CN1157641A - 金刚相碳管及其化学气相沉积制造方法 - Google Patents

金刚相碳管及其化学气相沉积制造方法 Download PDF

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CN1157641A
CN1157641A CN95194966A CN95194966A CN1157641A CN 1157641 A CN1157641 A CN 1157641A CN 95194966 A CN95194966 A CN 95194966A CN 95194966 A CN95194966 A CN 95194966A CN 1157641 A CN1157641 A CN 1157641A
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buddha
warrior attendant
elongated
taenidium
diamond
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CN1049018C (zh
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P·G·帕特里奇
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Qinetiq Ltd
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Mitsubishi Heavy Industries Ltd
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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
    • 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
    • C23C16/271—Diamond only using hot filaments
    • 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
    • C23C16/44—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 method of coating
    • C23C16/4418—Methods for making free-standing articles

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  • Chemical & Material Sciences (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)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

一种采用化学气相沉积(CVD)技术使金刚生长以制造空心金刚管的方法。将合适的基材，典型的是丝材，如具有金刚核晶中心的钨、钼、铜或硅的丝材制成螺旋丝，然后将螺旋丝置于或通过CVD室，让金刚沉积在螺旋丝上。设定合适的螺旋丝间距和直径使金刚沉积在螺旋丝上，直至金刚的生长表面熔融，形成空心的金刚管。

Description

金刚相碳管及其化学气相沉积制造方法
本发明所涉及的是细长基材的镀金刚相碳膜方法，采用的是化学气相沉积技术。本发明
特别涉及采用化学气相沉积技术来制造具有金刚相碳内外壁的空心管(空心金刚管〕。
金刚相碳(以下简称金刚〕的化学气相沉积是金刚在基材上沉积或生长，从气态的母体物质开始沉积。金刚化学气相生长领域的早期研究工作重点是让很薄的薄膜在平面的基材上生长。后来的研究已进展到在非平面基材上的镀膜(参见PW May et al，Proc 3rd Int Symp DiamondMeter，Honolulu 1993，Proceedings Volume PV93-17，ed.J P Dismukesand KV Ravi(Electrochem Soc Pennington，NJ)，P1036)。该领域的进展包括制造金刚镀膜的金属丝(如，CU、Ti和W)和空心金刚管的成型，其方法是在成型后接着就用腐蚀法除去丝状基材。但是，由于腐蚀长丝的困难，通过腐蚀法来制造长空心管的工作严重受阻。
用金刚在SiC丝上和陶瓷丝上镀模的工作也是大家所熟知的(分别参见PW May et al ibid and，PW May et al，Journal of Materialsscience Letters，13，P247-249，1994)。
这类丝材适于掺进要求其为基本上不传导的复合材料中。
按照本发明，在其表面经过处理以便形成金刚核晶中心的细长基材上镀金刚膜的方法包括如下步骤：
1.将细长的材料缠绕成基本上的螺旋几何形，其中，螺旋丝的间距小于螺旋丝的直径。
2.通过化学气相沉积法使金刚沉积在细长的基材上，将它包住，使沉积在螺旋丝邻近的缝隙中的金刚的生长表面熔融，使螺旋丝的缝隙闭合，形成空心金刚管。
适用的细长材料是那些预成型后能保持螺旋几何形的材料。典型的材料是W、Cu、Mo和Si等金属，众所周知，这类金属材料在金刚化学气相沉积室的气态环境中基本上是不会起反应的。但是，其它材料，如，能与金刚化学气相沉积气体的母体起反应的金属(例如，钢)也适用于金刚化学沉积法，其方法是，在进行预处理使其形成核晶中心之前，在反应性材料表面沉积一层抑制阻隔层。选用合适的细长材料将会使这种材料在空心金刚管内起到增强构件的作用。
虽然采用燃烧炬法的常压CVD工艺〔例如，等离子弧喷嘴和氧乙炔炬)可以和合适的基材温度调节装置一起使用，以防止基材的加热温度超过1000℃，但在压力低于40Torr的真空室中进行的化学气相沉积法仍然是优选的方法。
在CVD室中对细长材料进行镀膜过程中，重要的是，材料要均匀地浸没在反应气体中。典型的作法是在一个长丝反应器中完成上述镀模，该长丝要垂直放置，并将细长材料与长丝平行地挂起来(或让细长材料平行地通过长丝反应器，以便进行连续处理〕，细长材料与长丝之间的距离约为5×10-6m。在这种设备中，对于尺寸[与材料细长轴(丝状材料的径向轴)成正交的轴尺寸]小于200×10-6m的材料来说，很容易得到均匀的金刚沉积物。尺寸大于200×10-6m的材料会出现阴影效应，若将该材料置于该设备的长丝盘管内，就可克服这种效应。
在材料表面形成核晶中心的典型方法包括：用金刚砂那样的磨料来研磨，或将细长材料通过粒度为1-3×10-6m的金刚砂浆液。将热的钨丝从一个金刚模头中拉过来制造钨丝则可使其内部形成核晶中心。
为了按照本发明的详细实施方案来制造独立的(free standing)金刚管，要成型的细长材料必须有足够大的间距，以便在沉积的金刚生长表面“熔融”之前能均匀地沉积在细长材料的整个表面上。因此，在采用如下所述螺旋几何形细长材料时，按照本发明的方法所沉积的金刚将会均匀地在细长材料的任何特殊部位生长，使螺旋丝的间距逐渐缩小。当沉积金刚连续生长的时间足够长，螺旋丝间距的平面上每个生长面都紧接在一起，致使金刚表面熔融时，螺旋丝的间距就会闭合。
金属丝状细长材料的螺旋间距大于丝直径的两倍，这是典型的。如果螺旋丝间距比上述标准小，管的内壁上将会有部分裸露的细长材料。在制造本发明的空心金刚管时，细长材料的间距也需要小于细长材料的螺旋丝直径。这就可以确保制造出来的是空心管而不是封闭管。按照本发明实施方案制造的空心金刚管的具体内外径和壁厚将取决于细长螺旋丝的间距，对于本领域的普通技术人员来说，这是显而易见的。用这种方法制造独立空心金刚管时，不需要象现有技术所描述的那样用腐蚀方法除去其中的基料，其优点是在金刚管内起到增强作用，对本领域的技术人员来说，这也是显而易见的。
本领域的技术人员也将清楚，本发明的管子可用作导热性能良好的轻质结构组件，或选择用来为小型装置传送冷却剂。
现在仅举例对本发明进行描述。
将经适当预处理的细长丝材，例如钨，缠在一个坚固的圆柱形成卷模子上。适合的成卷模子包括另一段钨丝或一段的SiC纤维。适合的成卷模子直径为10至200×10-6m。缠绕细长材料以后，缠绕细长材料的脱模方法能使制得的盘丝很容易从模子上脱下来。
将螺旋丝状细长材料排列在标准的热长丝反应器中，通过化学气相沉积法使金刚沉积。在静态的细长材料镀膜时，CVD室中排列的材料必须垃紧和固定好。在排列细长材料时，借重力拉紧或挂上弹簧就可作到这点。
CVD室通常是适合于在几十托下操作的真空室。除加热外的其它活化形式包括：放电、射频、或微波等离子体、聚焦激光束和燃烧法。典型的气体混合物包括含过量氢的烃类。适用烃类的例子包括，如甲烷、丙酮、乙炔和乙醇，常用的烃/氢比约为1％∶99％。为了提高生长速率还可任选地加入其它气体。适用的添加气包括氧或CF4。按照这种标准的化学气相沉积法，也可以往气体混合物中添加BCl3，以便涂布(p-doping)生长的金刚。
将细长材料加热至适当温度，典型的是700℃以上。通常是由一个独立的加热器单元来加热或由一种气体活化源〔例如，等离子体或热丝的辐射热〕来加热。
生长速率会随热的输入量而变化。典型的生长速率约为1-4×10- 6m/hr，但据引证，用100KW微波系统，可使生长速率达50-100×10-6m/hr。生长速率还将取决于具体采用CVD方法时的许多其它因素，这将是本领域技术人员显而易见的。但是，如果真空室的压力为20Torr，氢气流速为200sccm，甲烷流速为2sccm，钽丝加热至约2000℃，钨丝加热至约900℃，热丝与细长材料之间的典型间距保持为5×10-6m，生长速率就可达1×10-6m/hr。

Claims (6)

1.一种细长基材的金刚镀膜方法，该基材的表面经预处理以形成金刚核晶中心，该方法包括如下步骤：
(i)将细长材料缠绕成基本上的螺旋几何形，其中，螺旋丝的间距小于螺旋丝的直径，和
(ii)通过化学气相沉积法使金刚沉积在细长的基材上，包裹住该细长基材，让沉积在邻近的螺旋丝缝隙中的金刚的生长表面熔融，以便使螺旋丝的缝隙闭合，形成空心的金刚管。
2.权利要求1的方法，其中，该细长材料选自钨、铜、钼和硅。
3.权利要求1的方法，其中，细长材料能与金刚化学气相沉积的母体物质起反应，在其外表沉积有一层抑制阻隔层。
4.按照权利要求1-3中的任一方法，其中，该细长材料是具有基本上圆形横断面的金属丝。
5.权利要求4的方法，其中螺旋丝的间距大于金属丝的直径的两倍。
6.根据权利要求1的方法生产的空心金刚管。
CN95194966A 1994-07-18 1995-07-17 金刚石相碳管及其化学气相沉积制造方法 Expired - Fee Related CN1049018C (zh)

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GB9414444A GB9414444D0 (en) 1994-07-18 1994-07-18 Cvd diamond coating of elongate substrate material
GB9414444.1 1994-07-18

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US6413681B1 (en) * 1997-05-21 2002-07-02 Shin-Etsu Chemical Co., Ltd. Diamond film for x-ray lithography and making method
JP3933058B2 (ja) * 2002-02-25 2007-06-20 日立化成工業株式会社 マイクロ流体システム用支持ユニット及びその製造方法
CN1320157C (zh) * 2003-12-06 2007-06-06 厦门大学 集硅片加热沉积于一体的化学气相沉积方法
KR100927288B1 (ko) * 2004-02-18 2009-11-18 히다치 가세고교 가부시끼가이샤 마이크로 유체시스템용 지지유닛
US8480970B2 (en) * 2004-11-30 2013-07-09 Hitachi Chemical Co., Ltd. Analytical pretreatment device
CN101072635A (zh) * 2004-12-09 2007-11-14 日立化成工业株式会社 微流体系统用支持单元及其制造方法
US7462087B2 (en) * 2005-10-31 2008-12-09 Hewlett-Packard Development Company, L.P. Display device
JP5483228B2 (ja) * 2008-10-20 2014-05-07 学校法人東京理科大学 導電性ダイヤモンド中空ファイバー膜及び導電性ダイヤモンド中空ファイバー膜の製造方法
KR101829907B1 (ko) 2011-09-02 2018-02-19 엘에스전선 주식회사 탄소 동소체로 코팅된 선재를 포함하는 본딩 와이어
WO2015192872A1 (en) * 2014-06-16 2015-12-23 European Space Agency Methods for production of alloy wires and shaped alloy components from mixed metal halides
CN117071061B (zh) * 2023-08-28 2024-04-19 北京左文科技有限公司 一种空心金刚石晶体的制备方法

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GB342648A (en) * 1929-09-26 1931-01-26 Philips Nv Improvements in or relating to the manufacture of tubes of highly refractory material
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US5096736A (en) * 1990-08-07 1992-03-17 General Electric Company Cvd diamond for coating twist drills
JPH04168264A (ja) * 1990-11-01 1992-06-16 Vacuum Metallurgical Co Ltd 金属材料の弾性限度制御方法およびこの方法によって製造されたバネ材
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GB9700456D0 (en) 1997-02-26
EP0772699B1 (en) 1998-09-30
MY131786A (en) 2007-08-30
DE69505135T2 (de) 1999-02-18
DE69505135D1 (de) 1998-11-05
US5798143A (en) 1998-08-25
KR970704906A (ko) 1997-09-06
JP3803373B2 (ja) 2006-08-02
JPH10502971A (ja) 1998-03-17
CN1049018C (zh) 2000-02-02
GB9414444D0 (en) 1994-09-07
WO1996002685A1 (en) 1996-02-01
GB2304737B (en) 1997-09-03
EP0772699A1 (en) 1997-05-14
GB2304737A (en) 1997-03-26

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