JPH11352533A - Wavelength conversion crystal and its production as well as laser apparatus using the same - Google Patents
Wavelength conversion crystal and its production as well as laser apparatus using the sameInfo
- Publication number
- JPH11352533A JPH11352533A JP15711998A JP15711998A JPH11352533A JP H11352533 A JPH11352533 A JP H11352533A JP 15711998 A JP15711998 A JP 15711998A JP 15711998 A JP15711998 A JP 15711998A JP H11352533 A JPH11352533 A JP H11352533A
- Authority
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- Japan
- Prior art keywords
- crystal
- wavelength conversion
- conversion crystal
- laser
- wavelength
- 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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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、レーザの入射光の
波長を半分にする波長変換結晶及びその製造方法並びに
この結晶を用いたレーザ発振装置に関する。更に詳しく
は、耐潮解性を有するＬｉＲｂＢ6Ｏ10で表される波長
変換結晶及びその製造方法並びにこの結晶を用いたレー
ザ発振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 wavelength conversion crystal for halving the wavelength of incident light of a laser, a method for manufacturing the same, and a laser oscillator using the crystal. More specifically, the present invention relates to a wavelength conversion crystal represented by LiRbB 6 O 10 having deliquescent resistance, a method for producing the same, and a laser oscillation device using the crystal.
【０００２】[0002]
【従来の技術】ＹＡＧ等の赤外固体レーザとこの種の波
長変換結晶を用いて作られる紫外域又は可視域の短波長
固体レーザは、従来のＡｒガスレーザやエキシマレーザ
と比較して、より安全でメインテナンスが容易である
上、低価格で小型化し得る特長がある。入射光の波長を
半分にして出射する上記波長変換結晶は、信頼性の高い
短波長固体レーザには必要不可欠な結晶である。しかし
ながら、この波長変換結晶として十分に満足できる結晶
はこれまで存在せず、多くの研究者が良好な特性を示す
波長変換結晶を見い出すべく、現在活発な研究を行って
いる。2. Description of the Related Art A short-wavelength solid-state laser in the ultraviolet or visible range made using an infrared solid-state laser such as YAG and a wavelength conversion crystal of this kind is more secure than conventional Ar gas lasers and excimer lasers. In addition, maintenance is easy, and there is a feature that the size can be reduced at a low price. The wavelength conversion crystal that emits the wavelength of the incident light by half is an indispensable crystal for a highly reliable short-wavelength solid-state laser. However, there is no crystal which is sufficiently satisfactory as this wavelength conversion crystal so far, and many researchers are currently conducting active research to find a wavelength conversion crystal exhibiting good characteristics.
【０００３】従来、この種の波長変換結晶として、透過
波長領域が紫外域まで広がったホウ酸系のＢＢＯ（Ｂａ
Ｂ2Ｏ4）、ＬＢＯ（ＬｉＢ3Ｏ5）などの非線形光学結晶
が知られている。また近年ＬＢＯ結晶のＬｉの一部をＣ
ｓで置換したＣＬＢＯ（ＣｓＬｉＢ3Ｏ18）の結晶が開
発されている。ＣＬＢＯ結晶は、ＬＢＯ結晶とほぼ同じ
非線形光学定数の値を有する。しかし、このＣＬＢＯ結
晶は吸湿性があり、この吸湿により結晶が自発的に砕け
る潮解性があり、良質な結晶ができない不具合がある。
この点を解消するために、ＣＬＢＯ結晶のＣｓの一部又
は全部をＲｂ、Ｋ及びＴｌと置換した組成で表される結
晶が提案されている（特開平８−２９５５０７）。この
中で特にＣｓをＲｂで全部置換したＬｉＲｂＢ6Ｏ
10（ＬＲＢＯ）の結晶は容易に製造でき、かつ安全性が
高い特長がある。Conventionally, as this type of wavelength conversion crystal, boric acid-based BBO (Ba) whose transmission wavelength range has been extended to the ultraviolet range.
Nonlinear optical crystals such as B 2 O 4 ) and LBO (LiB 3 O 5 ) are known. In recent years, part of Li of LBO crystal has been replaced with C
A crystal of CLBO (CsLiB 3 O 18 ) substituted with s has been developed. CLBO crystals have substantially the same nonlinear optical constant values as LBO crystals. However, the CLBO crystal has a hygroscopic property, and has a deliquescent property in which the crystal spontaneously breaks due to the moisture absorption, so that a high-quality crystal cannot be obtained.
In order to solve this problem, there has been proposed a crystal having a composition in which part or all of Cs in a CLBO crystal is substituted with Rb, K and Tl (Japanese Patent Application Laid-Open No. 8-295507). Among them, LiRbB 6 O in which Cs is entirely replaced with Rb
The crystal of 10 (LRBO) can be easily manufactured and has high safety.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記ＢＢＯ、
ＬＢＯ及びＣＬＢＯの結晶は勿論のこと、上記ＲＬＢＯ
の結晶においても、得られた結晶は水分を吸収するとい
う吸湿性を有し、波長変換の効率が劣化する問題点があ
った。またこの水分は結晶を加工するときに大気中から
吸収されるばかりでなく、育成後の冷却中の結晶に大気
中から吸着して白濁化し、かつ結晶を取扱う際に形状が
崩れる潮解性を有する致命的な欠点があった。本発明の
目的は、紫外域まで波長変換することができ、かつ耐潮
解性を有するＲｂＬｉＢ6Ｏ10で表される波長変換結晶
及びその製造方法並びにこの結晶を用いたレーザ発振装
置を提供することにある。However, the above BBO,
Not only LBO and CLBO crystals, but also RLBO
In the above crystal, there is a problem that the obtained crystal has a hygroscopic property of absorbing moisture and the wavelength conversion efficiency is deteriorated. In addition, this moisture is not only absorbed from the atmosphere when processing the crystal, but also adsorbs from the air to the cooled crystal after growing from the atmosphere to make it cloudy, and has a deliquescence that the shape collapses when handling the crystal. There was a fatal drawback. SUMMARY OF THE INVENTION An object of the present invention is to provide a wavelength conversion crystal represented by RbLiB 6 O 10 capable of wavelength conversion up to the ultraviolet region and having deliquescence resistance, a method for manufacturing the same, and a laser oscillation device using the crystal. It is in.
【０００５】[0005]
【課題を解決するための手段】請求項１に係る発明は、
ＬｉＲｂＢ6Ｏ10で表され、耐潮解性を有することを特
徴とする波長変換結晶である。このＬｉＲｂＢ6Ｏ10で
表される波長変換結晶は、Ｂ−Ｏ構造を有するため紫外
域まで波長変換することができ、ハイパワー領域での波
長変換ではＢＢＯに勝る特性を有する。特に本発明の波
長変換結晶は耐潮解性を有するために、結晶を大気中に
放置しても結晶の形状が崩れることもない。The invention according to claim 1 is
A wavelength conversion crystal represented by LiRbB 6 O 10 and having deliquescent resistance. Since the wavelength conversion crystal represented by LiRbB 6 O 10 has a BO structure, it can perform wavelength conversion up to the ultraviolet region, and has characteristics superior to BBO in wavelength conversion in a high power region. In particular, since the wavelength conversion crystal of the present invention has deliquescence resistance, the shape of the crystal does not collapse even when the crystal is left in the air.
【０００６】請求項２に係る発明は、リチウムの炭酸塩
又はホウ酸塩と、ルビジウムの炭酸塩と、ホウ酸又は無
水ホウ酸とを所定量秤量して融解し、この融液からＬｉ
ＲｂＢ6Ｏ10で表される波長変換結晶を育成した後、こ
の波長変換結晶を大気中で冷却することにより波長変換
結晶を製造する方法において、育成後の波長変換結晶の
温度が１５０℃まで低下したときに上記波長変換結晶を
相対湿度が２０％以下の室温の雰囲気中に移して放置し
室温まで冷却することを特徴とする波長変換結晶の製造
方法である。育成後の結晶の降温過程で、結晶の温度が
１５０℃まで低下して時点で、相対湿度が２０％以下の
室温の雰囲気中に移して放置し室温まで冷却することに
より、結晶化の全過程において水分の吸着が防止され、
得られた結晶は白濁化せず、また型くずれもなく、耐潮
解性を示す。According to a second aspect of the present invention, a predetermined amount of lithium carbonate or borate, rubidium carbonate, boric acid or boric acid is weighed and melted.
After growing the wavelength conversion crystal represented by RbB 6 O 10 , in a method of manufacturing the wavelength conversion crystal by cooling the wavelength conversion crystal in the air, the temperature of the grown wavelength conversion crystal is reduced to 150 ° C. A method for producing a wavelength conversion crystal, characterized in that the wavelength conversion crystal is moved to an atmosphere at a room temperature having a relative humidity of 20% or less and left to cool to room temperature. At the time when the temperature of the crystal is lowered to 150 ° C. in the temperature decreasing process of the crystal after the growth, the crystal is transferred to an atmosphere having a relative humidity of 20% or less at room temperature, left to cool to room temperature, and the entire process of crystallization is performed. The adsorption of moisture is prevented at
The obtained crystals do not become cloudy, do not lose their shape, and show deliquescent resistance.
【０００７】請求項３に係る発明は、図３に示すように
レーザ媒質１１から発生したレーザ光の光路に耐潮解性
を有するＬｉＲｂＢ6Ｏ10で表される波長変換結晶１２
が設けられたことを特徴とするレーザ発振装置である。
レーザ媒質１１から発生したレーザ光を本発明の波長変
換結晶１２に照射すると、この波長変換結晶１２で波長
変換されたレーザ光が出射される。According to a third aspect of the present invention, there is provided a wavelength conversion crystal 12 represented by LiRbB 6 O 10 having deliquescent resistance in an optical path of a laser beam generated from a laser medium 11 as shown in FIG.
Is provided.
When the laser light generated from the laser medium 11 is irradiated on the wavelength conversion crystal 12 of the present invention, the laser light whose wavelength has been converted by the wavelength conversion crystal 12 is emitted.
【０００８】[0008]
【発明の実施の形態】本発明の上記結晶を製造するとき
の出発原料は、リチウムの炭酸塩又はホウ酸塩と、ルビ
ジウムの炭酸塩と、ホウ酸又は無水ホウ酸である。これ
らを所定量秤量して加熱融解することにより融液を得た
後、この融液から結晶を育成させる。本発明のＬＲＢＯ
の結晶化温度は７２０℃以下で、一致融解を示すので、
結晶の育成方法としては、チョクラルスキー（ＣＺ）
法、ブリッジマン法、浮遊帯域融解（ＦＺ）法などを採
用することができる。ＬＲＢＯの結晶化速度はホウ酸系
の光学結晶の中でＣＬＢＯ結晶に比べれば幾分遅いが、
ＢＢＯ結晶やＬＢＯ結晶の結晶化速度より速く、これら
の結晶と比べて、ＬＲＢＯ結晶はより短時間で育成する
ことができる。育成後のＬＲＢＯ結晶は、結晶の温度が
１５０℃に低下するまでは育成炉の大気中で育成炉のヒ
ータへの印加電圧を徐々に下げることにより冷却し、１
５０℃に到達した時点でこの結晶を育成炉から取出し、
相対湿度が２０％以下の室温の雰囲気中に移して放置し
室温まで冷却する。この相対湿度が２０％以下の室温の
雰囲気としては、ドライボックス、デシケータ又は降温
プロファイルをプログラム制御された恒温恒湿槽の各内
部雰囲気が挙げられる。上記雰囲気でＬＲＢＯ結晶は結
晶体が保有する熱を放散しながら徐々に室温まで冷却さ
れる。上記育成炉から相対湿度が低い雰囲気に移すとき
の結晶の温度は好ましくは１２０℃であり、また移され
る雰囲気の好ましい相対湿度は１５％以下である。BEST MODE FOR CARRYING OUT THE INVENTION Starting materials for producing the above crystals of the present invention are lithium carbonate or borate, rubidium carbonate, and boric acid or boric anhydride. After weighing these in a predetermined amount and melting them by heating to obtain a melt, crystals are grown from the melt. LRBO of the present invention
Has a crystallization temperature of 720 ° C. or lower and shows consistent melting.
Czochralski (CZ)
Method, Bridgman method, floating zone melting (FZ) method, or the like can be employed. The crystallization rate of LRBO is somewhat lower than that of CLBO crystal among boric acid-based optical crystals,
The crystallization speed of the BBO crystal and the LBO crystal is faster than that of these crystals, so that the LRBO crystal can be grown in a shorter time. The grown LRBO crystal is cooled by gradually lowering the voltage applied to the heater of the growing furnace in the atmosphere of the growing furnace until the temperature of the crystal decreases to 150 ° C.
When the temperature reaches 50 ° C., the crystal is taken out of the growth furnace,
It is moved to an atmosphere at a room temperature having a relative humidity of 20% or less and left to cool to room temperature. Examples of the atmosphere at room temperature where the relative humidity is 20% or less include the respective internal atmospheres of a dry box, a desiccator, or a thermo-hygrostat in which a temperature-lowering profile is program-controlled. In the above atmosphere, the LRBO crystal is gradually cooled to room temperature while dissipating the heat of the crystal. The temperature of the crystal when it is transferred from the growth furnace to an atmosphere having a low relative humidity is preferably 120 ° C., and the preferable relative humidity of the transferred atmosphere is 15% or less.
【０００９】本発明のＬＲＢＯ結晶は単結晶の状態で非
線形光学材料として、図３に示すレーザ発振装置に用い
ることができる。このレーザ発振装置ではレーザ媒質１
１の基本波長のレーザ光をレーザ媒質１１の光路に設け
られたこのＬＲＢＯ単結晶１２に照射すれば、照射され
たＬＲＢＯ単結晶１２の入射光はこの単結晶中で波長変
換されて高調波を出射する。これによりこのＬＲＢＯ結
晶を短波長光源として利用できる。レーザ媒質として
は、ｄｙｅ（色素）レーザ、固体レーザ、半導体レーザ
等が挙げられる。また本発明のＬＲＢＯ結晶を焼結して
多結晶のセラミック体の非線形光学材料として使用し、
可視領域よりも長い波長のレーザ光をこのセラミック体
に照射することにより可視化することができる。これは
例えば、ＹＡＧを用いた１．０６μｍのレーザ光をこの
セラミック体に照射すると０．５３μｍの可視光が出射
され、レーザ光のビーム形状や強度分布などのビーム形
状を見ることができる。The LRBO crystal of the present invention can be used as a nonlinear optical material in a single crystal state in the laser oscillation device shown in FIG. In this laser oscillation device, the laser medium 1
By irradiating the LRBO single crystal 12 provided on the optical path of the laser medium 11 with the laser light having the fundamental wavelength of 1, the incident light of the irradiated LRBO single crystal 12 is wavelength-converted in the single crystal to reduce harmonics. Emit. Thereby, this LRBO crystal can be used as a short wavelength light source. Examples of the laser medium include a dye laser, a solid-state laser, and a semiconductor laser. Further, the LRBO crystal of the present invention is sintered and used as a nonlinear optical material of a polycrystalline ceramic body,
The ceramic body can be visualized by irradiating the ceramic body with laser light having a wavelength longer than the visible region. For example, when the ceramic body is irradiated with a laser beam of 1.06 μm using YAG, for example, visible light of 0.53 μm is emitted, and the beam shape of the laser beam and the beam shape such as the intensity distribution can be seen.
【００１０】[0010]
【実施例】次の本発明の実施例を比較例とともに説明す
る。 ＜実施例１＞ＬＲＢＯ結晶をチョクラルスキー法により
育成した。先ず炭酸リチウム（Ｌｉ2ＣＯ3）と炭酸ルビ
ジウム（Ｒｂ2ＣＯ3）と酸化ホウ素（Ｂ2Ｏ3）をモル比
でＬｉ2ＣＯ3：Ｒｂ2ＣＯ3：Ｂ2Ｏ3＝１：１：６となる
ように秤量し均一に混合した。内径約６０ｍｍ、高さ約
６０ｍｍの白金ルツボをたて型炉の中に配置し、ルツボ
の中に上記混合粉を３回に分けて入れ、８５０℃に保っ
て混合粉を融解した。最終的に融液はルツボの容積の８
０％を占めた。上記モル比と同一にして別に作製した種
結晶をシードホルダに取付けた後、この種結晶を７５０
℃の温度に調整された融液表面に接触させ、この温度で
２時間維持しながら、種結晶を引上げて直径約１ｃｍ、
長さ約５ｃｍのＬＲＢＯ結晶を育成した。育成後のＬＲ
ＢＯ結晶は、結晶の温度が１２０℃に低下するまでは育
成炉の大気中で育成炉のヒータへの印加電圧を徐々に下
げることにより冷却し、１２０℃に到達した時点でこの
結晶を育成炉から取出し、素早く相対湿度２０％、温度
３０℃に調整されたドライボックスの中に入れた。ＬＲ
ＢＯ結晶の温度は結晶近傍に熱電対を設けて測定した。
このドライボックスの中で５時間放置した後、３０℃の
温度を有するＬＲＢＯ結晶をドライボックスから取出し
た。The following examples of the present invention will be described together with comparative examples. <Example 1> LRBO crystals were grown by the Czochralski method. First, lithium carbonate (Li 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), and boron oxide (B 2 O 3 ) have a molar ratio of Li 2 CO 3 : Rb 2 CO 3 : B 2 O 3 = 1: 1: Then, the mixture was weighed so as to be 6 and uniformly mixed. A platinum crucible having an inner diameter of about 60 mm and a height of about 60 mm was placed in a vertical furnace, and the mixed powder was put into the crucible in three portions and kept at 850 ° C. to melt the mixed powder. Finally, the melt has a volume of 8 crucibles.
Accounted for 0%. After attaching a seed crystal separately prepared in the same molar ratio as above to a seed holder, this seed crystal was 750
Contact with the melt surface adjusted to a temperature of 0 ° C., while maintaining the temperature at this temperature for 2 hours, the seed crystal is pulled up to a diameter of about 1 cm,
An LRBO crystal having a length of about 5 cm was grown. LR after rearing
The BO crystal is cooled by gradually lowering the voltage applied to the heater of the growing furnace in the atmosphere of the growing furnace until the temperature of the crystal decreases to 120 ° C., and when the temperature reaches 120 ° C., the BO crystal is cooled. , And quickly placed in a dry box adjusted to a relative humidity of 20% and a temperature of 30 ° C. LR
The temperature of the BO crystal was measured by providing a thermocouple near the crystal.
After standing in this dry box for 5 hours, the LRBO crystal having a temperature of 30 ° C. was taken out of the dry box.
【００１１】＜比較例１＞実施例１と同一の条件で実施
例１と同一のＬＲＢＯ結晶を育成した。この結晶を育成
した後、育成炉のヒータへの印加電圧を徐々に下げ、結
晶の温度が１２０℃になった時点で、ヒータの電源を切
った。大気中の育成炉中で結晶が３０℃の室温になるま
で５時間放置した。Comparative Example 1 The same LRBO crystal as in Example 1 was grown under the same conditions as in Example 1. After growing this crystal, the voltage applied to the heater of the growth furnace was gradually lowered, and when the temperature of the crystal reached 120 ° C., the power of the heater was turned off. The crystal was left in a growth furnace in the air for 5 hours until the crystal reached room temperature of 30 ° C.
【００１２】＜比較評価＞実施例１のドライボックスか
ら取出した室温のＬＲＢＯ結晶と、比較例１の育成炉か
ら取出した室温のＬＲＢＯ結晶のそれぞれの状態を写真
撮影した。その結果をそれぞれ図１（実施例１）及び図
２（比較例１）に示す。図１及び図２から明らかなよう
に、比較例１のＬＲＢＯ結晶は大気中の水分を吸収して
白濁化し、潮解により結晶が割れたのに対して、実施例
１のＬＲＢＯ結晶は割れずに透明であった。また得られ
た実施例１及び比較例１のＬＲＢＯ結晶を手で強く握り
しめ、形状の崩れの有無を調べたところ、比較例１のＬ
ＲＢＯ結晶は脆くて形が崩れた。これに対して実施例１
のＬＲＢＯ結晶は緻密で固い結晶体であって形状の変化
は全くなかった。<Comparative Evaluation> Photographs were taken of the respective states of the room temperature LRBO crystal taken out of the dry box of Example 1 and the room temperature LRBO crystal taken out of the growth furnace of Comparative Example 1. The results are shown in FIG. 1 (Example 1) and FIG. 2 (Comparative Example 1). As is clear from FIG. 1 and FIG. 2, the LRBO crystal of Comparative Example 1 absorbed the moisture in the atmosphere and became cloudy, and the crystal was cracked by deliquescence, whereas the LRBO crystal of Example 1 was not broken. It was transparent. Further, the obtained LRBO crystals of Example 1 and Comparative Example 1 were strongly grasped by hand, and the presence or absence of shape collapse was examined.
The RBO crystal was brittle and collapsed. On the other hand, Embodiment 1
The LRBO crystal was a dense and hard crystal and did not change its shape at all.
【００１３】[0013]
【発明の効果】以上述べたように、本発明の波長変換結
晶は、ＬｉＲｂＢ6Ｏ10で表される結晶であるため、Ｂ
−Ｏ構造を有することから紫外域まで波長変換すること
ができ、ハイパワー領域での波長変換ではＢＢＯに勝る
特性を示す。特にこの結晶は耐潮解性を有すため、大気
中に放置しても結晶は容易に白濁化せず、加工の際など
の取扱い時に細かいクラックに起因して割れたり形状が
崩れたりすることがない。As described above, since the wavelength conversion crystal of the present invention is a crystal represented by LiRbB 6 O 10 ,
Due to the -O structure, wavelength conversion can be performed up to the ultraviolet region, and the wavelength conversion in the high power region shows characteristics superior to BBO. In particular, since this crystal has deliquescence resistance, the crystal does not easily become cloudy even when left in the air, and may break or lose its shape due to fine cracks during handling such as processing. Absent.
【図１】実施例１の室温まで冷却後のＬＲＢＯ結晶の状
態を示す写真図。FIG. 1 is a photograph showing the state of an LRBO crystal after cooling to room temperature in Example 1.
【図２】比較例１の室温まで冷却後のＬＲＢＯ結晶の状
態を示す写真図。FIG. 2 is a photograph showing the state of an LRBO crystal after cooling to room temperature in Comparative Example 1.
【図３】本発明のレーザ発振装置の構成図。FIG. 3 is a configuration diagram of a laser oscillation device of the present invention.
１１ レーザ媒質 １２ 波長変換結晶 11 Laser medium 12 Wavelength conversion crystal
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年６月５日[Submission date] June 5, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図１[Correction target item name] Fig. 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図１】 FIG.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図２[Correction target item name] Figure 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図２】 FIG. 2
【手続補正書】[Procedure amendment]
【提出日】平成１０年７月７日[Submission date] July 7, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Correction target item name] Name of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【発明の名称】 波長変換結晶及びその製造方法並びに
これを用いたレーザ装置METHOD Name of the Invention Wavelength conversion crystals and their manufacture as well as lasers equipment using the same
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Correction target item name] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００１[Correction target item name] 0001
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００１】[0001]
【発明の属する技術分野】本発明は、レーザの入射光の
波長を半分にする波長変換結晶及びその製造方法並びに
この結晶を用いたレーザ発振装置に関する。更に詳しく
は、耐潮解性を有するＬｉＲｂＢ6Ｏ10で表される波長
変換結晶及びその製造方法並びにこの結晶を用いたレー
ザ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 wavelength conversion crystal for halving the wavelength of incident light of a laser, a method for manufacturing the same, and a laser oscillator using the crystal. More specifically, a wavelength conversion crystal represented by LiRbB 6 O 10 having deliquescence resistance, a method for producing the same, and a laser using the crystal.
It relates to The equipment.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記ＢＢＯ、
ＬＢＯ及びＣＬＢＯの結晶は勿論のこと、上記ＬＲＢＯ
の結晶においても、得られた結晶は水分を吸収するとい
う吸湿性を有し、波長変換の効率が劣化する問題点があ
った。またこの水分は結晶を加工するときに大気中から
吸収されるばかりでなく、育成後の冷却中の結晶に大気
中から吸着して白濁化し、かつ結晶を取扱う際に形状が
崩れる潮解性を有する致命的な欠点があった。本発明の
目的は、紫外域まで波長変換することができ、かつ耐潮
解性を有するＬｉＲｂＢ6Ｏ10で表される波長変換結晶
及びその製造方法並びにこの結晶を用いたレーザ装置を
提供することにある。However, the above BBO,
Not only LBO and CLBO crystals, but also LRBO
In the above crystal, there is a problem that the obtained crystal has a hygroscopic property of absorbing moisture and the wavelength conversion efficiency is deteriorated. In addition, this moisture is not only absorbed from the atmosphere when processing the crystal, but also adsorbs from the air to the cooled crystal after growing from the atmosphere to make it cloudy, and has a deliquescence that the shape collapses when handling the crystal. There was a fatal drawback. An object of the present invention may be a wavelength converting to ultraviolet region, and provide lasers equipment using the wavelength conversion crystal and a method for manufacturing the same, and the crystal represented by LiRb B 6 O 10 having耐潮disintegratable Is to do.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００５[Correction target item name] 0005
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００５】[0005]
【課題を解決するための手段】請求項１に係る発明は、
ＬｉＲｂＢ6Ｏ10で表され、耐潮解性を有することを特
徴とする波長変換結晶である。このＬｉＲｂＢ6Ｏ10で
表される波長変換結晶は、Ｂ−Ｏ構造を有するため紫外
域まで波長変換することができ、またハイパワー領域で
の波長変換ではＢＢＯに勝る特性を有する。特に本発明
の波長変換結晶は耐潮解性を有するために、結晶を大気
中に放置しても結晶の形状が崩れることもない。The invention according to claim 1 is
A wavelength conversion crystal represented by LiRbB 6 O 10 and having deliquescent resistance. The LiRbB 6 O 10 in the wavelength conversion represented crystal, B-O structure can be wavelength-converted to ultraviolet region because it has, also has the property over BBO in wavelength conversion at high power region. In particular, since the wavelength conversion crystal of the present invention has deliquescence resistance, the shape of the crystal does not collapse even when the crystal is left in the air.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００７】請求項３に係る発明は、図３に示すように
レーザ媒質１１から発生したレーザ光の光路に耐潮解性
を有するＬｉＲｂＢ6Ｏ10で表される波長変換結晶１２
が設けられたことを特徴とするレーザ装置である。レー
ザ媒質１１から発生したレーザ光を本発明の波長変換結
晶１２に照射すると、この波長変換結晶１２で波長変換
されたレーザ光が出射される。According to a third aspect of the present invention, there is provided a wavelength conversion crystal 12 represented by LiRbB 6 O 10 having deliquescent resistance in an optical path of a laser beam generated from a laser medium 11 as shown in FIG.
A lasers equipment, characterized in that is provided. When the laser light generated from the laser medium 11 is irradiated on the wavelength conversion crystal 12 of the present invention, the laser light whose wavelength has been converted by the wavelength conversion crystal 12 is emitted.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】本発明のＬＲＢＯ結晶は単結晶の状態で非
線形光学材料として、図３に示すレーザ装置に用いるこ
とができる。このレーザ装置ではレーザ媒質１１の基本
波長のレーザ光をレーザ媒質１１の光路に設けられたこ
のＬＲＢＯ単結晶１２に照射すれば、照射されたＬＲＢ
Ｏ単結晶１２の入射光はこの単結晶中で波長変換されて
高調波を出射する。これによりこのＬＲＢＯ結晶を短波
長光源として利用できる。レーザ媒質としては、ｄｙｅ
（色素）レーザ、固体レーザ、半導体レーザ等が挙げら
れる。また本発明のＬＲＢＯ結晶を焼結して多結晶のセ
ラミック体の非線形光学材料として使用し、可視領域よ
りも長い波長のレーザ光をこのセラミック体に照射する
ことにより可視化することができる。これは例えば、Ｙ
ＡＧを用いた１．０６μｍのレーザ光をこのセラミック
体に照射すると０．５３μｍの可視光が出射され、レー
ザ光のビーム形状や強度分布などのビーム形状を見るこ
とができる。[0009] LRBO crystals of the invention as the nonlinear optical material in the form of single crystals, can be used in lasers equipment shown in FIG. It is irradiated with laser light of a fundamental wavelength of the laser medium 11 in this lasers equipment in this LRBO single crystal 12 provided in the optical path of the laser medium 11, irradiated LRB
The incident light of the O single crystal 12 is subjected to wavelength conversion in the single crystal and emits a harmonic. Thereby, this LRBO crystal can be used as a short wavelength light source. As the laser medium, dye
(Dye) lasers, solid-state lasers, semiconductor lasers, and the like. Further, the LRBO crystal of the present invention can be sintered and used as a nonlinear optical material of a polycrystalline ceramic body, and can be visualized by irradiating the ceramic body with laser light having a wavelength longer than the visible region. This is, for example, Y
When the ceramic body is irradiated with 1.06 μm laser light using AG, 0.53 μm visible light is emitted, and the beam shape of the laser light and the beam shape such as the intensity distribution can be seen.
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Correction target item name] Brief description of drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図面の簡単な説明】[Brief description of the drawings]
【図１】実施例１の室温まで冷却後のＬＲＢＯ結晶の状
態を示す写真図。FIG. 1 is a photograph showing the state of an LRBO crystal after cooling to room temperature in Example 1.
【図２】比較例１の室温まで冷却後のＬＲＢＯ結晶の状
態を示す写真図。FIG. 2 is a photograph showing the state of an LRBO crystal after cooling to room temperature in Comparative Example 1.
【図３】本発明のレーザ装置の構成図。FIG. 3 is a block diagram of a laser The equipment of the present invention.
【符号の説明】 １１ レーザ媒質 １２ 波長変換結晶[Description of Signs] 11 Laser medium 12 Wavelength conversion crystal
───────────────────────────────────────────────────── フロントページの続き (72)発明者 ナーヒー ビンセント 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社総合研究所内 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Nahee Vincent 1-297 Kitabukurocho, Omiya City, Saitama Prefecture Mitsubishi Materials Research Institute
Claims (3)
有することを特徴とする波長変換結晶。1. A wavelength conversion crystal represented by LiRbB 6 O 10 and having deliquescence resistance.
ジウムの炭酸塩と、ホウ酸又は無水ホウ酸とを所定量秤
量して融解し、この融液からＬｉＲｂＢ6Ｏ10で表され
る波長変換結晶を育成した後、前記波長変換結晶を大気
中で冷却することにより前記波長変換結晶を製造する方
法において、 前記育成後の波長変換結晶の温度が１５０℃まで低下し
たときに前記波長変換結晶を相対湿度が２０％以下の室
温の雰囲気中に移して放置し室温まで冷却することを特
徴とする波長変換結晶の製造方法。2. A predetermined amount of lithium carbonate or borate, rubidium carbonate, boric acid or boric acid is weighed and melted, and a wavelength represented by LiRbB 6 O 10 is obtained from the melt. After growing the conversion crystal, in the method of manufacturing the wavelength conversion crystal by cooling the wavelength conversion crystal in the air, the wavelength conversion crystal when the temperature of the grown wavelength conversion crystal is reduced to 150 ℃ Is transferred to an atmosphere at a room temperature having a relative humidity of 20% or less and left to cool to room temperature.
光路に耐潮解性を有するＬｉＲｂＢ6Ｏ10で表される波
長変換結晶(12)が設けられたことを特徴とするレーザ発
振装置。3. A laser oscillation device comprising a wavelength conversion crystal (12) represented by LiRbB 6 O 10 having deliquescence resistance provided in an optical path of laser light generated from a laser medium (11).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15711998A JPH11352533A (en) | 1998-06-05 | 1998-06-05 | Wavelength conversion crystal and its production as well as laser apparatus using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15711998A JPH11352533A (en) | 1998-06-05 | 1998-06-05 | Wavelength conversion crystal and its production as well as laser apparatus using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11352533A true JPH11352533A (en) | 1999-12-24 |
Family
ID=15642639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15711998A Withdrawn JPH11352533A (en) | 1998-06-05 | 1998-06-05 | Wavelength conversion crystal and its production as well as laser apparatus using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11352533A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984151A (en) * | 2010-11-22 | 2011-03-09 | 中国科学院新疆理化技术研究所 | Di lithium tetra borate rubidium nonlinear optic crystal, preparation method and application thereof |
| CN102212882A (en) * | 2011-05-12 | 2011-10-12 | 中国科学院新疆理化技术研究所 | Non-linear optical crystal of rubidium lithium borate compound, preparation method thereof and application thereof |
-
1998
- 1998-06-05 JP JP15711998A patent/JPH11352533A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984151A (en) * | 2010-11-22 | 2011-03-09 | 中国科学院新疆理化技术研究所 | Di lithium tetra borate rubidium nonlinear optic crystal, preparation method and application thereof |
| CN102212882A (en) * | 2011-05-12 | 2011-10-12 | 中国科学院新疆理化技术研究所 | Non-linear optical crystal of rubidium lithium borate compound, preparation method thereof and application thereof |
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