JPH0629150B2 - Fluoride glass containing rare earth - Google Patents
Fluoride glass containing rare earthInfo
- Publication number
- JPH0629150B2 JPH0629150B2 JP2115497A JP11549790A JPH0629150B2 JP H0629150 B2 JPH0629150 B2 JP H0629150B2 JP 2115497 A JP2115497 A JP 2115497A JP 11549790 A JP11549790 A JP 11549790A JP H0629150 B2 JPH0629150 B2 JP H0629150B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- rare earth
- light
- zrf
- fluoride glass
- 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.)
- Expired - Lifetime
Links
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
- C03C3/325—Fluoride glasses
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、希土類含有フッ化物ガラスに関し、特に、赤
外光を吸収して可視光を発することができ、赤外光から
可視光への波長変換材料として広く応用できるガラスに
関するものである。Description: TECHNICAL FIELD The present invention relates to a rare earth-containing fluoride glass, and more particularly, it can absorb infrared light and emit visible light. The present invention relates to glass that can be widely applied as a wavelength conversion material.
（従来の技術） フッ化物を原料として作製したフッ化物ガラスは、酸化
物ガラスより広範囲で、紫外光領域から赤外光領域に亘
る広い波長範囲の光を透過し得る点で優れたガラスであ
り、光学部品や赤外光伝送ファイバー、光通信ファイバ
ーなどの用途への応用が広く研究されている。(Prior Art) Fluoride glass made from a fluoride is a glass that is superior to oxide glass in that it can transmit light in a wide wavelength range from the ultraviolet light region to the infrared light region. , Optical components, infrared light transmission fiber, optical communication fiber, and other applications have been widely studied.
また、フッ化物ガラスは、酸化物ガラスに比べて希土類
元素を多く含有できる性質を有しており、希土類イオン
の蛍光発光を応用した各種発光ガラス、更には、レーザ
ー発振用ガラスなどへの応用も盛んに研究されている。Further, the fluoride glass has a property of containing a large amount of rare earth elements as compared with the oxide glass, and thus it can be applied to various light emitting glasses to which fluorescence emission of rare earth ions is applied, and further to laser oscillation glass and the like. Has been actively studied.
一般に、希土類イオンの蛍光発光は、基底準位の電子を
紫外光などのエネルギーの高い光で励起し、その励起電
子がエネルギーの低い準位に遷移する過程で起こる。し
たがって、一般には励起光（入射光）のエネルギーより
高いエネルギーを有する光は放出されない。In general, the fluorescence emission of rare earth ions occurs in the process in which electrons of the ground level are excited by light having a high energy such as ultraviolet light, and the excited electrons transit to a low energy level. Therefore, generally, light having energy higher than that of the excitation light (incident light) is not emitted.
しかし、フッ化物ガラス中では、上述の励起光よりもエ
ネルギーの高い光（すなわち、励起光よりも波長が短い
光）が蛍光として放出される過程がかなりの確率で発生
する。この一番の原因は、フッ化物ガラスが酸化物系な
どよりも、より長い波長の赤外光を透過し得ることにあ
る。すなわち、赤外光の透過限界波長が長波長側にある
ほど、一度励起された電子がより下のエネルギー準位に
遷移して行くまでの、その励起準位での平均滞留時間が
長くなり、更に、同じ励起光を吸収してより高いエネル
ギー準位まで励起される、２段階励起の過程が起こり易
くなることによる。したがって、この過程を利用する
と、赤外光を入射してより波長の短い可視領域の光を放
出させることができる。However, in the fluoride glass, a process in which light having a higher energy than the above-described excitation light (that is, light having a shorter wavelength than the excitation light) is emitted as fluorescence occurs with a considerable probability. The main reason for this is that fluoride glass can transmit infrared light having a longer wavelength than oxide glasses. That is, as the transmission limit wavelength of infrared light is on the longer wavelength side, the average residence time at the excitation level becomes longer until the electron once excited transitions to a lower energy level, Furthermore, the process of two-step excitation in which the same excitation light is absorbed and excited to a higher energy level is likely to occur. Therefore, by utilizing this process, infrared light can be incident to emit light in the visible region having a shorter wavelength.
従来より、フッ化物ガラス系の中では、ＺｒＦ4、Ｂａ
Ｆ2を主成分とする系（ＺｒＦ4系）や、ＴｈＦ4、Ｚｎ
Ｆ2、ＢａＦ2を主成分とする系（ＴｈＦ4系）、またＡ
ｌＦ3、ＲＦ2（Ｒ：アルカリ土類金属）を主成分とする
系（ＡｌＦ3系）が、安定してガラスを作製できるガラ
ス形成系として知られている。これらの系において、Ｅ
ｒＦ3、ＹｂＦ3を添加して作製したガラスは、Ｅｒ3+、
Ｙｂ3+イオンの吸収帯がある約９００〜１１００nmの近
赤外光を吸収して、Ｅｒ3+イオンが緑色光（５５０nm付
近）及び赤色光（６６５nm付近）を発することが確認さ
れている。Conventionally, among fluoride glass systems, ZrF 4 , Ba
F 2 -based system (ZrF 4 system), ThF 4 , Zn
A system mainly composed of F 2 and BaF 2 (ThF 4 system), and A
A system containing AlF 3 and RF 2 (R: alkaline earth metal) as a main component (AlF 3 system) is known as a glass forming system capable of stably producing glass. In these systems, E
The glass produced by adding rF 3 and YbF 3 is Er 3+ ,
It has been confirmed that the Er 3+ ion emits green light (near 550 nm) and red light (near 665 nm) by absorbing near-infrared light of about 900 to 1100 nm which has an absorption band of Yb 3+ ion.
（発明が解決しようとする課題） 上述した２段階励起によるＥｒ3+イオンの蛍光発光を効
率良く発生させるためには、主として、（イ）赤外光透
過限界波長ができるだけ長波長側にあるガラス、また、
（ロ）Ｅｒ、Ｙｂを多く含有し得るガラスほど有利であ
る。特に、Ｙｂは増感剤としての働きをするため、その
含有量が多いほど発光効率が改善される。(Problems to be Solved by the Invention) In order to efficiently generate the fluorescence emission of Er 3+ ions by the above-mentioned two-step excitation, (a) a glass whose infrared transmission limit wavelength is as long as possible is mainly used. ,Also,
(B) The glass that can contain a large amount of Er and Yb is more advantageous. In particular, since Yb acts as a sensitizer, the higher the content, the more the luminous efficiency is improved.
このような観点では、ＺｒＦ4系は（イ）の点で優れ、
ＡｌＦ3系は（ロ）の点で優れたガラス系である。ま
た、ＴｈＦ4系は、（イ）、（ロ）の点で他の２系より
も優れているが、Ｔｈ自身が放射性であり、実用上好ま
しくない。したがって、ＴｈＦ4系以外に、（イ）、
（ロ）共に優れたガラス系を見い出すことができれば、
より効率良く赤外光を吸収して可視光を発する安全なガ
ラスが得られる。From this point of view, the ZrF 4 system is superior in (a),
The AlF 3 system is a glass system excellent in (b). Further, the ThF 4 system is superior to the other 2 systems in terms of (a) and (b), but Th itself is radioactive, which is not preferable in practical use. Therefore, in addition to the ThF 4 system, (a),
(B) If we can find excellent glass systems,
A safe glass that more efficiently absorbs infrared light and emits visible light can be obtained.
本発明は、上記従来技術の問題点を解決し、希土類元素
を多量に含有させることができ、赤外光透過限界波長が
できるだけ長波長側にし得る希土類含有フッ化物ガラス
を提供することを目的とするものである。The present invention aims to provide a rare earth-containing fluoride glass that solves the above-mentioned problems of the prior art, can contain a large amount of rare earth elements, and can have the infrared light transmission limit wavelength on the long wavelength side as much as possible. To do.
（課題を解決するするための手段） 本発明者は、前記課題を解決し得る希土類含有フッ化物
ガラス系について鋭意研究を重ねた結果、上述のＺｒＦ
4系に類似したＺｒＦ4−ＢａＦ2−ＬａＦ3−ＡｌＦ3−
ＮａＦ系を基礎組成とすると、これに多量の希土類元素
（Ｅｒ、Ｙｂ）を含有させることができることを見い出
し、ここに本発明をなしたものである。(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies on a rare earth-containing fluoride glass system that can solve the above problems, and as a result, the above-mentioned ZrF
ZrF 4 --BaF 2 --LaF 3 --AlF 3 --similar to the 4 system
It has been found that a basic composition of NaF can contain a large amount of rare earth elements (Er, Yb), and the present invention has been made here.
すなわち、本発明は、ＺｒＦ4：４０〜５０％、Ｂａ
Ｆ2：２０〜２５％、ＬａＦ3：２〜５％、ＡｌＦ3：２
〜８％、ＮａＦ：０．１〜６％、ＩｎＦ3：０．４〜
０．８％及びＮａＣｌ：０〜６％からなるガラスであっ
て、更にＥｒＦ3及びＹｂＦ3を合計で１５〜２５％含む
ことを特徴とする希土類含有フッ化物ガラスを要旨とす
るものである。That is, in the present invention, ZrF 4 : 40 to 50%, Ba
F 2: 20~25%, LaF 3 : 2~5%, AlF 3: 2
~8%, NaF: 0.1~6%, InF 3: 0.4~
A glass made of 0.8% and NaCl: 0 to 6%, further containing 15 to 25% of ErF 3 and YbF 3 in total, which is a gist of a rare earth-containing fluoride glass.
（作用） 本発明のガラスは、前述のＺｒＦ4系に類似したＺｒＦ4
−ＢａＦ2−ＬａＦ3−ＡｌＦ3−ＮａＦ系を基礎組成と
するものである。具体的には、ＺｒＦ4：４０〜５０
％、ＢａＦ2：２０〜２５％、ＬａＦ3：２〜５％、Ａｌ
Ｆ3：２〜８％、ＮａＦ：０．１〜６％、ＩｎＦ3：０．
４〜０．８％からなる組成である。このような組成を持
つ成分系とするのは、ＺｒＦ4及びＢａＦ2を主成分とす
るＺｒＦ4系が持つ赤外光透過限界波長を長波長側にで
きる利点と、ＡｌＦ3及びＲＦ2（Ｒ：アルカリ土類金
属）を主成分とするＡｌＦ3系が持つ希土類元素を多く
含有し得る利点を共に有効に利用するためである。(Function) The glass of the present invention has a ZrF 4 similar to the ZrF 4 system described above.
It is an -BaF 2 -LaF 3 -AlF 3 -NaF type the base composition. Specifically, ZrF 4 : 40-50
%, BaF 2 : 20 to 25%, LaF 3 : 2 to 5%, Al
F 3: 2~8%, NaF: 0.1~6%, InF 3: 0.
The composition is 4 to 0.8%. The component system having such a composition has the advantage that the infrared light transmission limit wavelength of the ZrF 4 system containing ZrF 4 and BaF 2 as the main components can be set to the long wavelength side, and AlF 3 and RF 2 (R This is because both the advantages of AlF 3 containing Alkaline Earth Metals as a main component and containing a large amount of rare earth elements can be effectively utilized.
但し、本発明では、この成分系に希土類元素のＥｒ及び
Ｙｂをより多く含有し得るように、一般のガラス組成系
よりＺｒＦ4含有量を減らし、ＬａＦ3、ＡｌＦ3の含有
量を増加させたものである。これにより、従来の組成で
はＥｒ、Ｙｂの含有可能最大量が９％程度であったとこ
ろを、１５〜２５％へと大幅に増量することができる。
より好ましい範囲は、ＺｒＦ4は４０〜４６％、ＬａＦ3
は４〜５％、ＡｌＦ3は４〜８％である。However, in the present invention, the ZrF 4 content is decreased and the LaF 3 and AlF 3 contents are increased as compared with the general glass composition system so that the rare earth elements Er and Yb can be contained in a larger amount in this component system. It is a thing. As a result, it is possible to significantly increase the maximum content of Er and Yb from about 9% in the conventional composition to 15 to 25%.
A more preferable range is 40 to 46% for ZrF 4 and LaF 3
Is 4 to 5% and AlF 3 is 4 to 8%.
各成分とも上限値以上及び下限値以下ではそれぞれ成分
系の利点を効果的に発揮し得えず、またＹｂ希土類元素
のＥｒ及びＹｂを上述の如く多量に含有させることが困
難となる。Above the upper limit and below the lower limit of each component, the advantages of the component system cannot be effectively exhibited, and it becomes difficult to incorporate Er and Yb of Yb rare earth elements in a large amount as described above.
なお、必要に応じて、ＮａＣｌを６％まで安定的に添加
でき、これによりガラスの赤外光透過限界波長をより長
波長側に移動させることが可能である。If necessary, NaCl can be stably added up to 6%, whereby the infrared light transmission limit wavelength of glass can be shifted to a longer wavelength side.
したがって、本発明では、これらの特徴を活かすことに
より、より効率の良い赤外光吸収−可視光発光過程をガ
ラス中で起こすことができる。Therefore, in the present invention, by utilizing these characteristics, a more efficient infrared light absorption-visible light emission process can be caused in glass.
次に本発明の実施例を示す。Next, examples of the present invention will be described.
（実施例） 第１表に示す組成のガラスを、乾燥窒素雰囲気のグロー
ブボックス中で、金ルツボを用いて８００〜９００℃の
温度で溶融して作製した。(Example) A glass having the composition shown in Table 1 was produced by melting in a glove box in a dry nitrogen atmosphere using a gold crucible at a temperature of 800 to 900 ° C.
これらの試作ガラスは約４０mm×３０mm×５mmの大きさ
である。These trial glasses are about 40 mm × 30 mm × 5 mm in size.
また、試作ガラスのうちのNO.３のガラスにおいて、Ｎ
ｄ：ＹＡＧレーザー光（１．０６４μｍ、約３００mw）
を入射した時の可視領域の発光スペクトルを第１図に示
す。これより、効率よく赤外光を吸収して可視光を発す
るガラスであることがわかる。勿論、他の試作ガラスも
同様の発光スペクトルを示すことを確認した。In addition, in the No. 3 glass among the prototype glasses, N
d: YAG laser light (1.064 μm, about 300 mw)
FIG. 1 shows the emission spectrum in the visible region when is incident. From this, it can be seen that the glass efficiently absorbs infrared light and emits visible light. Of course, it was confirmed that other prototype glasses also showed similar emission spectra.
（発明の効果） 以上詳述したように、本発明によれば、特定の組成の成
分系で希土類元素の含有量を多くできるので、赤外光
（９００〜１１００nm）を吸収して可視光（５５０、６
６５nm付近）を発するところから、赤外光から可視光へ
の波長変換材料として広く応用できる。特に、近赤外領
域に発振線を有するＮｄ：ＹＡＧレーザー、各種半導体
レーザーなどの発振光波長変換、光路モニターなどとし
て利用可能である。 (Effects of the Invention) As described in detail above, according to the present invention, since the content of the rare earth element can be increased in the component system of the specific composition, infrared light (900 to 1100 nm) is absorbed and visible light ( 550, 6
Since it emits around 65 nm), it can be widely applied as a wavelength conversion material from infrared light to visible light. In particular, it can be used as an Nd: YAG laser having an oscillation line in the near infrared region, wavelength conversion of oscillation light of various semiconductor lasers, an optical path monitor, and the like.
第１図は実施例で得られたガラスにおいてＮｄ：ＹＡＧ
レーザー光（１．０６４μｍ、約３００mw）を入射した
時の可視領域の発光スペクトルを示す図である。FIG. 1 shows Nd: YAG in the glasses obtained in the examples.
It is a figure which shows the emission spectrum of a visible region at the time of making a laser beam (1.064 micrometer, about 300 mw) incident.
Claims (2)
〜５０％、ＢａＦ2：２０〜２５％、ＬａＦ3：２〜５
％、ＡｌＦ3：２〜８％、ＮａＦ：０．１〜６％及びＩ
ｎＦ3：０．４〜０．８％と、更にＥｒＦ3及びＹｂＦ3
を合計で１５〜２５％含有することを特徴とする希土類
含有フッ化物ガラス。1. ZrF 4 : 40 in% by weight (hereinafter the same)
~50%, BaF 2: 20~25% , LaF 3: 2~5
%, AlF 3: 2~8%, NaF: 0.1~6% and I
nF 3 : 0.4 to 0.8%, further ErF 3 and YbF 3
15 to 25% in total of the rare earth-containing fluoride glass.
含有するものである請求項１に記載の希土類含有フッ化
物ガラス。2. The rare earth-containing fluoride glass according to claim 1, wherein the glass further contains NaCl: 6% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2115497A JPH0629150B2 (en) | 1990-05-01 | 1990-05-01 | Fluoride glass containing rare earth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2115497A JPH0629150B2 (en) | 1990-05-01 | 1990-05-01 | Fluoride glass containing rare earth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0412035A JPH0412035A (en) | 1992-01-16 |
| JPH0629150B2 true JPH0629150B2 (en) | 1994-04-20 |
Family
ID=14663975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2115497A Expired - Lifetime JPH0629150B2 (en) | 1990-05-01 | 1990-05-01 | Fluoride glass containing rare earth |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629150B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319087A (en) * | 2013-06-04 | 2013-09-25 | 中山大学 | Rare earth phosphate scintillating glass and preparation method of same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5368290A (en) * | 1992-01-16 | 1994-11-29 | Fujitsu Limited | Paper transport mechanism |
| CN1042217C (en) * | 1993-08-12 | 1999-02-24 | 武汉大学 | Preparing fluozirconate glass by homogeneous coprecipitation method |
| CN1313404C (en) * | 2005-08-24 | 2007-05-02 | 中国科学院上海光学精密机械研究所 | Preparation method of low refractivity glass doped with erbium, fluorine and phosphor |
| CN102167975A (en) * | 2011-02-23 | 2011-08-31 | 蚌埠市德力防伪材料有限责任公司 | Infrared anti-counterfeiting luminous material and preparation method and application thereof |
| CN113816604B (en) * | 2021-10-21 | 2022-11-15 | 中国计量大学 | Fluoride laser glass with high erbium doping and low hydroxyl content of 3.5 microns and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6027621A (en) * | 1983-07-27 | 1985-02-12 | Agency Of Ind Science & Technol | Infrared transmission glass |
| JPS62278144A (en) * | 1986-05-26 | 1987-12-03 | Nippon Telegr & Teleph Corp <Ntt> | Infrared optical fiber |
| JPS63112440A (en) * | 1986-10-30 | 1988-05-17 | Sumitomo Electric Ind Ltd | Fiber laser medium and light amplifier using the same |
| JPS63143508A (en) * | 1986-12-05 | 1988-06-15 | Kokusai Denshin Denwa Co Ltd <Kdd> | Preform for fluoride glass fiber and its production |
-
1990
- 1990-05-01 JP JP2115497A patent/JPH0629150B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319087A (en) * | 2013-06-04 | 2013-09-25 | 中山大学 | Rare earth phosphate scintillating glass and preparation method of same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0412035A (en) | 1992-01-16 |
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