TW444067B - Process for preparing aligned carbon nanotubes and metal nanolines in the nanotubes - Google Patents

Process for preparing aligned carbon nanotubes and metal nanolines in the nanotubes Download PDF

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TW444067B
TW444067B TW88109351A TW88109351A TW444067B TW 444067 B TW444067 B TW 444067B TW 88109351 A TW88109351 A TW 88109351A TW 88109351 A TW88109351 A TW 88109351A TW 444067 B TW444067 B TW 444067B
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substrate
metal
carbon
nano
patent application
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TW88109351A
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Chinese (zh)
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Han-Jang Shr
Shang-Hua Tsai
Jr-Wei Jau
Jau-Lin Li
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Shr Han Jang
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Abstract

The present invention provides a process for preparing aligned carbon nanotubes and metal nanolines in the nanotubes. The process includes subjecting a metal-coated or metal compound-coated substrate to chemical vapor deposition with a carbon-containing reaction gas in a microwave plasma enhanced system, so as to form a plurality of carbon nanotubes on the substrate and metal nanolines in the carbon nanotubes. The carbon nanotubes are perpendicular to the substrate and are parallel to each other.

Description

4 44067 五 '發明說明α) 本發明係 管及其内之奈 化學氣相沈積 内之奈米金屬 氣相沈積法來 線,亦是首次 破管。 破基村料 示器、電子儀 化鑽石膜、以 等,都被報導 果0 有關於一種製造具有 米金屬線的方法,特 法來製造具有垂畜排 線的方法。本發明是 製造與基板垂直排列 在微波電漿化學氣相 具有場發射電子特性 盗專專。而 地1碳 艴處理過的鑽石、非 可在相當低的電場下 垂直排列特性的奈米碳 別有關於使用微波電漿 列特性的奈米碳管及其 首次利用微波電漿化學 的奈米碳管、奈米金屬 沈積中同時成長與触刻 ’可應用於平板狀的顯 基材料’諸如鑽石、氮 晶質碳以及奈米碳管 ’產生電子場發射的效 1 9 9 1年,藉著高電流電弧法(大約丨〇 〇 Α與2 〇 ν ),並 以石墨為電極,奈米碳管首次被成功地合成出來。它們是 由一層或^層的片狀石墨以同心圓的方式捲曲所構成,而 且通常在管子的兩端是封口的◦見NATURE," Hel ical4 44067 V. Description of the invention α) The tube of the present invention and its nano-chemical vapor deposition The nano-metal vapor phase deposition method is also the first time that the tube is broken. Broken village indicators, electronic instrumented diamond membranes, etc. have all been reported. 0 is related to a method of manufacturing a wire with a meter, and a method of manufacturing a wire with a vertical barn. The invention is a pirate specializing in manufacturing a vertical arrangement with a substrate in a microwave plasma chemical vapor phase and having field emission electron characteristics. The ground carbon is a diamond treated with carbon, and the nano-carbon that can not be arranged vertically under a relatively low electric field. The carbon nanotubes that use microwave plasma characteristics and the first time that they use microwave plasma chemistry are nano-carbons. Simultaneous growth and engraving in the deposition of carbon tubes and nanometer metals' Applicable to flat-shaped display substrates' such as diamond, nitrogen crystalline carbon and nanometer carbon tubes' generating electron field emission effects 1 1991 With the high current arc method (approximately 〇〇Α and 〇ν), and graphite as an electrode, nano carbon tubes were successfully synthesized for the first time. They are made up of one or more layers of flake graphite rolled in concentric circles, and are usually sealed at both ends of the tube. See NATURE, " Hel ical

Microtubules of Graphitic Carbon", Iijima, S.,Microtubules of Graphitic Carbon ", Iijima, S.,

Vol_ 354,pp· 56-58,Nov. 7, i991.的報導。它們的 直徑通常是數十埃,同時長度大約為幾微米(从m)。由於 它們的奈米級構造,以及高長/寬比,所以奈米碳管提供 了一個可應用在場發射源上的全新構造。同時相較於傳統 的塊材而s ’其具有更加優良電子場發射的特性。 在以利用電弧放電的方法製備奈米碳管時,要如何去 控制它們的大小以及排列方向,仍然是一個未解的習題。Report of Vol. 354, pp. 56-58, Nov. 7, i991. Their diameter is usually tens of angstroms and their length is about a few microns (from m). Due to their nanoscale construction and high aspect ratio, the carbon nanotubes provide a completely new construction that can be applied to field emission sources. At the same time, s' has more excellent electron field emission characteristics compared to traditional bulk materials. How to control the size and arrangement of carbon nanotubes by arc discharge is still an unsolved problem.

第4頁 五、發明說明(2) 而這個問題嚴重地阻礙了研究奈米碳管的特性與應用的進 展。然而’有一些將合成好的粉末狀奈米碳管,再經由另 一製程步驟,以得到具有排列特性之奈米碳管的報導,也 曾經陸續的被發表。笫一個方法被描述在SCIENCE, "Aligned Carbon Nanotube Films: Production and Optical and Electronic Properties1',de Heer et al.,Vol. 268,May 12,1995.之中。將含有粉末狀奈 米碳管(10 ± 5 nra寬,1-5 //m長)的ethanol溶液,通 過具有0. 2 # m大小孔洞的陶瓷片過濾,然後將在陶瓷片 上的黑色沈積物,轉移到一個塑膠的表面。如此一來,便 可獲得一片具有垂直排列奈米碳管的黑色膜。 而最近幾年的發展方向是利用化學氣相沈積法來製造 與基板垂直的奈米碳管,其中一種方法是熱分解化學氣相 沈積法在見SCIENCE, "Large-Scale Synthesis of Aligned Carbon Nanotubes", Li et a 1. , Vo 1. 274,Page 4 V. Description of the invention (2) This problem seriously hinders the progress of studying the characteristics and applications of carbon nanotubes. However, there have been reports that some synthesized carbon nanotubes in powder form are subjected to another process step to obtain aligned carbon nanotubes.笫 A method is described in Science, " Aligned Carbon Nanotube Films: Production and Optical and Electronic Properties 1 ', de Heer et al., Vol. 268, May 12, 1995 .. The ethanol solution containing powdery carbon nanotubes (10 ± 5 nra wide, 1-5 // m long) was filtered through a ceramic sheet with holes of 0.2 # m size, and the black deposits on the ceramic sheet were then filtered And transferred to a plastic surface. In this way, a black film with vertically aligned carbon nanotubes can be obtained. In recent years, the development direction is to use chemical vapor deposition to produce nano carbon tubes perpendicular to the substrate. One method is thermal decomposition chemical vapor deposition. See Science, " Large-Scale Synthesis of Aligned Carbon Nanotubes ", Li et a 1., Vo 1. 274,

Dec. 6, 1996 'APPLIED PHYSICS LETTERS, "EpitaxialDec. 6, 1996 'APPLIED PHYSICS LETTERS, " Epitaxial

Carbon Nanotube Film Se1f-Organ i zed by Sublimation Decomposition of Silicon Carbide1’, Kusunoki et al., Vol. 71, No. 18, Nov. 3, 1997與SCIENCE,Carbon Nanotube Film Se1f-Organ i zed by Sublimation Decomposition of Silicon Carbide1 ’, Kusunoki et al., Vol. 71, No. 18, Nov. 3, 1997 and Science,

Self-Oriented Regular Arrays of Carbon Nano tubes and Their Field Emission Properties", Fan et a 1., Vol. 283,Jan. 22,1 999。然而上面的主要缺點是製程 溫度過高,都在700 °C以上,甚至高達1700 °C,因而不適 合於目前的半導體製程。Self-Oriented Regular Arrays of Carbon Nano tubes and Their Field Emission Properties ", Fan et a 1., Vol. 283, Jan. 22, 1 999. However, the main disadvantage of the above is that the process temperature is too high, all above 700 ° C, and even as high as 1700 ° C, so it is not suitable for the current semiconductor process.

第5頁 444 Ο 6 7 五、發明說明(3) 另一大類的化學氣相沈積法是利用電漿輔助化學氣相 沈積法’優點是製程溫度比熱分解化學氣相沈積法低。目 前文獻上被報導出來有兩種方法,一是電漿辅助熱燈絲化 學氣相沈積法,見Science,"Synthesis of Large Arrays of Well-Aligned Carbon Nanotubes on Glass", Ren et a 1. , Vo 1. 282, Nov. 6, 1998。另一種是電子迴 旋共振微波電漿化學氣相沈積法,見APPLIED PHYSICS LETTERS, "Well-Aligned Carbon Nitride Nanotubes Synthesized in Anodic Alumina by Electron Cyclotron Resonance Chemical Vapor Deposition", Sung et al., Vol. 74, No. 2, Jan. 11, 1999 。 目前以化學氣相沈積法來製造奈米碳管的技術中,均 需要觸媒來引發成核與成長,而且基板的選用也是一個重 點15目前成長垂直於基板之奈米碳管所用的基板有用鎳箔 (見APPLIED PHYSICS LETTERS, "Growth of Highly Oriented Carbon Nanotubes by Plasma-enhanced Hot Filament Chemical Vapor Deposition",Huang et a 1., Vol. 73,No. 26,Dec. 28,1998)、利用濺鍍法將鎳鍍 在玻璃基板(見SCIENCE, "Synthesis of Large Arrays of Well-Aligned Carbon Nanotubes on Glass", Ren et al·,Vol. 282,Nov. 6,1 998)、利用蒸鍍法將鐵鍍在陽 極處理過後的矽晶片上(見SCIENCE, 11 Sel f-Oriented Regular Arrays of Carbon Nanotubes and Their Field Emission Properties", Fan et al., Vol. 283, Jan.Page 5 444 〇 6 7 V. Description of the invention (3) Another type of chemical vapor deposition method is the use of plasma-assisted chemical vapor deposition method. The advantage is that the process temperature is lower than the thermal decomposition chemical vapor deposition method. At present, two methods have been reported in the literature, one is plasma-assisted thermal filament chemical vapor deposition, see Science, " Synthesis of Large Arrays of Well-Aligned Carbon Nanotubes on Glass ", Ren et a 1., Vo 1. 282, Nov. 6, 1998. The other is electron cyclotron resonance microwave plasma chemical vapor deposition method, see APPLIED PHYSICS LETTERS, " Well-Aligned Carbon Nitride Nanotubes Synthesized in Anodic Alumina by Electron Cyclotron Resonance Chemical Vapor Deposition ", Sung et al., Vol. 74, No. 2, Jan. 11, 1999. In the current technology of manufacturing carbon nanotubes by chemical vapor deposition, catalysts are required to induce nucleation and growth, and the selection of substrates is also an important point. 15 The substrates currently used for growing carbon nanotubes perpendicular to the substrates are useful Nickel foil (see APPLIED PHYSICS LETTERS, " Growth of Highly Oriented Carbon Nanotubes by Plasma-enhanced Hot Filament Chemical Vapor Deposition ", Huang et a 1., Vol. 73, No. 26, Dec. 28, 1998), using sputtering Plating nickel on a glass substrate (see Science, " Synthesis of Large Arrays of Well-Aligned Carbon Nanotubes on Glass ", Ren et al., Vol. 282, Nov. 6, 1 998), Iron is plated on the anodized silicon wafers (see Science, 11 Sel f-Oriented Regular Arrays of Carbon Nanotubes and Their Field Emission Properties ", Fan et al., Vol. 283, Jan.

第6頁 4· 44 Ο 6 7 五、發明說明(4) 22, 1999)、利用溶膠一凝膠的方法,把鐵的奈米顆粒鑲 埋在中孔洞二氧化矽作為基板(見SCIENCE,” Large_ScalePage 4 · 44 Ο 6 7 V. Explanation of the invention (4) 22, 1999), using the sol-gel method, iron nano-particles are embedded in the mesoporous silicon dioxide as a substrate (see Science, " Large_Scale

Synthesis of Aligned Carbon Nanotubes1',Li et al., Vol· 274, Dec· 6, 1996)等等。 目前’亦有人研究將金屬包在奈米碳管中,這樣的奈 求構造可作觸媒應用,有應用價值的潛力,見CHEMICAL & ENGINEERING NEWS, "Filled Carbon Nanotubes Could Lead to Improved Catalysts and Biosensors",Synthesis of Aligned Carbon Nanotubes 1 ', Li et al., Vol. 274, Dec. 6, 1996) and so on. At present, some people have also researched to encapsulate metal in carbon nanotubes. Such nanostructures can be used as catalysts and have potential for application. See CHEMICAL & ENGINEERING NEWS, " Filled Carbon Nanotubes Could Lead to Improved Catalysts and Biosensors ",

Michael Freemantle,Vol. 74,July 15,1 9 9 6。此外, 文獻中指出被蝕刻而開口的奈米碳管具有更低的電子場發 射的起始電場,lSCIENCE,"UnravelingNanotubes-Field-Emission from an Atomic Wire", Rinzler et al.,Vol. 269,Sep‘ 15,1 995。 然而,目前尚未有文獻報導利用微波電漿化學氣相沈 積法製造出與基板垂直排列的奈米碳管以及其内之奈米金 屬線。 因此,本發明之目的即為提供一種簡單的方法,可同 時合成出與基板垂直排列的奈米碳管以及包在奈米碳管内 的奈米金屬線,且奈米碳管的頂端被蝕刻而開口。目前尚 未有報導其它製程可同時達成上述的目的。 為達成本發明之目的,本發明製造具有垂直排列特性 的奈米碳管及其内之奈米金屬線的方法包括:在微波電漿 系統中’以表面鍍有金屬或金屬化合物之基板為基材,使 含碳反應氣體進行化學氣相沈積,以在基板上成長複數個Michael Freemantle, Vol. 74, July 15, 1 9 9 6. In addition, it is pointed out in the literature that the carbon nanotubes that are etched and opened have a lower initial electric field emission, lSCIENCE, " UnravelingNanotubes-Field-Emission from an Atomic Wire ", Rinzler et al., Vol. 269, Sep '15, 1 995. However, there are currently no reports in the literature of using a plasma plasma chemical vapor deposition method to fabricate nano-carbon tubes and nano-metal wires arranged perpendicular to the substrate. Therefore, an object of the present invention is to provide a simple method for synthesizing a nano carbon tube arranged perpendicularly to a substrate and a nano metal wire enclosed in the nano carbon tube, and a top end of the nano carbon tube is etched. Opening. No other processes have been reported to achieve the above objectives at the same time. In order to achieve the purpose of the present invention, a method of manufacturing a nano carbon tube having a vertical alignment characteristic and a nano metal wire therein includes: in a microwave plasma system, 'based on a substrate plated with a metal or a metal compound on a surface thereof. Materials, chemical vapor deposition of carbon-containing reactive gases to grow multiple substrates

4.44 0674.44 067

所得之奈米後 五、發明說明(5) ' ,涞碳管以及在奈米碳管内的奈米金屬線 管為垂直於基板,且彼此平行排列。 圖式之簡單說明: 第1圖顯示本發明所使用之MPE_CVD系統。 第2圖顯示本發明奈米碳管成長機制的示咅圖。 第3圖顯示依據本發明實施例1所得之排歹:整齊 妷s之掃描式電子顯微鏡照片,放大倍率為兩萬倍。水 第4圖顯示依據本發明實施例丨所得之單根奈米碳 穿透式電子顯微鏡的照片,放大倍率為八萬倍。 的 第5圖顯示依據本發明實施例2所得之利用旋艘_法製 的基材上所成長之奈米碳管的掃描式電子顯微鏡照片 率為一萬一千倍。 標號說明: 1〜電源供應器,2〜進氣口,3〜冷卻水進水口,4〜壓力 計,5〜出氣口,6~熱電偶,7〜基座,8~試片,9〜導波管, 1 0 -•磁控管。 10〜基板’20~圓球狀的觸媒,3〇、31〜碳管,21〜奈米 金屬線’ 3 2〜頂端被餘刻開口的碳管。 本發明提供一種新穎、簡單的方法,用來同時合成垂 直於基板、且彼此平行排列的奈米碳管以及奈米碳管内之 奈米金屬線。方法是在微波電漿系統(MpE; microwave plasma enhanced system)中,以表面鍍有金屬或金屬化 合物之基板為基材’使含碳反應氣體進行化學氣相沈積 (CVD; chemical vapor deposition),以在基板上成長複After the obtained nanometer 5. Description of the invention (5) ', the carbon tube and the nano metal wire tube in the nano carbon tube are perpendicular to the substrate and arranged parallel to each other. Brief description of the drawings: Figure 1 shows the MPE_CVD system used in the present invention. Fig. 2 is a diagram showing a growth mechanism of a nano carbon tube according to the present invention. Fig. 3 shows a scanning electron microscope photograph of the arrangement of 歹: neat 妷 s obtained according to Example 1 of the present invention, with a magnification of 20,000 times. Water FIG. 4 shows a photograph of a single nano-carbon transmission electron microscope obtained according to Example 丨 of the present invention, with a magnification of 80,000 times. Fig. 5 shows a scanning electron microscope photograph of a nano-type carbon tube grown on a substrate made by a spinner method according to Example 2 of the present invention at a scanning electron microscope at a rate of 11,000 times. Explanation of symbols: 1 ~ power supply, 2 ~ air inlet, 3 ~ cooling water inlet, 4 ~ manometer, 5 ~ air outlet, 6 ~ thermocouple, 7 ~ base, 8 ~ test piece, 9 ~ guide Wave tube, 1 0-• magnetron. 10 to substrate ′ 20 to spherical catalyst, 30, 31 to carbon tube, 21 to nanometer metal wire ′ 3 2 to carbon tube whose tip is left open. The present invention provides a novel and simple method for simultaneously synthesizing nano carbon tubes perpendicular to a substrate and arranged parallel to each other and nano metal wires in the nano carbon tubes. The method is to use a plasma plasma enhanced system (MpE; microwave plasma enhanced system) to chemically vapor-deposit a carbon-containing reaction gas (CVD) using a substrate coated with a metal or a metal compound on the surface as a substrate. Grow on the substrate

第8頁 ί 444 0 6 7 五、發明說明(6) ' ! ----- 數個^米碳管以及在奈米碳管内的奈米金屬線。 直流偏壓為-5 0至 W ,人微Λ,電漿系統的較佳條件:微波功率為100至5剛 。成壓力為ΙχίΟ-3至1〇〇 T〇rr, -1 0 00 V,溫度為30〇 〇c 至1 500 1。 當進行本發明之MPE-CVD法時,除了含碳反應氣體之 外,最好是供應活化氣體,以使鍍在基板上之金屬(作為 觸媒)的表面活化。活化氣體可使用氫氣、氨氣、一氧化 碳、或其混合物。除了含碳反應氣體及活化氣體之外,本 發明MPE-CVD系統中亦可再供應鈍氣,以增加含碳反應氣 體的解離度,使電漿更為活化。鈍氣的例子如氦氣、氖 氣、氬氣、氪氣、和氣氣等。 依據本發明’在微波電漿系統中,奈米碳管及其内之 奈米金屬線的成長示意圖如第2圖所示。在初始時的階 段’表面鍍有金屬或金屬化合物的基板是在還原氣氛下 (活化氣體氣氛下)。基板上的金屬或金屬化合物是作為 成長奈米碳管的觸媒之用,故以下亦稱觸媒。在微波電漿 系統下,活化氣體所產生的電漿會加熱鍍有觸媒的基板, 而使得在基板1 0上的觸媒會形成圓球狀的觸媒2 0,見第 2(a)圖。 此時,再將含碳反應氣體通入反應腔中,此含碳的氣 體在微波的作用下會分解成為離子或自由基,然後在觸媒 的表面吸附與分解而使得碳在觸媒表面沈積並擴散至觸媒 内部。由於基材僅受到電漿的加熱,於是碳易在觸媒與基 材之間析出,如第2(b)圖之標號30、31所示。Page 8 ί 444 0 6 7 V. Description of the invention (6) '! ----- Several ^ m carbon tubes and nano metal wires in the nano carbon tubes. The DC bias voltage is -50 to W, the human micro Λ, the better conditions of the plasma system: the microwave power is 100 to 5 Gang. The forming pressure is from ΙΟΟ to 3 to 100 Torr, -1 to 00 V, and the temperature is from 300 to 1 5001. When carrying out the MPE-CVD method of the present invention, it is preferable to supply an activating gas in addition to the carbon-containing reaction gas to activate the surface of the metal (as a catalyst) plated on the substrate. The activating gas may be hydrogen, ammonia, carbon monoxide, or a mixture thereof. In addition to the carbon-containing reaction gas and the activation gas, a passive gas may be further supplied in the MPE-CVD system of the present invention to increase the dissociation degree of the carbon-containing reaction gas and make the plasma more active. Examples of inert gas are helium, neon, argon, krypton, and gas. In the microwave plasma system according to the present invention, the growth of the nano carbon tube and the nano metal wire therein is shown in FIG. 2. In the initial stage ', the substrate plated with a metal or a metal compound is under a reducing atmosphere (under an activating gas atmosphere). The metal or metal compound on the substrate is used as a catalyst for growing a carbon nanotube, so it is also referred to as a catalyst hereinafter. In a microwave plasma system, the plasma generated by the activating gas will heat the substrate coated with the catalyst, so that the catalyst on the substrate 10 will form a spherical catalyst 20, see section 2 (a). Illustration. At this time, a carbon-containing reaction gas is passed into the reaction chamber. The carbon-containing gas is decomposed into ions or radicals under the action of microwaves, and then adsorbed and decomposed on the surface of the catalyst to cause carbon to be deposited on the surface of the catalyst. And diffused into the catalyst. Since the base material is only heated by the plasma, carbon is easily precipitated between the catalyst and the base material, as shown by reference numerals 30 and 31 in Fig. 2 (b).

4 44 067 五、發明說明(7) 同時’在高濃度的活化氣體電漿下與高的負電壓下, 會造成非等向性的蝕刻奈米碳管,因而使得不垂直於基材 的奈米碳管(如第2(b)圖之碳管31)會被蝕刻而消失,而僅 留下垂直於基材的奈米碳管(如第2(b)圖之碳管30)。 隨著奈米碳管不斷地往上長,因為電流集中於奈米碳 管的頂端’所以在奈米碳管頂端的電場會比基材表面的電 場強。這使得奈米碳管不斷地被加熱,而使位於碳管3 〇頂 部的觸媒20熔化,隨著重力而沈入碳管中,因而形成奈米 金屬線21,見第2(c)、(d)圖。 由於作為觸媒之奈米金屬線2 1陷入碳管3 〇中,含碳源 的離子或自由基無法沈積於觸媒,故此時奈米碳管停止成 長。但此同時’ 一些會蝕刻奈米碳管的離子不斷轟擊奈米 碳管30頂端而最後造成奈米碳管開口,如第2(e)圖所示, 而形成本發明之頂端被餘刻而開口之奈米碳管32及其内之 奈米金屬線21。 依據本發明’鍍在基板上之金屬可為過渡性金屬或其 合金。過渡性金屬例如可為V 11 IB族金屬,具體的例子包 括鈀、鎳、鉑、鈷、及其混合物。鍍在基板上之金屬化合 物為過渡性金屬之化合物’例如過渡性金屬之化合物為過 渡性金屬之矽化物或碳化物,具體的例子如Pd3 S i、碳化 姑(cobalt carbide)、碳化錄(nickei carbide)等。 適用於本發明之基板並沒有特別的限制,只要其上可 鑛上金屬或金屬化合物以作為成長奈米破管的觸媒即可。 多孔性基板可為^夕基板、經陽極處理之;5夕基板、鋁陽極處4 44 067 V. Description of the invention (7) At the same time, under the high concentration of activated gas plasma and high negative voltage, it will cause anisotropic etching of the carbon nanotubes, thus making the carbon nanotubes not perpendicular to the substrate. Rice carbon tubes (such as the carbon tube 31 in FIG. 2 (b)) are etched and disappear, leaving only the carbon nanotubes (such as the carbon tube 30 in FIG. 2 (b)) perpendicular to the substrate. As the carbon nanotubes continue to grow upward, the electric field at the top of the carbon nanotubes is stronger than the electric field on the surface of the substrate because the current is concentrated on the top of the carbon nanotubes. This causes the nano carbon tube to be continuously heated, so that the catalyst 20 located on the top of the carbon tube 30 melts and sinks into the carbon tube with gravity, thereby forming a nano metal wire 21, see section 2 (c), (D) Figure. Since the nano-metal wire 21 as a catalyst is trapped in the carbon tube 30, ions or radicals containing a carbon source cannot be deposited on the catalyst, so the nano-carbon tube stops growing at this time. But at the same time, some ions that would etch the nano carbon tube constantly bombarded the top of the nano carbon tube 30 and finally caused the opening of the nano carbon tube, as shown in FIG. 2 (e). The open carbon nanotube 32 and the nano metal wire 21 therein. The metal plated on the substrate according to the present invention may be a transition metal or an alloy thereof. The transition metal may be, for example, a group V 11 IB metal, and specific examples include palladium, nickel, platinum, cobalt, and mixtures thereof. The metal compound plated on the substrate is a compound of a transition metal. For example, the compound of a transition metal is a silicide or carbide of a transition metal. Specific examples include Pd3 S i, cobalt carbide, and nickei. carbide) and so on. The substrate suitable for the present invention is not particularly limited, as long as a metal or a metal compound can be deposited thereon as a catalyst for growing a nanometer tube. Porous substrates can be substrates and anodized; substrates and aluminum anodes

第10頁 444067 — 五、發明說明(8) ~ ---- 理基板、氡化矽基板、及高分子基板等等。 '表面鍍有金屬或金屬化合物之基板,可使用物理氣相 沈積法、電化學方法、或旋鍍法,以將金屬或金屬化合物 鍍在基板上的。物理氣相沈積法例如濺鍍法或蒸鍍法,電 化學方法可為電鍍法或無電鍍法。 本發明所用之含碳反應氣體可為曱烷、乙烷、丙院、 乙快、苯、及其混合物。 依據本發明方法所得之較佳尺寸為,具有〇 至 300 βπι的長度,;[⑽至3〇〇 nm的直徑,且相鄰兩奈米碳管 之間的距離為1 nm至300 nm。 ^ 以下特舉數個實施例以更詳細說明本發明之方法、特 徵及優點,但並非用以限制本發明,本發明之範圍應以所 附之申請專利範圍為準。 " 實施例1 我們所使用的基材為表面鍍有鈀的多孔矽,製作方法 如下首先’將Boron-doped p-type (100)方向的石夕晶片 (其阻&值為1〇 〇cm)作陽極處理,其電解液為49% HF溶液 與乙醇和去離子水混合,比例為丨:2 : 3。陽極處理的電流 密度為5 _ 66 mA/cm2,時間為1〇分鐘。如此會產生一層厚 約8 0 0 nm具多孔性的矽。然後將鈀金屬無電鍍在多孔矽 上’其方法是將多孔矽浸置在含氯化鈀的溶液中4 〇分鐘, 即有還原的把於多孔妙上。 所使用之MPE-CVD系統如圖一所示,其電漿產生的部 位在基座7上方’磁控管1〇產生頻率為2.45 GHz的微波,Page 10 444067-V. Description of the invention (8) ~ ---- physical substrate, silicon substrate, polymer substrate, etc. 'For a substrate with a metal or metal compound on its surface, physical vapor deposition, electrochemical methods, or spin plating can be used to plate the metal or metal compound on the substrate. The physical vapor deposition method is, for example, a sputtering method or an evaporation method, and the electrochemical method may be a plating method or an electroless plating method. The carbon-containing reaction gas used in the present invention may be oxane, ethane, C-propane, ethane, benzene, and mixtures thereof. The preferred size obtained according to the method of the present invention is that it has a length of 0 to 300 βπ, a diameter of [⑽ to 300 nm, and a distance between two adjacent carbon nanotubes is 1 nm to 300 nm. ^ Several examples are given below to explain the method, features and advantages of the present invention in more detail, but not to limit the present invention. The scope of the present invention shall be based on the scope of the attached patent application. " Example 1 The base material we used was porous silicon plated with palladium on the surface. The manufacturing method was as follows. First, the Shi Xi wafer in the Boron-doped p-type (100) direction (the resistance value was 100). cm) for anodic treatment, and its electrolyte is 49% HF solution mixed with ethanol and deionized water in a ratio of 丨: 2: 3. The anodized current density was 5 66 mA / cm2 and the time was 10 minutes. This produces a layer of porous silicon with a thickness of about 800 nm. Then the palladium metal is electrolessly plated on the porous silicon. The method is to immerse the porous silicon in a solution containing palladium chloride for 40 minutes. The MPE-CVD system used is shown in Fig. 1. The plasma generating part is above the base 7. The magnetron 10 generates microwaves with a frequency of 2.45 GHz.

444 06 7 五、發明說明(9)444 06 7 V. Description of the invention (9)

此微波經由導波管9導入,如此,由進氣口2進入的反應氣 體會被激發,因而產生電漿。直流偏壓是由電源供應^j 所供應而施於試片8上。 B 本實施例中合成的奈来碳管的條件,首先基材在氫氣 的電漿令作處理,以活化把表面。壓力控制在3〇 Torr, 氫氣流量為100 seem,微波功率為1 100 w。經過十分鐘 後’再混入曱烧’總壓力仍維持3 〇 τ 〇 r r,氫氣與甲貌的 流量分別為8 0和0. 4 s c c m。微波功率亦為1 1 〇 〇评。負偏壓 為4 0 0 V,製程時間為2 0分鐘。 、 我們使用掃描式和穿透式電子顯微鏡來觀察所合成之 奈米礙管。第3圖顯示排列整齊的奈米碳管,而很明顯地 在每一根奈米碳管中心填有鈀的金屬而形成奈米鈀金屬 線。第4圖為一根奈米碳管的穿透式電子顯微鏡的照片, 顯示出中間有一條鈀的奈米金屬線,而且從照片上亦可看 到奈米碳管頂端是開口的。 實施例2 使用和實施例1相同的MPE-CVD系統和電漿製程條件, 但改變所使用的基材。基材的製作方法為,利用旋鍍法將 含觸媒的溶液旋鍍在B〇r〇n — d〇ped p-type (1〇〇)方向的石夕 晶片(其阻值為10 Ωαη)上,其條件為:旋轉速率3000 rpm ’旋轉時間為二十秒’共塗佈六次,溶液為5〇毫升的 純酒精(99_ 5%)加上5. 64 克SnCl2_ 2H20 再加上1. 45 克NiCl2. 610。再將旋鍍好的試片放入空氣爐中加熱,温度為6〇〇 C ’使之形成鎳錫的氧化物。如此的試片再放入微波電漿This microwave is introduced through the waveguide 9 so that the reaction gas entering through the air inlet 2 is excited, and a plasma is generated. The DC bias is applied to the test piece 8 by the power supply ^ j. B. The conditions of the synthesized carbon nanotubes in this embodiment are as follows. First, the substrate is treated with a plasma of hydrogen to activate the surface. The pressure was controlled at 30 Torr, the hydrogen flow rate was 100 seem, and the microwave power was 1 100 w. After ten minutes, the total pressure of the 'remixed with sintering' was still maintained at 30 τ τ r r, and the flow rates of hydrogen and formazan were 80 and 0.4 s c cm, respectively. The microwave power was also rated at 1100. The negative bias is 400 V and the process time is 20 minutes. We used scanning and transmission electron microscopes to observe the synthesized nano-tubes. Figure 3 shows the aligned carbon nanotubes, and it is clear that the center of each carbon nanotube is filled with palladium metal to form a nano-palladium metal wire. Figure 4 is a photograph of a transmission electron microscope of a nano carbon tube, showing a nano metal wire with palladium in the middle, and it can be seen from the photo that the top of the nano carbon tube is open. Example 2 The same MPE-CVD system and plasma process conditions were used as in Example 1, but the substrate used was changed. A method for producing a substrate is to spin-coat a catalyst-containing solution on a Shi Xi wafer in the direction of Boron-doped p-type (100) by a spin plating method (the resistance value is 10 Ωαη). The conditions are as follows: a rotation rate of 3000 rpm, a rotation time of twenty seconds, and a total of six coatings, a solution of 50 ml of pure alcohol (99_5%) plus 5.64 g of SnCl2_2H20 plus 1. 45 grams of NiCl2. 610. The spin-coated test piece was placed in an air furnace and heated to a temperature of 600 ° C to form a nickel-tin oxide. Such a test piece is then put into a microwave plasma

第12頁 444067 1、發明說明(ίο) 系統中,以成長垂直於基材的奈米碳管’成長的條件與實 施例1相同’但通入甲炫與氫氣的時間縮短為五分鐘。 第5圖為所得奈米碳管的掃描式電子顯微鏡的照片, 可看出成長的奈米碳管垂直於基材。 μ 由以上兩個實施例中我們可以清楚看到,藉由在 E-CVD系統中加上一個負直流偏壓,具有垂直於基板特 =、且彼此平行排列的奈米碳管,以及在 ::屬而;;可輕易地被:成“。而且,奈米碳“了= x雖IΓ 。*此的製輕大大有利於往後實際的應用。 限定=發==實施例揭露如上,然其並非用以 砷和範圍卜當可作更動=;者田在不脫離本發明之精 當视後附之申請專利範所界:者:此本發明之保護範圍 β屬?準。Page 12 444067 1. Description of the invention (ο) In the system, the conditions for growing a carbon nanotube that is perpendicular to the substrate are the same as those in the embodiment 1, but the time for introducing the Xuan and hydrogen is shortened to five minutes. FIG. 5 is a scanning electron microscope photograph of the obtained carbon nanotube, and it can be seen that the grown carbon nanotube is perpendicular to the substrate. μ From the above two examples, we can clearly see that by adding a negative DC bias to the E-CVD system, there are nano carbon tubes that are perpendicular to the substrate and are parallel to each other, and in: : Belongs to ;; can be easily: into ". And, nano carbon" L = xthough IΓ. * The light weight of this system is greatly beneficial to future practical applications. Restricted = issued = = The embodiment is disclosed as above, but it is not used for arsenic and the scope can be changed =; Zhe Tian is not bound by the scope of the patent application attached to the present invention: What is the scope of protection β? quasi.

Claims (1)

444 0 6 7 棄號 88109351 1.—種製造具有垂直排列特性的奈米碳管及其内之奈 米金屬線的方法,包括在微波電漿系統中,以表面鍍有$ 屬或金屬化合物之基板為基材’使含碳反應氣體進行化學 氣相沈積,以在基板上成長複數個奈米碳管以及在奈米碳 管内的奈米金屬線, π ~ 其中 該奈米後管為垂直於基板,且彼此平行排列, 該鐘在基板上之金屬為過渡性金屬或其合金,以及 該微波電漿合成條件:微波功率為100至5000 W,合 成壓力為lx 1〇_3至100 Torr,直流偏壓為-50至-1000 V,溫度為300 °C 至 1500 °C。 2.如申請專利範圍第1項所述之方法,其中該過渡性 金屬為VIIIB族金屬。 3 ·如申請專利範圍第2項所述之方法,其中該過渡性 金屬為擇自由紅、鎳、鉑、敍、及其混合物所組成之族群 中 〇 4·如申請專利範圍第1項所述之方法,其中該鍍在基 板上之金屬化合物為過渡性金屬之化合物。 5. 如申請專利範圍第4項所述之方法,其中該過渡性 金屬之化合物為過渡性金屬之矽化物或碳化物。 6. 如申請專利範圍第5項所述之方法’其中該過渡性 金屬之化合物為Pd3Si、碳化鈷(c〇balt carbide)、或礙 化鎳(nickel carbide) ° 7. 如申請專利範圍第1項所述之方法’其中該多孔性444 0 6 7 Abandoned number 88109351 1.—A method for manufacturing a nano carbon tube with a vertical alignment characteristic and a nano metal wire therein, including a microwave plasma system with a surface plated with a metal or metal compound The substrate is a substrate. The carbon-containing reaction gas is subjected to chemical vapor deposition to grow a plurality of nano-carbon tubes and nano-metal wires in the nano-carbon tube. Π ~ wherein the rear nano-tube is perpendicular to The substrate is arranged parallel to each other. The metal of the clock on the substrate is a transition metal or an alloy thereof, and the conditions for the synthesis of the microwave plasma: the microwave power is 100 to 5000 W, and the synthesis pressure is lx 10-30 to 100 Torr. The DC bias is -50 to -1000 V and the temperature is 300 ° C to 1500 ° C. 2. The method according to item 1 of the scope of patent application, wherein the transition metal is a Group VIIIB metal. 3. The method according to item 2 of the scope of the patent application, wherein the transition metal is in a group consisting of selective red, nickel, platinum, Syria, and mixtures thereof. A method in which the metal compound plated on the substrate is a compound of a transition metal. 5. The method according to item 4 of the scope of patent application, wherein the compound of the transition metal is a silicide or a carbide of the transition metal. 6. The method as described in item 5 of the scope of patent application, wherein the compound of the transition metal is Pd3Si, cobalt carbide, or nickel carbide ° The method of clause 'wherein the porosity 第14貰 444 067 --iS^881〇9351__年月 p 修正 ___ 六、申請專利範圍 基板為矽基板、經陽極處理之珍基板、鋁陽極處理基板、 氧化矽基板、或高分子基板。 8. 如申睛專利範圍第1項所述之方法,其中該表面鍍 有金屬或金屬化合物之基板是使用物理氣相沈積法、電化 學方法、或旋鍍法,以將金屬或金屬化合物鍍在基板上 的。 9. 如申請專利範圍第8項所述之方法,其中該物理氣 相沈積法為濺鍍法或蒸鍍法。 10‘如申請專利範圍第8項所述之方法,其中該電化學 方法為電鍍法或無電鍍法。 U.如申請專利範圍第1項所述之方法,其中該含碳反 應氣體為擇自由曱烷、乙烷、丙烷、乙炔、苯、及其混合 物所組成之族群中。 $ 1…如申請專利範圍第1項所述之方法,其中該含碳反 應乳體之化學氣相沈積係在活化氣體之存在下而進行的。 ^ 1 3 *如申請專利範圍第1 2項所述之方法’其中該活化 氣體為擇自由氫氣、氨氣、一氧化碳、及其混合物所組成 之族群中。 申請專利範圍第1項所述之方法,其中該所得之 …米&&具'有至3〇〇//m的長度,1 nm至300 nm的直 ’工且相鄰兩奈米破管之間的距離為1 nm至300 mn =Article 14 贳 444 067 --iS ^ 881〇9351__ month and month p amendment ___ 6. Scope of patent application The substrate is a silicon substrate, an anodized precious substrate, an aluminum anodized substrate, a silicon oxide substrate, or a polymer substrate. 8. The method as described in item 1 of Shenjing's patent scope, wherein the substrate coated with a metal or a metal compound on the surface is coated with a metal or a metal compound using a physical vapor deposition method, an electrochemical method, or a spin plating method On the substrate. 9. The method according to item 8 of the scope of patent application, wherein the physical vapor deposition method is a sputtering method or an evaporation method. 10 ' The method as described in item 8 of the scope of patent application, wherein the electrochemical method is an electroplating method or an electroless plating method. U. The method according to item 1 of the scope of patent application, wherein the carbon-containing reaction gas is a group consisting of selective free oxane, ethane, propane, acetylene, benzene, and a mixture thereof. $ 1 ... The method as described in item 1 of the scope of patent application, wherein the chemical vapor deposition of the carbon-containing reaction emulsion is performed in the presence of an activating gas. ^ 1 3 * The method according to item 12 of the scope of the patent application, wherein the activating gas is selected from the group consisting of hydrogen, ammonia, carbon monoxide, and mixtures thereof. The method described in the first patent application range, wherein the obtained ... meters & has a length of up to 300 // m, a straight line of 1 nm to 300 nm and two adjacent nanometers broken The distance between the tubes is 1 nm to 300 mn = 第15頁Page 15
TW88109351A 1999-06-05 1999-06-05 Process for preparing aligned carbon nanotubes and metal nanolines in the nanotubes TW444067B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7303723B2 (en) 2002-10-04 2007-12-04 The Ohio State University Research Foundation Method of forming nanostructures on ceramics
US8715790B2 (en) 2001-07-27 2014-05-06 University Of Surrey Production of carbon nanotubes
US8791395B2 (en) 2011-09-28 2014-07-29 National Taiwan University Nanotube heating device comprising carbon nanotube and manufacturing method thereof
US10968103B1 (en) * 2020-07-23 2021-04-06 The Florida International University Board Of Trustees Copper-filled carbon nanotubes and synthesis methods thereof
US11476464B1 (en) 2021-09-10 2022-10-18 The Florida International University Board Of Trustees Coated vertically aligned carbon nanotubes on nickel foam

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8715790B2 (en) 2001-07-27 2014-05-06 University Of Surrey Production of carbon nanotubes
US7303723B2 (en) 2002-10-04 2007-12-04 The Ohio State University Research Foundation Method of forming nanostructures on ceramics
US8791395B2 (en) 2011-09-28 2014-07-29 National Taiwan University Nanotube heating device comprising carbon nanotube and manufacturing method thereof
US10968103B1 (en) * 2020-07-23 2021-04-06 The Florida International University Board Of Trustees Copper-filled carbon nanotubes and synthesis methods thereof
US11476464B1 (en) 2021-09-10 2022-10-18 The Florida International University Board Of Trustees Coated vertically aligned carbon nanotubes on nickel foam
US11929504B2 (en) 2021-09-10 2024-03-12 The Florida International University Board Of Trustees Coated vertically aligned carbon nanotubes on nickel foam

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