JP2003137691A - Method of producing single crystal - Google Patents
Method of producing single crystalInfo
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- JP2003137691A JP2003137691A JP2001326513A JP2001326513A JP2003137691A JP 2003137691 A JP2003137691 A JP 2003137691A JP 2001326513 A JP2001326513 A JP 2001326513A JP 2001326513 A JP2001326513 A JP 2001326513A JP 2003137691 A JP2003137691 A JP 2003137691A
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- Prior art keywords
- single crystal
- producing
- crucible
- raw material
- oxide
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- Luminescent Compositions (AREA)
- Measurement Of Radiation (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、中性子線検出器に
用いられるシンチレータ単結晶の製造方法に関するもの
であり、とくに不純物を添加したＬｉ２Ｂ４Ｏ７（以下
ＬＢＯ）単結晶製造方法に適用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a scintillator single crystal used in a neutron beam detector, and particularly to a method for producing a doped Li 2 B 4 O 7 (hereinafter LBO) single crystal. To be done.
【０００２】[0002]
【従来の技術】従来、放射線検出器用酸化物単結晶は融
液成長法として知られるチョクラルスキー法やブリッジ
マン法で育成されている。2. Description of the Related Art Conventionally, an oxide single crystal for a radiation detector has been grown by the Czochralski method or Bridgman method known as a melt growth method.
【０００３】[0003]
【発明が解決しようとする課題】最近、本発明者らは中
性子シンチレータとして、銅、ニッケル、チタンなどの
不純物元素を添加した４ホウ酸リチウム単結晶（Ｌｉ２
Ｂ４Ｏ７）が有望であるとの結果を得た。しかし、従来
の上記単結晶育成法をそのまま適用しても良質な単結晶
は得られなかった。その主な原因は上記ホウ酸リチウム
の融液は粘度が高く原料酸化物が融液状態でも容易に混
ざらないことにある。そのため、育成した結晶中には異
物や気泡欠陥が多く存在し、光透過率が低下する。その
結果、中性子線刺激によって発生した光信号が単結晶内
部を損失無く伝播できず、検出器への取出し効率が低下
するという問題があった。本発明は、光透過率の高い良
質な不純物添加４ホウ酸リチウム単結晶を歩留り良く製
造する方法を提供する。Recently, the present inventors have proposed, as neutron scintillators, a lithium tetraborate single crystal (Li 2) to which an impurity element such as copper, nickel or titanium is added.
B 4 O 7 ) has shown promising results. However, a high quality single crystal could not be obtained even if the conventional single crystal growth method was applied as it was. The main cause is that the melt of the lithium borate has a high viscosity and the raw material oxides are not easily mixed even in the melt state. Therefore, many foreign matters and bubble defects are present in the grown crystal, and the light transmittance is reduced. As a result, there has been a problem that the optical signal generated by the neutron beam stimulation cannot propagate without loss inside the single crystal, and the extraction efficiency to the detector decreases. The present invention provides a method for producing a high-quality impurity-doped lithium tetraborate single crystal having high light transmittance with good yield.
【０００４】[0004]
【課題を解決するための手段】本発明は、［１］不純物
元素を添加したＬｉ２Ｂ４Ｏ７単結晶の製造方法であっ
て、次の工程を経ることを特徴とする単結晶製造方法で
ある。
ａ）所定の組成の酸化物原料を混合し、るつぼ中で１０
００℃以上に加熱溶融する、
ｂ）融液を鋳型に注ぎ固化させて単結晶育成用原料を作
製する、
ｃ）上記単結晶育成用原料を用いてブリッジマン法また
はチョクラルスキー法で単結晶化する。
本発明によれば、不純物元素を添加したＬｉ２Ｂ４Ｏ７
単結晶を製造するに当たり、まず、所定の組成の酸化物
原料を混合し、白金るつぼ中で約１０００℃以上に加熱
溶融する。ついで融液を鋳型に注ぎ固化させて単結晶育
成用原料を作製する。これは鋳型の形状によるが、円筒
型の鋳型を用いた場合は通常円柱状の多結晶もしくはガ
ラスロッドとして取出すことが出きる。鋳型の形状は単
結晶育成用のるつぼの形状に一致させることが好まし
く、円形もしくは正方形などの多角形を用いることが出
きる。そして、上記単結晶育成用原料を用いてブリッジ
マン法もしくはチョクラルスキー法で単結晶育成するこ
とで良質の単結晶が得られる。The present invention relates to [1] a method for producing a Li 2 B 4 O 7 single crystal doped with an impurity element, which is characterized by the following steps: Is. a) Mix oxide raw materials having a predetermined composition and mix them in a crucible for 10 times.
It is heated and melted at a temperature of 00 ° C. or higher, b) A melt is poured into a mold and solidified to prepare a single crystal growth raw material, and c) A single crystal is produced by the Bridgeman method or Czochralski method using the above single crystal growth raw material. Turn into. According to the present invention, Li 2 B 4 O 7 doped with an impurity element
In producing a single crystal, first, an oxide raw material having a predetermined composition is mixed and heated and melted in a platinum crucible at a temperature of about 1000 ° C. or higher. Then, the melt is poured into a mold and solidified to prepare a raw material for growing a single crystal. This depends on the shape of the mold, but when a cylindrical mold is used, it can usually be taken out as a cylindrical polycrystal or a glass rod. The shape of the mold is preferably matched with the shape of the crucible for growing a single crystal, and a polygon such as a circle or a square can be used. Then, a high quality single crystal is obtained by growing the single crystal by the Bridgman method or the Czochralski method using the above single crystal growing material.
【０００５】また、本発明は、［２］上記酸化物原料と
して粒径が約２ｍｍ以下の粒子状Ｌｉ２Ｂ４Ｏ７化合物
および粉末状添加元素酸化物を用いることを特徴とする
上記［１］に記載の単結晶製造方法である。そして、
［３］上記酸化物原料の純度が９９．９重量％以上であ
る上記［１］または上記［２］に記載の単結晶製造方法
である。上記酸化物原料として粒径は小さいほど好まし
いがＬｉ２Ｂ４Ｏ７組成の高純度溶融固化原料などを使
用する場合、予め約２ｍｍ以下の粒子状に粉砕した原料
および粉末状添加元素酸化物原料を用いることが好まし
い。また、上記酸化物原料の純度が９９．９重量％以上
であることが好ましく、９９．９９重量％以上であれば
さらに好ましい。[2] The present invention [2] is characterized in that a particulate Li 2 B 4 O 7 compound having a particle size of about 2 mm or less and a powdered additive element oxide are used as the oxide raw material. ] The method for producing a single crystal described in [1]. And
[3] The method for producing a single crystal according to the above [1] or [2], wherein the purity of the oxide raw material is 99.9% by weight or more. As the oxide raw material, the smaller the particle diameter is, the more preferable it is, but when using a high-purity melt-solidified raw material having a Li 2 B 4 O 7 composition, etc., a raw material and a powdered additive element oxide raw material which are previously pulverized into particles of about 2 mm or less. Is preferably used. The purity of the oxide raw material is preferably 99.9% by weight or more, and more preferably 99.99% by weight or more.
【０００６】また、本発明は、［４］上記不純物元素が
Ｃｕ、Ｎｉ、Ｔｉから選ばれなる上記［１］ないし上記
［３］のいずれかに記載の単結晶製造方法である。そし
て、［５］上記不純物元素の添加量が酸化物として０．
０１〜５重量％である上記［１］ないし上記［４］のい
ずれかに記載の単結晶製造方法である。上記添加不純物
元素は如何なるものにも適用できるが特に中性子シンチ
レータ用途にはＣｕ、Ｎｉ、Ｔｉなどから少なくと１つ
以上選ぶことが好ましい。上記不純物元素の添加量が酸
化物として０．０１〜５重量％である場合良好なシンチ
レータ特性が得られる。Further, the present invention is [4] the method for producing a single crystal according to any one of the above [1] to [3], wherein the impurity element is selected from Cu, Ni and Ti. Then, [5] the addition amount of the above-mentioned impurity element is 0.
The method for producing a single crystal according to any one of the above [1] to [4], which is from 0 to 5% by weight. Although the above-mentioned additional impurity element can be applied to any element, it is preferable to select at least one or more from Cu, Ni, Ti, etc., especially for neutron scintillator applications. When the added amount of the above impurity element is 0.01 to 5% by weight as an oxide, good scintillator characteristics can be obtained.
【０００７】また、本発明は、［６］上記製造工程にお
いて融液状態で撹拌を伴うことを特徴とする上記［１］
ないし上記［５］のいずれかに記載の単結晶製造方法で
ある。そして、［７］上記製造工程において融液状態で
３〜２４時間保持することを特徴とする上記［１］ない
し上記［６］のいずれかに記載の単結晶製造方法であ
る。また、［８］上記鋳型が白金または炭素で構成され
ていることを特徴とする上記［１］ないし上記［７］の
いずれかに記載の単結晶製造方法である。また、［９］
上記鋳型の断面形状が単結晶育成用るつぼの断面形状に
等しく、円形もしくは多角形であって、内寸法が単結晶
育成用るつぼの内寸法に比べて等しいか、または、小さ
いことを特徴とする上記［１］ないし上記［８］のいず
れかに記載の単結晶製造方法である。上記製造工程にお
いて融液状態で撹拌を伴なわせることで融液の均一化を
促進することができる。撹拌手段として白金製の撹拌治
具を使用することが好ましい。また、溶融後、室温（２
５℃）に取出してから溶融状態を保っている間にすばや
く撹拌し、再び１０００℃の溶融温度に保持することで
均一化が図れる。また、融液状態で３〜２４時間保持す
ることが好ましい。上記鋳型の材質として融液の濡れが
悪くかつ熱膨張係数がＬＢＯ結晶より小さいものが好ま
しい。特に白金製もしくは炭素製が好ましい。白金製の
鋳型を用いた場合、単結晶育成用原料ロッドを取出し難
い場合があるが、その場合は白金を破いて容易に取り出
すことができる。るつぼへの原料充填効率改善の観点か
ら上記鋳型はるつぼに比べて等しいかもしくは僅かに小
さな寸法にすることが好ましい。Further, the present invention [6] is characterized in that in the above manufacturing process, stirring is performed in a melt state.
To the single crystal production method according to any one of the above [5]. [7] The method for producing a single crystal according to any one of the above [1] to [6], characterized in that the melt state is maintained for 3 to 24 hours in the above production step. [8] The method for producing a single crystal according to any one of [1] to [7], wherein the template is made of platinum or carbon. Also, [9]
The cross-sectional shape of the mold is equal to the cross-sectional shape of the crucible for single crystal growth, circular or polygonal, the inner dimensions are equal to or smaller than the inner dimensions of the crucible for single crystal growth, or characterized by being small The method for producing a single crystal according to any one of [1] to [8] above. In the above manufacturing process, the homogenization of the melt can be promoted by agitation in the melt state. It is preferable to use a platinum-made stirring jig as the stirring means. Also, after melting, room temperature (2
Uniformity can be achieved by rapidly stirring after taking out at 5 ° C.) while maintaining the molten state and again holding at the melting temperature of 1000 ° C. Further, it is preferable to hold the melt state for 3 to 24 hours. It is preferable that the material of the mold is such that the wetting of the melt is poor and the coefficient of thermal expansion is smaller than that of the LBO crystal. Particularly, platinum or carbon is preferable. When a platinum mold is used, it may be difficult to take out the raw material rod for single crystal growth, but in that case, platinum can be broken and taken out easily. From the viewpoint of improving the efficiency of filling the crucible with the raw material, it is preferable that the mold has a size equal to or slightly smaller than that of the crucible.
【０００８】また、本発明は、［１０］ブリッジマン法
またはチョクラルスキー法で単結晶化する単結晶育成工
程において結晶育成速度を１時間当たり０．１〜１．０
ｍｍとすることを特徴とする上記［１］ないし上記
［９］のいずれかに記載の単結晶製造方法である。ま
た、［１１］上記単結晶育成工程において結晶育成用る
つぼが白金もしくは炭素からなり、その断面形状が円形
もしくは多角形であることを特徴とする上記［１］ない
し上記［１０］のいずれかに記載の単結晶製造方法であ
る。また、［１２］上記単結晶育成工程においてＴｉ不
純物を添加する場合、炭素製るつぼを使用し、かつ、還
元雰囲気もしくは中性雰囲気で育成することを特徴とす
る上記［１］ないし上記［１１］のいずれかに記載の単
結晶製造方法である。上記単結晶育成工程において結晶
育成速度を１時間当たり０．１〜１．０ｍｍにすること
で良質な単結晶が得られる。１．０ｍｍを超えて大きく
すると気泡欠陥が発生しやすくなる。また、育成速度は
遅い程良質の単結晶が得られやすいが、製造効率の観点
から０．１ｍｍ以上が好ましい。また、結晶育成用るつ
ぼ材料としては白金もしくは炭素が好ましい。特に、Ｔ
ｉ不純物を添加する場合は炭素製るつぼを使用し、か
つ、還元雰囲気もしくは中性雰囲気で育成することが好
ましい。空気雰囲気などの酸化性雰囲気中で育成する
と、シンチレーション特性が劣化する。その理由は明確
ではないが、還元もしくは中性雰囲気では、不純物元素
のＴｉが３価のイオンとなり易いが、酸化性雰囲気下で
は４価のイオンとなるためと推定される。Further, according to the present invention, in the single crystal growing step of [10] Bridgman method or Czochralski method, the crystal growth rate is 0.1 to 1.0 per hour.
mm is the method for producing a single crystal according to any one of the above [1] to [9]. [11] In any one of the above-mentioned [1] to [10], wherein the crucible for growing the crystal in the single-crystal growing step is made of platinum or carbon and its cross-sectional shape is circular or polygonal. It is the described method for producing a single crystal. [12] The above [1] to [11], wherein when a Ti impurity is added in the single crystal growing step, a carbon crucible is used and the growing is performed in a reducing atmosphere or a neutral atmosphere. The method for producing a single crystal according to any one of 1. A high-quality single crystal can be obtained by setting the crystal growth rate to 0.1 to 1.0 mm per hour in the single crystal growth step. If it exceeds 1.0 mm and becomes large, bubble defects are likely to occur. Further, the slower the growth rate, the easier it is to obtain a high-quality single crystal, but 0.1 mm or more is preferable from the viewpoint of production efficiency. Platinum or carbon is preferable as the crucible material for growing crystals. In particular, T
When the i impurity is added, it is preferable to use a carbon crucible and grow in a reducing atmosphere or a neutral atmosphere. When grown in an oxidizing atmosphere such as an air atmosphere, the scintillation characteristics deteriorate. The reason for this is not clear, but it is presumed that the impurity element Ti tends to become trivalent ions in a reducing or neutral atmosphere, but becomes tetravalent ions in an oxidizing atmosphere.
【０００９】[0009]
【実施例】（実施例１）ＬＢＯ原料として純度９９．９
９％の溶融固化した円盤状多結晶体を準備し、粒径が２
ｍｍ以下のサイズになるように乳鉢にて軽く粉砕した。
添加元素酸化物原料として純度９９．９９％の酸化第１
銅（Ｃｕ２Ｏ）粉末を準備した。粉砕したＬＢＯ原料１
００ｇに対して重量で０．０１５％の酸化第１銅を添加
・混合し、内径５０mm、外形７０mm高さ７０mmの白金製
るつぼに充填した。空気中で１０００℃に昇温し、１時
間後に室温（２５℃）に取出し、すばやく白金製の撹拌
棒で撹拌し、再び１０００℃で溶融し、溶融状態で３時
間保持した後、室温（２５℃）に取出し、異物（未溶解
物）が存在しないことを確認した。再び１０００℃に昇
温し、ついで白金製の鋳型（内径１９mm、長さ１６０ｍ
ｍ）に鋳込んだ。この場合、冷却固化物は容易に鋳型か
ら取出すことができなかった。そこで白金を破いて取出
し単結晶育成用原料ロッドとした。次に、３ゾーンの縦
型ブリッジマン炉を用いて単結晶育成を試みた。単結晶
育成用るつぼとして内径２０ｍｍ、高さ１６０mm、厚さ
０．３ｍｍの白金るつぼを用意した。種結晶として外径
１９．５mm、長さ３０mmの円柱状のＬＢＯ単結晶を用意
した。上記種結晶を上記るつぼに充填し、その上に単結
晶育成用原料ロッドを充填し、育成装置にセットした。
ついで３ゾーン育成炉を昇温し、定常になるのを待って
るつぼを上昇させ種結晶が約１５mm溶ける位置でるつぼ
を停止させ２４時間保持した。ついで毎時０．３ｍｍの
速度でるつぼを降下させて育成を完了した。育成した結
晶を取出した結果、透明で均一な単結晶が得られた。つ
いで育成した単結晶の上部、下部、中心部から夫々直径
２０mm、厚み５mmのサンプルを２枚合計６枚切出し研磨
した。研磨サンプルの紫外・可視領域の透過率を測定し
たところ、何れも３００ｎｍの波長で５０％以上、４０
０ｎｍ以上で９０％以上の透過率であった。また、中性
子線を照射して中性子検出感度を調べた結果、何れも従
来の単結晶に比べて一様に高い光出力が確認された。EXAMPLES Example 1 Purity 99.9 as LBO raw material
A 9% melt-solidified disk-shaped polycrystal was prepared and had a grain size of 2
Lightly crushed in a mortar so as to have a size of mm or less.
Oxide with a purity of 99.99% as a source of additive element oxide
Copper (Cu 2 O) powder was prepared. Crushed LBO raw material 1
0.015% by weight of cuprous oxide was added to and mixed with 00 g, and the mixture was filled in a platinum crucible having an inner diameter of 50 mm, an outer diameter of 70 mm and a height of 70 mm. The temperature was raised to 1000 ° C. in air, and after 1 hour, the mixture was taken out to room temperature (25 ° C.), quickly stirred with a platinum stirring rod, melted again at 1000 ° C., and held in the molten state for 3 hours, then at room temperature (25 Then, it was confirmed that no foreign matter (undissolved matter) was present. The temperature is raised again to 1000 ° C, and then a platinum mold (inner diameter 19 mm, length 160 m)
It was cast into m). In this case, the cooled solidified product could not be easily removed from the mold. Then, the platinum was broken and taken out to obtain a raw material rod for growing a single crystal. Next, an attempt was made to grow a single crystal using a 3-zone vertical Bridgman furnace. A platinum crucible having an inner diameter of 20 mm, a height of 160 mm, and a thickness of 0.3 mm was prepared as a crucible for growing a single crystal. A cylindrical LBO single crystal having an outer diameter of 19.5 mm and a length of 30 mm was prepared as a seed crystal. The seed crystal was filled in the crucible, and the raw material rod for growing a single crystal was filled on the crucible and set in the growing device.
Then, the temperature of the three-zone growth furnace was raised, the crucible waiting for the temperature to become steady was raised, and the crucible was stopped at a position where the seed crystal melted by about 15 mm, and was held for 24 hours. Then, the crucible was lowered at a speed of 0.3 mm per hour to complete the growth. As a result of taking out the grown crystal, a transparent and uniform single crystal was obtained. Then, two samples each having a diameter of 20 mm and a thickness of 5 mm were cut out from the upper, lower and central portions of the grown single crystal, and a total of 6 samples were cut and polished. When the transmittance of the polished sample in the ultraviolet / visible region was measured, it was found that both were 50% or more at a wavelength of 300 nm and 40% or less.
The transmittance was 90% or more at 0 nm or more. Moreover, as a result of irradiating the neutron beam and examining the neutron detection sensitivity, it was confirmed that the light output was uniformly higher than that of the conventional single crystal.
【００１０】（実施例２）実施例１において、酸化第1
銅の代わりに酸化ニッケル（ＮｉＯ）を用い、添加量と
して０．０２重量％とし、実施例１と同様な操作で単結
晶を作製した。評価の結果、単結晶全般に渡って均一な
結晶が得られた。また、中性子検出感度も一様に高いも
のであった。(Example 2) In Example 1, the first oxidation
Nickel oxide (NiO) was used instead of copper, the addition amount was 0.02% by weight, and a single crystal was produced by the same operation as in Example 1. As a result of the evaluation, a uniform crystal was obtained over the entire single crystal. The neutron detection sensitivity was also uniformly high.
【００１１】（実施例３）実施例１において育成速度を
１ｍｍ／ｈにして行ったところ、単結晶の1部に気泡欠
陥が見られた。しかし９０％以上は良質な単結晶であっ
た。(Example 3) When the growth rate was set to 1 mm / h in Example 1, bubble defects were found in a part of the single crystal. However, 90% or more was a high quality single crystal.
【００１２】（実施例４）実施例１において、酸化第1
銅の添加量を０．５重量％とし、同様な操作で単結晶を
作製した。評価の結果、単結晶の1部分に偏析が見られ
たが９０％以上に渡って均一な結晶が得られた。また、
中性子検出感度も一様に高いものであった。(Example 4) In Example 1, the first oxidation
A single crystal was produced by the same operation with the amount of copper added being 0.5% by weight. As a result of the evaluation, segregation was observed in one part of the single crystal, but a uniform crystal was obtained over 90% or more. Also,
The neutron detection sensitivity was also uniformly high.
【００１３】（実施例５）実施例１において、酸化第1
銅の代わりに酸化チタン（ＴｉＯ２）を用い、添加量と
して０．０２重量％とし、単結晶育成用るつぼとして、
内径２０ｍｍ、高さ１６０mm、厚さ３ｍｍの炭素製るつ
ぼを用意し、雰囲気を窒素雰囲気とした以外は実施例１
と同様な操作で単結晶を作製した。評価の結果、単結晶
全般に渡って均一な結晶が得られた。また、中性子検出
感度も一様に高いものであった。以上の実施例では、い
ずれもブリッジマン法を用いているが、公知のチョクラ
ルスキー法を適用しても育成条件を上記の範囲から大幅
に変更しない限り良質の単結晶が得られる。(Example 5) In Example 1, the first oxidation
Titanium oxide (TiO 2 ) was used instead of copper, the addition amount was 0.02% by weight, and a crucible for growing a single crystal was obtained.
Example 1 except that a carbon crucible having an inner diameter of 20 mm, a height of 160 mm and a thickness of 3 mm was prepared and the atmosphere was a nitrogen atmosphere.
A single crystal was produced by the same operation as. As a result of the evaluation, a uniform crystal was obtained over the entire single crystal. The neutron detection sensitivity was also uniformly high. In all of the above examples, the Bridgman method is used, but even if the known Czochralski method is applied, a good quality single crystal can be obtained unless the growth conditions are significantly changed from the above range.
【００１４】[0014]
【発明の効果】本発明により、光透過率の高い良質な不
純物元素添加４ホウ酸リチウム単結晶を歩留り良く製造
することができ、良質の中性子シンチレータ単結晶を得
ることができた。According to the present invention, a good quality neutron scintillator single crystal with a high light transmittance can be produced with a good yield of a good quality impurity element-doped lithium tetraborate single crystal.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ３０Ｂ 15/00 Ｃ３０Ｂ 15/00 Ｚ 15/10 15/10 Ｇ０１Ｔ 1/202 Ｇ０１Ｔ 1/202 3/06 3/06 (72)発明者 石橋 浩之 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 (72)発明者 ナチムス セングツトバン 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 (72)発明者 石井 満 東京都調布市下石原一丁目54番１号 株式 会社第一機電内 Ｆターム(参考） 2G088 FF09 GG10 JJ37 4G077 AA02 BD07 CD01 EC05 EC10 EG01 EG02 EH09 MA01 MA02 PA16 PD01 PD02 4H001 CA08 CF02 XA03 XA05 XA08 YA22 YA28 YA29 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C30B 15/00 C30B 15/00 Z 15/10 15/10 G01T 1/202 G01T 1/202 3/06 3 / 06 (72) Inventor Hiroyuki Ishibashi 48, Wadai, Tsukuba, Ibaraki Pref., Hitachi Chemical Co., Ltd. Research Institute (72) Inventor, Natimus Sengtu Toban 48, Wadai, Tsukuba, Ibaraki, Hitachi Co., Ltd. (72) Invention Person Ishii Mitsuru 1-54-1, Shimoishihara, Chofu-shi, Tokyo Stock company Dai-ichi Denki F-term (reference) 2G088 FF09 GG10 JJ37 4G077 AA02 BD07 CD01 EC05 EC10 EG01 EG02 EH09 MA01 MA02 PA16 PD01 PD02 4H001 CA08 CF02 XA03 XA05 XA05 XA05 YA22 YA28 YA29
Claims (12)
結晶の製造方法であって、次の工程を経ることを特徴と
する単結晶製造方法、 ａ）所定の組成の酸化物原料を混合し、るつぼ中で１０
００℃以上に加熱溶融する、 ｂ）融液を鋳型に注ぎ固化させて単結晶育成用原料を作
製する、 ｃ）上記単結晶育成用原料を用いてブリッジマン法また
はチョクラルスキー法で単結晶化する。1. A method for producing a Li 2 B 4 O 7 single crystal to which an impurity element is added, comprising the following steps: a) an oxide raw material having a predetermined composition Mix and mix in crucible 10
It is heated and melted at a temperature of 00 ° C. or higher, b) A melt is poured into a mold and solidified to prepare a single crystal growth raw material, and c) A single crystal is produced by the Bridgeman method or Czochralski method using the above single crystal growth raw material. Turn into.
下の粒子状Ｌｉ２Ｂ４Ｏ７化合物および粉末状添加元素
酸化物を用いることを特徴とする請求項１に記載の単結
晶製造方法。2. The method for producing a single crystal according to claim 1, wherein a particulate Li 2 B 4 O 7 compound having a particle size of about 2 mm or less and a powdered additive element oxide are used as the oxide raw material. .
以上である請求項１または請求項２に記載の単結晶製造
方法。3. The purity of the oxide raw material is 99.9% by weight.
It is above, The single crystal manufacturing method of Claim 1 or Claim 2.
選ばれなる請求項１ないし請求項３のいずれかに記載の
単結晶製造方法。4. The method for producing a single crystal according to claim 1, wherein the impurity element is selected from Cu, Ni and Ti.
０．０１〜５重量％である請求項１ないし請求項４のい
ずれかに記載の単結晶製造方法。5. The method for producing a single crystal according to claim 1, wherein the impurity element is added in an amount of 0.01 to 5% by weight as an oxide.
伴うことを特徴とする請求項１ないし請求項５のいずれ
かに記載の単結晶製造方法。6. The method for producing a single crystal according to claim 1, wherein stirring is performed in a melt state in the production process.
４時間保持することを特徴とする請求項１ないし請求項
６のいずれかに記載の単結晶製造方法。7. In the above-mentioned manufacturing process, 3 to 2 in a melt state.
The method for producing a single crystal according to claim 1, which is held for 4 hours.
いることを特徴とする請求項１ないし請求項７のいずれ
かに記載の単結晶製造方法。8. The method for producing a single crystal according to claim 1, wherein the template is made of platinum or carbon.
ぼの断面形状に等しく、円形もしくは多角形であって、
内寸法が単結晶育成用るつぼの内寸法に比べて等しい
か、または、小さいことを特徴とする請求項１ないし請
求項８のいずれかに記載の単結晶製造方法。9. The cross-sectional shape of the mold is equal to the cross-sectional shape of the crucible for growing a single crystal, and is circular or polygonal,
9. The method for producing a single crystal according to claim 1, wherein the inner size is equal to or smaller than the inner size of the crucible for growing a single crystal.
ー法で単結晶化する単結晶育成工程において結晶育成速
度を１時間当たり０．１〜１．０ｍｍとすることを特徴
とする請求項１ないし請求項９のいずれかに記載の単結
晶製造方法。10. The crystal growth rate is 0.1 to 1.0 mm per hour in the single crystal growth step of single crystallizing by the Bridgman method or the Czochralski method. 10. The method for producing a single crystal according to any of 9.
用るつぼが白金もしくは炭素からなり、その断面形状が
円形もしくは多角形であることを特徴とする請求項１な
いし請求項１０のいずれかに記載の単結晶製造方法。11. The crystal growth crucible in the single crystal growth step is made of platinum or carbon, and the cross-sectional shape thereof is circular or polygonal, according to any one of claims 1 to 10. Single crystal manufacturing method.
物を添加する場合、炭素製るつぼを使用し、かつ、還元
雰囲気もしくは中性雰囲気で育成することを特徴とする
請求項１ないし請求項１１のいずれかに記載の単結晶製
造方法。12. The method according to claim 1, wherein when the Ti impurity is added in the single crystal growth step, a carbon crucible is used and the growth is performed in a reducing atmosphere or a neutral atmosphere. A method for producing a single crystal according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007008734A (en) * | 2005-06-28 | 2007-01-18 | Chichibu Fuji Co Ltd | Lithium tetraborate single crystal and method for growing the same |
| JP2009040684A (en) * | 2002-12-25 | 2009-02-26 | Japan Science & Technology Agency | Method of manufacturing fluoride crystal, and crucible |
| CN113802176A (en) * | 2021-08-02 | 2021-12-17 | 江苏布里其曼科技股份有限公司 | Single crystal copper growth process |
-
2001
- 2001-10-24 JP JP2001326513A patent/JP4044315B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009040684A (en) * | 2002-12-25 | 2009-02-26 | Japan Science & Technology Agency | Method of manufacturing fluoride crystal, and crucible |
| JP2007008734A (en) * | 2005-06-28 | 2007-01-18 | Chichibu Fuji Co Ltd | Lithium tetraborate single crystal and method for growing the same |
| JP4746925B2 (en) * | 2005-06-28 | 2011-08-10 | 株式会社秩父富士 | Lithium tetraborate single crystal and its growth method |
| CN113802176A (en) * | 2021-08-02 | 2021-12-17 | 江苏布里其曼科技股份有限公司 | Single crystal copper growth process |
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|---|---|
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