JP2002129154A - Luminescent material and light source apparatus using the same - Google Patents
Luminescent material and light source apparatus using the sameInfo
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- JP2002129154A JP2002129154A JP2000331796A JP2000331796A JP2002129154A JP 2002129154 A JP2002129154 A JP 2002129154A JP 2000331796 A JP2000331796 A JP 2000331796A JP 2000331796 A JP2000331796 A JP 2000331796A JP 2002129154 A JP2002129154 A JP 2002129154A
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- light
- light source
- emitting material
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、発光材料及びそれ
を用いた光源装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting material and a light source device using the same.
【０００２】[0002]
【従来の技術】これまで発光材料として用いられたペロ
ブスカイト構造を有する酸化物は、全て発光中心として
外来の希土類元素などを用いていたため、その発光波長
や材料の選択性に制限があった。一例としてＮｄをドー
プしたＹＡｌＯ3 は、レーザー材料として知られている
が、その発光波長はＮｄイオンで決まる狭い波長領域に
限定される。また、電子遷移が禁制であるため振動子強
度が小さく、レーザー材料としてコンパクトな装置を実
現することが困難であった。2. Description of the Related Art All of the oxides having a perovskite structure which have been used as a light emitting material have been limited to the emission wavelength and the selectivity of the material since all of them use a foreign rare earth element as a light emission center. As an example, Nd-doped YAlO 3 is known as a laser material, but its emission wavelength is limited to a narrow wavelength range determined by Nd ions. Further, since electron transition is forbidden, the oscillator strength is small, and it has been difficult to realize a compact device as a laser material.
【０００３】一方、ペロブスカイト以外の結晶性発光材
料としては、各種の蛍光体やレーザー結晶が知られてい
るが、いずれも同様の欠点を有している。[0003] On the other hand, as a crystalline luminescent material other than perovskite, various phosphors and laser crystals are known, but all have similar disadvantages.
【０００４】母結晶自体を発光させる試みとしては発明
者らによって還元雰囲気下で作製したＬａＡｌＯ3 を用
いた発光材料が得られている。この材料は広い発光スペ
クトルを有し、発光材料として有用な特徴を備えている
が、発光強度が十分でなく、かつ安定な結晶成長が困難
であるなどの問題点があった〔Ｙ．Ｋａｗａｂｅ，Ａ．
Ｙａｍａｎａｋａ，Ｅ．Ｈａｎａｍｕｒａ，Ｔ．Ｋｉｍ
ｕｒａ，Ｙ．Ｔａｋｉｇｕｃｈｉ，Ｈ．Ｋａｎ，ａｎｄ
Ｙ．Ｔｏｋｕｒａ“Ｐｈｏｔｏｌｕｍｉｎｅｓｃｅｎ
ｃｅ ｏｆ ｐｅｒｏｖｓｋｉｔｅ ｌａｎｔｈａｎｕ
ｍ ａｌｕｍｉｎａｔｅ ｓｉｎｇｌｅ ｃｒｙｓｔａ
ｌｓ”Ｊ．Ａｐｐｌ．Ｐｈｙｓ．８７，７５９４（２０
００）〕。In an attempt to cause the mother crystal itself to emit light, a luminescent material using LaAlO 3 prepared under a reducing atmosphere has been obtained by the present inventors. This material has a broad emission spectrum and has useful characteristics as a light emitting material, but has problems such as insufficient light emission intensity and difficulty in stable crystal growth [Y. Kawabe, A .;
Yamanaka, E .; Hanamura, T .; Kim
ura, Y .; Takeguchi, H .; Kan, and
Y. Tokura "Photoluminescen
ce of perovskite lanthanu
m aluminate single crysta
ls "J. Appl. Phys. 87, 7594 (20
00)].
【０００５】[0005]
【発明が解決しようとする課題】上記したように、固体
レーザーに代表される固体光源は、使用する光学活性材
料によりピーク波長、パワー、ＣＷかパルスかの動作モ
ード、効率などが決まってしまうため、幅広い光学活性
材料が求められている。酸化物は耐環境性に優れ、Ｎ
ｄ：ＹＡｌＯ3 などの多くの光学活性材料が見出されて
いる。超伝導材料として注目のペロブスカイト型酸化物
も発光材料として開発が試みられているが、Ｔｉ：Ｌａ
ＡｌＯ3 のように発光中心となる元素（Ｔｉ）を添加し
たものであり、母体からの発光は川辺らの報告〔上記技
術文献〕があるが、発光強度が弱く、光学活性材料とし
て十分に使えるものではなかった。As described above, a solid-state light source represented by a solid-state laser has a peak wavelength, a power, an operation mode of CW or pulse, an efficiency, and the like determined by an optically active material to be used. There is a need for a wide range of optically active materials. Oxide is excellent in environmental resistance, N
Many optically active materials such as d: YAlO 3 have been found. Perovskite-type oxides, which have attracted attention as superconducting materials, have also been developed as light-emitting materials, but Ti: La
It is a substance to which an element (Ti) serving as a luminescence center is added, such as AlO 3 , and the light emission from the matrix is reported by Kawabe et al. [The above-mentioned technical literature], but the light emission intensity is weak and can be sufficiently used as an optically active material It was not something.
【０００６】本発明は、上記状況に鑑みて、近紫外から
赤外の範囲で室温で安定なより強い発光強度を有する発
光材料及びそれを用いた光源装置を提供することを目的
とする。SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a luminescent material having a stronger luminescence intensity which is stable at room temperature in a range from near ultraviolet to infrared and a light source device using the same.
【０００７】[0007]
【課題を解決するための手段】本発明は、上記目的を達
成するために、 〔１〕酸素分圧が大気より低い雰囲気下で作製したＡＢ
Ｏ3 組成のペロブスカイト型化合物を主たる構成要素と
する発光材料であって、ＡもしくはＢの一部、もしくは
両方の一部が、他の元素Ａ′，Ｂ′に所定の添加量だけ
置換されることを特徴とする発光材料。ただし、Ａ，
Ａ′はＩａ族、IIａ族または希土類を含むIIIｂ族元素
であり、Ｂ，Ｂ′はVIｂからIIｂまでの遷移金属または
IIIａ族元素である。In order to achieve the above object, the present invention provides: [1] an AB fabricated under an atmosphere having an oxygen partial pressure lower than the atmosphere;
A light-emitting material mainly composed of a perovskite-type compound having an O 3 composition, wherein a part of A or B or both of them are replaced with other elements A ′ and B ′ by a predetermined amount. A light emitting material characterized by the above. However, A,
A 'is a group Ia, IIa or group IIIb element containing a rare earth element, and B and B' are transition metals from VIb to IIb or
It is a group IIIa element.
【０００８】〔２〕上記〔１〕記載の発光材料におい
て、前記Ａが IIIｂ族元素であり、前記Ｂが IIIａ族元
素であることを特徴とする。[2] The luminescent material according to [1], wherein A is a group IIIb element and B is a group IIIa element.
【０００９】〔３〕上記〔２〕記載の発光材料におい
て、前記Ａ′がIIａ族であることを特徴とする。[3] The luminescent material according to [2], wherein A 'is a group IIa.
【００１０】〔４〕上記〔３〕記載の発光材料におい
て、前記Ｂがアルミニウムであることを特徴とする。[4] The luminescent material according to [3], wherein B is aluminum.
【００１１】〔５〕上記〔３〕記載の発光材料におい
て、前記Ａがイットリウム、またはランタン及びそれら
の混合物であることを特徴とする。[5] The luminescent material according to [3], wherein A is yttrium, lanthanum, or a mixture thereof.
【００１２】〔６〕上記〔１〕、〔２〕、〔３〕、
〔４〕又は〔５〕記載の発光材料であって、前記所定の
添加量は１０％以下であることを特徴とする。[6] The above [1], [2], [3],
The luminescent material according to [4] or [5], wherein the predetermined amount is 10% or less.
【００１３】〔７〕上記〔１〕、〔２〕、〔３〕、
〔４〕、〔５〕又は〔６〕記載の発光材料を用いた光源
装置。[7] The above [1], [2], [3],
A light source device using the light emitting material according to [4], [5] or [6].
【００１４】〔８〕上記〔７〕記載の発光材料を用いた
光源装置であって、駆動源として放電装置、または電流
注入装置、または紫外光励起源を具備する。[8] A light source device using the light emitting material according to the above [7], comprising a discharge device, a current injection device, or an ultraviolet light excitation source as a driving source.
【００１５】[0015]
〔９〕上記〔１〕記載の発光材料を用いた
光源装置であって、材料の有する光学利得による増幅効
果を利用した光源装置。[9] A light source device using the light emitting material according to [1], wherein the light source device uses an amplification effect by an optical gain of the material.
【００１６】[0016]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。Embodiments of the present invention will be described below in detail.
【００１７】まず、本発明の発光材料の製造方法につい
て説明する。First, a method for producing a luminescent material of the present invention will be described.
【００１８】本発明のＡＢＯ3 化合物のＡ位置の元素と
しては IIIｂ族のＬａ，Ｙなどがその代表的なものであ
るが、これに限定されるものではなく、その他希土類や
IIａ族、さらにはその混合組成であってもよい。また、
Ｂ位置の化合物はＡｌ等 IIIａ族元素またはIVｂ−IIｂ
の遷移金属が好ましいが、同様にそれに限定されるもの
ではない。Ａ′，Ｂ′についてもＡ，Ｂと同様の選択が
可能である。The element at the A position of the ABO 3 compound of the present invention is, for example, La, Y of the IIIb group, but is not limited thereto.
Group IIa or a mixture thereof may be used. Also,
The compound at the B position is a group IIIa element such as Al or group IVb-IIb
Are preferred, but are not limited thereto. A 'and B' can be selected in the same manner as A and B.
【００１９】（１）第１実施例（結晶成長Ｃａ：ＹＡｌ
Ｏ3 ） Ｙ2 Ｏ3 ５．１６２ｇとＡｌ2 Ｏ3 １１．３２０ｇとＣ
ａＯ０．０５７ｇを混合し、直径６ｍｍのゴム風船につ
め、ニチデン機械（株）製ＳＰＴ１１９−１０Ｔにて３
００Ｍｐａの静水圧力を印加し原料棒を作製した。その
原料棒を大気中１０００℃で４時間焼成し、ニチデン機
械（株）製ＳＣ−Ｍ５０ＸＳにて水素濃度４％のアルゴ
ン・水素混合ガス雰囲気中で成長させた。キセノン電球
電流は、５８Ａに設定し、成長速度は２０．０５ｍｍ／
時間に設定した。その結果、直径３．７ｍｍ、長さ２５
ｍｍの単結晶体が得られた。(1) First Embodiment (Crystal Growth Ca: YAl
O 3 ) 5.162 g of Y 2 O 3, 11.320 g of Al 2 O 3 and C
0.057 g of aO were mixed, packed in a rubber balloon having a diameter of 6 mm, and mixed with Nichiden Machine Co., Ltd. SPT119-10T.
A raw material rod was produced by applying a hydrostatic pressure of 00 Mpa. The raw material rod was fired in the air at 1000 ° C. for 4 hours, and was grown in an argon / hydrogen mixed gas atmosphere having a hydrogen concentration of 4% by SC-M50XS manufactured by Nichiden Machine Co., Ltd. The xenon bulb current was set at 58 A and the growth rate was 20.05 mm /
Set to time. As a result, the diameter was 3.7 mm and the length was 25.
mm was obtained.
【００２０】（２）第２実施例（結晶成長Ｃａ：ＬａＡ
ｌＯ3 ） Ｌａ2 Ｏ3 ８．０６５ｇとＡｌ2 Ｏ3 ２．５４９ｇとＣ
ａＯ０．０２９ｇを混合し、直径６ｍｍのゴム風船につ
め、ニチデン機械（株）製ＳＰＴ１１９−１０Ｔにて３
００Ｍｐａの静水圧力を印加し原料棒を作製した。その
原料棒を大気中１０００℃で２５６時間焼成し、ニチデ
ン機械（株）製ＳＣ−Ｍ５０ＸＳにて水素濃度４％のア
ルゴン・水素混合ガス雰囲気中で成長させた。キセノン
電球電流は７５Ａに設定し、成長速度は２０．００ｍｍ
／時間に設定した。その結果、直径３．８ｍｍ、長さ１
３ｍｍの単結晶体が得られた。(2) Second Embodiment (Crystal Growth Ca: LaA)
(IO 3 ) 8.065 g of La 2 O 3, 2.549 g of Al 2 O 3 and C
0.029 g of aO were mixed, packed in a rubber balloon having a diameter of 6 mm, and mixed with Nichiden Machine Co., Ltd. SPT119-10T.
A raw material rod was produced by applying a hydrostatic pressure of 00 Mpa. The raw material rod was fired in the atmosphere at 1000 ° C. for 256 hours, and was grown in an argon / hydrogen mixed gas atmosphere having a hydrogen concentration of 4% by SC-M50XS manufactured by Nichiden Kikai Co., Ltd. Xenon bulb current is set to 75A, growth rate is 20.00mm
/ Hour. As a result, the diameter was 3.8 mm and the length was 1
A 3 mm single crystal was obtained.
【００２１】（３）第３実施例（結晶成長Ｂａ：ＬａＡ
ｌＯ3 ） Ｌａ2 Ｏ3 ８．５３７ｇとＡｌ2 Ｏ3 ２．６７１ｇとＢ
ａＯ０．０８６ｇを混合し、直径６ｍｍのゴム風船につ
め、ニチデン機械（株）製ＳＰＴ１１９−１０Ｔにて３
００Ｍｐａの静水圧力を印加し原料棒を作製した。その
原料棒を大気中１０００℃で２１５時間焼成し、ニチデ
ン機械（株）製ＳＣ−Ｍ５０ＸＳにて水素濃度４％のア
ルゴン・水素混合ガス雰囲気中で成長させた。キセノン
電球電流は７３Ａに設定し、成長速度は２０．０６ｍｍ
／時間に設定した。その結果、直径３．５ｍｍ、長さ１
５ｍｍの単結晶体が得られた。(3) Third Embodiment (Crystal Growth Ba: LaA)
lO 3) La 2 O 3 8.537g and Al 2 O 3 2.671g and B
0.086 g of aO was mixed, packed in a rubber balloon having a diameter of 6 mm, and mixed with Nichiden Machine Co., Ltd. SPT119-10T.
A raw material rod was produced by applying a hydrostatic pressure of 00 Mpa. The raw material rod was fired in the atmosphere at 1000 ° C. for 215 hours, and was grown by SC-M50XS manufactured by Nichiden Kikai Co., Ltd. in an argon / hydrogen mixed gas atmosphere having a hydrogen concentration of 4%. The xenon bulb current was set to 73A and the growth rate was 20.06mm
/ Hour. As a result, the diameter was 3.5 mm and the length was 1
A single crystal of 5 mm was obtained.
【００２２】（４）第４実施例（Ｓｒ：ＬａＡｌＯ3 ） ＳｒＣＯ3 を１２５０℃で１２時間熱処理することによ
って作製したＳｒＯ０．０３６ｇとＬａ2 Ｏ3 ５．６９
９ｇとＡｌ2 Ｏ3 １．７８４ｇとを混合し、直径６ｍｍ
のゴム風船につめ、ニチデン機械（株）製ＳＰＴ１１９
−１０Ｔにて３００Ｍｐａの静水圧力を印可し原料棒を
作製した。その原料棒を大気中１０００℃で１６時間焼
成し、ニチデン機械（株）製ＳＣ−Ｍ５０ＸＳにて水素
濃度４％のアルゴン・水素混合ガス雰囲気中で成長させ
た。キセノン電球電流は７６Ａに設定し、成長速度は２
０．０１ｍｍ／時間に設定した。その結果、直径３．６
ｍｍ、長さ４２ｍｍの単結晶体が得られた。(4) Fourth Embodiment (Sr: LaAlO 3 ) 0.036 g of SrO produced by heat-treating SrCO 3 at 1250 ° C. for 12 hours and 5.69 of La 2 O 3
9 g and 1.784 g of Al 2 O 3 were mixed, and the diameter was 6 mm.
Packed with rubber balloons, SPT119 manufactured by Nichiden Machine Co., Ltd.
A raw material rod was produced by applying a hydrostatic pressure of 300 Mpa at -10T. The raw material rod was fired in the air at 1000 ° C. for 16 hours, and grown in SC-M50XS manufactured by Nichiden Machine Co., Ltd. in an argon / hydrogen mixed gas atmosphere having a hydrogen concentration of 4%. The xenon bulb current was set at 76 A and the growth rate was 2
It was set to 0.01 mm / hour. As a result, a diameter of 3.6
A single crystal having a length of 42 mm and a length of 42 mm was obtained.
【００２３】（５）第５実施例（Ｃａ：ＧｄＡｌＯ3 ） Ｇｄ2 Ｏ3 ８．９７４ｇとＡｌ2 Ｏ3 ２．４９８ｇとＣ
ａＯ０．０２８ｇを混合し、直径６ｍｍのゴム風船につ
め、ニチデン機械（株）製ＳＰＴ１１９−１０Ｔにて３
００Ｍｐａの静水圧力を印加し原料棒を作製した。その
原料棒を大気中６００℃で１６０時間焼成し、ニチデン
機械（株）製ＳＣ−Ｍ５０ＸＳにて水素濃度４％のアル
ゴン・水素混合ガス雰囲気中で成長させた。キセノン電
球電流は６３Ａに設定し、成長速度は２０．０５ｍｍ／
時間に設定した。その結果、直径３．１ｍｍ、長さ３７
ｍｍの単結晶体が得られた。(5) Fifth Embodiment (Ca: GdAlO 3 ) 8.974 g of Gd 2 O 3, 2.498 g of Al 2 O 3 and C
0.028 g of aO were mixed, packed in a rubber balloon having a diameter of 6 mm, and mixed with Nichiden Machine Co., Ltd. SPT119-10T.
A raw material rod was produced by applying a hydrostatic pressure of 00 Mpa. The raw material rod was fired in the air at 600 ° C. for 160 hours, and was grown by SC-M50XS manufactured by Nichiden Machine Co., Ltd. in an argon / hydrogen mixed gas atmosphere having a hydrogen concentration of 4%. The xenon bulb current was set at 63 A and the growth rate was 20.05 mm /
Set to time. As a result, the diameter was 3.1 mm and the length was 37.
mm was obtained.
【００２４】次に、上記した発光材料の測定について説
明する。Next, the measurement of the luminescent material will be described.
【００２５】（１）第１及び第２実施例で得られたＣ
ａ：ＹＡｌＯ3 ，Ｃａ：ＬａＡｌＯ3結晶の発光スペク
トルを、３５５ｎｍのレーザーで照射したところ、Ｃ
ａ：ＹＡｌＯ3 については緑色、Ｃａ：ＬａＡｌＯ3 に
ついては赤色のそれぞれ強い発光が得られた。発光スペ
クトルをアクトン社製の分光器・３２０ｉとプリンスト
ンインスツルメント社製のＣＣＤ・ＩＭＡＸ５１２を用
いて、図１に示す実験装置で測定した結果を図２に示
す。(1) C obtained in the first and second embodiments
When the emission spectrum of a: YAlO 3 , Ca: LaAlO 3 crystal was irradiated with a 355 nm laser,
Green light was obtained for a: YAlO 3 and red light was obtained for Ca: LaAlO 3 . FIG. 2 shows the results of measuring the emission spectrum using the spectroscope 320i manufactured by Acton and the CCD IMAX512 manufactured by Princeton Instruments, using the experimental apparatus shown in FIG.
【００２６】図１は本発明の発光材料の実験装置（その
１）の構成図、図２は実験装置で測定した結果を示す図
である。FIG. 1 is a configuration diagram of a light emitting material experimental device (No. 1) of the present invention, and FIG. 2 is a diagram showing a result measured by the experimental device.
【００２７】図１において、１はレーザー、２は波長変
換結晶、３はダイクロイックミラー、４はフィルター、
５，６は反射ミラー、７はレンズ、８は試料、９はステ
ージ、１０は試料８からの発光、１１は分光器、１２は
光検出器、１３はパーソナルコンピュータ（ＰＣ）であ
る。In FIG. 1, 1 is a laser, 2 is a wavelength conversion crystal, 3 is a dichroic mirror, 4 is a filter,
5, 6 are reflection mirrors, 7 is a lens, 8 is a sample, 9 is a stage, 10 is light emission from the sample 8, 11 is a spectroscope, 12 is a photodetector, and 13 is a personal computer (PC).
【００２８】そこで、レーザー１より出射された１．０
６４μｍの光を複数の波長変換結晶２に入射し、発生し
た３５５ｎｍの紫外光をダイクロイックミラー３及びフ
ィルター４によって取り出し、ミラー５，６を用いるこ
とにより所定の伝搬方向に調整し、さらに、レンズ７を
用いて試料８に照射する。試料８の位置はステージ９に
よって微調整される。Therefore, the 1.0 light emitted from the laser 1
Light of 64 μm is incident on the plurality of wavelength conversion crystals 2, and the generated 355 nm ultraviolet light is extracted by the dichroic mirror 3 and the filter 4, adjusted in a predetermined propagation direction by using mirrors 5 and 6, and Irradiate the sample 8 using. The position of the sample 8 is finely adjusted by the stage 9.
【００２９】上記の紫外光を照射することによって試料
８より発生した発光１０はレンズによって分光器１１に
導かれ、装着された光検出器１２によって検出される。
この時、光検出器１２とレーザー１が同期するようにＰ
Ｃ１３によって制御されると同時に発光強度がＰＣ１３
に転送される。The light emission 10 generated from the sample 8 by irradiating the ultraviolet light is guided to the spectroscope 11 by the lens, and is detected by the mounted photodetector 12.
At this time, P is set so that the photodetector 12 and the laser 1 are synchronized.
The emission intensity is controlled by PC13 and at the same time PC13
Is forwarded to
【００３０】図２において、横軸は波長であり、縦軸は
ＰＬ強度（相対強度）を示している。上段は第２実施例
の試料に基づく結果であり、下段は第１実施例の試料に
基づく結果を表している。In FIG. 2, the horizontal axis represents wavelength, and the vertical axis represents PL intensity (relative intensity). The upper part shows the result based on the sample of the second embodiment, and the lower part shows the result based on the sample of the first embodiment.
【００３１】（２）第１実施例で得られたＣａ：ＹＡｌ
Ｏ3 の緑色発光の発光寿命をプリンストンインスツルメ
ント社製のＣＣＤ・ＩＭＡＸ５１２を用いて測定した結
果は１６ｎｓであった。結果を図３に示す。(2) Ca: YAl obtained in the first embodiment
The result of measuring the emission lifetime of the green light emission of O 3 using a CCD IMAX512 manufactured by Princeton Instruments Inc. was 16 ns. The results are shown in FIG.
【００３２】図３は本発明の発光材料の実験装置（その
２）による結果を示す図であり、横軸に時間（ｎｓ）、
縦軸に発光強度を示している。FIG. 3 is a diagram showing the results of a light emitting material of the present invention using an experimental device (No. 2), where the horizontal axis represents time (ns),
The vertical axis shows the light emission intensity.
【００３３】（３）Ｃａ：ＹＡｌＯ3 を３５５ｎｍのパ
ルスレーザー光で励起し、図４に示す実験装置を用い
て、同時に透過光強度を波長可変レーザーを用いて測定
したところ４８０ｎｍから５５０ｎｍの範囲で透過光が
増幅されていることが確認された。(3) Ca: YAlO 3 was excited by a pulse laser beam of 355 nm, and the transmitted light intensity was simultaneously measured using a wavelength variable laser using the experimental apparatus shown in FIG. It was confirmed that the transmitted light was amplified.
【００３４】図４は本発明の発光材料の実験装置（その
２）の構成図である。FIG. 4 is a block diagram of a light emitting material experimental apparatus (part 2) of the present invention.
【００３５】この図において、２１はレーザー、２２，
２４，２５はミラー、２３は波長可変レーザー、２６は
試料、２７は光検出器、２８はオシロスコープである。In this figure, 21 is a laser, 22,
24 and 25 are mirrors, 23 is a tunable laser, 26 is a sample, 27 is a photodetector, and 28 is an oscilloscope.
【００３６】そこで、３５５ｎｍの波長を有するレーザ
ー２１をミラー２２を用いて試料２６に照射すると同時
に波長可変レーザー２３からの出射光を２４，２５のミ
ラーによって方向を調整し、試料２６に入射し、その透
過光を光検出器２７及びオシロスコープ２８を用いてモ
ニターすることにより、透過の増減を観測するようにし
ている。Then, the laser 21 having a wavelength of 355 nm is irradiated on the sample 26 by using the mirror 22 and at the same time, the direction of the light emitted from the wavelength tunable laser 23 is adjusted by the mirrors 24 and 25 to be incident on the sample 26. By monitoring the transmitted light using a photodetector 27 and an oscilloscope 28, an increase or decrease in transmission is observed.
【００３７】以下に２つの比較例について説明する。Hereinafter, two comparative examples will be described.
【００３８】（１）第１の比較例（ＬａＡｌＯ3 の発光
スペクトル） 第２実施例と同じ方法で作製したＣａを含まない結晶の
発光スペクトルを２６６ｎｍのレーザーで照射したとこ
ろ緑色の発光が得られた。発光強度は、第１実施例に比
べて１／２０であった。発光スペクトルをアクトン社製
の分光器・３２０ｉとプリンストンインスツルメント社
製のＣＣＤ・ＩＭＡＸ５１２を用いて測定した結果を図
５に示す。３５５ｎｍで励起した場合はさらに弱い発光
しか観測されなかった。(1) First Comparative Example (Emission Spectrum of LaAlO 3 ) When the emission spectrum of a Ca-free crystal produced by the same method as in the second example was irradiated with a 266 nm laser, green emission was obtained. Was. The emission intensity was 1/20 as compared with the first example. FIG. 5 shows the results of measurement of the emission spectrum using a spectrometer 320i manufactured by Acton and a CCD IMAX512 manufactured by Princeton Instruments. When excited at 355 nm, only weaker emission was observed.
【００３９】図５は第１の比較例の測定結果を示す図で
あり、横軸に波長（ｎｍ）、縦軸に発光スペクトル強度
（相対単位）を示している。FIG. 5 is a diagram showing the measurement results of the first comparative example, in which the horizontal axis represents wavelength (nm) and the vertical axis represents emission spectrum intensity (relative unit).
【００４０】（２）第２の比較例（ＬａＡｌＯ3 の利得
の測定） ＬａＡｌＯ3 を３５５ｎｍおよび２６６ｎｍのパルスレ
ーザー光で励起し、上記（３）に例示したものと同じ実
験装置を用いて、同時に透過光強度を白色光を測定した
ところ、光の増幅は観測されず、吸収の増大が観測され
た。[0040] (2) (Measurement of gain LaAlO 3) a second comparative example LaAlO 3 was excited by a pulse laser beam of 355nm and 266 nm, using the same experimental apparatus as illustrated above (3), at the same time When the transmitted light intensity was measured for white light, no amplification of light was observed, and an increase in absorption was observed.
【００４１】なお、本発明は上記実施例に限定されるも
のではなく、本発明の趣旨に基づいて種々の変形が可能
であり、これらを本発明の範囲から排除するものではな
い。It should be noted that the present invention is not limited to the above-described embodiment, but various modifications are possible based on the spirit of the present invention, and these are not excluded from the scope of the present invention.
【００４２】[0042]
【発明の効果】以上、詳細に説明したように、本発明に
よれば、ＡＢＯ3 化合物のＡまたはＢの位置の元素の一
部を別種の元素Ａ′，Ｂ′で置換することにより、より
強い発光強度を有する結晶が安定に作製可能であること
を見出した。また、その発光スペクトルや強度、及び発
光寿命がＡ′，Ｂ′の種類や濃度によって制御可能であ
ることを明らかにした。また、これらの手法によって作
製された化合物の一部をパルス紫外光源で強く励起する
ことにより光学的利得を有することが示された。ここで
置換する元素の率は、１０％以下、より望ましくは２％
〜０．０００１％である。As described above in detail, according to the present invention, by substituting a part of the element at the position of A or B of the ABO 3 compound with another element A 'or B', It has been found that a crystal having a strong luminescence intensity can be stably produced. Further, it has been clarified that the emission spectrum, intensity, and emission lifetime can be controlled by the types and concentrations of A 'and B'. In addition, it was shown that some of the compounds prepared by these techniques had an optical gain by being strongly excited by a pulsed ultraviolet light source. Here, the ratio of the element to be replaced is 10% or less, more preferably 2%.
~ 0.0001%.
【図１】本発明の発光材料の実験装置（その１）の構成
図である。FIG. 1 is a configuration diagram of a light emitting material experimental device (part 1) of the present invention.
【図２】実験装置で測定した結果を示す図である。FIG. 2 is a diagram showing a result measured by an experimental device.
【図３】本発明の発光材料の実験装置（その２）による
結果を示す図である。FIG. 3 is a view showing a result of a light emitting material of the present invention using an experimental device (No. 2).
【図４】本発明の発光材料の実験装置（その２）の構成
図である。FIG. 4 is a configuration diagram of a light emitting material experimental device (part 2) of the present invention.
【図５】第１の比較例の測定結果を示す図である。FIG. 5 is a diagram showing measurement results of a first comparative example.
１，２１ レーザー ２ 波長変換結晶 ３ ダイクロイックミラー ４ フィルター ５，６ 反射ミラー ７ レンズ ８，２６ 試料 ９ ステージ １０ 試料からの発光 １１ 分光器 １２，２７ 光検出器 １３ パーソナルコンピュータ ２２，２４，２５ ミラー ２３ 波長可変レーザー ２８ オシロスコープ 1, 21 laser 2 wavelength conversion crystal 3 dichroic mirror 4 filter 5, 6 reflection mirror 7 lens 8, 26 sample 9 stage 10 light emission from sample 11 spectroscope 12, 27 photodetector 13 personal computer 22, 24, 25 mirror 23 Tunable laser 28 oscilloscope
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀内 大嗣 北海道札幌市西区発寒３条２−７−20 (72)発明者 猿倉 信彦 愛知県岡崎市竜美南２−３−１明大寺住宅 ６−403 (72)発明者 大竹 秀幸 愛知県岡崎市六名本町13−９−302 Ｆターム(参考） 4H001 CA04 XA08 XA13 XA39 XA57 XA64 YA20 YA38 YA56 5F072 AC10 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Daiji Horiuchi 3-7-20-20, Satsuro, Nishi-ku, Sapporo, Hokkaido (72) Inventor Nobuhiko Sarukura 2-3-1 Ryuminami, Okazaki-shi, Aichi Pref. 403 (72) Inventor Hideyuki Otake 13-9-302, Rokunamachi, Okazaki-shi, Aichi F-term (reference) 4H001 CA04 XA08 XA13 XA39 XA57 XA64 YA20 YA38 YA56 5F072 AC10
Claims (9)
したＡＢＯ3 組成のペロブスカイト型化合物を主たる構
成要素とする発光材料であって、ＡもしくはＢの一部、
もしくは両方の一部が、他の元素Ａ′，Ｂ′に所定の添
加量だけ置換されることを特徴とする発光材料。ただ
し、Ａ，Ａ′はＩａ族、IIａ族または希土類を含む III
ｂ族元素であり、Ｂ，Ｂ′はVIｂからIIｂまでの遷移金
属またはIIIａ族元素である。1. A light-emitting material mainly composed of a perovskite-type compound having an ABO 3 composition prepared in an atmosphere having an oxygen partial pressure lower than that of the atmosphere, and a part of A or B;
Alternatively, a light emitting material characterized in that a part of both are replaced with other elements A 'and B' by a predetermined addition amount. However, A and A 'include group Ia, group IIa or rare earths.
B and B 'are transition metals from VIb to IIb or Group IIIa elements.
Ａが IIIｂ族元素であり、前記Ｂが IIIａ族元素である
ことを特徴とする発光材料。2. The luminescent material according to claim 1, wherein said A is a group IIIb element and said B is a group IIIa element.
Ａ′がIIａ族であることを特徴とする発光材料。3. The luminescent material according to claim 2, wherein said A ′ is a group IIa.
Ｂがアルミニウムであることを特徴とする発光材料。4. The luminescent material according to claim 3, wherein said B is aluminum.
Ａがイットリウム、またはランタン及びそれらの混合物
であることを特徴とする発光材料。5. The light emitting material according to claim 3, wherein said A is yttrium, lanthanum, and a mixture thereof.
材料であって、前記所定の添加量は１０％以下であるこ
とを特徴とする発光材料。6. The luminescent material according to claim 1, wherein the predetermined amount is 10% or less.
発光材料を用いた光源装置。7. A light source device using the light emitting material according to claim 1, 2, 3, 4, 5, or 6.
置であって、駆動源として放電装置、または電流注入装
置、または紫外光励起源を具備する光源装置。8. A light source device using the light emitting material according to claim 7, comprising a discharge device, a current injection device, or an ultraviolet light excitation source as a driving source.
置であって、材料の有する光学利得による増幅効果を利
用した光源装置。9. A light source device using the light emitting material according to claim 1, wherein the light source device utilizes an amplification effect by an optical gain of the material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005042669A1 (en) * | 2003-10-30 | 2005-05-12 | Japan Science And Technology Agency | Electroluminescent material and electroluminescent element using the same |
| JP2006278102A (en) * | 2005-03-29 | 2006-10-12 | Japan Science & Technology Agency | Electroluminescent element |
| JP2008147084A (en) * | 2006-12-12 | 2008-06-26 | Japan Science & Technology Agency | Oxide electroluminescent element |
| JP2016050249A (en) * | 2014-08-29 | 2016-04-11 | 株式会社トクヤマ | Deep ultraviolet emission material |
-
2000
- 2000-10-31 JP JP2000331796A patent/JP3768398B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005042669A1 (en) * | 2003-10-30 | 2005-05-12 | Japan Science And Technology Agency | Electroluminescent material and electroluminescent element using the same |
| JPWO2005042669A1 (en) * | 2003-10-30 | 2007-11-29 | 独立行政法人科学技術振興機構 | Electroluminescent material and electroluminescent device using the same |
| EP1702971A4 (en) * | 2003-10-30 | 2008-09-10 | Japan Science & Tech Agency | Electroluminescent material and electroluminescent element using the same |
| US7674399B2 (en) * | 2003-10-30 | 2010-03-09 | Japan Science And Technology Agency | Electroluminescent material and electroluminescent element using the same |
| JP4751973B2 (en) * | 2003-10-30 | 2011-08-17 | 独立行政法人科学技術振興機構 | Electroluminescent material and electroluminescent device using the same |
| JP2006278102A (en) * | 2005-03-29 | 2006-10-12 | Japan Science & Technology Agency | Electroluminescent element |
| JP2008147084A (en) * | 2006-12-12 | 2008-06-26 | Japan Science & Technology Agency | Oxide electroluminescent element |
| JP2016050249A (en) * | 2014-08-29 | 2016-04-11 | 株式会社トクヤマ | Deep ultraviolet emission material |
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