JPH06321574A - Rare earth element-containing calcogenide glass and optical fiber - Google Patents
Rare earth element-containing calcogenide glass and optical fiberInfo
- Publication number
- JPH06321574A JPH06321574A JP5139522A JP13952293A JPH06321574A JP H06321574 A JPH06321574 A JP H06321574A JP 5139522 A JP5139522 A JP 5139522A JP 13952293 A JP13952293 A JP 13952293A JP H06321574 A JPH06321574 A JP H06321574A
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- JP
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- Prior art keywords
- glass
- rare earth
- earth element
- optical fiber
- added
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/041—Non-oxide glass compositions
- C03C13/043—Chalcogenide glass compositions
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、希土類添加カルコ
ゲナイドガラスおよびこのカルコゲナイドガラスを利用
した光ファイバ、さらに詳細には希土類が添加された光
ファイバレーザまたは光ファイバ増幅器用のカルコゲナ
イド光ファイバ材料に関するものである。TECHNICAL FIELD The present invention relates to a rare earth-doped chalcogenide glass and an optical fiber using the chalcogenide glass, and more particularly to a chalcogenide optical fiber material for rare-earth-doped optical fiber laser or optical fiber amplifier. is there.
【０００２】[0002]
【従来の技術】近来、光ファイバのコアに希土類イオン
を添加した光ファイバレーザや光ファイバ増幅器の研究
開発が盛んに行われている。これは希土類イオンの４ｆ
殻内遷移による誘導放出遷移を利用したものであり、希
土類添加石英ファイバやフッ化物ファイバが増幅媒体と
して用いられてきた。４ｆ殻内遷移による誘導放出の量
子効率は、レーザ始準位のエネルギーレベルとそのレベ
ルの直ぐ下に位置するエネルギーレベルとのエネルギー
間隔によって決まる。これは、希土類が添加された母体
の格子振動による多音子放出によるためである。すなわ
ち、そのエネルギー間隔が狭いと多音子放出によるレー
ザ始準位からその直下のレベルへの無輻射遷移による緩
和が起こりやすく量子効率が低下してしまう。このよう
な多音子放出緩和による量子効率の低い遷移の量子孔率
を改善するには希土類が添加されている母体として格子
振動エネルギーの低いものを用いればよい。2. Description of the Related Art Recently, research and development of optical fiber lasers and optical fiber amplifiers in which rare earth ions are added to the core of an optical fiber have been actively conducted. This is 4f of rare earth ion
It utilizes the stimulated emission transition due to the transition in the shell, and rare-earth-doped silica fiber and fluoride fiber have been used as amplification media. The quantum efficiency of stimulated emission due to the transition in the 4f shell is determined by the energy interval between the energy level of the laser energy level and the energy level immediately below that level. This is due to the emission of multitones due to the lattice vibration of the base material to which the rare earth element is added. That is, if the energy interval is narrow, relaxation due to non-radiative transition from the laser initial level to the level immediately below due to multi-phonon emission is likely to occur, resulting in a decrease in quantum efficiency. In order to improve the quantum porosity of the transition having low quantum efficiency due to the relaxation of the emission of multi-phonons, it is sufficient to use a rare earth element having a low lattice vibration energy.
【０００３】[0003]
【発明が解決する問題点】格子振動エネルギーの低いフ
ァイバ素材としてカルコゲナイドガラスが知られてい
る。カルコゲナイドガラスの格子振動エネルギーは３０
０〜４００ｃｍ-1であり、石英ガラスの格子振動エネル
ギー（１１００ｃｍ-1）と比較すると３分の１から４分
の１に近い値を持ち、また、フッ化物ガラス（５００ｃ
ｍ-1）と比較しても２０％から７０％程度小さい値であ
るため、多音子放出緩和による量子効率の低い遷移の量
子孔率を上げるには適したファイバ素材といえる。DISCLOSURE OF THE INVENTION Chalcogenide glass is known as a fiber material having low lattice vibration energy. The lattice vibration energy of chalcogenide glass is 30.
It is 0 to 400 cm −1, which is close to one third to one quarter of the lattice vibration energy of quartz glass (1100 cm −1 ), and the fluoride glass (500 c
Since it is a value that is about 20% to 70% smaller than that of m −1 ), it can be said that the fiber material is suitable for increasing the quantum porosity of transitions having low quantum efficiency due to relaxation of multiphonon emission.
【０００４】しかし、これまでファイバ化できる素材と
して知られているＡｓＳ系ガラスやＧｅＳ系ガラスへの
希土類の溶解度は低く、希土類を添加したカルコゲナイ
ドガラスファイバは得られていないというのが現状であ
る。However, the solubility of rare earths in AsS-based glass and GeS-based glass, which have been known as fiber-forming materials, is low, and the chalcogenide glass fiber doped with rare earths has not yet been obtained.
【０００５】本発明の目的は、従来のカルコゲナイドガ
ラスの組成を改良し、希土類元素の添加が可能なガラス
を実現するとともに、希土類添加カルコゲナイド光ファ
イバを提供することにある。An object of the present invention is to improve the composition of conventional chalcogenide glass, realize a glass to which a rare earth element can be added, and provide a rare earth element-containing chalcogenide optical fiber.
【０００６】[0006]
【問題点を解決するための手段】上述の問題点を解決す
るため、本発明による希土類添加カルコゲナイドガラス
は、Ｓ、Ｓｅ、Ｔｅ元素を陰イオンとするカルコゲナイ
ドガラスにおいて、Ａｌ、Ｇａ、Ｔｌ、Ｉｎ、Ｓｂ、Ｂ
ｉのうち少なくとも一種類以上の元素を含み、かつ少な
くとも一種類以上の希土類元素を含んだことを特徴とす
る。In order to solve the above-mentioned problems, the rare earth-added chalcogenide glass according to the present invention is a chalcogenide glass containing S, Se, and Te elements as anions, and contains Al, Ga, Tl, and In. , Sb, B
Among i, at least one kind of element is contained, and at least one kind of rare earth element is contained.
【０００７】また、本発明は上述のような希土類添加カ
ルコゲナイドガラスを使用した光ファイバに関するもの
であり、Ｓ、Ｓｅ、Ｔｅ元素のいずれか一種類以上を陰
イオンとするカルコゲナイドガラスであって、Ａｌ、Ｇ
ａ、Ｔｌ、Ｉｎ、Ｓｂ、Ｂｉのうち少なくとも一種類以
上の元素を含み、かつ少なくとも一種類以上の希土類元
素が添加されたカルコゲナイドガラスをコア素材とする
ことを特徴とすることを特徴とする。The present invention also relates to an optical fiber using the above-mentioned rare earth-doped chalcogenide glass, which is a chalcogenide glass containing at least one of S, Se and Te elements as anions, , G
It is characterized in that the core material is a chalcogenide glass containing at least one kind of element selected from a, Tl, In, Sb, and Bi, and containing at least one kind of rare earth element.
【０００８】すなわち、本発明はＡｓ−Ｓ系、Ｇｅ−Ｓ
系、Ｇｅ−Ｐ−Ｓ系、Ａｓ−Ｇｅ−Ｓ系、Ａｓ−Ｓ−Ｓ
ｅ系、Ａｓ−Ｇｅ−Ｓ−Ｓｅ系、Ｇｅ−Ｓ−Ｓｅ系、Ａ
ｓ−Ｓ−Ｂｒ系、Ａｓ−Ｓ−Ｃｌ系、Ａｓ−Ｓ−Ｉ系、
Ａｓ−Ｓ−Ｔｅ系、Ａｓ−Ｇｅ−Ｓ−Ｔｅ系等のカルコ
ゲナイドガラスまたはこれら２つ以上のガラス系の混合
ガラスににＩｎ、Ｇａ、Ｓｂ、Ａｌ、Ｔｌ、Ｂｉ等の周
期律表上のIIIb族、Vb族の元素を添加することを最も主
要な特徴とする。That is, the present invention is an As-S system, a Ge-S system.
System, Ge-P-S system, As-Ge-S system, As-S-S
e system, As-Ge-S-Se system, Ge-S-Se system, A
s-S-Br system, As-S-Cl system, As-S-I system,
On a periodic table of In, Ga, Sb, Al, Tl, Bi, etc. in a chalcogenide glass such as As-S-Te system, As-Ge-S-Te system or a mixed glass of two or more of these glass systems. The main feature is to add elements of IIIb group and Vb group.
【０００９】従来のＡｓ−Ｓ系、Ｇｅ−Ｓ系、Ｇｅ−Ｐ
−Ｓ系、Ａｓ−Ｇｅ−Ｓ系、Ａｓ−Ｓ−Ｓｅ系、Ａｓ−
Ｇｅ−Ｓ−Ｓｅ系、Ｇｅ−Ｓ−Ｓｅ系等のカルコゲナイ
ドガラスへの希土類元素の溶解度は低く、希土類元素を
これらガラスに添加するとき土類の析出や析出相が核と
なった結晶化が起こり、透明ガラスが得にくいという欠
点があった。しかし、IIIb族、またはVb族の元素をガラ
ス成分に加えることによりカルコゲナイドガラス中への
希土類元素の溶解を増加させることができ、透過特性の
良好なファイバ用ガラス素材が得られた。これは、IIIb
族、Vb族の硫化物にＬｎ3+（Ｌｎ：希土類）が添加され
るとガラス中でIIIb族、Vb族元素と共有結合を持たない
Ｓ2-イオンが生じ、ガラス形成に適したＡＳ4（Ａ：III
b族、またはVb族元素）構造と希土類（Ｌｎ3+）の位置
エネルギーが低くなるイオンサイトが同時に形成され
る。したがって、IIIb族、またはVb族の硫化物を上記の
カルコゲナイドガラスに添加するとガラスが安定化する
とともに、希土類の溶解度が上がることになる。また、
本発明により、従来知られていないファイバ化可能な熱
安定性に優れた希土類添加カルコゲナイドガラスを量産
化に適した溶融法により作製することが可能になった。Conventional As-S system, Ge-S system, Ge-P
-S system, As-Ge-S system, As-S-Se system, As-
The solubility of rare earth elements in chalcogenide glasses such as Ge-S-Se series and Ge-S-Se series is low, and when the rare earth elements are added to these glasses, precipitation of earth or crystallization with a precipitation phase as a nucleus occurs. However, there is a drawback that it is difficult to obtain transparent glass. However, III b group, or V b group elements can increase the solubility of the rare earth element into the chalcogenide glass in by adding a glass component, the glass material for good fiber transmission characteristics were obtained. This is III b
Family, V b Group Ln 3+ sulfide: If (Ln rare earth) is added III b group in a glass, S 2-ions occurs without a covalent bond with V b group element, suitable for glass formation AS 4 (A: III
An ion site where the potential energy of the b- group or V b- group element) structure and the rare earth (Ln 3+ ) becomes low is simultaneously formed. Accordingly, III b group, or together with the glass when the V b group of sulfide is added to the above chalcogenide glass is stabilized, so that the solubility of the rare earth is increased. Also,
According to the present invention, it has become possible to manufacture a rare earth-doped chalcogenide glass excellent in thermal stability, which has not been heretofore known, by a melting method suitable for mass production.
【００１０】希土類元素としては、Ｐｒ、Ｃｅ、Ｎｄ、
Ｓｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙ
ｂのうちの一種以上を挙げることができる。As rare earth elements, Pr, Ce, Nd,
Sm, Eu, Tb, Gd, Dy, Er, Ho, Tm, Y
One or more of b can be mentioned.
【００１１】以下、実施例により説明するが、本発明は
実施例により限定されるものではない。Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.
【００１２】[0012]
【実施例１】Ａｓ2Ｓ3（１００−ｘ）−Ｇａ2Ｓ3（ｘ）
（ｘはモル比）系において０＜ｘ≦３０の範囲でＧａ2
Ｓ3をＡｓ2Ｓ3に添加したガラスにＰｒ2Ｓ3を加え、石
英アンプル中で１０００℃で４時間溶融したのち、空気
中で石英アンプルを放冷してガラスを作製した。Ｐｒの
添加量（ｃ）が、０＜ｃ≦１重量％の時に均一度の高い
ガラスが得られた。Example 1 As 2 S 3 (100-x) -Ga 2 S 3 (x)
(X is a molar ratio) In the range of 0 <x ≦ 30, Ga 2
S 3 of the Pr 2 S 3 in addition to glass added to the As 2 S 3, then melted for 4 hours at 1000 ° C. in a quartz ampoule, to prepare a glass was allowed to cool quartz ampoule in air. When the added amount (c) of Pr was 0 <c ≦ 1% by weight, a glass having high uniformity was obtained.
【００１３】Ｐｒの添加原料としてＰｒＣｌ3、ＰｒＢ
ｒ3、ＰｒＩ3を用いてもガラス化することができた。ま
た、希土類元素としては、Ｐｒ以外にＣｅ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ
を０＜ｃ≦１重量％（ｃ：希土類元素添加量。以下同
じ）添加した場合でも透明ガラスを得ることができた。PrCl 3 and PrB are used as raw materials for adding Pr.
Vitrification could also be achieved using r 3 and PrI 3 . Further, as the rare earth element, besides Pr, Ce, Nd, S
m, Eu, Tb, Gd, Dy, Er, Ho, Tm, Yb
Even if 0 <c ≤ 1% by weight (c: amount of rare earth element added; the same applies hereinafter), transparent glass could be obtained.
【００１４】[0014]
【実施例２】Ａｓ2Ｓ3（１００−ｘ）−Ｉｎ2Ｓ3（ｘ）
（ｘはモル比）系において０＜ｘ≦３０の範囲でＩｎ2
Ｓ3をＡｓ2Ｓ3に添加したガラスにＰｒ2Ｓ3を加え、石
英アンプル中で１０００℃で４時間溶融したのち、空気
中で石英アンプルを放冷してガラスを作製した。Ｐｒの
添加量（ｃ）が、０＜ｃ≦１重量％の時に均一度の高い
ガラスが得られた。Example 2 As 2 S 3 (100-x) -In 2 S 3 (x)
(X is a molar ratio) In 2 in the range of 0 <x ≦ 30
S 3 of the Pr 2 S 3 in addition to glass added to the As 2 S 3, then melted for 4 hours at 1000 ° C. in a quartz ampoule, to prepare a glass was allowed to cool quartz ampoule in air. When the added amount (c) of Pr was 0 <c ≦ 1% by weight, a glass having high uniformity was obtained.
【００１５】Ｐｒの添加原料としてＰｒＣｌ3、ＰｒＢ
ｒ3、ＰｒＩ3を用いてもガラス化することができた。ま
た、希土類元素としては、Ｐｒ以外にＣｅ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ
を０＜ｃ≦１重量％添加した場合でも透明ガラスを得る
ことができた。PrCl 3 and PrB are used as raw materials for adding Pr.
Vitrification could also be achieved using r 3 and PrI 3 . Further, as the rare earth element, besides Pr, Ce, Nd, S
m, Eu, Tb, Gd, Dy, Er, Ho, Tm, Yb
Even if 0 <c ≤ 1% by weight was added, transparent glass could be obtained.
【００１６】[0016]
【実施例３】Ａｓ2Ｓ3（１００−ｘ）−Ｓｂ2Ｓ3（ｘ）
（ｘはモル比）系において０＜ｘ≦５０の範囲でＳｂ2
Ｓ3をＡｓ2Ｓ3に添加したガラスにＰｒ2Ｓ3を加え、石
英アンプル中で１０００℃で４時間溶融したのち、空気
中で石英アンプルを放冷してガラスを作製した。Ｐｒの
添加量（ｃ）が、０＜ｃ≦１重量％の時に均一度の高い
ガラスが得られた。Example 3 As 2 S 3 (100-x) -Sb 2 S 3 (x)
(X is a molar ratio) Sb 2 in the range of 0 <x ≦ 50
S 3 of the Pr 2 S 3 in addition to glass added to the As 2 S 3, then melted for 4 hours at 1000 ° C. in a quartz ampoule, to prepare a glass was allowed to cool quartz ampoule in air. When the added amount (c) of Pr was 0 <c ≦ 1% by weight, a glass having high uniformity was obtained.
【００１７】Ｐｒの添加原料としてＰｒＣｌ3、ＰｒＢ
ｒ3、ＰｒＩ3を用いてもガラス化することができた。ま
た、希土類元素としては、Ｐｒ以外にＣｅ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ
を０＜ｃ≦１重量％添加した場合でも透明ガラスを得る
ことができた。PrCl 3 and PrB are used as raw materials for adding Pr.
Vitrification could also be achieved using r 3 and PrI 3 . Further, as the rare earth element, besides Pr, Ce, Nd, S
m, Eu, Tb, Gd, Dy, Er, Ho, Tm, Yb
Even if 0 <c ≤ 1% by weight was added, transparent glass could be obtained.
【００１８】以上の実施例では、ＡｓＳ系ガラスの組成
をＡｓ2Ｓ3に限定したが、Ｇａ、Ｉｎ、Ｓｂが添加され
る組成はＡｓ2Ｓ3に限定されるものではない。また、希
土類元素の添加濃度も１重量％以下に限定されるわけで
はなく、ガラスを溶融後、急冷すれば１重量％以上の希
土類元素の添加も可能となる。Ｇａ、Ｉｎ、Ｓｂはいず
れか２つ以上を同時にＡｓＳ系ガラスに添加してもガラ
ス化可能である。In the above examples, the composition of the AsS glass was limited to As 2 S 3, but the composition to which Ga, In and Sb are added is not limited to As 2 S 3 . Further, the concentration of the rare earth element added is not limited to 1% by weight or less. If the glass is melted and then rapidly cooled, the addition of 1% by weight or more of the rare earth element becomes possible. Any two or more of Ga, In, and Sb can be vitrified by simultaneously adding them to the AsS glass.
【００１９】[0019]
【実施例４】ＧｅＳ2Ｓｅ2（１００−ｘ）−Ｇａ2Ｓ
3（ｘ）（ｘはモル比）系において０＜ｘ≦３０の範囲
でＧａ2Ｓ3をＧｅＳ2Ｓｅ2に添加したガラスにＰｒ2Ｓ3
を加え、石英アンプル中で１０００℃で４時間溶融した
のち、空気中で石英アンプルを放冷してガラスを作製し
た。Ｐｒの添加量（ｃ）が、０＜ｃ≦１重量％の時に均
一度の高いガラスが得られた。Example 4 GeS 2 Se 2 (100-x) -Ga 2 S
In a 3 (x) (x is a molar ratio) system, Pr 2 S 3 was added to a glass in which Ga 2 S 3 was added to GeS 2 Se 2 in the range of 0 <x ≦ 30.
Was added and melted in a quartz ampoule at 1000 ° C. for 4 hours, and then the quartz ampoule was allowed to cool in air to produce glass. When the added amount (c) of Pr was 0 <c ≦ 1% by weight, a glass having high uniformity was obtained.
【００２０】Ｐｒの添加原料としてＰｒＣｌ3、ＰｒＢ
ｒ3、ＰｒＩ3を用いてもガラス化することができた。ま
た、希土類元素としては、Ｐｒ以外にＣｅ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ
を０＜ｃ≦１重量％添加した場合でも透明ガラスを得る
ことができた。PrCl 3 and PrB are used as raw materials for adding Pr.
Vitrification could also be achieved using r 3 and PrI 3 . Further, as the rare earth element, besides Pr, Ce, Nd, S
m, Eu, Tb, Gd, Dy, Er, Ho, Tm, Yb
Even if 0 <c ≤ 1% by weight was added, transparent glass could be obtained.
【００２１】[0021]
【実施例５】ＧｅＳ2Ｓｅ2（１００−ｘ）−Ｉｎ2Ｓ
3（ｘ）（ｘはモル比）系において０＜ｘ≦３０の範囲
でＩｎ2Ｓ3をＧｅＳ2Ｓｅ2に添加したガラスにＰｒ2Ｓ3
を加え、石英アンプル中で１０００℃で４時間溶融した
のち、空気中で石英アンプルを放冷してガラスを作製し
た。Ｐｒの添加量（ｃ）が、０＜ｃ≦１重量％の時に均
一度の高いガラスが得られた。Example 5 GeS 2 Se 2 (100-x) -In 2 S
In a 3 (x) (x is a molar ratio) system, Pr 2 S 3 was added to a glass obtained by adding In 2 S 3 to GeS 2 Se 2 in the range of 0 <x ≦ 30.
Was added and melted in a quartz ampoule at 1000 ° C. for 4 hours, and then the quartz ampoule was allowed to cool in air to produce glass. When the added amount (c) of Pr was 0 <c ≦ 1% by weight, a glass having high uniformity was obtained.
【００２２】Ｐｒの添加原料としてＰｒＣｌ3、ＰｒＢ
ｒ3、ＰｒＩ3を用いてもガラス化することができた。ま
た、希土類元素としては、Ｐｒ以外にＣｅ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ
を０＜ｃ≦１重量％添加した場合でも透明ガラスを得る
ことができた。PrCl 3 and PrB are used as raw materials for adding Pr.
Vitrification could also be achieved using r 3 and PrI 3 . Further, as the rare earth element, besides Pr, Ce, Nd, S
m, Eu, Tb, Gd, Dy, Er, Ho, Tm, Yb
Even if 0 <c ≤ 1% by weight was added, transparent glass could be obtained.
【００２３】[0023]
【実施例６】ＧｅＳ2Ｓｅ2（１００−ｘ）−Ｓｂ2Ｓ
3（ｘ）（ｘはモル比）系において０＜ｘ≦５０の範囲
でＳｂ2Ｓ3をＧｅＳ2Ｓ3に添加したガラスにＰｒ2Ｓ3を
加え、石英アンプル中で１０００℃で４時間溶融したの
ち、空気中で石英アンプルを放冷してガラスを作製し
た。Ｐｒの添加量（ｃ）が、０＜ｃ≦１重量％の時に均
一度の高いガラスが得られた。Example 6 GeS 2 Se 2 (100-x) -Sb 2 S
3 (x) (x is a molar ratio) based at 0 <x ≦ 50 the Sb 2 S 3 in the range of the glass added to GeS 2 S 3 and Pr 2 S 3 was added, 4 hours at 1000 ° C. in a quartz ampoule After melting, the quartz ampoule was allowed to cool in air to produce glass. When the added amount (c) of Pr was 0 <c ≦ 1% by weight, a glass having high uniformity was obtained.
【００２４】Ｐｒの添加原料としてＰｒＣｌ3、ＰｒＢ
ｒ3、ＰｒＩ3を用いてもガラス化することができた。ま
た、希土類元素としては、Ｐｒ以外にＣｅ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ
を０＜ｃ≦１重量％添加した場合でも透明ガラスを得る
ことができた。PrCl 3 and PrB are used as raw materials for adding Pr.
Vitrification could also be achieved using r 3 and PrI 3 . Further, as the rare earth element, besides Pr, Ce, Nd, S
m, Eu, Tb, Gd, Dy, Er, Ho, Tm, Yb
Even if 0 <c ≤ 1% by weight was added, transparent glass could be obtained.
【００２５】以上の実施例（４〜６）では、ＧｅＳＳｅ
系ガラスの組成をＧｅＳ2Ｓｅ2に限定したが、Ｇａ、Ｉ
ｎ、Ｓｂが添加される組成はＧｅＳ2Ｓｅ2に限定される
ものではない。また、希土類元素の添加濃度も１重量％
以下に限定されるわけではなく、ガラスを溶融後、急冷
すれば１重量％以上の希土類元素の添加も可能となる。
Ｇａ、Ｉｎ、Ｓｂはいずれか２つ以上を同時にＧｅＳＳ
ｅ系ガラスに添加してもガラス化可能である。In the above embodiments (4 to 6), GeSSe is used.
Although the composition of the system glass is limited to GeS 2 Se 2 , Ga, I
The composition to which n and Sb are added is not limited to GeS 2 Se 2 . Also, the concentration of rare earth elements added is 1% by weight.
It is not limited to the following, and if the glass is melted and then rapidly cooled, it is possible to add 1% by weight or more of a rare earth element.
Any two or more of Ga, In, and Sb are simultaneously GeSS
Even if added to e-type glass, it can be vitrified.
【００２６】[0026]
【実施例７】Ｇｅ−Ｓ系、Ｇｅ−Ｐ−Ｓ系、Ａｓ−Ｇｅ
−Ｓ系、Ａｓ−Ｓ−Ｓｅ系、Ａｓ−Ｇｅ−Ｓ−Ｓｅ系、
Ａｓ−Ｓ−Ｂｒ系、Ａｓ−Ｓ−Ｃｌ系、Ａｓ−Ｓ−Ｉ
系、Ａｓ−Ｓ−Ｔｅ系、Ａｓ−Ｇｅ−Ｓ−Ｔｅ系ガラス
にＧａ2Ｓ3、Ｉｎ2Ｓ3またはＳｂ2Ｓ3のいずれか１種類
以上を添加したガラスにＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅ
ｕ、Ｔｂ、Ｇｄ、Ｄｙ、Ｅｒ、Ｈｏ、Ｔｍ、Ｙｂ等の希
土類の硫化物、塩化物、臭化物またはヨウ化物を加え、
石英アンプル中で１０００℃４時間溶融した後、空気中
で放冷して均一な透明ガラスを得ることができた。Example 7 Ge-S system, Ge-P-S system, As-Ge
-S system, As-S-Se system, As-Ge-S-Se system,
As-S-Br system, As-S-Cl system, As-S-I
System, As-S-Te system, As-Ge-S-Te-based glass Ga 2 S 3, In 2 S 3 or Sb 2 S Ce on glass doped with any one or more of the 3, Pr, Nd, Sm, E
u, Tb, Gd, Dy, Er, Ho, Tm, Yb and other rare earth sulfides, chlorides, bromides or iodides are added,
After melting in a quartz ampoule at 1000 ° C. for 4 hours, it was allowed to cool in air to obtain a uniform transparent glass.
【００２７】また、Ｇａ、Ｉｎ、Ｓｂの代わりにＡｌ、
Ｔｌ、Ｂｉ等を添加しても希土類が添加されたカルコゲ
ナイドガラスを得ることができた。Ａｌ、Ｔｌ、Ｂｉの
希土類元素の溶解度を増加させる効果は実施例１〜６の
成分のガラスに対しても確認できた。Al, instead of Ga, In and Sb,
Even with the addition of Tl, Bi, etc., a chalcogenide glass containing a rare earth element could be obtained. The effect of increasing the solubility of rare earth elements such as Al, Tl, and Bi was confirmed for the glasses of the components of Examples 1 to 6.
【００２８】[0028]
【実施例８】実施例１〜７で述べたカルコゲナイドガラ
スにＰｒを５００ｐｐｍ添加したガラスをコアガラスと
し、クラッドガラスとしてＺｒＦ4系フッ化物ガラス（"
Fluoride glass fiber optics" I. Aggarwal 編集 Acad
emic Press 1991参照）、リン酸ガラスまたは鉛ガラス
（”ガラスハンドブック”作花他編集、朝倉書店、昭和
５０年）、またはカルコゲナイドガラスをクラッドガラ
スとしてロッドインチューブ法によりコア径２μｍのフ
ァイバを作製した。このファイバ２０ｍを増幅用ファイ
バとして１．３μｍ帯の光増幅を行ったところ、１．０
２μｍの励起光２０ｍｗで１５ｄＢ以上の信号利益を得
ることができた。Example 8 The glass obtained by adding 500 ppm of Pr to the chalcogenide glass described in Examples 1 to 7 was used as the core glass, and the ZrF 4 system fluoride glass (“
Fluoride glass fiber optics "I. Aggarwal Editor Acad
emic Press 1991), phosphate glass or lead glass (edited by Sakuhana et al., "Glass Handbook", Asakura Shoten, 1975), or chalcogenide glass was used as a cladding glass to fabricate a fiber with a core diameter of 2 μm by the rod-in-tube method. . Optical amplification of 1.3 μm band was performed using this fiber 20 m as an amplification fiber.
A signal benefit of 15 dB or more could be obtained with 20 mw of 2 μm excitation light.
【００２９】Ｐｒの代わりにＣｅ（５μｍのレーザ発
振）、Ｎｄ（１．０４μｍのレーザ発振）、Ｓｍ（０．
５９μｍのレーザ発振）、Ｅｕ（０．６１μｍのレーザ
発振）、Ｇｄ（０．３１μｍのレーザ発振）、Ｔｂ
（０．５４μｍのレーザ発振）、Ｄｙ（３μｍのレーザ
発振）、Ｈｏ（２μｍのレーザ発振）、Ｅｒ（１．５μ
ｍのレーザ発振）、Ｔｍ（１．９μｍのレーザ発振）、
Ｙｂ（１μｍのレーザ発振）を添加したカルコゲナイド
ガラスをコアとしてそれぞれの波長で発振するファイバ
レーザを構成することができた。Instead of Pr, Ce (laser oscillation of 5 μm), Nd (laser oscillation of 1.04 μm), Sm (0.
59 μm laser oscillation), Eu (0.61 μm laser oscillation), Gd (0.31 μm laser oscillation), Tb
(Laser oscillation of 0.54 μm), Dy (laser oscillation of 3 μm), Ho (laser oscillation of 2 μm), Er (1.5 μm)
m laser oscillation), Tm (1.9 μm laser oscillation),
It was possible to construct a fiber laser that oscillates at each wavelength with the chalcogenide glass containing Yb (1 μm laser oscillation) added as the core.
【００３０】[0030]
【発明の効果】以上説明したように、本発明では、格子
振動エネルギーの小さなカルコゲナイドガラスを母体と
した希土類添加ガラスを提供することができ、このガラ
スを希土類添加光ファイバのコア素材として用いれば、
希土類元素の４ｆ殻内遷移の量子効果を飛躍的に高めた
高効率なファイバレーザまたはファイバ増幅器を構成す
ることができる。特に希土類元素のうち、Ｐｒを添加し
たカルコゲナイドガラスをコア素材として用いれば、
１．３μｍ用の光ファイバ増幅器用のファイバとして現
在使用されているＰｒ添加ファイバよりも量子効率が１
０倍以上高いＰｒ添加ファイバを得ることができ、高効
率な１．３μｍ帯光ファイバ増幅器を構成できるという
利点がある。As described above, according to the present invention, it is possible to provide a rare earth-doped glass having a chalcogenide glass having a small lattice vibration energy as a matrix, and using this glass as a core material of a rare earth-doped optical fiber,
It is possible to construct a highly efficient fiber laser or fiber amplifier in which the quantum effect of the transition in the 4f shell of the rare earth element is dramatically enhanced. Of the rare earth elements, if chalcogenide glass containing Pr is used as the core material,
Quantum efficiency is 1 compared to Pr-doped fiber currently used as a fiber for 1.3 μm optical fiber amplifier
There is an advantage that a Pr-doped fiber which is 0 times or more higher can be obtained and a highly efficient 1.3 μm band optical fiber amplifier can be constructed.
【００３１】また、光ファイバ増幅器以外にも、Ｔｍや
Ｅｒなどを添加したカルコゲナイドガラスを用いれば高
効率なアップコンバージョンファイバレーザ等を構成で
きるという利点もある。In addition to the optical fiber amplifier, the use of chalcogenide glass doped with Tm, Er or the like has the advantage that a highly efficient up-conversion fiber laser can be constructed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 須藤 昭一 東京都千代田区内幸町１丁目１番６号 日 本電信電話株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoichi Sudo 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corporation
Claims (2)
コゲナイドガラスにおいて、Ａｌ、Ｇａ、Ｔｌ、Ｉｎ、
Ｓｂ、Ｂｉのうち少なくとも一種類以上の元素を含み、
かつ少なくとも一種類以上の希土類元素を含んだことを
特徴とする希土類添加カルコゲナイドガラス。1. A chalcogenide glass containing S, Se, and Te elements as anions, in which Al, Ga, Tl, In,
Containing at least one element of Sb and Bi,
A rare earth-added chalcogenide glass characterized by containing at least one kind of rare earth element.
を陰イオンとするカルコゲナイドガラスであって、Ａ
ｌ、Ｇａ、Ｔｌ、Ｉｎ、Ｓｂ、Ｂｉのうち少なくとも一
種類以上の元素を含み、かつ少なくとも一種類以上の希
土類元素が添加されたカルコゲナイドガラスをコア素材
とすることを特徴とすることを特徴とする光ファイバ。2. A chalcogenide glass having at least one of S, Se and Te elements as anions, which comprises A
l, Ga, Tl, In, Sb, Bi containing at least one or more kinds of elements, and at least one or more kinds of rare earth elements are added to the chalcogenide glass as a core material. Optical fiber to do.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13952293A JP3268540B2 (en) | 1993-05-18 | 1993-05-18 | Rare earth-doped chalcogenide glass, its production method and optical fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13952293A JP3268540B2 (en) | 1993-05-18 | 1993-05-18 | Rare earth-doped chalcogenide glass, its production method and optical fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06321574A true JPH06321574A (en) | 1994-11-22 |
| JP3268540B2 JP3268540B2 (en) | 2002-03-25 |
Family
ID=15247253
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13952293A Expired - Fee Related JP3268540B2 (en) | 1993-05-18 | 1993-05-18 | Rare earth-doped chalcogenide glass, its production method and optical fiber |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5764661A (en) * | 1994-11-24 | 1998-06-09 | Hoya Corporation | Laser glasses and laser glass fibers |
| WO2001099241A3 (en) * | 2000-06-20 | 2002-05-23 | Corning Inc | RARE EARTH ELEMENT-DOPED Bi-Sb-Al-Si GLASS AND ITS USE IN OPTICAL AMPLIFIERS |
| EP1843495A1 (en) * | 1997-02-14 | 2007-10-10 | Nippon Telegraph and Telephone Corporation | Light source |
| JP2018177555A (en) * | 2017-04-05 | 2018-11-15 | 日本電気硝子株式会社 | Chalcogenide glass |
| CN114656143A (en) * | 2022-04-02 | 2022-06-24 | 中国科学院西安光学精密机械研究所 | Rare earth ion doped chalcogenide gain glass and low-temperature synthesis preparation method thereof |
-
1993
- 1993-05-18 JP JP13952293A patent/JP3268540B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5764661A (en) * | 1994-11-24 | 1998-06-09 | Hoya Corporation | Laser glasses and laser glass fibers |
| EP1843495A1 (en) * | 1997-02-14 | 2007-10-10 | Nippon Telegraph and Telephone Corporation | Light source |
| WO2001099241A3 (en) * | 2000-06-20 | 2002-05-23 | Corning Inc | RARE EARTH ELEMENT-DOPED Bi-Sb-Al-Si GLASS AND ITS USE IN OPTICAL AMPLIFIERS |
| JP2018177555A (en) * | 2017-04-05 | 2018-11-15 | 日本電気硝子株式会社 | Chalcogenide glass |
| CN114656143A (en) * | 2022-04-02 | 2022-06-24 | 中国科学院西安光学精密机械研究所 | Rare earth ion doped chalcogenide gain glass and low-temperature synthesis preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3268540B2 (en) | 2002-03-25 |
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