JPH06182184A - Synthesis of single crystal diamond - Google Patents
Synthesis of single crystal diamondInfo
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- JPH06182184A JPH06182184A JP4341940A JP34194092A JPH06182184A JP H06182184 A JPH06182184 A JP H06182184A JP 4341940 A JP4341940 A JP 4341940A JP 34194092 A JP34194092 A JP 34194092A JP H06182184 A JPH06182184 A JP H06182184A
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- diamond
- solvent
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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
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ら
れている。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型とよばれる）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。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
で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 Physi
cal Chemistry, vol.75, No.12 (1971) p1838 に示され
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号明細書には、Ｆｅ溶媒にＡ
ｌ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ると記載されている。Ａ
ｌ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、ｐ１６〜にＴｉやＺｒ
を溶媒金属に添加することで結晶中の窒素が除去された
という報告がある。2. Description of the Related Art Decorative diamonds currently on the market are used by selecting those which are colorless and transparent and have few internal defects from those mainly produced in South Africa and Russia. Natural ornamental diamonds are the most sold gemstones. Moreover, there are laser windows and IR anvil cells as optical parts using diamond, but in each case, transparent diamond (called type IIa) that does not absorb light in the infrared region is selected from natural rough stones. Is used. However, the production of transparent and colorless rough stones is extremely low, and there are problems with stable supply and prices. On the other hand, artificially synthesized diamond is usually colored yellow because it is incorporated in the crystal lattice of nitrogen in the solvent when synthesized under ultrahigh pressure and high temperature, but it is colorless and transparent by adding a nitrogen getter to the solvent. You can get a diamond. As this nitrogen getter, for example, The Journal of Physi
Al is well known as shown in cal Chemistry, vol.75, No.12 (1971) p1838. In particular,
U.S. Pat. No. 4,034,066 describes Fe solvent as A
It is described that a gem-grade colorless and transparent diamond single crystal can be obtained by adding 3 to 5% by weight of 1. A
Examples of the use of nitrogen getters other than 1 include, for example, Research Report No. 39 of Inorganic Materials Research Institute, p.
There is a report that nitrogen in the crystal was removed by adding the to the solvent metal.
【０００３】[0003]
【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（以下
インクルージョンと呼ぶ）て、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。とくにＴｉやＺｒを窒
素ゲッターとして用いた場合は合成中に溶媒中に生成し
たＴｉＣやＺｒＣなどの炭化物が原因でより多くのイン
クルージョンが結晶中に取り込まれるようになる。However, since the synthetic cost of a colorless and transparent synthetic diamond is much higher than that of natural diamond, industrial production has not been carried out. The reason for this is that, in addition to requiring expensive and special equipment for synthesis, when Al or the like is added as a nitrogen getter, the solvent is taken into the crystal as the amount of addition increases (hereinafter referred to as inclusion), This is because the number of defective crystals increases, and thus 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, more inclusions are taken into the crystal due to carbides such as TiC and ZrC formed in the solvent during the synthesis.
【０００４】本発明者らが行った実験による結果では、
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％（約１
２体積％）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１ｍ
ｇ／ｈｒ以下にする必要があった。この成長速度では、
たとえば１カラット（２００ｍｇ）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、Ｔｉ、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。しかし、これらは炭化物を形成しやすく、成長速度
を大幅に低下させたとしてもＴｉＣやＺｒＣなどの炭化
物の影響で、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、無色透明でインクルージョのほと
んどない結晶を、安価にしかも安定して合成できる方法
を提供し、人工合成ダイヤモンドの装飾用途又は光学部
品用途への使用を可能とするものである。According to the result of the experiment conducted by the present inventors,
When Al is used as a nitrogen getter and uniformly mixed with a solvent metal, in order to synthesize a colorless and transparent diamond crystal, the addition amount thereof is at least 4% by weight (about 1%) with respect to the solvent.
2% by volume), but in this case the growth rate is 1 m in order to grow crystals without inclusion inclusion.
It was necessary to make it g / hr or less. At this growth rate,
For example, it takes 200 hours or more to synthesize 1 carat (200 mg) crystals, and the production cost becomes enormous. Further, when a substance having a higher reactivity with nitrogen than Al, such as Ti or Zr, is uniformly added to the solvent as a nitrogen getter, even if the addition amount is 1% by weight, colorless and transparent crystals are obtained. However, these tend to form carbides, and even if the growth rate is greatly reduced, good quality crystals are hardly obtained due to the influence of carbides such as TiC and ZrC. The present invention solves such a problem, provides a method of synthesizing a colorless and transparent crystal having almost no inclusions stably at low cost, and makes it possible to use an artificial synthetic diamond for a decorative use or an optical component use. To do.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、ＴｉやＺ
ｒを窒素ゲッターとして溶媒に添加して成長させたダイ
ヤモンド結晶を観察したところ、インクルージョンのほ
とんどは種結晶を起点として連続して結晶中に取り込ま
れていることがわかった。さらに、詳細に調べると成長
初期に種結晶面上に生成したＴｉＣやＺｒＣなどの炭化
物がインクルージョンの起点となっていることがわかっ
た。そこで本発明者らは、成長初期に種面上に炭化物生
成を防ぐため溶媒と種結晶の間にあらかじめＣｕ，Ａ
ｇ，Ａｕ，Ｚｎ，Ｃｄなど、それ自体炭化物を作らず、
加えて、ＴｉＣやＺｒＣやＮｂＣなどのIVａ族もしくは
Ｖａ族元素の炭化物を分解する働きのなる金属板を配置
したところ、種面上にほとんど炭化物を生成しないこと
を見いだした。その結果、炭化物を起点としたインクル
ージョンの巻き込みを防ぐことができ、このため、従来
の２倍以上の早い成長速度でも、良質なIIａ結晶が得ら
れることを確認した。The present inventors have found that Ti and Z
Observation of a diamond crystal grown by adding r to a solvent as a nitrogen getter showed that most of the inclusions were continuously incorporated into the crystal starting from the seed crystal. Furthermore, detailed examination revealed that carbides such as TiC and ZrC formed on the seed crystal surface at the initial stage of growth were the starting points of inclusion. Therefore, in order to prevent the formation of carbides on the seed surface at the initial stage of growth, the present inventors have previously prepared Cu and A between the solvent and the seed crystal.
g, Au, Zn, Cd, etc. do not form carbides themselves,
In addition, when a metal plate having a function of decomposing carbides of IVa group or Va group elements such as TiC, ZrC, and NbC was arranged, it was found that almost no carbides were formed on the seed surface. As a result, inclusion of inclusions originating from carbides can be prevented, and it has been confirmed that good quality IIa crystals can be obtained even at a growth rate twice or more faster than the conventional one.
【０００６】本発明は温度差法によるダイヤモンド結晶
合成において、溶媒金属に、窒素ゲッターとしてＴｉ，
Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａから選ばれる一種もしくは
二種以上の金属を添加し、さらに前記溶媒金属と種結晶
との間にＣｕ，Ａｇ，Ａｕ，Ｚｎ，Ｃｄから選ばれる一
種もしくは二種以上からなる金属板を配置した状態でダ
イヤモンドの合成を開始することを特徴とするものであ
る。本発明において溶媒金属と種結晶との間に配置され
る金属板の厚みは０．０１ｍｍ以上、１ｍｍ以下である
ことが好ましい。また、窒素ゲッターとして用いられる
Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａから選ばれる一種も
しくは二種以上の金属の含有量は、溶媒金属に対して
０．２〜１０重量％であることが好ましい。窒素ゲッタ
ーとしてのこれら金属は、他の金属、例えば、Ａｌ、Ｃ
ｕ、Ｓｉ、Ｓｎ等との合金の形で添加することもでき
る。また、溶媒金属は、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り、且つ
０．１〜６．０重量％の炭素を含むことが好ましい。In the present invention, in the diamond crystal synthesis by the temperature difference method, the solvent metal, Ti as a nitrogen getter,
One or two or more metals selected from Zr, Hf, V, Nb and Ta are added, and one or two metals selected from Cu, Ag, Au, Zn and Cd between the solvent metal and the seed crystal. The present invention is characterized in that the synthesis of diamond is started in a state where the above metal plate is arranged. In the present invention, the thickness of the metal plate arranged between the solvent metal and the seed crystal is preferably 0.01 mm or more and 1 mm or less. The content of one or more metals selected from Ti, Zr, Hf, V, Nb, and Ta used as a nitrogen getter is preferably 0.2 to 10% by weight with respect to the solvent metal. . These metals as nitrogen getters include other metals such as Al, C.
It can also be added in the form of an alloy with u, Si, Sn or the like. The solvent metals are Fe, Co, Ni, Mn, Cr.
It is preferable that it is composed of one or more selected from the above and contains 0.1 to 6.0% by weight of carbon.
【０００７】図１は本発明の一具体例であってダイヤモ
ンド結晶合成用の試料室構成を示す概略断面図である。
溶媒金属２には窒素ゲッターとしてＴｉ，Ｚｒ，Ｈｆ，
Ｖ，Ｎｂ，Ｔａが添加され、この溶媒金属と種結晶４の
間にＣｕ，Ａｇ，Ａｕ，Ｚｎ，Ｃｄから選ばれる金属板
３が配置される。１は炭素源、５は絶縁体、６は黒鉛ヒ
ーター、７は圧力媒体である。この金属板３の厚みは
０．０１ｍｍ未満では効果は不十分で、１ｍｍをこえる
とＣｕ，Ａｇ，Ａｕ，Ｚｎ，Ｃｄなどの金属がダイヤモ
ンドの結晶成長に悪影響を及ぼし、結晶が多結晶化した
り、埋め残しのある不良結晶となってしまう。また溶媒
２に窒素ゲッターとして添加するＴｉ，Ｚｒ，Ｈｆ，
Ｖ，Ｎｂ，Ｔａの添加量としては、０．２重量％未満で
は窒素は十分に除去されず、合成されたダイヤモンドは
黄色みを帯びた結晶となる。一方、１０重量％をこえる
と多結晶化や自然核発生が多くなり、良質なダイヤモン
ド結晶が得られなくなる。FIG. 1 is a schematic sectional view showing the structure of a sample chamber for synthesizing a diamond crystal, which is one embodiment of the present invention.
The solvent metal 2 includes Ti, Zr, Hf, as a nitrogen getter,
V, Nb, and Ta are added, and the metal plate 3 selected from Cu, Ag, Au, Zn, and Cd is arranged between the solvent metal and the seed crystal 4. 1 is a carbon source, 5 is an insulator, 6 is a graphite heater, and 7 is a pressure medium. If the thickness of the metal plate 3 is less than 0.01 mm, the effect is insufficient, and if it exceeds 1 mm, metals such as Cu, Ag, Au, Zn, and Cd adversely affect the crystal growth of diamond, and the crystal becomes polycrystalline. , Which results in a defective crystal with an unfilled portion. Further, Ti, Zr, Hf, which is added to the solvent 2 as a nitrogen getter,
If the added amount of V, Nb, or Ta is less than 0.2% by weight, nitrogen is not sufficiently removed, and the synthesized diamond becomes yellowish crystals. On the other hand, if it exceeds 10% by weight, polycrystallization and natural nucleation increase, and a good quality diamond crystal cannot be obtained.
【０００８】ここで、２の溶媒金属はＦｅ，Ｃｏ，Ｎ
ｉ，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％の炭素をあらかじめ添加しておくのが好ま
しい。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、このような種
結晶溶解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％をこえると、自然核発生がおこり
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 of 2 are Fe, Co, N.
It is a metal consisting of one or more selected from i, Mn, and Cr, and is 0.1 to prevent seed crystal dissolution.
It is preferable to add 6.0% by weight of carbon 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 inhibitor such as Pt on the seed crystal. It is not preferable to dispose because of causing polycrystallization and inclusion inclusion. Also,
When the amount of carbon added exceeds 6% by weight, spontaneous nucleation is likely to occur, and 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.
【０００９】[0009]
【作用】本発明ではＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ
など、窒素との反応性の高い元素を窒素ゲッターとする
ため、少量の添加でほとんど窒素を含まない無色透明な
IIａ型のダイヤモンド結晶が得られ、また、溶媒と種結
晶の間に、炭化物生成防止のために、Ｃｕ，Ａｇ，Ａ
ｕ，Ｚｎ，Ｃｄの金属板をあらかじめ配置した状態で合
成を開始する構成になっているため、インクルージョン
の混入を大幅に抑えることができる。その結果、従来よ
りかなり速い成長速度でも良質なIIａ型ダイヤモンド結
晶が得られるようになる。また、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。In the present invention, Ti, Zr, Hf, V, Nb, Ta are used.
For example, the element that has high reactivity with nitrogen is used as a nitrogen getter.
IIa type diamond crystals are obtained, and Cu, Ag, A are added between the solvent and the seed crystal to prevent carbide formation.
Since the composition is started in the state where the metal plates of u, Zn, and Cd are arranged in advance, inclusion can be greatly suppressed. As a result, good quality IIa type diamond crystals can be obtained even at a much higher growth rate than before. The seed crystal, carbon source, etc. used in the present invention may be those known in the technical field of this type. Further, the conditions for synthesis by the temperature difference method can be appropriately selected.
【００１０】[0010]
【実施例】以下実施例により本発明をさらに詳細に説明
する。実施例１ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｆ
ｅ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、さらに窒素ゲッターと
して平均粒径５０ミクロンのＴｉ粉末を１．５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。図１に示す試料室構成で炭素源１にはダ
イヤモンドの粉末、種結晶４には直径５００ミクロンの
ダイヤモンド結晶３個を用いた。種結晶４と溶媒２の間
に配置する金属板３としては厚み０．２ｍｍのＣｕ板を
用いた。そして、炭素源１と種結晶４部に約３０℃の温
度差がつくように加熱ヒーター６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１
３００℃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
ンクルージョンのほとんどない良質なIIａ型のダイヤモ
ンド結晶が得られた。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量を測定するといずれも
０．３重量％以下であった。The present invention will be described in more detail with reference to the following examples. Example 1 High purity F having a particle size of 50 to 100 microns as a raw material of a solvent
e powder, Co powder, and graphite powder were used and blended so that Fe: Co: C = 60: 40: 4.5 (weight ratio). To this, 1.5% by weight of Ti powder having an average particle size of 50 μm was further added as a nitrogen getter, and they were sufficiently mixed. This mixed powder is pressed and molded,
Degassed and fired (20 mm diameter, 10 mm thickness)
Was used as the solvent. In the sample chamber structure shown in FIG. 1, diamond powder was used as the carbon source 1, and three diamond crystals having a diameter of 500 μm were used as the seed crystals 4. As the metal plate 3 arranged between the seed crystal 4 and the solvent 2, a Cu plate having a thickness of 0.2 mm was used. Then, the carbon source 1 and the seed crystal 4 were set in the heater 6 so that there was a temperature difference of about 30 ° C. Using an ultrahigh pressure generator, the pressure was 5.5 GPa and the temperature was 1
The temperature was maintained at 300 ° C. for 70 hours to synthesize diamond. As a result, a colorless and transparent 0.7-0.9 carat type IIa diamond crystal of good quality with almost no inclusion was obtained. When the nitrogen concentration in the crystal was measured by ESR, all were 0.1 ppm or less. When the inclusion amount was measured with a magnetic balance, all were 0.3% by weight or less.
【００１１】実施例２ 種結晶４と溶媒２の間に配置する金属板３に厚み０．５
ｍｍのＣｕ板を用いた他は実施例１と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。実施例３ 種結晶４と溶媒２の間に配置する金属板３に厚み０．２
ｍｍのＡｇ板を用いた他は実施例１と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。実施例４ 種結晶４と溶媒２の間に配置する金属板３に厚み０．３
ｍｍのＡｕ板を用いた他は実施例１と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。 Example 2 A metal plate 3 placed between a seed crystal 4 and a solvent 2 has a thickness of 0.5.
Diamond was synthesized in the same manner as in Example 1 except that a Cu plate of mm was used. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained. Example 3 A metal plate 3 arranged between a seed crystal 4 and a solvent 2 has a thickness of 0.2.
Diamond was synthesized in the same manner as in Example 1 except that an Ag plate of mm was used. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained. Example 4 A metal plate 3 arranged between a seed crystal 4 and a solvent 2 has a thickness of 0.3.
Diamond was synthesized in the same manner as in Example 1 except that an Au plate of mm was used. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained.
【００１２】実施例５ 種結晶４と溶媒２の間に配置する金属板３に厚み０．０
５ｍｍのＡｕ板を用いた他は実施例１と同様にしてダイ
ヤモンドの合成を行った。その結果、実施例１とほとん
ど同じ良質なIIａ型ダイヤモンド結晶が得られた。実施例６ 種結晶４と溶媒２の間に配置する金属板３に厚み０．２
ｍｍのＺｎ板を用いた他は実施例１と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。実施例７ 溶媒２に添加する窒素ゲッターに粒径４４ミクロン以下
（平均１０ミクロン）のＺｒ粉末を溶媒に対し３重量％
添加した他は実施例１と同様にしてダイヤモンドの合成
を行った。その結果、実施例１とほとんど同じ良質なII
ａ型ダイヤモンド結晶が得られた。 Example 5 A metal plate 3 placed between a seed crystal 4 and a solvent 2 has a thickness of 0.0
Diamond was synthesized in the same manner as in Example 1 except that a 5 mm Au plate was used. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained. Example 6 A metal plate 3 placed between a seed crystal 4 and a solvent 2 has a thickness of 0.2.
Diamond was synthesized in the same manner as in Example 1 except that a Zn plate of mm was used. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained. Example 7 Zr powder having a particle size of 44 microns or less (average of 10 microns) was added to a nitrogen getter added to solvent 2 in an amount of 3% by weight based on the solvent.
Diamond was synthesized in the same manner as in Example 1 except that the diamond was added. As a result, II of almost the same quality as in Example 1
An a-type diamond crystal was obtained.
【００１３】実施例８ 溶媒２に添加する窒素ゲッターに粒径４４ミクロン以下
（平均１０ミクロン）のＡｌＴｉ合金粉末を溶媒に対し
３重量％添加した他は実施例１と同様にしてダイヤモン
ドの合成を行った。その結果、実施例１とほとんど同じ
良質なIIａ型ダイヤモンド結晶が得られた。実施例９ 溶媒２に添加する窒素ゲッターとしてＡｌＴｉ合金粉末
の代わりに、ＣｕＴｉ、ＳｎＴｉ又はＳｉ5 Ｔｉ6 合金
粉末を用いた他は実施例８と同様にしてダイヤモンドの
合成を行った。その結果、いずれの場合も、実施例１と
ほとんど同じ良質なIIａ型ダイヤモンド結晶が得られ
た。実施例１０ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｆ
ｅ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と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。 Example 8 Synthesis of diamond was carried out in the same manner as in Example 1 except that 3% by weight of AlTi alloy powder having a particle size of 44 microns or less (average of 10 microns) was added to the solvent in the nitrogen getter added to the solvent 2. went. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained. Example 9 Diamond was synthesized in the same manner as in Example 8 except that CuTi, SnTi, or Si 5 Ti 6 alloy powder was used instead of the AlTi alloy powder as the nitrogen getter added to the solvent 2. As a result, in each case, a good quality IIa diamond crystal, which is almost the same as that of Example 1, was obtained. Example 10 High-purity F having a particle size of 50 to 100 microns as a solvent raw material
e powder, Ni powder, Co powder, and graphite powder were used, and blended so as to be Fe: Ni: Co: C = 60: 30: 10: 4.2 (weight ratio), in the same manner as in Example 1. Diamond was synthesized. As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained.
【００１４】実施例１１ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｆ
ｅ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（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
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。 実施例１２ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｆ
ｅ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と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。 実施例１３ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｃ
ｏ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た他は実施例１と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。[0014]Example 11 High-purity F with a particle size of 50-100 microns as a solvent raw material
e powder, Ni powder, Mn powder, graphite powder
Fe: Ni: Mn: C = 60: 30: 10: 4 (weight
The same as in Example 1 except that the composition was
The synthesis of Mondo was performed. As a result, almost the same as in Example 1.
The same good quality IIa type diamond crystal was obtained. Example 12 High-purity F with a particle size of 50-100 microns as a solvent raw material
Diamond powder was prepared in the same manner as in Example 1 except that e powder, Ni powder, and graphite powder were used and blended so that Fe: Ni: C = 70: 30: 3.5 (weight ratio).
The synthesis of Mondo was performed. As a result, almost the same as in Example 1.
The same good quality IIa type diamond crystal was obtained. Example 13 High-purity C with a particle size of 50-100 microns as a solvent raw material
Diamond powder was used in the same manner as in Example 1 except that Co powder and graphite powder were blended so that Co: C = 100: 4.7 (weight ratio).
The synthesis of Mondo was performed. As a result, almost the same as in Example 1.
The same good quality IIa type diamond crystal was obtained.
【００１５】実施例１４ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｎ
ｉ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た他は実施例１と同様にしてダイヤ
モンドの合成を行った。その結果、実施例１とほとんど
同じ良質なIIａ型ダイヤモンド結晶が得られた。 Example 14 High-purity N having a particle size of 50 to 100 μm as a solvent raw material
Diamond was synthesized in the same manner as in Example 1 except that the i powder and the graphite powder were used and were mixed so that Ni: C = 100: 4.2 (weight ratio). As a result, a good quality IIa type diamond crystal, which is almost the same as in Example 1, was obtained.
【００１６】比較例１ 溶媒と種結晶の間に金属板を配置せずに、他は実施例１
と同様にダイヤモンドの合成を試みた。窒素含有量の少
ない（約０．１ｐｐｍ）の結晶が得られたが、インクル
ージョンの巻き込み量は約１．５重量％と多く、良質な
結晶は得られなかった。実施例１５ 溶媒と種結晶の間に配置するＣｕ板の厚みを２ｍｍとし
た他は実施例１と同様にダイヤモンドの合成を試みた。
成長したダイヤモンド結晶は表面に埋め残しの多い骸晶
状となった。実施例１６ 窒素ゲッターとして溶媒に添加するＴｉの量を１５重量
％とした他は実施例１と同様にダイヤモンドの合成を試
みた。種結晶から成長した結晶は多結晶化していた。COMPARATIVE EXAMPLE 1 No metal plate was placed between the solvent and the seed crystal, and the other example was used.
The synthesis of diamond was tried in the same manner as in. Crystals with a low nitrogen content (about 0.1 ppm) were obtained, but the inclusion amount was about 1.5% by weight, and a good quality crystal could not be obtained. Example 15 An attempt was made to synthesize diamond in the same manner as in Example 1 except that the thickness of the Cu plate placed between the solvent and the seed crystal was 2 mm.
The grown diamond crystals were in the form of skeletal crystals with many unfilled surfaces. Example 16 An attempt was made to synthesize diamond as in Example 1, except that the amount of Ti added to the solvent as a nitrogen getter was 15% by weight. The crystal grown from the seed crystal was polycrystallized.
【００１７】実施例１７ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｆ
ｅ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、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の合成を行った。
その結果、種結晶は溶媒中に完全に溶解してしまい、ダ
イヤモンドの成長は不充分であった。実施例１８ 溶媒の原料として粒径５０〜１００ミクロンの高純度Ｆ
ｅ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
モンドの合成を行った。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、良質なダイヤモンド結晶はほとんど得られなか
った。 Example 17 High-purity F having a particle size of 50 to 100 μm as a solvent raw material
e powder, Ni powder, and Co powder were used, blended in such a manner that Fe: Ni: Co = 60: 30: 10 (weight ratio), and graphite was not added. The synthesis was carried out.
As a result, the seed crystal was completely dissolved in the solvent, and the diamond growth was insufficient. Example 18 High-purity F having a particle size of 50 to 100 microns as a solvent raw material
Diamond powder was prepared in the same manner as in Example 1 except that Fe powder, Ni powder, Co powder, and graphite powder were mixed so that Fe: Ni: Co: C = 60: 30: 10: 10 (weight ratio). The synthesis was carried out. As a result, a large number of natural nuclei of diamond were generated from places other than the seed crystal, and the crystals interfered with each other, so that a good quality diamond crystal was hardly obtained.
【００１８】[0018]
【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ないダイヤモン
ド結晶を、安価に安定して合成できる。本方法によって
合成ダイヤモンドを装飾用途、光学部品などに利用する
ことが可能なものとなる。As described above, according to the present invention,
A colorless and transparent diamond crystal with almost no inclusion can be stably synthesized at low cost. This method makes it possible to use synthetic diamond for decorative purposes, optical parts, and the like.
【図１】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概略断面図である。FIG. 1 is a schematic cross-sectional view showing the structure of a sample chamber for crystal synthesis, which is one specific example of the present invention.
１：炭素源 ２：溶媒金属（窒素ゲッターを含む） ３：金属板 ４：種結晶 ５：絶縁体 ６：黒鉛ヒーター ７：圧力媒体 1: Carbon source 2: Solvent metal (including nitrogen getter) 3: Metal plate 4: Seed crystal 5: Insulator 6: Graphite heater 7: Pressure medium
Claims (4)
おいて、溶媒金属に窒素ゲッターとしてＴｉ，Ｚｒ，Ｈ
ｆ，Ｖ，Ｎｂ，Ｔａから選ばれる一種もしくは二種以上
の金属を添加し、かつ、前記溶媒金属と種結晶との間に
Ｃｕ，Ａｇ，Ａｕ，Ｚｎ，Ｃｄから選ばれる一種もしく
は二種以上からなる金属板を配置した状態でダイヤモン
ドの合成を開始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, Ti, Zr, H as a nitrogen getter is used as a solvent metal.
One or more metals selected from f, V, Nb and Ta, and one or more metals selected from Cu, Ag, Au, Zn and Cd between the solvent metal and the seed crystal. A method for synthesizing a diamond single crystal, characterized in that synthesis of diamond is started in a state where a metal plate made of is placed.
れる金属板の厚みは０．０１ｍｍ以上、１ｍｍ以下であ
ることを特徴とする請求項１記載のダイヤモンド単結晶
の合成方法。2. The method for synthesizing a diamond single crystal according to claim 1, wherein the metal plate arranged between the solvent metal and the seed crystal has a thickness of 0.01 mm or more and 1 mm or less.
ｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａから選ばれる一種もし
くは二種以上の金属の含有量が、溶媒金属に対して０．
２〜１０重量％であることを特徴とする請求項１または
２記載のダイヤモンド単結晶の合成方法。3. T used as the nitrogen getter
The content of one or more metals selected from i, Zr, Hf, V, Nb and Ta is 0.
The method for synthesizing a diamond single crystal according to claim 1 or 2, wherein the content is 2 to 10% by weight.
ｎ，Ｃｒの中から選ばれる一種もしくは二種以上からな
り、且つ０．１〜６．０重量％の炭素を含むことを特徴
とする請求項１または２または３記載のダイヤモンド単
結晶の合成方法。4. The solvent metal is Fe, Co, Ni, M.
The method for synthesizing a diamond single crystal according to claim 1, 2 or 3, which is composed of one or more selected from n and Cr and contains 0.1 to 6.0% by weight of carbon. .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34194092A JP3259384B2 (en) | 1992-12-22 | 1992-12-22 | Method of synthesizing diamond single crystal |
| KR1019930013401A KR940014144A (en) | 1992-01-22 | 1993-07-16 | Manufacturing method of diamond single crystal |
| EP93306785A EP0603995A1 (en) | 1992-12-22 | 1993-08-26 | Process for the synthesising diamond single crystals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34194092A JP3259384B2 (en) | 1992-12-22 | 1992-12-22 | Method of synthesizing diamond single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06182184A true JPH06182184A (en) | 1994-07-05 |
| JP3259384B2 JP3259384B2 (en) | 2002-02-25 |
Family
ID=18349942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34194092A Expired - Fee Related JP3259384B2 (en) | 1992-01-22 | 1992-12-22 | Method of synthesizing diamond single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3259384B2 (en) |
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| 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 |
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1992
- 1992-12-22 JP JP34194092A patent/JP3259384B2/en not_active Expired - Fee Related
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| US7323049B2 (en) * | 1997-04-04 | 2008-01-29 | Chien-Min Sung | High pressure superabrasive particle synthesis |
| US7368013B2 (en) | 1997-04-04 | 2008-05-06 | Chien-Min Sung | Superabrasive particle synthesis with controlled placement of crystalline seeds |
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