JPH05138000A - Method for synthesizing diamond single crystal - Google Patents
Method for synthesizing diamond single crystalInfo
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- JPH05138000A JPH05138000A JP30181391A JP30181391A JPH05138000A JP H05138000 A JPH05138000 A JP H05138000A JP 30181391 A JP30181391 A JP 30181391A JP 30181391 A JP30181391 A JP 30181391A JP H05138000 A JPH05138000 A JP H05138000A
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- diamond
- powder
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、装飾用途や光学部品な
どに用いられる無色で透明なダイヤモンド単結晶の合成
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing colorless and transparent diamond single crystals used for decorative purposes and optical parts.
【０００２】[0002]
【従来の技術】現在市販されている装飾用ダイヤモンド
としては、主に南アフリカ、ソビエト連邦より産出され
るものの中から、無色透明で内部欠陥の少ないものを選
別して用いている。天然装飾用ダイヤモンドは宝石の中
でも最も販売量が多い。また、ダイヤモンドを用いた光
学部品として、レーザー窓やＩＲアンビルセルなどがあ
るが、いずれも天然原石の中から赤外領域に光の吸収の
ない透明なダイヤモンド（IIａ型と呼ばれる）が選ばれ
て用いられている。しかし、透明無色な原石の産出は極
めて少なく、安定供給や価格に問題がある。2. Description of the Related Art As decorative diamonds currently on the market, colorless and transparent ones having few internal defects are selected from those mainly produced in South Africa and the Soviet Union. Natural ornamental diamonds are the most sold gemstones. Moreover, there are laser windows, IR anvil cells, etc. as optical parts using diamond, but in each case, transparent diamond (called type IIa) which does not absorb light in the infrared region is selected from natural rough stones. It is used. However, the production of transparent and colorless rough stones is extremely low, and there are problems with stable supply and prices.
【０００３】一方、人工合成によるダイヤモンドは通
常、超高圧高温下で合成する際に、溶媒中の窒素が結晶
格子内に取り込まれるために黄色く着色してしまうが、
溶媒中に窒素ゲッターを添加することにより無色透明の
ダイヤモンドを得ることができる。この窒素ゲッターと
しては、たとえば、The Journal of Physical Chemistr
y, vol.75, No.12 (1971) p1838 に記載されているよう
に、Ａｌがよく知られている。具体的には、米国特許第
４０３４０６６号明細書において、Ｆｅ溶媒にＡｌを３
〜５重量％添加することにより宝石級の無色透明なダイ
ヤモンド単結晶が得られたと記載されている。Ａｌ以外
の窒素ゲッターを用いた例として、たとえば無機材質研
究所研究報告書第３９号（1984）第１６〜１９頁に、Ｔ
ｉやＺｒを溶媒金属に添加することにより結晶中の窒素
が除去されたという報告がある。On the other hand, artificially synthesized diamond is usually colored yellow when it is synthesized under ultrahigh pressure and high temperature because nitrogen in the solvent is taken into the crystal lattice.
A colorless and transparent diamond can be obtained by adding a nitrogen getter to the solvent. Examples of this nitrogen getter include the Journal of Physical Chemistr.
Al is well known as described in y, vol.75, No.12 (1971) p1838. Specifically, in U.S. Pat. No. 4,034,066, the Fe solvent contains 3% Al.
It is described that a gem-grade colorless and transparent diamond single crystal was obtained by adding -5% by weight. As an example using a nitrogen getter other than Al, see, for example, Research Report of the Institute for Inorganic Materials No. 39 (1984) pp. 16-19, T.
There is a report that nitrogen in crystals was removed by adding i or Zr to a solvent metal.
【０００４】[0004]
【発明が解決しようとする課題】しかし、特に無色透明
の合成ダイヤモンドは合成コストが天然装飾用ダイヤモ
ンドよりはるかに高くなるため、工業生産は行われてい
ない。この理由は、合成には高価で特殊な装置が必要で
ある上に、Ａｌなどを窒素ゲッターとして添加した場
合、その添加量の増加に従って、溶媒が結晶中に取り込
まれて（以下インクルージョン）不良結晶となることが
多くなるため、良質な結晶とするためには成長速度を大
幅に下げる必要があるからである。特にＴｉやＺｒを窒
素ゲッターとして用いた場合は、合成途中に溶媒中に生
成した炭化物（ＴｉＣ，ＺｒＣなど、カ−バイドとも称
する）が結晶中に取り込まれるため、完全な結晶は得ら
れなくなる。However, since the synthetic cost of synthetic colorless and transparent diamond is much higher than that of natural ornamental diamond, industrial production is not carried out. This is because the synthesis requires an expensive and special device, and when Al or the like is added as a nitrogen getter, the solvent is taken into the crystal (inclusion) and the defective crystal is added as the addition amount increases. This is because the growth rate must be significantly reduced in order to obtain good quality crystals. In particular, when Ti or Zr is used as a nitrogen getter, a carbide (TiC, ZrC, etc., also referred to as a carbide) generated in the solvent during the synthesis is taken into the crystal, and a complete crystal cannot be obtained.
【０００５】本発明者等が行った実験の結果によると、
窒素ゲッターとしてＡｌを用いて溶媒金属に均一混合し
た場合、無色透明なダイヤモンド結晶を合成するために
は、その添加量は溶媒に対し少なくとも４重量％必要で
あるが、この場合インクルージョンの巻き込みなしに結
晶成長させるためには、成長速度を１ｍｇ／ｈｒ以下に
する必要がある。この場合、たとえば１カラット（２０
０ｍｇ）の結晶を合成するには２００時間の合成時間を
要し、製造コストは膨大なものとなる。また、Ｔｉ、Ｚ
ｒなど、Ａｌより窒素との反応性の高い物質を窒素ゲッ
ターとして溶媒に均一添加した場合、添加量は１重量％
でも無色透明な結晶となるが、成長速度を大幅に低下さ
せたとしてもインクルージョン（カーバイド）が多く、
良質な結晶は殆ど得られない。本発明はこのような問題
を解決し、窒素ゲッターを加えて無色透明でしかもイン
クルージョのない良質なダイヤモンド単結晶を容易に製
造できる新規な製法の提供を目的とするものである。According to the results of experiments conducted by the present inventors,
When Al is used as a nitrogen getter and homogeneously mixed with a solvent metal, in order to synthesize a colorless and transparent diamond crystal, the addition amount is required to be at least 4% by weight with respect to the solvent, but in this case, without inclusion of inclusions. In order to grow crystals, the growth rate needs to be 1 mg / hr or less. In this case, for example, 1 carat (20
It takes 200 hours to synthesize 0 mg of crystals, and the production cost is enormous. Also, Ti, Z
When a substance such as r having a higher reactivity with nitrogen than Al is uniformly added to the solvent as a nitrogen getter, the addition amount is 1% by weight.
However, it becomes a colorless and transparent crystal, but even if the growth rate is significantly reduced, there are many inclusions (carbides),
Almost no good crystals are obtained. It is an object of the present invention to solve such a problem and to provide a new production method by which a nitrogen getter can be added to easily produce a colorless and transparent high-quality diamond single crystal without inclusion.
【０００６】[0006]
【課題を解決するための手段】本発明は、温度差法によ
るダイヤモンド単結晶合成において、窒素ゲッターとし
てＡｌ−Ｘ系金属間化合物（ＸはＴｉ、Ｚｒ、Ｈｆ、
Ｖ、Ｎｂ及びＴａから選ばれる元素を表す）を添加した
溶媒金属を用いることを特徴とするものである。本発明
において、前記溶媒金属としては、Ｆｅ、Ｃｏ、Ｎｉ、
Ｍｎ及びＣｒの中から選ばれる一種もしくは二種以上か
らなる金属であり、０．１〜６．０重量％の炭素を含む
ものが特に好ましい。また、本発明における前記窒素ゲ
ッターとして添加するＡｌ−Ｘ系金属間化合物（ＸはＴ
ｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ及びＴａから選ばれる元素を
表す）の添加量は、前記溶媒金属に対して０．１〜５重
量％であることが特に好ましい。According to the present invention, an Al-X intermetallic compound (X is Ti, Zr, Hf,
A solvent metal added with (representing an element selected from V, Nb and Ta) is used. In the present invention, as the solvent metal, Fe, Co, Ni,
A metal composed of one or more selected from Mn and Cr, and particularly preferably containing 0.1 to 6.0% by weight of carbon. Further, the Al—X based intermetallic compound (X is T is added as the nitrogen getter in the present invention.
The addition amount of i, Zr, Hf, V, Nb and Ta) is particularly preferably 0.1 to 5% by weight based on the solvent metal.
【０００７】上記の問題を解決するため、本発明者ら
は、添加する窒素ゲッターについて種々検討したとこ
ろ、溶媒中にＡｌを添加すると同時に、Ｔｉ、Ｚｒ、Ｈ
ｆなどの窒素との反応性の高い元素を添加すれば、窒素
の除去効率が上がり、またＴｉＣやＺｒＣなど合成中に
溶媒中に生成した炭化物が結晶に取り込まれることが少
なくなり、比較的はやい成長速度でも良質なIIａタイプ
のダイヤモンド結晶が得られることを見いだした。さら
に検討を重ねたところ、ＡｌとＴｉからなる金属間化合
物などを窒素ゲッターとして用いれば、さらに窒素の除
去効率が上がり、またＴｉＣなどの炭化物の生成が大幅
に抑えられ、インクルージョンの混入がかなり少なくな
ることがわかった。その結果、従来の２倍程度の速い成
長速度でも良質なIIａ結晶が得られることを確認し、本
発明を完成するに至った。In order to solve the above problems, the present inventors have made various studies on the nitrogen getter to be added, and as a result of adding Al to the solvent, Ti, Zr, H
By adding an element having a high reactivity with nitrogen such as f, the removal efficiency of nitrogen is increased, and the carbides such as TiC and ZrC produced in the solvent during the synthesis are less likely to be incorporated into the crystal, which is relatively quick. It has been found that a good quality IIa type diamond crystal can be obtained even at the growth rate. Upon further study, if an intermetallic compound composed of Al and Ti is used as a nitrogen getter, the removal efficiency of nitrogen is further increased, the formation of carbides such as TiC is significantly suppressed, and the inclusion of inclusions is considerably reduced. I found out. As a result, it was confirmed that a good quality IIa crystal could be obtained even at a growth rate about twice as fast as the conventional one, and the present invention was completed.
【０００８】図１は本発明の一具体例であって、結晶合
成用の試料室構成を示す図であり、２はＡｌ−Ｘ系金属
間化合物（ＸはＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ及びＴａか
ら選ばれる元素を表す）の粉末が予め添加されている溶
媒金属である。なお、図１中、１は炭素源、３は種結
晶、４は絶縁体、５は黒鉛ヒーター、６は圧力媒体を示
す。金属間化合物の例として、たとえばＡｌ−Ｔｉ系金
属間化合物としては、ＡｌＴｉ，Ａｌ3 Ｔｉ，Ａｌ2 Ｔ
ｉ，ＡｌＴｉ3 などが、Ａｌ−Ｚｒ系金属間化合物とし
ては、ＡｌＺｒ，Ａｌ3 Ｚｒ，Ａｌ2 Ｚｒ，Ａｌ3 Ｚｒ
2 ，Ａｌ3 Ｚｒ5 ，Ａｌ2 Ｚｒ3 ，ＡｌＺｒ2 ，ＡｌＺ
ｒ3 などが、Ａｌ−Ｈｆ系金属間化合物としては、Ａｌ
Ｈｆ，Ａｌ3 Ｈｆ，Ａｌ2 Ｈｆ，Ａｌ3 Ｈｆ2 、Ａｌ3
Ｈｆ4 ，Ａｌ 2 Ｈｆ3 などが挙げられる。その他、Ａｌ
−Ｖ系、Ａｌ−Ｈｆ系、Ａｌ−Ｔａ系金属間化合物各種
も用いることができる。これらの金属間化合物の添加量
はできるだけ少ない方が好ましいが、溶媒金属に対して
０．１重量％より少ないと窒素が十分に除去されずに結
晶がかなり黄色味を帯びてくる。また、５重量％を越え
ると、結晶中にインクルージョンが多く取り込まれるよ
うになる。FIG. 1 shows one embodiment of the present invention, which is a crystal
It is a figure which shows the sample chamber structure for production, 2 is an Al-X type metal.
Intermetallic compound (X is Ti, Zr, Hf, V, Nb and Ta?
(Representing an element selected from the
It is a medium metal. In FIG. 1, 1 is a carbon source and 3 is a seed.
Crystal, 4 is an insulator, 5 is a graphite heater, 6 is a pressure medium
You As an example of the intermetallic compound, for example, Al-Ti-based gold
As the intergeneric compound, AlTi, Al3Ti, Al2T
i, AlTi3Are Al-Zr intermetallic compounds
For AlZr, Al3Zr, Al2Zr, Al3Zr
2, Al3ZrFive, Al2Zr3, AlZr2, AlZ
r3As an Al-Hf intermetallic compound, Al
Hf, Al3Hf, Al2Hf, Al3Hf2, Al3
HfFour, Al 2Hf3And so on. Others, Al
-V type, Al-Hf type, Al-Ta type intermetallic compounds
Can also be used. Addition amount of these intermetallic compounds
Is preferably as small as possible, but for solvent metals
If it is less than 0.1% by weight, nitrogen will not be removed sufficiently and will be bonded.
Crystals become yellowish. Also, over 5% by weight
Then, many inclusions will be taken into the crystal.
Growls
【０００９】ここで図１の溶媒金属２は、Ｆｅ，Ｃｏ，
Ｎｉ，Ｍｎ，Ｃｒの中から選ばれる一種もしくは二種以
上からなる金属であり、種結晶溶解防止のため０．１〜
６．０重量％の炭素を予め添加しておく。炭素添加量が
０．１重量％未満もしくは炭素を含まない溶媒金属を用
いた場合、種結晶上にＰｔなどの種結晶溶解防止材を配
置する必要があるが、種結晶防止材を配置することは多
結晶化やインクルージョンの巻き込みの原因となり、好
ましくない。また、炭素添加量が６重量％を越えると、
自然核発生が起こりやすくなり、種結晶以外の部所より
結晶成長するため結晶同士が干渉し、良質な結晶が得ら
れなくなる。Here, the solvent metal 2 in FIG. 1 is Fe, Co,
It is a metal composed of one or two or more selected from Ni, Mn and Cr, and is 0.1 to prevent the dissolution of seed crystals.
Carbon of 6.0% by weight is added in advance. When a solvent metal containing less than 0.1% by weight of carbon or containing no carbon is used, it is necessary to dispose a seed crystal dissolution preventing material such as Pt on the seed crystal. However, disposing a seed crystal preventing material. Is undesirable because it causes polycrystallization and inclusion inclusion. When the amount of carbon added exceeds 6% by weight,
Spontaneous nucleation is likely to occur, and the crystals grow from a portion other than the seed crystal, so that the crystals interfere with each other and a good quality crystal cannot be obtained.
【００１０】本発明に用いる種結晶、炭素源等はこの種
の技術分野で公知のものを用いることができる。また、
温度差法による合成の条件等は適宜選択することができ
る。具体的な例は後記する実施例に挙げられる。The seed crystal, carbon source and the like used in the present invention may be those known in this type of technical field. Also,
The conditions for synthesis by the temperature difference method can be appropriately selected. Specific examples are given in Examples described later.
【００１１】[0011]
【作用】本発明によるダイヤモンド合成方法によると、
Ａｌ−Ｘ系金属間化合物（ＸはＴｉ、Ｚｒ、Ｈｆ、Ｖ、
Ｎｂ及びＴａから選ばれる元素を表す）を窒素ゲッター
として溶媒金属に添加する。その結果、従来よりかなり
速い成長速度でも良質なIIａダイヤモンド結晶が得られ
る。この理由について、Ａｌ−Ｔｉ系の金属間化合物を
例にして次に具体的に述べる。先にも述べたように、Ａ
ｌのみを窒素ゲッターとして用いた場合は、無色透明な
ダイヤモンド結晶を合成するためには、４重量％以上と
いう多量の添加を必要とする。そのためインクルージョ
ンが結晶中に取り込まれ易く、良質な結晶とするために
は成長速度を１ｍｇ／ｈｒ以下にする必要がある。また
Ｔｉのみを窒素ゲッターとして添加した場合、添加量は
〜１重量％という微量でも無色透明な結晶となるが、Ｔ
ｉＣが溶媒中に多量に生成し、たとえ結晶の成長速度を
大幅に低下させたとしてもインクルージョン（カーバイ
ド）の混入が多く、良質な結晶は殆ど得られない。しか
し、窒素ゲッターとしてＴｉを添加するとともに、低粘
性で炭化物を形成しないＡｌを同時に添加することで、
生成したＴｉＣを溶媒金属中に拡散させることができ、
インクルージョンの混入をある程度抑えることができ
る。さらに本発明のように、ＡｌとＴｉからなる金属間
化合物たとえばＡｌＴｉやＡｌ3 Ｔｉ、ＡｌＴｉ3 など
を添加した場合、孤立したＴｉがなくなるためＴｉＣの
生成が減少し、またたとえ分解してＴｉＣが生成しても
Ａｌが近傍に存在するため、これによりＴｉＣは容易に
溶媒中に拡散される。その結果、インクルージョンのな
い良質な結晶がかなり得やすくなる。また、窒素の除去
効率も、Ｔｉと同程度で、１重量％程度の微量の添加量
でも殆ど窒素が除去される。以上のように、窒素ゲッタ
ーとしてＡｌ−Ｔｉ系の金属間化合物を用いることによ
り、ＡｌもしくはＴｉを単独もしくは複合で用いる場合
より、速い成長速度で無色透明でインクルージョンのな
い良質なIIａダイヤモンド結晶IIａダイヤモンド結晶を
合成することが可能となる。具体的にはＡｌ−Ｔｉ金属
間化合物を溶媒金属に対し１重量％添加した場合、成長
速度２．５ｍｇ／ｈｒでも、無色透明な良質なIIａダイ
ヤモンド結晶が得られる。According to the diamond synthesis method of the present invention,
Al-X intermetallic compound (X is Ti, Zr, Hf, V,
(Representing an element selected from Nb and Ta) is added to the solvent metal as a nitrogen getter. As a result, a good quality IIa diamond crystal can be obtained even at a much higher growth rate than before. The reason for this will be specifically described below by taking an Al—Ti based intermetallic compound as an example. As mentioned earlier, A
When only 1 is used as the nitrogen getter, a large amount of 4% by weight or more is required to synthesize colorless and transparent diamond crystals. Therefore, inclusions are easily incorporated into the crystal, and the growth rate needs to be 1 mg / hr or less in order to obtain a good quality crystal. Further, when only Ti is added as a nitrogen getter, colorless and transparent crystals are obtained even if the addition amount is as small as 1% by weight.
Even if a large amount of iC is generated in the solvent and the crystal growth rate is significantly reduced, inclusion (carbide) is mixed in a large amount, and a good crystal is hardly obtained. However, by adding Ti as a nitrogen getter and simultaneously adding Al that has low viscosity and does not form carbide,
The generated TiC can be diffused into the solvent metal,
Inclusion can be suppressed to some extent. Further, when an intermetallic compound composed of Al and Ti, such as AlTi, Al 3 Ti, and AlTi 3 is added as in the present invention, the formation of TiC is reduced because the isolated Ti is eliminated, and even if TiC is decomposed, TiC Since Al exists in the vicinity even if it is generated, TiC is easily diffused in the solvent. As a result, it becomes quite easy to obtain a good quality crystal without inclusion. Further, the removal efficiency of nitrogen is about the same as that of Ti, and most of the nitrogen is removed even with a small addition amount of about 1% by weight. As described above, by using an Al-Ti-based intermetallic compound as the nitrogen getter, a high-quality IIa diamond crystal IIa diamond that is colorless and transparent at a faster growth rate and has no inclusion compared to the case of using Al or Ti alone or in combination. It becomes possible to synthesize crystals. Specifically, when 1% by weight of Al-Ti intermetallic compound is added to the solvent metal, colorless and high-quality IIa diamond crystals can be obtained even at a growth rate of 2.5 mg / hr.
【００１２】[0012]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれに限定されるものではない。 実施例１ 溶媒の原料として粒径５０〜１００μｍの高純度Ｆｅ粉
末、Ｃｏ粉末、グラファイト粉末を用い、 Ｆｅ：Ｃｏ：Ｃ＝６０：４０：４．５（重量比） となるように配合した。これにさらに平均粒径５０μｍ
のＡｌＴｉ金属間化合物粉末（約５重量％のＡｌＴｉ3
を含む）を、溶媒金属量に対して１重量％添加し、十分
に混合した。この混合粉末を型押し成形し、脱ガス、焼
成したもの（直径２０ｍｍ、厚み１０ｍｍ）を溶媒とし
た。炭素源にはダイヤモンドの粉末、種結晶には直径約
５００μｍのダイヤモンド結晶３個を用いた。図１に示
す試料室構成で、炭素源と種部に約３０℃の温度差がつ
くように加熱ヒーター内にセットした。これを超高圧発
生装置を用いて、圧力５．５ＧＰａ、温度１３００℃で
７０時間保持し、ダイヤモンドの合成を行った。その結
果、０．７〜０．９カラットの無色透明なインクルージ
ョンの殆どない良質なIIａ型のダイヤモンド結晶３個が
得られた。ＥＳＲにより結晶中の窒素濃度を測定する
と、いずれも０．１ｐｐｍ以下であった。磁気天秤によ
りインクルージョン濃度を測定すると、いずれも０．３
重量％以下であった。EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 High-purity Fe powder, Co powder, and graphite powder having a particle size of 50 to 100 μm were used as a raw material of a solvent, and they were compounded so that Fe: Co: C = 60: 40: 4.5 (weight ratio). Average particle size of 50 μm
AlTi intermetallic compound powder (about 5% by weight of AlTi 3
1% by weight based on the solvent metal amount, and mixed well. This mixed powder was pressed, degassed and fired (diameter 20 mm, thickness 10 mm), and used as a solvent. Diamond powder was used as a carbon source, and three diamond crystals having a diameter of about 500 μm were used as seed crystals. The sample chamber configuration shown in FIG. 1 was set in a heater so that a temperature difference of about 30 ° C. was created between the carbon source and the seed portion. This was held at a pressure of 5.5 GPa and a temperature of 1300 ° C. for 70 hours using an ultrahigh pressure generator to synthesize diamond. As a result, three good quality IIa type diamond crystals of 0.7 to 0.9 carat having almost no colorless and transparent inclusions were obtained. When the nitrogen concentration in the crystal was measured by ESR, all were 0.1 ppm or less. When the inclusion concentration was measured with a magnetic balance, both were 0.3
It was less than weight%.
【００１３】実施例２〜４ ＡｌＴｉ金属間化合物粉末の添加量を溶媒金属量に対し
て０．５、２．０、４．０重量％と変えた他は実施例１
と同様にして、ダイヤモンド合成を行った。いずれも
０．８カラット前後の良質なIIａ型ダイヤモンド結晶が
得られた。窒素濃度およびインクルージョン量の測定結
果を実施例１とあわせて表１に示す。Examples 2 to 4 Example 1 except that the amount of AlTi intermetallic compound powder added was changed to 0.5, 2.0 and 4.0% by weight with respect to the amount of solvent metal.
Diamond synthesis was performed in the same manner as in. In each case, a good quality IIa diamond crystal of about 0.8 carat was obtained. The measurement results of the nitrogen concentration and the inclusion amount are shown in Table 1 together with that of Example 1.
【００１４】[0014]
【表１】 [Table 1]
【００１５】窒素量は０．２ｐｐｍ以下では殆ど無色透
明で、装飾用途や光学部品等に用いるには問題とならな
い。また、インクルージョン量は０．５重量％以下では
種結晶付近、すなわち結晶の下部のごく一部に分布して
いるだけであり、少し研磨することで除去できるため、
殆ど問題とならない程度である。したがって、いずれも
装飾用途、光学部品用途に適用可能な品質を有する。ま
た、成長速度は２〜２．５ｍｇ／ｈｒであり、これは従
来技術で同様の結晶を合成するための限界成長速度の２
倍以上である。When the amount of nitrogen is 0.2 ppm or less, it is almost colorless and transparent, and it is not a problem when it is used for decorative purposes or optical parts. Further, when the inclusion amount is 0.5% by weight or less, it is distributed in the vicinity of the seed crystal, that is, in a very small part of the lower part of the crystal, and can be removed by polishing a little,
There is almost no problem. Therefore, both have a quality applicable to decoration applications and optical component applications. In addition, the growth rate is 2 to 2.5 mg / hr, which is 2 which is the limit growth rate for synthesizing a similar crystal in the conventional technique.
More than double.
【００１６】実施例５ ＡｌＴｉ金属間化合物粉末の代わりに、ＡｌＺｒ金属間
化合物粉末を用いた他は実施例１と同様にして、本発明
によりダイヤモンド結晶を合成した。その結果、実施例
１と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得られ
た。Example 5 Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that AlZr intermetallic compound powder was used instead of AlTi intermetallic compound powder. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１７】実施例６ ＡｌＴｉ金属間化合物粉末のかわりに、ＡｌＨｆ金属間
化合物粉末を用いた他は実施例１と同様にして、本発明
によりダイヤモンド結晶を合成した。その結果、実施例
１と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得られ
た。Example 6 Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that AlHf intermetallic compound powder was used instead of AlTi intermetallic compound powder. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１８】実施例７ 実施例１に示したＡｌＴｉ金属間化合物粉末の代わり
に、ＡｌＴｉ3 金属間化合物（約２０％のＡｌＴｉを含
む）粉末を用いた他は実施例１と同様にして、本発明に
よりダイヤモンド結晶を合成した。その結果、実施例１
と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得られ
た。Example 7 This example was prepared in the same manner as in Example 1 except that AlTi 3 intermetallic compound powder (containing about 20% AlTi) was used in place of the AlTi intermetallic compound powder shown in Example 1. A diamond crystal was synthesized according to the invention. As a result, Example 1
Almost the same quality as type IIa diamond crystal was obtained.
【００１９】実施例８ 実施例１に示したＡｌＴｉ金属間化合物粉末の代わり
に、Ａｌ3 Ｔｉ金属間化合物（約１０％のＡｌＴｉを含
む）粉末を用いた他は実施例１と同様にして、本発明に
よりダイヤモンド結晶を合成した。その結果、実施例１
と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得られ
た。Example 8 In the same manner as in Example 1 except that Al 3 Ti intermetallic compound (containing about 10% AlTi) powder was used in place of the AlTi intermetallic compound powder shown in Example 1, Diamond crystals were synthesized according to the present invention. As a result, Example 1
Almost the same quality as type IIa diamond crystal was obtained.
【００２０】実施例９ 実施例１に示したＡｌＴｉ金属間化合物粉末の代わり
に、Ａｌ3 Ｖ金属間化合物粉末を用いた他は実施例１と
同様にして、本発明によりダイヤモンド結晶を合成し
た。その結果、実施例１と殆ど同じ、良質なIIａ型ダイ
ヤモンド結晶が得られた。Example 9 Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that Al 3 V intermetallic compound powder was used instead of the AlTi intermetallic compound powder shown in Example 1. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２１】実施例１０ 実施例１に示したＡｌＴｉ金属間化合物粉末の代わり
に、Ａｌ3 Ｎｂ金属間化合物粉末を用いた他は実施例１
と同様にして、本発明によりダイヤモンド結晶を合成し
た。その結果、実施例１と殆ど同じ、良質なIIａ型ダイ
ヤモンド結晶が得られた。Example 10 Example 1 was repeated except that Al 3 Nb intermetallic compound powder was used in place of the AlTi intermetallic compound powder shown in Example 1.
Diamond crystals were synthesized according to the present invention in the same manner as. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２２】実施例１１ 溶媒の原料として粒径５０〜１００μｍの高純度Ｆｅ粉
末、Ｎｉ粉末、Ｃｏ粉末、グラファイト粉末を用い、 Ｆｅ：Ｎｉ：Ｃｏ：Ｃ＝６０：３０：１０：４．２（重
量比） となるように配合し、その他は実施例１と同様にして本
発明に従いダイヤモンド結晶を合成した。その結果、実
施例１と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得
られた。Example 11 High-purity Fe powder, Ni powder, Co powder, and graphite powder having a particle size of 50 to 100 μm were used as a solvent raw material, and Fe: Ni: Co: C = 60: 30: 10: 4.2 ( (Weight ratio), and other conditions were the same as in Example 1 to synthesize diamond crystals according to the present invention. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２３】実施例１２ 溶媒の原料として粒径５０〜１００μｍの高純度Ｆｅ粉
末、Ｎｉ粉末、Ｍｎ粉末、グラファイト粉末を用い、 Ｆｅ：Ｎｉ：Ｍｎ：Ｃ＝６０：３０：１０：４．０（重
量比） となるように配合し、その他は実施例１と同様にして本
発明に従いダイヤモンド結晶を合成した。その結果、実
施例１と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得
られた。Example 12 High-purity Fe powder, Ni powder, Mn powder, and graphite powder having a particle size of 50 to 100 μm were used as a solvent raw material, and Fe: Ni: Mn: C = 60: 30: 10: 4.0 ( (Weight ratio), and other conditions were the same as in Example 1 to synthesize diamond crystals according to the present invention. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２４】実施例１３ 溶媒の原料として粒径５０〜１００μｍの高純度Ｆｅ粉
末、Ｎｉ粉末、グラファイト粉末を用い、 Ｆｅ：Ｎｉ：Ｃ＝７０：３０：３．５（重量比） となるように配合し、その他は実施例１と同様にして本
発明に従いダイヤモンド結晶を合成した。その結果、実
施例１と殆ど同じ、良質なIIａ型ダイヤモンド結晶が得
られた。Example 13 High-purity Fe powder, Ni powder, and graphite powder having a particle size of 50 to 100 μm were used as a solvent raw material, and Fe: Ni: C = 70: 30: 3.5 (weight ratio) was set. A diamond crystal was synthesized according to the present invention in the same manner as in Example 1 except for blending. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２５】実施例１４ 溶媒の原料として粒径５０〜１００μｍの高純度Ｃｏ粉
末とグラファイト粉末を用い、 Ｃｏ：Ｃ＝１００：４．７（重量比） となるように配合し、合成温度条件を１３５０℃にした
他は実施例１と同様にして本発明に従いダイヤモンド結
晶を合成した。その結果、実施例１と殆ど同じ、良質な
IIａ型ダイヤモンド結晶が得られた。Example 14 High purity Co powder having a particle size of 50 to 100 μm and graphite powder were used as a raw material of a solvent, and they were mixed so that Co: C = 100: 4.7 (weight ratio), and the synthesis temperature conditions were changed. Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that the temperature was set to 1350 ° C. As a result, the quality is almost the same as that of the first embodiment.
A type IIa diamond crystal was obtained.
【００２６】実施例１５ 溶媒の原料として粒径５０〜１００μｍの高純度Ｎｉ粉
末とグラファイト粉末を用い、 Ｎｉ：Ｃ＝１００：４．２（重量比） となるように配合し、合成温度条件を１３５０℃にした
他は実施例１と同様にして本発明に従いダイヤモンド結
晶を合成した。その結果、実施例１と殆ど同じ、良質な
IIａ型ダイヤモンド結晶が得られた。Example 15 High-purity Ni powder having a particle size of 50 to 100 μm and graphite powder were used as a raw material of a solvent, and they were mixed so that Ni: C = 100: 4.2 (weight ratio), and the synthesis temperature conditions were changed. Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that the temperature was set to 1350 ° C. As a result, the quality is almost the same as that of the first embodiment.
A type IIa diamond crystal was obtained.
【００２７】実施例１６ ＡｌＴｉ金属間化合物粉末を金属溶媒量に対し１重量％
添加するかわりに、ＡｌＴｉ金属間化合物粉末０．５重
量％、ＡｌＺｒ金属間化合物粉末０．５重量％を添加し
た他は実施例１と同様にした、本発明に従いダイヤモン
ド結晶を合成した。その結果、実施例１と殆ど同じ、良
質なIIａ型ダイヤモンド結晶が得られた。Example 16 1% by weight of AlTi intermetallic compound powder based on the amount of metal solvent
Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that 0.5% by weight of AlTi intermetallic compound powder and 0.5% by weight of AlZr intermetallic compound powder were added instead of the addition. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２８】比較例１〜６ ＡｌＴｉ金属間化合物粉末を添加せず、かわりに平均粒
径５０μｍのＴｉ粉末もしくはＡｌ粉末を添加した。こ
れらの添加量を種々変えた他は実施例１と同様にして、
ダイヤモンド結晶の合成を試みた。得られたダイヤモン
ド結晶の窒素濃度およびインクルージョン濃度の測定結
果を表２にまとめて示す。Comparative Examples 1 to 6 AlTi intermetallic compound powder was not added, but Ti powder or Al powder having an average particle size of 50 μm was added instead. In the same manner as in Example 1 except that the amounts of these added were changed,
We tried to synthesize diamond crystals. Table 2 shows the measurement results of the nitrogen concentration and the inclusion concentration of the obtained diamond crystals.
【表２】 [Table 2]
【００２９】いずれの結晶も窒素量が多く黄色いため、
もしくはインクルージョンが多すぎるため、装飾用途や
光学部品等には用いることができないものであった。Since all the crystals have a large amount of nitrogen and are yellow,
Or, since it has too many inclusions, it cannot be used for decorative purposes and optical parts.
【００３０】比較例７ 溶媒の原料として粒径５０〜１００μｍの高純度Ｆｅ粉
末、Ｎｉ粉末、Ｃｏ粉末を用い、 Ｆｅ：Ｎｉ：Ｃｏ＝６０：３０：１０（重量比） となるように配合し、炭素（グラファイト）を添加しな
かった他は実施例１と同様にして、ダイヤモンド結晶の
合成を試みた。その結果、種結晶は溶媒中に完全に溶解
して消失してしまい、ダイヤモンドの成長は認められな
かった。Comparative Example 7 High-purity Fe powder, Ni powder, and Co powder having a particle size of 50 to 100 μm were used as a raw material of a solvent, and they were mixed so that Fe: Ni: Co = 60: 30: 10 (weight ratio). The synthesis of diamond crystals was attempted in the same manner as in Example 1 except that carbon (graphite) was not added. As a result, the seed crystal was completely dissolved in the solvent and disappeared, and no diamond growth was observed.
【００３１】比較例８ 溶媒の原料として粒径５０〜１００μｍの高純度Ｆｅ粉
末、Ｎｉ粉末、Ｃｏ粉末、グラファイト粉末を用い、 Ｆｅ：Ｎｉ：Ｃｏ：Ｃ＝６０：３０：１０：７（重量
比） となるように配合した他は実施例１と同様にして、ダイ
ヤモンド結晶の合成を試みた。その結果、種結晶以外の
ところよりダイヤモンドが多数自然核発生し、このため
結晶同士が干渉し、良質な結晶は殆ど得られなかった。Comparative Example 8 High purity Fe powder, Ni powder, Co powder and graphite powder having a particle size of 50 to 100 μm were used as a raw material of a solvent, and Fe: Ni: Co: C = 60: 30: 10: 7 (weight ratio). ) The synthesis of diamond crystals was attempted in the same manner as in Example 1 except that the compounding was performed as follows. As a result, a large number of natural nuclei of diamond were generated from areas other than the seed crystal, and the crystals interfered with each other, so that a good quality crystal was hardly obtained.
【００３２】[0032]
【発明の効果】以上説明したように、本発明によれば無
色透明でインクルージョンのほとんど無いダイヤモンド
結晶を、安価に安定して合成できる。本発明の方法によ
って合成ダイヤモンドを装飾用途、光学部品用途などに
利用することが可能である。As described above, according to the present invention, a colorless and transparent diamond crystal having almost no inclusion can be stably synthesized at low cost. According to the method of the present invention, synthetic diamond can be used for decorative purposes, optical parts, etc.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の一具体例における結晶合成用の試料室
構成を示す概略説明図である。FIG. 1 is a schematic explanatory diagram showing a structure of a sample chamber for crystal synthesis in one specific example of the present invention.
１ 炭素源 ２ 窒素ゲッターとしてのＡｌ−Ｘ金属間化合物を添加
された溶媒金属 ３ 種結晶 ４ 絶縁体 ５ 黒鉛ヒーター ６ 圧力媒体DESCRIPTION OF SYMBOLS 1 Carbon source 2 Al-X as a nitrogen getter Solvent metal to which an intermetallic compound is added 3 Seed crystal 4 Insulator 5 Graphite heater 6 Pressure medium
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年１１月２７日[Submission date] November 27, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【特許請求の範囲】[Claims]
Claims (3)
において、窒素ゲッターとしてＡｌ−Ｘ系金属間化合物
（ＸはＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ及びＴａから選ばれ
る元素を表す）を添加した溶媒金属を用いることを特徴
とするダイヤモンド単結晶の合成方法。1. A solvent in which an Al—X intermetallic compound (X represents an element selected from Ti, Zr, Hf, V, Nb and Ta) is added as a nitrogen getter in the diamond single crystal synthesis by the temperature difference method. A method for synthesizing a diamond single crystal characterized by using a metal.
ｎ及びＣｒの中から選ばれる一種もしくは二種以上から
なる金属であり、且つ０．１〜６．０重量％の炭素を含
むことを特徴とするダイヤモンド単結晶の合成方法。2. The solvent metal is Fe, Co, Ni, M.
A method for synthesizing a diamond single crystal, which is a metal composed of one or more selected from n and Cr and contains 0.1 to 6.0% by weight of carbon.
Ｘ系金属間化合物（ＸはＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ及
びＴａから選ばれる元素を表す）の添加量は前記溶媒金
属に対して０．１〜５重量％であることを特徴とするダ
イヤモンド単結晶の合成方法。3. The Al- added as the nitrogen getter.
The addition amount of the X-based intermetallic compound (X represents an element selected from Ti, Zr, Hf, V, Nb and Ta) is 0.1 to 5% by weight with respect to the solvent metal. Diamond single crystal synthesis method.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30181391A JP3206050B2 (en) | 1991-11-18 | 1991-11-18 | Method of synthesizing diamond single crystal |
| DE69215021T DE69215021T2 (en) | 1991-02-15 | 1992-02-14 | DIAMOND SYNTHESIS PROCEDURE |
| US08/307,493 US6129900A (en) | 1991-02-15 | 1992-02-14 | Process for the synthesis of diamond |
| PCT/JP1992/000149 WO1992014542A1 (en) | 1991-02-15 | 1992-02-14 | Process for synthesizing diamond |
| EP92905002A EP0525207B1 (en) | 1991-02-15 | 1992-02-14 | Process for synthesizing diamond |
| IE920846A IE920846A1 (en) | 1991-03-14 | 1992-03-16 | A process for the synthesis of diamond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30181391A JP3206050B2 (en) | 1991-11-18 | 1991-11-18 | Method of synthesizing diamond single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05138000A true JPH05138000A (en) | 1993-06-01 |
| JP3206050B2 JP3206050B2 (en) | 2001-09-04 |
Family
ID=17901473
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30181391A Expired - Lifetime JP3206050B2 (en) | 1991-02-15 | 1991-11-18 | Method of synthesizing diamond single crystal |
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| Country | Link |
|---|---|
| JP (1) | JP3206050B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7404399B2 (en) | 2003-10-10 | 2008-07-29 | Sumitomo Electric Industries, Ltd. | Diamond tool, synthetic single crystal diamond and method of synthesizing single crystal diamond, and diamond jewelry |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA110325C2 (en) | 2009-07-03 | 2015-12-25 | Australian Biomedical Company Pty Ltd | Medicinal carbohydrates for treating respiratory conditions |
-
1991
- 1991-11-18 JP JP30181391A patent/JP3206050B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7404399B2 (en) | 2003-10-10 | 2008-07-29 | Sumitomo Electric Industries, Ltd. | Diamond tool, synthetic single crystal diamond and method of synthesizing single crystal diamond, and diamond jewelry |
| EP2468392A2 (en) | 2003-10-10 | 2012-06-27 | Sumitomo Electric Industries, Ltd. | Diamond tool, synthetic single crystal diamond and method for synthesizing single crystal diamond, and diamond jewelry |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3206050B2 (en) | 2001-09-04 |
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