1237840 玖、發明說明： 【發明所屬之技術領域】 本發明係有關於一種奈米碳管(carb〇nnan〇tubeS)的生產方法及裝置，特 別是一種以高溫熱電漿喷射流(thermal Plasma jet)加熱碳源前驅物 (precursor)，且無須添加催化劑(catalyst-free)，即可合成奈米碳管的方法及 其裝置。 【先前技術】 奈米碳管(carbon nanotubes)應用的潛力深廣’在聲、光、電、磁、 熱、力、能、生化等領域中，具重大的潛在應用前景。奈米碳管具備了 強度高、韌性高、可撓性佳、可導電(具導體和半導體的特性，依幾何春 結構含長度、管徑、層數而定）、導熱性高、表面積大、質量輕等優異 的特性。 奈米碳管的高縱橫比(aspect ratio)和小頂端曲率半徑(tip radius of curvature)等特性很適合用於電子場發射(eiectron field emission)。在場發 射平面顯示器（field emission display，FED)中用來取代金屬微尖(metal microtip) ’可賦予更高亮度的效果。微電子元如咖⑼ 的導線愈來愈細，製程技術即將臨近奈米碳管的幾何尺寸範圍（直徑 MOOnm)，故奈米碳管亦有製作導線、開關、電晶體和整流二極體的潛 力0 奈米碳管的機械強度為鋼鐵的1〇〇倍，而密度僅為鋼鐵的1/6，比 強度(specific strength)為已知材料中最大者，機械彈性甚佳，即使彎曲 角度大於90度仍然不會折斷，為非常好的增強添加劑⑽如妳如㈣ 哗継〇,可用以強化複合材料，具有質量輕、質地柔軟、強度高的特性， 非ί»適a It作防彈衣。奈米碳管作成的原子力顯微術⑼⑽匕 miC„，AFM)探針細長，且有彈性，碰撞物體表面不會折斷， 深入物體坑洞，進行量測，* 丁里，則而侍到更精確的表面構造，所以可取代現有 的石夕採針。 描2 tit内和管外均可作為儲存瓣子的場所’若用來製作電 ° "㈤ 、池電能儲存能力。奈米碳管的内徑和氫分子相近，所 1237840 儲存氫的密度南’亦是氫的最佳儲存器。奈米碳管的 加 體η:大幅改變，其錄度為傳統金屬氧二感^器二 曙Η。以上，為一甚佳的感測器製作材料。 致生量產化(SCale_Up)受到習知生產技術的限制，導 管目前常里用高的問題，進而限制奈米碳管的應. 積法(catalytic Ch 口〗方法有電弧放電法(a"。此勃㈣、催化化學氣相沈 ablation)^ ^ ^ C»-CVD)^ 入气習二㈣3電，成法在反應腔的陰㈣圣以石墨棒作為電極，通 陽極石3二=二3氣體’施加直流電源後，在兩電極間會產生電弧放電。 ，氣化’在陰極石祕上沉躺形成絲碳管。其缺 成物混有大1的雜相，含非晶質碳、碳微粒及煤灰等。奈米碳管的 二二&而且雜質多，故須要進行分離和純化過程，以去除雜質。已知的先 剛技術，如1998年11月3日公告的美國專利第5,83〇,326號。 ，知的電弧放電合成法(arc charging)為將固態石墨蒸發成原子態後，再 f排列組合成奈米碳f，合成速輸慢。且作為碳·石墨棒電極的尺 寸較小，產$因較到限制，難以大量生產。由於傳統的奈米碳管產量較 f，常在製程中添加少量金屬催化議媒），以增加其產量。在陽極石墨棒 中添加過渡族金屬顆粒，常用的有鐵(Fe)、始(c。）、鎳⑽等或其合金。 然而，這些催化劑充填在陽極石墨電轉中間的小孔中，會降低反應物的 均勻性而影響到奈米碳管的品質。已知的先前技術，如1999年6月Μ曰 公告的美國專利第5,916,642號。 習知的催化化學氣相沈積合成法(catalytic-CVD)有熱化學氣相沈積合 成法(themial CVD)和電漿輔助化學氣相沈積合成法(plasma enhanced CVD)，這兩者都須要使用金屬催化劑，常用的催化劑為過渡族金屬或其金 屬合金。習知的熱化學氣相沈積合成法將碳氫化合物氣體如苯(C6h6)、甲 烧(CH4)、乙炔((¾)、乙渐(¾)等或其混合物在電氣加熱爐中熱解後， :儿積於含金屬催化劑層的基底上而形成奈米碳管。在熱解溫度約·〜1〇〇〇 °〇：下，碳氫化合物在催化劑表面會熱解成碳原子及氫氣，氫氣隨著惰性氣 .1237840 體流走，而碳原子會和催化劑反應而形成奈米碳管。其缺點是電氣加熱爐 升溫速率較慢，奈米碳管合成時間較長。已知的先前技術，如2000年1〇 月10日公告的美國專利第6，129,901號。 另一方面，習知的電漿辅助化學氣相沈積合成法，利用電漿加熱來熱 解碳氫化合物，使碳原子和催化劑有足夠能量起反應而形成奈米碳管。其 優點為製程溫度可較低約3〇〇〜8〇〇°C，以射頻、微波等電漿加熱，可在短時 間内升高溫度，加速分解碳氫化合物，而降低奈米碳管合成時間。但其缺 點是該製程須在較高真空下操作。如2〇〇1年7月1日公告的中華民國專利 公報第444067號中以及2001年12月18日公告的美國專利公報第6331209 號中。且部分電槳化學氣相沈積合成法，例如電子迴旋共振(electr〇n cydotron resonance，ECR)微波電聚化學氣相沈積合成法，須更高真空(約 lxl(T3mmHg)製程，將會進一步再加重合成成本。已知的先前技術，如1999 年1月12日公告的中華民國專利公報第4526〇4號。 翕知的催化化學氣相沈積合成法，須要在金屬催化劑的作用下，使碳 源分解產生碳原子，以合成奈米碳管。其缺點為合成溫度低，奈米碳管結 構缺陷多。若當催化劑的含量增加時，奈米碳管的合成速率可以較快，但 疋所製彳f的產物除了含有奈米碳管外，還含有非晶質碳以及反射所用的 催化劑金屬顆粒和金屬碳化物等不純物。合成物的分離和純化較困難，這 些不純物在純化後仍或錢少存在，且分離和純化也再度提高了夺米碳 管的製造成本。不僅部分奈米碳管端點的催化劑還被石墨包裹著，無法將 ^去除，最後仍然留存著。而且分離純化過程中的強酸強鹼會破壞奈米碳 官的表層結構，這些都會嚴重影響奈米碳f的性能及其應用性。 這種習知的催化化學氣相沈積合成法所需要的含催化劑 備過程繁複’關精基底爾理，催倾職和催 等f 陽極處雌等伽濺鑛、熱蒸鑛、電子束蒸鍵、_ 她鑛法將不同種類、比例和用量的金屬催化劑塗佈在基底 ^ 膜，其後以電漿蝕刻或退火熱處理，使催化 / y / 小為奈米級。催化_膜形式應用二=rr否:= 1237840 率降低，奈米碳管的產量也隨著大幅減少。 此外’ f知技藝尚有—種新發展的雜—氧化碳自氧化還娜肋1237840 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method and a device for producing carbon nanotubes, especially a high-temperature thermal plasma jet (thermal Plasma jet) Method and device for synthesizing carbon nanotubes by heating a carbon source precursor without adding catalyst-free. [Previous technology] The application potential of carbon nanotubes is deep. It has great potential application prospects in the fields of sound, light, electricity, magnetism, heat, force, energy, and biochemistry. Nano carbon tubes have high strength, high toughness, good flexibility, and can be conductive (with the characteristics of conductors and semiconductors, depending on the length, diameter, and number of layers of the geometric spring structure), high thermal conductivity, large surface area, Excellent characteristics such as light weight. The high aspect ratio and small tip radius of curvature of nanometer carbon tubes are very suitable for eiectron field emission. It is used in the field emission display (FED) to replace the metal microtip, which can give a higher brightness effect. The wires of microelectronic elements such as coffee are getting thinner and thinner, and the process technology is approaching the geometric size range (diameter MOOnm) of carbon nanotubes. Therefore, carbon nanotubes also have wires, switches, transistors, and rectifier diodes. Potential 0 The mechanical strength of carbon nanotubes is 100 times that of steel, and the density is only 1/6 of that of steel. The specific strength is the largest of known materials, and the mechanical elasticity is very good, even if the bending angle is greater than It will not break at 90 degrees. It is a very good reinforcing additive, such as you. It can be used to strengthen composite materials. It has the characteristics of light weight, soft texture and high strength. It is not suitable for bulletproof clothing. Atomic force microscopy miC „(AFM) probes made of nano carbon tubes are slender and flexible, and they will not break when they collide with the surface of the object. They will penetrate deep into the pits of the object and perform measurements. Precise surface structure, so it can replace the existing Shixi mining needles. The inside and outside of the tube can be used as a place to store the petals. 'If used to make electricity " ㈤, pool electricity storage capacity. Nano carbon tube The inner diameter of the carbon nanotube is similar to that of the hydrogen molecule, so the density of 1237840 hydrogen storage is also the best storage for hydrogen. The addition of nano carbon tubes η: greatly changed, and its recording is the traditional metal oxygen sensor ^以上. The above is a very good material for sensor production. Mass production (SCale_Up) is limited by the conventional production technology, the current problem of high catheter use, which limits the application of carbon nanotubes. The method (catalytic Ch method) includes arc discharge (a " this method, catalytic chemical vapor deposition ablation) ^ ^ ^ C »-CVD) ^ Into the gas eruption 3 electricity, the method in the reaction chamber Yin Saint uses graphite rods as electrodes and passes anode stone 3 2 = 2 3 gas' after applying DC power, An arc discharge will occur between the two electrodes. The gasification 'lays down on the cathode stone to form a silk carbon tube. The missing material is mixed with a large heterogeneous phase, including amorphous carbon, carbon particles and coal ash. There are many impurities in rice carbon tubes, and there are many impurities, so a separation and purification process is required to remove impurities. Known prior techniques, such as US Patent No. 5,83,0,326 issued on November 3, 1998 The known arc charging method is to evaporate solid graphite into an atomic state, and then arrange it in f to form nano-carbon f. The synthesis speed is slow. And the size of the electrode as a carbon graphite rod is small, producing $ Due to the limitation, it is difficult to mass-produce. Because the output of traditional nano carbon tubes is relatively f, a small amount of metal catalyst is often added in the process to increase its output. Adding transition group metal particles to anode graphite rods is commonly used There are iron (Fe), starting (c.), Nickel hafnium, etc. or their alloys. However, these catalysts are filled in the small holes in the middle of the anode graphite electrorotation, which will reduce the uniformity of the reactants and affect the carbon nanotubes. Quality. Known prior art, such as June 1999 U.S. Patent No. 5,916,642. Conventional catalytic chemical vapor deposition synthesis methods include thermal chemical vapor deposition synthesis (themial CVD) and plasma enhanced chemical vapor deposition synthesis (plasma enhanced CVD), Both of these require the use of metal catalysts. Commonly used catalysts are transition metals or metal alloys. Conventional thermochemical vapor deposition synthesis processes hydrocarbon gases such as benzene (C6h6), methylbenzene (CH4), and acetylene ( (¾), ethene (¾), etc. or a mixture thereof is pyrolyzed in an electric heating furnace, and then deposited on a substrate containing a metal catalyst layer to form a nano carbon tube. At a pyrolysis temperature of about ~~ 100 °°: hydrocarbons will be pyrolyzed on the catalyst surface into carbon atoms and hydrogen. The hydrogen will flow away with the inert gas, 1237840, and the carbon atoms will react with the catalyst. Carbon nanotubes are formed. The disadvantage is that the heating rate of the electric heating furnace is slow, and the synthesis time of the carbon nanotube is longer. Known prior art, such as US Patent No. 6,129,901, issued October 10, 2000. On the other hand, the conventional plasma-assisted chemical vapor deposition synthesis method uses plasma heating to pyrolyze hydrocarbons, so that the carbon atoms and the catalyst have sufficient energy to react to form nano carbon tubes. The advantage is that the process temperature can be lowered by about 300 ~ 800 ° C. Heating by plasma, such as radio frequency and microwave, can increase the temperature in a short time, accelerate the decomposition of hydrocarbons, and reduce the synthesis of nano carbon tubes. time. The disadvantage is that the process must be operated under a higher vacuum. Such as the Republic of China Patent Gazette No. 444067 published on July 1, 2001 and the US Patent Gazette No. 6331209 published on December 18, 2001. And some electro-chemical paddle chemical vapor deposition synthesis methods, such as electron cyclotron resonance (ECR) microwave electropolymerization chemical vapor deposition synthesis methods, require a higher vacuum (about lxl (T3mmHg)) process, and will be further Increase the cost of synthesis. Known prior technologies, such as the Republic of China Patent Gazette No. 4526804 published on January 12, 1999. The known catalytic chemical vapor deposition synthesis method requires the use of a metal catalyst to make carbon Carbon atoms are generated by source decomposition to synthesize carbon nanotubes. The disadvantages are that the synthesis temperature is low and there are many defects in the structure of carbon nanotubes. If the content of the catalyst is increased, the synthesis rate of carbon nanotubes can be faster, but In addition to the carbon nanotubes, the products of 彳 f also contain impurities such as amorphous carbon and catalyst metal particles and metal carbides used for reflection. Isolation and purification of the compounds are difficult. These impurities are still expensive after purification. It is rare, and separation and purification have once again increased the manufacturing cost of carbon nanotubes. Not only the catalyst at the end of some carbon nanotubes is also wrapped with graphite, which cannot be removed. It still exists afterwards. And the strong acid and alkali during the separation and purification process will destroy the surface structure of the nanocarbon, which will seriously affect the performance and application of the nanocarbon f. This conventional catalytic chemical vapor deposition synthesis The catalyst preparation process required by the method is complicated, including the basic principle of smelting, catalyzing, and so on. The anode anode splatter, thermal steam ore, electron beam steam bond, _ her ore method will be different types, proportions and The amount of metal catalyst is coated on the substrate ^ film, followed by plasma etching or annealing heat treatment, so that the catalysis / y / small is nanometer level. Catalysis _ film form application 2 = rr no: = 1237840 rate reduction, nano carbon The output of the tube has also been greatly reduced. In addition, there is still a new technology-a newly developed heterogeneous-carbon oxide self-oxidation and Naib
Ig pressure CO disproportionation)法，以一負介栌為舻调々辨 化劑作用下，_氧化參DU、^ 祕石厌為奴觀體，在金屬催 當反應溫度和勤^和碳，雜錢組合縣米碳管。 f 成率也隨之增加。其優點為所合成的奈米碳 ^弁寸二:，八缺點為須要在高打操作，_有安全上的考量。已知 、::V ’ 1999年1〇月12日公告的美國專利第5,965,267號。 石户言ίίί雷㈣發合成法利用雷射光束照射石墨，使石墨乾材上的 上而形成奈米碳管°所合成的奈米碳管的純度較 寸過小，：:了:平二作業較易。然而’其作為碳輸材的尺( I，為了r 這種習知的製程由於奈米碳管的產量較 ίϋ合料Tf末燒結法成型，製備較不易。此雖然可^得ΪΪ碳 的⑽，但疋為了去除產物中的金屬催化劑，仍須進行純化後處理。 、名知的f射紐合成法在高溫下使_碳源氣化，再進行結構重排， 純度的奈米碳管。但雷射合成設備價貴，成本較高，難以應 6 183 71 里4 /上。已知的先前技術’如雇年2月6日公告的美國專利第 【發明内容】Ig pressure CO disproportionation) method, using a negative mediator as the mediator, _Oxidation DU, ^ Mi Shiyan is a slave, in the metal catalyst reaction temperature and carbon and carbon, miscellaneous money Combination county rice carbon tube. The f yield also increases. Its advantages are the synthesized nano carbon ^ 弁 inch 2 :, eight disadvantages are that it requires high-end operation, and there are safety considerations. It is known that U.S. Patent No. 5,965,267 issued on October 12, 1999. Shihuyan Yan The light-emitting synthesis method uses a laser beam to irradiate graphite to form a carbon nanotube on the graphite dry material. The synthesized carbon nanotube has a purity that is too small compared to an inch. :::: Heiji operation Easier. However, its scale as a carbon transport material (I, for the conventional manufacturing process of r), due to the production of nano carbon tubes, the production of carbon nanotubes is more difficult than the Tf sintering method, which is difficult to prepare. Although this can be obtained However, in order to remove the metal catalyst from the product, it still needs to be purified after treatment. The well-known f-ray synthesis method vaporizes the carbon source at a high temperature, and then restructures the carbon nanotubes with purity. However, laser synthesis equipment is expensive and costly, and it is difficult to respond to 6 183 71 li 4 / up. Known prior art 'such as US Patent No. [Feeding Content] published on February 6,
’無須催化劑以及高 本發明的主要目在提供一種具有高產量，低成本 品質的奈米碳管合成方法。 人占太㈣主要係以高溫熱電聚喷射流(themial Pl_㈣作為熱源加熱， 己成不米碳管的原料為含碳的_，液態或是絲的碳源前驅物，在不添 加催化劑(CatalySt-：free)情況下，於高溫而低壓的反應腔内合成奈米碳管。本 發巧職成本碳源作為前_，於高溫誦。。以上石墨化後，生成的奈 /笞^、、、、°ae度向、結構缺陷少和純度尚等特點，並大幅提昇奈米碳管的 品質和合成速率。 ” 本發明的另一目在提供一種用以連續合成奈米碳管的裝置。 1237840 _ 所揭露的裝置’具有—低壓反應腔，其内設置有—電聚產 了//不同電性的第—電極和—基底(第二電#藉由不同J 生，電场在其一者之間構成一電漿反應區，用以產生高溫熱電毅嘴 「Γ為·源前驅物則以—碳源前驅物的送料裝置連續地被送人電襞反庫 可讓合成的奈米碳管沉積在基底上；本發麵設計的基底為; 八又计，可配合-收集單元的運作，將基底上的奈米碳管收集 進行奈米碳管的連續生產。 文 本發明更揭路了-種可以提高離子化程度的電漿系統，主要係在電激 系統外圍提供-磁場以成為一種磁控電漿系統，磁場由圍繞著電襞系統 的環形電磁場線圈(sdenddfielded)所產生，以提供一個固定的軸向磁場， ，由磁械制使氣體分預獅從絲運動變姻餘義，㈣增加鲁 氣體分子的碰撞機率’提高離子化的程度以及電漿的密度和均句度。 有關本發明之詳細說明及技術内容，現就配合圖式說明如下。 【實施方式】 依據本發明所提出以熱電漿喷射流合成奈米碳管的方法，其較佳的 施方法，包括： k供一低壓的反應腔體並將電漿生成氣體(plasma gas)送入反應腔體，· 提供一直流電漿產生單元，其具有不同電性的第一電極和一基底(第二 電極），藉由不同之電性所產生的電場在其二者之間構成一電漿反應區，用 以和電漿生成氣體反應產生高溫熱電漿喷射流(thermai piasma jet)作為熱 源，且此電漿噴射流方向是朝向前述的基底； 提供一碳源前驅物的送料單元，用以連續地供給含碳的固態，液態或 是氣態的碳源前驅物進入高溫熱電漿喷射流之中，以在基底表面合成奈米 碳管；以及 提供一收集手段，用以收集在前述基底上合成的奈米碳管。 高溫的熱電漿噴射流的產生方式，舉凡熟悉此一技術領域之人士，在 瞭解本發明下文的說明後，將會發現其可以利用直流電漿系統、高頻電襞 系統、或是微波電漿系統之中的任一者加以實現。 10 1237840 喷射流加収咖：纟綱溫熱電漿 漿喷射清方純體外_供—磁場的手段，用以在高溫的熱電 動從直^運動料:關定的軸向磁場，藉由磁場的作用使氣體分子的運 = 狀運動，從而增加雜生成過程中«分子的碰撞 機羊“離子化的程細及絲的密度和均自度。 [實’將針對肋纽上述綠雜佳實關裝置作一說明。 的供-/5 _圖」揭7F 了實現上述^法之I置㈣—種較佳實關，這個裝置 内體4〇採橫置式設計，藉由真空果7〇將低壓反應腔體4〇 出，再經由供氣單元72供給電漿生成氣體如氬(Ar)、或 疋f e㈣性氣體，並使低壓反應腔體4Q内的壓力保持7〇〇 mmHg)低壓狀態(流量5〜251/min)。 、X； 2電聚產生單元2〇，基本上包含有：第一電極2卜基底(第二電極)30 以一、電漿生成氣體引至前述二者之間的氣體通路22,第一電極21與基底 (第-電極)30分別具有不同的電性(一者為陰極，一者為陽極），而此二者的 ^用P為用以產生電聚所需的電極。介於第一電極21絲底(第二電極))〇 -者之間處即構成-電漿反應區，在第_電極21與基底(第二電極)3〇間施 加可調整的直流電流(50〜400 amp)以產生電弧，就能使電聚生成氣體 解離成電漿，而沿陰極的軸向朝陽極形成一高溫熱電漿喷射流23。直 流電衆產生單元20所使用的電極，其中第一電極21係為陰極的鶴電極， 基底(第一電極)3〇則為陽極電極且採鋼質設計，另以直流電銲機(wgding machine，圖中未示)作為產生直流電漿的電源供應器。在這個實施例，直 流電漿產生單元20和碳源前驅物11的送料單元1〇彼此結合在一起或採一 體的設=，換句話說就是來自送料單元10的碳源前驅物n係經過直流電 產生單元20内部的送料管路而被送至位於第一電極？！和基底(第二電 極)30之間的電漿反應區。 一般而言高溫熱電漿噴射流23具有高熱能。電漿由直流電漿產生單元 20所產生，高溫熱電漿噴射流23在陰陽兩電極間起始點火，可以速迅且有 效地提供大量高溫的熱量。在低壓反應腔體4〇中，含碳的固態，液態或是 11 1237840 氣態的碳源前驅物11被送料嚴分、、 23之中，且私電狀舰的㈣鱗漿喷射流 -Hfr 3的方向是朝向前述的基底％，利用苴 =^細halpy)和反應性(峨軸y)與碳源前驅物u進行反應，人成 運動(如圖中虛線箭頭所示），用以Gruff/是可以作直線 奈米碳管的連續°生產絲早搞運作，將基底％上的絲碳管收集，以利The main purpose of the present invention is to provide a method for synthesizing carbon nanotubes with high yield and low cost. Renzhantai㈣ is mainly heated by high temperature thermoelectric polymerized jet (themial Pl_㈣) as the heat source. The raw material of the carbon tube is carbon-containing, liquid or silk carbon source precursor. No catalyst is added (CatalySt- : Free), carbon nanotubes are synthesized in a high-temperature and low-pressure reaction chamber. The carbon source of the present invention is used as a carbon source at high temperature. After the above graphitization, the resulting nano / 笞 ^ ,,,, , ° ae orientation, few structural defects and purity, etc., and greatly improve the quality and synthesis rate of carbon nanotubes. "Another object of the present invention is to provide a device for continuous synthesis of carbon nanotubes. 1237840 _ The disclosed device has a low-voltage reaction chamber, which is provided with a first electrode and a substrate with different electrical properties and / or a substrate (the second electric # is generated by a different electric field, and the electric field is in one of them. A plasma reaction zone is formed between them to generate a high-temperature thermoelectric nozzle. Γ is the source precursor. The feeding device of the carbon source precursor is continuously sent to the electric reactor. The synthesized nano carbon tube can be deposited. On the base; the base of the hair surface design is; -The operation of the collection unit collects the carbon nanotubes on the substrate for continuous production of the carbon nanotubes. The invention of the text opens the way-a plasma system that can increase the degree of ionization, mainly provided on the periphery of the electrical excitation system -Magnetic field to become a magnetron plasma system. The magnetic field is generated by a toroidal electromagnetic field coil (sdenddfielded) surrounding the electric system to provide a fixed axial magnetic field. Changing the meaning of marriage and increasing the collision probability of Lu's gas molecules' increasing the degree of ionization and the density and uniformity of the plasma. The detailed description and technical content of the present invention will now be described with drawings. According to the present invention, a method for synthesizing nano carbon tubes by using a thermo-plasma jet is provided. The method includes: k supplying a low-pressure reaction chamber and sending plasma gas into the reaction chamber. Provide a direct current plasma generating unit, which has a first electrode with a different electrical property and a substrate (a second electrode), and an electric field generated by the different electrical properties constitutes between the two. Forming a plasma reaction zone for reacting with a plasma generating gas to generate a high temperature thermoplasma jet as a heat source, and the direction of the plasma jet is toward the aforementioned substrate; and a feeding unit for providing a carbon source precursor For continuously supplying carbon-containing solid, liquid, or gaseous carbon source precursors into a high-temperature thermoplasma jet to synthesize carbon nanotubes on the substrate surface; and providing a collecting means for collecting Nano-tubes synthesized on the substrate. The generation method of high-temperature thermo-plasma jets. For those who are familiar with this technical field, after understanding the following description of the present invention, they will find that they can use DC plasma system and high-frequency electricity. It can be implemented by any of the tritium system or the microwave plasma system. 10 1237840 Jet flow to collect coffee: the 纟 gang warm plasma plasma sprays the pure pure body_supply-magnetic field method, used at high temperature The thermoelectric motor moves from a straight material: a fixed axial magnetic field, and the movement of gas molecules is caused by the action of the magnetic field, thereby increasing the «molecular collision machine sheep" in the process of heterogeneity. The ionization process is fine and the density and homogeneity of the silk. [Real 'will make a description of the above-mentioned green miscellaneous real-life device of RiNiu. The supply of -5 _ Figure "Reveals 7F to achieve the above I method to achieve a better practice-the internal body of this device 40 adopts a horizontal design, and the low-pressure reaction chamber 40 by vacuum fruit 70. Out, and then supply a plasma-generating gas such as argon (Ar) or 疋 f e ㈣ gas through the gas supply unit 72, and maintain the pressure in the low-pressure reaction chamber 4Q to 700mmHg) low-pressure state (flow rate 5 ~ 251 / min). , X; 2 The electropolymerization generating unit 20 basically includes: the first electrode 2 and the substrate (second electrode) 30, and the gas generated by the plasma is introduced to the gas path 22 between the two, the first electrode 21 and the substrate (first electrode) 30 respectively have different electrical properties (one is a cathode and one is an anode), and P of the two is an electrode required for generating electropolymerization. A plasma reaction zone is formed between the first electrode 21 and the wire bottom (second electrode)), and an adjustable DC current is applied between the first electrode 21 and the substrate (second electrode) 30. 50 ~ 400 amp) to generate an electric arc, which can dissociate the electricity generated gas into a plasma, and form a high-temperature thermoplasma jet 23 toward the anode along the axis of the cathode. The electrodes used in the DC power generation unit 20, where the first electrode 21 is a crane electrode of the cathode, the base (first electrode) 30 is an anode electrode and is made of steel, and a DC welding machine (wgding machine, figure (Not shown) as a power supply for generating DC plasma. In this embodiment, the direct current plasma generating unit 20 and the feeding unit 10 of the carbon source precursor 11 are combined with each other or adopt an integrated design =, in other words, the carbon source precursor n from the feeding unit 10 is generated by direct current. The feed line inside the unit 20 is sent to the first electrode? !! And a plasma reaction zone between the substrate (second electrode) 30. Generally speaking, the high-temperature thermoplasma jet 23 has high thermal energy. The plasma is generated by the direct-current plasma generating unit 20, and the high-temperature thermoplasma jet 23 starts to ignite between the two electrodes, which can quickly and efficiently provide a large amount of high-temperature heat. In the low-pressure reaction chamber 40, a carbon-containing solid, liquid, or 11 1237840 gaseous carbon source precursor 11 is severely divided into feeds, 23 and 23, and the squeezing scale jet of private electric ships-Hfr 3 The direction is toward the aforementioned base%, using 苴 = ^ fine halpy) and reactivity (E axis y) to react with the carbon source precursor u, and human motion (as shown by the dashed arrow in the figure) is used for Gruff / It can be used for the continuous ° production of straight carbon nanotubes to produce silk early, and collect the silk carbon tubes on the base% to facilitate
=以收集奈米叙管的收集單元(collector)，包含有一可移動的刮刀別 以及-位_刀5G之下方敝餘^ 51，刮刀％可赠人傾反應 10Π’/Τ合「第1圖」中向左方移動之基底3G的移動位置^ 積=底3G之表面的奈米碳管刮下，使基底3()哺其絲的表面，而舌 侧可以糊真空吸取的方式㈣進人裝㈣袋的收集容崇 5 m，^6龍原來之表_基底3g就可以再度魏至侧的位置 以便顧與第-電極21協随生高溫熱電时射流…如此不斷地進行 奈米，官的合成和收集_作’以連續地生產奈米碳f。真空果7〇抽出 的廢氣，職再㈣;t H和銳纽Μ 71處讀再槪 [實施例二] ，2圖」揭示了貫現上述方法之裝置的另—種較佳實施例，這個裝 置的低壓反應腔體40仍然採橫置式設計，在這個實補，直流電浆產 元20和碳源前驅物u的送料單元1〇或衡採各自獨立的設計，換句話說 就是來自送料單元1G的碳源前驅物丨丨可罐由電驗生單元2()的外部 料管路進人·反應區。其中的_種方式則是湘—石墨棒3卜將碳源前 驅物11自電漿反應區的下方向上送人，此—石墨棒31為中空的管狀物， 可以作旋轉運動。碳源前驅物u可經此石墨棒31進人電漿反應區。石 墨棒31的電極性為陽極。另外，碳源前驅物n也可經與直流電毅產生單 元20同一方向的外部送料管路1〇1進入電漿反應區。 適合本發明之方法及裝置的碳源前驅物，包括有： 含碳的固態碳源前驅物，包含了例如：奈米碳黑(carb〇nblack)、 12 1237840 碳六十(C6〇，fullerene)、奈米碳球(carb〇n nan〇ball)、或是萘(naphthalene). 等固態碳材或碳氫化合物。 含碳的液態碳源前驅物，包含了例如··笨（benzene)、甲苯 (toluene)、或是二甲苯(Xylene)等液態碳氳化合物。 含碳的氣態碳源前驅物，包含了例如··甲烷(methane)、乙炔 (acetylene)、或是乙烯(ethylene)等氣體碳氫化合物。 若使用固態碳源前驅物，碳源前驅物的送料單元1〇可以使用螺 旋式供料器（screw feeder)送料；若使用液態碳源前驅物，可以使用液 態泵(diaphragm pump)加壓傳輸；若使用氣態碳源前驅物，可以從氣 體鋼瓶(gas cylinder)或其類似物提供。 依據本發明所揭露的方法，其較佳的實施例更包括了在電漿系統鲁 外圍提供一磁場以成為一種磁控電漿系統，這個磁場係由圍繞著電 漿低壓反應腔體40的環形電磁場線圈（s〇ien〇id fieid c〇ii)6〇在通入電 流（0.5〜1.5 amp)後所產生（見「第1>2圖」），用以在高溫熱電漿噴射 流23的方向提供一個固定的軸向磁場，藉由磁場的作用使氣體分子 的運動從直線運動變成螺旋狀運動，從而增加氣體分子的碰撞機 率，提高離子化的程度以及電漿的密度和均勻度。 以下就以一較佳的例子，說明利用本發明之方法及裝置合成奈米 碳管的過程。 ” ^ [合成奈米碳管之實例] 在此選擇奈米碳黑(carbon black)固態碳材作為碳源前驅物1丨。碳 黑為黑色粉粒，具有碳環基本結構，粒徑約1〇〜1〇〇 nm。以真空泵％ 將低壓反應腔體40内的氣體排出，再經由供氣單元72供給電漿生 成氣體-氬(Ar)，並使壓力保持在1〇〇mmHg，流量1〇1/min，然後在第 一電極21與基底(第二電極)3〇兩個電極間施加15〇amp直流電流，以使 ΙΧΑιΟ解離成電聚，沿第一電極21(陰極)的軸向朝基底(第二電極加(陽 極)形成一南溫熱電漿喷射流23，在高溫熱電漿噴射流23作用下，快迷 升溫力「口熱至3000 C以上，時間6〇sec即可使奈米碳黑合成奈米碳營。、 「第3圖」顯示了本發明以奈米碳黑前驅物所合成的奈米碳管的掃描 13 1237840 電子顯微鏡照片。從此圖可見纖維狀的奈米碳管。石墨結構若有缺陷，則 導致螺旋(helical)狀的奈米碳管的形成。由高溫熱電漿喷射流合成的奈米碳 管較直不彎，顯現出較佳的石墨化程度。「第4圖」則顯示了本發明以奈米 碳黑前驅物所合成的奈米碳管的高解析穿透式電子顯微鏡照片。從此圖可 見中空核心和圍繞著核心的筆直晶格條紋的奈米碳管。奈米碳管的壁層平 行於其中心軸，既筆直不彎曲，也不纏繞在一起，此為高度石墨化的特徵。 選用奈米碳黑作為碳源前驅物合成奈米碳管，乃經由固態反應轉換 (solid-state transformation)而成。奈米碳管由固態反應(solid reacti〇n)生成， 而不經由氣化的氣態反應(gas phase reacti〇n)，反應速率較快且反應時間短。 因此，以奈米碳黑作為碳源前驅物的高溫熱電漿喷射流加熱法，可以加速 奈米碳管的合成速率。 奈米叙黑可當作奈米碳管形成和生長的建構方塊(building block)。這些 固態碳材，不僅可當作奈米碳管的前驅物，而且可提昇奈米碳管產量。且 以奈米碳黑為前驅物合成的奈米碳管所含的雜質較少，所得奈米碳管的純 度較向，可使純化處理減到較低。以高溫熱電漿喷射流合成奈米碳管，可 提高奈米碳管的產量和降低價格。 [發明的功效] 本發明以高溫的熱電漿噴概加熱低成本的碳源前驅物，無須添加催 化劑，就可合成結構缺陷少和高純度的奈米碳管。 而^透過本發明所揭露的裝置，其中的電極皆為可移動式的設計，配 a碳源前驅物的珊單元連續地輸人碳源前驅物，都可提高其產能。 發明的技術内容已透過上述的實施例揭露如前，惟其僅為本發 申-二|=例而已’料能以之限林發明之賴範圍，即凡依本發明 蚁專利範圍所作之均等變化與修飾，皆應仍屬本發明保護之範圍。 【圖式簡單說明】 m!本=之方法的裝置的第一種較佳實施例構造，其中 電水產生早凡和妷源前驅物送料單元為一體者。 2圖’揭示了實現本發明之方法的裝置的第二種較佳實施例構造，其中 .1237840 電漿產生單元和碳源前驅物送料單元為各自獨立者。 第3圖，顯示依據本發明之方法以奈米碳黑作為碳源前驅物所合成的奈米 碳管的掃描電子顯微鏡照片。 第4圖，顯示依據本發明之方法以奈米碳黑作為前驅物所合成的奈米碳管 的高解析穿透式電子顯微鏡照片。 【圖式符號說明】 10，10a.........碳源前驅物的送料單元 101..........外部送料管路 11............碳源前驅物 20 ............直流電漿產生單元 21 ............第一電極 23 30 31 40 50 51 •氣體通路 •高溫熱電漿噴射流 •基底(第二電極） •石墨棒 •低壓反應腔體 •刮刀 •收集容器 60...........電磁線圈 70 ............真空泵 71 ............過濾器和廢氣處理單元 72 ............供氣單元 15= The collector for collecting nanometer tubes includes a movable scraper blade and -bit_knives below 5G ^ 51, the scraper% can give people a tilt response of 10Π '/ Τ 合 「第 1 图The position of the base 3G moving to the left in the center of the center of the left side ^ Product = the carbon nanotubes on the surface of the base 3G are scraped off, so that the base 3 () feeds the surface of the silk, and the tongue can be sucked into the person by vacuum suction The bagged collection of Rong Chong 5 m, ^ 6 Dragon's original table _ 3g of the base can be repositioned to the side to allow for the jet flow during the high-temperature thermoelectricity associated with the -electrode 21 ... Synthesis and collection _ for 'continuous production of nano carbon f. The exhaust gas extracted by the vacuum fruit 70 is re-assigned; t H and Renewal M 71 are read again [Example 2], Figure 2 reveals another preferred embodiment of the device implementing the above method. This The low-pressure reaction chamber 40 of the device still adopts a horizontal design. In this supplement, the feeding unit 10 of the DC plasma production unit 20 and the carbon source precursor u or the independent mining unit are designed separately, in other words, from the feeding unit 1G. The carbon source precursor can be introduced into the reaction zone by the external material pipeline of the electric test unit 2 (). One of the methods is that the Xiang-graphite rod 3 sends the carbon source precursor 11 upward from below the plasma reaction zone. The graphite rod 31 is a hollow tube and can be rotated. The carbon source precursor u can enter the plasma reaction zone through the graphite rod 31. The polarity of the graphite rod 31 is an anode. In addition, the carbon source precursor n can also enter the plasma reaction zone via an external feeding pipe 101 in the same direction as the direct current generating unit 20. Carbon source precursors suitable for the method and device of the present invention include: carbon-containing solid carbon source precursors, including, for example, carbon black (carbon black), 12 1237840 carbon sixty (fullerene) , Carbon carbon balls (carbon nanball), or naphthalene. And other solid carbon materials or hydrocarbons. The carbon-containing liquid carbon source precursor includes, for example, a liquid carbon halide compound such as benzene, toluene, or xylene. Carbon-containing gaseous carbon source precursors include, for example, gaseous hydrocarbons such as methane, acetylene, or ethylene. If a solid carbon source precursor is used, the feeding unit 10 of the carbon source precursor can be fed by a screw feeder; if a liquid carbon source precursor is used, a liquid pump (diaphragm pump) can be used for pressure transmission; If a gaseous carbon source precursor is used, it can be provided from a gas cylinder or the like. According to the method disclosed in the present invention, its preferred embodiment further includes providing a magnetic field around the plasma system to form a magnetron plasma system. The magnetic field is formed by a ring surrounding the plasma low-pressure reaction cavity 40. Electromagnetic field coil (s〇ien〇id Fieid Co.) 6〇 generated after the current (0.5 ~ 1.5 amp) is applied (see "Figure 1 > 2"), used to direct the direction of the high temperature thermoplasma jet 23 A fixed axial magnetic field is provided, and the motion of the gas molecules is changed from linear motion to spiral motion by the action of the magnetic field, thereby increasing the collision probability of the gas molecules, increasing the degree of ionization, and the density and uniformity of the plasma. In the following, a preferred example is used to describe the process of synthesizing carbon nanotubes using the method and device of the present invention. ^ [Example of synthetic nano carbon tube] Here, carbon black solid carbon material is selected as the carbon source precursor 1 丨 Carbon black is a black powder with a basic structure of carbon rings and a particle size of about 1 〇 ～ 100nm. The gas in the low-pressure reaction chamber 40 is exhausted with a vacuum pump%, and then a plasma is generated through the gas supply unit 72 to generate gas-argon (Ar), and the pressure is maintained at 100mmHg, and the flow rate is 1 〇1 / min, and then apply a 150 amp DC current between the two electrodes of the first electrode 21 and the substrate (second electrode) 30, so as to dissociate the IXΑιΟ into an electropolymer, along the axis of the first electrode 21 (cathode) A south temperature thermoplasma jet 23 is formed toward the substrate (the second electrode plus (anode). Under the action of the high temperature thermoplasma jet 23, the heating force is quickly increased to 3,000 C or higher in a time of 60 seconds. Nano-carbon black synthesizes nano-carbon camps. "Figure 3" shows a scan of a 1237840 electron microscope photograph of a nano-carbon tube synthesized from a nano-carbon black precursor of the present invention. From this figure, a fibrous nano can be seen. Carbon tubes. If the graphite structure is defective, it leads to the formation of helical nano carbon tubes. The nano carbon tube synthesized by the warm plasma plasma jet is relatively straight and not curved, showing a better degree of graphitization. "Figure 4" shows the nano carbon tube synthesized by the nano carbon black precursor of the present invention. High-resolution transmission electron microscope photo. From this figure, you can see the hollow core and the straight carbon nanotubes surrounding the core. The wall of the carbon nanotube is parallel to its central axis, and it is neither straight nor curved. Twisted together, this is a highly graphitized feature. Nano carbon black is selected as a carbon source precursor to synthesize a carbon nanotube, which is formed by solid-state transformation. Nano carbon tubes are formed by solid-state reactions ( solid reacti〇n), without gas phase reaction (gas phase reactio), the reaction rate is fast and the reaction time is short. Therefore, the high temperature thermoelectric plasma jet with nanometer carbon black as the carbon source precursor The heating method can accelerate the synthesis rate of nano carbon tubes. Nano black can be used as building blocks for the formation and growth of nano carbon tubes. These solid carbon materials can not only be used as precursors of nano carbon tubes Material, and can promote The output of rice carbon tubes. Nano carbon tubes synthesized with nano carbon black as precursors contain less impurities, and the purity of the obtained carbon tubes is more oriented, which can reduce the purification treatment. Jet stream synthesis of nano carbon tubes can increase the output of nano carbon tubes and reduce the price. [Effect of the invention] The present invention uses a high-temperature thermo-plasma spray to heat low-cost carbon source precursors, and can be synthesized without adding a catalyst. Nano-carbon tube with few structural defects and high purity. ^ Through the device disclosed in the present invention, the electrodes are all movable design, and the unit with a carbon source precursor is continuously input human carbon source precursor. Can increase their productivity. The technical content of the invention has been disclosed through the above-mentioned embodiments, but it is only for the purpose of this application-the two examples are only limited to the scope of the invention, that is, all the equivalent changes made according to the scope of the ant patent of the invention And modifications should still fall within the protection scope of the present invention. [Brief description of the diagram] The structure of the first preferred embodiment of the device of the method of m! Ben =, in which electro-hydraulic generation Zaofan and Wuyuan precursor feeding unit are integrated. Fig. 2 'discloses the structure of the second preferred embodiment of the apparatus for implementing the method of the present invention, in which the .1237840 plasma generating unit and the carbon source precursor feeding unit are independent of each other. Fig. 3 shows a scanning electron microscope photograph of a carbon nanotube synthesized using carbon black as a carbon source precursor according to the method of the present invention. Fig. 4 shows a high-resolution transmission electron microscope photograph of a carbon nanotube synthesized using the carbon black as a precursor according to the method of the present invention. [Illustration of Symbols] 10, 10a ...... Feeding unit 101 for carbon source precursor ......... External feeding pipe 11 ......... ... carbon source precursor 20 ............ DC plasma generating unit 21 ............ first electrode 23 30 31 40 50 51 • gas passage • High-temperature thermo-plasma jet • substrate (second electrode) • graphite rod • low-pressure reaction chamber • scraper • collection container 60 ........... electromagnetic coil 70 .......... ..Vacuum pump 71 ............ Filter and exhaust gas treatment unit 72 ............ Air supply unit 15