JPH0891995A - Growth method of titanium diboride single crystal - Google Patents
Growth method of titanium diboride single crystalInfo
- Publication number
- JPH0891995A JPH0891995A JP5301310A JP30131093A JPH0891995A JP H0891995 A JPH0891995 A JP H0891995A JP 5301310 A JP5301310 A JP 5301310A JP 30131093 A JP30131093 A JP 30131093A JP H0891995 A JPH0891995 A JP H0891995A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- rod
- titanium diboride
- crystal
- sintered
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 47
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910033181 TiB2 Inorganic materials 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 7
- 229910052796 boron Inorganic materials 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000008710 crystal-8 Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 17
- 239000010936 titanium Substances 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 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
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Solid Thermionic Cathode (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フローティング・ゾー
ン(ＦＺ)法による二ホウ化チタン単結晶の育成法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for growing a titanium diboride single crystal by a floating zone (FZ) method.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】二ホウ
化チタンは、現在、高温構造材や複合体の強化材として
の利用が検討されている。その単結晶の利用としては、
融点が高く、仕事関数及び蒸気圧が低いことから、長寿
命・高輝度電子放射材料として期待されている。この利
用には、純度の高い高品質大型単結晶が必要である。BACKGROUND OF THE INVENTION Titanium diboride is currently being investigated for use as a reinforcing material for high temperature structural materials and composites. The use of the single crystal is as follows.
Since it has a high melting point and a low work function and vapor pressure, it is expected as a long-life and high-brightness electron emitting material. High-quality large single crystals with high purity are required for this use.
【０００３】高純度な二ホウ化チタン単結晶の育成法と
しては、育成温度が高く、不純物が蒸発により除去され
るＦＺ法が適している。しかしながら、融点における蒸
気圧が高いことから、安定な融帯移動による育成が行わ
れておらず、試料は多結晶化しているのが実情である。The FZ method, which has a high growth temperature and removes impurities by evaporation, is suitable as a method for growing a high-purity titanium diboride single crystal. However, since the vapor pressure at the melting point is high, stable growth of the zone has not been carried out, and the sample is actually polycrystallized.
【０００４】本発明は、上記従来技術の欠点を解消し、
再現性良く欠陥の少ない良質な大型二ホウ化チタン単結
晶を得る方法を提供することを目的とするものである。The present invention solves the above-mentioned drawbacks of the prior art,
It is an object of the present invention to provide a method for obtaining a high quality large-sized titanium diboride single crystal with good reproducibility and few defects.
【０００５】[0005]
【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ＦＺ法による二ホウ化チタン
単結晶育成における育成上の問題点を調べた結果、次の
ことが判明した。In order to solve the above problems, the inventors of the present invention investigated the problems in the growth of titanium diboride single crystal by the conventional FZ method, and found the following. did.
【０００６】すなわち、二ホウ化チタン単結晶の育成温
度が２７９０℃と高く、蒸発が非常に激しく、その速度
は、例えば炭化チタン結晶の育成に比較すると約４０倍
激しいため、その蒸発物がワークコイルに付着し放電を
引き起こすこと、及び蒸発物が成長した結晶表面に付着
し、その部分から針状結晶が成長し、ヒートシンクとな
ることで単結晶化を阻害していることが判明した。That is, the growth temperature of the titanium diboride single crystal is as high as 2790 ° C., and the evaporation is very vigorous, and the rate thereof is about 40 times as vigorous as that of the growth of the titanium carbide crystal. It was found that the particles adhered to the coil to cause electric discharge, and the evaporated material adhered to the surface of the grown crystal, and needle-like crystals grew from the area, which served as a heat sink to inhibit single crystallization.
【０００７】そこで、結晶育成時の蒸発による問題を生
じさせないように、育成条件を検討した結果、蒸発速度
は雰囲気圧を上げることにより抑制し、更に育成速度を
高速にすることで相対的に蒸発速度を下げることによ
り、良質な二ホウ化チタン単結晶が得られることを見出
した。Therefore, as a result of examining the growth conditions so as not to cause a problem due to evaporation during crystal growth, the evaporation rate is suppressed by increasing the atmospheric pressure, and the evaporation rate is relatively increased by increasing the growth rate. It was found that a good quality titanium diboride single crystal can be obtained by decreasing the speed.
【０００８】すなわち、本発明は、フローティング・ゾ
ーン法により、二ホウ化チタン単結晶を育成するに際
し、雰囲気ガス圧を５気圧以上３０気圧以下とし、育成
速度を３〜１２cm／hとすることを特徴とする良質二ホ
ウ化チタン単結晶の育成法を要旨としている。That is, according to the present invention, when a titanium diboride single crystal is grown by the floating zone method, the atmospheric gas pressure is set to 5 atm or more and 30 atm or less and the growth rate is set to 3 to 12 cm / h. The main point is a method for growing high-quality titanium diboride single crystals.
【０００９】[0009]
【作用】以下に本発明を更に詳細に説明する。The present invention will be described in more detail below.
【００１０】まず、本発明において用いられる装置の一
例を図１に示す。図中、１と１′はそれぞれ上軸と下軸
の駆動部、２と２′はそれぞれ上軸と下軸、３と３′は
ホルダー、４はワークコイル、５は原料焼結棒、６は融
帯、７は単結晶、８は種結晶又は初期融帯形成用の焼結
棒である。First, an example of an apparatus used in the present invention is shown in FIG. In the figure, 1 and 1'are drive parts for upper and lower shafts, 2 and 2'respectively upper and lower shafts, 3 and 3'holders, 4 work coils, 5 raw material sintering rods, 6 Is a melt zone, 7 is a single crystal, 8 is a seed crystal or a sintered rod for forming an initial melt zone.
【００１１】試料の加熱は、ワークコイル４に高周波電
流を流すことにより、試料に誘導電流を生じさせ、その
ジュール熱により行う。このようにして、形成された融
帯６に上方より原料棒５を送り込み、下方より単結晶７
を育成する。The heating of the sample is performed by applying a high-frequency current to the work coil 4 to generate an induced current in the sample and the Joule heat of the induced current. In this way, the raw material rod 5 is fed into the thus formed melt zone 6 from above, and the single crystal 7 is fed from below.
To train.
【００１２】次に本発明による単結晶育成の手順を示
す。まず、原料の二ホウ化チタン粉末とホウ素粉末(又
はチタン金属粉末)を所定比によく混合後、結合剤とし
て少量の樟脳を加え、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
性ガス中で千数百℃に加熱し、原料焼結棒を作製する。Next, a procedure for growing a single crystal according to the present invention will be described. First, the raw materials titanium diboride powder and boron powder (or titanium metal powder) were mixed well in a predetermined ratio, and then a small amount of camphor was added as a binder, and a rubber press (2000 kg / cm 2 ) was added.
To produce a dust bar. This powder compact rod is heated to a few thousand and several hundred degrees Celsius in vacuum or in an inert gas to prepare a raw material sintered rod.
【００１３】得られた焼結棒５を上軸２にホルダー３を
介してセットし、下軸２′には種結晶(又は初期融帯形
成用の焼結棒)８をホルダーを介してセットする。両者
の５と８の間に初期融帯の組成を制御するためのホウ素
焼結体(又はチタン金属円盤)を挾む。次にホウ素焼結体
(又はチタン金属円盤)とその周辺を加熱により溶融さ
せ、融帯６を形成させ、上軸２と下軸２′を下方に移動
させて単結晶７を育成する。The sintered rod 5 thus obtained is set on the upper shaft 2 via the holder 3, and the seed crystal (or the sintered rod for forming the initial melt zone) 8 is set on the lower shaft 2'through the holder. To do. Between both 5 and 8, a boron sintered body (or a titanium metal disk) for controlling the composition of the initial zone is sandwiched. Next, boron sintered body
(Or the titanium metal disk) and its periphery are melted by heating to form a melt zone 6, and the upper shaft 2 and the lower shaft 2'are moved downward to grow a single crystal 7.
【００１４】このとき、下軸２′の移動速度、すなわ
ち、結晶育成速度は、育成中常に一定に保持する。その
移動速度範囲は３〜１２cm／hとする必要がある。好ま
しくは、６cm／h以上９cm／h以下である。この育成速度
により相対的に蒸発速度を下げることができる。At this time, the moving speed of the lower shaft 2 ', that is, the crystal growth speed is kept constant during the growth. The moving speed range needs to be 3 to 12 cm / h. It is preferably 6 cm / h or more and 9 cm / h or less. The evaporation rate can be relatively reduced by this growth rate.
【００１５】育成速度と結晶性の関係を、ヘリウム雰囲
気圧１１気圧の下で定比組成の原料棒を用いて調べた。
その結果、３cm／h以下の育成速度では結晶表面に針状
結晶が成長し安定な融帯移動(育成)が行えなかった。せ
いぜい２cmの結晶が得られる程度であった。一方、１２
cm以上の育成速度では結晶に粒界が多数入り、単結晶と
はならなかった。したがって、育成速度は３〜１２cm／
hとし、６〜９cm/ｈが再現性が良く好ましい速度であ
る。The relationship between the growth rate and crystallinity was investigated under a helium atmosphere pressure of 11 atm using a raw material rod having a stoichiometric composition.
As a result, acicular crystals grew on the crystal surface at a growth rate of 3 cm / h or less, and stable zone transfer (growth) could not be performed. At most, crystals of 2 cm were obtained. On the other hand, 12
At a growth rate of cm or more, many grain boundaries were included in the crystal, and a single crystal was not obtained. Therefore, the growth rate is 3-12 cm /
h is 6 to 9 cm / h, which is a preferable speed with good reproducibility.
【００１６】上軸２の移動速度、すなわち、原料棒の融
帯への供給速度は、原料棒の密度が低いので、それを補
償して原料棒とほぼ同じ直径をもつ単結晶が育成される
ように設定する。The moving speed of the upper shaft 2, that is, the feeding speed of the raw material rod to the melt zone is low because the density of the raw material rod is low, so that a single crystal having substantially the same diameter as the raw material rod is grown by compensating for it. To set.
【００１７】雰囲気としては、この結晶の育成では放電
が起こり易いので、イオン化ポテンシャルの最も大きい
ヘリウムガスを用いるのが好ましい。これは、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。
アルゴンガスも可能である。更に蒸発速度は、雰囲気圧
の−０.７乗に比例するので、通常の雰囲気圧である数
気圧より高く設定することが肝要である。As the atmosphere, it is preferable to use helium gas, which has the largest ionization potential, because discharge is likely to occur in the growth of this crystal. This is to prevent the discharge generated in the high frequency work coil portion.
Argon gas is also possible. Furthermore, since the evaporation rate is proportional to the -0.7 power of the atmospheric pressure, it is important to set it higher than the normal atmospheric pressure of several atmospheres.
【００１８】すなわち、育成する結晶の長さにも依存す
るが、安定に５〜６cmの結晶を育成するには、５気圧程
度でも可能ではあるが、１０気圧以上の圧力が好まし
い。一方、３０気圧以上では結晶に粒界が入り結晶性が
低下するので、雰囲気圧は５〜３０気圧の範囲とする。
雰囲気圧の制御により蒸発速度を１／３から２／３に抑
制することができる。That is, although depending on the length of the crystal to be grown, it is possible to grow a crystal of 5 to 6 cm stably at about 5 atm, but a pressure of 10 atm or more is preferable. On the other hand, when the pressure is 30 atm or more, the crystallinity deteriorates due to the inclusion of grain boundaries in the crystal, so the atmospheric pressure is set to the range of 5 to 30 atm.
By controlling the atmospheric pressure, the evaporation rate can be suppressed from 1/3 to 2/3.
【００１９】原料については、蒸発速度を相対的に低下
させるため育成速度を高くするので、単結晶化が容易な
ように高純度原料を使用するのか好ましい。特に、タン
グステンのように蒸気圧の低い不純物を含まない原料を
使用するのがよい。蒸気圧の高い不純物は、多量含まれ
ない限り、育成時に蒸発により完全に除去され、育成に
障害を与えないためである。With respect to the raw material, the growth rate is increased to lower the evaporation rate relatively, so it is preferable to use a high-purity raw material so that single crystallization is easy. In particular, it is preferable to use a raw material such as tungsten that does not contain impurities having a low vapor pressure. This is because impurities having a high vapor pressure are completely removed by evaporation during the growth and do not hinder the growth unless they are contained in a large amount.
【００２０】更に、融帯組成の結晶性への影響を調べ
た。定比組成を持つ原料棒を用いると、育成中定比組成
より少しチタン過剰な組成で蒸発するので、融帯組成
(Ｂ／Ｔi原子比)は常に２.３(±０.１)になった。すな
わち、この組成(Ｂ／Ｔi＝２.３)の融液より蒸発する蒸
発物は定比組成(Ｂ／Ｔi＝２)となっていた。Further, the influence of the zone composition on the crystallinity was investigated. When a raw material rod with a stoichiometric composition is used, it evaporates in a composition with a slight titanium excess over the stoichiometric composition during growth.
(B / Ti atomic ratio) was always 2.3 (± 0.1). That is, the evaporation material evaporated from the melt having this composition (B / Ti = 2.3) had a stoichiometric composition (B / Ti = 2).
【００２１】融帯組成は、原料棒の組成で制御する。融
帯組成をよりホウ素過剰(Ｂ／Ｔi＞２.３)にすると育成
温度(加熱電力)が下がり、再現性よく良質な結晶が得ら
れる。しかしながら、融帯組成がＢ／Ｔi＝３.１になる
と、融帯直上に形成される傘状のものが大きくなり(ワ
ークコイルを原料棒が通過しなくなり)育成が困難にな
る。その際の原料焼結棒の組成(原子比Ｂ／Ｔi)は２.２
である。The melt zone composition is controlled by the composition of the raw material rod. When the composition of the zone is made to have an excessive amount of boron (B / Ti> 2.3), the growth temperature (heating power) is lowered, and good quality crystals with good reproducibility can be obtained. However, when the zone composition becomes B / Ti = 3.1, the umbrella-shaped one formed directly above the zone becomes large (the raw material bar does not pass through the work coil) and it becomes difficult to grow. The composition (atomic ratio B / Ti) of the raw material sintered rod at that time is 2.2.
Is.
【００２２】一方、原料棒組成をチタン過剰(Ｂ／Ｔi＜
２)にすることで融帯組成をより定比に近付ける(すなわ
ち、Ｂ／Ｔi＜２.３)と、育成温度が高くなりチタンの
蒸発が増加し、育成上好ましくない。融帯組成がＢ／Ｔ
i＜２.１の領域では、良質結晶育成の再現性が悪い。し
たがって、好ましい融帯組成は２.１〜３.１の範囲であ
る。On the other hand, the composition of the raw material rod is set to be titanium excess (B / Ti
By making the composition 2), the composition of the zone becomes closer to the stoichiometric ratio (that is, B / Ti <2.3), the growth temperature becomes higher and the evaporation of titanium increases, which is not preferable for the growth. B / T composition
In the region of i <2.1, the reproducibility of good quality crystal growth is poor. Therefore, the preferable zone composition is in the range of 2.1 to 3.1.
【００２３】次に本発明の実施例を示す。Next, examples of the present invention will be described.
【実施例】【Example】
【００２４】市販の二ホウ化チタン粉末に結合剤として
樟脳を少量加え、直径１０mmのゴム袋に詰め円柱形にし
た。これを２０００kg／cm2のラバープレスを行い圧粉
体を得た。この圧粉体を真空中、１８００℃で加熱し、
直径９mm、長さ１２cm程度の焼結棒を得た。密度は約５
８％であった。A small amount of camphor was added to a commercially available titanium diboride powder as a binder, and the resulting mixture was packed in a rubber bag having a diameter of 10 mm to form a cylindrical shape. This was subjected to 2000 kg / cm 2 rubber pressing to obtain a green compact. Heating the green compact at 1800 ° C. in vacuum,
A sintered rod having a diameter of 9 mm and a length of 12 cm was obtained. Density is about 5
It was 8%.
【００２５】この焼結棒を図１に示すＦＺ育成炉の上軸
にホルダーを介して固定し、下軸には二ホウ化チタン焼
結体を固定した。両者の間に０.１g程度のホウ素焼結体
を挾み、融帯組成を制御した。育成炉に７気圧のアルゴ
ンを充填した後、高周波コイル(内径１６mm、３巻２段)
によりホウ素焼結体とその周辺部を溶かし初期融帯を形
成し、９cm／hの育成速度で下方に移動させ、全長６c
m、直径０.９cmの単結晶を育成した。融帯組成はＢ／Ｔ
i＝２.３であった。This sintered rod was fixed to the upper shaft of the FZ growth furnace shown in FIG. 1 via a holder, and the lower shaft was fixed to a titanium diboride sintered body. A boron sintered body of about 0.1 g was sandwiched between the two to control the melt zone composition. After filling the growing furnace with 7 atmospheres of argon, a high frequency coil (inner diameter 16 mm, 3 windings, 2 steps)
To melt the boron sintered body and its surroundings to form an initial melt zone, and move it downward at a growth rate of 9 cm / h to achieve a total length of 6c.
A single crystal with m and a diameter of 0.9 cm was grown. Melt zone composition is B / T
i was 2.3.
【００２６】単結晶の粒界密度については、結晶棒終端
部から(１０１０)面を切り出し、鏡面研磨の後、エッチ
ング(硝酸：塩酸＝１：３の液で１分程度)して測定し
た。その結果、結晶は厚さ１mmの多結晶の皮で囲まれる
が、その中に粒界は全く含まない良質な単結晶であっ
た。The grain boundary density of the single crystal was measured by cutting out the (1010) plane from the end of the crystal rod, mirror-polishing, and then etching (about 1 minute with a solution of nitric acid: hydrochloric acid = 1: 3). As a result, the crystal was surrounded by a 1-mm-thick polycrystalline skin, but it was a good-quality single crystal containing no grain boundaries.
【００２７】[0027]
【発明の効果】以上説明したように、本発明によれば、
亜粒界を含まない良質な大型二ホウ化チタン単結晶が得
られる。As described above, according to the present invention,
A good quality large titanium diboride single crystal containing no subgrain boundaries can be obtained.
【図１】本発明に用いられる単結晶育成装置の一例を示
す説明図である。FIG. 1 is an explanatory diagram showing an example of a single crystal growth apparatus used in the present invention.
１ 上軸駆動部 １′ 下軸駆動部 ２ 上軸 ２′ 下軸 ３ ホルダー ３′ ホルダー ４ ワークコイル ５ 原料焼結棒 ６ 融帯 ７ 単結晶 ８ 種結晶又は初期融帯形成用の焼結棒 1 Upper shaft drive unit 1'Lower shaft drive unit 2 Upper shaft 2'Lower shaft 3 Holder 3'Holder 4 Work coil 5 Raw material sintering rod 6 Melt zone 7 Single crystal 8 Sinter rod for forming seed crystal or initial zone
Claims (2)
ウ化チタン単結晶を育成するに際し、雰囲気ガス圧を５
気圧以上３０気圧以下とし、育成速度を３〜１２cm／h
とすることを特徴とする良質二ホウ化チタン単結晶の育
成法。1. When growing a titanium diboride single crystal by the floating zone method, the atmospheric gas pressure is set to 5
The pressure is higher than 30 atm and the growth rate is 3-12 cm / h.
And a method for growing a high-quality titanium diboride single crystal characterized by:
ウムガスを用いる請求項１に記載の方法。2. The method according to claim 1, wherein argon gas or helium gas is used as the atmospheric gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5301310A JP2580523B2 (en) | 1993-11-05 | 1993-11-05 | Growth method of titanium diboride single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5301310A JP2580523B2 (en) | 1993-11-05 | 1993-11-05 | Growth method of titanium diboride single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0891995A true JPH0891995A (en) | 1996-04-09 |
| JP2580523B2 JP2580523B2 (en) | 1997-02-12 |
Family
ID=17895314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5301310A Expired - Lifetime JP2580523B2 (en) | 1993-11-05 | 1993-11-05 | Growth method of titanium diboride single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2580523B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089596A (en) * | 2001-09-11 | 2003-03-28 | National Institute For Materials Science | Boride single crystal and substrate for semiconductor formation |
-
1993
- 1993-11-05 JP JP5301310A patent/JP2580523B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089596A (en) * | 2001-09-11 | 2003-03-28 | National Institute For Materials Science | Boride single crystal and substrate for semiconductor formation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2580523B2 (en) | 1997-02-12 |
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