JPH11300194A - Diamond anvil for ultra high pressure generation - Google Patents
Diamond anvil for ultra high pressure generationInfo
- Publication number
- JPH11300194A JPH11300194A JP10113166A JP11316698A JPH11300194A JP H11300194 A JPH11300194 A JP H11300194A JP 10113166 A JP10113166 A JP 10113166A JP 11316698 A JP11316698 A JP 11316698A JP H11300194 A JPH11300194 A JP H11300194A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- anvil
- high pressure
- ultra
- crystal
- 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
- 239000010432 diamond Substances 0.000 title claims abstract description 117
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 113
- 239000013078 crystal Substances 0.000 claims abstract description 65
- 239000012535 impurity Substances 0.000 claims abstract description 37
- 230000007547 defect Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 9
- 238000002679 ablation Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 61
- 229910052757 nitrogen Inorganic materials 0.000 description 31
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010979 ruby Substances 0.000 description 3
- 229910001750 ruby Inorganic materials 0.000 description 3
- 238000005079 FT-Raman Methods 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001028 reflection method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
- B30B11/004—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses involving the use of very high pressures
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
(57)【要約】
【課題】 １００ＧＰａ以上の超高圧の発生の際にも壊
れることが少なく、また、レーザーを照射した際のルミ
ネッセンスやアブレーションなどの問題のない超高圧発
生用ダイヤモンドアンビルを提供すること。
【解決手段】 高圧下の温度差法により合成された不純
物量３ｐｐｍ以下のダイヤモンド単結晶から作製された
超高圧発生用ダイヤモンドアンビルであり、アンビルの
先端部（超高圧を発生させる部分）に、結晶欠陥を含ま
ず、合成ダイヤモンド結晶の＜００１＞方向と、アンビ
ルの加圧方向とのなす角が３度以下であることを特徴と
する超高圧発生用ダイヤモンドアンビル。
(57) [Summary] [Problem] To provide a diamond anvil for generating an ultra-high pressure that is hardly broken even when an ultra-high pressure of 100 GPa or more is generated and has no problem such as luminescence or ablation when irradiated with a laser. thing. SOLUTION: This is a diamond anvil for generating an ultra-high pressure made from a diamond single crystal having an impurity amount of 3 ppm or less synthesized by a temperature difference method under a high pressure, and a crystal is formed at a tip portion (a portion generating an ultra-high pressure) of the anvil. An ultra-high pressure generation diamond anvil, which is free from defects and has an angle between the <001> direction of the synthetic diamond crystal and the anvil pressing direction of 3 degrees or less.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、超高圧発生用ダイ
ヤモンドアンビルに関するもので、特に、１００ＧＰａ
以上の超高圧の発生の際にも壊れることが少なく、ま
た、レーザーを照射した際のルミネッセンスやアブレー
ションなどの問題のない超高圧発生用ダイヤモンドアン
ビルを提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diamond anvil for generating an ultrahigh pressure, and more particularly to a diamond anvil for generating a high pressure.
An object of the present invention is to provide a diamond anvil for generating an ultra-high pressure which is hardly broken even when the above-mentioned ultra-high pressure is generated, and which has no problem such as luminescence and ablation when irradiated with a laser.
【０００２】[0002]
【従来の技術】超高圧下での固体物性の研究や新物質の
高圧合成の研究にダイヤモンド単結晶性のアンビルが広
く使用されている。従来の超高圧発生用ダイヤモンドア
ンビルは、天然ダイヤモンド結晶の中から適当な原石を
選択し、製作されたものであった。また、ごく一部で
は、合成Ｉｂ型ダイヤモンド（約１００ｐｐｍの窒素不
純物を含む）が使用されている。 また、赤外用光学部
品としてのダイヤモンドアンビルとして、高純度合成ダ
イヤモンド（IIａ型）を用いる例がある（特開平４−２
８５８２８号公報）が、超高圧発生目的のものではな
く、試料を加圧により薄くするためのもので、発生可能
な圧力も１ＧＰａ以下である。2. Description of the Related Art Diamond single-crystal anvils are widely used in research on solid physical properties under ultra-high pressure and research on high-pressure synthesis of new substances. Conventional diamond anvils for generating ultra-high pressure have been produced by selecting an appropriate rough from natural diamond crystals. In addition, only a small portion uses synthetic Ib type diamond (containing about 100 ppm of nitrogen impurities). There is also an example in which a high-purity synthetic diamond (IIa type) is used as a diamond anvil as an infrared optical component (Japanese Patent Laid-Open No. 4-2).
No. 85828) is not for the purpose of generating an ultra-high pressure, but for making a sample thinner by applying pressure, and the pressure that can be generated is 1 GPa or less.
【０００３】[0003]
【発明が解決しようとする課題】超高圧発生用ダイヤモ
ンドアンビル用として従来用いられていた天然ダイヤモ
ンドは結晶欠陥や不純物が多く、これらは圧縮による破
壊の起点となる。そのため、従来の天然ダイヤモンド製
アンビルは、品質が安定せず、発生可能圧力や寿命が大
きくバラつく。また、窒素不純物を多量に含むため、光
学的な測定に問題があり、ラマン分光測定時や、試料加
熱のためアルゴンイオンレーザーやＹＡＧレーザーを試
料部に照射した場合にアンビルのダイヤモンドからルミ
ネッセンス光が発生したり、ダイヤモンドアンビルの破
壊やアブレーションが起こるといった問題があった。The natural diamond which has been conventionally used as a diamond anvil for generating an ultra-high pressure has many crystal defects and impurities, and these are the starting points of destruction by compression. For this reason, the quality of the conventional natural diamond anvil is not stable, and the available pressure and life are greatly varied. In addition, there is a problem in optical measurement because it contains a large amount of nitrogen impurities, and luminescence light is emitted from diamonds on the anvil during Raman spectroscopy or when the sample is irradiated with an argon ion laser or YAG laser to heat the sample. And the diamond anvil is destroyed or ablated.
【０００４】合成ダイヤモンドでは、合成Ｉｂ型ダイヤ
モンドが市販されているが、孤立置換型窒素不純物によ
る光の吸収があり、圧力検定用のルビー蛍光の測定が十
分行うことができない。また、上記のようなルミネッセ
ンスやアブレーションの問題は避けられない。さらに、
窒素不純物の不均一な分布から生じる内部歪が原因で、
超高圧発生時にダイヤモンドアンビルが壊れやすいとい
う問題がある。本発明は上記従来技術の問題点を解消す
ることができ、特に、１００ＧＰａ以上の超高圧の発生
の際にも壊れることが少なく、また、レーザーを照射し
た際のルミネッセンスやアブレーションなどの問題のな
い超高圧発生用ダイヤモンドアンビルを提供することを
目的とする。As a synthetic diamond, a synthetic Ib type diamond is commercially available. However, since light is absorbed by an isolated substitution type nitrogen impurity, ruby fluorescence cannot be sufficiently measured for pressure verification. Further, the problems of luminescence and ablation as described above are inevitable. further,
Due to the internal strain resulting from the uneven distribution of nitrogen impurities,
There is a problem that the diamond anvil is easily broken when an ultra-high pressure is generated. The present invention can solve the above-mentioned problems of the prior art, and in particular, is less likely to break even when an ultra-high pressure of 100 GPa or more is generated, and has no problem such as luminescence or ablation when irradiated with a laser. It is intended to provide a diamond anvil for generating an ultra-high pressure.
【０００５】[0005]
【課題を解決するための手段】上記の目的は、本発明の
下記の態様により達成することができる。 （１）高圧下の温度差法により合成された不純物量３ｐ
ｐｍ以下のダイヤモンド単結晶から作製された超高圧発
生用ダイヤモンドアンビルであり、アンビルの先端部
（超高圧を発生させる部分）に、結晶欠陥を含まず、合
成ダイヤモンド結晶の＜００１＞方向と、アンビルの加
圧方向とのなす角が３度以下であることを特徴とする超
高圧発生用ダイヤモンドアンビル。 （２）前記合成ダイヤモンド結晶は、＜００１＞方向に
平行な線状の転位欠陥を含まないことを特徴とする上記
（１）に記載の超高圧発生用ダイヤモンドアンビル。 （３）不純物量が０．１ｐｐｍ以下の上記（１）又は
（２）に記載の超高圧発生用ダイヤモンドアンビル。 （４）ダイヤモンドアンビルの上面と下面の平行度が１
分以下であることを特徴とする上記（１）〜（３）のい
ずれかに記載の超高圧発生用ダイヤモンドアンビル。The above objects can be achieved by the following aspects of the present invention. (1) Impurity amount 3p synthesized by temperature difference method under high pressure
An ultra-high pressure generation diamond anvil made from a diamond single crystal having a diameter of not more than pm. A diamond anvil for generating an ultra-high pressure, wherein the angle formed by the pressure direction of the diamond is 3 degrees or less. (2) The diamond anvil for ultrahigh pressure generation according to (1), wherein the synthetic diamond crystal does not include a linear dislocation defect parallel to the <001> direction. (3) The diamond anvil for generating an ultra-high pressure according to the above (1) or (2), wherein the amount of impurities is 0.1 ppm or less. (4) The parallelism between the upper and lower surfaces of the diamond anvil is 1
Minutes or less, the diamond anvil for generating an ultra-high pressure according to any one of the above (1) to (3).
【０００６】[0006]
【発明の実施の形態】天然ダイヤモンドは、多くの窒素
不純物を含み、地球内部の複雑な成長履歴を反映して、
全ての天然ダイヤモンドは結晶内に多くの歪や結晶欠陥
をもち、結晶によるバラツキも大きい。天然ダイヤモン
ドからは、不純物や結晶欠陥を含まない高い品質の結晶
を安定して入手することはほとんど不可能である。これ
に対し、ダイヤモンドが熱力学的に安定な高圧高温条件
で育成される合成ダイヤモンド単結晶は、天然ダイヤモ
ンドよりはるかに結晶性に優れ、品質も安定している。
しかし、通常の合成ダイヤモンドは、窒素を孤立置換型
不純物として数十ｐｐｍから数百ｐｐｍ含み（Ｉｂ
型）、各種の特性に影響を及ぼす。特に、紫外域と赤外
域に窒素不純物による強い吸収が生じる。また、この窒
素不純物は結晶中に不均一に分布しており、このため、
結晶内部に少なからず歪が生じる。DETAILED DESCRIPTION OF THE INVENTION Natural diamond contains many nitrogen impurities and reflects the complex growth history inside the earth.
All natural diamonds have many strains and crystal defects in the crystal, and there is great variation due to the crystal. It is almost impossible to stably obtain high-quality crystals free from impurities and crystal defects from natural diamond. On the other hand, a synthetic diamond single crystal in which diamond is grown under high pressure and high temperature conditions that are thermodynamically stable has much better crystallinity than natural diamond and stable quality.
However, ordinary synthetic diamond contains tens to hundreds of ppm of nitrogen as an isolated substitutional impurity (Ib
Type), and affect various characteristics. In particular, strong absorption by nitrogen impurities occurs in the ultraviolet region and the infrared region. Also, this nitrogen impurity is unevenly distributed in the crystal,
Not a little distortion occurs inside the crystal.
【０００７】この合成ダイヤモンドの窒素不純物は、窒
素ゲッターを溶媒に添加することで除去できるが、イン
クルージョンを含み易くなり良質な結晶が得られなくな
る。しかし、本発明者らにより、窒素ゲッターを添加し
ても良質な結晶が得られる方法が提示された（Sumiya e
t al., Diamond and Related Materials, 5, 1359(199
6) ）。窒素不純物を３ｐｐｍ以下、特に０．１ｐｐｍ
以下に制御した高純度合成ダイヤモンド結晶（IIａ型）
は、例えば、次のような方法により得ることができる。
すなわち、炭素源として高純度黒鉛、溶媒金属としてＦ
ｅ−Ｃｏ等を用い、窒素ゲッターとしてＴｉを１．０〜
２．０重量％の割合で溶媒に添加する。得られた原料系
は、種結晶と共に超高圧発生装置内に配置し、圧力約
５．５ＧＰａ、温度約１３５０℃に数〜数十時間、炭素
源と種結晶部間の温度差２０〜５０℃として種結晶上に
ダイヤモンドを生長させる。このようにして、窒素不純
物を３ｐｐｍ以下に制御した高純度合成ダイヤモンド結
晶（IIａ型）は、不純物による結晶欠陥や歪がない。こ
のため、硬度、強度などの機械的特性が向上し、品質の
バラツキも小さくなると考えられる。また、紫外域の２
７０ｎｍに若干窒素不純物による吸収があるものの、そ
れ以外は不純物による吸収がない。窒素量を０．１ｐｐ
ｍ以下にすれば２７０ｎｍの吸収も見られず、紫外か
ら、遠赤外まで透明な結晶が得られる。[0007] Nitrogen impurities in the synthetic diamond can be removed by adding a nitrogen getter to the solvent, but the inclusion tends to include inclusions, so that good quality crystals cannot be obtained. However, the present inventors have proposed a method by which a good-quality crystal can be obtained even when a nitrogen getter is added (Sumiya e).
t al., Diamond and Related Materials, 5, 1359 (199
6)). 3ppm or less of nitrogen impurities, especially 0.1ppm
High purity synthetic diamond crystal (IIa type) controlled as follows
Can be obtained, for example, by the following method.
That is, high-purity graphite as a carbon source and F as a solvent metal
Using e-Co or the like, Ti
2.0% by weight are added to the solvent. The obtained raw material system is placed together with the seed crystal in an ultra-high pressure generator, at a pressure of about 5.5 GPa, a temperature of about 1350 ° C. for several to several tens of hours, and a temperature difference between the carbon source and the seed crystal part of 20 to 50 ° C. To grow diamond on the seed crystal. Thus, the high-purity synthetic diamond crystal (IIa type) in which the nitrogen impurity is controlled to 3 ppm or less has no crystal defects or distortion due to the impurity. For this reason, it is considered that mechanical properties such as hardness and strength are improved, and variations in quality are reduced. In addition, ultraviolet 2
At 70 nm, there is some absorption by nitrogen impurities, but otherwise there is no absorption by impurities. 0.1 pp of nitrogen
If it is less than m, absorption at 270 nm is not observed, and a transparent crystal from ultraviolet to far infrared can be obtained.
【０００８】本発明者等は、この高純度合成ダイヤモン
ドの機械的特性を詳細に調べたところ、天然ダイヤモン
ドや従来の合成ダイヤモンドに見られない特徴を有する
ことを見いだした。表１に、窒素量の異なる合成ダイヤ
モンド結晶の（１００）面の＜１００＞方向及び＜１１
０＞方向のヌープ硬度を測定した結果を示す。（１０
０）面＜１００＞方向のヌープ硬度は、図１に示すよう
に、窒素量の減少とともに向上する。窒素量１ｐｐｍ以
下のものは、硬度１００００ｋｇ／ｍｍ2 以上と高硬度
である。また、窒素が３ｐｐｍ以下の合成ダイヤモンド
結晶においては、（１００）面＜１１０＞方向は正常な
ヌープ圧痕が形成されず、非常に硬いことを示す。図２
に、窒素量０．１ｐｐｍの合成IIａ型ダイヤモンド結晶
と、６０〜２４０ｐｐｍの窒素を含むＩｂ型ダイヤモン
ド結晶、及び天然のＩａ型ダイヤモンド結晶（凝集型窒
素不純物を約１０００ｐｐｍ含む）の（１００）面上の
各方位のヌープ硬度の測定結果を示す。The present inventors have examined the mechanical properties of the high-purity synthetic diamond in detail and found that the high-purity synthetic diamond has characteristics not found in natural diamond and conventional synthetic diamond. Table 1 shows the <100> direction and <11> of the (100) plane of synthetic diamond crystals having different nitrogen contents.
The result of measuring the Knoop hardness in the 0> direction is shown. (10
0) The Knoop hardness in the <100> plane increases as the amount of nitrogen decreases, as shown in FIG. Those having a nitrogen content of 1 ppm or less have high hardness of 10,000 kg / mm 2 or more. In the case of a synthetic diamond crystal containing 3 ppm or less of nitrogen, a normal Knoop indentation is not formed in the (100) plane <110> direction, indicating that the crystal is very hard. FIG.
On the (100) plane of a synthetic IIa diamond crystal having a nitrogen amount of 0.1 ppm, an Ib type diamond crystal containing 60 to 240 ppm of nitrogen, and a natural Ia type diamond crystal (containing about 1000 ppm of aggregated nitrogen impurities) 3 shows the measurement results of the Knoop hardness in each direction.
【０００９】天然Ｉａ型ダイヤモンドや通常の合成Ｉｂ
型ダイヤモンドは（１００）面上では＜１００＞方向が
＜１１０＞方向より硬いが、不純物量３ｐｐｍ以下の合
成IIａ型ダイヤモンドはこれとは逆の傾向を示し、特に
＜１１０＞方向は、ヌープ圧子による圧痕が形成され
ず、極めて硬い。これは、合成IIａ型ダイヤモンド結晶
は圧子押し込みによる変形の起点となる不純物、欠陥が
極めて少ないためと考えられる。なお、不純物３ｐｐｍ
を越えるとこの傾向は見られなくなり、天然Ｉａ型ダイ
ヤモンド結晶や合成Ｉｂ型ダイヤモンド結晶と同様の傾
向を示すようになる。 このように、不純物を３ｐｐｍ
以下に制御した高純度合成IIａ型ダイヤモンド結晶は、
従来の合成ダイヤモンドや天然ダイヤモンドより機械的
特性に非常に優れることが明らかとなった。また、合成
IIａ型ダイヤモンドは、不純物による光学的な吸収がな
く、このため、レーザーを照射したときに、ルミネッセ
ンスやアブレーションを起こすことがない。[0009] Natural Ia type diamond and ordinary synthetic Ib
In the type diamond, the <100> direction is harder than the <110> direction on the (100) plane, but the synthetic IIa type diamond having an impurity amount of 3 ppm or less shows the opposite tendency. In particular, the <110> direction is a Knoop indenter. No indentation is formed, and it is extremely hard. This is presumably because the synthetic IIa type diamond crystal has very few impurities and defects which are the starting points of deformation due to indentation. In addition, impurity 3ppm
When the ratio exceeds 1, this tendency is not observed, and the same tendency as the natural Ia type diamond crystal and the synthetic Ib type diamond crystal is obtained. Thus, the impurities are 3 ppm
The high-purity synthetic type IIa diamond crystal controlled as follows:
It has become clear that the mechanical properties are much better than conventional synthetic diamonds and natural diamonds. Also synthetic
Type IIa diamond has no optical absorption due to impurities, and therefore does not cause luminescence or ablation when irradiated with laser.
【００１０】一方、合成ダイヤモンドは一般に、種結晶
を起点として、図３のような線状の転位欠陥を有するこ
とがＸ線トポグラフで観察できる。この欠陥が超高圧発
生部にあると、破壊の原因となる。この転位欠陥は、種
結晶の欠陥が原因と考えられ、欠陥の少ない結晶の種を
用いることで、大幅に低減できる。特に、＜００１＞方
向の転位欠陥はほとんど除去することができる。On the other hand, it can be observed by an X-ray topograph that a synthetic diamond generally has a linear dislocation defect as shown in FIG. 3 starting from a seed crystal. If this defect is present in the ultrahigh-pressure generating section, it causes destruction. This dislocation defect is considered to be caused by a seed crystal defect, and can be greatly reduced by using a crystal seed having few defects. In particular, dislocation defects in the <001> direction can be almost completely removed.
【００１１】以上の知見から、不純物量を３ｐｐｍ以
下、好ましくは０．１ｐｐｍ以下で、超高圧発生部に欠
陥（線状転位欠陥）のないダイヤモンドアンビルを作製
した。不純物量３ｐｐｍ以下の高純度ダイヤモンド（II
ａ型）の合成は、高圧高温下での温度差法によるダイヤ
モンド結晶合成において、高純度な炭素源、Ｆｅ−Ｃｏ
溶媒を用い、溶媒にＴｉなどの窒素ゲッターを添加する
ことで可能である。また、低欠陥ダイヤモンド結晶から
切り出した結晶を種にすることで、種面上＜００１＞方
向に延びる線状の転位欠陥のないダイヤモンドの合成が
可能である。こうして得られたダイヤモンド結晶の＜０
０１＞方向が、アンビルの加圧軸方向と平行となるよう
にすることで、超高圧発生部には転位欠陥がないアンビ
ルを作製することができる。ダイヤモンドの＜００１＞
方向とアンビルの加圧軸方向のズレ角は３度以下が好ま
しい。３度を越えるとアンビルが圧壊しやすくなるから
である。また、ダイヤモンドアンビルの上下面の平行度
は１分以下が好ましい。１分を越えると、超高圧発生
時、アンビルに不均一な応力がかかり壊れ易くなるから
である。こうして、従来のダイヤモンドアンビルよりは
るかに壊れ難く、また、光学的な問題のないダイヤモン
ドアンビルが得られた。Based on the above findings, a diamond anvil having an impurity amount of 3 ppm or less, preferably 0.1 ppm or less and having no defect (linear dislocation defect) in an ultrahigh pressure generating portion was produced. High-purity diamond with an impurity amount of 3 ppm or less (II
a)) is a high purity carbon source, Fe-Co in a diamond crystal synthesis by a temperature difference method under high pressure and high temperature.
It is possible by using a solvent and adding a nitrogen getter such as Ti to the solvent. In addition, by using a crystal cut from a low defect diamond crystal as a seed, it is possible to synthesize diamond having no linear dislocation defect extending in the <001> direction on the seed surface. <0 of the diamond crystal thus obtained
By setting the <01> direction to be parallel to the direction of the pressure axis of the anvil, an anvil having no dislocation defect in the ultrahigh-pressure generating portion can be manufactured. <001> of diamond
It is preferable that the misalignment angle between the direction and the pressure axis direction of the anvil be 3 degrees or less. If it exceeds 3 degrees, the anvil is easily crushed. The parallelism between the upper and lower surfaces of the diamond anvil is preferably 1 minute or less. If the time exceeds 1 minute, when an ultrahigh pressure is generated, uneven stress is applied to the anvil and the anvil is easily broken. In this way, a diamond anvil which is much harder to break than a conventional diamond anvil and has no optical problem was obtained.
【００１２】[0012]
【実施例】（実施例１）高圧下の温度差法によるダイヤ
モンド結晶の合成において、原料に高純度黒鉛、溶媒に
Ｆｅ−Ｃｏ溶媒を用い、窒素ゲッターとしてＴｉを１．
５重量％、溶媒に添加し、種結晶に低欠陥のダイヤモン
ド結晶を用い（００１）面を種面にして、圧力５．５Ｇ
Ｐａ、温度１３５０℃、合成時間２０時間で、約１カラ
ットの高純度IIａ型ダイヤモンド単結晶を合成した。得
られたダイヤモンド結晶は、無色透明で、紫外可視スペ
クトル、赤外スペクトルとも、窒素などの不純物による
吸収がほとんど認められず、不純物０．１ｐｐｍ以下の
高純度IIａ型結晶であることを確認した。また、圧力検
定用ルビー蛍光測定が可能であることを確認した。ま
た、ＦＴ−ラマン分光によるルミネッセンスの発光は見
られなかった。さらに、試料部加熱のために照射するＹ
ＡＧレーザーによるアブレーションも見られなかった。
また、偏光顕微鏡観察より、内部歪がほとんどなく、Ｘ
線トポグラフ観察から、種結晶上＜００１＞方向の線状
欠陥はほとんど見られなかった。このダイヤモンド結晶
から、０．３カラット、先端面５０μｍ（２段テーパ
ー）のダイヤモンドアンビルを以下のように作製した。
まず、レーザー反射法による平行度測定を行いながら、
上下面の平行度を１分以内になるように研磨した。次
に、アンビルのＺ軸方向が、ダイヤモンドの＜００１＞
方向とのなす角度が３°以下となるように、ダイヤモン
ド側面を研磨し、アンビルの形状に仕上げた。こうして
作製したダイヤモンドアンビルで、超高圧発生実験を行
ったところ、１００ＧＰａを越える超々高圧の安定発生
が可能であった。超高圧下での試料部のラマン分光測定
時に、ルミネッセンス等の問題はなかった。また、レー
ザーアブレーションによる高温実験も可能であった。な
お、上記レーザー反射法による平行度測定を行いながら
する研磨は特開平４−２８５８２８号公報、［００１
３］〜［００１４］に記載された方法によって行った。EXAMPLES Example 1 In the synthesis of diamond crystals by the temperature difference method under high pressure, high-purity graphite was used as a raw material, an Fe—Co solvent was used as a solvent, and Ti was used as a nitrogen getter.
5% by weight, added to a solvent, using a low-defect diamond crystal as a seed crystal, with the (001) plane as the seed plane and a pressure of 5.5 G
About 1 carat of high-purity type IIa diamond single crystal was synthesized at Pa, a temperature of 1350 ° C., and a synthesis time of 20 hours. The obtained diamond crystal was colorless and transparent, and almost no absorption due to impurities such as nitrogen was recognized in both the ultraviolet visible spectrum and the infrared spectrum, and it was confirmed that the diamond crystal was a high-purity type IIa crystal having an impurity of 0.1 ppm or less. It was also confirmed that ruby fluorescence measurement for pressure verification was possible. No luminescence was observed by FT-Raman spectroscopy. Further, Y irradiated for heating the sample portion
No ablation by the AG laser was observed.
In addition, according to observation with a polarizing microscope, there was almost no internal strain, and X
From the line topographic observation, almost no linear defect in the <001> direction was found on the seed crystal. From this diamond crystal, a diamond anvil of 0.3 carats and a tip surface of 50 μm (two-step taper) was prepared as follows.
First, while measuring the parallelism by the laser reflection method,
The upper and lower surfaces were polished so that the parallelism was within 1 minute. Next, the Z-axis direction of the anvil matches the <001> of the diamond.
The diamond side surface was polished so that the angle with the direction was 3 ° or less, and finished in an anvil shape. When an ultra-high pressure generation experiment was performed on the diamond anvil thus manufactured, stable generation of an ultra-high pressure exceeding 100 GPa was possible. At the time of Raman spectroscopy measurement of the sample portion under ultra-high pressure, there was no problem such as luminescence. High temperature experiments by laser ablation were also possible. Polishing while measuring the parallelism by the laser reflection method is described in JP-A-4-285828, [001].
3] to [0014].
【００１３】（比較例１）窒素ゲッターを用いずに、他
は実施例１と同様にしてダイヤモンドを合成した。得ら
れたダイヤモンドは、約１カラットの窒素不純物を含ん
だＩｂ型結晶で、黄色を呈していた。赤外吸収スペクト
ルより見積もった窒素量は約６０ｐｐｍであった。偏光
顕微鏡観察より、窒素不純物の不均一分布に対応した内
部歪が見られた。この合成Ｉｂ型ダイヤモンド結晶よ
り、実施例１と同様のダイヤモンドアンビルを作製し
た。紫外可視分光測定により、６００ｎｍ付近より窒素
不純物による吸収がみられた。この吸収のため、ルビー
蛍光の測定が困難であった。また、ＦＴ−ラマンによる
蛍光が見られた。そして、ＹＡＧレーザー照射によりダ
イヤモンドの照射部がえぐれてしまうことがわかった。
このダイヤモンドアンビルを用いて超高圧発生実験を行
ったが、約８５ＧＰａで破壊した。Comparative Example 1 Diamond was synthesized in the same manner as in Example 1 except that a nitrogen getter was not used. The resulting diamond was about 1 carat of type Ib crystals containing nitrogen impurities and had a yellow color. The amount of nitrogen estimated from the infrared absorption spectrum was about 60 ppm. Observation with a polarizing microscope revealed internal strains corresponding to the non-uniform distribution of nitrogen impurities. From this synthetic Ib type diamond crystal, a diamond anvil similar to that of Example 1 was produced. By ultraviolet-visible spectroscopy, absorption by nitrogen impurities was observed at around 600 nm. Due to this absorption, it was difficult to measure ruby fluorescence. In addition, fluorescence due to FT-Raman was observed. Then, it was found that the irradiated portion of the diamond was clogged by the YAG laser irradiation.
An ultra-high pressure generation experiment was performed using this diamond anvil, but it was broken at about 85 GPa.
【００１４】（比較例２）種結晶に市販の合成ダイヤモ
ンド砥粒を用いた他は実施例１と同様にしてダイヤモン
ドを合成した。得られたダイヤモンドは、約１カラット
で、窒素不純物０．１ｐｐｍ以下のIIａ型結晶であっ
た。この合成ダイヤモンドをＸ線トポグラフで観察した
ところ、種結晶部から線状の転位欠陥が多くみられ、＜
００１＞方向にも見られた。この合成ダイヤモンド結晶
より、実施例１と同様のダイヤモンドアンビルを作製し
た。このダイヤモンドアンビルは、光の吸収やルミネッ
センス、アブレーションなどの光学的な問題はほとんど
見られなかった。このダイヤモンドアンビルを用いて超
高圧実験を行った。１００ＧＰａまでの圧力発生が可能
であったが、実験後、アンビルの先端を観察すると、小
さなクラックやカケが見られた。Comparative Example 2 A diamond was synthesized in the same manner as in Example 1 except that a commercially available synthetic diamond abrasive was used as a seed crystal. The obtained diamond was about 1 carat and was a type IIa crystal having a nitrogen impurity of 0.1 ppm or less. When this synthetic diamond was observed with an X-ray topograph, many linear dislocation defects were observed from the seed crystal part.
001> direction. From this synthetic diamond crystal, a diamond anvil similar to that of Example 1 was produced. The diamond anvil had almost no optical problems such as light absorption, luminescence and ablation. An ultra-high pressure experiment was performed using this diamond anvil. Although pressure generation up to 100 GPa was possible, small cracks and chips were observed when the tip of the anvil was observed after the experiment.
【００１５】[0015]
【表１】 ＊圧痕が形成されないため測定不可[Table 1] * Measurement is not possible because no indentation is formed
【００１６】[0016]
【発明の効果】高圧下の温度差法により合成された不純
物量３ｐｐｍ以下の機械的特性に非常に優れたダイヤモ
ンド単結晶より、ダイヤモンド単結晶の＜００１＞方向
とアンビルの加圧軸方向のズレ角が３度以下となるよう
アンビル形状に仕上げることにより超高圧発生部には転
位欠陥のないアンビルとすることができる。こうして、
従来のダイヤモンドアンビルよりはるかに壊れ難く、光
学的に問題のないアンビルが得られる。The difference between the <001> direction of the diamond single crystal and the direction of the pressure axis of the anvil is greater than that of the diamond single crystal synthesized by the temperature difference method under high pressure and having excellent mechanical properties with an impurity amount of 3 ppm or less. By finishing the anvil so that the angle is 3 degrees or less, the anvil having no dislocation defect in the ultrahigh-pressure generating portion can be obtained. Thus,
An anvil that is much harder to break than conventional diamond anvils and has no optical problems is obtained.
【図１】図１は、本発明による合成ダイヤモンドを含む
各種合成ダイヤモンド結晶の（１００）＜１００＞のヌ
ープ硬度と不純物量との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the (100) <100> Knoop hardness and the amount of impurities of various synthetic diamond crystals including the synthetic diamond according to the present invention.
【図２】図２は、本発明による合成ダイヤモンドを含む
各種ダイヤモンド結晶の（１００）面上のヌープ硬度の
異方性を示すグラフである。FIG. 2 is a graph showing the anisotropy of Knoop hardness on the (100) plane of various diamond crystals including the synthetic diamond according to the present invention.
【図３】図３は、通常の合成ダイヤモンドに見られる線
状欠陥の入り方を示す概略図である。FIG. 3 is a schematic diagram showing how linear defects appear in a normal synthetic diamond.
Claims (4)
物量３ｐｐｍ以下のダイヤモンド単結晶から作製された
超高圧発生用ダイヤモンドアンビルであり、アンビルの
先端部（超高圧を発生させる部分）に、結晶欠陥を含ま
ず、合成ダイヤモンド単結晶の＜００１＞方向と、アン
ビルの加圧方向とのなす角が３度以下であることを特徴
とする超高圧発生用ダイヤモンドアンビル。1. An ultra-high pressure generating diamond anvil made from a diamond single crystal having an impurity amount of 3 ppm or less synthesized by a temperature difference method under a high pressure, wherein the anvil has a tip (a part generating an ultra high pressure) An ultra-high pressure generation diamond anvil, which does not contain crystal defects and has an angle between the <001> direction of the synthetic diamond single crystal and the pressing direction of the anvil of 3 degrees or less.
１＞方向に平行な線状の転位欠陥を含まないことを特徴
とする請求項１に記載の超高圧発生用ダイヤモンドアン
ビル。2. The synthetic diamond single crystal of claim 1
The diamond anvil for generating an ultra-high pressure according to claim 1, wherein the diamond anvil does not include a linear dislocation defect parallel to the 1> direction.
又は２に記載の超高圧発生用ダイヤモンドアンビル。3. The method according to claim 1, wherein the amount of impurities is 0.1 ppm or less.
Or the diamond anvil for generating an ultrahigh pressure according to 2.
行度が１分以下であることを特徴とする請求項１〜３の
いずれかに記載の超高圧発生用ダイヤモンドアンビル。4. The diamond anvil according to claim 1, wherein the parallelism between the upper surface and the lower surface of the diamond anvil is 1 minute or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10113166A JPH11300194A (en) | 1998-04-23 | 1998-04-23 | Diamond anvil for ultra high pressure generation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10113166A JPH11300194A (en) | 1998-04-23 | 1998-04-23 | Diamond anvil for ultra high pressure generation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11300194A true JPH11300194A (en) | 1999-11-02 |
Family
ID=14605235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10113166A Pending JPH11300194A (en) | 1998-04-23 | 1998-04-23 | Diamond anvil for ultra high pressure generation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11300194A (en) |
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| JP2006508881A (en) * | 2002-09-20 | 2006-03-16 | エレメント シックス リミテッド | Single crystal diamond |
| JP2009518259A (en) * | 2004-12-09 | 2009-05-07 | エレメント シックス テクノロジーズ （プロプライアタリー）リミテッド | A method for improving the crystal integrity of diamond crystals. |
| JP2011219306A (en) * | 2010-04-09 | 2011-11-04 | National Institute For Materials Science | Gadolinium sulfide type structure yttrium oxide and production method therefor |
| JPWO2022210723A1 (en) * | 2021-03-31 | 2022-10-06 |
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| JPH07148426A (en) * | 1993-10-08 | 1995-06-13 | Sumitomo Electric Ind Ltd | Synthetic diamond, manufacturing method thereof, and diamond strain measuring method |
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| JP2006508881A (en) * | 2002-09-20 | 2006-03-16 | エレメント シックス リミテッド | Single crystal diamond |
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| JPWO2022210723A1 (en) * | 2021-03-31 | 2022-10-06 | ||
| WO2022210723A1 (en) * | 2021-03-31 | 2022-10-06 | 住友電気工業株式会社 | Single-crystal diamond and diamond composite comprising same |
| EP4317544A4 (en) * | 2021-03-31 | 2024-08-28 | Sumitomo Electric Industries, Ltd. | SINGLE CRYSTAL DIAMOND AND DIAMOND COMPOSITE |
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