JP2010024476A5 - Diamond-like carbon manufacturing apparatus, manufacturing method, and industrial product - Google Patents
Diamond-like carbon manufacturing apparatus, manufacturing method, and industrial product Download PDFInfo
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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その抵抗率が十分低い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 the resistivity impurity doping can not be obtained sufficiently low have D LC film.
電気伝導がｐ形伝導で抵抗率が１オームセンチメートル以下、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、抵抗率が１オームセンチメートル以下で、且つ高硬度のＤＬＣを得るためのＤＬＣ製造方法を提供することにある。
また、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。
Electrical conductivity is resistivity p-type conduction is 1 ohm-cm or less, a Vickers hardness of 2000 or more DLC films are not obtained.
The problem to be solved by the present invention is to provide a DLC manufacturing method for obtaining a DLC having a resistivity of 1 ohm centimeter or less and high hardness.
It is another object of the present invention to provide a DLC film manufacturing apparatus capable of forming a film on a large area substrate surface at a high speed.
本発明によるＤＬＣ製造装置は、炭化水素系原料ガス雰囲気の容器(1)内に、放電プラズマを発生させる放電プラズマ発生手段と、前記容器(1)の内部で支持用電極(5)により支持されている被加工基材(6)を、摂氏２００度以上に加熱するとともに、加熱温度を一定の温度範囲に保持する加熱手段(8,9)と、前記被加工基材(6)に前記支持用電極(5)を通じて１ｋＶ以上のパルス電圧を印加するパルス電圧印加手段(7)とを備え、前記容器(1)内で前記放電プラズマに接触し且つ前記加熱手段(8,9)によって加熱されている前記被加工基材(6)に、前記パルス電圧を所定時間印加することにより、当該被加工基材(6)の表面にグラファイト微結晶とダイヤモンド微結晶とが混在した、その抵抗率が１キロオームセンチメートル以下となるＤＬＣ、好ましくはｐ形伝導の特性を示すＤＬＣを堆積させることを特徴とする。
ｐ形伝導とは、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。このＤＬＣ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くとも、ｐ形伝導となる。
A DLC production apparatus according to the present invention is supported by a discharge plasma generating means for generating discharge plasma in a vessel (1) of a hydrocarbon-based source gas atmosphere, and a support electrode (5) inside the vessel (1). The substrate to be processed (6) is heated to 200 degrees Celsius or higher, and the heating means (8, 9) for maintaining the heating temperature in a certain temperature range, and the support to the substrate to be processed (6) Pulse voltage applying means (7) for applying a pulse voltage of 1 kV or more through the electrode (5), contacting the discharge plasma in the vessel (1) and being heated by the heating means (8, 9). By applying the pulse voltage to the workpiece substrate (6) for a predetermined time, graphite microcrystals and diamond crystallites are mixed on the surface of the workpiece substrate (6). DLC less than 1 kilohm centimeter, preferably p-type conductivity It is characterized by depositing DLC exhibiting characteristics .
The p-type conduction 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 electrical conduction mechanism is a sp3 bonded diamond microcrystal existing in an amorphous carbon film. This is what is considered to be hole conduction based on lattice defects. This DLC has p-type conduction without doping with a p-type dopant such as boron or magnesium which is a group 3 element or group 2 element of the periodic table.
本発明のＤＬＣ製造装置における実施の一態様では、前記放電プラズマ発生手段は、前記容器内で前記支持用導電体に対向して配置された誘導結合型の高周波アンテナ(2)と、この高周波アンテナ(2)に前記容器(1)の外部から高周波電力を給電する高周波電力供給手段(3,4)とを含み、前記支持用電極(5)により支持された前記被加工基材(6)の表面と前記高周波アンテナ(2)との間の空間に、放電プラズマを発生させるように構成されている。
より好ましくは、前記放電プラズマ発生手段(2,3,4)は、単位立方センチメートル当たり５×１０ １０ 個以上の密度の放電プラズマを前記空間に発生させるものである。
In one embodiment of the DLC manufacturing apparatus of the present invention, the discharge plasma generating means includes an inductively coupled high-frequency antenna (2) disposed opposite to the support conductor in the container, and the high-frequency antenna. (2) includes high-frequency power supply means (3,4) for supplying high-frequency power from the outside of the container (1), and the workpiece base (6) supported by the support electrode (5). A discharge plasma is generated in a space between the surface and the high-frequency antenna (2).
More preferably, the discharge plasma generating means (2,3,4) is a discharge plasma of the unit cubic centimeter per 5 × 10 10 or more a density which is generated in the space.
本発明のＤＬＣ製造装置における前記パルス電圧印加手段(7)は、例えば、マイクロ秒オーダのパルス幅を有する負極性のパルス電圧又は前記パルス幅を有する負極性の交番パルス電圧を印加し、前記加熱手段(8,9)は、前記被加工基材(6)をイオン照射、又はイオン照射と電気ヒータとにより加熱するように構成する。The pulse voltage applying means (7) in the DLC manufacturing apparatus of the present invention applies, for example, a negative pulse voltage having a pulse width on the order of microseconds or a negative alternating pulse voltage having the pulse width, and the heating The means (8, 9) is configured to heat the substrate (6) to be processed by ion irradiation or ion irradiation and an electric heater.
本発明のＤＬＣ製造装置により堆積した前記ＤＬＣは、ダイヤモンド微結晶がグラファイト微結晶よりも多いことが好ましい。 The DLC deposited by the DLC manufacturing apparatus of the present invention preferably has more diamond crystallites than graphite crystallites .
本発明のＤＬＣの製造方法は、支持用電極(5)で支持された被加工基材(6)が配置された容器(1)内を炭化水素系原料ガス雰囲気で所定気圧に維持するとともに、その容器(1)内に放電プラズマを発生させ、さらに、前記被加工基材(6)を、摂氏２００度以上の温度範囲で加熱した状態で、前記被加工基材(6)に前記支持用電極(5)を通じて１ｋＶ以上のパルス電圧を所定時間印加することにより、当該被加工基材(6)の表面に、グラファイト微結晶とダイヤモンド微結晶とが混在した、その抵抗率が１キロオームセンチメートル以下となるＤＬＣを堆積させることを特徴とする。The method for producing DLC of the present invention maintains the inside of the container (1) in which the substrate to be processed (6) supported by the supporting electrode (5) is disposed at a predetermined pressure in a hydrocarbon-based source gas atmosphere, In the container (1), discharge plasma is generated, and further, the substrate to be processed (6) is heated in a temperature range of 200 degrees Celsius or more, and the substrate to be processed (6) is used for the support. By applying a pulse voltage of 1 kV or more for a predetermined time through the electrode (5), graphite microcrystals and diamond crystallites are mixed on the surface of the substrate to be processed (6), and the resistivity is 1 kilohm centimeter. The following DLC is deposited.
本発明の製造方法における実施の一態様では、前記炭化水素系原料ガスが、六員環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。 In one embodiment of the production method of the present invention, the hydrocarbon-based 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.
より好ましい態様では、前記炭化水素系原料ガスが、さらに、アルゴンガスと水素ガスの少なくとも一方をさらに混合したガスである。In a more preferred embodiment, the hydrocarbon-based source gas is a gas obtained by further mixing at least one of argon gas and hydrogen gas.
本発明の製造方法において、より好ましくは、堆積した前記ＤＬＣを、その抵抗率が１キロオームセンチ以下、その硬度がビッカース硬度２０００以上、その含有水素量が１０アトミックパーセント以下となるまで、アニール処理を行う。 In the production method of the present invention, more preferably, the deposited DLC is annealed until the resistivity is 1 kilohm centimeter or less, the hardness is 2000 Vickers hardness or more, and the hydrogen content is 10 atomic percent or less. Do.
本発明は、上記製造方法により製造されるＤＬＣを工業製品に適用することができる。In the present invention, DLC produced by the above production method can be applied to industrial products.
この工業製品は、上述した本発明のダイヤモンドライクカーボン製造装置によって製造された、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とが混在したダイヤモンドライクカーボンによりコーティングされたものである。 This industrial product is coated with diamond-like carbon in which sp2-bonded graphite crystallites and sp3-bonded diamond crystallites are mixed, manufactured by the above-described diamond-like carbon manufacturing apparatus of the present invention.
本発明によれば、その抵抗率が１キロオームセンチメートル以下、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, the resistivity of 1 kg ohm-cm or less, a Vickers hardness of 2000 or more DLC film 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.
Claims (10)
前記容器(1)の内部で支持用電極(5)により支持されている被加工基材(6)を、摂氏２００度以上に加熱するとともに、加熱温度を一定の温度範囲に保持する加熱手段(8,9)と、
前記被加工基材(6)に前記支持用電極(5)を通じて１ｋＶ以上のパルス電圧を印加するパルス電圧印加手段(7)とを備え、
前記容器(1)内で前記放電プラズマに接触し且つ前記加熱手段(8,9)によって加熱されている前記被加工基材(6)に、前記パルス電圧を所定時間印加することにより、当該被加工基材(6)の表面にグラファイト微結晶とダイヤモンド微結晶とが混在した、その抵抗率が１キロオームセンチメートル以下となるダイヤモンドライクカーボンを堆積させる、
ダイヤモンドライクカーボン製造装置。 A discharge plasma generating means for generating a discharge plasma in a vessel (1) of a hydrocarbon-based source gas atmosphere;
Heating means for heating the workpiece substrate (6) supported by the supporting electrode (5) inside the container (1) to 200 degrees Celsius or higher and maintaining the heating temperature within a certain temperature range ( 8,9) and
Pulse voltage applying means (7) for applying a pulse voltage of 1 kV or more to the workpiece substrate (6) through the support electrode (5);
By applying the pulse voltage to the workpiece substrate (6) in contact with the discharge plasma in the vessel (1) and heated by the heating means (8, 9) for a predetermined time, Depositing diamond-like carbon with graphite microcrystals and diamond microcrystals mixed on the surface of the processed substrate (6) and having a resistivity of 1 kilohm centimeter or less;
Diamond-like carbon production equipment.
請求項１記載のダイヤモンドライクカーボン製造装置。 The discharge plasma generating means includes an inductive coupling type high frequency antenna (2) disposed opposite to the supporting conductor in the container, and a high frequency from the outside of the container (1) to the high frequency antenna (2). High frequency power supply means (3, 4) for supplying power, and a space between the surface of the substrate (6) to be processed supported by the support electrode (5) and the high frequency antenna (2) Is configured to generate a discharge plasma,
The diamond-like carbon manufacturing apparatus according to claim 1.
請求項２記載のダイヤモンドライクカーボン製造装置。 The discharge plasma generating means (2, 3, 4) generates discharge plasma having a density of 5 × 10 10 or more per cubic centimeter in the space.
The diamond-like carbon manufacturing apparatus according to claim 2.
前記加熱手段(8,9)は、前記被加工基材(6)をイオン照射、又はイオン照射と電気ヒータとにより加熱する、
請求項１、２又は３記載のダイヤモンドライクカーボン製造装置。 The pulse voltage application means (7) applies a negative pulse voltage having a pulse width on the order of microseconds or a negative alternating pulse voltage having the pulse width,
The heating means (8, 9) is to heat the substrate to be processed (6) by ion irradiation, or ion irradiation and an electric heater.
The diamond-like carbon manufacturing apparatus according to claim 1, 2 or 3.
請求項１乃至４のいずれかの項記載のダイヤモンドライクカーボン製造装置。 More diamond crystallites in the deposited diamond-like carbon than the graphite crystallites,
The diamond-like carbon manufacturing apparatus according to any one of claims 1 to 4.
ダイヤモンドライクカーボンの製造方法。 The inside of the container (1) in which the substrate to be processed (6) supported by the supporting electrode (5) is arranged is maintained at a predetermined pressure in a hydrocarbon-based raw material gas atmosphere, and discharge plasma is contained in the container (1). In addition, a pulse of 1 kV or higher is applied to the substrate to be processed (6) through the support electrode (5) in a state where the substrate to be processed (6) is heated in a temperature range of 200 degrees Celsius or higher. By applying a voltage for a predetermined time, a diamond-like carbon having a resistivity of 1 kilohm centimeter or less, in which graphite crystallites and diamond crystallites are mixed, is deposited on the surface of the substrate (6). ,
A method for producing diamond-like carbon.
請求項６記載の製造方法。 The hydrocarbon-based 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 Claim 6.
請求項７記載の製造方法。 The hydrocarbon-based source gas is a gas obtained by further mixing at least one of argon gas and hydrogen gas.
The manufacturing method of Claim 7.
請求項７又は８記載のダイヤモンドライクカーボンの製造方法。 The deposited diamond-like carbon is annealed until the resistivity is 1 kilohm centimeter or less, the hardness is Vickers hardness 2000 or more, and the hydrogen content is 10 atomic percent or less.
The method for producing diamond-like carbon according to claim 7 or 8.
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| JP5150861B2 (en) * | 2008-12-29 | 2013-02-27 | 日本アイ・ティ・エフ株式会社 | Hard carbon film and method for forming the same |
| US9183965B2 (en) | 2010-11-30 | 2015-11-10 | Nomura Plating Co., Ltd. | Conductive hard carbon film and method for forming the same |
| JP5603433B2 (en) * | 2010-12-28 | 2014-10-08 | キヤノンアネルバ株式会社 | Carbon film manufacturing method and plasma CVD method |
| WO2013133110A1 (en) * | 2012-03-09 | 2013-09-12 | 株式会社ユーテック | Cvd device |
| JP6383910B2 (en) * | 2012-11-27 | 2018-09-05 | 地方独立行政法人山口県産業技術センター | Plasma CVD apparatus and film manufacturing method |
| DE102013005926B4 (en) * | 2013-04-04 | 2015-12-03 | Eagleburgmann Germany Gmbh & Co. Kg | Mechanical seal assembly with different hard sliding surfaces |
| JP6234860B2 (en) | 2014-03-25 | 2017-11-22 | 株式会社Ｓｃｒｅｅｎホールディングス | Film forming apparatus and film forming method |
| US10249495B2 (en) | 2016-06-28 | 2019-04-02 | Applied Materials, Inc. | Diamond like carbon layer formed by an electron beam plasma process |
| JP2017059844A (en) * | 2016-11-18 | 2017-03-23 | 株式会社大木工藝 | Electric double layer capacitor |
| US11043375B2 (en) | 2017-08-16 | 2021-06-22 | Applied Materials, Inc. | Plasma deposition of carbon hardmask |
| WO2019199681A1 (en) | 2018-04-09 | 2019-10-17 | Applied Materials, Inc. | Carbon hard masks for patterning applications and methods related thereto |
| SG11202009289PA (en) * | 2018-05-03 | 2020-11-27 | Applied Materials Inc | Pulsed plasma (dc/rf) deposition of high quality c films for patterning |
| CN110965022B (en) * | 2018-09-28 | 2021-12-24 | 长鑫存储技术有限公司 | Method for forming semiconductor structure |
| CN114008761A (en) | 2019-07-01 | 2022-02-01 | 应用材料公司 | Tuning film properties by optimizing plasma-coupled materials |
| US11664226B2 (en) | 2020-06-29 | 2023-05-30 | Applied Materials, Inc. | Methods for producing high-density carbon films for hardmasks and other patterning applications |
| US11664214B2 (en) | 2020-06-29 | 2023-05-30 | Applied Materials, Inc. | Methods for producing high-density, nitrogen-doped carbon films for hardmasks and other patterning applications |
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| JPH0361369A (en) * | 1989-07-29 | 1991-03-18 | Idemitsu Petrochem Co Ltd | Manufacture of diamond like carbon film |
| JPH1192935A (en) * | 1997-09-19 | 1999-04-06 | Daido Steel Co Ltd | Wear resistant hard carbon coating |
| JP4929531B2 (en) * | 2001-04-27 | 2012-05-09 | 住友電気工業株式会社 | Conductive hard carbon film |
| JP4134315B2 (en) * | 2003-01-14 | 2008-08-20 | 独立行政法人産業技術総合研究所 | Carbon thin film and manufacturing method thereof |
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