JP3008466B2 - Selective growth method of diamond thin film using diamond fine powder - Google Patents
Selective growth method of diamond thin film using diamond fine powderInfo
- Publication number
- JP3008466B2 JP3008466B2 JP2254416A JP25441690A JP3008466B2 JP 3008466 B2 JP3008466 B2 JP 3008466B2 JP 2254416 A JP2254416 A JP 2254416A JP 25441690 A JP25441690 A JP 25441690A JP 3008466 B2 JP3008466 B2 JP 3008466B2
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- JP
- Japan
- Prior art keywords
- diamond
- fine powder
- thin film
- substrate
- powder
- 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.)
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Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は、ダイヤモンド薄膜形成を選択的に形成する
方法に関するものである。Description: FIELD OF THE INVENTION The present invention relates to a method for selectively forming a diamond thin film.
(従来の技術および発明が解決しようとする課題) ダイヤモンドは、すべての物質の中で最高の硬度と熱
伝導度をもち、研磨材、カッターなど広く工業的に利用
されている。ダイヤモンドの合成は高温高圧法による製
造法が広く知られている。高圧高温法によるダイヤモン
ド合成法は製造方法が複雑であること、製造装置が大型
になり経済的でないことなど、ダイヤモンド製造法とし
ては種々の難点がある。一方、最近開発された低圧気相
法によるダイヤモンドの合成はその製造方法が簡単で、
経済的なダイヤモンドの製造方法である。気相法による
ダイヤモンド合成は、薄膜状ダイヤモンドの合成に特徴
がある。ダイヤモンド薄膜は半導体レーザー、LSIデバ
イスの放熱板などの電子材料、また高温半導体としても
注目され研究が進んでいる。(Problems to be Solved by the Prior Art and the Invention) Diamond has the highest hardness and thermal conductivity among all materials, and is widely used industrially such as abrasives and cutters. A method for producing diamond by a high-temperature and high-pressure method is widely known. The diamond synthesis method by the high-pressure and high-temperature method has various difficulties as a diamond manufacturing method, such as a complicated manufacturing method, a large-sized manufacturing apparatus, and uneconomical. On the other hand, the synthesis of diamond by the recently developed low-pressure gas phase method is simple in its production method,
This is an economical diamond production method. Diamond synthesis by the vapor phase method is characterized by the synthesis of thin film diamond. Diamond thin films are attracting attention as electronic materials such as semiconductor lasers, heat sinks for LSI devices, and high-temperature semiconductors, and are being studied.
低圧気相法によるダイヤモンド薄膜形成の難点の一つ
は、均一な薄膜が得難いことである。シリコンやタング
ステンを基板として、ダイヤモンドを成長させると、塊
状のダイヤモンド粒子が成長し、表面が荒れて、滑らか
な膜が得られない。この問題の解決策として、ダイヤモ
ンド薄膜形成に先だって、基板に前処理を施すことが提
案されている。たとえば、粒径数ミクロン程度のダイヤ
モンド粉末の懸濁液に基板を浸し、一定時間超音波で撹
拌すると、ダイヤモンド薄膜の成長が促進され、滑から
な膜が形成されることがある。その理由としてこの前処
理によって基板表面に“きず”が生じ、結晶成長核の密
度が5桁も増大するため考えられている。しかしなが
ら、この従来の方法は再現性に欠け必ずしも滑らかな膜
が形成されるとは限らない。One of the difficulties of forming a diamond thin film by the low-pressure gas phase method is that it is difficult to obtain a uniform thin film. When diamond is grown using silicon or tungsten as a substrate, massive diamond particles grow, the surface becomes rough, and a smooth film cannot be obtained. As a solution to this problem, it has been proposed to pretreat the substrate before forming the diamond thin film. For example, when a substrate is immersed in a suspension of diamond powder having a particle diameter of about several microns and stirred for a certain period of time by ultrasonic waves, the growth of a diamond thin film is promoted, and a smooth film may be formed. It is considered that the reason for this is that the pretreatment causes "flaws" on the substrate surface and increases the density of crystal growth nuclei by five orders of magnitude. However, this conventional method lacks reproducibility and does not always form a smooth film.
本発明は、表面が滑らかで、均質なダイヤモンド薄膜
を再現性よくしかも選択的に形成する方法を提供するこ
とを目的としている。An object of the present invention is to provide a method for selectively forming a uniform diamond thin film having a smooth surface with good reproducibility.
(課題を解決するための手段) 本発明の選択成長方法は、ダイヤモンド粉末を種結晶
として基板表面に形成しそのあとダイヤモンド薄膜を選
択的に形成する。種結晶として粒径数十nm以下のダイヤ
モンド微粉末を用い、これを基板表面に高密度に埋め込
み、これを成長核としてホモエピタキシャルで表面が滑
らかで均質な薄膜が形成できる。ダイヤモンド薄膜を選
択的に形成する方法は、まず、基板の全表面にダイヤモ
ンド微粉末種結晶を植えこみ、通常のリソグラフィー技
術に従ってパターン形成をする。つぎに、パターン形成
の保護膜で被覆されていない基板表面にあるダイヤモン
ド微粉末を酸素プラズマ気中で反応させ、これらのダイ
ヤモンド微粉末をエッチングし除く。つづいて、保護膜
を一除去し基板上のダイヤモンド微粉末を露出させ、通
常のダイヤモンドの低圧気相成長にしたがって、該当基
板上のダイヤモンド微粉末が残っている部分に、ダイヤ
モンドを選択的に成長させる。(Means for Solving the Problems) In the selective growth method of the present invention, diamond powder is formed as a seed crystal on a substrate surface, and then a diamond thin film is selectively formed. A diamond fine powder having a particle size of several tens of nm or less is used as a seed crystal, which is buried at a high density on the substrate surface, and a homogenous thin film having a smooth surface can be formed by using this as a growth nucleus. As a method for selectively forming a diamond thin film, first, a diamond fine powder seed crystal is implanted on the entire surface of a substrate, and a pattern is formed according to a usual lithography technique. Next, the diamond fine powder on the substrate surface not covered with the protective film for pattern formation is reacted in an oxygen plasma atmosphere, and the diamond fine powder is etched away. Next, the protective film is removed to expose the diamond fine powder on the substrate, and diamond is selectively grown on the portion of the substrate where the diamond fine powder remains, in accordance with ordinary low-pressure vapor deposition of diamond. Let it.
ダイヤモンド微粉末の除去には、酸素プラズマによる
化学反応を利用する他に、イオン照射、イオンスパッ
タ、電子線照射など物理的方法によりダイヤモンド微粉
末を破壊する方法も有効である。ダイヤモンド薄膜を形
成する基板材料は、ダイヤモンドが気相成長できるもの
であれば、その種類に格別の限定はなく、たとえば、酸
化物、窒化物、半導体、金属、半金属があげられる。低
圧気相法ではダイヤモンドを形成する方法は、熱気相
法、プラズマ気相法、電子衝撃気相法等のダイヤモンド
製造方法であればどれでもよい。In order to remove the diamond fine powder, a method of destroying the diamond fine powder by a physical method such as ion irradiation, ion sputtering, or electron beam irradiation is effective other than utilizing a chemical reaction by oxygen plasma. The substrate material for forming the diamond thin film is not particularly limited as long as diamond can be grown in a vapor phase, and examples thereof include oxides, nitrides, semiconductors, metals, and metalloids. In the low pressure gas phase method, any method for forming diamond may be used as long as it is a diamond manufacturing method such as a thermal gas phase method, a plasma gas phase method, and an electron impact gas phase method.
なお、微粉末を植えこむ前に基板上に、SiO2、Si3N4
等の保護膜のパターンを形成しておき、そのあと微粉末
を植えこみ、保護膜をエッチング等で除去し、保護膜が
形成されていなかった部分にのみ微粉末を残す方法を用
いてもよい。また微粉末を全面に植えこんだあと、収束
イオンビーム、収束電子ビームを所望の部分に照射して
その部分の微粉末を破壊し、そのあと薄膜成長を行なう
と選択的に薄膜を形成できる。Before the fine powder is implanted, SiO 2 , Si 3 N 4
A method may be used in which a pattern of a protective film such as that described above is formed, fine powder is then implanted, the protective film is removed by etching or the like, and the fine powder is left only in portions where the protective film was not formed. . Further, after the fine powder is implanted on the entire surface, a focused ion beam or a focused electron beam is irradiated to a desired portion to destroy the fine powder in that portion, and then a thin film is grown, whereby a thin film can be selectively formed.
本発明の方法が従来のダイヤモンド薄膜の選択形成技
術と相違する点は、ダイヤモンド薄膜形成に先だって、
粒径数十nmのダイヤモンド微粉末を基板表面に人為的に
形成しそれを種結晶にすることにより、表面な滑らかで
均質なダイヤモンド薄膜が再現よく製造できる点にあ
る。前述の従来の方法では、基板の前処理により基板表
面に何らかのきずを生じさせ、結晶成長核を増加するこ
とに主眼がおかれていたが、結晶成長核の実体は不明で
あった。本発明者は滑らかなダイヤモンド薄膜が形成さ
れるのは基板につけたきずのためではなく、きずをつけ
るために用いた粒径数ミクロン程度のダイヤモンド粉末
の一部が微粉末となり超音波によって基板表面に植えこ
まれた場合であることを発見した。従来はダイヤモンド
粉末は基板にきずをつけるために用いていたので常に
「植えこみ」が生じるとは限らず再現性が悪かったので
ある。The point that the method of the present invention differs from the conventional diamond thin film selective formation technique is that prior to the formation of the diamond thin film,
By artificially forming a diamond fine powder having a particle size of several tens of nanometers on the substrate surface and using it as a seed crystal, a uniform and smooth diamond thin film surface can be produced with good reproducibility. In the above-mentioned conventional method, although the main focus has been on increasing the number of crystal growth nuclei by generating some flaws on the substrate surface due to the pretreatment of the substrate, the substance of the crystal growth nucleus was unknown. The inventor of the present invention did not form a smooth diamond thin film not only because of the flaws on the substrate, but also part of the diamond powder with a particle size of several microns It was discovered that it was planted in. Conventionally, diamond powder was used to scratch the substrate, so that "planting" did not always occur and reproducibility was poor.
このような方法を用いるこの発明の装置について説明
すると、この装置は、ダイヤモンド微粉末を基板上に形
成する装置、ダイヤモンド微粉末を除去する装置、ダイ
ヤモンド薄膜を形成する装置からなっている。後者は、
内部を真空減圧状態とすることのできる加熱炉と、加熱
炉内に炭化水素ガスと水素ガスの混合ガスを供給する供
給系と、加熱炉内に基板を支持する系と、炭化水素ガス
と水素ガスを反応性ガスにする系からなっている。The apparatus of the present invention using such a method will be described. The apparatus comprises an apparatus for forming diamond fine powder on a substrate, an apparatus for removing diamond fine powder, and an apparatus for forming a diamond thin film. The latter is
A heating furnace capable of reducing the pressure inside the furnace, a supply system for supplying a mixed gas of hydrocarbon gas and hydrogen gas into the heating furnace, a system for supporting a substrate in the heating furnace, a hydrocarbon gas and hydrogen It consists of a system that converts gas into reactive gas.
(実施例) 第2図は、ダイヤモンド微粉末を基板表面に形成する
ための装置の一例を示したもので、超音波発生装置
(1)に連結された金属円盤(2)とこれに平行に設置
された基板(3)からなっている。基板はマイクロメー
ター(4)で金属板と垂直に可動する架台(5)に固定
される。また架台はチャック(6)により回転モーター
(7)にとりつけ、基板面と垂直な軸の回りに連続に回
転する。金属円盤(2)と基板(3)及び基板の架台
(5)は、水、アルコール、アセトン等の溶液に研磨
材、カッター等で使う粒径十ミクロン程度の通常のダイ
ヤモンド粉末が懸濁させた液を容れた容器(8)に浸さ
れている。金属円盤(2)と基板(3)の間隙を300μ
mと近接させ、10分程度超音波発生装置(1)により撹
拌し、基板をとりだして洗浄後、乾燥する。これによっ
て10μmのダイヤモンド粉体が互いに衝突して粉砕し粒
径数十nm以下のダイヤモンド微粉末が基板表面に高密度
に埋め込まれる。つまり超音波によって粉末が基板につ
きささり、それが欠けて微粉末がうめこまれるわけであ
る。(Example) FIG. 2 shows an example of an apparatus for forming a diamond fine powder on a substrate surface. The apparatus includes a metal disk (2) connected to an ultrasonic generator (1) and a metal disk (2). It consists of an installed substrate (3). The substrate is fixed by a micrometer (4) to a gantry (5) movable vertically to the metal plate. The gantry is attached to a rotating motor (7) by a chuck (6) and continuously rotates around an axis perpendicular to the substrate surface. The metal disk (2), the substrate (3), and the pedestal (5) of the substrate were prepared by suspending an ordinary diamond powder having a particle diameter of about 10 microns used in an abrasive, a cutter, or the like in a solution of water, alcohol, acetone, or the like. It is immersed in a container (8) containing the liquid. 300μ gap between metal disk (2) and substrate (3)
m, stirred by an ultrasonic generator (1) for about 10 minutes, taken out of the substrate, washed, and dried. As a result, diamond powders of 10 μm collide with each other and pulverize, and diamond fine powders having a particle size of several tens nm or less are embedded at high density on the substrate surface. That is, the powder is brought into contact with the substrate by the ultrasonic wave, and the fine powder is buried by the chipping.
第1図は、第2図の方法で作成した基板上のパターン
形成工程の一例を示したものである。全面にダイヤモン
ド微粉末(9)を形成したシリコン基板(3)に、パタ
ーン形成するための保護膜たとえばフォトレジスト膜
(12)を塗布する((a)図)。この膜に、通常のリソ
グラフィ技術で線幅0.5μmのパターン(12)を形成
し、保護膜で被覆されない部分のダイヤモンド微粉末
(9)を、酸素プラズマ(圧力4×10-2Pa)に10分間露
出してエッチングし除去する((b)図)。つぎに、ダ
イヤモンド微粉を除去した基板(3)を、適当な溶媒例
えばアセトンに浸し保護膜を除去する((c)図)。な
お、微粉末を植えこむ前に基板(3)上に、SiO2、Si3N
4等の保護膜のパターンを形成しておき、その後微粉末
を植えこみ、保護膜をエッチング等で除去し、保護膜が
形成されていなかった部分にのみ微粉末を残す方法を用
いても良い。このシリコン基板をダイヤモンド薄膜形成
装置に移し、試料温度850℃、炭化水素ガスと水素ガス
の体積混合比1%の混合ガス(圧力5x103Pa)雰囲気中
で、60分間熱処理した。その結果、ダイヤモンド微粉末
9上に厚さと幅がともに0.5μmのダイヤモンド薄膜の
パターン14が形成されていることを確認した((d)
図)。第1図(a)〜(d)の工程を数回行なったが常
に同じ薄膜パターンが得られ、再現性があることを確認
した。FIG. 1 shows an example of a pattern forming step on a substrate prepared by the method of FIG. A protective film for forming a pattern, for example, a photoresist film (12) is applied to a silicon substrate (3) having a diamond fine powder (9) formed on the entire surface (FIG. 7A). On this film, a pattern (12) having a line width of 0.5 μm is formed by a usual lithography technique, and the diamond fine powder (9) not covered with the protective film is exposed to oxygen plasma (pressure 4 × 10 -2 Pa) for 10 times. Then, it is exposed for a minute, etched and removed (FIG. 7B). Next, the substrate (3) from which the diamond fine powder has been removed is immersed in a suitable solvent such as acetone to remove the protective film (FIG. (C)). Before the fine powder is implanted, SiO 2 , Si 3 N
A method may be used in which a pattern of a protective film such as 4 is formed, fine powder is implanted thereafter, the protective film is removed by etching or the like, and the fine powder is left only in a portion where the protective film was not formed. . This silicon substrate was transferred to a diamond thin film forming apparatus, and heat-treated for 60 minutes in a mixed gas (pressure 5 × 10 3 Pa) atmosphere having a sample mixing temperature of 850 ° C. and a hydrocarbon gas / hydrogen gas volume ratio of 1%. As a result, it was confirmed that a diamond thin film pattern 14 having both a thickness and a width of 0.5 μm was formed on the diamond fine powder 9 ((d)).
Figure). Although the steps shown in FIGS. 1A to 1D were performed several times, the same thin film pattern was always obtained, and it was confirmed that reproducibility was obtained.
(発明の効果) 本発明によれば、基板上にダイヤモンド薄膜の選択成
長を再現性よく行なうことができた。(Effect of the Invention) According to the present invention, selective growth of a diamond thin film on a substrate can be performed with good reproducibility.
第1図は本発明の実施例の選択成長法を示す断面図、第
2図はダイヤモンド微粉末を基板上にうめこむ装置の概
概略図。なお、図中の番号の次のものを示している。 1……超音波発生器、2……金属円盤、3……基板試
料、4……マイクロメーター、5……基板支持台、6…
…チャック、7……回転モーター、8……容器、9……
ダイヤモンド微粉末、10……フォトレジスト膜、11……
ダイヤモンド薄膜。FIG. 1 is a sectional view showing a selective growth method according to an embodiment of the present invention, and FIG. 2 is a schematic diagram showing an apparatus for embedding diamond fine powder on a substrate. The numbers following the numbers in the figure are shown. 1 ... Ultrasonic generator, 2 ... Metal disk, 3 ... Substrate sample, 4 ... Micrometer, 5 ... Substrate support, 6 ...
... Chuck, 7 ... Rotary motor, 8 ... Container, 9 ...
Diamond fine powder, 10 ... Photoresist film, 11 ...
Diamond thin film.
Claims (2)
せた溶液中に基板を浸し、超音波を発生させることで前
記数十ミクロンのダイアモンド粉末を数十nmのダイアモ
ンド微粉末に粉砕し、基板に埋め込まれた前記数十nm以
下のダイアモンド微粉末を種結晶としてダイアモンドを
選択的に形成することを特徴とするダイヤモンド薄膜の
選択成長方法。A substrate is immersed in a solution in which diamond powder of several tens of microns is suspended, and ultrasonic waves are generated to pulverize the diamond powder of several tens of microns into diamond fine powder of several tens of nm. And selectively forming diamond using the diamond fine powder of several tens of nm or less embedded as a seed crystal.
ンドを選択成長する面とが対向していることを特徴とす
る請求項1記載のダイヤモンド薄膜の選択成長方法。2. The method for selectively growing a diamond thin film according to claim 1, wherein a base for generating ultrasonic waves and a surface of the substrate on which diamond is selectively grown face each other.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2254416A JP3008466B2 (en) | 1990-09-25 | 1990-09-25 | Selective growth method of diamond thin film using diamond fine powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2254416A JP3008466B2 (en) | 1990-09-25 | 1990-09-25 | Selective growth method of diamond thin film using diamond fine powder |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04132690A JPH04132690A (en) | 1992-05-06 |
JP3008466B2 true JP3008466B2 (en) | 2000-02-14 |
Family
ID=17264676
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JP2254416A Expired - Fee Related JP3008466B2 (en) | 1990-09-25 | 1990-09-25 | Selective growth method of diamond thin film using diamond fine powder |
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JP (1) | JP3008466B2 (en) |
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1990
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JPH04132690A (en) | 1992-05-06 |
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