JPH06165929A - Method for synthesizing diamond single crystal - Google Patents
Method for synthesizing diamond single crystalInfo
- Publication number
- JPH06165929A JPH06165929A JP43A JP32079992A JPH06165929A JP H06165929 A JPH06165929 A JP H06165929A JP 43 A JP43 A JP 43A JP 32079992 A JP32079992 A JP 32079992A JP H06165929 A JPH06165929 A JP H06165929A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- crystal
- crystals
- powder
- solvent
- 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.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 90
- 239000010432 diamond Substances 0.000 title claims abstract description 57
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 7
- 230000002194 synthesizing effect Effects 0.000 title claims description 3
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 31
- 229910052719 titanium Inorganic materials 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 239000002245 particle Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910008332 Si-Ti Inorganic materials 0.000 description 2
- 229910006749 Si—Ti Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910008329 Si-V Inorganic materials 0.000 description 1
- 229910008341 Si-Zr Inorganic materials 0.000 description 1
- 229910021127 SiZr2 Inorganic materials 0.000 description 1
- 229910006768 Si—V Inorganic materials 0.000 description 1
- 229910006682 Si—Zr Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
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、ロシア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, those which are colorless and transparent and have few internal defects are selected from those mainly produced in South Africa and Russia. Natural ornamental diamonds are the most sold gemstones. Also, as optical parts using diamond, there are laser windows and IR anvil cells.
In each case, a transparent diamond (called type IIa) that does not absorb light in the infrared region is selected and used from natural rough stones. 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、例えば、The Journal of Physical Chemistry,
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４０
３４０６６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、例えば無機材質研究所研
究報告書第３９号（1984）第１６〜１９頁に、ＴｉやＺ
ｒ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. As this nitrogen getter, for example, The Journal of Physical Chemistry,
vol.75, No.12 (1971) As described in p1838,
Al is well known. Specifically, US Patent No. 40
In the specification of No. 34066, Al is added to a Fe solvent in an amount of 3 to 5
It is described that a gem-grade colorless and transparent diamond single crystal was obtained by adding it by weight%. As an example using a nitrogen getter other than Al, see, for example, Research Report No. 39 (1984), pages 16 to 19 of the Research Institute for Inorganic Materials, Ti and Z.
There is a report that nitrogen in crystals was removed by adding r to the 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、カーバイドとも称
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 called a carbide) generated in the solvent during the synthesis is taken into the crystal, and a perfect 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、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時間以上の合成時
間を要し、製造コストは膨大なものとなる。また、Ｔ
ｉ、Ｚｒ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。本発明はかかる問
題点を解決し、無色透明でしかもインクルージョンの殆
どないダイヤモンド単結晶を、安価に安定して合成でき
る新規な製法を提供し、人工合成ダイヤモンドの装飾用
途または光学部品用途への使用を可能にすることを意図
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 uniformly mixed with a solvent metal, the amount of addition is at least 4% by weight with respect to the solvent in order to synthesize a colorless and transparent diamond crystal, but in this case, inclusion is not involved. 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 or more to synthesize 0 mg) of crystals, and the manufacturing cost is enormous. Also, T
When a substance having a higher reactivity with nitrogen than Al, such as i and Zr, is uniformly added to the solvent as a nitrogen getter, the addition amount is 1
Although the crystals become colorless and transparent even by weight%, even if the growth rate is significantly reduced, inclusions (carbides) are large and almost no good crystals are obtained. The present invention solves such a problem, provides a new production method which can stably synthesize a diamond single crystal which is colorless and transparent and has almost no inclusion, at low cost, and to use artificial synthetic diamond for decoration or optical parts. Is intended to enable.
【０００６】[0006]
【課題を解決するための手段】上記の問題を解決するた
め、本発明者らが種々検討したところ、溶媒中にＳｉを
添加すれば溶媒中の炭素の活量が上がり、そのため成長
中の結晶表面の埋め残しが少なくなって、インクルージ
ョンの混入がある程度抑えられることがわかった。ま
た、Ｔｉ，Ｚｒ，、Ｈｆなど炭化物を形成しやすい元素
を窒素ゲッターとして添加する場合に、同時にＳｉを溶
媒中に添加すれば、ＴｉＣやＺｒＣなど合成中に溶媒中
に生成した炭化物が溶解・分解され、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の育成が
可能であることを見いだした。さらに検討を重ねたとこ
ろ、ＳｉとＴｉ，Ｚｒなどからなる金属間化合物などを
窒素ゲッターとして添加すれば、より効果的であり、ま
たＴｉＣなどの炭化物の生成自体が大幅に抑えられるこ
とが判った。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。[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have made various investigations. As a result, when Si is added to the solvent, the activity of carbon in the solvent is increased, and therefore, the growing crystal It was found that the unfilled surface was reduced and inclusions were suppressed to some extent. Further, when an element that easily forms carbides such as Ti, Zr, and Hf is added as a nitrogen getter, if Si is added to the solvent at the same time, TiC, ZrC, and other carbides formed in the solvent during synthesis are dissolved. It has been found that it is possible to grow a high quality IIa type diamond crystal that has been decomposed and has a relatively rapid growth rate. Further investigations have revealed that the addition of an intermetallic compound such as Si and Ti or Zr as a nitrogen getter is more effective, and the formation of carbide such as TiC itself can be significantly suppressed. . 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.
【０００７】すなわち、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Ｓｉ−
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Ｓｉ−Ｘ系金属間化合物（ＸはＴｉ、Ｚ
ｒ、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０．１〜１０重量％
であることが特に好ましい。That is, according to the present invention, in the diamond single crystal synthesis by the temperature difference method, Si-is used as a nitrogen getter.
It is characterized by using a solvent metal to which an X-based intermetallic compound (X represents an element selected from Ti, Zr, Hf, V, Nb and Ta) is added. In the present invention, the solvent metal is a metal composed of one or more selected from Fe, Co, Ni, Mn and Cr, and contains 0.1 to 6.0% by weight of carbon. Particularly preferred. Further, a Si—X based intermetallic compound (X is Ti, Z is added as the nitrogen getter in the present invention.
represents an element selected from r, Hf, V, Nb and Ta)
The addition amount of 0.1 to 10 wt% with respect to the solvent metal
Is particularly preferable.
【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、溶媒金属２中にＳｉ
−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）の粉末を予め添加し
ておく。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Ｓｉ−Ｔｉ系金属間化合
物としては、Ｓｉ 2 Ｔｉ，ＳｉＴｉ，Ｓｉ3 Ｔｉ5 など
が挙げられる。Ｓｉ−Ｚｒ系金属間化合物としては、Ｓ
ｉ2 Ｚｒ，ＳｉＺｒ，Ｓｉ4 Ｚｒ5 ，ＳｉＺｒ2 などが
挙げられる。その他Ｓｉ−Ｖ系、Ｓｉ−Ｈｆ系、Ｓｉ−
Ｔａ系金属間化合物の各種も用いることができる。これ
らのＳｉ−Ｘ系金属間化合物の添加量は少ない方が好ま
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、１０重量％を越えると、多結晶化や自然核発
生が多くなり、良質な結晶が得られなくなる。FIG. 1 shows one embodiment of the present invention, which is a crystal
It is a figure which shows the sample chamber structure for synthesis | combination, Si is contained in the solvent metal 2.
-X-based intermetallic compound (X is Ti, Zr, Hf, V, Nb
And an element selected from Ta) are added in advance.
Keep it. In FIG. 1, 1 is a carbon source, 3 is a seed crystal, and 4 is a seed crystal.
An insulator, 5 is a graphite heater, and 6 is a pressure medium. metal
As an example of the intermetallic compound, for example, a Si--Ti based intermetallic compound
As an object, Si 2Ti, SiTi, Si3TiFiveSuch
Is mentioned. As the Si-Zr-based intermetallic compound, S
i2Zr, SiZr, SiFourZrFive, SiZr2etc
Can be mentioned. Others Si-V type, Si-Hf type, Si-
Various types of Ta-based intermetallic compounds can also be used. this
It is preferable that the amount of the Si-X intermetallic compound added is small.
However, if it is less than 0.1% by weight with respect to the solvent metal,
Crystals are rather yellowish due to insufficient element removal
It Also, if it exceeds 10% by weight, polycrystallization or spontaneous nuclear generation occurs.
The amount of raw material increases, and good quality crystals cannot be obtained.
【０００９】ここで図１の２の溶媒金属は、Ｆｅ，Ｃ
ｏ，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溶媒
金属量に対し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 metals 2 in FIG. 1 are Fe and C.
O, Ni, Mn, and Cr, which are one or more metals selected from the group consisting of 0.1 to 6.0% by weight of carbon with respect to the amount of solvent metal to prevent seed crystal dissolution. deep. 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 inhibitor such as Pt on the seed crystal, but dispose a seed crystal inhibitor. Is undesirable because it causes polycrystallization and inclusion inclusion. If the amount of carbon added exceeds 6% by weight, spontaneous nucleation tends to occur,
Since the crystals grow from a portion other than the seed crystal, 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、
溶媒中にＳｉ−Ｘ系金属間化合物（ＸはＴｉ、Ｚｒ、Ｈ
ｆ、Ｖ、Ｎｂ及びＴａから選ばれる元素を表す）を窒素
ゲッター且つインクルージョン混入防止材として添加し
ておく。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、Ｓｉ−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、Ｔｉのみを窒素ゲッタ
ーとして用いた場合、窒素との反応性が高いので添加量
は〜１重量％という微量でも無色透明なダイヤモンド結
晶となるが、ＴｉＣが溶媒中に多量に生成する。そのた
め結晶成長が阻害されたり、また結晶の成長速度を大幅
に低下させたとしても、このＴｉＣが結晶中に取り込ま
れたりして、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、ＴｉＣを溶
解・分解する働きのあるＳｉを同時に添加することによ
り、溶媒中のＴｉＣの影響によるインクルージョンの混
入を抑えることができる。Ｓｉを添加すれば溶媒中の炭
素の活量が上がり、そのため成長中の結晶表面の埋め残
しが少なくなって、溶媒の巻き込み（インクルージョ
ン）自体がある程度抑えられる。さらにＴｉとＳｉから
なる金属間化合物、例えばＳｉＴｉなどを添加した場
合、より効果的であり、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Ｓｉ−Ｔｉ系の金属間化合
物を用いることにより、ＡｌやＴｉなどの従来の窒素ゲ
ッターを用いる場合より、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ダイヤモンド結晶を合
成することが可能となる。具体的には例えばＳｉＴｉ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,
Si-X intermetallic compound (X is Ti, Zr, H in a solvent)
(representing an element selected from f, V, Nb, and Ta) is added as a nitrogen getter and an inclusion mixing prevention material. 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 a Si—Ti based intermetallic compound as an example. As described above, when only Ti is used as the nitrogen getter, the reactivity with nitrogen is high, so even if the addition amount is up to 1% by weight, a colorless and transparent diamond crystal can be obtained. Generate a large amount. Therefore, even if the crystal growth is hindered, or even if the crystal growth rate is significantly reduced, the TiC is taken into the crystal, and a good crystal is hardly obtained. However, by adding Ti as a nitrogen getter and Si having a function of dissolving and decomposing TiC at the same time, inclusion of inclusions due to the influence of TiC in the solvent can be suppressed. When Si is added, the activity of carbon in the solvent is increased, so that the unfilled portion of the crystal surface during growth is reduced, and the inclusion of the solvent itself is suppressed to some extent. Furthermore, when an intermetallic compound composed of Ti and Si, such as SiTi, is added, it is more effective, and it becomes easy to obtain a good quality crystal. Further, the removal efficiency of nitrogen is about the same as that of Ti, and most of the nitrogen is removed even by adding a trace amount of about 1% by weight. As described above, by using the Si-Ti-based intermetallic compound as the nitrogen getter, a high-quality IIa diamond crystal that is colorless and transparent and has no inclusion at a higher growth rate than in the case of using a conventional nitrogen getter such as Al or Ti. Can be synthesized. Specifically, for example, when 1 wt% of SiTi intermetallic compound is added to the solvent metal, a colorless and high-quality IIa diamond crystal 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。これにさらに添加材として平均
粒径５０μｍのＳｉＴｉ金属間化合物粉末を溶媒金属量
（グラファイトを除く）に対し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 be specifically described below 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). 1 wt% of SiTi intermetallic compound powder having an average particle size of 50 μm was added as an additive to the solvent metal amount (excluding graphite), and they were sufficiently mixed. 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 the 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２〜５ ＳｉＴｉ金属間化合物粉末の添加量を溶媒金属量（グラ
ファイトを除く）０．５、２．０、４．０、８．０重量
％と変えた他は実施例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。いずれの
結晶も窒素濃度は０．２ｐｐｍ以下、インクルージョン
量は０．３重量％以下であった。Examples 2 to 5 Example 1 except that the amount of SiTi intermetallic compound powder added was changed to 0.5, 2.0, 4.0, and 8.0% by weight of solvent metal (excluding graphite). Diamond was synthesized according to the present invention in the same manner as in. In each case, a good quality IIa diamond crystal of about 0.8 carat was obtained. Each crystal had a nitrogen concentration of 0.2 ppm or less and an inclusion amount of 0.3% by weight or less.
【００１４】実施例６ 添加材としてＳｉＴｉ金属間化合物粉末に代えてＳｉ3
Ｔｉ5 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 Si 3 was used as an additive instead of SiTi intermetallic compound powder.
Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that Ti 5 intermetallic compound powder was used. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１５】実施例７ 添加材としてＳｉＴｉ金属間化合物粉末に代えてＳｉＺ
ｒ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 7 Instead of SiTi intermetallic compound powder as an additive, SiZ
Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that r intermetallic compound powder was used. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１６】実施例８ 添加材としてＳｉＴｉ金属間化合物粉末に代えてＳｉＺ
ｒ2 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 8 SiZ was used as an additive instead of SiTi intermetallic compound powder.
Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that r 2 intermetallic compound powder was used. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１７】実施例９ 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 9 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 ( A diamond crystal was synthesized according to the present invention in the same manner as in Example 1 except that the weight ratio was adjusted. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１８】実施例１０ 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 10 High purity Fe powder, Ni powder, Mn 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: Mn: C = 60: 30: 10: 4.0 ( A diamond crystal was synthesized according to the present invention in the same manner as in Example 1 except that the weight ratio was adjusted. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００１９】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、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 11 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. Diamond crystals were synthesized according to the present invention in the same manner as in Example 1 except that the components were blended. As a result, a good quality IIa diamond crystal, which is almost the same as in Example 1, was obtained.
【００２０】実施例１２ 溶媒の原料として粒径５０〜１００μｍの高純度Ｃｏ粉
末、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 12 High purity 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 blended 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 changed 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.
【００２１】実施例１３ 溶媒の原料として粒径５０〜１００μｍの高純度Ｎｉ粉
末、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 13 High-purity Ni 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 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 changed 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.
【００２２】比較例１ ＳｉＴｉ金属間化合物を添加せず、かわりに平均粒径５
０μｍのＴｉ粉末を１重量％添加した他は実施例１と同
様にして、ダイヤモンド結晶の合成を試みた。窒素量が
約０．２ｐｐｍと少ない結晶が得られたが、成長量は一
個あたり約０．３カラットと少なかった。また多くのＴ
ｉＣが結晶中に見られ、溶媒の巻き込みも約１．３重量
％と多く、良質な結晶は得られなかった。Comparative Example 1 No SiTi intermetallic compound was added, but instead the average particle size was 5
An attempt was made to synthesize a diamond crystal in the same manner as in Example 1 except that 1% by weight of 0 μm Ti powder was added. Although a crystal having a small amount of nitrogen of about 0.2 ppm was obtained, the amount of growth was as small as about 0.3 carat per piece. Also many T
iC was found in the crystals, and the amount of solvent entrainment was as large as about 1.3% by weight, and good crystals could not be obtained.
【００２３】比較例２ ＳｉＴｉ金属間化合物を添加せず、かわりに平均粒径５
０μｍのＳｉ粉末とＴｉ粉末をそれぞれ０．５重量％添
加した他は実施例１と同様にして、ダイヤモンド結晶の
合成を試みた。０．８カラット前後で窒素量が薬０．２
ｐｐｍと少ない結晶が得られたが、インクルージョン量
は０．７重量％とやや多かった。Comparative Example 2 No SiTi intermetallic compound was added, but instead the average particle size was 5
An attempt was made to synthesize a diamond crystal in the same manner as in Example 1 except that 0.5% by weight of Si powder and 0.5% by weight of Ti powder were added. Around 0.8 carat, the nitrogen content is 0.2
Although crystals as small as ppm were obtained, the inclusion amount was a little large at 0.7% by weight.
【００２４】比較例３ ＳｉＴｉ金属間化合物の添加量を１５重量％とした他は
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。種結晶から成長した結晶は多結晶化しており、良質
な単結晶は得られなかった。Comparative Example 3 An attempt was made to synthesize diamond crystals in the same manner as in Example 1 except that the amount of SiTi intermetallic compound added was 15% by weight. The crystal grown from the seed crystal was polycrystallized, and a good single crystal could not be obtained.
【００２５】比較例４ 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 4 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 Fe: Ni: Co = 60: 30: 10 (weight ratio) was compounded. The synthesis of diamond crystals was tried in the same manner as in Example 1 except that carbon was not added. As a result, the seed crystal was completely dissolved in the solvent and disappeared, and no diamond growth was observed.
【００２６】比較例５ 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
モンド結晶を合成した。その結果、種結晶以外の所より
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 5 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). ] A diamond crystal was synthesized in the same manner as in Example 1 except that the above composition was added. As a result, a large number of diamonds were naturally nucleated from places other than the seed crystal, and the crystals interfered with each other.
【００２７】[0027]
【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
単結晶を、安価に安定して合成できる。本発明の方法に
より、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 single 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Ｓｉ−Ｘ系金属間化合物を添
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1 Carbon source 2 Si-X intermetallic compound as a nitrogen getter Solvent metal 3 Seed crystal 4 Insulator 5 Graphite heater 6 Pressure medium
Claims (3)
おいて、溶媒金属中にＳｉ−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）を添加することを特徴とするダイヤモンド単結晶
の合成方法。1. In a diamond crystal synthesis by a temperature difference method, a Si—X based intermetallic compound (X is T
i, Zr, Hf, V, Nb and Ta) are added).
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.
ｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ及びＴａから選ばれる元素を
表す）の添加量は該溶媒金属に対して０．１〜１０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 Si—X intermetallic compound (X is T
The amount of addition of i, Zr, Hf, V, Nb and Ta) is 0.1 to 10% by weight with respect to the solvent metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43A JPH06165929A (en) | 1992-11-30 | 1992-11-30 | Method for synthesizing diamond single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43A JPH06165929A (en) | 1992-11-30 | 1992-11-30 | Method for synthesizing diamond single crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06165929A true JPH06165929A (en) | 1994-06-14 |
Family
ID=18125376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP43A Pending JPH06165929A (en) | 1992-11-30 | 1992-11-30 | Method for synthesizing diamond single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06165929A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600766A (en) * | 2012-03-30 | 2012-07-25 | 常熟市怡华金刚石有限公司 | Method for synthesizing gem grade diamond by using cubic press |
| CN102600768A (en) * | 2012-03-30 | 2012-07-25 | 常熟市怡华金刚石有限公司 | Indirect heating-type synthesis assembly for high-temperature and high-pressure artificial single crystal synthesis by using cubic press |
| CN115041099A (en) * | 2022-07-19 | 2022-09-13 | 彭伟华 | Diamond synthesis block and preparation method of diamond |
| CN117123143A (en) * | 2023-07-14 | 2023-11-28 | 山东中科润晶新材料有限公司 | Method for synthesizing special-shaped dodecahedron diamond |
-
1992
- 1992-11-30 JP JP43A patent/JPH06165929A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600766A (en) * | 2012-03-30 | 2012-07-25 | 常熟市怡华金刚石有限公司 | Method for synthesizing gem grade diamond by using cubic press |
| CN102600768A (en) * | 2012-03-30 | 2012-07-25 | 常熟市怡华金刚石有限公司 | Indirect heating-type synthesis assembly for high-temperature and high-pressure artificial single crystal synthesis by using cubic press |
| CN115041099A (en) * | 2022-07-19 | 2022-09-13 | 彭伟华 | Diamond synthesis block and preparation method of diamond |
| CN115041099B (en) * | 2022-07-19 | 2023-11-17 | 彭伟华 | Diamond synthetic block and preparation method of diamond |
| CN117123143A (en) * | 2023-07-14 | 2023-11-28 | 山东中科润晶新材料有限公司 | Method for synthesizing special-shaped dodecahedron diamond |
| CN117123143B (en) * | 2023-07-14 | 2024-02-23 | 山东中科润晶新材料有限公司 | Method for synthesizing special-shaped dodecahedron diamond |
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