WO2021090793A1 - Appareil de formation de film et procédé de formation de film pour film dlc - Google Patents

Appareil de formation de film et procédé de formation de film pour film dlc Download PDF

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Publication number
WO2021090793A1
WO2021090793A1 PCT/JP2020/041015 JP2020041015W WO2021090793A1 WO 2021090793 A1 WO2021090793 A1 WO 2021090793A1 JP 2020041015 W JP2020041015 W JP 2020041015W WO 2021090793 A1 WO2021090793 A1 WO 2021090793A1
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WIPO (PCT)
Prior art keywords
film
gas
reaction
reaction vessel
supply pipe
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PCT/JP2020/041015
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English (en)
Japanese (ja)
Inventor
英児 佐藤
坂本　仁志
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株式会社クリエイティブコーティングス
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Publication of WO2021090793A1 publication Critical patent/WO2021090793A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only

Definitions

  • the present invention relates to a film forming apparatus and a film forming method for a DLC (Diamond Like Carbon) film.
  • the DLC film is an amorphous film in which graphite bonds having a hexagonal crystal structure and diamond bonds having a cubic crystal structure are mixed.
  • a PVD (Physical Vapor Deposition) method and a CVD (Chemical Vapor Deposition) method are known.
  • the PVD method such as the sputtering method and the ion vapor deposition method
  • the surface of the DLC film is rough and the wear resistance is low as compared with the CVD method.
  • Patent Document 1 uses a compound gas of C and F, for example, C 4 F 8 gas, a hydrocarbon gas, for example, C 2 H 4 gas, and a CO gas as film forming gas in the RF plasma CVD method.
  • Patent Document 1 discloses a method in which this film-forming gas is turned into plasma to generate an active species, and a CF film is formed on a semiconductor wafer by the active species at a process temperature of 400 ° C.
  • Patent Document 1 points out that graphite bonds and diamond bonds are mixed in the CF film. Further, Patent Document 1 discloses that the addition of CO gas causes more diamond bonds than graphite bonds.
  • the film formation target had to be heated to 250 ° C. or higher. If it is a substrate such as a semiconductor wafer, the mounting table may be heated. However, if the film-forming target is not a substrate but a three-dimensional structure, particularly a structure having an uneven film-forming surface, it is difficult to uniformly heat the film, and the film can be formed at room temperature without the need for forced heating. It was desired.
  • An object of the present invention is to provide a film forming apparatus and a film forming method capable of forming a DLC film by enabling a low temperature process and suppressing the generation of particles and by-products.
  • One aspect of the present invention is Reaction vessel and A support portion that supports the film formation target in the reaction vessel and A rotating part that rotates the support part and A first supply pipe for supplying a raw material gas containing a hydrocarbon to the reaction vessel via a first valve, and a first supply pipe.
  • a reaction gas containing hydrogen radicals activated by inductively coupled plasma is introduced into the reaction vessel filled with the raw material gas at a pressure higher than the pressure in the reaction vessel via the second valve.
  • the present invention relates to a film forming apparatus for attracting carbon ions generated by the reaction of the raw material gas and the reaction gas to the film forming target by the negative bias and depositing a DLC film on the film forming target.
  • the hydrogen radical generated by activating the reaction gas with inductively coupled plasma abstracts hydrogen in the hydrocarbon, which is the raw material gas in the reaction vessel, at the room temperature level to generate carbon ions. can do.
  • a reaction gas containing a hydrogen radical activated by an inductively coupled plasma is contained in a reaction vessel filled with a raw material gas introduced via a first valve and a first supply pipe. Is supplied to the reaction vessel via the second valve and the second supply pipe at a pressure higher than the pressure in the reaction vessel. As a result, it is possible to prevent the raw material gas and the reaction gas from flowing back into the second supply pipe.
  • the raw material gas supplied to the first supply pipe can be as an additional gas containing H 2 O, HF or HCl.
  • the additive gas, H 2 O can impart hydrophilicity to the film-forming object.
  • Cl - - Negative ions F resulting from the addition is a gas HF or HCl, it is possible to impart water repellency to the film-forming target.
  • the reaction gas before activation supplied to the second supply pipe can include CF 4 , C 2 F 6 , C 3 F 8 , O 2 or O 3 as an additive gas. ..
  • Water repellency can be imparted to the film-forming target by the negative ions F ⁇ generated from the added gases CF 4 , C 2 F 6 , and C 3 F 8.
  • Hydrophilicity can be imparted to the film-forming target by the active oxygen generated from the added gases O 2 and O 3.
  • increasing the absolute value of the negative bias applied by the DC power source increases the diamond bond contained in the DLC film, and decreasing the absolute value includes the diamond bond in the DLC film.
  • the graphite bond can be increased. In this way, the ratio of the diamond bond to the graphite bond can be changed according to the application to be formed.
  • the induction coil provided in the second supply pipe and the high frequency power supply connected to the induction coil are further provided.
  • the diamond bond contained in the DLC film can be increased, and by decreasing the power, the graphite bond contained in the DLC film can be increased. In this way, the ratio of diamond bond to graphite bond can be changed by the power of the high frequency power supply.
  • Another aspect of the present invention is The support portion that supports the film formation target is rotated in the reaction vessel, A negative bias is applied to the film formation target via the support portion, After the raw material gas was introduced into the reaction vessel from the first supply pipe via the first valve, the first valve was closed to set the inside of the reaction vessel as the first pressure. After the reaction gas was introduced into the reaction vessel from the second supply pipe via the second valve at a second pressure higher than the first pressure, the second valve was closed.
  • the present invention relates to a film forming method in which carbon ions generated by the reaction of the raw material gas and the reaction gas are attracted to the film forming target by the negative bias to deposit a DLC film on the film forming target.
  • the other method of the present invention can be suitably carried out by the film forming apparatus which is one aspect of the present invention, and can exhibit the same action and effect as one aspect of the present invention.
  • the timing of starting the rotation of the support portion and the start of applying the negative bias may be before or after the introduction of the raw material gas.
  • FIG. 1 shows a film-forming device according to an embodiment.
  • the film forming apparatus 10 has, for example, a reaction vessel 20 made of quartz.
  • the reaction vessel 20 has a raw material gas introduction port 30, a reaction gas introduction port 40, and an exhaust port 50.
  • a support portion 60 for placing and supporting the film-forming object 1 is provided inside and outside the reaction vessel 20.
  • a rotating portion, for example, a motor 70 that rotates the support portion 60 is provided outside the reaction vessel 20.
  • a DC power source 80 that applies a negative bias to the film forming object 1 via the support portion 60 is provided outside the reaction vessel 20.
  • the first supply pipe 100 is connected to the raw material gas introduction port 30.
  • the first valve 120 When the first valve 120 is in the open state, the first supply pipe 100 supplies the raw material gas at the flow rate controlled by the flow rate controller 130 from the raw material gas container 110 to the raw material gas introduction port 30.
  • a second supply pipe 200 is connected to the reaction gas introduction port 40.
  • the second supply pipe 200 is provided with a reaction gas activator 210 and a second valve 230.
  • the reaction gas container 220 supplies the reaction gas to the reaction gas activator 210.
  • the reaction gas activated by the reaction gas activating device 210 is supplied to the reaction gas introduction port 40 by the second supply pipe 200 via the second valve 230.
  • the source gas is a hydrocarbon, such as CH 4 , C 2 H 2 , or C 2 H 4 .
  • the activated reaction gas is an H radical (H * ). It is possible to react a hydrocarbon with an H radical (H * ) to extract hydrogen in the hydrocarbon at room temperature level to generate carbon ions. A carbon ion is attracted to the film forming target 1 to which a negative bias is applied to form a DLC film.
  • An exhaust pipe 300 is connected to the exhaust port 50.
  • the exhaust pipe 300 is provided with an exhaust pump 310 and an exhaust valve 320.
  • the control unit 400 controls the film formation operation of the DLC film, and can control the valves 120, 230, 320, the motor 70, the DC power supply 80, the high frequency power supply 212, and the exhaust pump 310.
  • FIG. 2 shows an example of the reaction gas container 220 and the reaction gas activator 210.
  • the reaction gas is, for example, water vapor H 2 O, which activates water vapor to generate H radicals (H *).
  • the reaction gas container 220 includes a humidifier 240 in which water 2 is stored and an inert gas container 250.
  • an inert gas such as argon Ar from the inert gas container 250 is introduced through the pipe 260.
  • the water 2 bubbled by the argon Ar becomes steam gas and is supplied to the second supply pipe 200.
  • an induction coil 270 is provided around the second supply pipe 200 made of quartz.
  • the high frequency power supply 212 shown in FIG. 1 is connected to the induction coil 270.
  • the electromagnetic energy applied by the induction coil 270 is 20 W and the frequency is 13.56 MHz.
  • the induction coil 270 generates inductively coupled plasma 3 of the reaction gas in the second supply pipe 200.
  • Ar + H 2 O ⁇ Ar * + OH * + H * , and H radicals (H * ) can be generated.
  • the reaction gas container 220 of FIG. 1 may contain, for example, HF as the reaction gas.
  • HF is activated by the reaction gas activating device 210
  • HF ⁇ H * + H + + F * + F ⁇ and H radicals (H * ) can be generated.
  • H * H radicals
  • an additive gas may be added to the raw material gas and / or the reaction gas. Therefore, as shown in FIG. 3, the additive gas container 140 and the flow rate controller 150 may be connected to the first supply pipe 100. In addition to or instead of this, the additive gas container 280 may be connected to the reaction gas activator 210, as shown in FIG.
  • the DLC film formed can be made water-repellent (hydrophobic) by the additive gas added to the raw material gas and / or the reaction gas.
  • HF or HCl can be mentioned as the additive gas for water repellency contained in the additive gas container 140.
  • Examples of the additive gas for water repellency contained in the additive gas container 280 include fluorocarbon CxFy, for example, CF 4 , C 2 F 6 or C 3 F 8 .
  • the DLC film formed can be made hydrophilic by the additive gas added to the raw material gas and / or the reaction gas.
  • the DLC film can have hydrophilicity by forming highly hydrophilic functional groups (OH, CHO, COOH, etc.) on the surface of the DLC film.
  • H 2 O can be mentioned.
  • Examples of the hydrophilic additive gas contained in the additive gas container 280 include O 2 and O 3 that generate active oxygen.
  • FIG. 5 is a timing chart showing a DLC film forming method.
  • valves 120, 230 and 320 are closed.
  • the first valve 120 is opened, and the raw material gas from the raw material gas container 110 is supplied to the reaction vessel 20 via the first supply pipe 100 and the first valve 120.
  • P1 be the first pressure in the reaction vessel 20 when the first valve 120 is closed at time t2.
  • the second valve 230 is opened, and the reaction gas containing hydrogen radicals activated by the reaction gas activator 210 is passed through the second supply pipe 200 and the second valve 230 to the reaction vessel. It is supplied to 20.
  • the reaction gas activated by the reaction gas activating device 210 needs a pressure at which plasma can be generated.
  • the second pressure P2 capable of generating plasma in the reaction gas activator 210 is, for example, 5 to 15 Pa.
  • the first pressure P1 in the reaction vessel 20 is set to P1 ⁇ P2, for example, when the second pressure P2 is 10 Pa, the first pressure P1 is set to, for example, about 1 Pa, which is preferably an order of magnitude lower.
  • the raw material gas does not flow back toward the second supply pipe 200 via the second valve 230.
  • the raw material gas and the reaction gas do not react in the second supply pipe 200 and the reaction gas activating device 210.
  • the raw material gas reacts with hydrogen radicals in the reaction vessel 20 to generate carbon ions, so that the DLC film is started to be formed on the film formation target 1. Therefore, at least before the time t3 when the second valve 230 is opened, for example, at time t2, the motor 70 is rotated, and the DC power supply 80 applies a negative bias to the film forming target 1. In this way, carbon ions are attracted to the rotated film forming object 1 by the negative bias, and the DLC film is formed on the film forming object 1.
  • This film forming operation is continued until the time t5 when the exhaust valve 320 is opened and the inside of the reaction vessel 20 is exhausted by the exhaust pump 310. At time t6 after time t5, the motor 70 and the DC power supply 80 are turned off. At the time t7 when the exhaust is finished, the film formation operation of the DLC film is finished.
  • the hydrogen radical generated by activating the reaction gas by inductively coupled plasma can extract hydrogen in the hydrocarbon which is the raw material gas in the reaction vessel 20 at the room temperature level to generate carbon ions. it can. Therefore, the DLC film can be deposited at the room temperature level without forcibly heating the film-forming object. This point is superior to the RF plasma CVD method in which the film formation target must be heated to 250 ° C. or higher.
  • the film-forming object 1 is not a substrate but a three-dimensional structure, particularly a structure having an uneven film-forming surface, it is difficult to uniformly heat the film. It is also suitable for film formation.
  • a film-forming object having a DLC film is used for various purposes.
  • the surface of the film-forming object 1 can be made hydrophilic or water-repellent by using the additive gas shown in FIGS. 3 and / or 4.
  • the ratio of the diamond bond and the graphite bond in the DLC film can be changed according to the application of the film forming target 1. For example, increasing the absolute value of the negative bias applied by the DC power supply 80 increases the diamond bond contained in the DLC film, and decreasing the absolute value increases the graphite bond contained in the DLC film. it can.
  • increasing the power of the high frequency power supply 212 can increase the diamond bond contained in the DLC film, and decreasing the power can increase the graphite bond contained in the DLC film. This point is superior to Patent Document 1 in which the ratio is controlled by the addition / non-addition of CO gas.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un appareil de formation de film (10) comprenant : un récipient de réaction (20) ; une partie de support (60) pour supporter un film (1) à former dans le récipient de réaction ; une partie rotative (70) pour faire tourner la partie de support ; un premier tuyau d'alimentation (100) pour fournir un gaz de matière première contenant des hydrocarbures au récipient de réaction par l'intermédiaire d'une première vanne (130) ; un second tuyau d'alimentation (200) pour fournir, par l'intermédiaire d'une seconde vanne (230), un gaz de réaction comprenant des radicaux d'hydrogène activés par un plasma à couplage inductif, dans le récipient de réaction rempli du gaz de matière première, sous une pression supérieure à la pression interne du récipient de réaction ; et une source d'alimentation en courant continu (80) pour l'application, à travers la partie de support, d'une polarisation négative sur le film à former, les ions carbone générés par la réaction entre le gaz de matière première et le gaz de réaction étant attirés, par la polarisation négative, vers le film à former, et le film DLC étant déposé sur le film à former.
PCT/JP2020/041015 2019-11-06 2020-11-02 Appareil de formation de film et procédé de formation de film pour film dlc WO2021090793A1 (fr)

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JP2019-201442 2019-11-06
JP2019201442 2019-11-06

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5935092A (ja) * 1982-08-23 1984-02-25 Sumitomo Electric Ind Ltd ダイヤモンドの気相合成法
JPS61189634A (ja) * 1985-02-19 1986-08-23 Canon Inc 堆積膜形成法
JPS6425984A (en) * 1987-03-23 1989-01-27 Canon Kk Formation of deposited film
JPH04318173A (ja) * 1991-04-17 1992-11-09 Ishikawajima Harima Heavy Ind Co Ltd 反応ガス前処理ｃｖｄ法
JP2010531931A (ja) * 2007-06-28 2010-09-30 サブ−ワン テクノロジー， インコーポレイテッド ダイアモンドイド前駆体を用いた内面へのダイアモンド状炭素被膜の作製方法
JP2013102200A (ja) * 2007-04-02 2013-05-23 Hitachi Kokusai Electric Inc 基板処理装置、基板処理方法及び半導体装置の製造方法
JP2014053130A (ja) * 2012-09-06 2014-03-20 Nariyasu Machida 電気デバイス
JP2014517499A (ja) * 2011-04-07 2014-07-17 ピコサン オーワイ プラズマ源による原子層堆積
JP2018199319A (ja) * 2017-05-29 2018-12-20 株式会社都ローラー工業 Ｃｄ又は／及びｄｌｃ固着基材とそれら基材を使用した製品

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5935092A (ja) * 1982-08-23 1984-02-25 Sumitomo Electric Ind Ltd ダイヤモンドの気相合成法
JPS61189634A (ja) * 1985-02-19 1986-08-23 Canon Inc 堆積膜形成法
JPS6425984A (en) * 1987-03-23 1989-01-27 Canon Kk Formation of deposited film
JPH04318173A (ja) * 1991-04-17 1992-11-09 Ishikawajima Harima Heavy Ind Co Ltd 反応ガス前処理ｃｖｄ法
JP2013102200A (ja) * 2007-04-02 2013-05-23 Hitachi Kokusai Electric Inc 基板処理装置、基板処理方法及び半導体装置の製造方法
JP2010531931A (ja) * 2007-06-28 2010-09-30 サブ−ワン テクノロジー， インコーポレイテッド ダイアモンドイド前駆体を用いた内面へのダイアモンド状炭素被膜の作製方法
JP2014517499A (ja) * 2011-04-07 2014-07-17 ピコサン オーワイ プラズマ源による原子層堆積
JP2014053130A (ja) * 2012-09-06 2014-03-20 Nariyasu Machida 電気デバイス
JP2018199319A (ja) * 2017-05-29 2018-12-20 株式会社都ローラー工業 Ｃｄ又は／及びｄｌｃ固着基材とそれら基材を使用した製品

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