JP2010024476A - Diamond-like carbon and manufacturing method thereof - Google Patents

Diamond-like carbon and manufacturing method thereof Download PDF

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JP2010024476A
JP2010024476A JP2008184765A JP2008184765A JP2010024476A JP 2010024476 A JP2010024476 A JP 2010024476A JP 2008184765 A JP2008184765 A JP 2008184765A JP 2008184765 A JP2008184765 A JP 2008184765A JP 2010024476 A JP2010024476 A JP 2010024476A
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diamond
carbon
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gas
dlc film
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JP2010024476A5 (en
JP4704453B2 (en
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Yasuo Suzuki
泰雄 鈴木
Masanori Watanabe
正則 渡邉
Kenjiro Nakajima
堅志郎 中嶋
Tadao Toda
忠夫 戸田
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Plasma Ion Assist Co Ltd
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<P>PROBLEM TO BE SOLVED: To provide a DLC thin film material which is p-type conduction in electric conduction, and has low resistivity and high hardness, to provide a manufacturing method of the DLC film, and to provide an industrial product using the DLC film. <P>SOLUTION: In the diamond-like carbon in which p-type dopant such as boron and magnesium of III group elements or II group elements of the Periodic Table, its electric conduction of p-type conduction. High concentration plasma of hydrocarbon gas of low molecular quantity is generated, and a base material to be worked is installed so as to be brought into contact with discharge plasma. The temperature of the base material is kept at ≥200°C, the positive and negative or negative pulse voltage of ≥1 kV is applied to the base material to manufacture a p-type conduction DLC film on the surface of the base material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、電気伝導がｐ形伝導であって、高硬度、低抵抗率のダイヤモンドライクカーボン及びその製造方法に関する。 The present invention relates to diamond-like carbon having electrical conductivity of p-type conductivity and high hardness and low resistivity, and a method for producing the same.

ダイヤモンドライクカーボン（以下、ＤＬＣと略記する）は硬度が非常に高く、耐摩耗性、摺動性等に優れていることから、超硬工具、金型や摺動部品等の皮膜材料として開発され、実用化されている。また、ゴム材料やプラスチックなど有機材料表面に比較的低温でＤＬＣ皮膜をコーティングすることができるため、これら有機材料表面へのコーティング技術が研究開発され応用展開されようとしている。 Diamond-like carbon (hereinafter abbreviated as DLC) is extremely hard and has excellent wear resistance, sliding properties, etc., so it has been developed as a coating material for carbide tools, molds and sliding parts. Has been put to practical use. In addition, since a DLC film can be coated on a surface of an organic material such as a rubber material or plastic at a relatively low temperature, a coating technique for the surface of the organic material is being researched and applied.

また、ＤＬＣ膜は耐薬品性に優れ、腐食性環境における金属電極表面の耐蝕性コーティング膜、特に燃料電池等の電極板の耐食性被膜として低抵抗率のＤＬＣ膜が研究開発されている。更に、環境に優しい太陽電池材料として低抵抗率のｎ形及びｐ形の半導体ＤＬＣ膜が要望されている。 In addition, the DLC film has excellent chemical resistance, and a low-resistance DLC film has been researched and developed as a corrosion-resistant coating film on the surface of a metal electrode in a corrosive environment, particularly as a corrosion-resistant film on an electrode plate of a fuel cell or the like. Furthermore, low resistivity n-type and p-type semiconductor DLC films are desired as environmentally friendly solar cell materials.

ＤＬＣの製膜方法としては、炭化水素ガスを用いたパルスＤＣプラズマＣＶＤ法や直流プラズマＣＶＤ法、また固体炭素を原料としたスパッタリング法やアークイオンプレーティング法など多くの製膜方法が開発されている。しかし、得られるＤＬＣ膜特性は製膜方法によって著しく異なる。また、同じ製法でも製膜装置、製膜条件が異なれば、得られるＤＬＣ膜の物性が異なるなど、用途に応じたＤＬＣ膜の研究開発が行われている。 As a film forming method for DLC, many film forming methods such as a pulsed DC plasma CVD method and a direct current plasma CVD method using hydrocarbon gas, a sputtering method using a solid carbon as a raw material, and an arc ion plating method have been developed. Yes. However, the obtained DLC film characteristics vary significantly depending on the film forming method. In addition, even if the film forming apparatus and the film forming conditions are different even in the same manufacturing method, research and development of a DLC film according to the application has been performed, such as different physical properties of the obtained DLC film.

特許文献１には、スパッタ蒸着法及び真空アーク蒸着法によって、ｓｐ２結合性結晶の少なくとも一部が膜厚方向に連続的に連なった構造を持つ高い導電性を有する硬質炭素皮膜に関する技術が開示されている。しかし、これらの製膜方法では、固体黒鉛を原料とするため、ドロップレット（マイクロパーティクル）やピンホールのような欠陥が発生し易く、例えば、電極板の耐蝕被膜としての使用が困難とされている。 Patent Document 1 discloses a technique relating to a highly conductive hard carbon film having a structure in which at least a part of sp 2 bonding crystals are continuously connected in the film thickness direction by a sputter deposition method and a vacuum arc deposition method. Has been. However, in these film forming methods, since solid graphite is used as a raw material, defects such as droplets (microparticles) and pinholes are likely to occur. For example, it is difficult to use as a corrosion-resistant coating on electrode plates. Yes.

一方、炭化水素ガスを用いたプラズマＣＶＤ法については、非特許文献１にパルスＤＣプラズマＣＶＤ技術が開示されている。本従来例では、パルス化した数百Ｖの負のＤＣ電圧を被加工基材に印加して炭化水素系ガスの放電プラズマを発生させ、被加工基材表面に高硬度のＤＬＣ膜を生成する方法である。炭化水素系ガスを用いたプラズマＣＶＤ法によって成膜されたＤＬＣ膜は、一般に、水素原子を１５〜３０アトミックパーセント含有しており、絶縁物に近い電気抵抗を有し、ドーパント元素を添加しないで抵抗率１キロオームセンチメートル以下のＤＬＣ膜を得ることは困難とされている。 On the other hand, as for the plasma CVD method using hydrocarbon gas, Non-Patent Document 1 discloses a pulsed DC plasma CVD technique. In this conventional example, a pulsed negative DC voltage of several hundred volts is applied to a substrate to be processed to generate a hydrocarbon-based gas discharge plasma, thereby generating a DLC film having a high hardness on the surface of the substrate to be processed. Is the method. A DLC film formed by a plasma CVD method using a hydrocarbon-based gas generally contains 15 to 30 atomic percent of hydrogen atoms, has an electrical resistance close to an insulator, and does not add a dopant element. It is difficult to obtain a DLC film having a resistivity of 1 kilohm centimeter or less.

また、低抵抗ＤＬＣ膜を製膜する方法が非特許文献２に開示されている。本従来技術では、プラズマイオン注入・成膜法（ＰＢＩＩ／Ｄ法）の一つで、プラズマ発生容器内に被加工基材を載置して基材支持電極板に正負のパルス高電圧を印加する方法である。正パルス電圧を印加して前記被加工基材表面にトルエンガスの放電プラズマを発生させ、引き続いて負の高電圧パルスを印加してＤＬＣ膜を生成する。また、正パルス電圧を印加することによって被加工基材を電子ビーム加熱し、製膜中に熱処理を行っている。 Further, Non-Patent Document 2 discloses a method for forming a low-resistance DLC film. This conventional technology is one of the plasma ion implantation and film formation methods (PBII / D method). A substrate to be processed is placed in a plasma generation vessel and positive and negative pulsed high voltages are applied to the substrate support electrode plate. It is a method to do. A positive pulse voltage is applied to generate a discharge plasma of toluene gas on the surface of the substrate to be processed, and then a negative high voltage pulse is applied to generate a DLC film. Further, the substrate to be processed is heated with an electron beam by applying a positive pulse voltage, and heat treatment is performed during film formation.

この製膜方法で基板温度を４００度Ｃ（以下℃と記す）に保持し、−２０ｋＶの負のパルス電圧を印加することによって、抵抗率１ミリオームセンチ程度の非常に低抵抗なＤＬＣ膜が得られている。しかし、導電性のグラファイト微結晶を多く含むと考えられ、抵抗率の低下とともに硬度も低下して抵抗率１ミリオームセンチのとき硬度はＨｖ５４０まで低下するなどの課題があった。 By this film forming method, the substrate temperature is maintained at 400 ° C. (hereinafter referred to as “° C.”), and a negative pulse voltage of −20 kV is applied to obtain a very low resistance DLC film having a resistivity of about 1 milliohm centimeter. It has been. However, it is thought that it contains a lot of conductive graphite microcrystals, and there is a problem that the hardness decreases to Hv540 when the resistivity is 1 milliohm centimeter as the resistivity decreases.

更に、特許文献２には、基板上にＮ層、Ｉ層、Ｐ層の半導体層を積層した太陽電池の全ての層、或いは何れかの層をＤＬＣ薄膜で形成する技術が開示されている。本実施例では、Ｐ層を形成するためにボロン化合物を、Ｎ層を形成するために燐化合物をドーピングする技術が開示されている。しかし、不純物ドーピングでは十分低いｐ形ＤＬＣ膜が得られないという課題があった。 Further, Patent Document 2 discloses a technique of forming all or any layer of a solar cell in which N, I, and P semiconductor layers are stacked on a substrate with a DLC thin film. In this embodiment, a technique of doping a boron compound to form a P layer and a phosphorus compound to form an N layer is disclosed. However, there is a problem that a sufficiently low p-type DLC film cannot be obtained by impurity doping.

特開２００２−３２７２７１号公報JP 2002-327271 A 特開２００２−３３４９７号公報JP 2002-33497 A （株）シーエムシー出版 ２００８年発行「ＤＬＣの応用技術」４１−４９頁CMC Publishing Co., Ltd. Published in 2008, "Application technology of DLC", pages 41-49 Ｎｅｗ Ｄｉａｍｏｄ ａｎｄ Ｆｒｏｎｔｉｅｒ Ｃａｒｂｏｎ Ｔｅｃｈｎｏｌｏｇｙ．Ｖｏｌ．１６，Ｎｏ．１，ｐ３３−３８（２００６）New Diamond and Frontier Carbon Technology. Vol. 16, no. 1, p33-38 (2006)

電気伝導がｐ形伝導で抵抗率が１オームセンチ以下、ビッカース硬度２０００以上のＤＬＣ膜は得られていない。本発明が解決しようとする課題は、電気伝導がｐ形の低抵抗率、且つ高硬度のＤＬＣ膜を提供することにある。また、前記ＤＬＣ膜の製造方法及び大面積基板表面に高速度で製膜できるＤＬＣ膜製造装置を提供することを目的としている。 A DLC film having p-type conductivity, a resistivity of 1 Ωcm or less, and a Vickers hardness of 2000 or more has not been obtained. The problem to be solved by the present invention is to provide a DLC film having a p-type low resistivity and high hardness. It is another object of the present invention to provide a method for producing the DLC film and a DLC film production apparatus capable of producing a film on the surface of a large area substrate at a high speed.

本発明は、周期律表の３族元素又は２族元素であるボロンやマグネシウム等のｐ形ドーパントをドーピングしないＤＬＣ膜であって、その電気伝導がｐ形伝導であることを特徴とする。ここで云うｐ形伝導ＤＬＣ膜は、熱プローブ測定でｐ形伝導を示すもの、又はホール測定等でｎ形伝導を示さないもので、その電気伝導機構が非晶質炭素膜中に存在するｓｐ３結合のダイヤモンド微結晶の格子欠陥に基づく正孔の伝導と考えられるものを云う。 The present invention is a DLC film not doped with a p-type dopant such as boron or magnesium, which is a group 3 element or group 2 element of the periodic table, and is characterized in that its electrical conduction is p-type conduction. The p-type conductive DLC film referred to here is one that shows p-type conduction by thermal probe measurement, or one that does not show n-type conduction by hole measurement or the like, and its electric conduction mechanism is sp present in the amorphous carbon film. This refers to what is considered to be hole conduction based on lattice defects of three- bond diamond crystallites.

本発明では、前記ＤＬＣ膜の抵抗率が１キロオームセンチ以下であり、硬度がビッカース硬度２０００以上であることを特徴とする。また、ＤＬＣ膜に含まれる水素量が１０アトミックパーセント以下であることを特徴とする。 In the present invention, the DLC film has a resistivity of 1 kilohm centimeter or less and a hardness of 2000 or more in Vickers hardness. Further, the amount of hydrogen contained in the DLC film is 10 atomic percent or less.

前記ＤＬＣ膜を得るために、真空容器内に炭化水素系原料ガスを導入し、放電プラズマ発生手段によって前記真空容器内に放電プラズマを発生させ、該放電プラズマに接するように被加工基材を設置し、該被加工基材の温度を２００℃以上に保持し、該被加工基材に１ｋＶ以上の正負又は負のパルス電圧を印加して前記被加工基材表面にＤＬＣ膜を製膜する。 In order to obtain the DLC film, a hydrocarbon-based source gas is introduced into the vacuum vessel, discharge plasma is generated in the vacuum vessel by the discharge plasma generating means, and the substrate to be processed is placed in contact with the discharge plasma. Then, the temperature of the substrate to be processed is maintained at 200 ° C. or higher, and a positive / negative or negative pulse voltage of 1 kV or higher is applied to the substrate to be processed to form a DLC film on the surface of the substrate to be processed.

前記放電プラズマ発生手段としては高密度プラズマが発生できる誘導結合型高周波放電を用いることを特徴とする。単位立方センチメートル当たり５×１０１０個以上のプラズマ密度が得られる放電プラズマ発生手段であれば、前記誘導結合型高周波放電に限られるもではない。 As the discharge plasma generating means, inductively coupled high frequency discharge capable of generating high density plasma is used. The discharge plasma generating means is not limited to the inductively coupled high-frequency discharge as long as the plasma density is 5 × 10 10 or more per unit cubic centimeter.

本発明によれば、前記被加工基材に負の高電圧パルスを印加して加速された高エネルギーイオンを照射しながら製膜するが、被加工基材の温度、照射イオンのエネルギー及び照射量によってＤＬＣ膜の特性が変化する。前記負のパルス電圧は１ｋＶ以上、好ましくは５ｋＶ乃至２５ｋＶである。また、前記被加工基材の温度は２００℃以上、好ましくは３００℃乃至５００℃であることを特徴とする。 According to the present invention, a film is formed while irradiating high energy ions accelerated by applying a negative high voltage pulse to the substrate to be processed, but the temperature of the substrate to be processed, the energy of irradiation ions, and the irradiation amount As a result, the characteristics of the DLC film change. The negative pulse voltage is 1 kV or more, preferably 5 kV to 25 kV. Further, the temperature of the substrate to be processed is 200 ° C. or higher, preferably 300 ° C. to 500 ° C.

前記被加工基材は製膜中のイオン照射によって加熱することができるが、所定の温度範囲に保持するために電気ヒータ等を用いた外部加熱による温度制御も可能である。被加工基材の温度を３００℃乃至５００℃に保持し、イオン照射することによって、ＤＬＣ膜中の水素濃度を制御することが可能で、高硬度、低抵抗率のＤＬＣ膜を製造することができる。本発明では、被加工基材に負のパルス電圧を印加しながら製膜する。 The substrate to be processed can be heated by ion irradiation during film formation, but temperature control by external heating using an electric heater or the like is also possible in order to keep it within a predetermined temperature range. By maintaining the temperature of the substrate to be processed at 300 ° C. to 500 ° C. and irradiating with ions, the hydrogen concentration in the DLC film can be controlled, and a DLC film having high hardness and low resistivity can be manufactured. it can. In this invention, it forms into a film, applying a negative pulse voltage to a to-be-processed base material.

ＤＬＣ膜を製造するための原料ガスとして、低分子量炭化水素ガス、例えばメタン、エタン、プロパン、アセチレン、エチレンガスの少なくとも一つを含む炭化水素ガスを使用する。また、前記原料ガスとアルゴンガス又は／及び水素ガスの混合ガスとすることが出来る。 As a raw material gas for producing the DLC film, a low molecular weight hydrocarbon gas, for example, a hydrocarbon gas containing at least one of methane, ethane, propane, acetylene, and ethylene gas is used. Moreover, it can be set as the mixed gas of the said source gas and argon gas or / and hydrogen gas.

本発明によれば、請求項５から１２に記載の何れかの製造方法によって製造したダイヤモンドライクカーボンを製膜温度以上の温度でアニールすることによって、前記ＤＬＣ膜の抵抗率を所望の値に調整することができる。アニール温度は好ましくは４００℃乃至７００℃である。 According to the present invention, the resistivity of the DLC film is adjusted to a desired value by annealing the diamond-like carbon produced by any one of the production methods according to claims 5 to 12 at a temperature equal to or higher than the film-forming temperature. can do. The annealing temperature is preferably 400 ° C. to 700 ° C.

本発明によるｐ形ダイヤモンドライクカーボンは、太陽電池材料など半導体材料、燃料電池などの電極表面への耐蝕性コーティング材料、超硬工具などの耐磨耗性コーティング材料、摺動部品の低摩擦係数コーティング材料などとして広く工業製品に適用できる。 The p-type diamond-like carbon according to the present invention is a semiconductor material such as a solar cell material, a corrosion-resistant coating material on the electrode surface of a fuel cell, an abrasion-resistant coating material such as a carbide tool, and a low friction coefficient coating of a sliding part. Widely applicable to industrial products as materials.

本発明によれば、電気伝導がｐ形伝導で抵抗率が１キロオームセンチ以下、ビッカース硬度２０００以上のＤＬＣ膜が得られる。また、大面積基材表面に前記ＤＬＣ膜を高速度で製造することができ、生産性の高いＤＬＣ膜製造装置を提供することができる。 According to the present invention, a DLC film having a p-type conductivity, a resistivity of 1 kilo-ohm centimeter or less, and a Vickers hardness of 2000 or more can be obtained. Moreover, the said DLC film can be manufactured on a large area base-material surface at high speed, and a DLC film manufacturing apparatus with high productivity can be provided.

前記真空容器内に誘導結合型高周波アンテナとこれに対向して被加工基材を配置し、炭化水素系原料ガスを導入して、前記誘導結合型高周波アンテナに高周波電力を給電して真空容器内に放電プラズマを発生させる。該放電プラズマに接するように被加工基材を設置し、該被加工基材の温度を２００℃以上に保持し、該被加工基材に１ｋＶ以上の正負又は負のパルス電圧を印加して前記被加工基材表面にＤＬＣ膜を堆積させる。 An inductively coupled high-frequency antenna and a substrate to be processed are disposed in the vacuum container so as to face the same, a hydrocarbon-based raw material gas is introduced, and high-frequency power is supplied to the inductively coupled high-frequency antenna so A discharge plasma is generated. The substrate to be processed is placed in contact with the discharge plasma, the temperature of the substrate to be processed is maintained at 200 ° C. or higher, and a positive or negative pulse voltage of 1 kV or higher is applied to the substrate to be processed. A DLC film is deposited on the surface of the substrate to be processed.

（実施例１）
以下、本発明の実施の形態に係るｐ形ＤＬＣ膜の製造方法について図を参照しながら説明する。図１に本発明によるＤＬＣ膜製造装置の一実施例の断面模式図を示す。なお、図１には便宜上、本発明の一実施例としてＤＬＣ膜製造装置の要部構成を示しているが、本発明はこれに限定されるものではない。 Example 1
Hereinafter, a method for manufacturing a p-type DLC film according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an embodiment of a DLC film manufacturing apparatus according to the present invention. For the sake of convenience, FIG. 1 shows the main configuration of a DLC film manufacturing apparatus as an embodiment of the present invention, but the present invention is not limited to this.

図１に示すように、真空容器１内に誘導結合型高周波アンテナ２と、これに対向して被加工基材支持電極５を配置し、該基材支持電極の表面に前記被加工基材６が固定されている。該基材支持電極５の裏面には被加工基材を加熱するための加熱板９が取りつけてある。１０はフィードスルー、１１は原料ガス導入口、１２は真空排気口である。 As shown in FIG. 1, an inductively coupled high-frequency antenna 2 and a substrate supporting electrode 5 to be processed are disposed in a vacuum container 1 so as to face the antenna, and the substrate 6 to be processed is disposed on the surface of the substrate supporting electrode. Is fixed. A heating plate 9 for heating the substrate to be processed is attached to the back surface of the substrate supporting electrode 5. 10 is a feedthrough, 11 is a source gas inlet, and 12 is a vacuum exhaust port.

放電プラズマ発生用高周波アンテナ２はフィードスルー１０を介して真空容器１内に導入されている。該高周波アンテナ２の一端は整合器４を介して高周波電源３に接続され、他端は接地されている。高周波電源３は周波数１３．５６ＭＨｚ、０．３ｋＷ〜３ｋＷの出力を有する。また、高周波電源３は連続した高周波電力及び周波数０．５ｋＨｚ〜３ｋＨｚの高周波バーストを供給することができる。 A high frequency antenna 2 for generating discharge plasma is introduced into the vacuum vessel 1 through a feedthrough 10. One end of the high-frequency antenna 2 is connected to a high-frequency power source 3 through a matching unit 4 and the other end is grounded. The high frequency power source 3 has a frequency of 13.56 MHz and an output of 0.3 kW to 3 kW. The high-frequency power source 3 can supply continuous high-frequency power and a high-frequency burst having a frequency of 0.5 kHz to 3 kHz.

基材支持電極５はパルス電源７に接続されていて、基材支持電極５を介して被加工基材６にパルス電圧が印加される。パルス電源７はパルス電圧１ｋＶ〜２５ｋＶ、パルス幅１マイクロ秒〜１００マイクロ秒（以下、μｓと記す）、繰り返し周波数１ｋＨｚ〜３ｋＨｚのパルス電圧を供給することができる。被加工基材の温度は基材支持電極５の裏面に取りつけられた加熱板９によって加熱され、その温度は基材温度制御器８によって所定温度に維持される。 The substrate support electrode 5 is connected to a pulse power source 7, and a pulse voltage is applied to the workpiece substrate 6 through the substrate support electrode 5. The pulse power source 7 can supply a pulse voltage having a pulse voltage of 1 kV to 25 kV, a pulse width of 1 microsecond to 100 microsecond (hereinafter referred to as μs), and a repetition frequency of 1 kHz to 3 kHz. The temperature of the substrate to be processed is heated by a heating plate 9 attached to the back surface of the substrate support electrode 5, and the temperature is maintained at a predetermined temperature by the substrate temperature controller 8.

本実施例では、誘導結合型高周波アンテナ２から１０ｃｍ離れた位置に高周波アンテナに対向して基材支持電極５を設置して、その表面にシリコン基板及び石英基板を取り付けた。真空容器内を予め高真空に排気して十分ガス出しした後、原料ガス導入口１１から水素ガス２０％とアルゴンガス８０％の混合ガスを導入して圧力０．６パスカルに調整し、周波数１３．５６ＭＨｚ、出力１ｋＷの高周波電力を誘導結合型高周波アンテナ２に供給して放電プラズマを発生させ、基材支持電極５を３００℃に制御して−１０ｋＶのパルス電圧を印加して前記基板表面のクリーニングを行った。 In this example, the base material supporting electrode 5 was installed facing the high frequency antenna at a position 10 cm away from the inductively coupled high frequency antenna 2, and a silicon substrate and a quartz substrate were attached to the surface. After evacuating the inside of the vacuum vessel to a high vacuum and discharging the gas sufficiently, a mixed gas of hydrogen gas 20% and argon gas 80% is introduced from the raw material gas inlet 11 to adjust the pressure to 0.6 Pascal, and the frequency 13 A high frequency power of .56 MHz and an output of 1 kW is supplied to the inductively coupled high frequency antenna 2 to generate discharge plasma, the substrate support electrode 5 is controlled to 300 ° C., and a pulse voltage of −10 kV is applied to the substrate surface. Cleaning was performed.

次ぎに、原料ガスとしてメタンガス３０％とアセチレンガス７０％の混合ガスを導入し、予め基板温度を４００℃に加熱し、ガス圧を０．５パスカルに調整し、前記高周波アンテナ２に７００Ｗの電力を給電して放電プラズマを発生させた。基材支持電極５には−２０ｋＶ、パルス幅５マイクロ秒、繰り返し周波数１ｋＨｚのパルス電圧を印加した。基板はイオンの衝突によって加熱されるため、加熱板に加える電力を制御してほぼ４５０℃に保持した。 Next, a mixed gas of methane gas 30% and acetylene gas 70% is introduced as a raw material gas, the substrate temperature is preliminarily heated to 400 ° C., the gas pressure is adjusted to 0.5 Pascal, and the high-frequency antenna 2 has a power of 700 W. To generate discharge plasma. A pulse voltage of −20 kV, a pulse width of 5 microseconds, and a repetition frequency of 1 kHz was applied to the substrate support electrode 5. Since the substrate was heated by the collision of ions, the electric power applied to the heating plate was controlled and maintained at about 450 ° C.

３時間の製膜で、厚さ２．３マイクロメートル（以下、μｍと記す）のＤＬＣ膜を得た。膜色はダークシルバーであった。本実施例で得られたＤＬＣ膜のＡＦＭによって測定した表面モホロジーを図２に示す。図２から明らかなように約８０ｎｍの微結晶の集合体であることが分かる。また、ＸＲＤによるＸ線解析結果を図３に示す。２４度と４５度近辺のブロードなピークはｓｐ２結合のグラファイト微結晶によるものであり、５０度付近の鋭いピークはｓｐ３結合のダイヤモンド微結晶（２００面）によるものである。本発明によるＤＬＣ膜は非晶質炭素の中にｓｐ２結合のグラファイト微結晶とｓｐ３結合のダイヤモンド微結晶が混在しているものであることが明らかになった。 A DLC film having a thickness of 2.3 micrometers (hereinafter referred to as μm) was obtained by film formation for 3 hours. The film color was dark silver. FIG. 2 shows the surface morphology measured by AFM of the DLC film obtained in this example. As can be seen from FIG. 2, it is an aggregate of about 80 nm microcrystals. Moreover, the X-ray-analysis result by XRD is shown in FIG. Broad peak near 24 degrees and 45 degrees is due to graphite crystallites of sp 2 bond, sharp peak near 50 degrees is due to sp 3 bonds the diamond crystallites (200 surface). DLC film according to the present invention has revealed that those diamond crystallites of the graphite crystallites and the sp 3 bonds sp 2 bonds in the amorphous carbon are mixed.

熱プローブによる測定結果では強いｐ形伝導特性を示した。また、東洋テクニカ製Ｒｅｓｉｔｅｓｔ、８３００シリーズ、ホール測定システムによるホール電圧測定でもｐ形伝導特性を示し、抵抗率は９．７ミリオームセンチ（以下、ｍΩｃｍと記す）、ホール移動度は１９ｃｍ２／Ｖ・ｓｅｃ、キャリア濃度は３．４×１０１９／ｃｍ３であった。更に、４探針測定器Ｎａｐｓｏｎ、ＲＴ−７による測定結果では、抵抗率は９．４ｍΩｃｍであった。ビッカース硬度計による硬度測定結果では、Ｈｖ３０００であった。 The measurement result with the thermal probe showed strong p-type conduction characteristics. In addition, Toyo Technica Research, 8300 series, Hall voltage measurement by Hall measurement system also shows p-type conduction characteristics, resistivity is 9.7 milliohm centimeter (hereinafter referred to as mΩcm), and hole mobility is 19 cm 2 / V · sec, and the carrier concentration was 3.4 × 10 19 / cm 3 . Furthermore, the resistivity was 9.4 mΩcm as a result of measurement using a four-probe measuring device Napson, RT-7. The hardness measurement result by the Vickers hardness tester was Hv3000.

（実施例２）
基板温度を２００℃、パル電圧を−４ｋＶとし、他の製膜条件は実施例１と同一条件で製膜した結果、３時間で厚さ３．１μｍのＤＬＣ膜を得た。ビッカース硬度計による測定結果では、Ｈｖ１７００であった。本実施例で得られたＤＬＣ膜は絶縁性膜であって、４探針測定では評価できなかった。 (Example 2)
The substrate temperature was 200 ° C., the pal voltage was −4 kV, and other film formation conditions were the same as in Example 1. As a result, a 3.1 μm thick DLC film was obtained in 3 hours. The measurement result with a Vickers hardness tester was Hv1700. The DLC film obtained in this example was an insulating film and could not be evaluated by 4-probe measurement.

真空中で、４４０℃で１時間アニールすると、４探針法による測定結果、抵抗率は１５０Ωｃｍに低下した。更に、６３０℃で１時間アニールすると、抵抗率は１４０ｍΩｃｍまで低下し、ホール測定装置では８７ｍΩｃｍの抵抗率を得た。正孔移動度は１．６ｃｍ２／Ｖ・ｓｅｃ、キャリア濃度は４．５×１０１９／ｃｍ３であった。また、熱プローブによる測定結果では強いｐ形伝導特性を示した。 When annealed in vacuum at 440 ° C. for 1 hour, the resistivity decreased to 150 Ωcm as a result of measurement by the 4-probe method. Further, after annealing at 630 ° C. for 1 hour, the resistivity decreased to 140 mΩcm, and the Hall measuring device obtained a resistivity of 87 mΩcm. The hole mobility was 1.6 cm 2 / V · sec, and the carrier concentration was 4.5 × 10 19 / cm 3 . The measurement result with the thermal probe showed strong p-type conduction characteristics.

（実施例３）
実施例１と同様、原料ガスとしてメタンガス３０％とアセチレンガス７０％の混合ガスを導入し、誘導結合型アンテナ２から１０ｃｍ離れた位置に基材支持電極５を設置して、その表面に高周波アンテナに対向してシリコン基板を係止した。予め基板温度を４００℃に加熱し、ガス圧を０．５パスカルに調整し、高周波アンテナ２に２ｋＷの高周波電力を給電して放電プラズマを発生させた。基板ホルダには−１４．２ｋＶ、パルス幅５マイクロ秒、繰り返し周波数１ｋＨｚのパルス電圧を印加した。基板はイオンの衝突によって加熱されるため、加熱板に加える電力を制御してほぼ４００℃に保持した。 (Example 3)
As in Example 1, a mixed gas of methane gas 30% and acetylene gas 70% was introduced as a raw material gas, and a substrate support electrode 5 was installed at a position 10 cm away from the inductively coupled antenna 2, and a high frequency antenna was formed on the surface thereof. The silicon substrate was locked to face. The substrate temperature was previously heated to 400 ° C., the gas pressure was adjusted to 0.5 Pascal, and 2 kW of high-frequency power was supplied to the high-frequency antenna 2 to generate discharge plasma. A pulse voltage of -14.2 kV, a pulse width of 5 microseconds, and a repetition frequency of 1 kHz was applied to the substrate holder. Since the substrate was heated by the collision of ions, the power applied to the heating plate was controlled and kept at approximately 400 ° C.

１時間の成膜で、厚さ１．８μｍのＤＬＣ膜を得た。膜色はダークシルバーであった。熱プローブによる測定結果では強いｐ形伝導特性を示した。４探針測定器Ｎａｐｓｏｎ、ＲＴ−７による測定結果では、抵抗率は１６．７ｍΩｃｍであった。また、ホール測定システムによるホール電圧測定でもｐ形伝導特性を示し、抵抗率は１５．７ｍΩｃｍ、正孔移動度は１１ｃｍ２／Ｖ・ｓｅｃ、キャリア濃度は４．２×１０１９／ｃｍ３であった。更に、ビッカース硬度計による硬度測定結果では、Ｈｖ２４００であった。 A DLC film having a thickness of 1.8 μm was obtained by film formation for 1 hour. The film color was dark silver. The measurement result with the thermal probe showed strong p-type conduction characteristics. As a result of measurement using a four-probe measuring instrument Napson, RT-7, the resistivity was 16.7 mΩcm. Also, the Hall voltage measurement by the Hall measurement system showed p-type conduction characteristics, the resistivity was 15.7 mΩcm, the hole mobility was 11 cm 2 / V · sec, and the carrier concentration was 4.2 × 10 19 / cm 3. It was. Furthermore, the hardness measurement result by the Vickers hardness tester was Hv2400.

本発明によるＤＬＣ膜のキャリアの伝導機構は、ｓｐ２結合のグラファイト微結晶による電子伝導とｓｐ３結合のダイヤモンド微結晶による正孔伝導との両方の伝導機構によるものと考えられる。本発明によるＤＬＣ膜はグラファイト微結晶よりもダイヤモンド微結晶が多く生成されていて、ダイヤモンド微結晶による正孔伝導が主流となってｐ形半導体特性を示すものである。 Conduction mechanism of the carrier of the DLC film according to the present invention is believed to be due to both the conduction mechanism of a hole conduction by electronic conduction and sp 3 bonds the diamond crystallites by graphite crystallites of sp 2 bonds. The DLC film according to the present invention produces more diamond crystallites than graphite crystallites, and exhibits p-type semiconductor characteristics mainly due to hole conduction by diamond crystallites.

本発明によれば、ＤＬＣ膜の硬度は、硬度の低いグラファイト微結晶と硬度の高いダイヤモンド微結晶の存在比で決まるものであると想定される。ダイヤモンド微結晶が多く含まれる本発明によるＤＬＣ膜は高硬度で、且つ低抵抗率のｐ形半導体ＤＬＣ膜が得られたものである。 According to the present invention, the hardness of the DLC film is assumed to be determined by the abundance ratio of low-hardness graphite microcrystals and high-hardness diamond microcrystals. The DLC film according to the present invention containing a large amount of diamond crystallites is a p-type semiconductor DLC film having high hardness and low resistivity.

本発明の完成に到る過程において得られた結果によると、放電プラズマＣＶＤによるＤＬＣ膜の物性は原料ガス、基板温度、プラズマ密度、基板に印加するパルス電圧など多くの要因に依存する。原料ガスとしてトルエンなど六員環等を有する炭化水素ガスを用いるとｓｐ２結合のグラファイト微結晶ができ易く、メタン、アセチレンなど低分子量の炭化水素ガスを採用するとｓｐ３結合のダイヤモンド微結晶が成長し易い。 According to the results obtained in the process of completing the present invention, the physical properties of the DLC film by discharge plasma CVD depend on many factors such as source gas, substrate temperature, plasma density, and pulse voltage applied to the substrate. When a hydrocarbon gas having a six-membered ring such as toluene is used as a raw material gas, sp 2 -bonded graphite microcrystals are easily formed, and when a low molecular weight hydrocarbon gas such as methane or acetylene is used, sp 3 -bonded diamond crystallites are grown. Easy to do.

基板温度は生成されるＤＬＣ膜に含まれる水素量を左右するもので、基板温度が高いほど水素量は減少し、４５０℃で成膜すると水素の含有量は５アトミックパーセントまで低下する。水素の含有量の低下はｓｐ２結合及びｓｐ３結合の微結晶の増加に寄与し、抵抗率低減の大きな要因と考えられる。 The substrate temperature affects the amount of hydrogen contained in the generated DLC film. The higher the substrate temperature, the lower the amount of hydrogen. When the film is formed at 450 ° C., the hydrogen content decreases to 5 atomic percent. A decrease in the hydrogen content contributes to an increase in sp 2 bond and sp 3 bond microcrystals, which is considered to be a major factor in reducing the resistivity.

基板表面のプラズマ密度及び基板に印加するパルス電圧はＤＬＣ膜の成長速度のみならず、ＤＬＣ膜の伝導形、抵抗率及び硬度に大きな影響を与える要因である。ＤＬＣ膜の成長メカニズムは放電により生成されるＣＨＸラジカル及びＣＨＸイオン等が基板表面に堆積し、基板に印加する負のパルス電圧によって加速された高エネルギーイオンの衝突によってＣＨＸが分解され、結晶化が進行するものと考えられている。 The plasma density on the substrate surface and the pulse voltage applied to the substrate are factors that greatly affect not only the growth rate of the DLC film but also the conductivity type, resistivity, and hardness of the DLC film. The growth mechanism of the DLC film is such that CH X radicals and CH X ions generated by discharge are deposited on the substrate surface, and CH X is decomposed by collision of high energy ions accelerated by a negative pulse voltage applied to the substrate. It is believed that crystallization proceeds.

プラズマ密度をｎｐ（ｃｍ−３）、電子温度をＴｅ（ｅＶ）、イオンの質量数をＭとするとき、イオン飽和電流密度Ｊｐｉは次式で表される。
Ｊｐｉ＝９．６×１０−１１（１／Ｍ）１／２（Ｔｅ）１／２ｎｐ （ｍＡ／ｃｍ２）
即ち、基板表面に入射するイオン電流密度は、プラズマ密度に比例する。また、イオンに対する空間電荷制限電流密度Ｊ０は、価数をＺ、電極間隔をｄ、印加電圧をＶ０とするとき、次式で表される。
Ｊ０＝５．５×１０−５（Ｚ／Ｍ）１／２Ｖ０ ３／２／ｄ２ （ｍＡ／ｃｍ２）
基板表面に負のパルス電圧を印加すると、基板に入射するイオン電流はパルス電圧の１．５乗に比例する。本願実施例では、基板表面のプラズマ密度は単位立方センチメートル当たり５×１０１０個乃至３×１０１１個程度、基板に印加するパルス電圧は−４ｋＶ乃至−２０ｋＶであった。ｐ形ＤＬＣ膜を得るには５×１０１０個以上のプラズマ密度が必要であった。 When the plasma density is n p (cm −3 ), the electron temperature is Te (eV), and the ion mass number is M, the ion saturation current density J pi is expressed by the following equation.
J pi = 9.6 × 10 −11 (1 / M) 1/2 (Te) 1/2 n p (mA / cm 2 )
That is, the ion current density incident on the substrate surface is proportional to the plasma density. Further, the space charge limited current density J 0 for ions is expressed by the following equation when the valence is Z, the electrode interval is d, and the applied voltage is V 0 .
J 0 = 5.5 × 10 −5 (Z / M) 1/2 V 0 3/2 / d 2 (mA / cm 2 )
When a negative pulse voltage is applied to the substrate surface, the ion current incident on the substrate is proportional to the 1.5th power of the pulse voltage. In this embodiment, the plasma density on the substrate surface was about 5 × 10 10 to 3 × 10 11 per cubic centimeter, and the pulse voltage applied to the substrate was −4 kV to −20 kV. In order to obtain a p-type DLC film, a plasma density of 5 × 10 10 or more was required.

図４に基板温度及びパルス電圧と得られたＤＬＣ膜の特性を示す。横軸は基板温度とパルス電圧の積、縦軸は硬度と抵抗率である。硬度と抵抗率は製膜中の基板温度とパルス電圧の積に大きく依存することが分かる。高硬度、低抵抗率、且つ正孔伝導特性を示すＤＬＣの製膜には一定量以上のイオン照射エネルギーが必要である。 FIG. 4 shows the substrate temperature and pulse voltage and the characteristics of the obtained DLC film. The horizontal axis is the product of the substrate temperature and the pulse voltage, and the vertical axis is the hardness and resistivity. It can be seen that the hardness and resistivity greatly depend on the product of the substrate temperature and the pulse voltage during film formation. DLC film formation with high hardness, low resistivity, and hole conduction characteristics requires a certain amount of ion irradiation energy.

本発明によれば、比較的低い基板温度、例えば、３００℃以下の温度で製造されたＤＬＣ膜は製造時の基板温度以上の温度、例えば、５００℃でアニールすることによって、ＤＬＣ膜の抵抗率を低減することができ、所望の抵抗率に調整することができる。アニール温度は、好ましくは４００℃乃至７００℃である。 According to the present invention, a DLC film manufactured at a relatively low substrate temperature, eg, 300 ° C. or lower, is annealed at a temperature higher than the substrate temperature at the time of manufacture, eg, 500 ° C. And can be adjusted to a desired resistivity. The annealing temperature is preferably 400 ° C. to 700 ° C.

前記実施例においては、放電プラズマ発生手段として誘導結合型高周波アンテナを採用したが、該誘導結合型高周波アンテナに限られるものではなく、十分な放電プラズマ密度が得られる放電プラズマ発生手段、例えば、マイクロ波放電プラズマ、ＥＣＲ放電プラズマ等を用いることができる。また、本実施例では負の高電圧パルスを印加したが、正のパルス電圧と負のパルス電圧を組み合わせた正負パルス電圧を印加することによって、更に高密度の放電プラズマを発生させることができ、本発明の課題解決に有効である。 In the above embodiment, the inductively coupled high frequency antenna is used as the discharge plasma generating means. However, the inductively coupled high frequency antenna is not limited to the inductively coupled high frequency antenna, and a discharge plasma generating means capable of obtaining a sufficient discharge plasma density, for example, a micro Wave discharge plasma, ECR discharge plasma, or the like can be used. Further, in this example, a negative high voltage pulse was applied, but by applying a positive and negative pulse voltage that combines a positive pulse voltage and a negative pulse voltage, it is possible to generate a higher density discharge plasma, This is effective for solving the problems of the present invention.

本発明によるＤＬＣ膜の製造方法を説明するための装置の断面模式図である。It is a cross-sectional schematic diagram of the apparatus for demonstrating the manufacturing method of the DLC film by this invention. 本発明で得られたＤＬＣ膜表面のＡＦＭ測定写真である。It is an AFM measurement photograph of the DLC film surface obtained by the present invention. 本発明で得られたＤＬＣのＸ線回折スペクトルを示す図面である。It is drawing which shows the X-ray-diffraction spectrum of DLC obtained by this invention. 基板温度及びパルス電圧と本発明で得られたＤＬＣ膜の硬度及び抵抗率の関係を示す図面である。It is drawing which shows the relationship between the substrate temperature and pulse voltage, and the hardness and resistivity of the DLC film obtained by the present invention.

符号の説明Explanation of symbols

１・・真空容器、２・・誘導結合型高周波アンテナ、３・・高周波電源、４・・整合器、５・・基板支持電極、６・・被加工基材、７・・パルス電源、８・・温度制御器、９・・ヒータ、１０・・フィードスルー、１１・・ガス導入口、１２・・真空排気口 1 .... Vacuum container, 2 .... Inductive coupling type high frequency antenna, 3 .... High frequency power supply, 4 .... Matching unit, 5 .... Substrate support electrode, 6 .... Substrate, 7 .... Pulse power supply, ...・ Temperature controller, 9 ・ ・ Heater, 10 ・ ・ Feed-through, 11 ・ ・ Gas inlet, 12 ・ ・ Vacuum exhaust port

Claims (16)

周期律表の３族元素又は２族元素であるボロンやマグネシウム等のｐ形ドーパントをドーピングしないダイヤモンドライクカーボンであって、その電気伝導がｐ形伝導であることを特徴とするダイヤモンドライクカーボン。 A diamond-like carbon which is not doped with a p-type dopant such as boron or magnesium which is a group 3 element or group 2 element of the periodic table, and whose electrical conduction is p-type conduction. 前記ダイヤモンドライクカーボンの抵抗率が１キロオームセンチ以下であることを特徴とする請求項１に記載のダイヤモンドライクカーボン。 The diamond-like carbon according to claim 1, wherein the resistivity of the diamond-like carbon is 1 kilo ohm centimeter or less. 前記ダイヤモンドライクカーボンの硬度がビッカース硬度２０００以上であることを特徴とする請求項１及び２に記載のダイヤモンドライクカーボン。 The diamond-like carbon according to claim 1 or 2, wherein the diamond-like carbon has a Vickers hardness of 2000 or more. 前記ダイヤモンドライクカーボンに含まれる水素量が１０アトミックパーセント以下であることを特徴とする請求項１から３のいずれかに記載のダイヤモンドライクカーボン。 The diamond-like carbon according to any one of claims 1 to 3, wherein the amount of hydrogen contained in the diamond-like carbon is 10 atomic percent or less. 真空容器内に炭化水素系原料ガスを導入し、放電プラズマ発生手段によって前記真空容器内に放電プラズマを発生させ、該放電プラズマに接するように被加工基材を設置し、該被加工基材の温度を２００度Ｃ以上に保持し、該被加工基材に１ｋＶ以上の正負又は負のパルス電圧を印加して前記被加工基材表面に請求項１から４の何れかに記載のダイヤモンドライクカーボンを製膜することを特徴とするダイヤモンドライクカーボンの製造方法。 A hydrocarbon-based source gas is introduced into the vacuum vessel, discharge plasma is generated in the vacuum vessel by the discharge plasma generating means, a workpiece substrate is placed in contact with the discharge plasma, and the workpiece substrate The diamond-like carbon according to any one of claims 1 to 4, wherein the diamond-like carbon according to any one of claims 1 to 4 is applied to a surface of the substrate to be processed by maintaining a temperature of 200 ° C or more and applying a positive or negative pulse voltage of 1 kV or more to the substrate to be processed. A method for producing diamond-like carbon, comprising: forming a film. 前記放電プラズマ発生手段が誘導結合型高周波放電であることを特徴とする請求項５に記載のダイヤモンドライクカーボンの製造方法。 6. The method of producing diamond-like carbon according to claim 5, wherein the discharge plasma generating means is inductively coupled high frequency discharge. 前記負のパルス電圧が５ｋＶ乃至２５ｋＶであることを特徴とする請求項５及び６のいずれかに記載のダイヤモンドライクカーボンの製造方法。 The method of producing diamond-like carbon according to claim 5, wherein the negative pulse voltage is 5 kV to 25 kV. 前記基板温度が３００度Ｃ乃至５００度Ｃであることを特徴とする請求項５から７の何れかに記載のダイヤモンドライクカーボンの製造方法。 The method for producing diamond-like carbon according to any one of claims 5 to 7, wherein the substrate temperature is 300 ° C to 500 ° C. 前記被加工基材をイオン照射によって加熱することを特徴とする請求項５から８の何れかに記載のダイヤモンドライクカーボンの製造方法。 The method for producing diamond-like carbon according to claim 5, wherein the substrate to be processed is heated by ion irradiation. 前記被加工基材を電気ヒータ及びイオン照射によって加熱することを特徴とする請求項５から９のいずれかに記載のダイヤモンドライクカーボンの製造方法。 The method for producing diamond-like carbon according to any one of claims 5 to 9, wherein the substrate to be processed is heated by an electric heater and ion irradiation. 前記炭化水素系原料ガスが六員環等を含まない低分子量炭化水素ガス、メタン、エタン、プロパン、アセチレン、エチレンガスの少なくとも一つを含むことを特徴とする請求項５から１０のいずれかに記載のダイヤモンドライクカーボンの製造方法。 The hydrocarbon source gas contains at least one of a low molecular weight hydrocarbon gas not containing a six-membered ring, methane, ethane, propane, acetylene, and ethylene gas. The manufacturing method of the diamond-like carbon of description. 前記炭化水素系原料ガスが請求項１１に記載の原料ガスとアルゴンガス又は／及び水素ガスの混合ガスであることを特徴とする請求項５から１０のいずれかに記載のダイヤモンドライクカーボンの製造方法。 The method for producing diamond-like carbon according to any one of claims 5 to 10, wherein the hydrocarbon-based source gas is a mixed gas of the source gas according to claim 11 and argon gas or / and hydrogen gas. . 請求項１から４のいずれかに記載のｐ形ダイヤモンドライクカーボンを３００度Ｃ以上の温度でアニールすることによって所望の抵抗率に調整することを特徴とするダイヤモンドライクカーボンの製造方法。 A method for producing diamond-like carbon, wherein the p-type diamond-like carbon according to any one of claims 1 to 4 is adjusted to a desired resistivity by annealing at a temperature of 300 ° C or higher. 、請求項５から１２のいずれかに記載の製造方法によって製造したダイヤモンドライクカーボンを、３００度Ｃ以上の温度でアニールすることによって所望の抵抗率に調整することを特徴とするダイヤモンドライクカーボンの製造方法。 A diamond-like carbon produced by the production method according to claim 5 is adjusted to a desired resistivity by annealing at a temperature of 300 ° C. or higher. Method. 請求項１から４いずれかに記載のｐ形ダイヤモンドライクカーボンを用いたことを特徴とする工業製品。 An industrial product using the p-type diamond-like carbon according to any one of claims 1 to 4. 請求項５から１３いずれかに記載の製造方法によって製造したダイヤモンドライクカーボンを用いたことを特徴とする工業製品。 An industrial product using diamond-like carbon produced by the production method according to claim 5.
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