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九六年一月 玖、發明說明· 曰修正頁 【發明領域】 本發明係_-縣米碳材料，尤其侧於_種超絲米碳管材料 及其製造方法。 【發明背景】 從 1991 年 li jima《S· Ii jima，Nature(London)354，56(1991)》發· 不米反f開始其生長方法已發展為报多種（電弧放電法、雷射沈積》 與化學軋相沈積料），但這些生長奈米碳管之方法所製造之奈米碳管之 長度-般只能達到微米量級，從而限制理論及實驗上對超長奈米碳管之 研丸。製造超長奈米碳管係一重點、難點，在理論與應用方面具有重要 意義。這裏所指的“超長，，係指奈米碳f之長度達到十釐㈣級。- 2002年8月28日公開之一篇專利號爲02100684之中國專利（由北京清_ 華大學朱宏偉、徐才錄等發明），提出採用立式浮動催化裂解法製造單壁 奈米碳管之方法，所製得的奈米碳管長度麟釐米，最長可賴釐求 直控可與人的頭髮絲相當。但該製造方法有以下缺陷，即由於受反應器 寸I?制催化劑在反應器晨停留時間不能過長，而且奈米碳管之生 長溫度較高，生長單壁奈米碳管之溫度爲100(TC左右。 【發明目的】 本發明之目的係提供—種錄低溫度下製造該奈米碳管繩之方法。Λ 【發明特徵】 、，本毛膝供種製造該奈米碳管繩之方法，其包括下列步驟：提供 一平整光滑之基底；將催化歉積於該基底上；將沈射催化劑之基底 6 130徹 29 年一月 日修正頁 體從而生絲米碳管_，射，_碳域餘魏叙 而 控制礙源氣之分壓低於，控制碳職之流速進而㈣槪_環1 度差至少· C ;以及，從奈米碳管_選定—包括複數奈米碳管束 之奈米碳管束片段，使雜伸I具拉伸該奈米碳管束片段，夺 片段端部触姐連接雜伸方向職奈米碳管繩。 …5束 【較佳實施例】 請參閱第―®，本㈣奈米碳㈣40包括魏奈米碳管料段 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=3〇 由複數相互平狀奈米碳辣2()顧。其巾，縣米碳管㈣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· 光滑之基底50(請參閱第三圖）’可選用p型或n型石夕基底或具氧化層之 石夕基底’本實施射 p _基底。於基底5Q上採用電子束蒸發法 熱沈積或難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_收）、钻㈣、錄㈤ 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 300〜40(TC，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 j塊放入；δ英舟中’在保護氣體存在條件下，在反應爐中力口熱一段 間使其達到一預定溫度，一般爲5〇〇〜7〇〇°c，優選爲65〇它。 7 130323^-^—^_ 九六年一月 日修正頁 -- -----1 說明書續頁 ' 再通入30 sccm碳源氣與300 sccm之保護 氣)5〜30分鐘，製得高度約微米之奈米碳管陣列1〇，請一併表^ 五圖及第六圖。 /弟 其中石厌源氣爲碳氳化合物，可爲乙炔、乙烧等，優選用乙块， 護氣體爲惰性氣體或氮氣。 μ呆 。爲得到可拉製奈米碳管繩之奈米碳管陣列，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。 生長奈米碳料狀基底平整統，可錢得位錄絲面之夺米 碳管生長得更㈣，㈣形麵直於基底之奈米碳管陣列。 τ、 奈米碳管_之生長速度快與碳源氣之分觀可以有效抑制盈定來 碳沈積於奈米碳管之表面’從而增加奈米碳管間之凡德瓦爾力。因耻 定形碳之沈魏度正咖韻氣之分壓，可輯過碳職與保護罐 體之流速比㈣碳職之賴。喊米碳料狀生魏度正比於催化1976, 发明 发明 发明 发明 发明 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 县 县 县 县 县 县 县 县 县 县BACKGROUND OF THE INVENTION From 1991, Li jima, S. Ii jima, Nature (London) 354, 56 (1991), the growth method has been developed into a variety of methods (arc discharge method, laser deposition). And chemical rolling phase deposits), but the length of the carbon nanotubes produced by these methods of growing carbon nanotubes can only reach the order of micrometers, thus limiting the theoretical and experimental research on ultra-long carbon nanotubes. pill. The manufacture of ultra-long carbon nanotubes is an important and difficult point, and is of great significance in theory and application. The term "ultra-long" refers to the length of nanocarbon f up to ten (four). - A patent entitled No. 02100684 published on August 28, 2002 (by Beijing Qing _ Hua University Zhu Hongwei, Xu Cailu et al.) proposed a method for manufacturing single-walled carbon nanotubes by using a vertical floating catalytic cracking method. The length of the carbon nanotubes produced is 5,000 cm long, and the longest can be determined to be comparable to human hair. However, the manufacturing method has the following drawbacks, that is, since the reactor is not too long in the morning of the reactor, and the growth temperature of the carbon nanotube is high, the temperature of the growing single-walled carbon nanotube is 100. [TC or so. [Object of the Invention] The object of the present invention is to provide a method for producing the carbon nanotube string at a low temperature. Λ [Inventive feature], the present knee is used for seed production of the carbon nanotube string The method comprises the steps of: providing a smooth and smooth substrate; catalyzing a catastrophic accumulation on the substrate; and modifying the substrate of the deposition catalyst 6 130 by the date of January 29 to produce the raw carbon nanotubes _, shot, _ The carbon domain, Wei Wei, and the control of the source The partial pressure is lower than that, and the flow rate of the carbon service is controlled, and (4) 槪_ring 1 degree difference is at least · C; and, from the carbon nanotube _ selected - including the carbon nanotube bundle of the plurality of carbon nanotube bundles, so that the hybrid extension I pull Extend the carbon nanotube bundle segment, and take the end of the segment to contact the miscellaneous direction of the carbon nanotube rope. ... 5 bundles [better embodiment] Please refer to the section -®, this (four) nanocarbon (four) 40 including Wei Naimi The carbon nanotubes adjacent carbon nanotube bundle segment ends 31 are connected to each other in turn, and each of the carbon nanotube bundles is 3 〇 〇 〇 相互 相互 相互 相互 相互 其 其 其 其 其 其 , 其 , , , , , , , , , , , , , , , , , , , , , The plurality of carbon nanotube tubes (not shown) and each of the carbon nanotube bundle segments 3 〇 have substantially equal lengths and the adjacent carbon nanotube bundle segment ends 31 are connected to each other by van der Waals force. ' See second diagram A flow chart of a method for manufacturing a carbon nanotube rope of the present invention. Providing a flat and smooth substrate 50 (see the third figure) 'optional p-type or n-type Shi Xi base or a stone base with an oxide layer' The p_substrate is applied. Thickness is formed on the substrate 5Q by electron beam evaporation, thermal deposition or difficult method. a metal catalyst 51 of a few nanometers to several hundred nanometers (see the fourth figure), in which one of the metal catalysts 51 can be taken, drilled (four), recorded (five) or one of its alloys, preferably using iron as a catalyst, depositing thickness It is about 5 nm. Then, the substrate 50 on which the catalyst 51 is deposited is annealed in air at an annealing temperature ranging from 300 to 40 (TC, for about 1 hour). After that, the substrate 5 is divided into a plurality of rectangular small pieces, each j block is placed; in the presence of a protective gas, in the presence of a protective gas, it is brought to a predetermined temperature in the reaction chamber for a period of time, generally 5 〇〇 7 7 ° ° C, preferably 65 〇 7 130323^-^—^_ January 1996 revised page ----1 Manual continuation page 'Re-into 30 sccm carbon source gas and 300 sccm shielding gas) 5~30 minutes Get a nanometer carbon nanotube array with a height of about 1 μm. Please combine the five and sixth figures. / brother, the stone source gas is a carbon ruthenium compound, which can be acetylene, ethylene, etc., preferably using an block, the gas is inert gas or nitrogen.呆 stay. In order to obtain a carbon nanotube array of pullable carbon nanotube ropes, the following three conditions must be met in the process of fabricating the carbon nanotube array: (1) the substrate is smooth and smooth; (2) the carbon nanotube array The growth rate is fast; (3) The partial pressure of the carbon source gas is low. The growth of the nano-carbon material-like base is flat, and the carbon tube can be grown more than the carbon surface. (4), (4) The carbon nanotube array with the shape directly opposite the base. The rapid growth of τ, carbon nanotubes and the carbon source gas can effectively suppress the carbon deposition on the surface of the carbon nanotubes, thereby increasing the van der Waals force between the carbon nanotubes. Because of the shame of the shape of the carbon, the degree of pressure of the tea is the same as that of the carbon tank. Shouting rice carbon material is similar to catalysis
劑與反雜之溫度差。心通過機碳源氣之騎_催倾之溫度， 而反應爐之溫度可以直接控制。 X 在本實施财，條顺職叙最低溫度_彳爲5g。 之分壓要低於20%，最好係低於1〇%。 〜、 請-:參閱第一圖，從奈米碳管陣列1〇中選定一包括複數奈米碳管 束之不米碳官束片段30,並使用拉伸工具拉伸該奈米碳管束片段洲， 8 ——— 使奈米破管繩4〇沿拉伸方向形成。 ^伸樹，奈姆恤3G在拉力F伽τ雜力方向伸長 f輪奈米碳管束片段端部31由於凡德關力之侧而相 在一起，形成奈米碳管繩40。 •伸_力之大小取決於所選絲碳管束4段3()之紐··該寬度越 見，所需要的力越大。由實驗資料得出〇1禮的力可以拉出細微米寬 之奈米碳管繩’而拉斷該奈米碳管_要G· 5mN的力。在本實施例中高， 度爲刚微米之奈米碳管陣列可以拉出長3_、寬2⑻微米 : 管繩。 ” —用該方法製造之奈米碳管腕括複數從奈米碳管_長出之奈米碳 f束片段’ S此每個奈米碳f束片段具社致鱗之長度且每個奈米= 管束片段由缝概平狀絲碳縣淑，射，奈轉管束片段端 部通過凡德瓦爾力相互連接。 相較於習知猶，本發如下伽：該方財製備奈械管陣列之 溫度較低；且奈米碳管陣列之生長高度不需很高，僅需1〇〇微米左右參 通過拉伸工具拉伸後可以得到幾十釐米甚至更長之奈米碳管繩。 綜上所述，本發明符合發明專利要件，爰依法提出專利申請。惟， 以上所述者僅為本發明之較佳實施例，舉凡熟悉本案技術之人士，在援 依本案發明精神所作之等效修飾或變化，皆應包含於以下之申請專利範 圍内。 □續次頁（發明說明頁不敷使用時，請註記並使用續頁） 9The temperature difference between the agent and the anti-hybrid. The heart passes through the carbon source of the machine, the temperature of the reactor, and the temperature of the reactor can be directly controlled. X In this implementation, the minimum temperature _ 彳 is 5g. The partial pressure should be less than 20%, preferably less than 1%. ~, Please -: Refer to the first figure, select a non-carbon carbon beam segment 30 including a plurality of carbon nanotube bundles from the carbon nanotube array 1 and stretch the carbon nanotube bundle segment using a stretching tool , 8 ——— The nano tube breaking rope 4 is formed along the stretching direction. ^Extension, Naim Shirt 3G is stretched in the direction of the rally F gamma τ. The end of the f-nano carbon nanotube bundle segment 31 is joined together by the side of the Guardian force to form the carbon nanotube rope 40. • The magnitude of the force depends on the length of the selected carbon nanotube bundle 4 (3). The larger the width, the greater the force required. From the experimental data, it can be concluded that the force of the 礼1 ceremony can pull out the fine-nano-wide carbon nanotube rope and pull off the carbon nanotube _ to force G·5mN. In this embodiment, the array of carbon nanotubes having a height of just a micron can be pulled out to a length of 3 mm and a width of 2 (8) micrometers: a pipe string. - The carbon nanotubes produced by this method consist of a number of carbon nanotubes from the carbon nanotubes _ grown in the nano carbon f-beam segment' S each of the nano carbon f-beam fragments with the length of the scale and each nai m = tube bundle fragment is made of slit flat wire silk carbon county, shot, and the end of the nai tube bundle segment is connected to each other by van der Waals force. Compared with the conventional judo, this hair is as follows: the square money preparation nai tube array The temperature is low; and the growth height of the carbon nanotube array is not required to be high, and only about 1 micron is required to be stretched by a stretching tool to obtain a carbon nanotube rope of several tens of centimeters or more. As described above, the present invention complies with the requirements of the invention patent, and the patent application is filed according to law. However, the above is only a preferred embodiment of the present invention, and those who are familiar with the technology of the present invention are equivalent in the spirit of the invention. Modifications or changes should be included in the scope of the following patent application. □ Continued page (Notes on the description page when the invention is not available, please note and use the continuation page) 9