200407259 玖、發明說明 内容、實 KSS說ΪΓ屬之技術領域、先雜術 【發明領域】 本毛明係關於-種奈米碳材料，尤其係關於一種超長奈米碳管材料 及其製造方法。 【發明背景】 攸 1991 年 h 扉《s· π 細，Nature(L〇nd〇n)啊 現奈米％官開始，其生長方法已發展為很多種（電弧放 與化學氣相沈積法等），但這些生長奈米碳管之方法所製造之奈米破I. 長度一般只能翻财量級，從祿_論及實驗上騎長奈米碳管之 超長奈米碳管係—重點、難點，在理論與應用方面具有重要 所指的“超長’’係、指奈米碳管之長度達到十釐米量級。 8^28g^^^_^^)JE4〇21〇〇 華大學朱宏偉、徐才鉢餘日日、⑯b ^射κ由北“ 太 $ 、'、、又月）’^出採用立式浮動催化裂解法製造單壁 直徑可與人咐賤 奸了賴屋未，< 尺寸之_，編^ 方対町缺陷，㈣於受反應器 長溫度較高，生界m山物間不月b過長，而且奈米碳管之生 【發明目的】 反管之溫度爲麵°C左右。 之目的储供—種超長尺寸之奈米碳管繩。 法。—目的係提供-種在較低溫度下製造該奈米碳管繩之方 6 200407259 【發明特徵】 本發明提供一種奈米碳管繩，其包括複數奈米碳管束片段，相鄰夺 米碳管束μ端部依次相互連接，且仙奈米碳管束技由複數相互平 行之奈米碳管束構成。其巾，該奈米碳管束包含奈純管，且每個 奈米碳管束諸具有大致㈣之長度及相鄰奈米碳管束片段端部通過凡 德瓦爾力相互連接。 本發明亦提供一種製造該奈米碳管繩之方法，其包括下列步驟：提 供-平滑基底’將催化舰積於該基底上，將沈積有慨歡基底於保籲 護氣體存在下蝴至—特定溫度後獻麵氣與賴氣體之混合氣體， 使催化J兵ί衣i兄之溫度差在5〇 c以上，且碳源氣分廢低於，反應5〜加 分鐘’奈米碳管陣列從基底長出。再從奈米碳管陣列中選定一包括複數 示米厌&束之示米石反官束片段，使用拉伸工具拉伸該奈米碳管束片段， 使奈米碳管繩沿拉伸方向職。其巾通過控制·氣之流速控制催化劑 與環境之溫度差，通過控制混合氣體之流速比测碳職之分壓。 【較佳實施例】 _ 請參閱第一圖，本發明奈米碳管繩4〇包括複數奈米碳管束片段3〇， 相鄰奈米碳管束片段端部31依次相互連接，且每個奈米碳管束片段％ 由複數相互平行之奈来碳管束2〇構成。其中，該奈米碳管束2Q包含複 數奈米碳管（未標示），且每個奈米碳管束片段3〇具有大致相等之長度及 相鄰奈米碳管束片段端部31通過凡德瓦爾力相互連接。 請參閱第二圖，本發明奈米碳管繩製造方法之流程圖。提供一平整 7 200407259 發明說明續頁， 光滑之基底50(請參閱第三圖），可選用p型或n型矽基底或具氧化層之 矽基底，本實施例中選用p型矽基底。於基底5〇上採用電子束蒸發法、 熱沈積或濺射法等方法形成厚度爲幾奈米到幾百奈米之金屬催化劑 51(請參閱第四圖），其中金屬催化劑51可爲鐵(Fe)、鈷(c〇)、鎳⑺〇 或其合金之一，優選用鐵爲催化劑，沈積厚度約爲5奈米。 而後將沈積有催化劑51之基底50在空氣中退火，退火溫度範圍爲 300〜400 C，時間約爲1〇小時。之後基底5〇被分割成許多矩形小塊，每 丨塊放入；5英舟中’在保護氣體存在條件下，在反應爐中力口熱一 時間使其達到一預定溫度，一般爲5〇〇~7〇(rc，優選爲65〇艺。 再通入30 sccm碳源氣與300 sccm之保護氣體(本實施例選用氬 氣)5〜30分鐘，製得高度約1〇〇微米之奈米碳管陣列1〇，請一併參閱第 五圖及第六圖。 ^其中碳源氣爲碳氫化合物，可爲乙块、乙烧等，優選用乙块，該保 護氣體爲惰性氣體或氮氣。 。爲制可拉製奈米碳管繩之奈米碳管_，在製造奈米碳管陣列過< 程中，必須滿足以下三個條件： (1) 基底平整光滑； (2) 奈米碳管陣列之生長速度快； (3) 碳源氣之分壓要低。 μ生長之基縣整光滑，可以使得贿基絲面之奈米 ^生長付更㈣，從而形成垂直於基底之奈米碳管陣列。 奈米碳管陣列之生長速度快與碳源氣之分壓低可以有效抑制無 8 200407259 發明說明、續頁 碳沈積於奈米碳管之表面，從而增加奈米碳管間之^德瓦爾力4無 定形碳之沈積速歧比於碳源氣之分壓，可⑽過酸舰氣與保護氣 體之流速比控繼源氣之分壓。而奈米碳管陣狀生長速度正比於催化 劑與反應爐之溫度差。可輯過輕麵氣之流速控織化劑之溫度， 而反應爐之溫度可以直接控制。 在本實施例中，催化劑與反應爐之最低溫度差控制爲5(rc，碳源氣 之分壓要低於2〇%，最好係低於1⑽。 請-併參閱第-圖，從奈米碳管陣列10中選定一包括複數奈米碳管籲 束20之奈米碳官束片段3Q，並使用拉伸工具拉伸該奈米碳管束片段洲， 使奈米碳管繩4〇沿拉伸方向形成。 在拉伸過程中’奈米碳管束片段3〇在拉力F作用下沿拉力方向伸長 之同日守’相鄰奈米碳管束片段端部3丨由於凡德瓦爾力之作用而相互連接 在一起，形成奈米碳管繩40。 *伸所用力之大小取決於所選奈米碳管束片段3〇之寬度:該寬度越 二的力越A。由實驗資料得出G.lmN的力可以拉出_微米寬# 之，米碳魏，而拉_奈米碳f繩需要G.5mN的力。在本實施例中高 =刚微米之奈米碳管陣列可以拉出長％鮮、寬職米之奈米碳 =方法製造之奈米碳管繩包括複數從奈米碳管_長出之奈米碳 二，’因此每個奈米碳管束片段具有大致相等之長度且每個奈米碳 ^通^由複數相互平行之奈米碳管束構成，其中，奈米碳管束片段端 4通過凡德瓦爾力相互連接。 9 2,0407259 相較於習知##-, 匕發8月說明_頁 、 叮，本發明具有如下優點·^~ -〜- 溫度較低；且奈米碳管陣列之 y =二中衣備奈純管陣列之 通過拉伸工呈杈柚化 、〜不’僅f⑽微米左右， 1 伸射崎到至更長之奈米碳管、繩。 、部上所述，本發明符合發财利要件，纽法提出專辦請。惟， 以上所述者僅為本發明之較佳實關，舉凡熟悉本紐術之人士，在援 依本案發珊神所作之等效修#或變化，皆應包含於以τ之巾請專利= 圍内。 .□續次頁（發明說明頁不敷使用時，請註記並使用續頁）200407259 发明, description of the invention, the technical field of the KSS theory, the field of incorporation [Invention field] The present Maoming is about a kind of nano carbon material, especially about an ultra-long nano carbon tube material and its manufacturing method . [Background of the invention] You 1991 h 扉 "s · π thin, Nature (London) ah now nano-% official began, its growth methods have been developed into many (arc discharge and chemical vapor deposition methods, etc.) However, the nanometer broken by these methods of growing carbon nanotubes I. The length can generally only be turned to the order of wealth. From the perspective of experiments and experiments, the ultra-long nanometer carbon tube system that rides long carbon nanotubes-the key point Difficulties, in terms of theory and application, it has an important meaning of the "ultra-long" system, which means that the length of the carbon nanotubes reaches the order of ten centimeters. 8 ^ 28g ^^^ _ ^^) JE4201 Zhu Hongwei, Xu Caibo, Yu Riri, ⑯b ^ She κ from North "Taiwan $, ',, and yue') ^ using vertical floating catalytic cracking method to make single-wall diameters can be commanded by others, and Lai Wuwei, < Dimensions of _, edit ^ Defects of Fangyao, due to the high temperature of the reactor, the length of the space between the mountains and the mountains, and the length of the carbon nanotubes are too long, and the birth of the nano-carbon tube [Objective] The temperature of the tube It is about ° C. The purpose of storage-a kind of ultra-long carbon nanotube rope. law. —The purpose is to provide a method for manufacturing the carbon nanotube rope at a lower temperature. 6 200407259 [Inventive features] The present invention provides a carbon nanotube rope, which includes a plurality of carbon nanotube bundle segments, adjacent rice carbon The ends of the tube bundle μ are sequentially connected to each other, and the nano carbon tube bundle technology is composed of a plurality of nano carbon tube bundles parallel to each other. The nano carbon tube bundle includes a nano tube, and each nano carbon tube bundle has a length of approximately ㈣ and the ends of adjacent nano carbon tube bundle segments are connected to each other by Van der Waals force. The present invention also provides a method for manufacturing the carbon nanotube rope, which includes the following steps: providing a smooth substrate to deposit a catalytic ship on the substrate, and depositing a deposited substrate in the presence of a protective gas to a specific substrate. After the temperature is provided, a mixture of facial gas and Lai gas is provided, so that the temperature difference between the catalyzed J Bing Yiyi and the carbon source gas is less than 50 ° C, and the carbon source gas fraction is lower than the reaction time. The substrate grows. Then select a nanometer anti-beam fragment including a plurality of nanometer & beams from the nanometer carbon tube array, and use a stretching tool to stretch the nanometer carbon tube bundle section to make the nanometer carbon tube rope along the stretching direction. Job. It controls the temperature difference between the catalyst and the environment by controlling the flow rate of gas, and measures the partial pressure of carbon by controlling the flow rate ratio of the mixed gas. [Preferred embodiment] _ Please refer to the first figure. The nano carbon tube rope 40 of the present invention includes a plurality of nano carbon tube bundle segments 30, and the end portions 31 of adjacent nano carbon tube bundle segments are connected to each other in sequence, and each nano The meter carbon tube bundle segment% is composed of a plurality of Nara carbon tube bundles 20 parallel to each other. Wherein, the nano carbon tube bundle 2Q includes a plurality of nano carbon tube bundles (not labeled), and each of the nano carbon tube bundle segments 30 has a substantially equal length and an end 31 of an adjacent nano carbon tube bundle segment passes a Van der Waals force. Interconnected. Please refer to the second figure for a flowchart of a method for manufacturing a nano carbon tube rope according to the present invention. Provide a flat 7 200407259 description of the invention continued, smooth substrate 50 (see Figure 3), p-type or n-type silicon substrate or a silicon substrate with an oxide layer can be selected. In this embodiment, a p-type silicon substrate is used. A metal catalyst 51 having a thickness of several nanometers to several hundred nanometers is formed on the substrate 50 by using an electron beam evaporation method, a thermal deposition method, or a sputtering method (see the fourth figure). The metal catalyst 51 may be iron ( Fe), cobalt (co), nickel alloy or one of its alloys, preferably using iron as a catalyst, with a deposition thickness of about 5 nm. Then, the substrate 50 on which the catalyst 51 is deposited is annealed in air, and the annealing temperature ranges from 300 to 400 C, and the time is about 10 hours. The substrate 50 is then divided into a number of small rectangular pieces, each of which is placed in a 5-inch boat. In the presence of a protective gas, it is heated in the reactor for a period of time to reach a predetermined temperature, generally 50. 〇 ~ 70 (rc, preferably 650). Then pass in 30 sccm carbon source gas and 300 sccm protective gas (argon gas is used in this embodiment) for 5 to 30 minutes, to obtain a height of about 100 microns. Meter carbon tube array 10, please refer to the fifth and sixth figures together. ^ Wherein the carbon source gas is a hydrocarbon, which can be block B, block 2, etc., block B is preferred, and the protective gas is an inert gas or Nitrogen ... In order to make a nano carbon tube that can be used to draw a nano carbon tube rope, the following three conditions must be met during the manufacture of the nano carbon tube array: (1) The substrate is flat and smooth; (2) The growth rate of nanometer carbon tube array is fast; (3) The partial pressure of carbon source gas should be low. Μ growth of the base is smooth, which can make the growth of nanometer ^ on the surface of the bristle wire more stable, thus forming perpendicular to the substrate. Nano carbon tube array. The rapid growth of nano carbon tube array and the low partial pressure of carbon source gas can effectively suppress 9 Description of the invention, continuation page Carbon is deposited on the surface of the carbon nanotubes, thereby increasing the ^ Deval force between the carbon nanotubes. 4 The deposition rate of amorphous carbon is proportional to the partial pressure of the carbon source gas. The velocity ratio of the gas and the protective gas controls the partial pressure of the source gas. The growth rate of the carbon nanotube array is proportional to the temperature difference between the catalyst and the reactor. The flow rate of the light surface gas can be controlled by the temperature of the weaving agent. The temperature of the reaction furnace can be controlled directly. In this embodiment, the minimum temperature difference between the catalyst and the reaction furnace is controlled to 5 (rc, the partial pressure of the carbon source gas should be less than 20%, preferably less than 1⑽. Please- And referring to FIG.- FIG., A nano carbon tube bundle segment 3Q including a plurality of nano carbon tube arrays 20 is selected from the nano carbon tube array 10, and the nano carbon tube bundle segment region is stretched using a stretching tool so that Nano carbon tube rope 40 is formed along the stretching direction. During the stretching process, the 'nano carbon tube bundle segment 30' is stretched in the direction of the tensile force by the pull force F and the end of the adjacent nano carbon tube bundle segment 3 丨They are connected to each other due to van der Waals force, forming a carbon nanotube rope 40. * Stretching force The size depends on the width of the selected carbon nanotube bundle segment 30: the greater the width, the greater the force A. From the experimental data, it can be concluded that the force of G.lmN can be pulled out of _μm width #, the carbon and carbon, and the _Nano carbon f rope requires G.5mN force. In this embodiment, high = just micron nanometer carbon tube array can pull out the long% fresh and wide nanometer carbon = nanometer carbon tube rope manufactured by the method Including a plurality of carbon nanotubes grown from carbon nanotubes_, therefore, each carbon nanotube bundle segment has approximately the same length and each carbon nanotube is composed of a plurality of carbon nanotube bundles parallel to each other, Among them, the ends 4 of the nano-carbon tube bundle segments are connected to each other by Van der Waals force. 9, 2,0407259 Compared with the conventional knowledge ##-, Dagger Hair August Description _ page, ding, the present invention has the following advantages ^ ~-~ -The temperature is relatively low; and y of nano carbon tube array = two middle garments, and the pure tube array is made of pomelo through stretching process, ~ not only about f⑽m, about 1 崎Meter carbon tube, rope. As mentioned above, the present invention is in line with the requirements for making money and profits, and Newfax proposed a special request. However, the above is only a good practice of the present invention. For those who are familiar with this technique, the equivalent repairs # or changes made by the gods in this case should be included in the towel with τ. Patents = within. . □ Continued pages (If the description page of the invention is insufficient, please note and use the continued pages)