JPH0688874B2 - Lanthanum boride single crystal and its growth method - Google Patents
Lanthanum boride single crystal and its growth methodInfo
- Publication number
- JPH0688874B2 JPH0688874B2 JP29135490A JP29135490A JPH0688874B2 JP H0688874 B2 JPH0688874 B2 JP H0688874B2 JP 29135490 A JP29135490 A JP 29135490A JP 29135490 A JP29135490 A JP 29135490A JP H0688874 B2 JPH0688874 B2 JP H0688874B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- lanthanum boride
- boride
- rare earth
- raw material
- 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
- 239000013078 crystal Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 36
- 229910052746 lanthanum Inorganic materials 0.000 title claims description 23
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims description 23
- 239000002994 raw material Substances 0.000 claims description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Solid Thermionic Cathode (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は融液法による硼化ランタン(LaB6)系単結晶の育
成法に関する。TECHNICAL FIELD The present invention relates to a method for growing a lanthanum boride (LaB 6 ) based single crystal by a melt method.
（従来の技術及び解決しようとする課題） 硼化ランタン単結晶は、現在、寿命の長い高輝度電子放
射材料として、走査型電子顕微鏡や電子描画装置などに
利用されている。この電子放射材料として用いる場合、
純度の高い高品質単結晶が必要である。(Prior Art and Problems to be Solved) A lanthanum boride single crystal is currently used as a high-brightness electron emitting material having a long life in a scanning electron microscope, an electron drawing apparatus, or the like. When used as this electron emitting material,
High quality single crystals with high purity are required.
硼化ランタン単結晶の育成法としては、溶液法、気相
法、融液法などが知られているが、高純度な単結晶を育
成するには、育成温度が高い融液法が適している。As a method for growing a lanthanum boride single crystal, a solution method, a vapor phase method, a melt method and the like are known, but a melt method with a high growth temperature is suitable for growing a high-purity single crystal. There is.
融液法としては、アークベルヌーイ法、フローテイング
・ゾーン法、ペヂェスタル法があるが、高品質単結晶を
育成するにはフローテイング・ゾーン法が適している。As the melt method, there are the Arc Bernoulli method, the floating zone method, and the pedestal method, but the floating zone method is suitable for growing a high quality single crystal.
従来、融液法による硼化ランタン単結晶の育成法におい
ては、単結晶の純度を高くするために、高純度の硼化ラ
ンタン原料が用いられてきた。しかし、この方法により
育成された単結晶中には多くの欠陥（例えば、粒界密度
で103cm/cm2）が存在するという欠点があった。このた
め、高品質な部分を選び、電子放射材として使用せざる
を得ないのが実情である。Conventionally, in the method for growing a lanthanum boride single crystal by the melt method, a high-purity lanthanum boride raw material has been used in order to increase the purity of the single crystal. However, there is a defect that many defects (eg, 10 3 cm / cm 2 in grain boundary density) are present in the single crystal grown by this method. Therefore, in reality, it is unavoidable to select a high quality portion and use it as an electron emitting material.
本発明は、上記従来技術の欠点を解消して、欠陥のない
良質な硼化ランタン系単結晶を提供することを目的とす
るものである。An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a good quality lanthanum boride single crystal free of defects.
（課題を解決するための手段） 前記課題を解決するため、本発明者らは、従来の融液法
において高純度の硼化ランタン原料を用いても単結晶中
に多くの欠陥が存在することに鑑みて、原料として、硼
化ランタン以外の材料を含有させることについて試み
た。その結果、硼化ランタンに硼化希土類（PrB6、NdB6、
SmB6、GdB6及びそれらの混合物）を含有させた材料を使
用したところ、単結晶中の粒界が減少することを見い出
した。特に、直径1cmの単結晶を育成する場合、20モル
％以上の上記硼化希土類を含有させると、すべての場合
で、全く粒界を含まない完全性の高い単結晶を育成でき
ることを知見し、ここに本発明をなしたものである。(Means for Solving the Problems) In order to solve the above problems, the present inventors have found that many defects exist in a single crystal even when a high-purity lanthanum boride raw material is used in a conventional melt method. In view of the above, an attempt was made to incorporate a material other than lanthanum boride as a raw material. As a result, lanthanum boride and rare earth boride (PrB 6 , NdB 6 ,
It has been found that the use of materials containing SmB 6 , GdB 6 and their mixtures) reduces the grain boundaries in the single crystal. In particular, in the case of growing a single crystal having a diameter of 1 cm, it was found that when containing 20 mol% or more of the rare earth boride, in all cases, it is possible to grow a highly complete single crystal containing no grain boundaries, The present invention has been made here.
すなわち、本発明は、化学式(La1-xMx)B6（但し、ＭはP
r、Nd、Sm、Gdで、0.01≦ｘ≦0.50）を有することを特
徴とする硼化ランタン系単結晶を要旨とするのである。That is, the present invention provides a compound represented by the chemical formula (La 1-x M x ) B 6 (where M is P
The gist is a lanthanum boride-based single crystal characterized in that r, Nd, Sm, and Gd have 0.01 ≦ x ≦ 0.50).
また、その製造法は、硼化ランタン系単結晶を融液法に
よって育成するに際し、原料として、１〜50モル％の硼
化希土類、又はそれら希土類の酸化物、水酸化物、塩化
物などを六硼化物換算で１〜50モル％含有する硼化ラン
タンを使用することを特徴とするものである。Further, the production method thereof, when growing a lanthanum boride-based single crystal by a melt method, as a raw material, 1 to 50 mol% rare earth boride, or oxides, hydroxides, chlorides or the like of these rare earths. A lanthanum boride content of 1 to 50 mol% in terms of hexaboride is used.
以下に本発明を更に詳述する。The present invention will be described in more detail below.
（作用） 本発明において用いられる単結晶育成法は融液法であ
り、前述の如く種々の方法が可能であるが、フローテイ
ング・ゾーン法（以下、「FZ法」という）は、大型で高
品位の単結晶が育成し易いので、好ましい。(Function) The single crystal growing method used in the present invention is a melt method, and various methods are possible as described above. However, the floating zone method (hereinafter, referred to as “FZ method”) is large and high. It is preferable because a single crystal of high quality is easily grown.
第１図はFZ法育成炉の概念図であり、１は上軸、１′は
下軸、２、２′はホルダー、３は焼結棒（原料）、３′
は初期融帯保持用焼結棒又は種結晶、４は育成した単結
晶、５は融帯、６は高周波ワークコイルである。Fig. 1 is a conceptual diagram of the FZ growth reactor, where 1 is an upper shaft, 1'is a lower shaft, 2'is a holder, 3 is a sintered rod (raw material), 3 '.
Is a sintered rod or seed crystal for holding the initial melt zone, 4 is a grown single crystal, 5 is a melt zone, and 6 is a high-frequency work coil.
原料としては、硼化ランタン粉末に硼化希土類粉末を１
〜50モル％混合し、これに結合剤として少量の樟脳を加
えて、ラバープレス（2000kg/cm2）により圧粉棒を作製
する。この圧粉棒を真空中又は不活性ガス雰囲気中で千
数百℃に加熱して、原料焼結棒を作製する。Lanthanum boride powder and rare earth boride powder are used as raw materials.
Mixing up to 50 mol%, adding a small amount of camphor as a binder to this, and making a dust bar by a rubber press (2000 kg / cm 2 ). This powder compact rod is heated to a few thousand and several hundred degrees Celsius in a vacuum or in an inert gas atmosphere to prepare a raw material sintered rod.
なお、原料焼結棒としては、上記の如く硼化希土類粉末
を使用する以外に、それら希土類の酸化物、水酸化物、
塩化物などと硼素を、六硼化物換算で１〜50モル％含有
させることも可能である。As the raw material sintered rod, in addition to the use of rare earth boride powder as described above, oxides of these rare earths, hydroxides,
It is also possible to contain chloride and the like and boron in an amount of 1 to 50 mol% in terms of hexaboride.
得られた原料焼結棒３を上軸１にホルダー２を介してセ
ットし、下軸１′には、初期融帯保持用の焼結棒又は種
結晶３′をホルダー２′を介してセットする。次に原料
焼結棒３の下端を高周波ワークコイル６からの誘導加熱
により溶融させ、融帯５を形成させ、上軸１と下軸１′
をゆっくり下方に移動させて単結晶４を育成する。The obtained raw material sintered rod 3 is set on the upper shaft 1 via the holder 2, and the lower rod 1'is set on the lower shaft 1'with the sintered rod or seed crystal 3'for holding the initial zone through the holder 2 '. To do. Next, the lower end of the raw material sintering rod 3 is melted by induction heating from the high frequency work coil 6 to form a fusion zone 5, and the upper shaft 1 and the lower shaft 1 '
Is slowly moved downward to grow the single crystal 4.
その時の育成速度は0.2〜5cm/h、好ましくは0.2〜2cm/h
である。雰囲気としては数気圧のアルゴン又はヘリウム
などの不活性ガスが用いられる。これは、蒸発の抑制と
高周波ワークコイル部分で発生する放電を防止するため
である。The growth rate at that time is 0.2 to 5 cm / h, preferably 0.2 to 2 cm / h.
Is. An inert gas such as argon or helium having a pressure of several atmospheres is used as the atmosphere. This is to suppress evaporation and to prevent discharge generated in the high frequency work coil portion.
かくして育成される単結晶は、化学式(La1-xMx)B6（但
し、ＭはPr、Nd、Sm、Gdで、0.01≦ｘ≦0.50）を有する
硼化ランタン系単結晶である。ここで、ｘが0.01未満で
は硼化物を添加した効果が殆ど見られない。すなわち、
単結晶中の粒界密度の減少が実験誤差の中に含まれてし
まう程度である。一方、硼化物を多量に添加すると、単
結晶が脆くなる。すなわち、ｘ＞0.50の組成領域では、
単結晶中にクラックが発生することがあり、実用上好ま
しくない。The single crystal thus grown is a lanthanum boride-based single crystal having the chemical formula (La 1-x M x ) B 6 (where M is Pr, Nd, Sm, and Gd, 0.01 ≦ x ≦ 0.50). Here, when x is less than 0.01, the effect of adding boride is hardly seen. That is,
The reduction of the grain boundary density in the single crystal is included in the experimental error. On the other hand, when a large amount of boride is added, the single crystal becomes brittle. That is, in the composition region of x> 0.50,
Cracks may occur in the single crystal, which is not practically preferable.
溶融方による育成法としては、上述の高周波加熱による
FZ法に限らず、赤外線集中加熱によるFZ法も可能であ
り、更には、FZ法以外に、融液より引き上げる引き上げ
法、アーク・ベルヌイ法。ペヂェスタル法も可能であ
り、それぞれの方法に適した原料調整を行う。As a growing method by the melting method, the above-mentioned high frequency heating is used.
The FZ method is not limited to the FZ method, and the FZ method by infrared concentrated heating is also possible. Further, in addition to the FZ method, the pulling method of pulling from the melt, the arc-Bernui method. The pedestal method is also possible, and the raw materials are adjusted to suit each method.
次に本発明の実施例を示す。Next, examples of the present invention will be described.
（実施例） 硼化ランタン粉末に所定比（ｘ＝0.02、0.1、0.2、0.
3、0.5）の硼化希土類粉末を添加し混合した後、結合剤
として樟脳を少量加えて再び混合した。この混合物を直
径12mmのゴム袋に詰めて円柱状にし、これを2000kg/cm2
のラバープレスして圧粉棒を得た。この圧粉棒を真空
中、1800℃で加熱して焼結棒を得た。(Example) To a lanthanum boride powder, a predetermined ratio (x = 0.02, 0.1, 0.2, 0.
3, 0.5) rare earth boride powder was added and mixed, and then a small amount of camphor as a binder was added and mixed again. This mixture was packed in a rubber bag with a diameter of 12 mm and made into a columnar shape, which was 2000 kg / cm 2
Was pressed with a rubber to obtain a dust bar. This dust bar was heated at 1800 ° C. in vacuum to obtain a sintered bar.
この焼結棒を第１図に示すFZ育成炉の上軸にホルダーを
介して固定し、下軸には(La1-xMx)B6単結晶を固定し
た。育成炉に７気圧のアルゴンを充填した後、高周波コ
イルにより原料焼結棒の下端を溶かして初期融帯を形成
し、1cm/hで下方に移動させて、〈100〉方位に単結晶を
育成した。The sintered rod was fixed to the upper shaft of the FZ growth furnace shown in FIG. 1 through a holder, and the (La 1-x M x ) B 6 single crystal was fixed to the lower shaft. After filling the growth furnace with argon at 7 atm, the lower end of the raw material sintering rod was melted by the high frequency coil to form the initial melt zone, which was moved downward at 1 cm / h, and the single crystal was grown in the <100> direction. did.
得られた単結晶は、直径1cm、長さ7cmであった。蒸発に
よる組成変化を、原料焼結棒と結晶棒終端部の分析から
調べたところ、添加した希土類の原子番号が大きくなる
程、蒸発による組成変化が大きくなった。例えば、30モ
ル％の希土類硼化物を添加した場合、Prでは１モル％、
Ndでは２モル％、Smでは４モル％、Gdでは５モル％が蒸
発により失われていた。The obtained single crystal had a diameter of 1 cm and a length of 7 cm. The composition change due to evaporation was examined by analysis of the raw material sintered rod and the end portion of the crystal rod. As the atomic number of the added rare earth increased, the composition change due to evaporation increased. For example, when 30 mol% of rare earth boride is added, Pr is 1 mol%,
2 mol% of Nd, 4 mol% of Sm, and 5 mol% of Gd were lost by evaporation.
育成した単結晶の粒界密度は、結晶終端部の（100）面
を切り出し、鏡面研磨した後、エッチング（硝酸：水＝
1:3の液で２〜３分）して測定した結果、第２図〜第５
図に示すように、硼化ランタンに硼化希土類を添加して
ゆくと粒界密度が減少し、30モル％以上添加すると粒界
が観察できなくなった。しかしながら、添加した希土類
の原子番号が大きい程、エッチピットが〈100〉方位に
幅広く並ぶ傾向が強くなった。単結晶中に粒界が存在し
ない領域は、育成する結晶の直径に依存し、細くなる
程、広くなった。The grain boundary density of the grown single crystal was determined by cutting out the (100) plane at the crystal end, mirror-polishing, and then etching (nitric acid: water =
2 to 5 minutes with a 1: 3 solution, and the results are shown in Figs.
As shown in the figure, when the rare earth boride was added to the lanthanum boride, the grain boundary density decreased, and when 30 mol% or more was added, the grain boundary could not be observed. However, the larger the atomic number of the added rare earth, the stronger the tendency for the etch pits to be widely arranged in the <100> direction. The region where grain boundaries do not exist in the single crystal depends on the diameter of the grown crystal and becomes wider as it becomes thinner.
（発明の効果） 以上詳述したとおり、本発明によれば、欠陥のない良質
な硼化ランタン系単結晶を提供することができ、敢えて
高純度硼化ランタン原料を使用しなくともよいので経済
的である。(Effects of the Invention) As described in detail above, according to the present invention, it is possible to provide a high-quality lanthanum boride-based single crystal free from defects, and it is not necessary to use a high-purity lanthanum boride raw material, which is economical. Target.
【図面の簡単な説明】 第１図はFZ育成炉の一例を説明する図、 第２図〜第５図はそれぞれ実施例で得られた単結晶の粒
界密度と硼化希土類添加量の関係を示す図である。 １……上軸、１′……下軸、２、２′……ホルダー、３
……焼結棒（原料）、３′……初期融帯保持用焼結棒又
は種結晶、４……育成した単結晶、５……融帯、６……
高周波ワークコイル。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram for explaining an example of an FZ growth furnace, and FIGS. 2 to 5 are the relationships between the grain boundary density of single crystals obtained in Examples and the amount of rare earth boride added. FIG. 1 ... Upper shaft, 1 '... Lower shaft, 2, 2' ... Holder, 3
...... Sintered rod (raw material), 3 '... Sintered rod or seed crystal for holding the initial zone, 4 ... Grown single crystal, 5 ... Zone, 6 ...
High frequency work coil.
Claims (3)
m、Gdで、0.01≦ｘ≦0.50）を有することを特徴とする
硼化ランタン系単結晶。1. A chemical formula (La 1-x M x ) B 6 (where M is Pr, Nd, S
A lanthanum boride-based single crystal having m and Gd of 0.01 ≦ x ≦ 0.50).
成するに際し、原料として、１〜50モル％の硼化希土類
（但し、PrB6、NdB6、SmB6、GbB6及びそれらの混合物）を
含有する硼化ランタンを使用することを特徴とする硼化
ランタン系単結晶の育成法。2. When growing a lanthanum boride-based single crystal by a melt method, as a raw material, 1 to 50 mol% of a rare earth boride (however, PrB 6 , NdB 6 , SmB 6 , GbB 6 and mixtures thereof) is used. ). A method for growing a lanthanum boride-based single crystal, which comprises using lanthanum boride containing a).
酸化物、水酸化物又は塩化物と、硼素を所定比に混合し
たものを用いる請求項２に記載の方法。3. The method according to claim 2, wherein, in place of the rare earth boride, a mixture of rare earth oxide, hydroxide or chloride and boron in a predetermined ratio is used.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29135490A JPH0688874B2 (en) | 1990-10-29 | 1990-10-29 | Lanthanum boride single crystal and its growth method |
| US07/706,197 US5238527A (en) | 1990-07-19 | 1991-05-28 | Lanthanum boride type single crystal and method for growing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29135490A JPH0688874B2 (en) | 1990-10-29 | 1990-10-29 | Lanthanum boride single crystal and its growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04164897A JPH04164897A (en) | 1992-06-10 |
| JPH0688874B2 true JPH0688874B2 (en) | 1994-11-09 |
Family
ID=17767848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29135490A Expired - Lifetime JPH0688874B2 (en) | 1990-07-19 | 1990-10-29 | Lanthanum boride single crystal and its growth method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688874B2 (en) |
-
1990
- 1990-10-29 JP JP29135490A patent/JPH0688874B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04164897A (en) | 1992-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2010079655A1 (en) | Reaction vessel for growing single crystal, and method for growing single crystal | |
| US5238527A (en) | Lanthanum boride type single crystal and method for growing the same | |
| JPH0688874B2 (en) | Lanthanum boride single crystal and its growth method | |
| JPH0686359B2 (en) | Rare earth boride single crystal and its growth method | |
| JPH0686358B2 (en) | Cerium boride single crystal and its growth method | |
| JPH0686357B2 (en) | Lanthanum boride single crystal and its growth method | |
| JP3755021B2 (en) | Growth method of rare earth hexaboride single crystals | |
| US5493984A (en) | Terbium aluminate and method for its production | |
| US6027670A (en) | Rare earth hexaboride electron-emitting material | |
| US5336362A (en) | Method for preparing yttrium 66 boride crystal for soft x-ray monochromator | |
| JP2730674B2 (en) | Growth method of rare earth hexaboride single crystals | |
| JP2949212B2 (en) | Growth method of lanthanum hexaboride single crystal | |
| JP2642882B2 (en) | Growth method of tungsten diboride single crystal | |
| Sinnema et al. | Crystal growth of R2T17 and R2Fe14B intermetallics (R= rare earth, T= Co, Fe) | |
| Tsai et al. | Growth of (FexMg1− x) 2SiO4 single crystals by the double pass floating zone method | |
| EP0018111B1 (en) | Method of producing ferrite single crystals | |
| JPH04198093A (en) | Method for growing lanthanum boride single crystal | |
| US5900054A (en) | Method of manufacturing oxide single crystal | |
| JP2580523B2 (en) | Growth method of titanium diboride single crystal | |
| JPH0751480B2 (en) | Method for growing lanthanum hexaboride single crystal | |
| JPS5812240B2 (en) | Method for producing hafnium carbide crystals | |
| JP2997762B2 (en) | Growth method of calcium hexaboride crystals | |
| JPH05319991A (en) | Method for growing lanthanum hexaboride single crystal | |
| JP2929007B1 (en) | Method for growing single crystal of group Va diboride | |
| JPH0672789A (en) | Production of compound single crystal, compound single crystal and optical laser oscillator or scintillator using the single crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |