JP2001115261A - Semiconductor element - Google Patents
Semiconductor elementInfo
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- JP2001115261A JP2001115261A JP2000280654A JP2000280654A JP2001115261A JP 2001115261 A JP2001115261 A JP 2001115261A JP 2000280654 A JP2000280654 A JP 2000280654A JP 2000280654 A JP2000280654 A JP 2000280654A JP 2001115261 A JP2001115261 A JP 2001115261A
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- diamond
- substrate
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- annealing
- film
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Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、半導体用基板材料や焼
結体材料あるいは金属材料の表面に密着性良好でかつ優
れた膜質を備えたダイヤモンド薄膜を形成する方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a diamond thin film having good adhesion and excellent film quality on the surface of a semiconductor substrate material, a sintered material, or a metal material.
【0002】[0002]
【従来の技術】人工ダイヤモンド材料合成の研究が古く
から行われ発展してきた。人工ダイヤモンドの合成方法
は、高圧合成法と大気圧ないし低圧の気相成長法に分け
ることが出来る。高圧合成法では温度差法・融剤法・爆
発等を利用した衝撃法によって、微結晶粒子・多結晶焼
結体・ミリメートルサイズの単結晶粒子等の様々な形式
のダイヤモンド材料を形成することが出来る。また気相
成長法はダイヤモンド薄膜を各種基板材料表面に形成す
る方法であり、ダイヤモンドライクカーボン(結晶構造
を持たず、かつダイヤモンドに近い硬度を持つ炭素材料
である。以下DLCと呼称する)を含めて広く研究が成
されている。2. Description of the Related Art Synthetic diamond material synthesis has been studied and developed for a long time. Methods of synthesizing artificial diamond can be divided into a high-pressure synthesis method and a vapor-phase growth method at atmospheric pressure or low pressure. In the high-pressure synthesis method, various types of diamond materials such as microcrystalline particles, polycrystalline sintered bodies, millimeter-sized single crystal particles, etc. can be formed by the impact method using the temperature difference method, flux method, explosion, etc. I can do it. The vapor phase growth method is a method of forming a diamond thin film on the surface of various substrate materials, including diamond-like carbon (a carbon material having no crystal structure and having a hardness close to that of diamond; hereinafter, referred to as DLC). Has been widely studied.
【0003】人工ダイヤモンドに関しては特有の硬度・
透明度・熱伝導性・高絶縁性等を利用して、様々な応用
が提案されてきた。例えば硬度と熱伝導性を利用して長
寿命切削工具材料や電子材料用ヒートシンクに、可視光
〜赤外線領域の透明度を利用して赤外線レーザ等の光学
窓材料に、高絶縁性を生かして電子デバイス材料にと、
多くの提案や研究が行われてきた。[0003] Artificial diamond has a specific hardness
Various applications have been proposed using transparency, thermal conductivity, high insulation properties, and the like. For example, utilizing the hardness and thermal conductivity for long-life cutting tool materials and heat sinks for electronic materials, utilizing the transparency in the visible to infrared range for optical window materials such as infrared lasers, and utilizing the high insulation properties of electronic devices. To the material,
Many proposals and studies have been made.
【0004】高圧合成法では、上記の応用例の内で切削
工具材料やヒートシンクに関してはようやく初歩的な実
用化が成されつつある様であるが、板や棒等単純形状の
試料しか得られず、また大きさも最大で10数mm角が限
度であるなどいまだ制約がある。ゆえに工作機械分野で
要求される複雑な形状の工具を提供するには、非常に不
利であると言える。[0004] In the high-pressure synthesis method, it seems that elementary practical use of cutting tool materials and heat sinks is finally being realized among the above-mentioned application examples, but only samples of simple shapes such as plates and rods can be obtained. In addition, there is still a limitation that the size is limited up to 10 mm square. Therefore, it can be said that providing a tool having a complicated shape required in the field of machine tools is extremely disadvantageous.
【0005】気相成長法は各種基体上にダイヤモンド薄
膜を形成する方法であり、上記の高圧合成ダイヤモンド
の持っていた大きさや形状の限界を解消し、半導体材料
等の多方面へダイヤモンド応用の可能性を広げることが
期待されている。対象となるのは工具だけでなく、半導
体素子などの開発の試みも盛んに行われている。[0005] The vapor phase growth method is a method of forming a diamond thin film on various substrates, which overcomes the size and shape limitations of the above-mentioned high-pressure synthetic diamond and enables diamond to be applied to various fields such as semiconductor materials. It is expected to expand their sexuality. Not only tools but also semiconductor devices are being actively developed.
【0006】[0006]
【発明が解決しようとする課題】上記の様に気相成長法
によって人工ダイヤモンドの応用範囲は大きく広がった
訳であるが、該手法を用いた各種ダイヤモンド製品にお
いて問題となっていることにダイヤモンド薄膜と基体と
の密着性がある。工具材料の様な機械的に過酷な環境に
晒されるもののみならず、ヒートシンク・半導体材料分
野においても基板上で薄膜の構造を安定に確保するとい
う意味で重要である。しかし基体材料の種類を問わず該
密着性は非常に貧弱である。As described above, the application range of artificial diamond has been greatly expanded by the vapor phase growth method, but the problem with various diamond products using this method is that the diamond thin film has a problem. And the substrate. Not only those exposed to mechanically severe environments such as tool materials, but also in the field of heat sinks and semiconductor materials are important in terms of ensuring a stable thin film structure on a substrate. However, the adhesion is very poor regardless of the type of the base material.
【0007】ダイヤモンド薄膜の密着性が脆弱な理由は
次のような事によると考えられている。 1.ダイヤモンド薄膜と基体との熱膨張率の差 ダイヤモンドの成膜基体は500〜800℃、方法によ
っては1000℃付近まで加熱する必要がある。例えば
代表的な半導体基板材料であるSi基板の熱膨張率は
2.4であるのに対してダイヤモンドのそれは1.0〜
1.5と小さくなっている。密着性は温度以外の成膜条
件によっても大きく変化する事が明らかになっている
が、この熱膨張率の差も非常に大きな影響を与えること
が知られている。It is believed that the reason why the adhesion of the diamond thin film is weak is as follows. 1. Difference in coefficient of thermal expansion between diamond thin film and substrate It is necessary to heat a diamond film-forming substrate to 500 to 800 ° C, or to around 1000 ° C depending on the method. For example, the coefficient of thermal expansion of a Si substrate, which is a typical semiconductor substrate material, is 2.4, whereas that of diamond is 1.0 to 1.0.
It is as small as 1.5. It has been found that the adhesion changes greatly depending on film forming conditions other than the temperature, but it is known that this difference in the coefficient of thermal expansion also has a very large effect.
【0008】2.ダイヤモンド薄膜に蓄積された内部応
力 完成したダイヤモンド薄膜の断面観察から、ダイヤモン
ド薄膜の成長は基板表面の核から結晶が等方的に成長し
ていき、成長途中で結晶粒子が衝突して成長方向が制限
されることによりテーパー状および/もしくは柱状の結
晶粒子へと構造を変化させられて、基板に対し概ね垂直
に異方成長した薄膜を形成していくと考えられている。
この為に膜の内部には非常に強い圧縮応力が蓄積される
ことになる。[0008] 2. Internal stress accumulated in the diamond thin film From observation of the cross section of the completed diamond thin film, in the growth of the diamond thin film, the crystal grows isotropically from the nucleus on the substrate surface, and crystal grains collide during growth and the growth direction changes. It is considered that the structure is changed into a tapered and / or columnar crystal particle by the restriction, and a thin film grown anisotropically substantially perpendicular to the substrate is formed.
For this reason, a very strong compressive stress is accumulated inside the film.
【0009】又、密着性を向上させるために、以下に示
す様な試みがなされてきた。 1.中間層形成 基体材料とダイヤモンドの中間の格子定数・熱膨張率を
有する材質の薄膜により両者の界面に緩衝帯として中間
層を設ける。例えば結晶性薄膜として窒化珪素・炭化珪
素(好ましくはβ型炭化珪素)・窒化硼素(好ましくは
立方晶窒化硼素)・炭化チタン・窒化チタン等を用い、
また成膜工程をより簡便化したければDLCや窒化珪素
・炭化珪素・窒化硼素・炭窒化硼素・炭化チタン・窒化
チタン等のアモルファス薄膜を用いても良い。これによ
り基板と薄膜間の熱膨張率差や格子定数差の解消を図
り、内部応力蓄積を緩和する。ただし中間層成膜機構が
介入するためどうしてもプロセスは煩雑化する。また半
導体デバイスとしての応用のためには中間層作成に伴う
電気的特性の変化等の影響を考慮する必要がある。Further, in order to improve the adhesion, the following attempts have been made. 1. Formation of Intermediate Layer An intermediate layer is provided as a buffer band at the interface between the base material and diamond by using a thin film of a material having an intermediate lattice constant and thermal expansion coefficient. For example, silicon nitride, silicon carbide (preferably β-type silicon carbide), boron nitride (preferably cubic boron nitride), titanium carbide, titanium nitride, or the like is used as the crystalline thin film.
In order to simplify the film forming process, an amorphous thin film such as DLC or silicon nitride, silicon carbide, boron nitride, boron carbonitride, titanium carbide, or titanium nitride may be used. As a result, the difference between the coefficient of thermal expansion and the difference in lattice constant between the substrate and the thin film is eliminated, and the accumulation of internal stress is reduced. However just process for the intermediate layer deposition mechanism intervenes is complicated. In addition, for application as a semiconductor device, it is necessary to consider the influence of a change in electrical characteristics due to the formation of the intermediate layer.
【0010】2.ダイヤモンド薄膜の内部応力低減 成膜時の加熱温度を低減させることによって、冷却時に
発生する歪を減少させ膜の剥離を防止する。ただし一般
にその成膜方法や成膜条件に適当な温度範囲以下の成膜
では、無定形炭素成分の生成により膜質が低下したり、
あるいは極端に成膜速度が低下したりする。膜中に窒素
等の不純物を導入する事によって結晶粒径を小さくし、
先に述べた結晶粒子のテーパー化による内部応力の蓄積
を緩和するという試みも成されているが、言うまでもな
く膜質は低下する。[0010] 2. Reduction of internal stress of diamond thin film By reducing the heating temperature at the time of film formation, distortion generated at the time of cooling is reduced, and peeling of the film is prevented. However, in general, when a film is formed under a temperature range suitable for the film forming method and the film forming conditions, the film quality is deteriorated due to generation of an amorphous carbon component,
Alternatively, the deposition rate is extremely reduced. The crystal grain size is reduced by introducing impurities such as nitrogen into the film,
Attempts have been made to alleviate the accumulation of internal stress due to the tapering of the crystal grains described above, but it goes without saying that the film quality deteriorates.
【0011】3.アンカー効果の利用 基体表面に機械的または化学的エッチングまたはレーザ
等にて微細な凹凸加工を施し、その後通常の前処理工程
を経てダイヤモンド成膜をおこなう。これにより基体表
面に微細なダイヤモンドアンカーが食い込んだ構造を形
成し、密着性良好なダイヤモンド薄膜を形成しようとい
うものである。特に工具材料の分野で提案された方法で
あるが、基体として用いられるWC焼結体において十分
な密着性が得られていない事からも明らかなように、基
体の表面とアンカー機能に準じたサイズの凹凸を明確に
差別化することが困難であり、実用的な方法には成って
いない。3. Utilization of anchor effect The surface of the substrate is subjected to fine unevenness processing by mechanical or chemical etching or laser or the like, and then a diamond film is formed through a normal pretreatment process. In this way, a structure in which fine diamond anchors bite into the substrate surface is formed, and a diamond thin film having good adhesion is formed. In particular, it is a method proposed in the field of tool materials, but as is clear from the fact that sufficient adhesion is not obtained in a WC sintered body used as a substrate, the size of the surface of the substrate and the size according to the anchor function are apparent. However, it is difficult to clearly differentiate the unevenness of the surface, and this is not a practical method.
【0012】[0012]
【課題を解決するための手段】本発明者らは上記課題を
解決するための手段として、一般に行われている各種方
法によってダイヤモンド薄膜を表面に形成した基板材料
へ、真空状態や減圧窒素または減圧酸素状態において
熱、電磁誘導、光によって加熱しアニールを行い、課題
とする密着性の脆弱さを解決することが可能である事を
見出した。以下本発明を説明する。Means for Solving the Problems As means for solving the above-mentioned problems, the present inventors applied a vacuum state, a reduced pressure nitrogen or a reduced pressure to a substrate material having a diamond thin film formed on its surface by various commonly used methods. It has been found that annealing can be performed by heating with heat, electromagnetic induction, and light in an oxygen state to solve the problem of weak adhesion. Hereinafter, the present invention will be described.
【0013】本発明でダイヤモンド成膜はどの様な方法
を用いても構わない。また基板あるいは基体材料の種類
は後述するアニール処理時を含めて1000±100℃
程度に保持可能な材料であれば何でも良い。この温度範
囲は下限に関しては基体材料の種類によってある程度変
更は可能であるが、上限に関してはこれ以上の温度では
ダイヤモンド薄膜の膜質劣化が著しい。また減圧酸素雰
囲気でアニールを行うならば、基体に耐酸化性が大きく
要求される。上記の一般に用いられている成膜方法にお
いて記載した材料はそのほとんどが該温度範囲において
十分な耐久性を有していることが明らかである。In the present invention, any method may be used for forming a diamond film. Further, the kind of the substrate or the base material is 1000 ± 100 ° C. including the time of the annealing process described later.
Any material can be used as long as it can be held to a certain degree. The lower limit of this temperature range can be changed to some extent depending on the type of the base material, but the upper limit of the temperature range is much higher, the quality of the diamond thin film deteriorates remarkably. If annealing is performed in a reduced-pressure oxygen atmosphere, the substrate is required to have high oxidation resistance. It is clear that most of the materials described in the above generally used film forming methods have sufficient durability in the above temperature range.
【0014】半導体材料基板、例えばSi、アルミナや
窒化珪素、炭化珪素、窒化硼素等を基にした焼結/単結
晶基板、石英ガラス基板等に必要に応じて適当な前処理
を施した後、熱フィラメント/プラズマCVD法やプラ
ズマジェット/アーク放電を用いて成膜を行えば良く、
その際大面積化が必要であれば大型の熱フィラメントや
有磁場プラズマを用いたCVD法が適当であろう。上記
方法の他にもDCアークや燃焼炎法によって成膜を行う
ことができる。A semiconductor material substrate, for example, a sintered / single crystal substrate based on Si, alumina, silicon nitride, silicon carbide, boron nitride, etc., a quartz glass substrate, etc. The film may be formed using a hot filament / plasma CVD method or a plasma jet / arc discharge.
At this time, if a large area is required, a CVD method using a large hot filament or a magnetic field plasma may be appropriate. In addition to the above method, film formation can be performed by a DC arc or a combustion flame method.
【0015】成膜した試料に対してアニールを行う方法
は、用いる処理容器が0.005〜10Torr好まし
くは0.1〜0.01Torr程度の真空度もしくは減
圧窒素雰囲気あるいは減圧酸素雰囲気に試料を保持し、
機械的に劣化を生じることなく該容器内の試料を700
〜1100℃に加熱可能な方法であれば何でも良い。例
えば真空状態の炉心管内部に試料を保持し、外部から管
状電気炉を用いて外部加熱を行う方法や、成膜装置が真
空成膜室と基板加熱機能を有しているならば該成膜装置
の基板/基体保持ステージ/ホルダに成膜処理を終えた
基板をそのまま保持し、ステージ/ホルダからの加熱に
よってアニールを行っても良い。またプラズマCVD同
様のプラズマ放電もしくは誘導加熱を電磁波により加え
ても良い。In the method of annealing the formed sample, the processing container to be used is to hold the sample in a vacuum of 0.005 to 10 Torr, preferably about 0.1 to 0.01 Torr, or in a reduced-pressure nitrogen atmosphere or a reduced-pressure oxygen atmosphere. And
The sample in the container is stored 700 times without mechanical deterioration.
Any method can be used as long as it can be heated to 1100 ° C. For example, a method in which a sample is held inside a furnace tube in a vacuum state and external heating is performed using a tubular electric furnace from outside, or the film formation is performed if the film formation apparatus has a vacuum film formation chamber and a substrate heating function. The substrate after the film formation process may be held as it is on the substrate / substrate holding stage / holder of the apparatus, and annealing may be performed by heating from the stage / holder. Further, plasma discharge or induction heating similar to plasma CVD may be applied by electromagnetic waves.
【0016】良好な赤外線透過性を示す窓材を有する減
圧チャンバー内に保持されたダイヤモンド薄膜試料の表
面に、ダイヤモンドが透明である波長において発振され
るレーザ光を走査させることによって、薄膜と基板の界
面に選択的な光加熱を加えることも非常に有効である。
ここで用いられるレーザ光源としては、例えばCO2ガ
スレーザに代表される赤外線レーザを中心として、幅広
く選択することが出来る。一部の半導体レーザを用いて
も良いであろう。By scanning a surface of a diamond thin film sample held in a reduced-pressure chamber having a window material exhibiting good infrared transmittance with laser light oscillated at a wavelength at which diamond is transparent, the thin film and the substrate are scanned. It is also very effective to apply selective light heating to the interface.
As the laser light source used here, for example, an infrared laser typified by a CO 2 gas laser can be widely selected. Some semiconductor lasers could be used.
【0017】アニール方法の如何を問わず、試料は真空
状態もしくは減圧窒素状態もしくは減圧酸素状態とする
ことが必要である。この理由に関しては十分に解明され
ていないが、本発明者らは次のように考えている。減圧
状態で加熱する際、熱エネルギーは炉心管内壁やホルダ
およびレーザ光によって試料に伝達されることになる
が、ダイヤモンド膜表面から上は減圧状態すなわち断熱
状態なので試料内部に熱の集中が起こり、それより薄膜
中の炭素と基体材料原子が相互拡散を起こし、両者のみ
により構成される中間層が形成される。Regardless of the annealing method, the sample must be in a vacuum state, a reduced pressure nitrogen state, or a reduced pressure oxygen state. Although the reason for this has not been sufficiently elucidated, the present inventors consider as follows. When heating under reduced pressure, heat energy is transmitted to the sample by the inner wall of the furnace tube, the holder, and the laser beam.However, heat is concentrated inside the sample because the upper part of the diamond film is in a reduced pressure state, that is, an adiabatic state. As a result, the carbon in the thin film and the base material atoms cause interdiffusion, and an intermediate layer composed only of both is formed.
【0018】従ってこの方法を用いる事により、工程を
複雑化する事無くまた膜の電気的特性への悪影響を気に
する事無く、強靱な結合力を有する中間層を形成するこ
とが可能となる。本発明者らはSiの場合はSi〜β−
SiC〜β−SiCとダイヤモンドの混相〜ダイヤモン
ド薄膜というグラデーション中間層が、他の材料の場合
にもそれに類似の中間層が形成されているのではないか
と考えている。特に減圧雰囲気を酸素によって形成する
ことは、密着性のみならず実施例で述べる様に膜質を向
上させる上で大変有効である。Therefore, by using this method, it is possible to form an intermediate layer having a strong bonding force without complicating the process and without worrying about adverse effects on the electrical characteristics of the film. . The present inventors have found that in the case of Si,
It is considered that a gradation intermediate layer from SiC to a mixed phase of β-SiC and diamond to a diamond thin film may form an intermediate layer similar to that of other materials. In particular, forming the reduced pressure atmosphere with oxygen is very effective in improving not only the adhesion but also the film quality as described in Examples.
【0019】[0019]
【実施例】〔実施例1〕本実施例は真空炉心管を外部か
ら加熱する構造の管状電気炉による真空アニール方法に
関する。試料は有磁場マイクロ波プラズマCVD装置を
用いてSi(100)基板上に成膜した多結晶ダイヤモ
ンド薄膜を用いた。その他単結晶ダイヤモンドや単結晶
の立方晶窒化硼素等の基板上にホモエピタキシャルない
しヘテロエピタキシャル成長させたダイヤモンド試料を
用いても良い。Embodiment 1 This embodiment relates to a vacuum annealing method using a tubular electric furnace having a structure in which a vacuum furnace tube is heated from the outside. As a sample, a polycrystalline diamond thin film formed on a Si (100) substrate using a magnetic field microwave plasma CVD apparatus was used. In addition, a diamond sample that is homoepitaxially or heteroepitaxially grown on a substrate such as single crystal diamond or single crystal cubic boron nitride may be used.
【0020】図1に装置図を示す。本装置は有磁場マイ
クロ波プラズマCVD装置として一般的なものであり、
試料は図の試料および試料ホルダー(1)において、マ
イクロ波導波管(5)に対向するように配置されてい
る。ここで試料および試料ホルダー(1)は予備室
(2)において試料交換の後、プラズマ反応室(3)に
搬送され、該試料ホルダー内部に組み込まれたヒーター
によって加熱される。この時予備室(2)およびプラズ
マ反応室(3)内は広域型ターボモレキュラーポンプ
(以下TMP)と粗引き用兼TMP背圧用ロータリーポ
ンプ(以下RP)および圧力調整バルブからなる排気系
(7)によって10-5Torr付近まで真空引きされて
いる。FIG. 1 shows an apparatus diagram. This device is general as a magnetic field microwave plasma CVD device,
The sample is arranged in the sample and the sample holder (1) in the figure so as to face the microwave waveguide (5). Here, the sample and the sample holder (1) are transferred to the plasma reaction chamber (3) after exchanging the sample in the preliminary chamber (2), and are heated by a heater incorporated in the sample holder. At this time, an exhaust system (7) comprising a wide-range turbomolecular pump (hereinafter referred to as TMP), a rotary pump for roughing and TMP back pressure (hereinafter referred to as RP), and a pressure regulating valve is provided in the preliminary chamber (2) and the plasma reaction chamber (3). To about 10 -5 Torr.
【0021】試料が設定温度に到達したのち、反応ガス
供給管(6)から反応ガスをプラズマ反応室(3)に導
入し、マイクロ波導波管(5)から投入されるマイクロ
波とマグネットコイル(4)より印加される磁場の効果
によって高密度なプラズマを発生させ、これにより成膜
を行う方法である。ここで試料および試料ホルダー
(1)は直流電源装置(8)からバイアス電圧を印加さ
れる。After the sample reaches the set temperature, a reaction gas is introduced into the plasma reaction chamber (3) from the reaction gas supply pipe (6), and the microwave supplied from the microwave waveguide (5) and the magnet coil ( 4) This is a method in which high-density plasma is generated by the effect of the applied magnetic field, and a film is formed by this. Here, a bias voltage is applied to the sample and the sample holder (1) from the DC power supply (8).
【0022】成膜条件は本方法で行われている一般的な
条件である。すなわち反応圧力0.5Torr、投入マ
イクロ波電力4kW(反射0kW)、磁場は導波管窓付
近で2.2kG、該導波管窓から約200mmの位置で8
75GのECR条件を形成するよう印加し、φ4inの
Si(100)基板を装着した試料ホルダー(1)をこ
の付近に配置した。試料ホルダー(1)からの基板加熱
設定温度は800℃、基板ホルダーに直流電源装置
(8)から印加されるバイアス電圧はDC50Vとし
た。反応ガス供給管(6)からプラズマ反応室に気化C
H3 OH50ccm、H2 100ccmを導入した。8
時間の成膜工程後、回収された試料はラマン分光分析か
ら1332cm-1のみに鋭いピークを示す結晶性が非常に
良好なダイヤモンドである事が確認された。このように
して得られた試料の中央部分を幅15mm長さ30mm切出
し、アニール試料とした。The film forming conditions are general conditions used in this method. That is, the reaction pressure is 0.5 Torr, the input microwave power is 4 kW (reflection is 0 kW), the magnetic field is 2.2 kW near the waveguide window, and 8 magnetic fields at a position approximately 200 mm from the waveguide window.
A sample holder (1) equipped with a φ4 in Si (100) substrate was placed in the vicinity of the sample holder so that the ECR condition of 75 G was formed. The substrate heating set temperature from the sample holder (1) was 800 ° C., and the bias voltage applied from the DC power supply (8) to the substrate holder was DC 50V. Vaporization from the reaction gas supply pipe (6) to the plasma reaction chamber
50 ccm of H 3 OH and 100 ccm of H 2 were introduced. 8
After the film forming process for a long time, the recovered sample was confirmed by Raman spectroscopy to be diamond having a very good crystallinity showing a sharp peak only at 1332 cm -1 . The central portion of the sample thus obtained was cut out to a width of 15 mm and a length of 30 mm to obtain an annealed sample.
【0023】真空アニールには図2に示すような均一加
熱範囲200mm、炉心管相入部内径約40mmの管状電気
炉(11)を使用した。炉心管(10)は減圧状態でなおか
つ1000℃近辺の加熱に耐えられる材質としてSUS
310を選択し、外径φ32mm、内径φ21mmのパイプ
とした。炉心管材料を例えば石英ガラス等に変更すれば
高周波誘導加熱等の電磁誘導加熱によるアニールも可能
である。炉心管内部の温度は、内部に挿入した細管内の
熱電対により観測した。実際のアニール前に予備実験を
行い、この温度測定方法と試料(1)表面の実温度との
差が約7〜9℃であることを確認している。本発明およ
び実施例でアニール条件として記載される温度はすべて
これに基づいて補正した試料表面の温度である。For the vacuum annealing, a tubular electric furnace (11) having a uniform heating range of 200 mm as shown in FIG. The furnace tube (10) is made of SUS as a material that can withstand heating at around 1000 ° C. under reduced pressure.
310 was selected to be a pipe having an outer diameter of 32 mm and an inner diameter of 21 mm. If the furnace tube material is changed to, for example, quartz glass, annealing by electromagnetic induction heating such as high-frequency induction heating is also possible. The temperature inside the reactor core tube was observed by a thermocouple inside the thin tube inserted inside. A preliminary experiment is performed before actual annealing to confirm that the difference between this temperature measurement method and the actual temperature of the surface of the sample (1) is about 7 to 9 ° C. All the temperatures described as the annealing conditions in the present invention and examples are the temperatures of the sample surface corrected based on this.
【0024】ダイヤモンド薄膜試料を、アルミナボート
を介して該炉心管(10)内の均一温度部分に設置し、
排気系装備のRPによって内部を0.01Torrに減
圧した。その後約1時間かけて設定温度である900℃
まで昇温し、5時間保持した。A diamond thin film sample is placed at a uniform temperature portion in the furnace tube (10) via an alumina boat,
The internal pressure was reduced to 0.01 Torr by the RP equipped with an exhaust system. After that, it takes about 1 hour to reach the set temperature of 900 ° C
And kept for 5 hours.
【0025】保持時間終了後、アニール前後のダイヤモ
ンド薄膜それぞれの表面に粘着テープ(事務用品として
出回っているもの、例えばビニルテープやセロファンテ
ープ等を充分使用できる)を張りつけ、引き剥がして密
着性を比較した。10点の−剥がし実験の結果、アニー
ルを行わない試料に関しては全て粘着テープによって完
全に剥離してしまったが、アニール試料に関しては10
点中3点に試料基板端で部分的な剥離が認められた程度
であり、明らかにアニールによって膜の密着性は大きく
向上していることが確認された。After the holding time, an adhesive tape (available as office supplies, for example, vinyl tape or cellophane tape can be used sufficiently) is attached to the surface of each of the diamond thin films before and after annealing, and peeled off to compare the adhesiveness. did. As a result of 10-peeling experiments, all of the samples not annealed were completely peeled off by the adhesive tape, while 10% of the annealed samples were removed.
At three of the points, partial exfoliation was observed at the end of the sample substrate, and it was confirmed that the adhesion of the film was clearly improved by annealing.
【0026】また本発明者らの実験によるとダイヤモン
ド薄膜の密着性は保持時間によって変化すること、およ
び残留ダイヤモンドの膜質も保持時間によって変化する
ことが判明している。例えば保持時間1時間のものより
5時間の試料の方が先の粘着テープ試験では明らかに良
好な付着力と密着性が得られた。しかしアニール後のダ
イヤモンド薄膜表面をラマン分光分析により評価したと
ころでは、アニール時間を長くすると膜質は低下する傾
向があり、本実施例でおこなった5時間のアニールはそ
の中庸値と言える。According to experiments by the present inventors, it has been found that the adhesion of the diamond thin film changes with the holding time, and that the film quality of the remaining diamond also changes with the holding time. For example, a sample having a retention time of 5 hours showed clearly better adhesion and adhesion in the above adhesive tape test than a sample having a retention time of 1 hour. However, when the surface of the diamond thin film after annealing was evaluated by Raman spectroscopy, the film quality tended to decrease as the annealing time was prolonged, and the 5-hour annealing performed in this example can be said to be a moderate value.
【0027】〔実施例2〕本実施例はCVD装置の反応
室内部で、成膜直後の試料をそのままの状態で加熱す
る。すでに述べたように、使用する成膜方法は熱フィラ
メント/マイクロ波プラズマ/有磁場マイクロ波プラズ
マ/DCプラズマ/アークプラズマ等、どの様な方法を
用いても良い。ただし試料ホルダー単体で加熱が可能な
ことが必要であり、一部のマイクロ波プラズマCVDの
様に発生したプラズマの熱によって誘導加熱を行う方法
は使用出来ない。本実施例では実施例1と同様に図1の
有磁場マイクロ波プラズマCVD装置を使用し、同一条
件で成膜を行った。通常の工程では成膜後基板を冷却す
るが、本実施例では800℃の加熱状態のままで反応ガ
ス供給管(6)のバルブを閉鎖し、予備室(2)および
プラズマ反応室(3)を真空引きし、約0.001To
rrに保持した。加熱状態の基板に対するガスの影響は
本実施例では特に認められなかった。この状態で約5時
間保持し、その後約2時間かけて室温まで冷却した。[Embodiment 2] In this embodiment, a sample immediately after film formation is heated as it is in a reaction chamber of a CVD apparatus. As described above, any method such as hot filament / microwave plasma / microwave plasma with magnetic field / DC plasma / arc plasma may be used as the film formation method. However, it is necessary that the sample holder alone can be heated, and a method of performing induction heating by the heat of the generated plasma such as a part of microwave plasma CVD cannot be used. In this embodiment, similarly to the first embodiment, a film was formed under the same conditions using the magnetic field microwave plasma CVD apparatus shown in FIG. In a normal process, the substrate is cooled after the film formation, but in this embodiment, the valve of the reaction gas supply pipe (6) is closed with the heating state at 800 ° C., and the preliminary chamber (2) and the plasma reaction chamber (3) are closed. Is evacuated to about 0.001 To
rr. The effect of the gas on the substrate in the heated state was not particularly recognized in this embodiment. This state was maintained for about 5 hours, and then cooled to room temperature over about 2 hours.
【0028】アニールを行った試料とアニールを行わな
かった試料の密着性を比較するために、実施例1と同様
の粘着テープ試験を行った。アニールした方は10個の
試料中2個の基板端に剥離が生じたのみなのに対して、
アニールを行わなかった試料は10個とも剥離してしま
い、ダイヤモンド成膜の後工程に真空アニールを加える
ことが密着性向上において非常に有効であることがわか
った。In order to compare the adhesiveness between the annealed sample and the unannealed sample, the same adhesive tape test as in Example 1 was performed. For the annealed one, two of the 10 samples had peeled off at the substrate edge,
All ten samples that had not been annealed were peeled off, indicating that applying vacuum annealing after the diamond film formation process was very effective in improving the adhesion.
【0029】〔実施例3〕本実施例では真空アニールを
レーザ光を用いて単一試料内で部分的に実施した。方法
としては真空チャンバー内部でレーザ加熱アニールを行
うものである。このレーザアニールを導入する利点とし
ては既に述べたように、アニールによる密着性と膜質の
変化をコントロールする事が容易になること、その膜質
や密着性の異なった部分で点状や線状の領域が形成でき
ること等がある。また例えば図3に示すように成膜室と
アニール室を連結し、マルチチャンバー化する事によっ
て、アズ・デポの状態でクリーンにアニール処理を行う
ことが出来、処理時間の短縮が可能となる。Embodiment 3 In this embodiment, vacuum annealing was partially performed in a single sample by using a laser beam. As a method, laser heating annealing is performed inside a vacuum chamber. As mentioned above, the advantages of introducing laser annealing are that it is easy to control the change in adhesion and film quality due to annealing, and it is possible to use dot-like or linear regions in areas where the film quality or adhesion differs. Can be formed. In addition, for example, as shown in FIG. 3, by connecting a film forming chamber and an annealing chamber to form a multi-chamber, it is possible to perform a clean annealing process in an as-deposited state, thereby shortening the processing time.
【0030】レーザ光は既に述べたようにダイヤモンド
に対して透明である必要がある。ここで切断等のダイヤ
モンド加工に一般に用いられているのはYAGレーザで
あり、条件によっては約1mm厚のダイヤモンドを切断す
ることが出来る。しかし本発明においては基体とダイヤ
モンド薄膜の界面状態の熱的変更であり、好ましくはダ
イヤモンド薄膜に影響を与える事無くこれを透過し基体
との界面にエネルギーを到達せしめる光源を使用するた
めに、レーザ光源はこの条件に基づいて選択される。The laser beam needs to be transparent to the diamond as described above. Here, a YAG laser is generally used for diamond processing such as cutting, and can cut diamond having a thickness of about 1 mm depending on conditions. However, in the present invention, it is a thermal change of the interface state between the substrate and the diamond thin film. Preferably, the laser is used to transmit light without affecting the diamond thin film and to transmit energy to the interface with the substrate. The light source is selected based on this condition.
【0031】本発明では赤外線レーザの一種であるCO
2 レーザを用いて行った。結晶性の良好なダイヤモンド
は赤外線領域において透明であるため、成膜時に膜質の
良好なダイヤモンド薄膜を作成しレーザ処理を行う事に
より、必要とする界面へのエネルギー供給が可能とな
る。この他にもダイヤモンドに吸収を起こさない波長の
レーザとして、一部の半導体レーザ等も用いることが出
来る。In the present invention, CO, a kind of infrared laser, is used.
This was performed using two lasers. Since diamond having good crystallinity is transparent in the infrared region, it is possible to supply energy to a required interface by forming a diamond thin film having good film quality at the time of film formation and performing laser processing. In addition, some semiconductor lasers and the like can be used as a laser having a wavelength that does not cause absorption by diamond.
【0032】本実施例では実施例1、2と同様の方法で
Si基板上に成膜したダイヤモンド薄膜試料に対して独
立レーザアニールチャンバーを用いてアニールをおこな
った。用いたアニールチャンバーは、光CVD装置を基
にして半導体装置のレーザアニール用に改造された装置
を用いた。図3を基に構成を説明する。レーザ発振器
(15)は赤外線のCO2 レーザである。レーザの出力
は100Wとした。またレーザは連続波(CW)として
投入したが、パルス投入することによって先の無定形成
分のコントロールが容易になる。In this embodiment, a diamond thin film sample formed on a Si substrate in the same manner as in Embodiments 1 and 2 was annealed using an independent laser annealing chamber. As the annealing chamber used, an apparatus modified for laser annealing of a semiconductor device based on an optical CVD apparatus was used. The configuration will be described with reference to FIG. The laser oscillator (15) is an infrared CO 2 laser. The output of the laser was 100 W. In addition, although the laser is applied as a continuous wave (CW), the application of a pulse facilitates the control of the amorphous portion.
【0033】φ4inの試料基板をそのまま試料ホルダ
ー(1)に装着しアニール室(12)内部に配置した。
このまま排気系(7)により10-2Torrに減圧し
た。石英ガラス製レーザ窓(13)を通してレーザ光
(14)をアニール室(12)に導入し、試料基板
(1)に照射する。この時レーザ光(14)を走査さ
せ、試料(1)中央部分に幅1μmのアニール領域を2
mm間隔で20本設けた。The φ4 inch sample substrate was mounted on the sample holder (1) as it was and placed inside the annealing chamber (12).
The pressure was reduced to 10 -2 Torr by the exhaust system (7). A laser beam (14) is introduced into the annealing chamber (12) through a quartz glass laser window (13), and is irradiated on the sample substrate (1). At this time, the laser beam (14) was scanned to form an annealed region having a width of 1 μm at the center of the sample (1).
20 were provided at mm intervals.
【0034】上記実施例1、2でおこなったような粘着
テープ試験に代えて、フッ酸・硝酸・酢酸(5:3:
3)の混合希釈エッチング液に試料を1.5時間浸積し
たところ、アニール領域を残してダイヤモンドが剥離し
た。該試料のSEM観察からアニール領域へのダイヤモ
ンドの残留が認められ、さらに残留ダイヤモンド領域を
顕微ラマンで評価したところ、成膜直後のラマン分光結
果よりも膜質が向上しているのが認められた。Instead of the pressure-sensitive adhesive tape test performed in Examples 1 and 2, hydrofluoric acid / nitric acid / acetic acid (5: 3:
When the sample was immersed in the mixed diluted etching solution of 3) for 1.5 hours, the diamond was peeled off except for the annealed area. From the SEM observation of the sample, diamond remained in the annealed region, and the remaining diamond region was evaluated by micro-Raman. As a result, it was found that the film quality was improved as compared with the Raman spectroscopic result immediately after the film formation.
【0035】〔実施例4〕本実施例では実施例1に示し
たアニールを減圧窒素環境において行った。実験の装置
方法に関しては実施例1とほぼ同じである。勿論実施例
2、3のアニール環境に減圧窒素を導入しても良い。有
磁場マイクロ波CVD装置によって実施例1〜3と同一
条件でSi基板上に作成したダイヤモンド薄膜試料を炉
心管内部に挿入し、N2 50sccmを反応容器内部に
流して自動圧力調整器により0.1Torrに圧力設定
し、安定後に外部管状電気炉によって約1時間かけて9
00℃まで加熱しそのまま5時間保持した。[Embodiment 4] In this embodiment, the annealing shown in Embodiment 1 was performed in a reduced pressure nitrogen environment. The experimental method is almost the same as that of the first embodiment. Of course, reduced pressure nitrogen may be introduced into the annealing environment of the second and third embodiments. A diamond thin film sample prepared on a Si substrate by a magnetic field microwave CVD apparatus under the same conditions as in Examples 1 to 3 was inserted into the furnace tube, 50 sccm of N 2 was flown into the reaction vessel, and the pressure was controlled by an automatic pressure controller. The pressure is set to 1 Torr, and after stabilization, 9 hours in an external tubular electric furnace for about 1 hour.
The mixture was heated to 00 ° C. and kept for 5 hours.
【0036】アニール終了後試料を取り出し、実施例1
と同様の粘着テープによる密着性比較を10点について
おこない、同様にアニール前よりも密着性が向上してい
ることが確認できた。After annealing was completed, the sample was taken out.
The adhesion was compared at 10 points using the same adhesive tape as in the above, and it was also confirmed that the adhesion was improved as compared with before the annealing.
【0037】〔実施例5〕本実施例では実施例4に示し
た減圧窒素環境アニールを減圧酸素環境において行っ
た。アニールの装置と方法に関しては実施例1、4とほ
ぼ同じである。また加熱方法を実施例2、3の方法でお
こなっても良い。ただし炉心管に関してはSUS310
から、同じ大きさの高純度アルミナ焼結体に変更した。
有磁場マイクロ波CVD装置によって実施例1〜4と同
一条件でSi基板上に作成したダイヤモンド薄膜を炉心
管内部に挿入し、O2 100sccmを反応容器内部に
流して自動圧力調整器により0.1Torrに圧力設定
し、安定後に外部管状電気炉によって約1時間かけて9
00℃まで加熱しそのまま5時間保持した。アニール終
了後試料を取り出し、実施例1や4同様に粘着テープに
よる密着性比較を10点についておこない、同様にアニ
ール前よりも密着性が向上していることを確認した。[Embodiment 5] In this embodiment, the annealing under reduced pressure nitrogen environment shown in Embodiment 4 was performed in a reduced pressure oxygen environment. The annealing apparatus and method are almost the same as those in the first and fourth embodiments. Further, the heating method may be performed by the methods of the second and third embodiments. However, for the core tube, SUS310
Was changed to a high-purity alumina sintered body of the same size.
A diamond thin film formed on a Si substrate by a magnetic field microwave CVD apparatus under the same conditions as in Examples 1 to 4 was inserted into the furnace tube, 100 sccm of O 2 was flowed into the reaction vessel, and 0.1 Torr by an automatic pressure controller. After the pressure has been stabilized, an external tubular electric furnace is used to stabilize the pressure for 9 hours.
The mixture was heated to 00 ° C. and kept for 5 hours. After the annealing, the sample was taken out, and the adhesion was compared with the adhesive tape at 10 points in the same manner as in Examples 1 and 4, and it was confirmed that the adhesion was similarly improved as compared with that before the annealing.
【0038】ここで酸素環境で行うことの利点は、ラマ
ン分光分析をアニール前後で行い、比較することによっ
て確認できる。アニール前の試料と実施例1と4の試料
すなわち減圧環境と減圧窒素環境においてアニールをお
こなった試料と、本実施例で得られた試料をそれぞれラ
マン分光分析によって比較したところ、実施例1と4で
得られた試料ではアニール前に比べて1332cm-1のピ
ークが低く、かつ1580cm-1に微弱ながらブロードの
増加が認められたのに対して、本実施例で得られた試料
ではむしろ1332cm-1のピークがより鋭くなってお
り、1580cm-1には全くブロードは認められなかっ
た。1332cm-1のピークの鋭さすなわち半値幅はダイ
ヤモンド薄膜の結晶性の目安となる事が良く知られてい
る。本発明の方法によれば酸素による無定形炭素除去効
果が得られ、膜の密着性と膜質を同時に改善する事が可
能である。Here, the advantage of performing in an oxygen environment can be confirmed by performing Raman spectroscopic analysis before and after annealing and comparing the results. When the sample before annealing, the sample of Examples 1 and 4, that is, the sample annealed in a reduced pressure environment and a reduced pressure nitrogen environment, and the sample obtained in this example were compared by Raman spectroscopy, the results of Examples 1 and 4 were compared. low peak of 1332 cm -1 as compared to before annealing the samples obtained in, and while weak to 1580 cm -1 with respect to the increase in broad was observed, rather the sample obtained in this example 1332 cm - The peak at 1 was sharper and no broadening was observed at 1580 cm -1 . It is well known that the sharpness of the peak at 1332 cm -1 , that is, the half width, is a measure of the crystallinity of a diamond thin film. According to the method of the present invention, an effect of removing amorphous carbon by oxygen is obtained, and it is possible to simultaneously improve the adhesion and the film quality of the film.
【0039】[0039]
【発明の効果】本発明によれば、異種材料による中間層
を設ける場合よりも単純な工程によって、ダイヤモンド
成膜試料の密着性を格段に向上させることが出来、また
密着性と膜質を同時に改善することが可能であり、本発
明によりダイヤモンドデバイスの実用化に一層の弾みが
付くことが期待される。According to the present invention, the adhesion of a diamond film-formed sample can be remarkably improved by a simpler process than the case of providing an intermediate layer made of a different material, and the adhesion and the film quality are simultaneously improved. It is expected that the present invention will provide further impetus to the practical use of diamond devices.
【図1】実施例1、3〜5で成膜に、実施例2では成膜
とアニールに用いた有磁場マイクロ波プラズマCVD装
置の概略図である。FIG. 1 is a schematic diagram of a magnetic field microwave plasma CVD apparatus used for film formation in Examples 1, 3 to 5, and for film formation and annealing in Example 2.
【図2】実施例1、4、5で用いたアニール装置の概略
図である。FIG. 2 is a schematic view of an annealing apparatus used in Examples 1, 4, and 5;
【図3】実施例3で紹介したマルチチャンバー・レーザ
アニール装置の概略図である。FIG. 3 is a schematic view of a multi-chamber laser annealing apparatus introduced in a third embodiment.
1 試料基板および試料ホルダー 3 プラズマ反応室 4 マグネット・コイル 5 マイクロ波導波管 6 反応ガス供給管 7 排気系 10 炉心管 11 管状電気炉 12 アニール室 13 レーザ窓 14 レーザ光 15 CO2 レーザ発振器 16 搬送バルブREFERENCE SIGNS LIST 1 sample substrate and sample holder 3 plasma reaction chamber 4 magnet coil 5 microwave waveguide 6 reaction gas supply pipe 7 exhaust system 10 core tube 11 tubular electric furnace 12 annealing room 13 laser window 14 laser beam 15 CO 2 laser oscillator 16 transport valve
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成12年10月6日(2000.10.
6)[Submission date] October 6, 2000 (2000.10.
6)
【手続補正1】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Correction target item name] Name of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【発明の名称】半導体素子[Title of the Invention] Semiconductor device
【手続補正2】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
Claims (1)
を減圧状態の酸素雰囲気中で加熱することによって、前
記基体と前記ダイヤモンドライクカーボンの間に中間層
を形成することを特徴とするダイヤモンドライクカーボ
ンの形成方法。1. A method of forming diamond-like carbon, comprising heating an diamond-like carbon in contact with a substrate in an oxygen atmosphere under reduced pressure to form an intermediate layer between the substrate and the diamond-like carbon. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000280654A JP3472253B2 (en) | 1992-12-21 | 2000-09-14 | Method of forming diamond film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35708992A JP3195093B2 (en) | 1992-12-21 | 1992-12-21 | Method of forming diamond film |
JP2000280654A JP3472253B2 (en) | 1992-12-21 | 2000-09-14 | Method of forming diamond film |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP35708992A Division JP3195093B2 (en) | 1992-12-21 | 1992-12-21 | Method of forming diamond film |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2001115261A true JP2001115261A (en) | 2001-04-24 |
JP3472253B2 JP3472253B2 (en) | 2003-12-02 |
Family
ID=30002137
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000280654A Expired - Fee Related JP3472253B2 (en) | 1992-12-21 | 2000-09-14 | Method of forming diamond film |
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---|---|
JP (1) | JP3472253B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008260670A (en) * | 2007-04-13 | 2008-10-30 | Univ Of Electro-Communications | Method for producing diamond-like carbon film |
RU2798440C1 (en) * | 2022-06-15 | 2023-06-22 | Акционерное общество "Научно-исследовательский институт микроэлектронной аппаратуры "Прогресс" (АО "НИИМА "Прогресс") | Method for relieving internal stresses in thin films of the topology of microwave microstrip boards using vacuum annealing |
-
2000
- 2000-09-14 JP JP2000280654A patent/JP3472253B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008260670A (en) * | 2007-04-13 | 2008-10-30 | Univ Of Electro-Communications | Method for producing diamond-like carbon film |
RU2798440C1 (en) * | 2022-06-15 | 2023-06-22 | Акционерное общество "Научно-исследовательский институт микроэлектронной аппаратуры "Прогресс" (АО "НИИМА "Прогресс") | Method for relieving internal stresses in thin films of the topology of microwave microstrip boards using vacuum annealing |
Also Published As
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---|---|
JP3472253B2 (en) | 2003-12-02 |
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