JPH0244100A - Growth method of titanium carbide single crystal - Google Patents
Growth method of titanium carbide single crystalInfo
- Publication number
- JPH0244100A JPH0244100A JP19411588A JP19411588A JPH0244100A JP H0244100 A JPH0244100 A JP H0244100A JP 19411588 A JP19411588 A JP 19411588A JP 19411588 A JP19411588 A JP 19411588A JP H0244100 A JPH0244100 A JP H0244100A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- titanium carbide
- tic
- sintered
- bar
- 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
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000013078 crystal Substances 0.000 title claims abstract description 41
- 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 title claims description 30
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000155 melt Substances 0.000 claims abstract description 12
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 abstract description 12
- 230000008018 melting Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 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
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
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炭化チタン単結晶の育成法の改良
に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for growing titanium carbide single crystals by a melt method.
炭化チタンは融点（３１００°Ｃ）、硬度（ビッカース
硬度３０００ ｋｇ／ｗ”）が高く、各種の超硬工具や
表面保護材として広く実用に供せられている。最近では
炭化チタンの格子定数（４，３２８人）が耐環境素子材
料などとして注目されている炭化ケイ素の格子定数（４
，３５９６人）に近く、かつ高温で安定なことから、そ
の基板結晶としての利用も検討されている。そのために
は大型で高品質な単結晶が要望されている。Titanium carbide has a high melting point (3100°C) and hardness (Vickers hardness 3000 kg/w"), and is widely used in various carbide tools and surface protection materials. Recently, the lattice constant of titanium carbide ( The lattice constant of silicon carbide (4,328 people), which is attracting attention as a material for environmentally resistant devices, etc.
, 3,596 people) and is stable at high temperatures, its use as a substrate crystal is also being considered. For this purpose, large-sized, high-quality single crystals are required.
従来技術
従来の炭化チタン単結晶の育成法としては、溶液法、気
相法、固相法、融液法が知られている。BACKGROUND OF THE INVENTION Conventional methods for growing titanium carbide single crystals include a solution method, a gas phase method, a solid phase method, and a melt method.
その中で、大型単結晶を育成するには融液法が適してい
る。融液法としては引き上げ法、アークヘルヌイ法、フ
ローティングゾーン法があるが、高品質の単結晶を育成
するにはフローティングゾーン法が適している。Among them, the melt method is suitable for growing large single crystals. Melt methods include the pulling method, the Arkherny method, and the floating zone method, but the floating zone method is suitable for growing high-quality single crystals.
融液法による炭化チタン単結晶の育成法においては、従
来単結晶の育成が容易なように高純度の炭化チタン原料
が用いられてきた。しかし、この方法で育成された単結
晶中には多くの欠陥（例えば粒界密度で１０” Ｃ１１
／ＣＩ” ）が存在する欠点があった。In the method of growing titanium carbide single crystals using the melt method, high-purity titanium carbide raw materials have conventionally been used to facilitate the growth of single crystals. However, the single crystal grown by this method has many defects (for example, grain boundary density of 10"C11
/CI'').
発明の目的
本発明は前記の従来法における欠点を解消せんとするも
のであり、その目的は炭化チタン単結晶中の欠陥（特に
粒界密度）を少なくし、大型で良質の炭化チタン単結晶
を育成する方法を提供するにある。Purpose of the Invention The present invention aims to eliminate the drawbacks of the conventional methods described above, and its purpose is to reduce defects (especially grain boundary density) in titanium carbide single crystals and to produce large, high-quality titanium carbide single crystals. It is to provide a method to cultivate.
発明の構成
本発明者らは前記目的を達成すべく研究の結果、融液法
によって炭化チタン単結晶を育成するに際し、炭化チタ
ンに対しタンタルまたはニオブもしくはそれらの混合物
を０．２〜１０重量％含有させて出発原料として使用す
ると、単結晶中の中心部分で粒界がなくなり全体におけ
る粒界密度が１０”ｃｔｓ ／ ｃｍ ”と従来の値（
１０’ ｃｔｓ／ｃｍ” ）より１桁も少な（なること
を知見し得た。この知見に基づいて本発明を完成した。Structure of the Invention As a result of research to achieve the above object, the present inventors found that when growing titanium carbide single crystals by the melt method, tantalum or niobium or a mixture thereof is added in an amount of 0.2 to 10% by weight based on titanium carbide. When used as a starting material, grain boundaries disappear in the central part of the single crystal, and the grain boundary density in the whole becomes 10"cts/cm", which is the conventional value (
10'cts/cm"). The present invention was completed based on this knowledge.
本発明の要旨は、炭化チタン単結晶を融液法によって育
成する方法において、０．２〜１０重量％のタンタルま
たはニオブもしくはそれらの混合物を含有させた炭化チ
タンを出発原料として使用することを特徴とする炭化チ
タン単結晶の育成法にある。タンタルまたはニオブもし
くはこれらの混合物が０．２重量％より少なく、また１
０重量％を超えると、共に粒界密度がふえる。従って、
０．２〜１０重量％の範囲であることが必要である。The gist of the present invention is to use titanium carbide containing 0.2 to 10% by weight of tantalum, niobium, or a mixture thereof as a starting material in a method for growing titanium carbide single crystals by a melt method. A method for growing titanium carbide single crystals. less than 0.2% by weight of tantalum or niobium or mixtures thereof and 1
If it exceeds 0% by weight, the grain boundary density will increase. Therefore,
It needs to be in the range of 0.2 to 10% by weight.
本発明の方法を大型で高品位の単結晶が育成し易いフロ
ーティングゾーン法（以下ＦＺ法と言う）によって図面
に基づいて実施ＢＭＡを説明する。The BMA method of the present invention will be explained based on the drawings using the floating zone method (hereinafter referred to as FZ method), which facilitates the growth of large, high-quality single crystals.
第１図はＦＺ法育成炉の概念図で、１は上軸、１′は下
軸、２．２′はホルダー、３は焼結棒、３′は初期融帯
形成用材、４は育成した単結晶、５は融帯、６は高周波
ワークコイルを示す。Figure 1 is a conceptual diagram of the FZ method growth furnace, where 1 is the upper shaft, 1' is the lower shaft, 2.2' is the holder, 3 is the sintered rod, 3' is the material for forming the initial melt zone, and 4 is the growing material. 5 is a single crystal, 5 is a melt zone, and 6 is a high frequency work coil.
炭化チタン粉末にタンタルまたはニオブ粉末を０．２〜
１０重量％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（１０００ｋｇ／ｃ＋ａｚ）により圧
粉体を作る。この圧粉体を真空中または不活性ガス雰囲
気中で２０００°Ｃに加熱して焼結棒を得る。この際焼
結棒の組成を厳密に制御するには、焼結体の組成分析を
行い、配合組成と焼結組成の対応を行うことが好ましい
。Add tantalum or niobium powder to titanium carbide powder from 0.2 to
A 10% by weight mixture is added, a small amount of camphor is added as a binder, and a green compact is made using a rubber press (1000 kg/c+az). This green compact is heated to 2000°C in vacuum or in an inert gas atmosphere to obtain a sintered rod. At this time, in order to strictly control the composition of the sintered rod, it is preferable to analyze the composition of the sintered body and match the blended composition to the sintered composition.
得られた焼結棒３を上軸１にホルダー２を介してセット
し、その下部に初期融帯形成用材３′として炭化チタン
単結晶または焼結棒をホルダー２′を介して固定支持す
る。次に初期融帯形成用材３′の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結晶を育
成する。The obtained sintered rod 3 is set on the upper shaft 1 via a holder 2, and a titanium carbide single crystal or a sintered rod is fixedly supported under the upper shaft 1 as an initial melting zone forming material 3' via the holder 2'. Next, the end of the initial melting zone forming material 3' is melted by induction heating from the high frequency work coil 6 to form a melting zone 5.
Crystals are grown by slowly moving the upper shaft 1 and lower shaft 1' downward.
その時の育成速度は０．２〜５ｃｍ／ｈ、好ましくは０
．７〜２ｃｍ／ｈである。雰囲気は散気圧のアルゴン。The growth rate at that time is 0.2 to 5 cm/h, preferably 0.
．． It is 7 to 2 cm/h. The atmosphere was diffused pressure argon.
ヘリウム等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間及び該コイルと試料間の放電
を抑制する作用をする。An inert gas such as helium is used. This has the effect of suppressing evaporation and electric discharge between the high frequency work coil and between the coil and the sample.
本発明の方法を実施するには、前記のフローティングゾ
ーン法に限らず、融液から引き上げることによる引き上
げ法、アークベルタイ法及びゾーンレベリング法（上下
軸に固定された試料間に炭素または金属円板をはさみ、
この円板と初期融帯形成材を溶かし融帯を形成させる。In order to carry out the method of the present invention, the method is not limited to the above-mentioned floating zone method, but also the pulling method by pulling up from the melt, the arc belt tie method, and the zone leveling method (carbon or metal disks are placed between the samples fixed on the upper and lower axes). scissors,
This disk and the initial melting zone forming material are melted to form a melting zone.
）によっても行うことができる。) can also be done.
実施例１． Ｔ１Ｃｏ、ｖｓの単結晶の育成Ｔ１Ｃｏ
、＊ｓ単結晶の育成には融帯組成をＣ／Ｔｉ−１，３，
供給焼結棒の組成をＣ／Ｔｉ−１，０２に制御するのが
よいことを予備実験で確かめた。Example 1. Growth of single crystal of T1Co, vs T1Co
, *s For the growth of single crystals, the fusion zone composition is C/Ti-1,3,
Preliminary experiments have confirmed that it is best to control the composition of the supplied sintered rod to C/Ti-1,02.
炭化チタン粉末に３原子％の炭素粉及び０．５重量％の
タンタル粉末を添加し混合後、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１０φのゴム袋
に詰め円柱状にし、これを１０００て゛
気圧弁ラバープレスして圧粉体を得た。この圧粉体を黒
鉛サセプターに納め、真空中２０００°Ｃで加熱して焼
結体を得た。After adding and mixing 3 atomic % carbon powder and 0.5 weight % tantalum powder to titanium carbide powder, a small amount of camphor was added as a binder and mixed again. This mixture was packed into a rubber bag with a diameter of 10 φ to form a cylinder, and the mixture was rubber pressed with a pressure valve at 1000 m to obtain a green compact. This green compact was placed in a graphite susceptor and heated at 2000°C in vacuum to obtain a sintered body.
これをＦＺ育成炉の上軸にホルダーを介して固定し、下
軸には炭化チタン単結晶＜１００ ＞を固定し、両者の
間に炭素円盤（約０．１ ｇ）を挟んだ。This was fixed to the upper shaft of the FZ growth furnace via a holder, a titanium carbide single crystal <100> was fixed to the lower shaft, and a carbon disk (approximately 0.1 g) was sandwiched between the two.
育成炉に７気圧のヘリウムを充填後、高周波加熱により
Ｔｉｃと黒鉛円盤を溶かし初期融帯を形成し、１．５ｃ
■／ｈで下方に移動させて＜１００ ＞方向に単結晶を
育成した。After filling the growth furnace with helium at 7 atm, high-frequency heating melts the Tic and graphite disks to form an initial melt zone, and the temperature rises to 1.5 c.
A single crystal was grown in the <100> direction by moving downward at a speed of 1/h.
得られた炭化チタン単結晶は、直径０．９Ｃ１１，長さ
６Ｃ■で、分析の結果、始端部、中央部、終端部の炭素
含量はそれぞれ１９．３２ 、１９．２５ 、１９．３
７重貴簡であり、組成にしてＣ／Ｔｉ−０，９５５、０
，９５１０．９５８であった。タンタルは結晶中に均一
に分布しており、濃度は炭化チタンの蒸発のため少し増
加し、０．５３重量％であった。単結晶中の粒界密度は
（１００）面をエツチングして測定した結果、２００ｃ
ｍ ／ ｃｍ ”でタンタルを含有させない場合のそれ
に比較して一桁近く低（なった。The obtained titanium carbide single crystal had a diameter of 0.9C11 and a length of 6C■, and as a result of analysis, the carbon contents at the starting end, center, and end were 19.32, 19.25, and 19.3, respectively.
It is a 7-fold precious paper, and its composition is C/Ti-0,955,0.
,9510.958. Tantalum was uniformly distributed in the crystal, and the concentration increased slightly due to evaporation of titanium carbide to 0.53% by weight. The grain boundary density in a single crystal was measured by etching the (100) plane, and was found to be 200c.
m/cm'', which was nearly an order of magnitude lower than that without tantalum.
実施例２． ７ｔＣｏ、ｑｓ単結晶の育成出発物質は炭
化チタン粉末に３原子％の炭素粉及び０．５重量％のニ
オブ粉末を添加混合して作製した。Example 2. A starting material for growing a 7tCo,qs single crystal was prepared by adding and mixing 3 atomic % carbon powder and 0.5 weight % niobium powder to titanium carbide powder.
単結晶の育成は実施例１と同様の手順により行った。The single crystal was grown using the same procedure as in Example 1.
得られた炭化チタン単結晶は、直径０．９ｃｍ、長さ６
ｃｍで、分析の結果、始端部、中央部、終端部の炭素含
量はそれぞれ、１９．２０ 、１９．２１ 、１９．３
０重量％であり、組成にしてＣ／Ｔｉ＝０．９４８ 、
０．９４８０．９４５であった。The obtained titanium carbide single crystal had a diameter of 0.9 cm and a length of 6 cm.
cm, and as a result of analysis, the carbon content at the beginning, middle, and end was 19.20, 19.21, and 19.3, respectively.
0% by weight, and the composition is C/Ti=0.948,
It was 0.9480.945.
ニオブは結晶中に均一に分布しており、濃度は炭化チタ
ンの蒸発のため約２％増加し、０．５１重量％であった
。単結晶中の粒界密度は、（１００）面をエツチングし
て測定した結果、２５０ ｃｍ／ｃｔｔｒ”で、ニオブ
を含有させない場合のそれに比較して一桁近く低くなっ
た。Niobium was uniformly distributed in the crystal, and the concentration increased by about 2% due to evaporation of titanium carbide to 0.51% by weight. The grain boundary density in the single crystal was measured by etching the (100) plane, and was found to be 250 cm/cttr'', which is nearly an order of magnitude lower than that in the case where niobium is not included.
発明の効果
本発明の方法によると、炭化チタン単結晶中の欠陥を少
なくし、大型で良質の炭化チタン単結晶を育成すること
ができる。Effects of the Invention According to the method of the present invention, defects in a titanium carbide single crystal can be reduced, and a large, high-quality titanium carbide single crystal can be grown.
第１図はＦＺ法の概念図である。
１：上軸、 １′ ：下軸、２．２’
：ホルダー ３：炭化チタン焼結棒、３ ：初期融帯
形成用材、
４：育成した炭化チタン単結晶、
５：融帯、 ６：高周波ワークコイル。
特許出願人 科学技術庁無機材質研究所長瀬 高
信 雄
第 １
＝５５FIG. 1 is a conceptual diagram of the FZ method. 1: Upper axis, 1': Lower axis, 2.2'
: Holder 3: Sintered titanium carbide rod, 3: Initial melting zone forming material, 4: Grown titanium carbide single crystal, 5: Melting zone, 6: High frequency work coil. Patent applicant Takashi Nagase, Institute of Inorganic Materials, Science and Technology Agency
Nobu Yudai 1 = 55
Claims (1)
おいて、０．２〜１０重量％のタンタルまたはニオブも
しくはそれらの混合物を含有させた炭化チタンを出発原
料として使用することを特徴とする炭化チタン単結晶の
育成法。 ２）融液法がフローティングゾーン法である特許請求の
範囲第１項の方法。[Claims] 1) In a method for growing titanium carbide single crystals by a melt method, titanium carbide containing 0.2 to 10% by weight of tantalum or niobium or a mixture thereof is used as a starting material. A method for growing titanium carbide single crystals characterized by: 2) The method according to claim 1, wherein the melt method is a floating zone method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19411588A JPH0244100A (en) | 1988-08-03 | 1988-08-03 | Growth method of titanium carbide single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19411588A JPH0244100A (en) | 1988-08-03 | 1988-08-03 | Growth method of titanium carbide single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0244100A true JPH0244100A (en) | 1990-02-14 |
| JPH0476353B2 JPH0476353B2 (en) | 1992-12-03 |
Family
ID=16319172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19411588A Granted JPH0244100A (en) | 1988-08-03 | 1988-08-03 | Growth method of titanium carbide single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0244100A (en) |
-
1988
- 1988-08-03 JP JP19411588A patent/JPH0244100A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0476353B2 (en) | 1992-12-03 |
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