TWI408246B - Manufacturing method for branched carbon nanotubes - Google Patents
Manufacturing method for branched carbon nanotubes Download PDFInfo
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- TWI408246B TWI408246B TW96121797A TW96121797A TWI408246B TW I408246 B TWI408246 B TW I408246B TW 96121797 A TW96121797 A TW 96121797A TW 96121797 A TW96121797 A TW 96121797A TW I408246 B TWI408246 B TW I408246B
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本發明涉及一種奈米碳管之製備方法，尤其涉及一種分枝型奈米碳管之製備方法。 The invention relates to a method for preparing a carbon nanotube, in particular to a method for preparing a branched carbon nanotube.
奈米碳管(CNTs)自90年代初由日本學者Iijima發現以來(Iijima S.,Nature,1991,354(7),56-58)，立即引起科學界及產業界之極大重視，係近年來國際科學研究之熱點。奈米碳管由六元環組成之石墨片層結構捲曲而形成之同心圓筒構成。分枝型奈米碳管因其三維管狀結構而具有獨特之電學開關性及導熱性。隨著現代電子工藝更一步地微型化，分枝型奈米碳管可作為電極材料、聚合物增強劑、電晶體或電化學產品而廣泛地應用於奈米尺度之電晶體、放大器或電極材料等方面。 Since the discovery of Japanese carbon nanotubes (CNTs) by Japanese scholar Iijima in the early 1990s (Iijima S., Nature, 1991, 354(7), 56-58), it has immediately attracted great attention from the scientific community and industry. A hot spot in international scientific research. The carbon nanotubes are composed of a concentric cylinder formed by a six-membered ring-shaped graphite sheet structure. Branched carbon nanotubes have unique electrical switching properties and thermal conductivity due to their three-dimensional tubular structure. As modern electronic processes are further miniaturized, branched carbon nanotubes can be widely used as nanometer-scale transistors, amplifiers or electrode materials as electrode materials, polymer enhancers, transistors or electrochemical products. etc.
先前之製備分枝型奈米碳管之方法有電弧放電法及化學氣相沈積法(Chemical Vapor Deposition,CVD)。其中，通過電弧放電法製備之分枝型奈米碳管之產率極低，從而限制了該方法之推廣。目前，CVD法為製備分枝型奈米碳管之主要方法。該方法為利用含有分枝型通孔之模板，於通孔中生長分枝型奈米碳管，或者利用揮發性有機金屬化合物於高溫下分解而得到分枝型奈米碳管 。然，利用模板之方法製備分枝型奈米碳管過程複雜，且所得到之奈米碳管之品質較差；利用有機金屬化合物分解之方法製備分枝型奈米碳管，因金屬催化劑係於氣相下分解，不容易實現分枝型奈米碳管之定位生長，不利於奈米碳管於微電子器件中之應用。 Previous methods for preparing branched carbon nanotubes include arc discharge and Chemical Vapor Deposition (CVD). Among them, the yield of the branched carbon nanotubes prepared by the arc discharge method is extremely low, thereby limiting the promotion of the method. At present, the CVD method is the main method for preparing branched carbon nanotubes. The method is to use a template containing branched through holes to grow a branched carbon nanotube in the through hole, or to decompose the volatile organic metal compound at a high temperature to obtain a branched carbon nanotube. . However, the process of preparing the branched carbon nanotubes by the template method is complicated, and the quality of the obtained carbon nanotubes is poor; the branched carbon nanotubes are prepared by the decomposition of the organometallic compounds, because the metal catalysts are Decomposition in the gas phase makes it difficult to achieve the localized growth of branched carbon nanotubes, which is not conducive to the application of nanocarbon tubes in microelectronic devices.
有鑒於此，提供一種可實現定位生長、有利於後期應用之分枝型奈米碳管之簡單製備方法實為必要。 In view of this, it is necessary to provide a simple preparation method of a branched carbon nanotube which can realize positioning growth and is advantageous for later application.
以下以實施例說明一種分枝型奈米碳管之製備方法，其包括以下步驟：提供一基底；形成一隔離層於該基底之表面；形成一催化劑層於該隔離層之表面，於奈米碳管之生長溫度下，催化劑層與隔離層之材料係互不浸潤；將表面形成有隔離層及催化劑層之基底置於一反應爐內；加熱使反應爐之溫度達到一預定溫度，通入保護氣退火一段時間後，再往反應爐內通入碳源氣，反應一段時間即得到分枝型奈米碳管。 The following is a description of a method for preparing a branched carbon nanotube, which comprises the steps of: providing a substrate; forming a separation layer on the surface of the substrate; forming a catalyst layer on the surface of the isolation layer, in the nanometer At the growth temperature of the carbon tube, the material of the catalyst layer and the separation layer are not wetted together; the substrate on which the separation layer and the catalyst layer are formed is placed in a reaction furnace; the temperature of the reaction furnace is brought to a predetermined temperature by heating, and the temperature is reached. After the shielding gas is annealed for a period of time, a carbon source gas is introduced into the reaction furnace, and a branched carbon nanotube is obtained for a certain period of time.
與先前技術相比，該分枝型奈米碳管之製備方法具有以下優點：(1)以乙炔、甲烷、乙烯等純碳氫氣體為碳源氣，降低了生產成本；(2)採用鍍膜之方法製備催化劑層，故可利用光刻等方法以實現奈米碳管之定位生長；(3)製備出之分枝型奈米碳管多數頂端包覆有金、銀、鉑等導電性佳之金屬，從而提高了奈米碳管與電路之電性連接，有利於奈米碳管之後期應用；(4)該方法製備之分枝型奈米碳管之產率可達到50%。 Compared with the prior art, the preparation method of the branched carbon nanotube has the following advantages: (1) using a pure hydrocarbon gas such as acetylene, methane or ethylene as a carbon source gas, thereby reducing the production cost; (2) using a coating film The catalyst layer is prepared by the method, so that the positioning growth of the carbon nanotubes can be realized by photolithography or the like; (3) the branched carbon nanotubes prepared are mostly coated with gold, silver, platinum and the like. The metal, thereby improving the electrical connection between the carbon nanotube and the circuit, is beneficial to the later application of the carbon nanotube; (4) the yield of the branched carbon nanotube prepared by the method can reach 50%.
10‧‧‧基底 10‧‧‧Base
12‧‧‧隔離層 12‧‧‧Isolation
14‧‧‧催化劑層 14‧‧‧ catalyst layer
16‧‧‧分枝型奈米碳管 16‧‧‧ Branched carbon nanotubes
圖1係本發明實施例中分枝型奈米碳管之製備過程示意圖。 1 is a schematic view showing the preparation process of a branched carbon nanotube in the embodiment of the present invention.
圖2係本發明實施例中所形成之分枝型奈米碳管之掃描電子顯微鏡(SEM)照片。 2 is a scanning electron microscope (SEM) photograph of a branched carbon nanotube formed in an embodiment of the present invention.
圖3係本發明實施例中分枝型奈米碳管之生長過程示意圖。 3 is a schematic view showing the growth process of a branched carbon nanotube in the embodiment of the present invention.
下面將結合附圖對本發明實施例作進一步之詳細說明。 The embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.
請參閱圖1，本發明提供一種分枝型奈米碳管之生長方法，具體包括以下步驟：步驟一：首先提供一基底10，並於該基底10之一表面沈積一隔離層12。基底10之材料可為矽、玻璃、石英等。該隔離層12為通過熱沈積、電子束蒸鍍或濺射等方法形成之氧化鋁、二氧化矽等材料，該隔離層12之厚度為大於1奈米(nm)。 Referring to FIG. 1 , the present invention provides a method for growing a branched carbon nanotube, which specifically includes the following steps: Step 1: First, a substrate 10 is provided, and an isolation layer 12 is deposited on one surface of the substrate 10. The material of the substrate 10 may be tantalum, glass, quartz or the like. The spacer layer 12 is made of a material such as alumina or cerium oxide formed by a method such as thermal deposition, electron beam evaporation, or sputtering. The thickness of the spacer layer 12 is greater than 1 nanometer (nm).
於本實施例中，基底10之材料為矽，隔離層12為通過電子束蒸鍍法形成於基底10上之厚度約為10 nm之氧化鋁層。 In the present embodiment, the material of the substrate 10 is tantalum, and the spacer layer 12 is an aluminum oxide layer having a thickness of about 10 nm formed on the substrate 10 by electron beam evaporation.
步驟二：形成一催化劑層14於隔離層12之表面。催化劑層14為通過熱沈積、電子束蒸鍍、或濺射等方法形成之金、銀、銅、鉑、鉛等導電性佳之貴金屬材料。該催化劑層之厚度為0.5nm至1.5nm。於奈米碳管之生長溫度下，催化劑層14與隔離層12之材料係互不浸潤。 Step 2: Form a catalyst layer 14 on the surface of the separator 12. The catalyst layer 14 is a noble metal material having good conductivity such as gold, silver, copper, platinum or lead formed by methods such as thermal deposition, electron beam evaporation, or sputtering. The catalyst layer has a thickness of from 0.5 nm to 1.5 nm. At the growth temperature of the carbon nanotubes, the material layers of the catalyst layer 14 and the separator 12 are not infiltrated with each other.
於本實施例中，催化劑層14為通過電子束蒸鍍法形成於隔離層12上之厚度為1nm之金層。 In the present embodiment, the catalyst layer 14 is a gold layer having a thickness of 1 nm formed on the separator 12 by electron beam evaporation.
步驟三：將表面依次形成有隔離層12與催化劑層14之基底10置於一反應爐內。該反應爐為先前CVD法中常用之管式反應爐，反應爐之直徑約為1英寸。 Step 3: The substrate 10 having the surface of the separator 12 and the catalyst layer 14 in this order is placed in a reactor. The reactor is a tubular reactor commonly used in previous CVD processes, and the reactor has a diameter of about 1 inch.
步驟四：加熱反應爐到一預定溫度，先通入保護氣退火一段時間後，再通入碳源氣反應一段時間，可於隔離層12之表面，沿平行於基底10表面之方向生長出分枝型奈米碳管16。 Step 4: heating the reaction furnace to a predetermined temperature, first annealing into the shielding gas for a period of time, and then introducing the carbon source gas for a certain period of time, and growing on the surface of the isolation layer 12 in a direction parallel to the surface of the substrate 10. Branch type carbon nanotubes 16.
本實施例中，反應爐溫度為880~950℃(攝氏度)，優選為900~950℃。該爐溫係由催化劑之種類來決定之，催化劑不同，爐溫會相差較大。保護氣包括氬氣與氫氣，其中氬氣之流量為0~140立方厘米/分鐘(sccm)，氫氣之流量約為200sccm。通入保護氣退火之時間為10-30分鐘。通入的氫氣主要作用係還原催化劑，以保持其催化活性。優選地，氬氣與氫氣流量比為140：200，反應時間為25分鐘。碳源氣為乙炔、甲烷、乙烯、一氧化碳或乙醇等氣體，通入碳源氣之流量為10~50sccm，反應時間為5分鐘至30分鐘。優選地，以乙炔作為碳源氣，流量為10~25sccm，反應時間為15分鐘。 In the present embodiment, the temperature of the reaction furnace is 880 to 950 ° C (degrees Celsius), preferably 900 to 950 ° C. The temperature of the furnace is determined by the type of catalyst. The catalysts are different and the furnace temperatures will vary greatly. The shielding gas includes argon gas and hydrogen gas, wherein the flow rate of the argon gas is 0 to 140 cubic centimeters per minute (sccm), and the flow rate of the hydrogen gas is about 200 sccm. The time for the annealing of the protective gas is 10-30 minutes. The hydrogen gas that is introduced mainly acts as a reduction catalyst to maintain its catalytic activity. Preferably, the argon to hydrogen flow ratio is 140:200 and the reaction time is 25 minutes. The carbon source gas is a gas such as acetylene, methane, ethylene, carbon monoxide or ethanol, and the flow rate of the carbon source gas is 10 to 50 sccm, and the reaction time is 5 minutes to 30 minutes. Preferably, acetylene is used as the carbon source gas, the flow rate is 10 to 25 sccm, and the reaction time is 15 minutes.
請參閱圖2及圖3，於本發明所提供之分枝型奈米碳管16之製備過程中，分枝型奈米碳管16之具體生長過程如下：催化劑層14在反應爐溫度之作用下熔化，由於催化劑層14與隔離層12互不浸潤，熔化之催化劑收縮成球形催化劑顆粒，且於隔離層12之表面具有流動性。碳源氣於熔化之催化劑顆粒表面分解、析出碳原子，從而沿平行於基底10之方向生長出奈米碳管。催化 劑顆粒位於奈米碳管之生長頂端。當兩個奈米碳管之生長頂端之催化劑顆粒相遇時，兩個較小之催化劑顆粒可合併成一個較大之催化劑顆粒，而後再從較大之催化劑顆粒上生長出新的奈米碳管，即可得到Y型之分枝型奈米碳管16(如圖2(a)及圖3(a)所示)。如果，該Y型之分枝型奈米碳管16之生長頂端之催化劑顆粒再與另一奈米碳管之催化劑顆粒相遇，則可得到多極的Y型之分枝型奈米碳管16(如圖3(b)所示)。同理，當兩個奈米碳管之催化劑顆粒頭對頭地正面相遇即得到┴字型或十型的分枝型奈米碳管16(如圖3(c)及圖3(d)所示)；當複數奈米碳管之催化劑顆粒同時相遇即得到多分枝型的分枝型奈米碳管16(如圖3(e)所示)；當一個奈米碳管之催化劑顆粒與另一奈米碳管之側壁相遇可得到L型的分枝型奈米碳管16(如圖2(b)及圖3(f)所示)。該方法製備之分枝型奈米碳管之產率為30%~50%。 Referring to FIG. 2 and FIG. 3, in the preparation process of the branched carbon nanotubes 16 provided by the present invention, the specific growth process of the branched carbon nanotubes 16 is as follows: the effect of the catalyst layer 14 on the temperature of the reaction furnace Under the melting, since the catalyst layer 14 and the separator 12 are not wetted with each other, the molten catalyst shrinks into spherical catalyst particles and has fluidity on the surface of the separator 12. The carbon source gas decomposes on the surface of the molten catalyst particles to precipitate carbon atoms, thereby growing the carbon nanotubes in a direction parallel to the substrate 10. catalytic The agent particles are located at the top of the growth of the carbon nanotubes. When the catalyst particles at the top of the growth of the two carbon nanotubes meet, the two smaller catalyst particles can be combined into one larger catalyst particle, and then a new carbon nanotube is grown from the larger catalyst particle. The Y-type branched carbon nanotube 16 can be obtained (as shown in Fig. 2(a) and Fig. 3(a)). If the catalyst particles of the growth tip of the Y-type branched carbon nanotube 16 meet another catalyst particle of the carbon nanotube, a multi-pole Y-type branched carbon nanotube 16 can be obtained. (As shown in Figure 3 (b)). Similarly, when the catalyst particles of the two carbon nanotubes meet head-to-head, the branched-type or ten-type branched carbon nanotubes 16 are obtained (as shown in Fig. 3(c) and Fig. 3(d). When the catalyst particles of the plurality of carbon nanotubes meet at the same time, a multi-branched branched carbon nanotube 16 is obtained (as shown in Fig. 3(e)); when one catalyst tube of the carbon nanotube is combined with another When the sidewalls of the carbon nanotubes meet, an L-shaped branched carbon nanotube 16 can be obtained (as shown in Fig. 2(b) and Fig. 3(f)). The yield of the branched carbon nanotubes prepared by the method is 30% to 50%.
該方法製備之分枝型奈米碳管16通過組裝將奈米碳管與電子電路之電極相連，從而保證奈米碳管與電路良好之歐姆接觸。另外，由於採用鍍膜方法製備催化劑，故可實現分枝型奈米碳管16之定位生長，有利於奈米碳管器件有選擇地定向地製備。 The branched carbon nanotubes 16 prepared by the method are connected to the electrodes of the electronic circuit by assembly, thereby ensuring good ohmic contact between the carbon nanotubes and the circuit. In addition, since the catalyst is prepared by the coating method, the localized growth of the branched carbon nanotubes 16 can be achieved, which is advantageous for the selective preparation of the carbon nanotube devices.
與先前技術相比，該分枝型奈米碳管之製備方法具有以下優點：(1)以乙炔、甲烷、乙烯等純碳氫氣體為碳源氣，降低了生產成本；(2)採用鍍膜之方法製備催化劑層，故可利用光刻等方法以實現奈米碳管之定位生長；(3)製備出之分枝型奈米碳管多數頂端包覆有金、銀、鉑等導電性佳之金屬，從而提高了奈米碳管與電路之電性連接，有利於奈米碳管之後期應用；(4)該 方法製備之奈米碳管之產率可達到50%。 Compared with the prior art, the preparation method of the branched carbon nanotube has the following advantages: (1) using a pure hydrocarbon gas such as acetylene, methane or ethylene as a carbon source gas, thereby reducing the production cost; (2) using a coating film The catalyst layer is prepared by the method, so that the positioning growth of the carbon nanotubes can be realized by photolithography or the like; (3) the branched carbon nanotubes prepared are mostly coated with gold, silver, platinum and the like. Metal, thereby improving the electrical connection between the carbon nanotubes and the circuit, which is beneficial to the later application of the carbon nanotubes; (4) The yield of the carbon nanotubes prepared by the method can reach 50%.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
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| US6325909B1 (en) * | 1999-09-24 | 2001-12-04 | The Governing Council Of The University Of Toronto | Method of growth of branched carbon nanotubes and devices produced from the branched nanotubes |
| US20060137741A1 (en) * | 2004-12-27 | 2006-06-29 | Samsung Electronics Co., Ltd. | Photoanode using carbon nanotubes, method of manufacturing the photoanode, and photovoltaic solar cell including the photoanode |
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| US6325909B1 (en) * | 1999-09-24 | 2001-12-04 | The Governing Council Of The University Of Toronto | Method of growth of branched carbon nanotubes and devices produced from the branched nanotubes |
| US20060137741A1 (en) * | 2004-12-27 | 2006-06-29 | Samsung Electronics Co., Ltd. | Photoanode using carbon nanotubes, method of manufacturing the photoanode, and photovoltaic solar cell including the photoanode |
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| EunJuBae,Yo-SepMin,UnjeongKimandWanjunPark,Nanotechnology,Vol.18,No.1,"Single-walledcarbonnanotubegrowthonglass",p015601,publishedon2006-12-08。 * |
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