JPH03236470A - Production of diamond - Google Patents
Production of diamondInfo
- Publication number
- JPH03236470A JPH03236470A JP2971290A JP2971290A JPH03236470A JP H03236470 A JPH03236470 A JP H03236470A JP 2971290 A JP2971290 A JP 2971290A JP 2971290 A JP2971290 A JP 2971290A JP H03236470 A JPH03236470 A JP H03236470A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- substrate
- film
- gas
- nucleation
- 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 98
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 87
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 44
- 230000006911 nucleation Effects 0.000 abstract description 32
- 238000010899 nucleation Methods 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000013078 crystal Substances 0.000 description 26
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001947 vapour-phase growth Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- -1 carbon ions Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［発明の目的コ
（産業上の利用分野）
本発明は、炭素を含むガスを分解して基体上にダイヤモ
ンドを析出させるダイヤモンドの気相合成峡に係り、特
に、薄膜状及び粒状ダイヤモンドの製造に適したダイヤ
モンドの製造方法に関する。Detailed Description of the Invention [Objective of the Invention (Industrial Application Field) The present invention relates to a diamond vapor phase synthesis method for depositing diamond on a substrate by decomposing a carbon-containing gas. The present invention relates to a diamond manufacturing method suitable for manufacturing diamond shaped and granular diamonds.
（従来の技術）
近年、低圧下で気相成長法によるダイヤモンド合成が可
能となり、この気相合成ダイヤモンドは工業的応用とし
て、工具被覆、耐食性保護膜、耐摩耗性摺動部材、スピ
ーカー振動板やバイブ等の成形体、ヒートシンク、光学
レンズ、発光素子、半導体等種々の用途か検討されてい
る。(Conventional technology) In recent years, it has become possible to synthesize diamond using the vapor phase growth method under low pressure, and this vapor phase synthesized diamond has been used in industrial applications such as tool coatings, corrosion-resistant protective films, wear-resistant sliding members, speaker diaphragms, etc. Various uses are being considered, including molded objects such as vibrators, heat sinks, optical lenses, light emitting elements, and semiconductors.
このダイヤモンドを気相から合成する方法として、各種
の化学気相成長法（ＣＶＤ法）や物理気相成長法（ＰＶ
Ｄ法）が知られている。いずれの方法であっても、ダイ
ヤモンドの析出は、下地あるいは基板と呼ばれる基体の
表面に行なわれるのが一般的であり、基体の材質や表面
状態がダイヤモンドの析出と密接な関係にある。例えば
、ダイヤモンドを膜として形成する場合には、基体上で
のダイヤモンドの結晶核形成密度を上げることにより膜
の緻密化と厚さの均一化を計らなければならないが、こ
の結晶核形成密度は基体の材質や基体の表面状態に影響
される。また、基体上の所望の個所にのみ選択的にダイ
ヤモンドを析出させる場合には、基体のその部分のみが
ダイヤモンドの析出に好都合な条件となっていることが
必要で、これも基体上での結晶核形成密度に深く関係し
ている。さらに、ダイヤモンド粒を製造する場合には、
粒どうしが接触・接合せずに独立した状態で成長するよ
うに、基体上の結晶核形成位置を調整することが必要に
なる。There are various chemical vapor deposition methods (CVD methods) and physical vapor deposition methods (PV
D method) is known. Regardless of the method, diamond is generally deposited on the surface of a base called a base or substrate, and the material and surface condition of the base are closely related to diamond deposition. For example, when forming diamond as a film, it is necessary to increase the density of diamond crystal nucleation on the substrate to make the film denser and more uniform in thickness. It is affected by the material and surface condition of the substrate. In addition, when selectively depositing diamond only on a desired location on a substrate, it is necessary that only that portion of the substrate has favorable conditions for diamond precipitation; It is closely related to nucleation density. Furthermore, when producing diamond grains,
It is necessary to adjust the crystal nucleation position on the substrate so that the grains grow independently without contacting or joining each other.
このように、基体はダイヤモンドの製造技術における重
要な因子であり、種々の目的を達成するためにダイヤモ
ンド析出前の基体に前処理を行うことが検討されている
。例えば、核形成密度を上げる、すなわち、核形成を容
易にする活性点を基体上に高密度につくるための基体表
面処理方法が提案されている。その代表的なものは、基
体表面に傷を付ける方法（以下、傷付は処理と呼ぶ）で
あり、傷付は処理方法として例えば、ワセリン中に分散
させたダイヤモンド粉を用いて鋭い擦り傷を付ける方法
（特公昭６２−２７０３９号公報）、表面粗さが１−５
３ （１〜５μｍＲ−１，）の条件の粗面とする方法（
特開昭６０−２００８９７号公報）、表面粗さが１．０
μｍ以下とする方法（特開昭６１−１２４５７３号公報
、同６２−１１３７９６号公報等）、研磨粉として１μ
ｍ以下の砥粒を用いる方法（特開昭６２−１０８７９８
号公報）、ダイヤモンドの微粉を混入させた液中に基体
を浸して超音波をかける方法（特開昭６１−１２１８５
９号公報、特開昭６２−２２６８８９号公報）等が知ら
れている。また、基体とダイヤモンド膜との密着性を高
めることを目的とした、２〜１０μｍのサイズの砥粒を
用いて傷付は処理を施す方法（特開昭６２−１０８７９
９号公報）か公知である。As described above, the substrate is an important factor in diamond manufacturing technology, and pretreatment of the substrate before diamond precipitation is being considered in order to achieve various purposes. For example, a substrate surface treatment method has been proposed to increase the nucleation density, that is, to create a high density of active sites on the substrate to facilitate nucleation. A typical method is to scratch the surface of the substrate (hereinafter, scratching is referred to as treatment), and the scratching is treated by, for example, making sharp scratches using diamond powder dispersed in Vaseline. method (Japanese Patent Publication No. 62-27039), surface roughness is 1-5
3. A method of roughening the surface under the conditions of (1 to 5 μmR-1,) (
JP-A No. 60-200897), surface roughness is 1.0
1μm or less (Japanese Unexamined Patent Publications No. 61-124573, No. 62-113796, etc.), 1μm as polishing powder
Method using abrasive grains of less than
(Japanese Unexamined Patent Publication No. 12185/1986), a method of applying ultrasonic waves by immersing the substrate in a liquid containing fine diamond powder
No. 9, Japanese Unexamined Patent Publication No. 62-226889), etc. are known. In addition, a method of treating scratches using abrasive grains with a size of 2 to 10 μm (Japanese Unexamined Patent Publication No. 62-10879) aims to improve the adhesion between the substrate and the diamond film.
No. 9) is publicly known.
一方、傷付は処理以外の基体前処理法としては、核形成
密度の増大や密着性向上などを目的として超硬合金基体
を研削して表面に加工歪を与える方法（特開昭６１−２
７０３７２号公報）、基体表面の活性化を目的とした、
Ａ「イオンを用いてイオンエツチングする方法（特開昭
６０−２００８９８号公報）、酸素プラズマのガスを基
体表面に吹き付ける方法（特開昭６１へ１７４３７６号
公報）、金属系基体表面に対して酸素を拡散処理する方
法（特開昭６１−９７１９４号公報）等が知られている
。On the other hand, as a substrate pretreatment method other than scratch treatment, there is a method of grinding a cemented carbide substrate and applying processing strain to the surface for the purpose of increasing the nucleation density and improving adhesion (Japanese Patent Laid-Open No. 61-2
70372), aimed at activating the substrate surface,
A: A method of ion etching using ions (Japanese Unexamined Patent Publication No. 60-200898), a method of spraying oxygen plasma gas onto the surface of the substrate (Japanese Unexamined Patent Publication No. 174376 to 1983), A method of performing a diffusion treatment (Japanese Unexamined Patent Publication No. 61-97194) is known.
以上の方法は、いずれもダイヤモンドの析出に好都合な
状態に基板表面を変化させるという点で共通しているか
、特に、傷付は処理はダイヤモンドの連続膜を形成する
際に広く用いられている有効な方法である。しかしなが
ら傷付は処理を行なっても、形成されたダイヤモンド膜
は、成長初期の核形成密度が小さいことに起因して表面
粗さが相当大きく、換言すれば、膜の表面の平滑度が小
さく、実用上問題になる場合がある。All of the above methods have in common that they change the substrate surface to a state favorable for diamond precipitation. In particular, scratch treatment is an effective method widely used to form a continuous diamond film. This is a great method. However, even if scratches are treated, the surface roughness of the formed diamond film is considerably large due to the low nucleation density at the initial stage of growth.In other words, the surface smoothness of the film is low. This may cause problems in practice.
膜の平滑度について詳しく説明すると、ダイヤモンド以
外の物質から成る基体上に形成されるダイヤモンド膜は
一般には多結晶膜であり、基体表面で核形成したダイヤ
モンドがこれ以外の場所で核形成せずにそれぞれ成長す
ることによって、基体全面を覆うダイヤモンド膜が形成
されるので、膜の表面粗さの程度は最外表にある結晶粒
の大きさに依存することととなる。例えば、傷付は処理
を施したＳｉ基体上に電子衝撃ＣＶＤ法を用いてダイヤ
モンドを析出させた場合、核形成密度は１０８〜１０９
個／Ｃｌ１１２であり、傷付は処理を施さない場合（１
０４個／ｃｍ２）に比べ各段に大きくなるが、得られた
膜の結晶粒の平均的な大きさは直径１μｍ以上あり、従
って鏡面のような平滑な表面の膜は得られない。そして
、膜を構成する結晶粒の大きさは成長初期の核形成密度
によって変化し、核形成密度が大きいほど膜の結晶粒は
微細になると考えられている。従って、表面粗さか小さ
い平滑な膜を得るためには、核形成密度を従来よりも一
層大きくする必要がある。To explain the smoothness of the film in detail, a diamond film formed on a substrate made of a substance other than diamond is generally a polycrystalline film, in which diamond nucleates on the substrate surface do not nucleate elsewhere. As a result of each growth, a diamond film covering the entire surface of the substrate is formed, so the degree of surface roughness of the film depends on the size of the crystal grains on the outermost surface. For example, when diamond is deposited using electron impact CVD on a Si substrate that has been subjected to scratch treatment, the nucleation density is 108 to 109.
/Cl112, and the damage is when no treatment is applied (1
Although the average size of the crystal grains in the obtained film is 1 μm or more in diameter, it is not possible to obtain a film with a mirror-like smooth surface. It is believed that the size of the crystal grains constituting the film changes depending on the nucleation density at the initial stage of growth, and the higher the nucleation density, the finer the crystal grains of the film will be. Therefore, in order to obtain a smooth film with low surface roughness, it is necessary to increase the nucleation density even higher than in the past.
また、基体表面の所望の位置に核形成するような場合、
例えば１μｍ以下の幅でダイヤモンドから成る連続線を
形成する場合には、線かはやけずに、連続して形成され
るために、境界形成すべき連続線の領域では高い結晶核
発生密度が要求される。しかし、従来技術では結晶核発
生密度が小さいので、形成し得る線の幅が大きくなり、
線の明瞭さも劣ることから、実用上の用途が限定されて
しまう不都合が生ずる傾向にある。In addition, when nucleation occurs at a desired position on the substrate surface,
For example, when forming a continuous line made of diamond with a width of 1 μm or less, a high crystal nucleation density is required in the area of the continuous line where the boundary should be formed in order to form the line continuously without burning. be done. However, in the conventional technology, the density of crystal nucleation is low, so the width of the lines that can be formed becomes large.
Since the clarity of the lines is also poor, there tends to be a disadvantage that the practical use is limited.
（発明が解決しようとする課題）
上述したように、従来のダイヤモンド製造方法では、基
体上の結晶核形成密度が小さいことに起因して、平滑な
表面の膜を形成しにくく、また、基体上の所望の位置の
みに、例えばダイヤモンドから成る微細なパターンを明
瞭に形成しにくいという問題があった。(Problems to be Solved by the Invention) As mentioned above, in the conventional diamond manufacturing method, it is difficult to form a film with a smooth surface due to the low crystal nucleation density on the substrate. There is a problem in that it is difficult to clearly form a fine pattern made of, for example, diamond only at a desired position.
本発明は、上記した従来技術の課題を解決するためにな
されたもので、その目的とするところは、結晶核形成密
度を増加させる、あるいは核形成位置を制御することに
より、平滑度が大きいダイヤモンド膜や、基体上の所望
の位置に大形のダイヤモンド粒を効率良く製造すること
ができ、また基体上にダイヤモンドから成る微細なパタ
ーンを明瞭に形成し得るダイヤモンドの製造方性を提供
することにある。The present invention was made in order to solve the problems of the prior art described above, and its purpose is to increase the crystal nucleation density or control the nucleation position so that diamonds with high smoothness can be produced. To provide a method for producing diamond that can efficiently produce large diamond grains at desired positions on a film or a substrate, and that can clearly form a fine pattern made of diamond on the substrate. be.
［発明の槽底］
（課題を解決するための手段とｆ”Ｆ Ｆｆ３）本発明
者等は、上記目的を達成すべく鋭意研究を重ねた結果、
ダイヤモンド析出処理前に、微小な凹凸を設けた基体表
面にフッ素、塩素、臭素、ヨウ素のうちの少なくとも１
種の元素を含む物質を作用させることにより上記目的が
達成できることを見出し、本発明を完成させるに至った
。[Bottom of the invention] (Means for solving the problem and f”F Ff3) As a result of intensive research to achieve the above object, the present inventors have discovered that
Before the diamond precipitation treatment, at least one of fluorine, chlorine, bromine, and iodine is applied to the surface of the substrate with minute irregularities.
The present inventors have discovered that the above object can be achieved by using a substance containing certain elements, and have completed the present invention.
すなわち、本発明のダイヤモンドの製造方法は、炭素を
含むガスを分解して基体上にダイヤモンドを析出させる
ダイヤモンドの製造方法において、前記基体表面上に凹
凸を設け、この凹凸部にフッ素、塩素、臭素及びヨウ素
から成る群の中から選ばれる少なくとも１種の元素を含
む物質を作用させた後、この基体上にダイヤモンドを析
出させることを特徴とする。That is, the diamond manufacturing method of the present invention is a diamond manufacturing method in which carbon-containing gas is decomposed to deposit diamond on a substrate, in which unevenness is provided on the surface of the substrate, and fluorine, chlorine, and bromine are added to the uneven portion. The method is characterized in that diamond is precipitated on the substrate after being treated with a substance containing at least one element selected from the group consisting of iodine and iodine.
以下に本発明をさらに詳しく説明する。The present invention will be explained in more detail below.
本発明は、反応容器中に基体を設置し、反応容器内に炭
素もしくは炭素化合物を含有する原料ガスを導入し、こ
の原料ガスの励起および分解によって生じた炭素の活性
化により前記基体表面にダイヤモンドを析出させるダイ
ヤモンドの製造方法において、まず、基体の前処理とし
て、ダイヤモンドを核形成し成長させたい基体表面の所
望の位置あるいは領域に対して微小な凹凸部を形成する
。In the present invention, a substrate is placed in a reaction vessel, a raw material gas containing carbon or a carbon compound is introduced into the reaction vessel, and carbon is activated by excitation and decomposition of this raw material gas to form diamonds on the surface of the substrate. In the method for producing diamond in which diamond is precipitated, first, as a pretreatment of the substrate, minute irregularities are formed at desired positions or regions on the surface of the substrate where diamond is to be nucleated and grown.
ここで、微小な凹凸部とは、基板表面を基準にして凹部
もしくは凸部が存在する状態であり、この凹凸部の形状
を直方体で近似した場合に縦、横、高さのそれぞれが１
μｍ以下であることが好ましい。当然ながら、この凹凸
部の形態は直方体である必要はなく、上記の縦と横と高
さの長さの実質的な意味は、基体表面を平面としてそれ
から始まる凹部あるいは凸部の体積が最大でも１μｍ３
および底面の面積か最大でも１μｍ２であることである
。Here, the minute unevenness is a state where there are depressions or protrusions based on the substrate surface, and when the shape of this unevenness is approximated by a rectangular parallelepiped, each of the length, width, and height is 1.
It is preferable that it is less than μm. Naturally, the form of this uneven part does not have to be a rectangular parallelepiped, and the actual meaning of the above-mentioned length, width, and height is that even if the volume of the concave or convex part starting from the base surface is the maximum, 1μm3
And the area of the bottom surface should be at most 1 μm2.
二のような微小な凹凸部を基体表面の所望の領域に形成
する方法はとくに限定されず、上述の寸法の凹凸を形成
可能な方法であればよい。例えば、いわゆる傷付は処理
、高い運動エネルギーを持つ粒子（イオン、クラスター
、粉末等）や流体（気体、液体等）を高速で衝突させて
、基体表面層の原子をたたき出す方法、気体物質に対し
て反応性の高い物質（酸、アルカリ等の化学薬品や反応
性のガス）を用いたいわゆるエツチング等の方法が適用
可能である。また、特に凸部は、基体上に基体物質と同
じあるいは異種の物質を堆積させることによって形成す
ることができるので、各種の物理蒸着法、化学蒸着法、
メツキ等の方法が適用可能である。The method for forming minute unevenness portions such as 2 above in a desired area of the substrate surface is not particularly limited, and any method may be used as long as it is capable of forming unevenness having the above-mentioned dimensions. For example, so-called scratching can be achieved by processing, by colliding particles with high kinetic energy (ions, clusters, powder, etc.) or fluids (gas, liquid, etc.) at high speed to knock out atoms on the surface layer of the substrate, and by A method such as so-called etching using a highly reactive substance (chemicals such as acid or alkali or reactive gas) can be applied. In addition, in particular, the convex portion can be formed by depositing the same or different material as the base material on the base material, so various physical vapor deposition methods, chemical vapor deposition methods,
The method of Metsuki et al. is applicable.
上記凹凸部を形成した基体についてダイヤモンドの成長
実験を行なった結果、ダイヤモンドの析出に先立ってこ
の基体の凹凸部にフッ素、塩素、臭素、ヨウ素のうちの
少なくとも１種の元素を含む物質（以下作用物質と称す
）を作用させることが、ダイヤモンドの結晶核形成密度
の増加に有効であることが見出された。上記作用物質は
無機物質に対する反応性が高いので、凹凸部物質と化学
的に反応しやすく、生じた反応生成物はガス化しやすい
ため容易に除去し得る。従って、その後のダイヤモンド
の核形成に悪影響を及ぼすような反応生成物が残留する
ことはない。As a result of conducting a diamond growth experiment on a substrate with the above-mentioned uneven portions, it was found that, prior to the precipitation of diamond, a substance containing at least one element among fluorine, chlorine, bromine, and iodine (hereinafter referred to as “active”) was formed in the uneven portions of the substrate. It has been found that applying a substance (referred to as a substance) to the diamond is effective in increasing the density of diamond crystal nucleation. Since the above-mentioned active substance has high reactivity with inorganic substances, it easily reacts chemically with the uneven material, and the generated reaction products are easily gasified and therefore can be easily removed. Therefore, no reaction products remain that would adversely affect subsequent diamond nucleation.
そして、基体の凹凸部に対して上記作用物質を作用させ
ることによってダイヤモンドの核形成密度が増加するが
、この場合に、形成されるダイヤモンド膜の厚さの均一
性は凹凸部の分布の均一性に左右されることがわかった
。すなわち、所望の領域に−様な厚さのダイヤモンド膜
を形成するためには、上記作用物質を作用させる前の凹
凸部が、その領域において均一に分散していることが必
要である。凹凸部の分布が偏っている場合には、連続膜
が形成されにくく、また連続膜が形成されたとしても厚
さの均一性が得られないという不都合が生じる。The diamond nucleation density increases by applying the above-mentioned active substance to the uneven portions of the substrate, but in this case, the uniformity of the thickness of the formed diamond film depends on the uniformity of the distribution of the uneven portions. It was found that it depends on That is, in order to form a diamond film of varying thickness in a desired region, it is necessary that the uneven portions be uniformly dispersed in that region before the above-mentioned active substance is applied. When the distribution of the uneven portions is uneven, it is difficult to form a continuous film, and even if a continuous film is formed, the thickness cannot be uniform.
一方、ダイヤモンド粒を独立に成長させ大形化したり、
所望の位置にのみダイヤモンド粒を成長させる場合には
、予め核形成位置を調整しておく必要があるが、このた
めには作用物質を作用させる前に、成長後のダイヤモン
ド粒の大きさを考慮して凹凸部の形成位置（凹凸部間の
間隔や配列様式等）を予め規則的に設定しておくのが好
都合である。すなわち、ダイヤモンド粒を大形化する場
合には、成長時に粒どうしの接触・接合が起こらないよ
うに核形成位置どうしの間に所定の間隔を確保すること
が必要であり、また、基体上の所望の位置にのみ、例え
ばダイヤモンドから成る微小な幅の線を形成する場合に
は、線上の核発生密度が大きく、かつ核形成位置が線上
に規則的な間隔を確保して並んでいることが必要であり
、このためには凹凸部が各場合に対応して規則的に配列
していることが好ましい。On the other hand, by growing diamond grains independently and increasing their size,
In order to grow diamond grains only at desired locations, it is necessary to adjust the nucleation position in advance, but for this purpose, the size of the diamond grains after growth must be considered before applying the agent. It is convenient to regularly set the formation positions of the uneven portions (the spacing between the uneven portions, the arrangement pattern, etc.) in advance. In other words, when increasing the size of diamond grains, it is necessary to maintain a predetermined distance between the nucleation positions so that the grains do not contact or join together during growth. When forming a minute width line made of diamond, for example, only at a desired position, it is necessary that the nucleation density on the line is high and that the nucleation positions are lined up at regular intervals on the line. This is necessary, and for this purpose, it is preferable that the uneven portions are regularly arranged corresponding to each case.
上記作用物質を凹凸部に作用させた後、ダイヤモンドの
析出を行うが、本発明方法は、炭素または炭素を構成成
分とする化学種を含有した原料ガスを放電または加熱に
よって分解、励起する反応過程を制御することによって
気相からダイヤモンドを析出させる方法に適用すること
ができる。例えばこのようなダイヤモンド気相成長とし
て、熱フィラメントによる熱分解を利用する化学気相成
長法、基体への電子衝撃を与えて分解、励起を促進させ
る化学気相成長法、マイクロ波放電や直流放電によるプ
ラズマを用いた化学気相成長法、加速した炭素イオンの
基体への衝突を利用するイオンビーム蒸着法等があり、
いずれの方法でもよい。After the above-mentioned active substance is applied to the uneven portion, diamond is precipitated.The method of the present invention involves a reaction process in which a raw material gas containing carbon or chemical species having carbon as a constituent is decomposed and excited by electric discharge or heating. It can be applied to a method of precipitating diamond from the gas phase by controlling the For example, such diamond vapor phase growth methods include chemical vapor deposition method that utilizes thermal decomposition using a hot filament, chemical vapor deposition method that applies electron bombardment to the substrate to promote decomposition and excitation, microwave discharge and DC discharge. chemical vapor deposition using plasma, and ion beam evaporation using accelerated carbon ions colliding with a substrate.
Either method may be used.
上述の気相成長法において用いる原料ガスは、反応過程
でダイヤモンドに転換し得る炭素源としての炭素もしく
は炭素化合物のガスを含むものであればよい。具体的に
は、ガス化した炭素やメタン、エタン、プロパン、アセ
チレン、アセトン、メタノール、エタノール、ブタノー
ル、アセトアルデヒド等の各種の炭化水素ガスや一酸化
炭素、二酸化炭素等のガスを挙げることができる。化学
気相成長法によって結晶性の良いダイヤモンドを製造す
る場合、原料ガス中に水素を混入させることが好ましい
。この水素の適量は他の反応条件によっても左右される
ため特に限定されないが、上述の炭素を成分とするガス
と水素ガスとの混合比として、（炭素を成分とするガス
）／（水素ガス）−０，００１〜１．０の範囲とするこ
とが好ましい。The raw material gas used in the above-mentioned vapor phase growth method may be any gas containing carbon or carbon compound gas as a carbon source that can be converted into diamond in the reaction process. Specifically, examples include gasified carbon, various hydrocarbon gases such as methane, ethane, propane, acetylene, acetone, methanol, ethanol, butanol, and acetaldehyde, and gases such as carbon monoxide and carbon dioxide. When producing diamond with good crystallinity by chemical vapor deposition, it is preferable to mix hydrogen into the raw material gas. The appropriate amount of hydrogen is not particularly limited as it depends on other reaction conditions, but the mixing ratio of the above-mentioned carbon-based gas and hydrogen gas is (carbon-based gas)/(hydrogen gas). It is preferably in the range of -0,001 to 1.0.
反応圧力については、ダイヤモンドの成長速度に深く関
わる条件であるか、他の反応条件によって左右されるた
め特に限定されない。一般には、圧力か高いと反応に寄
与する炭素の濃度が高まることに起因して成長速度が増
加する。結晶性の良いダイヤモンドを成長させるために
は合成反応の方法に応じた適切な圧力に設定する必要が
ある。The reaction pressure is not particularly limited because it is closely related to the growth rate of diamond or depends on other reaction conditions. Generally, higher pressure increases the growth rate due to the increased concentration of carbon contributing to the reaction. In order to grow diamond with good crystallinity, it is necessary to set an appropriate pressure depending on the method of synthesis reaction.
例えば、プラズマを用いた化学気相成長法の場合は、反
応圧力は０．１〜１０００ｔｏｒｒの範囲が望ましい。For example, in the case of chemical vapor deposition using plasma, the reaction pressure is preferably in the range of 0.1 to 1000 torr.
ガスの流量については、反応によって消費された原料ガ
スを補充するとともに、反応によって生成した不要なガ
ス成分（ダイヤモンドの成長に寄与しないか、もしくは
ダイヤモンドの成長に不都合となるガス成分）を反応容
器外に排出するために、原料ガスか反応容器に供給され
、かつ反応容器から排出するガスの流れがあることが必
要であるが、合成方法、合成装置に応したガス流量の設
定であれば特に限定されない。Regarding the gas flow rate, in addition to replenishing the raw material gas consumed by the reaction, unnecessary gas components generated by the reaction (gas components that do not contribute to diamond growth or are inconvenient for diamond growth) are removed from the reaction vessel. In order to discharge the raw material gas to the reaction vessel, it is necessary that there is a flow of gas to be supplied to the reaction vessel and to be discharged from the reaction vessel. Not done.
ダイヤモンド気相成長のための気相中での原料ガスの分
解、励起および基体上での析出反応を制御する条件とし
ては、特に限定されず、前述した各気相成長法に応じた
反応条件を設定すればよい。The conditions for controlling the decomposition and excitation of the raw material gas in the gas phase for diamond vapor phase growth and the precipitation reaction on the substrate are not particularly limited, and the reaction conditions corresponding to each of the vapor phase growth methods described above may be used. Just set it.
例えば、熱フイラメント法ではフィラメントを２０００
℃程度に加熱することが望ましく、基体温度としては６
００〜１０００℃の範囲が好ましい。For example, in the hot filament method, the filament is
It is desirable to heat to about ℃, and the substrate temperature is 6
The temperature range is preferably from 00 to 1000°C.
また、直流放電を用いた化学気相成長法では、放電とし
ては正規グロー放電よりもアーク放電側の領域を必要と
するので、直流印加電圧は、両極間距離及び反応圧カ一
定の条件下における正規グロー放電時の両極間電圧と同
等か又は高い値に設定することが好ましい。また、結晶
性の良いダイヤモンドを成長させるためには、基体温度
は６００〜１０００℃の範囲で比較的高温であることか
好ましい。In addition, in the chemical vapor deposition method using DC discharge, the area on the arc discharge side is required for the discharge compared to the regular glow discharge, so the DC applied voltage is It is preferable to set the voltage to a value equal to or higher than the voltage between the electrodes during normal glow discharge. Further, in order to grow diamond with good crystallinity, the substrate temperature is preferably relatively high in the range of 600 to 1000°C.
本発明によれば、基体上の所望の領域において結晶核形
成密度を増加させることができるので、微小な結晶粒か
ら成る事情な表面のダイヤモンド膜を効率良く形成する
ことができる上に、凹凸部を均一に分散させることによ
り結晶核形成位置を均一に分散できることから、厚さが
均一な膜の形成が可能となる。また、予め凹凸部を規則
的に分布させることにより結晶核形成位置を調整できる
ことから、核形成位置間に所定の間隔を確保して、独立
した大形のダイヤモンド粒を成長させることが可能とな
る。さらに、結晶核形成密度を増加させるとともに結晶
核形成位置を調整できることから、結晶核を基体上の線
上に高密度で、かつ規則的に配列させて、ダイヤモンド
から成る微細なパターンを明瞭に形成することが可能と
なる。According to the present invention, since the crystal nucleation density can be increased in a desired region on the substrate, it is possible to efficiently form a diamond film on an uneven surface consisting of minute crystal grains. By uniformly dispersing the crystal nucleation positions, it is possible to uniformly disperse the crystal nucleus formation positions, thereby making it possible to form a film with a uniform thickness. In addition, since the crystal nucleation positions can be adjusted by regularly distributing the uneven parts in advance, it is possible to secure a predetermined interval between the nucleation positions and grow independent large diamond grains. . Furthermore, since the crystal nucleation density can be increased and the crystal nucleation position can be adjusted, the crystal nuclei can be arranged in a line on the substrate in a high density and regularly, forming a clear fine pattern made of diamond. becomes possible.
（実施例） 以下に、本発明の実施例について図を用いて説明する。(Example) Embodiments of the present invention will be described below with reference to the drawings.
実施例１
まず、基体の前処理として、表面を鏡面仕上げした１０
０面のシリコン単結晶から成る基体を、平均粒径２０〜
３０μｍのダイヤモンド粉末を分散したエチルアルコー
ル中に入れて３０分間超音波振動を与えた。この基体表
面を走査型電子顕微鏡（ＳＥＭ）で調べると、多数の微
小な凹部（穴）が無秩序に、全面にわたって均一に分布
しているのが観察された。また、識別し得る穴の直径は
、最大でも１μｍで、０．５μｍ以下のものが大部分で
あった。Example 1 First, as a pretreatment of the substrate, the surface was mirror-finished.
A substrate consisting of a zero-plane silicon single crystal has an average grain size of 20~
A 30 μm diamond powder was placed in ethyl alcohol and subjected to ultrasonic vibration for 30 minutes. When the surface of this substrate was examined using a scanning electron microscope (SEM), it was observed that many minute recesses (holes) were randomly and uniformly distributed over the entire surface. Further, the diameter of the holes that could be identified was 1 μm at the maximum, and most of the holes were 0.5 μm or less.
この基体表面にフッ化炭素（ＣＦ４）を作用させるため
に第１図に示す装置を用いた。この装置はダイヤモンド
を析出させるためにも用いた。図において、この装置は
石英ガラス製反応容器１を有し、この反応容器１には、
反応容器１内にガスを供給するためのガス供給口２と、
反応容器１内で生じた不要なガスを容器外部に排出する
ためのガス排出口３とが設けられている。ガス供給口２
は不図示のガス供給装置に、ガス排出口３は不図示の排
気装置に接続されている。An apparatus shown in FIG. 1 was used to apply fluorocarbon (CF4) to the surface of this substrate. This equipment was also used to deposit diamond. In the figure, this apparatus has a reaction vessel 1 made of quartz glass, and this reaction vessel 1 includes:
a gas supply port 2 for supplying gas into the reaction vessel 1;
A gas discharge port 3 is provided for discharging unnecessary gas generated within the reaction vessel 1 to the outside of the vessel. Gas supply port 2
is connected to a gas supply device (not shown), and the gas discharge port 3 is connected to an exhaust device (not shown).
反応容器１内には、ダイヤモンド析出用の基体４を固定
するためのモリブデン製の基体ホルダ５が設けられてお
り、この基体ホルダー５の上部には、反応容器２内に導
入されたガスを熱分解するためのタングステン製のフィ
ラメント６が配置されている。このフィラメント６はモ
リブデン製の給電治具を７に固定されており、給電治具
７を介して電源（図示せず）から電流を供給される。A substrate holder 5 made of molybdenum for fixing a substrate 4 for diamond precipitation is provided in the reaction vessel 1, and the upper part of this substrate holder 5 is used to heat the gas introduced into the reaction vessel 2. A filament 6 made of tungsten is arranged for disassembly. This filament 6 is fixed to a power supply jig 7 made of molybdenum, and is supplied with current from a power source (not shown) via the power supply jig 7.
また、基体ホルダー５とフィラメント６は、基体ホルダ
ー５上の基体４に正電位が印加されるように、直流電源
８に接続されている。Further, the substrate holder 5 and the filament 6 are connected to a DC power source 8 so that a positive potential is applied to the substrate 4 on the substrate holder 5.
そして、前述したように凹部を設けた基体４に対して、
以下のようにしてフッ化炭素（ＣＦ４）を作用させた。Then, as described above, with respect to the base 4 provided with the recessed portion,
Fluorocarbon (CF4) was applied as follows.
まず、この基体４を基体ホルダー５に固定し、反応容器
１内を１０’Ｔｏｒｒに排気した後、フィラメント６を
２０００℃に加熱しながら、ＣＦ４ガスを流量１００ｃ
ｃ／分の条件で反応容器１内に流すとともに、基体ホル
ダー５に正の、フィラメント６に負の直流電位１５０ｖ
を印加し、基体の温度を８５０℃に３分間保持した。こ
のＣＦ４作用処理を終了した後、基体４表面をＳＥＭで
調べると、穴の分布状態は基体の前処理後に観察された
ときの分布状態と同様であるが、その輪郭は一層はっき
りし、平均的に１０％程度拡大化した穴が観察された。First, this substrate 4 is fixed to the substrate holder 5, and after evacuating the inside of the reaction vessel 1 to 10'Torr, CF4 gas is supplied at a flow rate of 100℃ while heating the filament 6 to 2000℃.
DC potential of 150 V is applied to the substrate holder 5 and negative to the filament 6.
was applied, and the temperature of the substrate was maintained at 850° C. for 3 minutes. When the surface of the substrate 4 is examined by SEM after this CF4 action treatment is completed, the distribution of holes is similar to that observed after the substrate pretreatment, but the outline is clearer and the average A hole enlarged by about 10% was observed.
この基体４を用いてダイヤモンドを析出させるためのＣ
ＶＤ処理を行なった。第１図の装置を用いて、まず、反
応容器１内を１０１トールに排気後、フィラメント６を
２０００℃に加熱しながら、メタン／水素の容積比１７
９９の混合ガスを圧力５０Ｔｏ ｒ ｒで反応容器１内
に流すとともに、基体ホルダー５に正の、フィラメント
６に負の直流電位１５０ｖを印加しながら、基体４の温
度を８５０℃に保持した。そして、析出反応を３０時間
継続させ基体４上にダイヤモンド膜を形成した後、ガス
の供給、フィラメント６の加熱、基体４への電位印加を
停止した。C for depositing diamond using this substrate 4
VD processing was performed. Using the apparatus shown in FIG. 1, first, after evacuating the inside of the reaction vessel 1 to 101 Torr, while heating the filament 6 to 2000°C, the methane/hydrogen volume ratio was 17.
The temperature of the substrate 4 was maintained at 850° C. while a positive DC potential of 150 V was applied to the substrate holder 5 and a negative DC potential was applied to the filament 6. After the deposition reaction was continued for 30 hours to form a diamond film on the substrate 4, the supply of gas, heating of the filament 6, and application of potential to the substrate 4 were stopped.
形成された膜を電子線回折およびラマン分光法で調べた
結果、結晶面間隔およびラマンバンドは天然ダイヤモン
ドの値に一致た。すなわち、この膜は結晶性の良いダイ
ヤモンドであることが確認された。この膜の表面をＳＥ
Ｍにより観察したところ、基体４全面に−様な膜が形成
され、この膜は粒径が最大でも０．５μｍの微細な結晶
粒から成ることが確認された。この膜の表面粗さは０゜
５μｍ以下であり、平滑度が大きかった。また、膜を基
体４とともに厚さ方向に割ってその断面をＳＥＭにより
観察した結果、膜の厚さが均一であることが確認された
。As a result of examining the formed film using electron diffraction and Raman spectroscopy, the crystal spacing and Raman band matched those of natural diamond. In other words, this film was confirmed to be diamond with good crystallinity. SE of the surface of this film
When observed using M, it was confirmed that a --like film was formed on the entire surface of the substrate 4, and that this film was composed of fine crystal grains with a maximum grain size of 0.5 μm. The surface roughness of this film was 0.5 μm or less, and its smoothness was high. Further, as a result of dividing the film along with the substrate 4 in the thickness direction and observing its cross section using SEM, it was confirmed that the thickness of the film was uniform.
比較のため、基板４に対してＣＦ４処理を施さなかった
こと以外は上記実施例１と同一条件でダイヤモンドの析
出を行なった。この結果、連続膜は形成されず、しかも
、析出したダイヤモンドの結晶粒は大きく、粒径は平均
１μｍであった。For comparison, diamond was deposited under the same conditions as in Example 1, except that the substrate 4 was not subjected to the CF4 treatment. As a result, no continuous film was formed, and the crystal grains of the precipitated diamond were large, with an average grain size of 1 μm.
実施例２
基体の前処理として、表面を鏡面仕上げした１００面の
シリコン単結晶から成る基体を熱酸化処理して、基体表
面に厚さ約０，７μｍの酸化物（Ｓｉ０２）層を形成し
、このＳ ｉ ０２層が直径１μｍの範囲で露出し、か
つこれが互いに２０μｍ間隔に規則的に配列したパター
ンを持つレジストマスクを形成した。これをフッ化アン
モニウム（ＮＨ４Ｆ）水溶液を用いてエツチングするこ
とにより、Ｓ ｉ ０２層を溶解し上記パターンで配列
したＳｉの露出部を基体表面に形成した。この基体を実
施例１て用いたのと同様の装置に設置し、実施例１と同
様のプロセスでＣＦ４処理とＣＶＤを行なった。ＣＶＤ
を１２時間行なった後、基体表面をＳＥＭにより観察し
たところ、上記のパターンの穴の位置に直径的１０μｍ
の大形のダイヤモンドの結晶が成長していた。Example 2 As a pretreatment of the substrate, a substrate consisting of a 100-sided silicon single crystal with a mirror-finished surface was subjected to thermal oxidation treatment to form an oxide (Si02) layer with a thickness of about 0.7 μm on the substrate surface, A resist mask was formed in which this S i 02 layer was exposed in a range of 1 μm in diameter and had a pattern in which these layers were regularly arranged at intervals of 20 μm. By etching this using an ammonium fluoride (NH4F) aqueous solution, the Si02 layer was dissolved and exposed Si arranged in the above pattern was formed on the surface of the substrate. This substrate was placed in the same apparatus as used in Example 1, and CF4 treatment and CVD were performed in the same process as in Example 1. CVD
After performing this for 12 hours, the substrate surface was observed using SEM, and it was found that there were holes of 10 μm in diameter at the positions of the holes in the above pattern.
Large diamond crystals were growing.
尚、上記第１．第２実施例においては、基体表面にＣＦ
４を作用させるＣＦ４処理時と、基体上にダイヤモンド
を析出させるダイヤモンド析出処理時に、同一の装置を
用いて同様にＣＶＤにより各分解処理を行うので、装置
構成や処理工程が簡単になるという利点がある。In addition, the above 1. In the second embodiment, CF is applied to the surface of the substrate.
The same equipment is used to perform each decomposition treatment by CVD during the CF4 treatment in which 4 is applied and the diamond precipitation treatment in which diamond is deposited on the substrate, so the advantage is that the equipment configuration and processing steps are simplified. be.
また、上記第１．第２実施例においてはダイヤモンド析
出処理前に基体表面に作用物質を作用させる方法として
、熱フィラメントによるＣＶＤ法を用いたが、本発明は
これに限定されるものではなく、例えば熱フィラメント
法以外の熱分解を利用した気相成長法、プラズマを利用
した気相成長法、光分解を利用した気相成長法等も適用
可能である。Also, the above 1. In the second embodiment, the CVD method using a hot filament was used as a method for applying the active substance to the surface of the substrate before the diamond precipitation treatment, but the present invention is not limited to this. Vapor growth methods using thermal decomposition, vapor growth methods using plasma, vapor growth methods using photolysis, etc. are also applicable.
さらに、本発明は上記第１．第２実施例に限定されるも
のではなく、種々変形実施が可能であることは勿論であ
る。Furthermore, the present invention provides the above-mentioned item 1. It goes without saying that the present invention is not limited to the second embodiment, and that various modifications can be made.
［発明の効果コ
以上説明したように、本発明方法によれば、微細な結晶
粒から成り、平滑度が大きく厚さが均一なダイヤモンド
膜や、大形のダイヤモンド粒を基体上に効率良く形成す
ることができる。また、基体上の所望の位置のみに、例
えばダイヤモンドから成る微細なパターンを明瞭に形成
することが可能となる。[Effects of the Invention] As explained above, according to the method of the present invention, a diamond film consisting of fine crystal grains with high smoothness and uniform thickness, and large diamond grains can be efficiently formed on a substrate. can do. Furthermore, it becomes possible to clearly form a fine pattern made of, for example, diamond only at a desired position on the substrate.
第１図は本発明の実施例に用いられる反応装置の構成を
概略的に示す縦断面図である。
１・・・反応容器 ２・・・ガス供給口３・・・ガ
ス排出口 ４・・・基体FIG. 1 is a longitudinal sectional view schematically showing the configuration of a reaction apparatus used in an example of the present invention. 1... Reaction container 2... Gas supply port 3... Gas discharge port 4... Substrate
Claims (1)
させるダイヤモンドの製造方法において、 前記基体表面上に凹凸を設け、この凹凸部にフッ素、塩
素、臭素及びヨウ素から成る群の中から選ばれる少なく
とも１種の元素を含む物質を作用させた後、この基体上
にダイヤモンドを析出させることを特徴とするダイヤモ
ンドの製造方法。[Claims] A method for producing diamond in which diamond is deposited on a substrate by decomposing a carbon-containing gas, the surface of the substrate being provided with unevenness, and the unevenness is filled with a group consisting of fluorine, chlorine, bromine, and iodine. 1. A method for producing diamond, which comprises treating a substance containing at least one element selected from the following with a substance, and then depositing diamond on the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2971290A JPH03236470A (en) | 1990-02-13 | 1990-02-13 | Production of diamond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2971290A JPH03236470A (en) | 1990-02-13 | 1990-02-13 | Production of diamond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03236470A true JPH03236470A (en) | 1991-10-22 |
Family
ID=12283723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2971290A Pending JPH03236470A (en) | 1990-02-13 | 1990-02-13 | Production of diamond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03236470A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262514A (en) * | 2006-03-29 | 2007-10-11 | Sumitomo Electric Ind Ltd | Chemical vapor deposition system |
-
1990
- 1990-02-13 JP JP2971290A patent/JPH03236470A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262514A (en) * | 2006-03-29 | 2007-10-11 | Sumitomo Electric Ind Ltd | Chemical vapor deposition system |
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