented by the illustrated), the general formula: a (M2, Eu) O · bAl 2 O 3 ( where, M2 is Mg, Ca, Sr, Ba , Zn, Li,
Rb and Cs represent at least one element, and a and b are numbers satisfying a> 0, b> 0, and 0.1 ≦ a / b ≦ 1.0). Europium-activated aluminate phosphor, and a general formula: a (M2, Eu v , Mn w ) O.bAl 2 O 3 (wherein M2 is Mg, Ca, Sr, Ba, Zn, Li,
At least one element selected from Rb and Cs, where a, b, v and w are a> 0, b> 0, 0.1 ≦ a / b
It is preferable to use at least one selected from divalent europium- and manganese-activated aluminate phosphors substantially represented by ≦ 1.0 and 0.001 ≦ w / v ≦ 0.2).

【００２９】また、緑色発光蛍光体としては、 一般式：ａ（Ｍ2，Ｅｕs，Ｍｎt）Ｏ・ｂＡｌ2Ｏ3 （式中、Ｍ2はＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｌｉ、
ＲｂおよびＣｓから選ばれる少なくとも1種の元素を示
し、ａ、ｂ、ｓおよびｔはａ＞0、ｂ＞0、0.1≦ａ／ｂ
≦1.0、0.3≦ｔ／ｓ≦5.0を満足する数である）で実質
的に表される2価のユーロピウムおよびマンガン付活ア
ルミン酸塩蛍光体、および 一般式：（Ｙ1-h-i-jＲhＴｂiＣｅj）2Ｏ3・ｋＳｉＯ2 （式中、ＲはＬａおよびＧｄから選ばれる少なくとも1
種の元素を示し、ｈ、ｉ、ｊおよびｋは5×10-4≦ｈ≦
0.3、0.05≦ｉ≦0.3、0.001≦ｊ≦0.15、0.8≦ｋ≦1.3
を満足する数である）で実質的に表される3価のテルビ
ウムおよびセリウム付活希土類珪酸塩蛍光体から選ばれ
る少なくとも1種を用いることが好ましい。Further, as the green-emitting phosphor of the general formula: a (M2, Eu s, Mn t) O · bAl 2 O 3 ( where, M2 is Mg, Ca, Sr, Ba, Zn, Li,
At least one element selected from Rb and Cs, where a, b, s and t are a> 0, b> 0, 0.1 ≦ a / b
A divalent europium- and manganese-activated aluminate phosphor substantially represented by ≦ 1.0 and 0.3 ≦ t / s ≦ 5.0, and a general formula: (Y 1-hij R h Tb i Ce j ) 2 O 3 · kSiO 2 (wherein R is at least 1 selected from La and Gd)
Represents a seed element, h, i, j and k are 5 × 10 −4 ≦ h ≦
0.3, 0.05 ≤ i ≤ 0.3, 0.001 ≤ j ≤ 0.15, 0.8 ≤ k ≤ 1.3
It is preferable to use at least one selected from trivalent terbium and cerium-activated rare earth silicate phosphors substantially represented by

【００３０】上記したような青色および緑色発光蛍光体
は、いずれも長波長紫外線の吸収効率に優れるものであ
り、従って長波長の紫外線で励起した際に青色光および
緑色光を効率よく得ることができる。このような青色お
よび緑色発光蛍光体などを、本発明の赤色発光蛍光体と
適宜に組合せて使用することによって、任意の色温度の
白色光や紫色、桃色、青緑色などの中間色光を効率よく
取り出すことができる。さらに、本発明の赤色発光蛍光
体は良好な温度特性を有することから、実使用時にＬＥ
Ｄランプの温度が上昇した場合においても、赤色発光蛍
光体の発光効率の低下を青色および緑色発光蛍光体と同
程度に押さえることができる。従って、任意の色温度の
白色光や各種中間色光の色再現性を大幅に向上させるこ
とが可能となる。The blue and green light emitting phosphors as described above are both excellent in absorption efficiency of long-wavelength ultraviolet light, and therefore, when excited by long-wavelength ultraviolet light, blue light and green light can be efficiently obtained. it can. By using such blue and green light emitting phosphors in an appropriate combination with the red light emitting phosphor of the present invention, it is possible to efficiently produce white light of any color temperature and intermediate color light of purple, pink, blue green, etc. You can take it out. Furthermore, since the red light-emitting phosphor of the present invention has good temperature characteristics, it is LE
Even when the temperature of the D lamp rises, the reduction in the luminous efficiency of the red light emitting phosphor can be suppressed to the same extent as that of the blue and green light emitting phosphors. Therefore, it is possible to significantly improve the color reproducibility of white light of any color temperature and various intermediate color lights.

【００３１】赤色、青色、緑色の各色発光成分の混合比
率は、目的とする発光色に応じて適宜設定することがで
きる。例えば、白色光を得る際には質量比で、青色発光
成分を65％以下、緑色発光成分を5〜65％の範囲、赤色
発光成分を15〜95％の範囲とすることが好ましい。この
ような混合比率によれば、例えば色温度2700K前後から8
000K前後の白色光を任意に得ることができ、さらには従
来の波長254nmで励起した三波長蛍光体と遜色のない明
るさが得られる。The mixing ratio of the red, blue, and green light emitting components can be appropriately set in accordance with the intended light emitting color. For example, when obtaining white light, it is preferable that the blue light emitting component is 65% or less, the green light emitting component is 5 to 65%, and the red light emitting component is 15 to 95% by mass ratio. According to such a mixing ratio, for example, from a color temperature of around 2700K to 8
White light of around 000K can be obtained arbitrarily, and the brightness is comparable to the conventional three-wavelength phosphor excited at a wavelength of 254 nm.

【００３２】本発明の発光装置は、上述したＬＥＤラン
プに限られるものではなく、例えば本発明の赤色発光蛍
光体を含む発光装置用蛍光体を塗料と共に塗布した発光
部と、この発光部に波長330〜390nmの長波長紫外線を放
射するブラックライトなどの光源とを具備する標識用の
表示装置などにも適用可能である。このような表示装置
は標識などに用いられ、その際の光源としてはＢａＳｉ
2Ｏ5：Ｐｂ蛍光体（ピーク波長:353nm）やＳｒＢ4Ｏ7：
Ｅｕ蛍光体（ピーク波長:370nm）などを用いたブラック
ライト（蛍光ランプ）が使用される。The light emitting device of the present invention is not limited to the above-mentioned LED lamp, and for example, a light emitting portion coated with a phosphor for a light emitting device including the red light emitting phosphor of the present invention together with a coating material, and the wavelength of the light emitting portion. It can also be applied to a display device for a sign, which is provided with a light source such as a black light which emits a long wavelength ultraviolet ray of 330 to 390 nm. Such a display device is used for a sign or the like, and as a light source in that case, BaSi is used.
2 O 5 : Pb phosphor (peak wavelength: 353 nm) or SrB 4 O 7 :
A black light (fluorescent lamp) using a Eu fluorescent substance (peak wavelength: 370 nm) or the like is used.

【００３３】[0033]

【実施例】次に、本発明の具体的な実施例およびその評
価結果について述べる。EXAMPLES Next, specific examples of the present invention and evaluation results thereof will be described.

【００３４】実施例１、比較例１ まず、Ｌａ2Ｏ3を291.5g、Ｅｕ2Ｏ3を20.14g、Ｓｍ2Ｏ3
を0.67g、Ｓを77.17g、Ｇａ2Ｏ3を0.029g、融剤として
のＮａ2ＣＯ3を109.3g、Ｋ3ＰＯ4を31.23gでそれぞれ正
確に秤量し、これらをボールミルを用いて十分に混合し
た。この原料混合物を蓋付きのアルミナるつぼに収容し
て、大気中にて1150℃で5時間焼成した。Example 1 and Comparative Example 1 First, 291.5 g of La 2 O 3 , 20.14 g of Eu 2 O 3 and Sm 2 O 3 were prepared.
0.67 g, S 77.17 g, Ga 2 O 3 0.029 g, Na 2 CO 3 as a fluxing agent 109.3 g, K 3 PO 4 31.23 g. Weigh them accurately using a ball mill. Mixed in. This raw material mixture was placed in an alumina crucible with a lid and fired in the air at 1150 ° C. for 5 hours.

【００３５】得られた焼成物を純水で洗浄することによ
って、不要な可溶成分を除去した。その後、焼成物をボ
ールミルで細かく粉砕し、硫酸および硝酸を添加してpH
が2.5の酸性領域を維持しながら酸洗浄を行い、さらに
純水で4回洗浄した。そして、洗浄した蛍光体粉末をろ
過、乾燥することによって、（Ｌａ0.938Ｅｕ0.060Ｓｍ
0.002）2Ｏ2Ｓ・0.0005Ｇａ2Ｏ3の組成を有する赤色発
光蛍光体を得た。By washing the obtained fired product with pure water
Thus, unnecessary soluble components were removed. After that,
Finely ground with a mill and add sulfuric acid and nitric acid to adjust the pH.
Acid cleaning while maintaining the acidic range of 2.5
It was washed 4 times with pure water. Then, wash the washed phosphor powder.
By overdrying, (La0.938Eu0.060Sm
0.002)2O2S ・ 0.0005Ga2O3With red composition
A photophosphor was obtained.

【００３６】一方、本発明との比較例１として、Ｇａ2
Ｏ3を固溶させない以外は実施例１と同組成の赤色発光
蛍光体（（Ｌａ0.938Ｅｕ0.060Ｓｍ0.002）2Ｏ2Ｓ）を
作製した。On the other hand, as Comparative Example 1 with the present invention, Ga 2
A red light emitting phosphor ((La 0.938 Eu 0.060 Sm 0.002 ) 2 O 2 S) having the same composition as in Example 1 was prepared except that O 3 was not dissolved.

【００３７】上述した実施例１および比較例１の各赤色
発光蛍光体について、380nmの長波長紫外線で励起した
際の発光輝度をそれぞれ測定した。発光輝度はまず各赤
色発光蛍光体を30℃の温度に保持した状態で測定した。
これら30℃での輝度は比較例１の赤色発光蛍光体の輝度
を100としたときの相対輝度として表１に示す。次い
で、各赤色発光蛍光体を90℃の温度に保持し、この状態
で発光輝度をそれぞれ測定した。これら90℃での輝度は
それぞれ30℃での輝度を100としたときの相対輝度とし
て表１に示す。With respect to each of the red-emitting phosphors of Example 1 and Comparative Example 1 described above, the emission brightness when excited with long-wavelength ultraviolet light of 380 nm was measured. The emission brightness was measured with each red-emitting phosphor kept at a temperature of 30 ° C.
The brightness at 30 ° C. is shown in Table 1 as a relative brightness when the brightness of the red light emitting phosphor of Comparative Example 1 is 100. Then, each red-emitting phosphor was maintained at a temperature of 90 ° C., and the emission brightness was measured in this state. The brightness at 90 ° C. is shown in Table 1 as the relative brightness when the brightness at 30 ° C. is 100.

【００３８】[0038]

【表１】 [Table 1]

【００３９】表１から明らかなように、実施例１による
赤色発光蛍光体は温度特性に優れ、周囲温度が90℃に上
昇した場合においても輝度の低下を大幅に抑制できるこ
とが分かる。従って、実施例１の赤色発光蛍光体をＬＥ
Ｄランプなどに用いることによって、周囲温度の変動に
対して安定にかつ効率よく発光を取り出すことができる
ＬＥＤランプなどを作製することが可能となる。As is clear from Table 1, the red-light-emitting phosphor according to Example 1 has excellent temperature characteristics and can significantly suppress the decrease in brightness even when the ambient temperature rises to 90 ° C. Therefore, the red light-emitting phosphor of Example 1 was LE
By using it for a D lamp or the like, it becomes possible to manufacture an LED lamp or the like that can take out light emission stably and efficiently against fluctuations in ambient temperature.

【００４０】実施例２〜１０、比較例２〜３ 表２に示す金属酸化物（Ｍ2Ｏ3）を各組成（ｍ）で固溶
させる以外は、それぞれ実施例１と同様にして、3価の
ＥｕおよびＳｍ付活酸硫化ランタン蛍光体を作製した。
これら各赤色発光蛍光体の30℃および90℃における輝度
を実施例１と同様にして測定した。その結果を表２に示
す。なお、表中の比較例２〜３は金属酸化物の添加量を
本発明の範囲外としたものであり、これらについても同
様に輝度を測定した。Examples 2 to 10 and Comparative Examples 2 to 3 In the same manner as in Example 1 except that the metal oxide (M 2 O 3 ) shown in Table 2 was dissolved in each composition (m), 3 Valent Eu and Sm activated lanthanum oxysulfide phosphors were made.
The brightness of each of these red-emitting phosphors at 30 ° C. and 90 ° C. was measured in the same manner as in Example 1. The results are shown in Table 2. In addition, in Comparative Examples 2 to 3 in the table, the amount of the metal oxide added was out of the range of the present invention, and the luminance was similarly measured for these.

【００４１】[0041]

【表２】 [Table 2]

【００４２】表２から明らかなように、ＧａやＩｎの酸
化物を所定の範囲で固溶させた実施例２〜１０による各
赤色発光蛍光体は、いずれも長波長紫外線で励起した際
に効率よく赤色光を得ることができ、その上で良好な温
度特性を有していることが分かる。As is clear from Table 2, each of the red-emitting phosphors according to Examples 2 to 10 in which Ga and In oxides were solid-soluted within a predetermined range had an efficiency when excited by long-wavelength ultraviolet light. It can be seen that red light can be obtained well and that it has good temperature characteristics.

【００４３】実施例１１、比較例４ まず、実施例１による赤色発光蛍光体と、（Ｓｒ0.73Ｂ
ａ0.22Ｃａ0.05）10（ＰＯ4）6・Ｃｌ2：Ｅｕ組成の青
色発光蛍光体と、3（Ｂａ，Ｍｇ）Ｏ・8Ａｌ2Ｏ 3：Ｅｕ
0.20，Ｍｎ0.40組成の緑色発光蛍光体とを用意した。こ
れら各色の蛍光体を、質量比で赤色発光成分が51.5％、
青色発光成分が18.0％、緑色発光成分が30.5％となるよ
うに秤量し、これらを十分に混合することによって、色
温度が5000K前後の白色発光蛍光体を得た。Example 11, Comparative Example 4 First, the red light emitting phosphor according to Example 1 and (Sr0.73B
a0.22Ca0.05)Ten(POFour)6・ Cl2: Eu composition blue
Color-emitting phosphor and 3 (Ba, Mg) O.8Al2O 3: Eu
0.20, Mn0.40A green light emitting phosphor having a composition was prepared. This
51.5% of the red light emitting component in the mass ratio of the phosphors of each color,
The blue emission component is 18.0% and the green emission component is 30.5%.
The color by mixing them well and mixing them well.
A white light emitting phosphor having a temperature of about 5000 K was obtained.

【００４４】一方、本発明との比較例４として、比較例
１による赤色発光蛍光体を使用する以外は、上記した実
施例１１と同様にして混合蛍光体（白色発光蛍光体）を
作製した。On the other hand, as Comparative Example 4 with the present invention, a mixed phosphor (white light emitting phosphor) was prepared in the same manner as in Example 11 except that the red light emitting phosphor according to Comparative Example 1 was used.

【００４５】このようにして得た各混合蛍光体（白色発
光蛍光体）を波長380nmの紫外線で励起し、かつ30℃お
よび90℃に保持したときの粉体色度を色度計（大塚電子
製、MCPD2000型）を用いて、それぞれ測定、評価した。
実施例１１および比較例４による各混合蛍光体の測定結
果を表３に示す。Each of the mixed phosphors (white-emitting phosphors) thus obtained was excited by ultraviolet rays having a wavelength of 380 nm, and the powder chromaticity when kept at 30 ° C. and 90 ° C. was measured by a chromaticity meter (Otsuka Electronics Co., Ltd.). Manufactured by MCPD2000 type).
Table 3 shows the measurement results of the mixed phosphors of Example 11 and Comparative Example 4.

【００４６】[0046]

【表３】 [Table 3]

【００４７】本発明の赤色発光蛍光体は温度特性に優
れ、周囲温度の変動に対して安定に高効率で赤色光を得
ることができる。従って、表３から明らかなように、白
色発光蛍光体に使用した際に、青色および緑色発光蛍光
体と同程度まで高温下での輝度の低下を抑制できること
から、粉体色度の変化が小さいことが分かる。さらに、
上記した実施例１１の混合蛍光体（白色発光蛍光体）を
用いて図２に示したＬＥＤランプを作製し、実使用条件
下でランプの点灯試験を行ったところ、白色光の色温度
の再現性に優れることが確認された。また、ブラックラ
イトを光源とする標識用表示装置においても同様に良好
な結果が得られた。The red-light-emitting phosphor of the present invention has excellent temperature characteristics and can stably obtain red light with respect to fluctuations in ambient temperature. Therefore, as is apparent from Table 3, when used in a white light emitting phosphor, it is possible to suppress a decrease in luminance at high temperatures to the same extent as in blue and green light emitting phosphors, and thus a change in powder chromaticity is small. I understand. further,
The LED lamp shown in FIG. 2 was manufactured using the mixed phosphor (white light emitting phosphor) of Example 11 described above, and a lighting test of the lamp was conducted under actual use conditions. As a result, the color temperature of white light was reproduced. It was confirmed that it has excellent properties. In addition, similarly good results were obtained also in a display device for a sign using a black light as a light source.

【００４８】実施例１２、比較例５ まず、実施例７による赤色発光蛍光体と、3（Ｂａ，Ｍ
ｇ）Ｏ・8Ａｌ2Ｏ3：Ｅｕ0.15組成の青色発光蛍光体
と、（Ｙ0.64Ｌａ0.10Ｔｂ0.25Ｃｅ0.01）2ＳｉＯ5組成
の緑色発光蛍光体とを用意した。これら各色の蛍光体
を、質量比で赤色発光成分が49.5％、青色発光成分が2
3.5％、緑色発光成分が27.0％となるように秤量し、こ
れらを十分に混合することによって、色温度が6500K前
後の白色発光蛍光体を得た。Example 12, Comparative Example 5 First, the red light-emitting phosphor according to Example 7 and 3 (Ba, M
g) O · 8Al 2 O 3 : a blue-emitting phosphor of Eu 0.15 composition was prepared and a green-emitting phosphor (Y 0.64 La 0.10 Tb 0.25 Ce 0.01) 2 SiO 5 composition. These phosphors of each color have a red emission component of 49.5% and a blue emission component of 2 by mass ratio.
The white light-emitting phosphor having a color temperature of about 6500K was obtained by weighing so that the amount of the green light emitting component was 3.5% and 27.0%, respectively, and thoroughly mixing them.

【００４９】一方、本発明との比較例５として、比較例
１による赤色発光蛍光体を使用する以外は、上記した実
施例１２と同様にして混合蛍光体（白色発光蛍光体）を
作製した。このようにして得た実施例１２および比較例
５による各混合蛍光体（白色発光蛍光体）の粉体色度を
実施例１１と同様にして測定、評価した。それらの測定
結果を表４に示す。On the other hand, as Comparative Example 5 with the present invention, a mixed phosphor (white light emitting phosphor) was prepared in the same manner as in Example 12 except that the red light emitting phosphor according to Comparative Example 1 was used. The powder chromaticity of each of the mixed phosphors (white-emitting phosphors) according to Example 12 and Comparative Example 5 thus obtained was measured and evaluated in the same manner as in Example 11. Table 4 shows the measurement results.

【００５０】[0050]

【表４】 [Table 4]

【００５１】本発明の赤色発光蛍光体は温度特性に優
れ、周囲温度の変動に対して安定に高効率で赤色光を得
ることができる。従って、表４から明らかなように、白
色発光蛍光体に使用した際に、青色および緑色発光蛍光
体と同程度まで高温下での輝度の低下を抑制できること
から、粉体色度の変化が小さいことが分かる。さらに、
上記した実施例１２の混合蛍光体（白色発光蛍光体）を
用いて図２に示したＬＥＤランプを作製し、実使用条件
下でランプの点灯試験を行ったところ、白色光の色温度
の再現性に優れることが確認された。また、ブラックラ
イトを光源とする標識用表示装置においても同様に良好
な結果が得られた。The red-light-emitting phosphor of the present invention has excellent temperature characteristics and can stably obtain red light with respect to fluctuations in ambient temperature. Therefore, as is clear from Table 4, when used in a white light emitting phosphor, it is possible to suppress a decrease in brightness at high temperatures to the same extent as the blue and green light emitting phosphors, and thus a change in powder chromaticity is small. I understand. further,
The LED lamp shown in FIG. 2 was produced using the mixed phosphor (white light emitting phosphor) of Example 12 described above, and a lighting test of the lamp was performed under actual use conditions. As a result, the color temperature of white light was reproduced. It was confirmed that it has excellent properties. In addition, similarly good results were obtained also in a display device for a sign using a black light as a light source.

【００５２】[0052]

【発明の効果】以上説明したように、本発明の赤色発光
蛍光体によれば、例えば長波長紫外線で励起した際の赤
色光の発光効率に優れるというＬａ2Ｏ2Ｓ：Ｅｕ，Ｓｍ
蛍光体の特徴を活かした上で、温度特性を大幅に改善す
ることができる。従って、そのような赤色発光蛍光体を
用いた紫外線励起発光装置によれば、種々の動作条件下
で任意の色温度の白色光や各種中間色光を効率および精
度よく取り出すことが可能となる。As described above, according to the red light-emitting phosphor of the present invention, La 2 O 2 S: Eu, Sm, which has excellent emission efficiency of red light when excited by long-wavelength ultraviolet light, is used.
The temperature characteristics can be significantly improved while taking advantage of the characteristics of the phosphor. Therefore, according to the ultraviolet excitation light emitting device using such a red light emitting phosphor, it is possible to efficiently and accurately extract white light of various color temperatures and various intermediate color lights under various operating conditions.

【図面の簡単な説明】[Brief description of drawings]

【図１】 本発明の発光装置をＬＥＤランプに適用した
一実施形態の概略構成を示す断面図である。FIG. 1 is a sectional view showing a schematic configuration of an embodiment in which a light emitting device of the present invention is applied to an LED lamp.

【符号の説明】[Explanation of symbols]

１……赤色発光蛍光体，２……蛍光体粒子，３……防湿
層，１１……紫外ＬＥＤチップ，１５……樹脂層，１６
……プレディップ材1 ... Red light-emitting phosphor, 2 ... Phosphor particles, 3 ... Moisture-proof layer, 11 ... UV LED chip, 15 ... Resin layer, 16
...... Pre-dip material

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 11/84 ＣＰＤ Ｃ０９Ｋ 11/84 ＣＰＤ 11/85 ＣＰＸ 11/85 ＣＰＸ Ｇ０９Ｆ 9/00 ３３７ Ｇ０９Ｆ 9/00 ３３７Ｚ Ｈ０１Ｌ 33/00 Ｈ０１Ｌ 33/00 Ｎ (72)発明者 横沢 信幸 神奈川県横浜市磯子区新杉田町８番地 株 式会社東芝横浜事業所内 (72)発明者 須藤 伸行 神奈川県横浜市磯子区新杉田町８番地 東 芝電子エンジニアリング株式会社内 (72)発明者 岩崎 剛 神奈川県横浜市磯子区新杉田町８番地 東 芝電子エンジニアリング株式会社内 Ｆターム(参考） 4H001 CA04 CA07 XA03 XA08 XA12 XA13 XA14 XA15 XA17 XA20 XA30 XA31 XA38 XA39 XA49 XA56 XA57 XA64 XA82 YA25 YA58 YA62 YA63 YA65 5F041 AA12 AA14 CA40 CA46 DA16 DA43 DA58 DB01 FF11 5G435 AA04 BB04 BB12 BB15 EE23 EE25 GG23 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09K 11/84 CPD C09K 11/84 CPD 11/85 CPX 11/85 CPX G09F 9/00 337 G09F 9/00 337Z H01L 33/00 H01L 33/00 N (72) Inventor Nobuyuki Yokozawa 8 Shinsita-cho, Isogo-ku, Yokohama-shi, Kanagawa Incorporated company Toshiba Yokohama Office (72) Inventor Nobuyuki Sudo 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Address Toshiba Electronics Engineering Co., Ltd. (72) Inventor Go Iwasaki 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa F-Terms (reference) within Toshiba Toshiba Electronics Engineering Co., Ltd. XA38 XA39 XA49 XA56 XA57 XA64 XA82 YA25 YA58 YA62 YA63 YA65 5F041 AA12 AA14 CA40 CA46 DA16 DA43 DA58 DB01 FF11 5G435 AA04 BB04 BB12 BB15 EE23 EE25 GG23

Claims (9)

【特許請求の範囲】[Claims] 【請求項１】 一般式：（Ｌａ1-x-yＥｕxＳｍy）2Ｏ2
Ｓ・mＭ2Ｏ3 （式中、ＭはＧａおよびＩｎから選ばれる少なくとも1
種の元素を示し、ｘ、ｙおよびｍはそれぞれ0.01≦ｘ≦
0.15、0.00005≦ｙ≦0.05、0.00001≦ｍ≦0.001を満足
する数である）で実質的に表される組成を有する3価の
ユーロピウムおよびサマリウム付活酸硫化ランタン蛍光
体からなることを特徴とする赤色発光蛍光体。1. A general formula: (La 1-xy Eu x Sm y) 2 O 2
S.mM 2 O 3 (wherein M is at least 1 selected from Ga and In)
Indicates the element of the species, x, y and m are 0.01 ≦ x ≦
0.15, 0.00005 ≦ y ≦ 0.05, 0.00001 ≦ m ≦ 0.001), which is a trivalent europium- and samarium-activated lanthanum oxysulfide phosphor having a composition substantially represented by Red emitting phosphor. 【請求項２】 請求項１記載の赤色発光蛍光体におい
て、 前記酸硫化ランタン蛍光体は波長330〜390nmの長波長紫
外線で励起した際に赤色光を発光することを特徴とする
赤色発光蛍光体。2. The red-light-emitting phosphor according to claim 1, wherein the lanthanum oxysulfide phosphor emits red light when excited by long-wavelength ultraviolet light having a wavelength of 330 to 390 nm. . 【請求項３】 請求項１記載の赤色発光蛍光体におい
て、 紫外線励起発光装置に用いられることを特徴とする赤色
発光蛍光体。3. The red-emitting phosphor according to claim 1, which is used in an ultraviolet-excited light-emitting device. 【請求項４】 紫外線を放射する光源と、 請求項１記載の赤色発光蛍光体を含み、かつ前記光源か
らの紫外線により励起されて可視光を発光させる発光装
置用蛍光体を有する発光部とを具備することを特徴とす
る発光装置。4. A light source that emits ultraviolet light, and a light emitting portion that includes the red light emitting phosphor according to claim 1 and that has a phosphor for a light emitting device that emits visible light when excited by the ultraviolet light from the light source. A light-emitting device comprising. 【請求項５】 請求項４記載の発光装置において、 前記発光装置用蛍光体は前記赤色発光蛍光体に加えて、
青色発光蛍光体および緑色発光蛍光体を含むことを特徴
とする発光装置。5. The light emitting device according to claim 4, wherein the phosphor for the light emitting device is in addition to the red light emitting phosphor.
A light emitting device comprising a blue light emitting phosphor and a green light emitting phosphor. 【請求項６】 請求項５記載の発光装置において、 前記発光装置用蛍光体は前記青色発光蛍光体として、 一般式：（Ｍ1，Ｅｕ）10（ＰＯ4）6・Ｃｌ2 （式中、Ｍ1はＭｇ、Ｃａ、ＳｒおよびＢａから選ばれ
る少なくとも1種の元素を示す）で実質的に表される2価
のユーロピウム付活ハロ燐酸塩蛍光体、 一般式：ａ（Ｍ2，Ｅｕ）Ｏ・ｂＡｌ2Ｏ3 （式中、Ｍ2はＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｌｉ、
ＲｂおよびＣｓから選ばれる少なくとも1種の元素を示
し、ａおよびｂはａ＞0、ｂ＞0、0.1≦ａ／ｂ≦1.0を満
足する数である）で実質的に表される2価のユーロピウ
ム付活アルミン酸塩蛍光体、および 一般式：ａ（Ｍ2，Ｅｕv，Ｍｎw）Ｏ・ｂＡｌ2Ｏ3 （式中、Ｍ2はＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｌｉ、
ＲｂおよびＣｓから選ばれる少なくとも1種の元素を示
し、ａ、ｂ、ｖおよびｗはａ＞0、ｂ＞0、0.1≦ａ／ｂ
≦1.0、0.001≦ｗ／ｖ≦0.2を満足する数である）で実
質的に表される2価のユーロピウムおよびマンガン付活
アルミン酸塩蛍光体から選ばれる少なくとも1種を含む
ことを特徴とする発光装置。6. The light-emitting device according to claim 5, wherein the phosphor for the light-emitting device is represented by the general formula: (M1, Eu) 10 (PO 4 ) 6 .Cl 2 (wherein M1 Represents at least one element selected from Mg, Ca, Sr and Ba) and is a divalent europium-activated halophosphate phosphor substantially represented by the general formula: a (M2, Eu) O.bAl 2 O 3 (In the formula, M 2 is Mg, Ca, Sr, Ba, Zn, Li,
Rb and Cs represent at least one element, and a and b are numbers satisfying a> 0, b> 0, and 0.1 ≦ a / b ≦ 1.0). Europium-activated aluminate phosphor, and a general formula: a (M2, Eu v , Mn w ) O.bAl 2 O 3 (wherein M2 is Mg, Ca, Sr, Ba, Zn, Li,
At least one element selected from Rb and Cs, where a, b, v and w are a> 0, b> 0, 0.1 ≦ a / b
≦ 1.0, 0.001 ≦ w / v ≦ 0.2) and at least one selected from the group consisting of divalent europium and manganese-activated aluminate phosphors. Light emitting device. 【請求項７】 請求項５または請求項６記載の発光装置
において、 前記発光装置用蛍光体は前記緑色発光蛍光体として、 一般式：ａ（Ｍ2，Ｅｕs，Ｍｎt）Ｏ・ｂＡｌ2Ｏ3 （式中、Ｍ2はＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｌｉ、
ＲｂおよびＣｓから選ばれる少なくとも1種の元素を示
し、ａ、ｂ、ｓおよびｔはａ＞0、ｂ＞0、0.1≦ａ／ｂ
≦1.0、0.3≦ｔ／ｓ≦5.0を満足する数である）で実質
的に表される2価のユーロピウムおよびマンガン付活ア
ルミン酸塩蛍光体、および 一般式：（Ｙ1-h-i-jＲhＴｂiＣｅj）2Ｏ3・ｋＳｉＯ2 （式中、ＲはＬａおよびＧｄから選ばれる少なくとも1
種の元素を示し、ｈ、ｉ、ｊおよびｋは5×10-4≦ｈ≦
0.3、0.05≦ｉ≦0.3、0.001≦ｊ≦0.15、0.8≦ｋ≦1.3
を満足する数である）で実質的に表される3価のテルビ
ウムおよびセリウム付活希土類珪酸塩蛍光体から選ばれ
る少なくとも1種を含むことを特徴とする発光装置。In the light emitting device of claim 7 according to claim 5 or claim 6, wherein said light emitting device for phosphor as the green-emitting phosphor of the general formula: a (M2, Eu s, Mn t) O · bAl 2 O 3 (where M2 is Mg, Ca, Sr, Ba, Zn, Li,
At least one element selected from Rb and Cs, where a, b, s and t are a> 0, b> 0, 0.1 ≦ a / b
A divalent europium- and manganese-activated aluminate phosphor substantially represented by ≦ 1.0 and 0.3 ≦ t / s ≦ 5.0, and a general formula: (Y 1-hij R h Tb i Ce j ) 2 O 3 · kSiO 2 (wherein R is at least 1 selected from La and Gd)
Represents a seed element, h, i, j and k are 5 × 10 −4 ≦ h ≦
0.3, 0.05 ≤ i ≤ 0.3, 0.001 ≤ j ≤ 0.15, 0.8 ≤ k ≤ 1.3
A light-emitting device containing at least one selected from the group consisting of trivalent terbium and cerium-activated rare earth silicate phosphors. 【請求項８】 請求項４ないし請求項７のいずれか１項
記載の発光装置において、 前記発光装置は、前記光源として波長350〜390nmの長波
長紫外線を放射する窒化物系化合物半導体層を有する発
光チップを具備するＬＥＤランプであることを特徴とす
る発光装置。8. The light-emitting device according to claim 4, wherein the light-emitting device has a nitride-based compound semiconductor layer that emits long-wavelength ultraviolet light having a wavelength of 350 to 390 nm as the light source. A light emitting device comprising an LED lamp having a light emitting chip. 【請求項９】 請求項４ないし請求項７のいずれか１項
記載の発光装置において、 前記発光装置は、前記光源として波長330〜390nmの長波
長紫外線を放射するブラックライトを具備する表示装置
であることを特徴とする発光装置。9. The light emitting device according to claim 4, wherein the light emitting device includes a black light as the light source, which emits long wavelength ultraviolet light having a wavelength of 330 to 390 nm. A light-emitting device characterized by being present.
JP2001360965A 2001-11-27 2001-11-27 Red-light-emitting phosphor and light emitter using the same Withdrawn JP2003160785A (en)

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