JP5586670B2 - Lithium lanthanum garnet phosphor and light emitting diode comprising the same - Google Patents
Lithium lanthanum garnet phosphor and light emitting diode comprising the same Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 40
- 239000002223 garnet Substances 0.000 title claims description 30
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 title claims description 27
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000005284 excitation Effects 0.000 description 9
- 229910052746 lanthanum Inorganic materials 0.000 description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000009877 rendering Methods 0.000 description 4
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical group [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- -1 samarium ions Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Description
本発明は蛍光体に関し、特に一般式に示すＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxリチウムランタンガーネット蛍光体及びこれらを備える発光ダイオードに関する。そのうち、０＜ｘ≦１．０，０≦ｙ≦２、Ｒはランタン金属の元素である。 The present invention relates to a phosphor, and more particularly, to a Li 5 La 3 -x Nb 2 -y Ta y O 12 R x lithium lanthanum garnet phosphor represented by a general formula and a light emitting diode including the same. Among them, 0 <x ≦ 1.0, 0 ≦ y ≦ 2, and R is an element of lanthanum metal.
省エネ、炭素軽減の意識台頭につれて、各国とも従来の光源に取り代わる白色発光ダイオード（Ｗｈｉｔｅ Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ，ＷＬＥＤ）の開発に取り掛かっている。発光ダイオードは高発光効率、低消費電力（電気消費量は従来の白熱灯の十分の一、蛍光灯の二分の一）、長寿命、低汚染、体積が小さい、操作反応が速いなどの長所を有し、従来の灯源では克服が難しい課題を解決できる。
現在はすでに白色発光ダイオードは交通信号灯、広告看板、自動車照明、携帯式装置及び表示装置などの素子に幅広く応用されている。このほか、白色発光ダイオードの低エネルギー消費及び低汚染の長所は、今日に推奨されている省エネ、炭素軽減のコンセプトに適っているため、グリーン照明エネルギーと名付けられている。
With the rise of awareness of energy saving and carbon reduction, each country is working on the development of white light emitting diodes (WLEDs) that replace conventional light sources. Light-emitting diodes have the advantages of high luminous efficiency, low power consumption (electricity is one-tenth of conventional incandescent lamps and half of fluorescent lamps), long life, low pollution, small volume, and quick operation response. It can solve problems that are difficult to overcome with conventional light sources.
At present, white light emitting diodes are already widely applied to elements such as traffic signal lights, advertisement signs, automobile lighting, portable devices and display devices. In addition, the low energy consumption and low pollution advantages of white light-emitting diodes are named green lighting energy because they meet the energy saving and carbon mitigation concepts recommended today.
日亜化学株式会社が１９９６年に青色光発光ダイオードを利用し、イットリウムアルミニウムガーネット（Ｙ3Ｏ5Ｏ12：Ｃｅ； Ｃｅｒｉｕｍ−ｄｏｐｅｄ Ｙｔｔｒｉｕｍ Ａｌｕｍｉｎｕｍ Ｇａｒｎｅｔ； ＹＡＧ：Ｃｅ）ドープの蛍光体を励起させ、青色光とＹＡＧ：Ｃｅが発光する黄色光を混合した後に白色光（米国特許ＵＳ ５，９９８，９２５号特許文献１）を形成した。
しかし、この種の白色発光ダイオードは出射光に発光領域に赤色光を欠いており演色性も低い（Ｒａ＜８０）。そこで、演色性を増強して白色光発光装置の適用性を高くするため、赤色蛍光体が添加されている。
現時点で、良く使用されている赤色蛍光体は（Ｃａ，Ｓｒ）ＡｌＳｉＮ3である（米国特許ＵＳ ７，５７３，１９０特許文献２）。しかし、赤色光の光出射は広帯域スペクトルに属し、スペクトル領域が７００ナノメータ（ｎｍ）を超える非可視光の部分は装置の効率が低下されるため、青色光励起に適した赤色蛍光体の開発は目下の重要課題である。
白光発光ダイオードは青色光ダイオードを利用するほか、紫外線発光ダイオードを使用し青、緑、赤三色蛍光体を励起することによって、白光を発光する方式がある。この種の結合方式は全スペクトル帯域を有し、高演色性の光源であるため、紫外線発光ダイオード用に適した蛍光体の開発は現時点の重要な研究目標である。
Nichia Corporation uses a blue light emitting diode in 1996 to excite a yttrium aluminum garnet (Y 3 O 5 O 12 : Ce-doped Yttrium Aluminum Garnet; YAG: Ce) doped phosphor. After mixing the light and the yellow light emitted by YAG: Ce, white light (US Pat. No. 5,998,925, Patent Document 1) was formed.
However, this type of white light emitting diode lacks red light in the light emitting region of the emitted light and has a low color rendering property (Ra <80). Therefore, a red phosphor is added in order to enhance the color rendering and increase the applicability of the white light emitting device.
At present, a commonly used red phosphor is (Ca, Sr) AlSiN 3 (US Pat. No. 7,573,190). However, the emission of red light belongs to the broadband spectrum, and the efficiency of the device is reduced in the part of invisible light whose spectral region exceeds 700 nanometers (nm), so the development of a red phosphor suitable for blue light excitation is currently being developed. It is an important issue.
In addition to using blue light diodes, white light emitting diodes use ultraviolet light emitting diodes to emit white light by exciting blue, green, and red tricolor phosphors. Since this type of coupling method has a full spectrum band and is a high color rendering light source, the development of a phosphor suitable for an ultraviolet light emitting diode is an important research goal at present.
１９８８年Ｍａｚｚａ氏らがＭａｔｅｒｉａｌ Ｌｅｔｔｅｒｓ（ｖｏｌ．７，ｐ．５）ジャーナル（非特許文献１）にてＬｉ5Ｌａ2Ｍ2Ｏ12（Ｍ＝Ｎｂ，Ｔａ）構造を発表しており、さらに、２００６年にはＣｕｓｓｅｎ氏らがＣｈｅｍｉｓｔｒｙ Ｃｏｍｍｕｎｉｃａｔｉｏｎ（ｖｏｌ．４，ｐ．４１２）において、中性子回折技術によりカチオン格子を鑑定し、Ｌｉ5Ｌａ2Ｍ2Ｏ12（Ｍ＝Ｎｂ，Ｔａ）の完全な構造データが提出した。これは一種のガーネット構造タイプに属する。
この構造の一般式はＡ3Ｂ2（ＸＯ4）3、Ａ、Ｂ通常は二価陽イオンまたは三価陽イオンであり、Ｘはほとんどシリカまたはアルミなどの元素より構成する。イットリウムアルミニウムガーネット（Ｙ3Ａｌ5Ｏ12；Ｙｔｔｒｉｕｍ Ａｌｕｍｉｎｕｍ Ｇａｒｎｅｔ；ＹＡＧ）、Ｌｉ5Ｌａ2Ｍ2Ｏ12のうちランタンとＭ（Ｎｂ及びＴａ）にそれぞれ式のＡ位置及びＢ位置に埋め込み、ランタンを埋め込む格子位置は八配位であり、その配位原子はすべて酸素原子である。この種の結晶化合物は簡単に作られるが、励起により可視光出射の特性を有しない。
In 1988, Mr. Mazza et al. Published the Li 5 La 2 M 2 O 12 (M = Nb, Ta) structure in the Material Letters (vol. 7, p. 5) journal (Non-patent Document 1). In 2006, Cussen et al. In Chemistry Communication (vol. 4, p. 412) identified the cation lattice by neutron diffraction technique, and the complete structure of Li 5 La 2 M 2 O 12 (M = Nb, Ta). Data submitted. This belongs to a kind of garnet structure type.
The general formula of this structure is A 3 B 2 (XO 4 ) 3 , A, B, usually a divalent cation or a trivalent cation, and X is almost composed of an element such as silica or aluminum. Of yttrium aluminum garnet (Y 3 Al 5 O 12 ; Yttrium Aluminum Garnet; YAG) and Li 5 La 2 M 2 O 12 , lanthanum and M (Nb and Ta) are embedded in the A and B positions of the formula, respectively. The lattice position to be embedded is octacoordinate, and all the coordination atoms are oxygen atoms. Although this type of crystalline compound is easily made, it does not have the property of emitting visible light upon excitation.
前述公知技術の課題に対して、本発明の目的は青色光または紫外光の励起により赤色蛍光またはその他帯域光の蛍光体を発光すると共に、演色性を増強し、かつ生産プロセスを簡素化するほか、低コストのリチウムランタンガーネット蛍光体及びこれらを備える発光ダイオードを提供することである。 In contrast to the above-mentioned problems of the known technology, the object of the present invention is to emit red fluorescent material or other band fluorescent material by exciting blue light or ultraviolet light, enhance color rendering properties and simplify the production process. Another object of the present invention is to provide a low-cost lithium lanthanum garnet phosphor and a light emitting diode including the same.
前述目的を達成するため、本発明のリチウムランタンガーネット蛍光体は固相反応法により合成し、その一般式はＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxである。そのうち、０＜ｘ≦１．０、０≦ｙ≦２、Ｒはランタン系金属元素であり、かつ蛍光体発光の中心である。そのうち、固相反応法に使用された焼結温度は９００〜１２００℃、焼結圧力は０．１〜０．９ＭＰａ、かつ合成の反応条件はＨ2と、Ｎ2と、を含める。この蛍光体は波長３５０〜５００ｎｍの発光ダイオードによって励起することができ、かつ出射の波長は４５０〜７００ｎｍである。 In order to achieve the above-mentioned object, the lithium lanthanum garnet phosphor of the present invention is synthesized by a solid phase reaction method, and the general formula thereof is Li 5 La 3-x Nb 2-y Ta y O 12 R x . Among them, 0 <x ≦ 1.0, 0 ≦ y ≦ 2, and R is a lanthanum-based metal element and is the center of phosphor emission. Among them, the sintering temperature used in the solid phase reaction method is 900 to 1200 ° C., the sintering pressure is 0.1 to 0.9 MPa, and the synthesis reaction conditions include H 2 and N 2 . This phosphor can be excited by a light emitting diode having a wavelength of 350 to 500 nm, and the emission wavelength is 450 to 700 nm.
一実施例において、焼結温度Ｔは１０５０℃であり、かつ合成反応雰囲気のＨ２及びＮ２の比例はそれぞれＨ2＝１０％、Ｎ2＝９０％である。 In one embodiment, the sintering temperature T is 1050 ° C., and the proportions of H2 and N2 in the synthesis reaction atmosphere are H 2 = 10% and N 2 = 90%, respectively.
前述目的に基づき、本発明において、もう一種のリチウムランタンガーネット蛍光体を備える発光ダイオードを提供し、リチウムランタンガーネット蛍光体と、発光チップからなり、リチウムランタンガーネット蛍光体の一般式はＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxである。そのうち、０＜ｘ≦１．０，０≦ｙ≦２，Ｒはランタン系金属元素である。 Based on the above object, in the present invention, a light emitting diode including another type of lithium lanthanum garnet phosphor is provided, which is composed of a lithium lanthanum garnet phosphor and a light emitting chip. The general formula of the lithium lanthanum garnet phosphor is Li 5 La 3. a -x Nb 2-y Ta y O 12 R x. Among them, 0 <x ≦ 1.0, 0 ≦ y ≦ 2, and R are lanthanum metal elements.
前述設計により、本発明で提供するリチウムランタンガーネット蛍光体は、ドープされるランタン系金属元素の違いによって、青色光帯域または紫外光帯域の光線を有効に吸収して、かつ青色緑色帯域または赤色帯域の光線を発光する。 Due to the above design, the lithium lanthanum garnet phosphor provided in the present invention effectively absorbs light in the blue light band or the ultraviolet light band depending on the lanthanum metal element to be doped, and in the blue green band or red band. The light beam is emitted.
本発明の内容のさらなる理解を図るため、以下にて図面と合わせて説明する。 In order to further understand the contents of the present invention, the following description will be made with reference to the drawings.
本発明のリチウムランタンガーネット蛍光体は固相反応法によって作られ、焼結温度は９００〜１２００℃、焼結圧力は０．１〜０．９ＭＰａ、化学式Ｌｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxによって示すことができる。そのうち、０＜ｘ≦１．０，０≦ｙ≦２、Ｒはランタン系金属元素であり、セリウムＣｅ、ユーロピウムＥｕ、プラセオジムＰｒ、ネオジムＮｄ、サマリウムＳｍ、テリビウムＴｂ、エルビウムＥｒ、イッテルビウムＹｂ及びジスプロシウムＤｙそのいずれかより選択する。さらに、前述リチウムランタンガーネット蛍光体及び発光チップを利用し、リチウムランタンガーネット蛍光体を備える発光ダイオードを作ることができる。
リチウムランタンガーネット蛍光体の一般式はＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxである。そのうち、０＜ｘ≦１．０、０≦ｙ≦２、Ｒはランタン金属の元素である。前述設計により、本発明で提供するリチウムランタンガーネット蛍光体は、ドープされるランタン系金属元素の違いによって、青色光帯域または紫外光帯域の光線を有効に吸収して、かつ青色緑色帯域または赤色帯域の光線を発光する。
一例として、Ｌｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxにおいて、Ｌａの格子位置に活性剤としてランタン系金属元素Ｒをドープすることによって、Ｌｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒx、０＜ｘ≦１．０、０≦ｙ≦２を作ることができる。そのうち、Ｒはプラセオジムイオンのとき、当該化合物を青色光によって励起すると、青緑色光と赤色光を発光し、もし、Ｒはセマリウムのとき、紫外光によって励起すると、青色蛍光を発光する。本発明のリチウムランタンガーネット蛍光体の好ましい実施例による配合は下表に示す。
The lithium lanthanum garnet phosphor of the present invention is produced by a solid phase reaction method, sintering temperature is 900-1200 ° C., sintering pressure is 0.1-0.9 MPa, chemical formula Li 5 La 3-x Nb 2-y Ta This can be indicated by y O 12 R x . Among them, 0 <x ≦ 1.0, 0 ≦ y ≦ 2, R is a lanthanum metal element, and cerium Ce, europium Eu, praseodymium Pr, neodymium Nd, samarium Sm, terbium Tb, erbium Er, ytterbium Yb and dysprosium Dy is selected from either of them. Furthermore, a light-emitting diode including a lithium lanthanum garnet phosphor can be manufactured using the above-described lithium lanthanum garnet phosphor and a light-emitting chip.
The general formula of the lithium lanthanum garnet phosphor is Li 5 La 3 -x Nb 2 -y Ta y O 12 R x . Among them, 0 <x ≦ 1.0, 0 ≦ y ≦ 2, and R is an element of lanthanum metal. Due to the above design, the lithium lanthanum garnet phosphor provided in the present invention effectively absorbs light in the blue light band or the ultraviolet light band depending on the lanthanum metal element to be doped, and in the blue green band or red band. The light beam is emitted.
As an example, in Li 5 La 3 -x Nb 2 -y Ta y O 12 R x , a lanthanum-based metal element R is doped as an activator at the lattice position of La to thereby form Li 5 La 3 -x Nb 2 -y. Ta y O 12 R x , 0 <x ≦ 1.0, 0 ≦ y ≦ 2 can be made. Among them, when R is a praseodymium ion, the compound emits blue-green light and red light when excited by blue light. If R is semalium, it emits blue fluorescence when excited by ultraviolet light. Formulations according to preferred embodiments of the lithium lanthanum garnet phosphor of the present invention are shown in the table below.
図１の本発明の好ましい実施例（Ａ）〜（Ｄ）のＸ線粉末解析像は、本発明の実施例（Ａ）〜（Ｄ）に基づいて製造されたＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒx（ｘ＝０．１；ｙ＝０または２；Ｒ＝Ｐｒ，Ｓｍ）サンプルをＸ線粉末解析像により、結晶相の純度を鑑定したものである。その結果が公知構造の標準スペクトルに一致していることから、本発明の実施例に基づき、合成された蛍光体のサンプルが純粋相であることが裏付けている。 The X-ray powder analysis images of preferred embodiments (A) to (D) of the present invention in FIG. 1 are Li 5 La 3 -x Nb 2 produced based on the embodiments (A) to (D) of the present invention. -y Ta y O 12 R x (x = 0.1; y = 0 or 2; R = Pr, Sm) A sample is used to identify the purity of the crystal phase based on an X-ray powder analysis image. The results are consistent with the standard spectra of known structures, confirming that the synthesized phosphor samples are pure phase based on the examples of the present invention.
図２の本発明の好ましい実施例（Ａ）〜（Ｄ）の励起スペクトルを参照して説明する。図からわかるように、本発明実施例（Ａ）〜（Ｄ） に基づいて製造されたＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒx（ｘ ＝ ０．１；ｙ＝０または２；Ｒ ＝ Ｐｒ， Ｓｍ）サンプルのうち、プラセオジムをドープされたサンプル（Ａ）、（Ｂ）は４３０〜４５０ｎｍ帯域の光源励起に適しており、青色発光ダイオードの励起波長帯域範囲に符合し、サマリウムイオンをドープされたサンプル（Ｃ）、（Ｄ）は３５０〜４３０ｎｍ域の光源励起に適しており、紫外光発光ダイオードの紫外光發光の励起波長帯域範囲に符合している。 This will be described with reference to the excitation spectra of the preferred embodiments (A) to (D) of the present invention shown in FIG. As can be seen, Li 5 La 3-x Nb 2-y Ta y O 12 R x (x = 0.1; y = 0 or 2; R = Pr, Sm) Among the samples, the samples doped with praseodymium (A) and (B) are suitable for light source excitation in the 430 to 450 nm band, and match the excitation wavelength band range of the blue light emitting diode, Samples (C) and (D) doped with samarium ions are suitable for excitation of the light source in the 350 to 430 nm region, and match the excitation wavelength range of the ultraviolet light fluorescence of the ultraviolet light emitting diode.
引き続き図３Ａの本発明の好ましい実施例（Ａ）〜（Ｂ）の発光スペクトル図を参照して説明する。図からわかるように、本発明の実施例（Ａ）〜（Ｂ） に基づいて製造されたＬｉ5Ｌａ2.9Ｎｂ2-yＴａyＯ12 Ｐｒ0.1（ｙ＝０または２）サンプルは、青色光の励起によって、青緑光と赤色光を発光できる。この種の蛍光体の出射波長帯域は４６０〜７００ ｎｍである。 The description will continue with reference to the emission spectrum diagrams of the preferred embodiments (A) to (B) of the present invention in FIG. 3A. As can be seen, the Li 5 La 2.9 Nb 2 -y Ta y O 12 Pr 0.1 (y = 0 or 2) sample produced according to Examples (A) to (B) of the present invention is blue light. Excitation of can produce blue-green light and red light. The emission wavelength band of this type of phosphor is 460 to 700 nm.
引き続き図３Ｂの本発明の好ましい実施例（Ｃ）〜（Ｄ）の発光スペクトル図を参照して説明する。図からわかるように、本発明の実施例（Ｃ）〜（Ｄ）に基づいて製造されたＬｉ5Ｌａ2.9Ｎｂ2-yＴａyＯ12Ｓｍ0.1（ｙ＝０または２）サンプルは、紫外光の励起によって、赤色光を発光できる。この種の蛍光体の出射波長帯域は５５０〜７００ ｎｍである。 The description will continue with reference to the emission spectrum diagrams of the preferred embodiments (C) to (D) of the present invention shown in FIG. 3B. As can be seen from the figure, the Li 5 La 2.9 Nb 2 -y Ta y O 12 Sm 0.1 (y = 0 or 2) sample produced according to the examples (C) to (D) of the present invention is ultraviolet light. Red light can be emitted by the excitation of. The emission wavelength band of this type of phosphor is 550 to 700 nm.
引き続き図４の本発明の好ましい実施例（Ａ）〜（Ｄ）の色度座標図を参照して説明する。本実施例（Ａ）〜（Ｄ）の発光スペクトルを国際照明委員会が制定された色度座標図に基づいて公式換算し、発光の色度座標を算出した後、座標図に表示する。図４に示すように、本発明の好ましい実施例の発光は赤色光帯域であることがわかる。 The description will be continued with reference to the chromaticity coordinate diagrams of the preferred embodiments (A) to (D) of the present invention shown in FIG. The emission spectra of the examples (A) to (D) are officially converted based on the chromaticity coordinate diagram established by the International Lighting Commission, and the chromaticity coordinates of the light emission are calculated, and then displayed on the coordinate diagram. As shown in FIG. 4, it can be seen that the emission of the preferred embodiment of the present invention is in the red light band.
前述とおり、本発明は斬新なリチウムランタンガーネット化合物からなる赤色光蛍光体を提供し、３５０〜４５０ｎｍの光波を有効に吸収した後、４５０〜７００ｎｍ帯域の光線を発光することができる。 As described above, the present invention provides a red phosphor composed of a novel lithium lanthanum garnet compound, and can effectively emit light in the 450 to 700 nm band after effectively absorbing a 350 to 450 nm light wave.
Claims (8)
焼結温度Ｔ及び焼結圧力Ｐの合成反応雰囲気により作られ、
前記リチウムランタンガーネット蛍光体の一般式はＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxであり、
そのうち、ｘ＝０．１、０≦ｙ≦２であり、
ＲはＰｒまたはＳｍであることを特徴とする、
リチウムランタンガーネット蛍光体。 A lithium lantern garnet phosphor,
Made by the synthetic reaction atmosphere of sintering temperature T and sintering pressure P,
The general formula of the lithium lanthanum garnet phosphor is Li5La3-xNb2-yTayO12Rx,
Among them , x = 0.1 , 0 ≦ y ≦ 2,
R is Pr or Sm ,
Lithium lanthanum garnet phosphor.
発光チップとからなり、
かつリチウムランタンガーネット蛍光体の一般式はＬｉ5Ｌａ3-xＮｂ2-yＴａyＯ12Ｒxであり、
そのうち、ｘ＝０．１、０≦ｙ≦２であり、
ＲはＰｒまたはＳｍであることを特徴とする、
請求項１ないし７のいずれか一項に記載のリチウムランタンガーネット蛍光体。 A lithium lantern garnet phosphor,
Consisting of a light emitting chip,
The general formula of the lithium lanthanum garnet phosphor is Li5La3-xNb2-yTayO12Rx,
Among them , x = 0.1 , 0 ≦ y ≦ 2,
R is Pr or Sm ,
The lithium lanthanum garnet phosphor according to any one of claims 1 to 7 .
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