JPH0586367A - Erbium-containing perovskite-type luminescent crystal and its production - Google Patents
Erbium-containing perovskite-type luminescent crystal and its productionInfo
- Publication number
- JPH0586367A JPH0586367A JP3271857A JP27185791A JPH0586367A JP H0586367 A JPH0586367 A JP H0586367A JP 3271857 A JP3271857 A JP 3271857A JP 27185791 A JP27185791 A JP 27185791A JP H0586367 A JPH0586367 A JP H0586367A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- crystal
- ions
- earth metal
- rare earth
- 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.)
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- Luminescent Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、発光材料として有用
で、光学用計測、光情報処理、光医療、光プロセッシン
グ等コヒーレント光を利用する光応用計測、光医療、光
プロセッシングの分野に於いて、発光材料、レーザー材
料、光増幅材料として有用なペロブスカイト型発光結晶
及びその製造方法に関する。BACKGROUND OF THE INVENTION The present invention is useful as a light emitting material, and is in the fields of optical measurement, optical information processing, optical medical treatment, optical applied measurement using coherent light such as optical processing, optical medical treatment, and optical processing. , A perovskite type light emitting crystal useful as a light emitting material, a laser material and a light amplifying material, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、ＡＢｘＬｎ１−ｘＡｌＯ４（Ａ：
アルカリ土類イオン、Ｂ：発光イオン、Ｌｎ：希土類イ
オン）で表される結晶で、発光性を有するものとして
は、発光イオンとしてＮｄ３＋、又はＥｒ３＋を用いた
ＣａＮｄ（又はＥｒ０．０５Ｙ０ ．９５ＡｌＯ４（Ｅ．
Ｆ．Ｋｕｓｔｏｖ ｅｔ ａｌ、Ｐｈｙｓ．ｓｔａｔ．
ｓｏｌ．４１，３７９（１９７７））、Ｎｄ３＋を用い
たＣａＮｄｘＧｄ１−ｘＡｌＯ４（Ｚ．Ｓ．Ａｐｐｅｎ
ｅｔ ａｌ、Ｉｎｏｒｇ．Ｍａｔｅｒ．（ＵＳＳＲ）
２１，７１６（１９８５））が知られている。2. Description of the Related Art Conventionally, AB x Ln 1-x AlO 4 (A:
A crystal represented by an alkaline earth ion, B: a light emitting ion, and Ln: a rare earth ion, which has a light emitting property, is CaNd (or Er 0.05 Y) using Nd 3+ or Er 3+ as a light emitting ion. 0 .95 AlO 4 (E.
F. Kustov et al, Phys. stat.
sol. 41,379 (1977)), CaNd x Gd 1-x AlO 4 with Nd 3+ (Z.S.Appen
et al, Inorg. Mater. (USSR)
21,716 (1985)) is known.
【０００３】しかし、上記結晶の内、ＣａＮｄｘＬｎ
１−ｘＡｌＯ４（Ｌｎ：Ｙ３＋、Ｇｄ３＋）について
は、最も強い発光が１０８０ｎｍ近辺であり、４５０〜
５００ｎｍ領域内での発光は弱く、又、上記Ｅｒを用い
た結晶についても、可視域の４５０〜５７０ｎｍ、更に
近赤外域の８４０〜８７０ｎｍ付近で発光は見られるが
その強度は必ずしも強いものではない。However, among the above crystals, CaNd x Ln
For 1-x AlO 4 (Ln: Y 3+ , Gd 3+ ), the strongest light emission is around 1080 nm, and 450 to
The light emission is weak in the 500 nm region, and even for the crystal using Er, the light emission is observed in the visible region of 450 to 570 nm and further in the near infrared region of 840 to 870 nm, but the intensity is not necessarily strong. ..
【０００４】[0004]
【発明が解決しようとする課題】本発明は、特に、４５
０〜５７０ｎｍ、又は８４０〜８７０ｎｍ領域内での発
光の強い発光材料、又、従来知られていない組成の結晶
で、発光材料として有用な希土類イオンを添加したペロ
ブスカイト型結晶を提供することを目的とするものであ
る。The present invention is particularly applicable to 45
An object is to provide a light emitting material having a strong light emission within a range of 0 to 570 nm or 840 to 870 nm, and a perovskite type crystal having a composition not known in the art and having a rare earth ion added, which is useful as a light emitting material. To do.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記課題
点の解決のため、従来のＮｄを添加したＣａＮｄｘＬｎ
１−ｘＡｌＯ４（Ｌｎ：Ｙ３＋、Ｇｄ３＋）とは、発光
イオンを異にしたもの、ホストペロブスカイト結晶の組
成を選択することに着目し種々の検討を行った結果本発
明を完成した。即ち本発明は、発光イオンとして、Ｅｒ
３イオンを含む、組成式ＡＢｘＬｎ１−ｘＡｌＯ
４（Ａ：Ｃａ２＋又はＳｒ２＋、Ｂ：Ｅｒ３＋、Ｌｎ：
Ｇｄ３＋、Ｌａ３＋から選ばれる一種、ｘ：０．００１
≦ｘ≦０．２）で表されるペロブスカイト型発光結晶に
関するものである。次に本発明を更に詳細に説明する。In order to solve the above problems, the inventors of the present invention have proposed CaNd x Ln containing CaNd x Ln containing conventional Nd.
The present invention has been completed as a result of various investigations focusing on the selection of the composition of the host perovskite crystal different from that of 1-x AlO 4 (Ln: Y 3+ , Gd 3+ ). That is, the present invention uses Er as the luminescent ion.
Composition formula AB x Ln 1-x AlO containing 3 ions
4 (A: Ca 2+ or Sr 2+ , B: Er 3+ , Ln:
One kind selected from Gd 3+ and La 3+ , x: 0.001
≦ x ≦ 0.2) and perovskite type light emitting crystals. Next, the present invention will be described in more detail.
【０００６】本発明で発光イオンとして用いるＥｒ３＋
の量は上記した組成式のｘで示すように０．００１≦ｘ
≦０．２であるが、この量が０．００１より小であると
結晶の発光強度が弱く、０．２より大であると濃度消光
を起こすので好ましくない。Er 3+ used as a luminescent ion in the present invention
Is 0.001 ≦ x as shown by x in the above composition formula.
≦ 0.2, but if this amount is smaller than 0.001, the luminescence intensity of the crystal is weak, and if it is larger than 0.2, concentration quenching occurs, which is not preferable.
【０００７】次に本発明の製造方法について説明する。Next, the manufacturing method of the present invention will be described.
【０００８】本発明の結晶を得るのに用いる原料は、結
晶を構成する夫々の成分の酸化物等を用いる。即ち、組
成式ＡＢｘＬｎ１−ｘＡｌＯ４に於いて、アルカリ土類
イオンＡ（Ａ：Ｃａ２＋又はＳｒ２＋）の炭酸塩又は酸
化物、希土類イオンＢ（Ｂ：Ｅｒ３＋）の酸化物、希土
類イオンンＬｎ（Ｌｎ：Ｇｄ３＋、Ｌａ３＋から選ばれ
る一種）の酸化物、及びＡｌの酸化物を用い、これらを
原子比で、Ａ：Ｂ：Ｌｎ：Ａｌ＝１：ｘ：１−ｘ：１
（０．００１≦ｘ≦０．２）の量比で混合し、この混合
物を不活性ガス、例えば、Ｎ２、Ａｒ、Ｈｅの雰囲気下
で、又は、酸化性ガス、例えば酸素を含んだガス雰囲気
下で溶融する。ここで用いる酸素を含んだガス雰囲気は
好ましくは酸素を０．１ｖｏｌ％以上含んだ雰囲気であ
る。As the raw material used for obtaining the crystal of the present invention, oxides of the respective constituents of the crystal are used. That is, in the composition formula AB x Ln 1-x AlO 4 , a carbonate or oxide of an alkaline earth ion A (A: Ca 2+ or Sr 2+ ), an oxide of a rare earth ion B (B: Er 3+ ), An oxide of a rare earth ion ion Ln (one selected from Ln: Gd 3+ and La 3+ ) and an oxide of Al are used, and these are represented by an atomic ratio of A: B: Ln: Al = 1: x: 1-x: 1
(0.001 ≦ x ≦ 0.2), and the mixture is mixed under an inert gas atmosphere such as N 2 , Ar, or He, or an oxidizing gas such as a gas containing oxygen. Melts under atmosphere. The oxygen-containing gas atmosphere used here is preferably an atmosphere containing 0.1 vol% or more of oxygen.
【０００９】還元性雰囲気でこれを行うと、得られる結
晶に酸素欠陥が生じ、これがカラーセンターとなり発光
材料としての品質の低下をもたらす。更に、発光イオン
の価数が２価となる場合があり、発光を阻害する原因と
なる。特に酸素を０．１ｖｏｌ％以上含んだ雰囲気で
は、結晶のカラーセンターの発生が非常に少なく、高品
質な結晶が得られる。When this is carried out in a reducing atmosphere, oxygen deficiency occurs in the obtained crystal, which becomes a color center and causes a deterioration in the quality of the light emitting material. Further, the valence of the luminescent ion may be divalent, which may cause the luminescence to be inhibited. In particular, in an atmosphere containing 0.1 vol% or more of oxygen, the generation of color centers of crystals is very small, and high quality crystals can be obtained.
【００１０】本発明の製造方法での溶融温度は１６５０
〜１８５０℃で、フローティングゾーン法、チョコラル
スキー法、ブリッジマン法等の方法で溶融固化して得
る。The melting temperature in the manufacturing method of the present invention is 1650.
It is obtained by melting and solidifying at ˜1850 ° C. by a floating zone method, Czochralski method, Bridgman method, or the like.
【００１１】[0011]
【実施例】次に本発明を実施例により更に詳細に説明す
る。EXAMPLES The present invention will now be described in more detail by way of examples.
【００１２】[0012]
【実施例１】ＣａＣＯ３、Ｅｒ２Ｏ３、Ｇｄ２Ｏ３、Ａ
ｌ２Ｏ３を、Ｃａ：Ｅｒ：Ｇｄ：Ａｌ＝１：０．０５：
０．９５：１となるように調製して混合した混合物を、
イリジウムルツボに入れて加熱し、１ｖｏｌ％の酸素を
含むＡｒガス雰囲気下、結晶の回転数を１０ｒｐｍ、引
上げ速度を１ｍｍ／ｈで、チョコラルスキー法により、
単結晶を得た。Example 1 CaCO 3 , Er 2 O 3 , Gd 2 O 3 and A
l 2 O 3 was added to Ca: Er: Gd: Al = 1: 0.05:
The mixture prepared and mixed so that it becomes 0.95: 1,
By placing in an iridium crucible and heating it, in an Ar gas atmosphere containing 1 vol% oxygen, the rotation speed of the crystal was 10 rpm, the pulling rate was 1 mm / h, and by the Czochralski method,
A single crystal was obtained.
【００１３】得られた結晶のＸ線回折の結果から、この
結晶は単相のペロブスカイト型結晶であることが確認さ
れた。又この結晶は、４７０ｎｍ付近、又は５４０〜５
７０ｎｍ、８４０〜８７０ｎｍの領域で強い発光が見ら
れた。Ｘ線回折の結果を図１に、図２に５４０〜５７０
ｎｍ、８４０〜８７０ｎｍの領域の発光スペクトルを示
す。 又、得られた結晶の元素分析の結果ＣａＥｒ
０．０４Ｇｄ０．９６ＡｌＯ４であった。From the result of X-ray diffraction of the obtained crystal, it was confirmed that this crystal was a single-phase perovskite type crystal. Also, this crystal is around 470 nm, or 540-5.
Strong light emission was observed in the regions of 70 nm and 840 to 870 nm. The results of X-ray diffraction are shown in FIG. 1 and 540 to 570 in FIG.
2 shows an emission spectrum in the region of nm, 840 to 870 nm. In addition, as a result of elemental analysis of the obtained crystal, CaEr
It was 0.04 Gd 0.96 AlO 4 .
【００１４】[0014]
【実施例２】ＳｒＣＯ３、Ｅｒ２Ｏ３、Ｇｄ２Ｏ３、Ａ
ｌ２Ｏ３を、Ｓｒ：Ｅｒ：Ｇｄ：Ａｌ＝１：０．０５：
０．９５：１となるように調製して混合した混合物を、
実施例１と同様の方法で単結晶を得た。Example 2 SrCO 3 , Er 2 O 3 , Gd 2 O 3 and A
l 2 O 3 was added to Sr: Er: Gd: Al = 1: 0.05:
A mixture prepared and mixed so as to be 0.95: 1,
A single crystal was obtained in the same manner as in Example 1.
【００１５】得られた結晶のＸ線回折の結果から、この
結晶は単相のペロブスカイト型結晶であることが確認さ
れた。又この結晶の発光スペクトルについても実施例１
で得た結晶と類似していた。From the result of X-ray diffraction of the obtained crystal, it was confirmed that this crystal was a single-phase perovskite type crystal. In addition, the emission spectrum of this crystal is also shown in Example 1.
It was similar to the crystals obtained in.
【００１６】[0016]
【発明の効果】本発明の発光結晶は発光強度が強く、光
学機器類の発光材料として有用である。The luminescent crystal of the present invention has a high luminescence intensity and is useful as a luminescent material for optical devices.
【図１】本発明の実施例で得た発光結晶のＸ線回折図FIG. 1 is an X-ray diffraction diagram of a light emitting crystal obtained in an example of the present invention.
【図２】本発明の実施例で得た発光結晶の発光スペクト
ルを示す図FIG. 2 is a diagram showing an emission spectrum of a light emitting crystal obtained in an example of the present invention.
Claims (2)
む、組成式ＡＢｘＬｎ１ −ｘＡｌＯ４（Ａ：Ｃａ２＋又
はＳｒ２＋、Ｂ：Ｅｒ３＋、Ｌｎ：Ｇｄ３＋、Ｌａ３＋
から選ばれる一種、ｘ：０．００１≦ｘ≦０．２）で表
されるペロブスカイト型発光結晶。1. A composition formula AB x Ln 1- x AlO 4 (A: Ca 2+ or Sr 2+ , B: Er 3+ , Ln: Gd 3+ , La 3+) containing Er 3+ ions as luminescent ions.
A perovskite type luminescent crystal represented by the following formula: x: 0.001 ≦ x ≦ 0.2).
Ｓｒ２＋）の炭酸塩又は酸化物、希土類イオンＢ（Ｂ：
Ｅｒ３＋）の酸化物、希土類イオンンＬｎ（Ｌｎ：Ｇｄ
３＋、Ｌａ３＋から選ばれる一種）の酸化物、及びＡｌ
の酸化物を、Ａ：Ｂ：Ｌｎ：Ａｌ（原子比）＝１：ｘ：
１−ｘ：１（ｘ：０．００１≦ｘ≦０．２）の量比で混
合し、不活性ガス又は酸化性ガス雰囲気下で溶融し固化
することを特徴とするペロブスカイト型発光結晶の製造
方法。2. Alkaline earth ion A (A: Ca 2+ or Sr 2+ ) carbonate or oxide, rare earth ion B (B:
Er 3+ ) oxide, rare earth ion Ln (Ln: Gd)
3+ , an oxide of La 3+ ), and Al
Of the oxide of A: B: Ln: Al (atomic ratio) = 1: x:
1-x: 1 (x: 0.001 ≤ x ≤ 0.2) mixed in a volume ratio, and melted and solidified in an inert gas or oxidizing gas atmosphere to produce a perovskite-type luminescent crystal Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3271857A JPH0586367A (en) | 1991-09-25 | 1991-09-25 | Erbium-containing perovskite-type luminescent crystal and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3271857A JPH0586367A (en) | 1991-09-25 | 1991-09-25 | Erbium-containing perovskite-type luminescent crystal and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0586367A true JPH0586367A (en) | 1993-04-06 |
Family
ID=17505855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3271857A Pending JPH0586367A (en) | 1991-09-25 | 1991-09-25 | Erbium-containing perovskite-type luminescent crystal and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0586367A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7184203B2 (en) * | 2003-02-21 | 2007-02-27 | Burgener Ii Robert H | Rare earth compounds having photo-luminescent properties and applications thereof |
-
1991
- 1991-09-25 JP JP3271857A patent/JPH0586367A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7184203B2 (en) * | 2003-02-21 | 2007-02-27 | Burgener Ii Robert H | Rare earth compounds having photo-luminescent properties and applications thereof |
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