JPH04139090A - Production of diamond - Google Patents
Production of diamondInfo
- Publication number
- JPH04139090A JPH04139090A JP2259010A JP25901090A JPH04139090A JP H04139090 A JPH04139090 A JP H04139090A JP 2259010 A JP2259010 A JP 2259010A JP 25901090 A JP25901090 A JP 25901090A JP H04139090 A JPH04139090 A JP H04139090A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- substrate
- gaseous
- gas
- base body
- 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 87
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 72
- 239000007789 gas Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 35
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 22
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 26
- 238000001556 precipitation Methods 0.000 abstract description 8
- 239000012495 reaction gas Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000008246 gaseous mixture Substances 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 50
- 239000013078 crystal Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 238000001947 vapour-phase growth Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 101100002917 Caenorhabditis elegans ash-2 gene Proteins 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
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WLQSSCFYCXIQDZ-UHFFFAOYSA-N arsanyl Chemical compound [AsH2] WLQSSCFYCXIQDZ-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- -1 carbon ions Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- PORFVJURJXKREL-UHFFFAOYSA-N trimethylstibine Chemical compound C[Sb](C)C PORFVJURJXKREL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明はダイヤモンドの製造方法に関し、特に薄膜状の
ダイヤモンドの製造に適した気相合成法に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method for producing diamond, and more particularly to a vapor phase synthesis method suitable for producing diamond in the form of a thin film.
（従来の技術）
近年、低圧下での気相成長法によるダイヤモンドの合成
が可能になってきている。気相合成ダイヤモンドの工業
的用途として、工具被覆、耐食性保護膜、耐摩耗摺動部
材、スピーカー振動板やバイブなどの成形体、ヒートシ
ンク、光学レンズ、発光素子、半導体など種々の用途が
検討されている（「ダイヤモンド薄膜」犬塚、沢辺、産
業図書、１９８７年； 「最新ダイヤモンド薄膜技術」
総合技術センター １９８８年； ＮＥＷ ＤＩＡＭＯ
ＮＤ、 Ｖｏｌ、３．Ｎｏ、３゜１９８７年；同Ｖｏ１
．４．Ｎｏ、２，１９８８年など参照）。(Prior Art) In recent years, it has become possible to synthesize diamond by vapor phase growth under low pressure. Various industrial uses for vapor-phase synthetic diamond are being considered, including tool coatings, corrosion-resistant protective films, wear-resistant sliding members, molded objects such as speaker diaphragms and vibrators, heat sinks, optical lenses, light-emitting elements, and semiconductors. ("Diamond thin film" Inuzuka, Sawabe, Sangyo Tosho, 1987; "Latest diamond thin film technology"
General Technology Center 1988; NEW DIAMO
ND, Vol. 3. No. 3゜1987; same Vol.1
．． 4. No. 2, 1988, etc.).
気相からダイヤモンドを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（ＰＶＤ法
）が知られている。いずれの方法でも、ダイヤモンドは
基体の表面に析出させるのが一般的である。ダイヤモン
ドを膜として応用するには、基体表面でのダイヤモンド
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−化を因る必要がある。ダイヤモンドの結晶核形
成密度は、基体の材質や表面状態によって影響を受ける
。Various chemical vapor deposition methods (CVD methods) and physical vapor deposition methods (PVD methods) are known as methods for synthesizing diamond from a gas phase. In either method, diamond is generally deposited on the surface of the substrate. In order to apply diamond as a film, it is necessary to increase the density of diamond crystal nucleation on the substrate surface to make the film denser and more uniform in thickness. Diamond crystal nucleation density is affected by the material and surface condition of the substrate.
例えば、現在までのところ、ダイヤモンド以外の物質か
らなる基体上に形成されるダイヤモンド膜は多結晶であ
る。この場合、ダイヤモンド膜の表面粗′さは最外表に
ある結晶粒の大きさに依存する。これは、基体表面にダ
イヤモンドの核がごく少数形成されるが、その他の場所
では核が形成されず、核を中心としてダイヤモンドが成
長し、基体全体を覆って膜が形成されるからである。し
たがって、表面粗さが小′さく、平滑な膜を得るために
は、核形成密度を高くする必要がある。また、ゲルマニ
ウム、銅などからなる基体上にダイヤモンドを形成した
場合、膜の密着性が充分ではなく、基体からダイヤモン
ド膜が剥離しやすいという問題がある。For example, to date, diamond films formed on substrates of materials other than diamond are polycrystalline. In this case, the surface roughness of the diamond film depends on the size of the crystal grains on the outermost surface. This is because a very small number of diamond nuclei are formed on the surface of the substrate, but no nuclei are formed elsewhere, and diamond grows around the nucleus to form a film covering the entire substrate. Therefore, in order to obtain a smooth film with low surface roughness, it is necessary to increase the nucleation density. Further, when diamond is formed on a substrate made of germanium, copper, etc., there is a problem that the adhesion of the film is not sufficient and the diamond film tends to peel off from the substrate.
従来、基体表面にダイヤモンドの核形成を容易にする活
性点を高密度に形成したり、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て、種々の基体表面処理
方法が提案されている。Conventionally, various substrate surface treatment methods have been proposed for the purpose of forming a high density of active sites that facilitate diamond nucleation on the substrate surface or increasing the adhesion between the substrate and the diamond film.
その代表的なものとして、基体表面に傷を付ける方法（
以下、傷付は処理と呼ぶ）が知られている。傷付は処理
に関しては、例えば特公昭６２−２７０３９号公報、特
開昭６２−１０８７９８号公報、特開昭６２−１０８７
９９号公報、特開昭８１−１２１８５９号公報、特開昭
６２−２２［１８８９号公報などが知られている。A typical method is to scratch the substrate surface (
Hereinafter, damage is referred to as treatment). Regarding the treatment of scratches, for example, Japanese Patent Publication No. 62-27039, Japanese Patent Application Laid-Open No. 62-108798, and Japanese Patent Application Laid-Open No. 62-1087
99, JP-A-81-121859, JP-A-62-22 [1889], etc. are known.
また、傷付は処理以外の基体表面処理方法として、以下
のような方法が知られている。基体として超硬合金を用
い、その表面を研削して加工歪を与える方法（特開昭６
１−２７０３７２号公報）、基体の表面をＡｒイオンを
用いてイオンエツチングする方法（特開昭８０−２００
８９８号公報）、基体の表面に酸素プラズマのガスを吹
き付ける方法（特開昭６ｌ−１７ｔ３７Ｂ号公報）、金
属系基体の表面に酸素を拡散処理する方法（特開昭８１
−９７１９４号公報）などである。In addition, the following methods are known as substrate surface treatment methods other than treatment for scratches. A method using cemented carbide as a base and grinding the surface to give processing strain (Japanese Patent Laid-Open No. 6
1-270372), a method of ion etching the surface of a substrate using Ar ions (Japanese Patent Laid-Open No. 80-200
No. 898), a method of spraying oxygen plasma gas onto the surface of a substrate (Japanese Unexamined Patent Publication No. 6L-17T37B), and a method of diffusing oxygen onto the surface of a metal substrate (Japanese Unexamined Patent Publication No. 81/1989).
-97194).
以上の方法はいずれも、基体の表面をダイヤモンドの析
出に好都合な状態に変化させるという点で共通している
。特に、傷付は処理はダイヤモンドの連続膜を形成する
のに広く用いられている方法である。しかし、基体の表
面に傷付は処理を施しても、成長初期の核形成密度が充
分に大きくなるわけではない。その結果、形成されるダ
イヤモンド膜は表面粗さが相当粗く、膜の表面の平滑度
が小さいため、前述した問題が本質的に解決されている
とはいえない。All of the above methods have in common that they change the surface of the substrate into conditions favorable for diamond precipitation. In particular, scratching is a widely used method for forming continuous films of diamond. However, even if the surface of the substrate is treated to remove scratches, the nucleation density at the initial stage of growth does not become sufficiently high. As a result, the surface of the diamond film formed is quite rough and the surface smoothness of the film is low, so it cannot be said that the above-mentioned problems are essentially solved.
また、ダイヤモンド膜を半導体部品の放熱板に応用する
場合、基体としてアルミニウム、ステンレス、ジルコニ
ウムなどの金属又は合金を用い、これらの基体上にダイ
ヤモンド膜を形成する。しかし、これらの基体上にＣＶ
Ｄ法又はＰＶＤ法によりダイヤモンド膜を形成しようと
しても、メタンガスなどの原料ガスから分解生成する炭
素原子が金属基体中に拡散してしまい、金属基体上にダ
イヤモンド膜が形成できないことが多い。更に、ダイヤ
モンド膜が形成されたとしても、基体とダイヤモンド膜
との熱膨張差のためにダイヤモンド膜が基体から剥離し
てしまうなどの問題がある。Furthermore, when a diamond film is applied to a heat sink of a semiconductor component, a metal or alloy such as aluminum, stainless steel, or zirconium is used as the base, and the diamond film is formed on these bases. However, CV on these substrates
Even if an attempt is made to form a diamond film by the D method or the PVD method, carbon atoms decomposed and produced from a source gas such as methane gas will diffuse into the metal substrate, and a diamond film cannot often be formed on the metal substrate. Furthermore, even if a diamond film is formed, there are problems such as the diamond film peeling off from the base due to the difference in thermal expansion between the base and the diamond film.
また、例えば特開昭８３−２２４２２５号公報に記載さ
れているように、単結晶シリコン基板上に炭化ケイ素中
間層を形成し、更にこの上にダイヤモンド層を形成する
方法が知られている。この場合、炭化ケイ素の格子定数
とダイヤモンドの格子定数とが比較的近いため、ダイヤ
モンドの結晶性が良好となる。しかも、ダイヤモンドと
同じ様式の共有結合で結合する炭化ケイ素が中間層とし
て介在しているので、ダイヤモンドの核形成密度が増加
し、ダイヤモンド膜の密着性の改善も期待できる。しか
し、この方法では、単結晶シリコン基板の炭化により炭
化ケイ素中間層を形成し、その後ダイヤモンドの気相成
長を行っているため、同一の装置を用いて連続的に反応
させることができず、製造効率が悪い。Furthermore, as described in, for example, Japanese Unexamined Patent Publication No. 83-224225, a method is known in which a silicon carbide intermediate layer is formed on a single crystal silicon substrate, and a diamond layer is further formed on this intermediate layer. In this case, since the lattice constant of silicon carbide and the lattice constant of diamond are relatively close, the crystallinity of diamond is good. Furthermore, since silicon carbide, which is bonded by covalent bonds in the same manner as diamond, is present as an intermediate layer, the density of diamond nucleation increases, and it is expected that the adhesion of the diamond film will be improved. However, in this method, a silicon carbide intermediate layer is formed by carbonizing a single-crystal silicon substrate, and then diamond is grown in a vapor phase. Therefore, it is not possible to carry out continuous reactions using the same equipment, and manufacturing ineffective.
（発明が解決しようとする課題）
前述したように、従来のダイヤモンドの製造方法では、
基体表面での結晶核形成密度が小さいことに起因して、
平滑な表面を有するダイヤモンド膜を形成しにくいとい
う問題があった。また、基体を構成する材質によっては
、ダイヤモンド膜の密着性が悪いという問題があった。(Problem to be solved by the invention) As mentioned above, in the conventional diamond manufacturing method,
Due to the low crystal nucleation density on the substrate surface,
There was a problem in that it was difficult to form a diamond film with a smooth surface. Furthermore, there is a problem in that the adhesion of the diamond film is poor depending on the material constituting the substrate.
本発明はこれらの問題点を解決するためになされたもの
であり、基体に傷付は処理を施すことなく、平滑な表面
を有し、基体との密着性が良好な膜状のダイヤモンドを
効率よく製造し得る方法を提供することを目的とする。The present invention was made to solve these problems, and it is possible to efficiently produce diamond in the form of a film that has a smooth surface and good adhesion to the substrate without applying any treatment to prevent scratches on the substrate. The purpose is to provide a method that can be easily manufactured.
［発明の構成］
（課題を解決するための手段と作用）
本発明のダイヤモンドの製造方法は、反応容器内に基体
及び固体状態のＳｉを設置し、原料ガスとして炭素源ガ
スと水素ガスとの混合ガスを供給し、前記固体状態のＳ
ｉを１０００℃以上に加熱した状態で、前記原料ガスを
分解することにより前記基体上に炭化けい素膜を形成す
る工程と、原料ガスとして前記工程よりも水素ガスに対
する炭素源ガスの割合が多い混合ガスを供給し、前記固
体状態のＳｉを１０００℃未満に加熱した状態で、前記
原料ガスを分解することにより前記基体上に形成された
炭化けい素膜上にダイヤモンド膜を形成する工程とを具
備したことを特徴とするものである。[Structure of the Invention] (Means and Effects for Solving the Problems) The method for producing diamond of the present invention includes installing a substrate and solid Si in a reaction vessel, and combining carbon source gas and hydrogen gas as raw material gases. A mixed gas is supplied, and the S in the solid state is
a step of forming a silicon carbide film on the substrate by decomposing the source gas in a state where i is heated to 1000° C. or higher, and the ratio of carbon source gas to hydrogen gas is higher than that in the step as the source gas. forming a diamond film on the silicon carbide film formed on the substrate by supplying a mixed gas and decomposing the raw material gas while heating the solid state Si to less than 1000 ° C. It is characterized by the following:
本発明における反応機構は以下のようなものである。第
１の工程では、基体のほかに設置された固体状態のＳｉ
を活性な水素と反応させシランとして蒸発させる。蒸発
したシランは基体上に堆積し、反応容器中で活性化した
炭素との引き抜き反応により、炭化けい素が析出する。The reaction mechanism in the present invention is as follows. In the first step, solid state Si placed in addition to the substrate is
is reacted with active hydrogen and evaporated as silane. The evaporated silane is deposited on the substrate, and silicon carbide is precipitated by an abstraction reaction with activated carbon in the reaction vessel.
第２の工程では、原料ガスの励起及び分解によって炭素
を活性化させて、基体上に形成された炭化けい素膜上に
ダイヤモンド膜を形成させる。In the second step, carbon is activated by excitation and decomposition of the source gas, and a diamond film is formed on the silicon carbide film formed on the substrate.
この方法では、第１の工程で基体上に炭化けい素を形成
させているので、表面が炭素の飽和状態となっており炭
素がそれ以上基体中に拡散せず、しかも炭化けい素は熱
膨張係数かダイヤモンドに近い値でありかつ結合様式が
ダイヤモンドと同じ共有結合であるため、第２の工程で
ダイヤモンドの核形成密度が増加し、平滑で密着性の良
好な膜状のダイヤモンドを製造することができる。また
、炭化けい素とダイヤモンドとは、２つの工程でわずか
に条件を変更する以外は、同一の装置を用いて連続的に
形成できるので、製造効率が高い。In this method, silicon carbide is formed on the substrate in the first step, so the surface is saturated with carbon and carbon does not diffuse further into the substrate, and silicon carbide expands thermally. Since the coefficient is close to that of diamond and the bonding mode is covalent bonding, which is the same as diamond, the nucleation density of diamond increases in the second step, producing smooth and film-like diamond with good adhesion. I can do it. Furthermore, since silicon carbide and diamond can be formed continuously using the same equipment except for slightly changing conditions in the two steps, manufacturing efficiency is high.
本発明において、炭化けい素及びダイヤモンドを析出さ
せるための具体的な方法は特に限定されない。例えば、
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など、いずれの
方法でもよい。炭化けい素とダイヤモンドとは、同一の
反応方式に基づいて、同一の装置を用いて連続的に形成
される。In the present invention, the specific method for precipitating silicon carbide and diamond is not particularly limited. for example,
Chemical vapor deposition method that utilizes thermal decomposition using a hot filament, chemical vapor deposition method that promotes decomposition and excitation by applying electron bombardment to the substrate, and chemical vapor deposition method that uses plasma generated by microwave discharge or DC discharge. , ion beam evaporation method that utilizes collision of accelerated carbon ions with a substrate, or any other method may be used. Silicon carbide and diamond are formed sequentially based on the same reaction method and using the same equipment.
本発明において、基体の材質は特に限定されず、シリコ
ンを用いることもできる。In the present invention, the material of the base is not particularly limited, and silicon can also be used.
本発明において、原料ガスは炭素源ガスを含む。In the present invention, the raw material gas includes a carbon source gas.
この炭素源ガスは、第１の工′程で蒸発したシランと反
応して炭化けい素に変化し得るものであり、また第２の
工程でダイヤモンドに変化し得るものであればよい。具
体的には、ガス化した炭素、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、−酸化炭素、二酸化炭素
などのガスが挙げられる。また、原料ガスは水素ガスを
含む。This carbon source gas may be any gas that can react with the evaporated silane in the first step and change into silicon carbide, and can also change into diamond in the second step. Specific examples include gases such as gasified carbon, methane, ethane, propane, acetylene, acetone, methanol, ethanol, butanol, acetaldehyde, carbon oxide, and carbon dioxide. Further, the raw material gas includes hydrogen gas.
水素ガスは、第１の工程では固体状態のＳｉと反応して
シランを発生させる作用を有し、第２の工程ではダイヤ
モンドの結晶性の改善する作用を有する。水素の適量は
、他の反応条件によっても左右されるために特に限定さ
れないが、
（炭素源ガス）／（水素ガス）の容積比は、第１の工程
では０．Ｏ１〜０．１の範囲とすることが好ましく、第
２の工程では水素ガスに対する炭素源ガスの割合を増加
させて０．１〜５．０の範囲とすることが好ましい。な
お、後述するように半導体ダイヤモンド膜を形成するよ
うな場合には、原料ガス中にｐ型又はｎ型の不純物源と
なるガスを含有させる。Hydrogen gas has the effect of reacting with solid state Si in the first step to generate silane, and has the effect of improving the crystallinity of the diamond in the second step. The appropriate amount of hydrogen is not particularly limited as it also depends on other reaction conditions, but the volume ratio of (carbon source gas)/(hydrogen gas) is 0. It is preferable to set it as the range of O1-0.1, and in the 2nd process, it is preferable to increase the ratio of carbon source gas with respect to hydrogen gas, and to set it as the range of 0.1-5.0. Note that, in the case of forming a semiconductor diamond film as described later, a gas serving as a p-type or n-type impurity source is contained in the raw material gas.
反応圧力は、炭化けい素及びダイヤモンドの成長速度に
大きく影響する条件であるが、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。The reaction pressure is a condition that greatly affects the growth rate of silicon carbide and diamond, but is not particularly limited because it is also influenced by other reaction conditions.
ガスの流量は、気相成長法や装置の規模にも左右される
ため、特に限定されない。一般的には、反応によって消
費された原料ガスを補充でき、かつ反応によって生成し
た不要なガス成分（炭化けい素及びダイヤモンドの成長
に寄与しないか又は成長に不都合となるガス成分）を反
応容器外に排出できる程度のガスの流れがあれば充分で
ある。The flow rate of the gas is not particularly limited because it depends on the vapor phase growth method and the scale of the apparatus. In general, it is possible to replenish the raw material gas consumed by the reaction, and remove unnecessary gas components generated by the reaction (gas components that do not contribute to the growth of silicon carbide and diamond or are inconvenient for the growth) outside the reaction vessel. It is sufficient if there is enough gas flow to discharge the gas.
気相中での原料ガスの分解・励起及び基体上での析出反
応を制御する条件も特に限定されず、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 source gas in the gas phase and the precipitation reaction on the substrate are not particularly limited either, and the reaction conditions may be set according to each vapor phase growth method.
例えば、熱フイラメント法ではフィラメントを２００Ｄ
〜３０００℃程度に加熱し、第１の工程では固体状態の
Ｓｉ（及び基体）の温度を１０００〜１４００℃の範囲
とし、第２の工程では基体（及びＳｉ）の温度を６００
〜１０００℃の範囲とすることが好ましい。For example, in the hot filament method, the filament is 200D
In the first step, the temperature of solid Si (and the substrate) is in the range of 1,000 to 1,400°C, and in the second step, the temperature of the substrate (and Si) is increased to about 600°C.
It is preferable to set it as the range of -1000 degreeC.
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、直流印加電圧を、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し、第１の工程では固体状態のＳ
ｔ（及び基体）の温度を１０００〜１４００℃の範囲と
し、第２の工程では基体（及びＳｉ）の温度を６００〜
１０００℃の範囲とすることが好ましい。固体状態のＳ
ｉの温度を、第１の工程では１０００℃以上、第２の工
程では１０００℃未満とするのは、第１の工程ではシラ
ンの蒸発を促進する必要があり、第２の工程ではシラン
の蒸発を抑制する必要があるためである。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 The voltage between the electrodes during normal glow discharge is set to a value that is equal to or higher than the voltage between the two electrodes, and in the first step, the solid state S
The temperature of t (and the substrate) is set in the range of 1000 to 1400°C, and in the second step, the temperature of the substrate (and Si) is set to 600 to 1400°C.
The temperature is preferably in the range of 1000°C. S in solid state
The reason why the temperature of i is set to 1000°C or more in the first step and less than 1000°C in the second step is because it is necessary to promote evaporation of silane in the first step, and to promote evaporation of silane in the second step. This is because it is necessary to suppress the
前述したように原料ガス中にｎ型不純物源又はｎ型不純
物源として、ホウ素、アルミニウム、ガリウム、インジ
ウム、タリウムの単体もしくはこれらの化合物のうち少
なくとも１種又は窒素、リン、ヒ素、アンチモンの単体
もしくはこれらの化合物のうち少なくとも１種含有させ
れば、半導体ダイヤモンが得られる。As described above, as an n-type impurity source or an n-type impurity source in the raw material gas, at least one of boron, aluminum, gallium, indium, and thallium alone or a compound thereof, or nitrogen, phosphorus, arsenic, and antimony alone or as an n-type impurity source. By containing at least one of these compounds, a semiconductor diamond can be obtained.
ｐ型半導体ダイヤモンドを製造する場合には周期表のｍ
ｂ族の元素の単体もしくはこれらの化合物が用いられる
。具体的には、Ｂ＜ Ａ １’ ％ Ｇ ａ 。When producing p-type semiconductor diamond, m on the periodic table
A simple substance of group b elements or a compound thereof may be used. Specifically, B<A1'% Ga.
Ｉ ｎ、Ｂ２ Ｈｂ 、Ｂ４ ＨＩＯＳＢ２’Ｏｔ、Ｃ
Ｈ３ＢＣＩ）２ 、［（ＣＨ３Ａｌ’ Ｂ ｒ２ ］
２、（ＣＨ３）２ ＡＩ ＣＩ、Ｃ（ＣＨ３）３ Ａ、
Ｃ）］２、Ｇａ２Ｈ６、（ＣＢ３ ） 、 Ｇａ。I n, B2 Hb, B4 HIOSB2'Ot, C
H3BCI)2 , [(CH3Al' B r2 ]
2, (CH3)2 AI CI, C(CH3)3 A,
C)]2, Ga2H6, (CB3), Ga.
（ＣＨ３）２ Ｇａ ＢＨ４、（ＣＨ３）３１ｎ。(CH3)2 Ga BH4, (CH3)31n.
ＣＣＨｓ ）３ Ｔｌｌなどのうち少なくとも１種が挙
げられる。At least one of CCHs)3Tll and the like can be mentioned.
ここで、例えばＢは融点が２２２５℃と高いので、電子
ビーム加熱又はスパッタ法により蒸発させて用いる。例
えば［（ＣＢ３ ） ３ ＡＩ７ ］２は常温では液体
であるが、揮発性なので加熱により気化させて用いる。Here, for example, since B has a high melting point of 2225° C., it is used after being evaporated by electron beam heating or sputtering. For example, [(CB3) 3 AI7 ]2 is a liquid at room temperature, but is volatile, so it is used after being vaporized by heating.
例えば８２Ｈ６は常温で気体なのでそのまま用いる。For example, 82H6 is a gas at room temperature, so it can be used as is.
ｎ型半導体ダイヤモンドを製造する場合には、周期表の
ｖｂ族の元素の単体又はこれらの化合物が用いられる。When producing n-type semiconductor diamond, single elements of group VB of the periodic table or compounds thereof are used.
具体的には、Ｎ２ 、Ｐ −、Ａ ｓ ｓＢ ｉｓ Ｓ
ｂ、ＮＨ３、ＰＨ３、Ａｓｈｓ、Ｎ２ ）１４ 、Ｐ２
０ｓ 、ＣＨ３Ａｓ Ｂ ｒ２、ＣＨ，ＡｓＨ２、（Ｃ
Ｈｉ ） ３Ａ Ｓ ％（ＣＨｘ ） ｓ Ｂ ｔ、
’（Ｃ２Ｈｓ ） ３ Ｂ １ｓＳｂＨ，、ｌ ＣＨ
２５ｂＣ１１、、ＣＨ，５ｂＨ２、（ＣＨ３）３ Ｓｂ
などのうち少なくとも１種が挙げられる。Specifically, N2, P −, A s sB is S
b, NH3, PH3, Ashs, N2)14, P2
0s, CH3As B r2, CH, AsH2, (C
Hi ) 3A S % (CHx ) s B t,
'(C2Hs) 3 B 1sSbH,,l CH
25bC11,,CH,5bH2,(CH3)3Sb
At least one of these is mentioned.
ここで、例えばＡｓは融点が８１７℃と高いので、抵抗
加熱により蒸発させて用いる。例えば（ＣＨ３）１Ｂｉ
は常温では液体であるが、揮発性なので加熱により気化
させて用いる。例えばＣＢ、ＡｓＨ２は常温では気体な
のでそのまま用いる。Here, for example, since As has a high melting point of 817° C., it is used after being evaporated by resistance heating. For example (CH3)1Bi
Although it is a liquid at room temperature, it is volatile, so it is used after being vaporized by heating. For example, CB and AsH2 are gases at room temperature, so they are used as they are.
反応ガス中のこれら元素の単体又はこれらの化合物と有
機化合物との適切な混合比は目的とする半導体特性及び
反応条件により左右されるので特に限定されないが、一
般的には原子比で（不純物）／（炭素） −ｔｏ−’
〜１０−２ノ範囲が好適である。The appropriate mixing ratio of these elements or their compounds and organic compounds in the reaction gas is not particularly limited as it depends on the desired semiconductor properties and reaction conditions, but in general, the atomic ratio (impurities) /(carbon) -to-'
A range of 10-2 is preferred.
（実施例） 以下、本発明の実施例を図面を参照して説明する。(Example) Embodiments of the present invention will be described below with reference to the drawings.
実施例１
第１図は本実施例において用いられた反応装置の概略構
成図である。第１図において、石英ガラス製の反応容器
１は反応ガス導入口２と真空排気口３とを有する。反応
ガス導入口２はガス供給装置（図示せず）に接続されて
いる。真空排気口３は真空ポンプ（図示せず）に接続さ
れている。反応容器１内にはモリブデン製の基体ホルダ
ー４が設けられ、この上に固体シリコン５及び基体６が
載せられる。基体ホルダー４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タル製のフィ
ラメント７が配置されている。このフィラメント７はモ
リブデン製の給電治具８に固定され、給電治具８を介し
て電源（図示せず）から給電される。基体ホルダー４と
フィラメント７との間には、基体ホルダー４上の固体シ
リコン５及び基体６に正電位゛が印加されように、直流
電源９が接続されている。Example 1 FIG. 1 is a schematic diagram of a reaction apparatus used in this example. In FIG. 1, a reaction vessel 1 made of quartz glass has a reaction gas inlet 2 and a vacuum exhaust port 3. The reaction gas inlet 2 is connected to a gas supply device (not shown). The vacuum exhaust port 3 is connected to a vacuum pump (not shown). A substrate holder 4 made of molybdenum is provided in the reaction vessel 1, and solid silicon 5 and a substrate 6 are placed thereon. A tantalum filament 7 for thermally decomposing the gas introduced into the reaction vessel 2 is disposed above the substrate holder 4 . This filament 7 is fixed to a power supply jig 8 made of molybdenum, and is supplied with power from a power source (not shown) via the power supply jig 8. A DC power source 9 is connected between the substrate holder 4 and the filament 7 so that a positive potential is applied to the solid silicon 5 and the substrate 6 on the substrate holder 4.
本実施例では、基体６として表面を鏡面仕上げした（１
００）面のシリコン単結晶を用いた。In this example, the surface of the base body 6 is mirror-finished (1
00) plane silicon single crystal was used.
反応容器１内を１０−’Ｔｏｒｒに排気した後、フィラ
メント７を２２００℃に加熱した。容積比でメタン／水
素−０、１／９９．９の混合ガスを反応容器１内に流し
、圧力を２００Ｔｏｒｒに維持した。炭化けい素の析出
反応を１時間継続させた後、容積比でメタン／水素−１
／９９の混合ガスを反応容器１内に流し、圧力を８０Ｔ
ｏｒｒに維持した。基体ホルダー４とフィラメント７と
の間に１５０ｖの直流電圧を印加しながら、固体シリコ
ン５及び基体６の温度を８５０’Ｃに保持した。析出反
応を３時間継続させ、基体６上にダイヤモンド膜を形成
させた後、ガスの供給、フィラメント７の加熱、基体６
への電圧印加を中止した。After evacuating the inside of the reaction vessel 1 to 10-' Torr, the filament 7 was heated to 2200°C. A mixed gas with a volume ratio of methane/hydrogen-0, 1/99.9 was flowed into the reaction vessel 1, and the pressure was maintained at 200 Torr. After continuing the precipitation reaction of silicon carbide for 1 hour, the volume ratio of methane/hydrogen-1
/99 mixed gas was flowed into the reaction vessel 1, and the pressure was set to 80T.
It was maintained at orr. While applying a DC voltage of 150 V between the substrate holder 4 and the filament 7, the temperature of the solid silicon 5 and the substrate 6 was maintained at 850'C. After continuing the precipitation reaction for 3 hours to form a diamond film on the substrate 6, gas is supplied, the filament 7 is heated, and the substrate 6 is heated.
The application of voltage to was discontinued.
得られたダイヤモンド膜を引っ掻いてみたところ、ダイ
ヤモンド膜は基体６であるシリコン単結晶から剥離せず
、密着性が良好であった。When the obtained diamond film was scratched, it was found that the diamond film did not peel off from the silicon single crystal that was the base 6 and had good adhesion.
ダイヤモンド膜を電子線回折及びラマン分光法で調べた
結果、結晶面間隔及びラマンバンドが天然ダイヤモンド
の値と一致し、この膜が結晶性の良好なダイヤモンド膜
であることが確認された。As a result of examining the diamond film using electron beam diffraction and Raman spectroscopy, the crystal spacing and Raman band matched those of natural diamond, confirming that this film was a diamond film with good crystallinity.
ダイヤモンド膜の表面を走査電子顕微鏡（ＳＥＭ）によ
り観察した結果、基体６全面に−様な膜が形成されてい
た。ダイヤモンド結晶の粒径は最大でも０ 、５ｇＩｍ
以下であった。また、ダイヤモンド膜を基体とともに厚
さ方向に割ってその断面をＳＥＭ観察した結果、膜の厚
さは均一であることが確認された。Observation of the surface of the diamond film using a scanning electron microscope (SEM) revealed that a --like film was formed over the entire surface of the substrate 6. The maximum particle size of diamond crystals is 0.5gIm
It was below. Further, as a result of dividing the diamond film together with the substrate in the thickness direction and observing the cross section with an SEM, it was confirmed that the thickness of the film was uniform.
比較のために、基体ホルダ４上に基体６として表面を鏡
面仕上げした（１００）面のＳｔ単結晶のみを載せ、炭
化けい素を析出させる反応を積極的に行わずに、前述し
たのと同一の条件でダイヤモンドの析出を行った。得ら
れたダイヤモンド膜を引っ掻いてみたところ、ダイヤモ
ンド膜は基体６であるシリコンから剥離してしまった。For comparison, only a (100)-plane St single crystal with a mirror-finished surface was placed on the substrate holder 4 as the substrate 6, and the same method as described above was carried out without actively carrying out the reaction to precipitate silicon carbide. Diamond precipitation was performed under the following conditions. When the obtained diamond film was scratched, the diamond film peeled off from the silicon substrate 6.
実施例２
第２図は本実施例において用いられた反応装置の概略構
成図である。第２図において、反応容器１０は反応ガス
導入口１１と真空排気口１２とを有する。Example 2 FIG. 2 is a schematic diagram of the reaction apparatus used in this example. In FIG. 2, a reaction vessel 10 has a reaction gas inlet 11 and a vacuum exhaust port 12.
反応ガス導入口１１はガス供給装置（図示せず）に接続
されている。真空排気口１２は真空ポンプ（図示せず）
に接続されている。反応容器ｌＯの下部には、接地され
たモリブデン製のリング状の陽極１３が設けられ、その
内部にモリブデン製の円形カゴ状の基体支持体１４が設
けられている。この基体支持体１４上に固体シリコン１
５及び基体１６が載せられる。反応容器ｌＯの上部には
、基体支持体１４に対向してモリブデン製の陰極１７が
設けられており、その内部にはタンタル製のフィラメン
ト１８が設置されている。陰極１７は反応容器ＩＯに対
してはシールドされており、高圧発生用の直流電源１９
に接続されている。The reaction gas inlet 11 is connected to a gas supply device (not shown). The vacuum exhaust port 12 is a vacuum pump (not shown)
It is connected to the. A grounded ring-shaped anode 13 made of molybdenum is provided at the bottom of the reaction vessel IO, and a circular cage-shaped substrate support 14 made of molybdenum is provided inside the anode 13 . Solid silicon 1 is placed on this base support 14.
5 and a substrate 16 are placed thereon. A cathode 17 made of molybdenum is provided at the upper part of the reaction vessel 10, facing the base support 14, and a filament 18 made of tantalum is installed inside the cathode 17. The cathode 17 is shielded from the reaction vessel IO, and is connected to a DC power source 19 for high voltage generation.
It is connected to the.
なお、第２図に示すような構成の場合、陰極１７に負の
電位が印加されるが、これとは異なり、陰極１７を接地
し、陽極１３又は基体支持体１４に正の電位を印加して
も原理的には等しい。Note that in the case of the configuration shown in FIG. 2, a negative potential is applied to the cathode 17, but unlike this, the cathode 17 is grounded and a positive potential is applied to the anode 13 or the base support 14. However, they are the same in principle.
本実施例では、基体６として表面を鏡面仕上げしたチタ
ンを用いた。In this example, titanium with a mirror-finished surface was used as the base 6.
反応容器１０内を１Ｏ−６Ｔｏｒｒに排気した。反応容
器ＩＯ内にメタン、水素化ひ素メチル、水素の混合ガス
を流し、圧力２００Ｔｏｒｒを維持した。メタンと水素
との容積比はメタン／水素−０，０５／９９．９５、メ
タン中の炭素と水素化ひ素メチル中のひ素との原子比は
１ ： １０−’に設定した。フィラメント１８に通電
して、フィラメント温度を２５００℃として、陰極１７
に高電圧を印加して放電を開始した。両電極間の距離１
．’５ｃｍ５放電電圧１０００Ｖ 、放電電流８００ｍ
Ａの条件で、陽極１３及び基体支持体１４の温度は約１
３００℃まで上昇した。反応中は原料ガスを４００９Ｃ
ＣＨの流量で流した。反応中に陽極１３及び基体支持体
１４の直上には陽光柱が観察された。以上の条件で炭化
けい素の析出反応を０．５時間継続させた。The inside of the reaction vessel 10 was evacuated to 10-6 Torr. A mixed gas of methane, methyl arsenide, and hydrogen was flowed into the reaction vessel IO, and the pressure was maintained at 200 Torr. The volume ratio of methane and hydrogen was set to methane/hydrogen-0.05/99.95, and the atomic ratio of carbon in methane to arsenic in methyl arsenide hydride was set to 1:10-'. When the filament 18 is energized and the filament temperature is 2500°C, the cathode 17
A high voltage was applied to start discharging. Distance between both electrodes 1
．． '5cm5 discharge voltage 1000V, discharge current 800m
Under conditions A, the temperature of the anode 13 and the base support 14 is approximately 1
The temperature rose to 300°C. During the reaction, the raw material gas is heated to 4009C.
It was flowed at a flow rate of CH. During the reaction, a positive column was observed directly above the anode 13 and the substrate support 14. The silicon carbide precipitation reaction was continued for 0.5 hours under the above conditions.
その後、反応容器ｌＯ内にメタン、ジボラン、水素の混
合ガスを流した。メタンと水素との容積比はメタン／水
素−１／９９、メタン中の炭素とジボラン中のほう素と
の原子比はｌ ： １０−’に設定した。Thereafter, a mixed gas of methane, diborane, and hydrogen was flowed into the reaction vessel IO. The volume ratio of methane and hydrogen was set to methane/hydrogen-1/99, and the atomic ratio of carbon in methane to boron in diborane was set to 1:10-'.
フィラメント１８に通電して、フィラメント温度を２５
００℃として、陰極１７に高電圧を印加して放電を開始
した。両電極間の距離１．５ｃｍ、放電電圧８００ｖ１
放電電流５００ｍ Ａの条件で、陽極１３及び基体支持
体１４の温度は約８５０℃まで上昇した。反応中は原料
ガスを４００９ＣＣＨの流量で流した。反応中に陽極１
３及び基体支持体１４の直上には陽光柱が観察された。The filament 18 is energized to raise the filament temperature to 25
The temperature was set at 00° C., and a high voltage was applied to the cathode 17 to start discharging. Distance between both electrodes 1.5cm, discharge voltage 800v1
Under conditions of a discharge current of 500 mA, the temperature of the anode 13 and the base support 14 rose to about 850°C. During the reaction, the raw material gas was flowed at a flow rate of 4009 CCH. Anode 1 during the reaction
A positive column was observed directly above 3 and the substrate support 14.
以上の条件でダイヤモンドの析出反応を１時間継続させ
た後、ガスの供給、フィラメント１８の加熱、基体１６
への電圧印加を中止した。After continuing the diamond precipitation reaction for one hour under the above conditions, the gas is supplied, the filament 18 is heated, and the base 16 is heated.
The application of voltage to was discontinued.
形成されたダイヤモンド膜は基体１６であるチタンから
剥離することなく、密着性が良好であった。The formed diamond film did not peel off from the titanium substrate 16 and had good adhesion.
ダイヤモンド膜を電子線回折及びラマン分光法で調べた
結果、結晶面間隔及びラマンバンドが天然ダイヤモンド
の値と一致し、この膜が結晶性の良好なダイヤモンド膜
であることが確認された。As a result of examining the diamond film using electron beam diffraction and Raman spectroscopy, the crystal spacing and Raman band matched those of natural diamond, confirming that this film was a diamond film with good crystallinity.
基板１６であるチタン側にインジウム、ダイヤモンド膜
側に銀ペーストを用いてそれぞれオーミック電極を形成
した。ダイヤモンド膜側を正、チタン側を負として電位
を印加し、整流特性を測定したところ、良好な整流特性
が得られた。Ohmic electrodes were formed using indium on the titanium side of the substrate 16 and silver paste on the diamond film side. When a potential was applied with the diamond film side as positive and the titanium side as negative, and the rectification characteristics were measured, good rectification characteristics were obtained.
比較のために、基体支持体１４上に基体１６として表面
を鏡面仕上げしたチタンのみを載せ、炭化けい素を析出
させる反応を積極的に行わずに、前述したのと同一の条
件でダイヤモンドの析出を行った。得られたダイヤモン
ド膜は基体１６であるチタンから剥離してしまった。For comparison, only titanium with a mirror-finished surface was placed as the substrate 16 on the substrate support 14, and diamond was precipitated under the same conditions as described above without actively performing a reaction to precipitate silicon carbide. I did it. The obtained diamond film peeled off from the titanium substrate 16.
［発明の効果コ
以上詳述したように本発明の方法を用いれば、微細な結
晶粒からなり表面が平滑で均一であり、しかも基体との
密着性が良好な膜状のダイヤモンドを効率よく製造する
ことができる。[Effects of the Invention] As detailed above, by using the method of the present invention, it is possible to efficiently produce diamond in the form of a film that is made of fine crystal grains, has a smooth and uniform surface, and has good adhesion to the substrate. can do.
第１図は本実施例１において用いられた反応装置の概略
構成図、第２図は本実施例２において用いられた反応装
置の概略構成図である。
１・・・反応容器、２・・・反応ガス導入口、３・・・
真空排気口、４・・・基体ホルダー ５・・・固体５ｉ
ｓ６・・・基体、７・・・フィラメント、８・・・給電
治具、９・・・直流電源、ｌＯ・・・反応容器、１１・
・・反応ガス導入口、１２・・・真空排気口、１３・・
・陽極、１４・・・基体支持体、１５・・・固体Ｓｉ、
１８・・・基体、１７・・・陰極、１８・・・フィラメ
ント、１９・・・直流電源。FIG. 1 is a schematic diagram of the reaction apparatus used in Example 1, and FIG. 2 is a schematic diagram of the reaction apparatus used in Example 2. 1... Reaction container, 2... Reaction gas inlet, 3...
Vacuum exhaust port, 4...Substrate holder 5...Solid 5i
s6...Substrate, 7...Filament, 8...Power supply jig, 9...DC power supply, lO...Reaction container, 11...
...Reaction gas inlet, 12...Vacuum exhaust port, 13...
- Anode, 14... Base support, 15... Solid Si,
18... Base, 17... Cathode, 18... Filament, 19... DC power supply.
Claims (1)
ガスとして炭素源ガスと水素ガスとの混合ガスを供給し
、前記固体状態のＳｉを１０００℃以上に加熱した状態
で、前記原料ガスを分解することにより前記基体上に炭
化けい素膜を形成する工程と、原料ガスとして前記工程
よりも水素ガスに対する炭素源ガスの割合が多い混合ガ
スを供給し、前記固体状態のＳｉを１０００℃未満に加
熱した状態で、前記原料ガスを分解することにより前記
基体上に形成された炭化けい素膜上にダイヤモンド膜を
形成する工程とを具備したことを特徴とするダイヤモン
ドの製造方法。A substrate and solid state Si are placed in a reaction vessel, a mixed gas of carbon source gas and hydrogen gas is supplied as a raw material gas, and the solid state Si is heated to 1000° C. or higher, and the raw material gas is A step of forming a silicon carbide film on the substrate by decomposition, and supplying a mixed gas having a higher ratio of carbon source gas to hydrogen gas than in the step as a raw material gas, and heating the solid state Si to a temperature below 1000°C. A method for manufacturing diamond, comprising the step of forming a diamond film on a silicon carbide film formed on the substrate by decomposing the source gas in a heated state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2259010A JPH04139090A (en) | 1990-09-28 | 1990-09-28 | Production of diamond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2259010A JPH04139090A (en) | 1990-09-28 | 1990-09-28 | Production of diamond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04139090A true JPH04139090A (en) | 1992-05-13 |
Family
ID=17328099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2259010A Pending JPH04139090A (en) | 1990-09-28 | 1990-09-28 | Production of diamond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04139090A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020095074A (en) * | 2001-06-06 | 2002-12-20 | 오오사카후 | Method for manfacturing a single crystal silicon carbide thin film and its manufacturing apparatus |
-
1990
- 1990-09-28 JP JP2259010A patent/JPH04139090A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020095074A (en) * | 2001-06-06 | 2002-12-20 | 오오사카후 | Method for manfacturing a single crystal silicon carbide thin film and its manufacturing apparatus |
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