JP2807282B2 - Method for producing beta-type barium metaborate single crystal - Google Patents
Method for producing beta-type barium metaborate single crystalInfo
- Publication number
- JP2807282B2 JP2807282B2 JP1245056A JP24505689A JP2807282B2 JP 2807282 B2 JP2807282 B2 JP 2807282B2 JP 1245056 A JP1245056 A JP 1245056A JP 24505689 A JP24505689 A JP 24505689A JP 2807282 B2 JP2807282 B2 JP 2807282B2
- Authority
- JP
- Japan
- Prior art keywords
- bab
- single crystal
- barium metaborate
- mol
- type barium
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は品質の良いベータ型メタホウ酸バリウム単結
晶を再現性良く得るための方法に関するものである。Description: FIELD OF THE INVENTION The present invention relates to a method for obtaining a good quality beta-type barium metaborate single crystal with good reproducibility.
高出力レーザー光の実用に際しては危険防止のため可
視光に変換する必要があり、そのために第２次高調波発
生（SHG）用の光学結晶が用いられる。ベータ型メタホ
ウ酸バリウムはKTiOPO4,LiNbO3等と同様の非線形光学結
晶であり、赤外から紫外に亘る広い透光領域を持ってい
ることや、温度許容度が大きいという利点があるため近
年注目されている結晶材料である。In practical use of high-power laser light, it is necessary to convert it into visible light in order to prevent danger. For this purpose, an optical crystal for second harmonic generation (SHG) is used. Beta-type barium metaborate is a non-linear optical crystal similar to KTiOPO 4 , LiNbO 3, etc., and has attracted attention in recent years because it has a wide light transmission range from infrared to ultraviolet and has a large temperature tolerance. Is a crystalline material.
ところでこのベータ型メタホウ酸バリウム（β−BaB2
O4）はBaB2O4の低温相であり、通常フラックス法により
製造されてきた。しかしフラックス法は単結晶中に不純
物が混入し易く、品質の良好な結晶が得にくい欠点があ
る。一方最近に至りβ−BaB2O4を引上法で製造する試み
が為された。この方法はBaB2O4の過冷却性を利用し、急
激な温度勾配下で単結晶を引上げるものである。しかし
ながらこの方法の場合過冷却の制御が困難であること、
急激な温度勾配は得られた結晶にクラックを生じ易い等
の欠点があり、安定して再現性良くβ−BaB2O4を育成す
ることは困難である。By the way, this beta-type barium metaborate (β-BaB 2
O 4 ) is the low temperature phase of BaB 2 O 4 and has usually been produced by the flux method. However, the flux method has a disadvantage that impurities are easily mixed into the single crystal, and it is difficult to obtain a high-quality crystal. On the other hand, recently, attempts have been made to produce β-BaB 2 O 4 by a pull-up method. This method utilizes a supercooling property of BaB 2 O 4 and pulls a single crystal under a rapid temperature gradient. However, in this method, it is difficult to control the supercooling,
A steep temperature gradient has the disadvantage that cracks easily occur in the obtained crystal, and it is difficult to stably grow β-BaB 2 O 4 with good reproducibility.
本発明は上記事情に鑑みて為されたもので、品質の良
いβ−BaB2O4を再現性良く製造するための方法を提供す
るものである。The present invention has been made in view of the above circumstances, and provides a method for producing high-quality β-BaB 2 O 4 with good reproducibility.
上記目的を達成するための本発明の方法は、Na2Oを0.
001〜20モル％含有せしめたBaB2O4−Na2O2元組成を原料
とし、引上法によりβ−BaB2O4単結晶を育成する点に特
徴がある。In order to achieve the above object, the method of the present invention uses Na 2 O at 0.
It is characterized in that a β-BaB 2 O 4 single crystal is grown by a pull-up method using a BaB 2 O 4 —Na 2 O 2 elementary composition containing 001 to 20 mol% as a raw material.
BaB2O4−Na2O2元状態図によれば、Na2Oのモル％が増
加するに従って液相線が右下りに低下し、Na2O約30モル
％で共融点に達する。この液相線の左側の領域における
高温側でα−BaB2O4が、低温側でβ−BaB2O4が析出し、
その境界はNa2O約21モル％である。従ってNa2O約21〜30
モル％の領域で引上法を適用すればフラックス法と同様
にβ−BaB2O4を得ることは可能と考えられる。しかしな
がらこの方法では不純物の混入が問題となる。本発明者
らはNa2Oが20モル％以下のBaB2O4−Na2O2元組成の領域
で引上法を試みたところ、驚くべきことに高品質のβ−
BaB2O4が容易に得られることを見出した。According to BaB 2 O 4 -Na 2 O2 binary phase diagram, the liquidus is lowered right down according mol% of Na 2 O is increased, it reaches a eutectic point in Na 2 O from about 30 mole%. The alpha-BaB at high temperature side in the left area of the liquidus 2 O 4 is, beta-BaB 2 O 4 is precipitated at the low temperature side,
The boundary is Na 2 O from about 21 mole%. Accordingly Na 2 O from about 21-30
It is considered that β-BaB 2 O 4 can be obtained by applying the pulling-up method in the mol% range, similarly to the flux method. However, in this method, mixing of impurities becomes a problem. The present inventors have attempted a pulling-up method in the range of BaB 2 O 4 —Na 2 O 2 in which the content of Na 2 O is 20 mol% or less.
BaB 2 O 4 was found to be easily obtained.
Na2Oは極めて少量でもβ−BaB2O4を育成でき、しかも
少量程不純物としての混入量が減少するので好都合であ
る。しかし、0.001モル％未満では安定した結晶化が困
難となるので、0.001〜20モル％の範囲とする必要があ
る。Even a very small amount of Na 2 O can grow β-BaB 2 O 4 , and the smaller the amount, the more the amount of impurities as impurities is reduced. However, if it is less than 0.001 mol%, stable crystallization becomes difficult, so it is necessary to be in the range of 0.001 to 20 mol%.
本発明において特にNa2O0.001〜21モル％の領域でβ
−BaB2O4が結晶化するのは非平衡であるが、その理由は
未だ明らかでない。In the present invention, particularly in the range of 0.001 to 21 mol% of Na 2 O, β
The crystallization of BaB 2 O 4 is non-equilibrium, but the reason is not yet clear.
実施例１ 塩化バリウム１モルとホウ酸２モルを水に溶解し、水
酸化ナトリウムを加えて沈澱物を得、これを濾過回収し
て焙焼し、Na2Oを１モル％含有するBaB2O4−Na2O混合物
を得た。この混合物を直径50mm、深さ50mmの白金ルツボ
に入れ、大気中、常圧にて高周波誘導加熱で溶融し、温
度を1070℃に保持し白金棒をシードとして回転数毎分10
回転、引上速度毎時3mmで３時間引上を続行した結果、
白金シード棒付近は多結晶であるが、育成に従って単結
晶領域を増し、直径が8mm、長さ15mmの、引上軸がＣ軸
の無色透明なβ−BaB2O4単結晶を得た。この結果はクラ
ックがなく、分析の結果Naは検出限界以下であった。Example 1 1 mol of barium chloride and 2 mol of boric acid were dissolved in water, sodium hydroxide was added to obtain a precipitate, which was collected by filtration, roasted, and dried with BaB 2 containing 1 mol% of Na 2 O. It was obtained O 4 -Na 2 O mixture. This mixture was placed in a platinum crucible having a diameter of 50 mm and a depth of 50 mm, melted by high-frequency induction heating at atmospheric pressure and normal pressure, the temperature was maintained at 1070 ° C., and a platinum rod was used as a seed to rotate at 10 rpm.
As a result of continuing the pulling at 3 mm / h for 3 hours,
Although the vicinity of the platinum seed rod is polycrystalline, the single crystal region was increased as it grew, and a colorless and transparent β-BaB 2 O 4 single crystal having a diameter of 8 mm and a length of 15 mm and a pulling axis of C axis was obtained. This result was free from cracks, and as a result of analysis, Na was below the detection limit.
実施例２ 炭酸バリウム１モルと酸化ホウ素１モルにNa2Oを0.01
モル添加し、焙焼してBaB2O4−Na2O混合物を得た。Example 2 0.01 mol of Na 2 O was added to 1 mol of barium carbonate and 1 mol of boron oxide.
Molar addition and roasting were performed to obtain a BaB 2 O 4 —Na 2 O mixture.
又、同様にNa2Oを８モル添加したBaB2O4−Na2O混合物
を得た。これらの２種のBaB2O4−Na2O混合物について実
施例１と同様の条件で引上を実施した所、クラックもな
く、Naの混入のないβ−BaB2O4単結晶が得られた。な
お、結晶育成時の融液温度はそれぞれ1080℃、1030℃で
あった。Further, to obtain a similarly BaB 2 O 4 -Na 2 O mixture and the Na 2 O and 8 moles added. When these two kinds of BaB 2 O 4 —Na 2 O mixtures were pulled up under the same conditions as in Example 1, a β-BaB 2 O 4 single crystal free of cracks and free of Na was obtained. Was. The melt temperature during crystal growth was 1080 ° C. and 1030 ° C., respectively.
本発明により品質の良いβ−BaB2O4単結晶を安定して
再現性良く得られるようになった。これにより大型の結
晶を得る見通しが得られ、β−BaB2O4の実用化に一歩前
進したと言える。According to the present invention, a high-quality β-BaB 2 O 4 single crystal can be obtained stably and with good reproducibility. As a result, the prospect of obtaining a large crystal can be obtained, and it can be said that a step forward has been made toward the practical use of β-BaB 2 O 4 .
Claims (1)
4−Na2O2元組成を原料とし、引上法により単結晶を育成
することを特徴とするベータ型メタホウ酸バリウム単結
晶の製造方法。1. A BaB 2 O with a Na 2 O the additional inclusion 0.001 mole%
A method for producing a beta-type barium metaborate single crystal, comprising growing a single crystal by a pulling method using a 4- Na 2 O 2 elemental composition as a raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1245056A JP2807282B2 (en) | 1989-09-22 | 1989-09-22 | Method for producing beta-type barium metaborate single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1245056A JP2807282B2 (en) | 1989-09-22 | 1989-09-22 | Method for producing beta-type barium metaborate single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03109297A JPH03109297A (en) | 1991-05-09 |
| JP2807282B2 true JP2807282B2 (en) | 1998-10-08 |
Family
ID=17127929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1245056A Expired - Lifetime JP2807282B2 (en) | 1989-09-22 | 1989-09-22 | Method for producing beta-type barium metaborate single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2807282B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63215598A (en) * | 1987-02-27 | 1988-09-08 | Agency Of Ind Science & Technol | Production of barium borate single crystal having low temperature phase |
| JPH0788270B2 (en) * | 1989-04-19 | 1995-09-27 | 日本電気株式会社 | Method for growing single crystal thin film |
-
1989
- 1989-09-22 JP JP1245056A patent/JP2807282B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03109297A (en) | 1991-05-09 |
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