JP2003041252A - Red color-emitting phosphor and light-emitting device using the same - Google Patents
Red color-emitting phosphor and light-emitting device using the sameInfo
- Publication number
- JP2003041252A JP2003041252A JP2001232365A JP2001232365A JP2003041252A JP 2003041252 A JP2003041252 A JP 2003041252A JP 2001232365 A JP2001232365 A JP 2001232365A JP 2001232365 A JP2001232365 A JP 2001232365A JP 2003041252 A JP2003041252 A JP 2003041252A
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- Prior art keywords
- light
- phosphor
- wavelength
- light emitting
- red
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、３５０ｎｍから４
２０ｎｍの長波長紫外線および短波長可視光線により励
起され赤色に発光する蛍光体及びその蛍光体を用いた発
光装置に関する。FIELD OF THE INVENTION The present invention is directed to 350 nm to 4 nm.
The present invention relates to a phosphor that emits red light when excited by long-wavelength ultraviolet light of 20 nm and short-wavelength visible light, and a light-emitting device using the phosphor.
【０００２】[0002]
【従来の技術】現在、主に使用されている長波長紫外線
および短波長可視光線（３５０ｎｍから４２０ｎｍ）で
励起する蛍光体としては、発光色が青色のＢａＭｇ2Ａ
ｌ16Ｏ2 7：Ｅｕ，（Ｓｒ，Ｃａ，Ｂａ）5（ＰＯ4）3Ｃ
ｌ：Ｅｕ、緑色のＢａＭｇ2Ａｌ1 6Ｏ27：Ｅｕ，Ｍｎ，
Ｚｎ2ＧｅＯ4：Ｍｎ、赤色のＹ2Ｏ2Ｓ：Ｅｕ、３．５Ｍ
ｇＯ・０．５ＭｇＦ2・ＧｅＯ2：Ｍｎがある。これら３
色の蛍光体を任意の割合で混合することによって、長波
長紫外線及び短波長可視光線で多くの発光色を作ること
ができる。しかし、白色系の場合、赤色成分のＹ2Ｏ
2Ｓ：Ｅｕ蛍光体の発光効率が他の蛍光体よりもかなり
低いために混合割合が多くなるといった問題があった。
更に、白色系では赤、緑、青の発光バランスにより白色
を得ることができるが、赤色成分の発光効率が悪いため
に緑、青系蛍光体の発光量を低く抑えなければならず、
高輝度の白色が得られなかった。 2. Description of the Related Art At present, as a phosphor excited mainly by long-wavelength ultraviolet rays and short-wavelength visible rays (350 nm to 420 nm), BaMg 2 A having an emission color of blue is used.
l 16 O 2 7: Eu, (Sr, Ca, Ba) 5 (PO 4) 3 C
1: Eu, green BaMg 2 Al 1 6 O 27 : Eu, Mn,
Zn 2 GeO 4 : Mn, red Y 2 O 2 S: Eu, 3.5M
There is gO · 0.5MgF 2 · GeO 2 : Mn. These 3
By mixing the color phosphors in an arbitrary ratio, many emission colors can be produced with long-wavelength ultraviolet light and short-wavelength visible light. However, in the case of white type, Y 2 O of red component
Since the emission efficiency of 2 S: Eu phosphor is much lower than that of other phosphors, there is a problem that the mixing ratio becomes large.
Furthermore, in the white system, white can be obtained by the red, green, and blue emission balance, but since the emission efficiency of the red component is poor, the emission amounts of the green and blue phosphors must be kept low.
No bright white color was obtained.
【０００３】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、長波長紫外線および
短波長可視光線（３５０ｎｍから４２０ｎｍ）は蛍光体
の吸収端と重なる。この問題を解決するためユーロピウ
ムで付活された希土類酸硫化物蛍光体が特開平１１−２
４６８５７号公報や特開２０００−１４４１３０号公報
で提案され、励起波長を長波長側へシフトすることが報
告されている。しかし、３７０ｎｍ付近の紫外ＬＥＤの
発光波長は、これら蛍光体の吸収端と重なるため紫外Ｌ
ＥＤの発光ピークのシフトにより発光量が著しく変化し
てしまう問題があった。The wavelength corresponding to the excitation energy of the electron pair of the oxide compound is in the ultraviolet region, and long-wave ultraviolet light and short-wave visible light (350 nm to 420 nm) overlap the absorption edge of the phosphor. In order to solve this problem, a rare earth oxysulfide phosphor activated by europium is disclosed in JP-A-11-2.
It has been proposed in Japanese Patent Laid-Open No. 46857 and Japanese Patent Laid-Open No. 2000-144130, and it is reported that the excitation wavelength is shifted to the long wavelength side. However, the emission wavelength of the ultraviolet LED near 370 nm overlaps with the absorption edge of these phosphors, and thus the ultraviolet L
There is a problem that the amount of emitted light changes significantly due to the shift of the emission peak of the ED.
【０００４】一方、発光ダイオード（ＬＥＤ：Light E
mitting Diode）は光を放射する半導体ダイオードであ
り、電気エネルギーを可視光または赤外光に変換するも
のである。特に可視光を利用するためにＧａＰやＧａＡ
ｓＰ，ＧａＡｌＡｓ等の発光材料で形成した発光チップ
を透明樹脂等で封止したＬＥＤランプとして広く使用さ
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、数字や文字を形どった樹脂ケースで封
止したディスプレイ型のＬＥＤランプも多用されてい
る。On the other hand, a light emitting diode (LED: Light E)
A mitting diode is a semiconductor diode that emits light and converts electric energy into visible light or infrared light. GaP and GaA in order to utilize visible light
It is widely used as an LED lamp in which a light emitting chip formed of a light emitting material such as sP or GaAlAs is sealed with a transparent resin or the like. Further, a display type LED lamp in which a light emitting material is fixed to the upper surface of a printed circuit board or a metal lead and sealed with a resin case in which numbers and letters are shaped is also widely used.
【０００５】又、発光チップの表面乃至発光ダイオード
の樹脂中に各種の蛍光体粉末を含有させることにより、
放射光の色を適正に調整することも可能である。即ち、
ＬＥＤランプの発光色は、青色から赤色まで各使用用途
に応じた可視光領域の発光を再現することができる。ま
た、発光ダイオードは半導体素子であるため、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
換作業も軽減化されることから、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，表示板等の各種表示装置の構成部品として広く使用
されている。Further, by incorporating various phosphor powders into the surface of the light emitting chip or the resin of the light emitting diode,
It is also possible to properly adjust the color of the emitted light. That is,
The emission color of the LED lamp can reproduce light emission in the visible light range from blue to red according to each intended use. Further, since the light emitting diode is a semiconductor element, it has a long life and high reliability, and when it is used as a light source, replacement work is reduced, so that portable communication equipment, personal computer peripheral equipment, OA equipment. It is widely used as a component of various display devices such as household electric appliances, audio equipment, various switches, backlight light sources, and display boards.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、最近で
は、上記各種表示装置の利用者の色彩感覚が更に向上
し、各種表示装置においても、微妙な色合いをより高精
細に再現できる機能が要求されている。また、１個の発
光ダイオードによって白色乃至各種の中間色を再現でき
る機能も強く求められている。However, recently, the user's sense of color of the above-mentioned various display devices has been further improved, and various display devices are required to have a function capable of reproducing a subtle color tone with higher precision. There is. There is also a strong demand for a function capable of reproducing white or various intermediate colors with one light emitting diode.
【０００７】そのため、ＬＥＤランプの発光チップの表
面に、さらに青色，赤色，緑色発光蛍光体を塗布した
り、発光ダイオードを構成する樹脂中（例えば、モール
ド部材、コーティング部材等）に上記各種蛍光体粉末を
含有させることにより、１個の発光ダイオードから白色
乃至任意の中間色を取り出すように構成することも試行
されている。Therefore, blue, red, and green light-emitting phosphors are further applied to the surface of the light-emitting chip of the LED lamp, or the above-mentioned various phosphors are contained in the resin (eg, mold member, coating member, etc.) that constitutes the light-emitting diode. Attempts have also been made to incorporate white powder to extract white to any intermediate color from a single light emitting diode.
【０００８】しかしながら、赤色発光蛍光体は、他の青
色，緑色発光蛍光体と比較して長波長紫外線および短波
長可視光線（３５０ｎｍから４２０ｎｍ）、特に波長３
７０ｎｍ前後の励起光に対して吸収が弱いといった問題
点があった。また、例えば赤色蛍光体Ｙ2Ｏ2Ｓ：Ｅｕや
特開平１１−２４６８５７号公報や特開２０００−１４
４１３０号公報で提案されているユーロピウムで付活さ
れた希土類酸硫化物蛍光体の励起波長は、３５０ｎｍよ
り長波長では急激に吸収強度が低下する。このことから
３５０ｎｍ〜３８０ｎｍを発光ピークとする励起光源、
例えば紫外ＬＥＤを励起光源に用いた場合、紫外ＬＥＤ
製造上で発生する発光ピークのシフトにより蛍光体の赤
色発光量が著しく変化し、微妙な色合いをより高精細に
再現することが難しい。However, the red-emitting phosphor has a long-wavelength ultraviolet light and a short-wavelength visible light (350 nm to 420 nm), especially a wavelength of 3 as compared with other blue- and green-emitting phosphors.
There is a problem that the absorption of excitation light around 70 nm is weak. Further, for example, the red phosphor Y 2 O 2 S: Eu, JP-A-11-246857 and JP-A-2000-14.
In the excitation wavelength of the rare earth oxysulfide phosphor activated by europium proposed in Japanese Patent No. 4130, the absorption intensity sharply decreases at a wavelength longer than 350 nm. From this, an excitation light source having an emission peak of 350 nm to 380 nm,
For example, when an ultraviolet LED is used as the excitation light source, the ultraviolet LED
The red emission amount of the phosphor changes remarkably due to the shift of the emission peak generated during manufacturing, and it is difficult to reproduce a subtle color tone with higher precision.
【０００９】本発明は、上記問題点を解決するためにな
されたものであり、長波長紫外線および短波長可視光線
（３５０ｎｍから４２０ｎｍ）、特に波長３７０ｎｍ前
後の励起光に対して赤色発光を効率よく放射でき、１個
の発光ダイオードから白色ないし任意の色調を取り出す
ために実用的に使用できる赤色発光蛍光体およびその蛍
光体を使用したＬＥＤランプを提供することを目的とす
る。The present invention has been made to solve the above problems, and efficiently emits red light for long-wavelength ultraviolet light and short-wavelength visible light (350 nm to 420 nm), particularly for excitation light having a wavelength of about 370 nm. It is an object of the present invention to provide a red-emitting phosphor that can emit light and can be practically used for extracting white or any color tone from a single light-emitting diode, and an LED lamp using the phosphor.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、上記目的
を達成するため、種々の組成からなる赤色発光蛍光体を
調製し、この組成成分の種類および添加量が蛍光体の励
起スペクトル分布および発光強度に及ぼす影響を実験に
より比較検討した。In order to achieve the above-mentioned object, the present inventors have prepared red light-emitting phosphors having various compositions, and the kind and addition amount of these composition components are the excitation spectrum distribution of the phosphor. And the influence on the emission intensity was compared and examined by experiments.
【００１１】その結果、ユーロピウムが低次元に配列し
た化合物、例えばＬｉＥｕＷ２Ｏ８において長波長紫外
線および短波長可視光線（３５０ｎｍから４２０ｎ
ｍ）、特に波長３７０ｎｍ前後の励起光を吸収し、赤色
発光を効率よく放射できることが可能な赤色発光蛍光体
が得られることを明らかにした。本発明は上記知見に基
づいて完成されたものである。As a result, in a compound in which europium is arranged in a low dimension, for example, LiEuW 2 O 8 , long-wavelength ultraviolet light and short-wavelength visible light (350 nm to 420 n).
m), in particular, it was clarified that a red-emitting phosphor capable of absorbing excitation light with a wavelength of about 370 nm and emitting red light efficiently can be obtained. The present invention has been completed based on the above findings.
【００１２】即ち、本発明に係る赤色発光蛍光体は、Ｅ
ｕ3+イオンが２次元または１次元に配列した蛍光体であ
ることを特徴とする。Ｅｕ3+イオンが2次元に配列した
状態とは、図６に示すようにＥｕ3+イオンが同一平面内
において縦・横方向に配列されている状態をいい、１次
元に配列した状態とは図７に示すようにＥｕ3+イオンが
同一平面内において縦方向（又は横方向）に配列されて
いる状態をいう。That is, the red light emitting phosphor according to the present invention is E
It is characterized in that it is a phosphor in which u 3+ ions are two-dimensionally or one-dimensionally arranged. The state in which Eu 3+ ions are arranged in two dimensions means a state in which Eu 3+ ions are arranged in the vertical and horizontal directions in the same plane as shown in FIG. 6, and the state in which they are arranged in one dimension As shown in FIG. 7, it means a state in which Eu 3+ ions are arranged in the vertical direction (or the horizontal direction) in the same plane.
【００１３】更に、組成がＡＥｕＸＬｎ（1‐Ｘ）Ｍ２
Ｏ８（但し、０<ｘ≦１、組成中のＡはＬｉ，Ｎａ，
Ｋ，ＲｂおよびＣｓからなる群より選ばれた少なくとも
１種であり、ＬｎはＹ，Ｌａ，ＧｄおよびＬｕからなる
群より選ばれた少なくとも１つであり、ＭはＷ又はＭｏ
からなる群より選ばれた少なくとも1種である。）で表
されることを特徴とする。また、最も好ましい組成はＬ
ｉＥｕＷ２Ｏ８である。Further, the composition is AEu X Ln (1-X) M 2
O 8 (however, 0 <x ≦ 1, A in the composition is Li, Na,
At least one selected from the group consisting of K, Rb and Cs, Ln is at least one selected from the group consisting of Y, La, Gd and Lu, and M is W or Mo.
It is at least one selected from the group consisting of. ) Is represented by. The most preferable composition is L
iEuW 2 O 8 .
【００１４】又、本発明に係る赤色発光蛍光体は、ＡＥ
ｕＸＬｎ（1‐Ｘ）Ｍ２Ｏ８（但し，０<ｘ≦１、組成中
のAはＬｉ，Ｎａ，Ｋ，ＲｂおよびＣｓからなる群より
選ばれた少なくとも1種であり、ＬｎはＹ，Ｌａ，Ｇｄ
およびＬｕからなる群より選ばれた少なくとも１つであ
り、ＭはＷまたはＭｏからなる群より選ばれた少なくと
も１種である）の組成であり、その粒子の平均粒子径が
５０μｍ以下であることを特徴とする。The red light emitting phosphor according to the present invention is AE
u X Ln (1-X) M 2 O 8 (where 0 <x ≦ 1, A in the composition is at least one selected from the group consisting of Li, Na, K, Rb and Cs, and Ln is Y, La, Gd
And at least one selected from the group consisting of Lu, and M is at least one selected from the group consisting of W or Mo), and the average particle size of the particles is 50 μm or less. Is characterized by.
【００１５】さらに、本発明に係る発光装置は蛍光体と
組み合わされた発光チップに通電することにより電気エ
ネルギーを可視光または赤外光に変換するＬＥＤにおい
て、上記発光チップ上に設けられた蛍光体層がＡＥｕＸ
Ｌｎ（1‐Ｘ）Ｍ２Ｏ８（但し、０<ｘ≦１、組成中のA
はＬｉ，Ｎａ，Ｋ，ＲｂおよびＣｓからなる群より選ば
れた少なくとも1種であり、ＬｎはＹ，Ｌａ，Ｇｄおよ
びＬｕからなる群より選ばれた少なくとも１つであり、
ＭはＷまたはＭｏからなる群より選ばれた少なくとも１
種である）であることを特徴とする。ここで、発光チッ
プ上に設ける上記蛍光体層は、少なくても1種以上の蛍
光体を単層又は複数層を層状に積層配置しても良いし、
複数の蛍光体を単一の層内に混合して配置しても良い。
上記発光チップ上に蛍光体層を設ける形態としては、発
光チップの表面を被覆するコーティング部材に蛍光体を
混合する形態、モールド部材に蛍光体を混合する形態、
或いはモールド部材に被せる被覆体に蛍光体を混合する
形態、更にはＬＥＤランプの投光側前方に蛍光体を混合
した透光可能なプレートを配置する形態等が挙げられ
る。Furthermore, the light emitting device according to the present invention is an LED which converts electric energy into visible light or infrared light by energizing a light emitting chip combined with a phosphor, and the phosphor provided on the light emitting chip. Layer is AEu X
Ln (1-X) M 2 O 8 (where 0 <x ≦ 1, A in the composition
Is at least one selected from the group consisting of Li, Na, K, Rb and Cs, Ln is at least one selected from the group consisting of Y, La, Gd and Lu,
M is at least 1 selected from the group consisting of W and Mo
It is a species). Here, the phosphor layer provided on the light emitting chip, at least one or more phosphors may be arranged in a single layer or a plurality of layers laminated in layers,
A plurality of phosphors may be mixed and arranged in a single layer.
As a form of providing the phosphor layer on the light emitting chip, a form of mixing the phosphor in a coating member that covers the surface of the light emitting chip, a form of mixing the phosphor in a mold member,
Alternatively, there may be mentioned a form in which a phosphor is mixed in a covering body to be covered on the mold member, and further, a form in which a translucent plate in which a phosphor is mixed is arranged in front of the light emitting side of the LED lamp.
【００１６】又、上記蛍光体は発光チップ上のモールド
部材に少なくても１種以上の蛍光体を添加しても良い。
更に、上記蛍光体の１種以上の蛍光体層を、発光ダイオ
ードの外側に設けても良い。発光ダイオードの外側に設
ける形態としては、発光ダイオードのモールド部材の外
側表面に蛍光体を層状に塗布する形態、或いは蛍光体を
ゴム，樹脂，エラストマー等に分散させた成形体（例え
ば、キャップ状）を作成し、これをＬＥＤに被覆する形
態、又は前記成形体を平板状に加工し、これをＬＥＤの
前方に配置する形態等が挙げられる。Further, at least one kind of phosphor may be added to the molding member on the light emitting chip.
Furthermore, one or more phosphor layers of the above phosphors may be provided outside the light emitting diode. As a form provided on the outside of the light emitting diode, a form in which the phosphor is applied in layers on the outer surface of the molding member of the light emitting diode, or a molded body in which the phosphor is dispersed in rubber, resin, elastomer or the like (for example, a cap shape) And a method of coating the LED on the LED or a method of processing the molded body into a flat plate shape and disposing the molded body in front of the LED.
【００１７】ここで、上記赤色発光蛍光体においてユー
ロピウムは励起光の吸収と発光中心として作用する。一
般的な酸化物系蛍光体では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る。母体結晶により励起光を
吸収し、その励起エネルギーを発光イオンに伝達し発光
するが、長波長紫外線および短波長可視光線（３５０ｎ
ｍから４２０ｎｍ）の吸収は十分でない。本発明の赤色
発光蛍光体は、発光イオンであるユーロピウムイオンが
直接、長波長紫外線および短波長可視光線（３５０ｎｍ
から４２０ｎｍ）を吸収している。このことから赤色発
光強度はユーロピウム濃度に依存し、ユーロピウム濃度
が最大のとき発光強度も最大となる。Here, in the above red-emitting phosphor, europium acts as an absorption center of excitation light and as an emission center. In a general oxide-based phosphor, the wavelength corresponding to the excitation energy of the electron pair is in the ultraviolet region. Excitation light is absorbed by the host crystal, and the excitation energy is transmitted to the light-emitting ions to emit light, but long-wavelength ultraviolet light and short-wavelength visible light (350 n
The absorption from m to 420 nm) is not sufficient. In the red-light-emitting phosphor of the present invention, the europium ion, which is a light-emitting ion, directly emits long-wavelength ultraviolet light and short-wavelength visible light (350 nm
To 420 nm). From this fact, the red emission intensity depends on the europium concentration, and the emission intensity also becomes maximum when the europium concentration is maximum.
【００１８】しかし、一般的な蛍光体において発光イオ
ン（付活剤）濃度は母体結晶に対し数モル％添加され、
それ以上の濃度では付活剤の間に共鳴伝達による交差
緩和が生じ、励起エネルギーの一部が失われる。付活
剤間の共鳴伝達による励起の回遊が生じ、これが結晶表
面や非発光中心への励起の移行と消滅を助長する。付
活剤同士が凝集あるいはイオン対を形成することによっ
て、非発光中心やキラー（蛍光抑制剤）に変わるなどの
理由によって濃度消光が起こることが知られている。However, in a general phosphor, the concentration of luminescent ions (activator) is several mol% with respect to the host crystal,
At higher concentrations, cross relaxation occurs due to resonance transfer between the activators, and some of the excitation energy is lost. Excitation migration occurs due to resonance transfer between activators, which promotes transfer and extinction of excitation to the crystal surface and non-emissive centers. It is known that concentration quenching occurs due to the reason that activators are aggregated or form ion pairs to change to non-luminous centers or killer (fluorescence suppressors).
【００１９】ところが、本発明の赤色発光蛍光体のよう
な発光イオンが、1次元や2次元のように低次元に配置し
ている化合物では、発光イオンが配列している層と層と
の間隔が広いため、励起エネルギーの回遊が制御される
ことによって濃度消光を示さない。このことからユーロ
ピウムイオンの４ｆ軌道内の不対電子によって長波長紫
外線および短波長可視光線（３５０ｎｍから４２０ｎ
ｍ）を効率よく吸収し赤色発光が得られる。However, in a compound such as the red-emitting phosphor of the present invention in which light-emitting ions are arranged in a low dimension such as one-dimensional or two-dimensional, the distance between the layers in which the light-emitting ions are arranged is large. Therefore, concentration quenching does not occur due to the controlled excursion of excitation energy. Therefore, due to unpaired electrons in the 4f orbit of the europium ion, long-wavelength ultraviolet light and short-wavelength visible light (350 nm to 420 n
m) is efficiently absorbed and red light emission is obtained.
【００２０】また、上記の赤色発光蛍光体の発光ピーク
は６１４ｎｍで、Ｙ２Ｏ２Ｓ：Ｅｕの発光ピークより短
波長側に位置している。このことから、これら2種類の
蛍光体を併用することにより赤色領域の発光面積が増加
されるため高輝度の白色を得ることも可能である。The emission peak of the above red-emitting phosphor is 614 nm, which is located on the shorter wavelength side than the emission peak of Y 2 O 2 S: Eu. From this, it is possible to obtain white light with high brightness because the emission area in the red region is increased by using these two types of phosphors in combination.
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施の形態を、以
下の実施例に基づいて説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below based on the following examples.
【実施例１】蛍光体構成原料として、ＷＯ３粉末を３．
９６ｇと、Ｅｕ２Ｏ３粉末を１．５０ｇと、Ｌｉ２ＣＯ
３粉末を０．３２ｇを正確に秤量し、これをボールミル
を使用して均一に混合して原料混合体とした。[Example 1] WO 3 powder was used as a phosphor constituent raw material.
96 g, 1.50 g of Eu 2 O 3 powder, Li 2 CO
0.32 g of the three powders were accurately weighed and uniformly mixed using a ball mill to obtain a raw material mixture.
【００２２】次に、得られた原料混合体を、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、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、篩い分け
を行い、ＬｉＥｕＷ２Ｏ８なる組成の赤色発光蛍光体を
調製した。Next, the obtained raw material mixture was put into an alumina crucible and fired at a temperature of 900 ° C. for 6 hours. The fired product obtained was thoroughly washed with pure water to remove unnecessary soluble components, and then finely pulverized with a ball mill and sieved to prepare a red-emitting phosphor having a composition of LiEuW 2 O 8 . .
【００２３】そして、上記赤色発光蛍光体ＬｉＥｕＷ２
Ｏ８について３８０ｎｍ励起下において、従来のＹ２Ｏ
２Ｓ：Ｅｕ３＋蛍光体を標準にして発光強度を測定した
ところ、図１に示すように、２．５倍という高い値が得
られた。ＬｉＥｕＷ２Ｏ８の発光ピークは６１４ｎｍ、
Ｙ２Ｏ２Ｓ：Ｅｕ３＋の発光ピークは６２４ｎｍである
ことから、これらの蛍光体を併用して用いると赤領域の
発光面積を増加させることができる。The red light emitting phosphor LiEuW 2
Under the excitation of 380 nm for O 8 , conventional Y 2 O
When the emission intensity was measured using the 2 S: Eu 3+ phosphor as a standard, a high value of 2.5 times was obtained as shown in FIG. The emission peak of LiEuW 2 O 8 is 614 nm,
Since the emission peak of Y 2 O 2 S: Eu 3+ is 624 nm, when these phosphors are used in combination, the emission area in the red region can be increased.
【００２４】また、上記赤色発光蛍光体ＬｉＥｕＷ２Ｏ
８の励起波長は、長波長紫外線および短波長可視光線
（３５０ｎｍ〜４２０ｎｍ）に位置していることから、
この範囲の波長を６１４ｎｍに変換することが可能であ
る。特に３８０ｎｍに最大吸収ピークがあるため３８０
ｎｍ前後に発光する励起光源について有効である。The red light emitting phosphor LiEuW 2 O
Since the excitation wavelength of 8 is located in long-wavelength ultraviolet light and short-wavelength visible light (350 nm to 420 nm),
It is possible to convert the wavelength in this range to 614 nm. Especially since there is a maximum absorption peak at 380 nm, 380
This is effective for an excitation light source that emits light of around nm.
【００２５】[0025]
【実施例２】赤色発光蛍光体としてＬｉＥｕＷ２Ｏ
８と、青色発光蛍光体としてＳｒ５（ＰＯ４）３Ｃｌ：
Ｅｕと、緑色発光蛍光体としてＢａＭｇ２Ａｌ16Ｏ27：
Ｅｕ，Ｍｎとを１０：３：３の割合でシリコーンゴムに
混合し、これを加熱プレス機を用いて図５に示すキャッ
プ形状に成形した。これを発光波長が３８０ｎｍの紫外
ＬＥＤの外側に被覆し、積分球中において２０ｍＡで点
灯させた。得られた分光分布を分光放射輝度計ＰＲ−７
０４（Photo Research製）で測色した。得られた分光
分布を図3に示す。赤色蛍光体にＹ２Ｏ２Ｓ：Ｅｕを用
いた場合と比較して２．３倍の輝度をもつ白色光が得ら
れた。Example 2 LiEuW 2 O as a red light emitting phosphor
8 and Sr 5 (PO 4 ) 3 Cl as a blue light emitting phosphor:
Eu and BaMg 2 Al 16 O 27 as green light emitting phosphor:
Eu and Mn were mixed with silicone rubber at a ratio of 10: 3: 3, and this was molded into a cap shape shown in FIG. 5 using a heating press machine. This was coated on the outside of an ultraviolet LED having an emission wavelength of 380 nm and turned on at 20 mA in an integrating sphere. The obtained spectral distribution is used as a spectral radiance meter PR-7.
The color was measured with 04 (Photo Research). The obtained spectral distribution is shown in FIG. White light having a brightness 2.3 times that of the case where Y 2 O 2 S: Eu was used for the red phosphor was obtained.
【００２６】[0026]
【実施例３】赤色発光蛍光体としてＬｉＥｕＷ２Ｏ８と
Ｙ２Ｏ２Ｓ：Ｅｕを、青色発光蛍光体としてＳｒ５（Ｐ
Ｏ４）３Ｃｌ：Ｅｕを、緑色発光蛍光体としてＢａＭｇ
２Ａｌ16Ｏ27：Ｅｕ，Ｍｎを１５：１５：３：３の割合
でシリコーンゴムに混合し、それを加熱プレス機を用い
てキャップ形状に成形した。これを発光波長が３８０ｎ
ｍの紫外ＬＥＤの外側に被覆し、積分球中において２０
ｍＡで点灯させた。得られた分光分布を分光放射輝度計
ＰＲ−７０４（Photo Research製）で測色した。得ら
れた分光分布を図4に示す。赤色蛍光体にＹ２Ｏ２Ｓ：
Ｅｕを用いた場合と比較して１．６倍の輝度をもつ白色
光が得られた。Example 3 LiEuW 2 O 8 and Y 2 O 2 S: Eu were used as red light emitting phosphors and Sr 5 (P was used as a blue light emitting phosphor.
O 4 ) 3 Cl: Eu as a green light emitting phosphor of BaMg
2 Al 16 O 27 : Eu, Mn was mixed with silicone rubber at a ratio of 15: 15: 3: 3, and the mixture was molded into a cap shape using a hot press machine. This has an emission wavelength of 380n
20 m in the integrating sphere
It was turned on at mA. The color of the obtained spectral distribution was measured with a spectral radiance meter PR-704 (manufactured by Photo Research). The spectral distribution obtained is shown in FIG. Y 2 O 2 S on the red phosphor:
White light having a brightness of 1.6 times that of the case of using Eu was obtained.
【００２７】図５は、上記した実施例２及び実施例３で
説明したキャップ形状の蛍光体入り被覆体を示し、具体
的には、発光ダイオード１におけるモールド部材２の外
側表面に、本発明に係る蛍光体をシリコーンゴムに混合
し、これをキャップ形状に形成した被覆体３を被せた発
光装置である。尚、蛍光体は、発光ダイオード１におけ
る発光素子４の外表面を被覆するコーティング部材に混
入しても、或いはモールド部材２に混入して、更には発
光ダイオードの投光方向前方に配置する透光シートに混
入してもよいものである。FIG. 5 shows the cap-shaped phosphor-containing coating described in the second and third embodiments. Specifically, according to the present invention, the outer surface of the mold member 2 in the light emitting diode 1 is used. This is a light-emitting device in which such a phosphor is mixed with silicone rubber and covered with a cover 3 formed in a cap shape. The phosphor may be mixed in a coating member that covers the outer surface of the light emitting element 4 in the light emitting diode 1, or may be mixed in the mold member 2, and is further arranged in front of the light emitting diode in the light projecting direction. It may be mixed in the sheet.
【００２８】[0028]
【発明の効果】以上説明の通り、本発明に係る赤色発光
蛍光体によれば、長波長紫外線および短波長可視光線励
起で強い発光強度をもつ赤色発光が得られる。また、Eu
3+イオンによって励起紫外線を効率良く吸収し、発光し
ているため励起波長がシフトしても影響を受けにくく、
安定した色調および発光強度を提供できる。As described above, according to the red light emitting phosphor of the present invention, red light emission having a strong light emission intensity can be obtained by excitation with long wavelength ultraviolet rays and short wavelength visible rays. Also, Eu
Excited ultraviolet light is efficiently absorbed by 3+ ions and emits light, so it is less affected even if the excitation wavelength shifts,
A stable color tone and emission intensity can be provided.
【００２９】また、本発明に係る赤色発光蛍光体と他の
蛍光体を組み合わせることにより、高輝度の白色光が得
られるばかりでなく安定した様々な色調を提供すること
ができる。By combining the red-light-emitting phosphor according to the present invention with another phosphor, not only high-intensity white light can be obtained, but also various stable color tones can be provided.
【図１】本発明に係る赤色発光蛍光体（ＬｉＥｕＷ２Ｏ
８）とＹ２Ｏ２Ｓ：Ｅｕ3+の発光スペクトル分布を示す
グラフである。FIG. 1 shows a red light emitting phosphor (LiEuW 2 O) according to the present invention.
8 ) is a graph showing the emission spectrum distributions of Y 2 O 2 S: Eu 3+ .
【図２】本発明に係る赤色発光蛍光体（ＬｉＥｕＷ２Ｏ
８）の励起スペクトル分布を示すグラフである。FIG. 2 shows a red light-emitting phosphor according to the present invention (LiEuW 2 O
8 is a graph showing the excitation spectrum distribution of 8 ).
【図３】実施例２による発光の分光分布を示すグラフで
ある。FIG. 3 is a graph showing a spectral distribution of light emission according to Example 2.
【図４】実施例3による発光の分光分布を示すグラフで
ある。FIG. 4 is a graph showing a spectral distribution of light emission according to Example 3.
【図５】発光ダイオードにおけるモールド部材の外側
に、蛍光体層を設けた発光装置を示す断面図である。FIG. 5 is a cross-sectional view showing a light emitting device in which a phosphor layer is provided outside a mold member in a light emitting diode.
【図６】Ｅｕ3+イオンが２次元に配列した化合物のモデ
ル図である。FIG. 6 is a model diagram of a compound in which Eu 3+ ions are two-dimensionally arranged.
【図７】Ｅｕ3+イオンが１次元に配列した化合物のモデ
ル図である。FIG. 7 is a model diagram of a compound in which Eu 3+ ions are one-dimensionally arranged.
１…発光ダイオード ２…モールド部材 ３…被覆体（キャップ形状） 1 ... Light emitting diode 2 ... Mold member 3 ... Cover (cap shape)
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H001 CA02 CA04 CA05 XA03 XA08 XA11 XA19 XA37 XA39 XA42 XA55 XA57 XA63 XA64 XA71 XA74 5F041 AA11 AA12 CA40 DA42 EE25 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4H001 CA02 CA04 CA05 XA03 XA08 XA11 XA19 XA37 XA39 XA42 XA55 XA57 XA63 XA64 XA71 XA74 5F041 AA11 AA12 CA40 DA42 EE25
Claims (13)
長波長紫外線及び短波長可視光線により励起され発光す
る蛍光体において、Ｅｕ3+イオンを２次元または１次元
に配列した蛍光体であることを特徴とする赤色発光蛍光
体。1. A phosphor that emits light by being excited by long-wavelength ultraviolet light and short-wavelength visible light having an emission wavelength of 350 nm to 420 nm and that is a phosphor in which Eu 3+ ions are two-dimensionally or one-dimensionally arranged. A red-emitting phosphor that does.
（1‐Ｘ）Ｍ２Ｏ８で表されることを特徴とする請求項
１記載の赤色発光蛍光体。但し，０＜ｘ≦１，組成中の
ＡはＬｉ，Ｎａ，Ｋ，Ｒｂ及びＣｓからなる群より選ば
れた少なくとも１種であり，ＬｎはＹ，Ｌａ，Ｇｄ及び
Ｌｕからなる群より選ばれた少なくとも１つであり，Ｍ
はＷまたはＭｏからなる群より選ばれた少なくとも１1
種である。2. The composition of the phosphor is AEu X Ln
The red-emitting phosphor according to claim 1, which is represented by (1-X) M 2 O 8 . Here, 0 <x ≦ 1, A in the composition is at least one selected from the group consisting of Li, Na, K, Rb and Cs, and Ln is selected from the group consisting of Y, La, Gd and Lu. At least one, M
Is at least 11 selected from the group consisting of W and Mo
It is a seed.
し，０<ｘ≦１，組成中のAはＬｉ，Ｎａ，Ｋ，Ｒｂ及び
Ｃｓからなる群より選ばれた少なくとも１種であり，Ｌ
ｎはＹ，Ｌａ，Ｇｄ及びＬｕからなる群より選ばれた少
なくとも１つであり，ＭはＷまたはＭｏからなる群より
選ばれた少なくとも１種である）で表される組成を有す
る赤色発光蛍光体において、その粒子径が５０μｍ以下
であることを特徴とする請求項２記載の赤色発光蛍光
体。3. AEu X Ln (1-X) M 2 O 8 (where 0 <x ≦ 1, A in the composition is at least one selected from the group consisting of Li, Na, K, Rb and Cs). And L
n is at least one selected from the group consisting of Y, La, Gd, and Lu, and M is at least one selected from the group consisting of W or Mo). The red-emitting phosphor according to claim 2, wherein the particle size of the body is 50 μm or less.
線及び短波長可視光線を発光する発光チップ上に、上記
請求項１乃至３の何れかに記載の蛍光体層を設けたこと
を特徴とする発光装置。4. A light-emitting device comprising the phosphor layer according to claim 1 provided on a light-emitting chip that emits long-wavelength ultraviolet light and short-wavelength visible light having a wavelength of 350 nm to 420 nm. .
蛍光体からなる複数の蛍光体層で構成されている請求項
４記載の発光装置。5. The light emitting device according to claim 4, wherein the phosphor layer is composed of a plurality of phosphor layers made of the phosphor according to claim 1.
複数の蛍光体を混合した単層構造である請求項４記載の
発光装置。6. The light emitting device according to claim 4, wherein the phosphor layer has a single layer structure in which the plurality of phosphors according to claim 1 or 2 are mixed.
線及び短波長可視光線を発光する発光ダイオードのモー
ルド部材に、上記請求項１又は２に記載の蛍光体を分散
させたことを特徴とする発光装置。7. A light emitting device, wherein the phosphor according to claim 1 or 2 is dispersed in a mold member of a light emitting diode that emits long-wavelength ultraviolet light and short-wavelength visible light of 350 nm to 420 nm.
線及び短波長可視光線を発光する発光ダイオードのモー
ルド部材に複数の蛍光体を分散させ，その蛍光体の１つ
に上記請求項１又は２に記載の蛍光体を用いたことを特
徴とする発光装置。8. A plurality of phosphors are dispersed in a mold member of a light emitting diode that emits long-wavelength ultraviolet light and short-wavelength visible light having a wavelength of 350 nm to 420 nm, and one of the phosphors is a phosphor according to claim 1 or 2. A light-emitting device using a phosphor.
線及び短波長可視光線を発光する発光ダイオードのモー
ルド部材の外側に、請求項１又は２に記載の蛍光体層を
設けたことを特徴とする発光装置。9. A light-emitting device comprising the phosphor layer according to claim 1 or 2 provided outside a mold member of a light-emitting diode that emits long-wavelength ultraviolet light and short-wavelength visible light having a wavelength of 350 nm to 420 nm. .
外線及び短波長可視光線を発光する発光ダイオードのモ
ールド部材の外側に、複数の発光層を設け，その発光層
の１つが上記請求項１又は２に記載の蛍光体である発光
装置10. A plurality of light emitting layers are provided outside a mold member of a light emitting diode that emits long-wavelength ultraviolet rays and short-wavelength visible rays of 350 nm to 420 nm, and one of the light emitting layers is the above-mentioned one or more. Light-emitting device that is a phosphor of
外線及び短波長可視光線を発光する発光ダイオードのモ
ールド部材の外側に、複数の蛍光体を混合した混合層を
設け，その蛍光体の１つに上記請求項１または２に記載
の蛍光体を用いた発光装置。11. A mixed layer in which a plurality of phosphors are mixed is provided outside a mold member of a light emitting diode which emits long-wavelength ultraviolet light and short-wavelength visible light having a wavelength of 350 nm to 420 nm, and one of the phosphors has the above-mentioned structure. A light emitting device using the phosphor according to Item 1 or 2.
は２に記載の蛍光体と、他の赤色発光蛍光体を少なくて
も1種混合することを特徴とする請求項４乃至１１の何
れか１項に記載の発光装置。12. The phosphor according to claim 1 or 2 as a red light-emitting phosphor, and at least one kind of the other red light-emitting phosphors are mixed together. The light emitting device according to item 1.
外線及び短波長可視光線を発光する発光ダイオードのモ
ールド部材の外側に、複数の蛍光体を混合した被覆体を
被せ、その蛍光体の１つに請求項１または２に記載の蛍
光体を用いた発光装置13. A phosphor containing a mixture of a plurality of phosphors is coated on the outside of a mold member of a light emitting diode that emits long-wavelength ultraviolet light and short-wavelength visible light having a wavelength of 350 nm to 420 nm, and one of the phosphors is provided. A light emitting device using the phosphor according to 1 or 2.
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| JP2005068412A (en) * | 2003-08-04 | 2005-03-17 | Fine Rubber Kenkyusho:Kk | Green light-emitting phosphor and light-emitting device |
| JP4525907B2 (en) * | 2003-08-04 | 2010-08-18 | 株式会社ファインラバー研究所 | Green light emitting phosphor and light emitting device |
| US7459846B2 (en) | 2003-11-01 | 2008-12-02 | Samsung Electro-Mechanics Co., Ltd. | Red phosphor and method of preparing the same, and red light emitting diode, white light emitting diode, and active dynamic liquid crystal device using the red phosphor |
| JP2005259825A (en) * | 2004-03-09 | 2005-09-22 | Mitsubishi Chemicals Corp | Light emitting device, illuminating apparatus using the same and display |
| JP4604516B2 (en) * | 2004-03-09 | 2011-01-05 | 三菱化学株式会社 | LIGHT EMITTING DEVICE, LIGHTING DEVICE USING SAME, AND DISPLAY |
| JP2005255747A (en) * | 2004-03-10 | 2005-09-22 | Fine Rubber Kenkyusho:Kk | Fluorescent member and semiconductor light emitting device |
| JP4535236B2 (en) * | 2004-03-10 | 2010-09-01 | 株式会社ファインラバー研究所 | Fluorescent member, fluorescent member manufacturing method, and semiconductor light emitting device |
| JP2006045575A (en) * | 2004-08-06 | 2006-02-16 | Samsung Electro Mech Co Ltd | Red fluorescent substance and method for producing the same |
| JP2006156505A (en) * | 2004-11-25 | 2006-06-15 | Koito Mfg Co Ltd | White light emitting module and lighting fixture for vehicle |
| JP2006348262A (en) * | 2005-05-17 | 2006-12-28 | Fine Rubber Kenkyusho:Kk | Light emitting device and red-emitting phosphor particle |
| KR101128672B1 (en) | 2005-05-17 | 2012-03-19 | 가부시키가이샤 화인 라버 겐큐쇼 | Light-emitting device and red light-emtting phosphor particle |
| WO2006126392A1 (en) * | 2005-05-23 | 2006-11-30 | Keio University | Fine particle and red fluorescence conversion medium using same |
| JP5009792B2 (en) * | 2005-05-23 | 2012-08-22 | 学校法人慶應義塾 | Fine particles and red fluorescence conversion medium using the same |
| KR101262409B1 (en) | 2005-05-23 | 2013-05-08 | 이데미쓰 고산 가부시키가이샤 | Fine particle and red fluorescence conversion medium using same |
| JP2007254517A (en) * | 2006-03-22 | 2007-10-04 | Niigata Univ | Composite oxide for phosphor and phosphor |
| US9518220B2 (en) | 2013-06-21 | 2016-12-13 | Panasonic Intellectual Property Management Co., Ltd. | Red phosphor material and light-emitting device |
| US9376617B2 (en) | 2014-10-23 | 2016-06-28 | Panasonic Intellectual Property Management Co., Ltd. | Fluorescent material and light-emitting device |
| JP2016146283A (en) * | 2015-02-09 | 2016-08-12 | パナソニックＩｐマネジメント株式会社 | Light emitting device, lighting fixture and lighting system |
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