TW200538389A

TW200538389A - A carbon nanotube and methods for making the same

Info

Publication number: TW200538389A
Application number: TW93115298A
Authority: TW
Inventors: Shou-Shan Fan; Liang Liu
Original assignee: Hon Hai Prec Ind Co Ltd
Priority date: 2004-05-28
Filing date: 2004-05-28
Publication date: 2005-12-01
Also published as: TWI335904B

Abstract

This invention relates to a carbon nanotube and methods for making the same. The carbon nanotube includes more than two carbon isotopes, wherein the proportion of the same carbon isotopes of mixture are arranged along a longitudinal direction of the carbon nanotube periodically or inperiodically. The methods of the present invention employ different isotope sources to synthesize the carbon nanotube. In chemical vapor deposition method, different isotope source gases are introduced alternatively; In arc discharge method, a power source is switched between different isotope anodes alternatively; In laser ablation method, a laser is directed on different isotope targets alternatively.

Description

200538389 五、發明說明（1) —-----—--- 【發明所屬之技術領域】本發明涉及一種奈米材料及其製備方法，特別涉及一種奈米碳管及其製備方法。【先前技術】奈米碳管係九十年代初才發現之一種新型一維夺米料。奈米碳管之特殊結構決定了其具有特殊之性質，如古抗張強度及高熱穩定性；隨著奈米碳管螺旋方式之變化^ 奈米碳管可呈現出金屬性或半金屬性等。由於奈米碳管獨特之機械及電學性質，使其在材料科學、化學、物理學等交叉學科領域具有廣闊之應用前景，可用作場發射器: 白光源、鐘二次電池、儲氫電池、陰極射線管或電晶體之電子發射源等。現有奈米碳管之製備方法主要有1 991年s. I i j ima在 Nature, 354, 56, Helical microtubules of graphitic carbon上公開之電狐放電法’1992年T.W. Ebbesen等人在 Nature, 358, 220, Large-scale Synthesis of Carbon200538389 V. Description of the invention (1) —----- —- [TECHNICAL FIELD OF THE INVENTION] The present invention relates to a nano material and a preparation method thereof, and particularly to a nano carbon tube and a preparation method thereof. [Prior technology] A new type of one-dimensional rice-receiving material, which was discovered in the early 1990s, is a carbon nanotube system. The special structure of the carbon nanotube determines its special properties, such as ancient tensile strength and high thermal stability; with the change of the spiral mode of the carbon nanotube, the carbon nanotube can be metallic or semi-metallic, etc. . Due to the unique mechanical and electrical properties of carbon nanotubes, they have broad application prospects in the interdisciplinary fields of materials science, chemistry, physics, etc., and can be used as field emitters: white light sources, clock secondary batteries, hydrogen storage batteries , Electron emission source of cathode ray tube or transistor, etc. The existing method of preparing carbon nanotubes mainly includes the electric fox discharge method published on Nature, 354, 56, Helical microtubules of graphitic carbon in 1 991 TW Ebbesen et al. In Nature, 358, 220 , Large-scale Synthesis of Carbon

Nanotubes上公開之雷射燒蝕法及1 9 96年W. Z. Li等人在 Science, 274, 1701, Large-Scale Synthesis ofLaser Ablation Methods Published on Nanotubes and W. Z. Li et al., Science, 274, 1701, Large-Scale Synthesis of

Aligned Carbon Nanotubes上公開之化學氣相沈積法等。同位素標示方法係研究奈米材料生長機理及奈米尺寸同位素結之有力工具，其係利用在奈米材料之合成過程中’將含有某一特定元素（一般係輕元素，如碳、彌、氮或氧）之同位素之反應物按照預定之濃度（以純物質或混合物之形式）及順序使其參與反應，從而製備出原位生長之同位Chemical vapor deposition methods and the like disclosed on Aligned Carbon Nanotubes. The isotope labeling method is a powerful tool for studying the growth mechanism of nanomaterials and the nano-sized isotope junctions. It is used in the synthesis of nanomaterials and will contain a specific element (generally light elements such as carbon, carbon, nitrogen, and nitrogen). Or oxygen) isotope reactants according to a predetermined concentration (in the form of pure substances or mixtures) and order to participate in the reaction, so as to prepare the in situ growth isotope

200538389200538389

五、發明說明（2) 素標不之奈米材料。然而，上述三種製備奈米碳管之方法中均沒乎摻有同位素之奈米碳管之合成。 ^及到【内容】綜上所述，為克服現有技術中不存在摻有同位太米碳管，本發明所要解決之技術問題係提供一種二素之奈米碳管。 > ’ Η位為克服現有技術中不存在摻有同位素之奈米碳管之制備方法，本發明所要解決之技術問題係提供一種摻有ς 素奈米碳管之製備方法。本發明解決上述技術問題之技術方案係··提供一種掺有同位素之奈米碳管’其係由兩種以上之單一同位素混二組成，其中，該混合成份之同位素混合比例沿管長方=^ 期性或非周期性變化。為製備上述摻有同位素之奈米碳管，本發明提供之第一種製備方法包括如下步驟：提供含有單一同位素之第一碳源氣、第二碳源氣及第三碳源氣；提供其上沈積有催化劑之基底；利用化學氣相沈積法’使第一碳源氣提供之碳之同位素發生反應並使反應生成之第一奈米碳管片段沈積於該基底上；反應預定時間後，將碳源切換至第二碳源氣上’同樣利用化學氣相沈積法’使第二碳源氣提供之碳之同位素發生反應，生成之第二奈米碳管片段生長於第一太米碳管片段之上；反應預定時間後，將碳源切換至第三石1 源氣上’同樣利用化學氣相沈積法，使第三碳源氣提供之V. Description of the invention (2) Non-standard nano materials. However, none of the above three methods for preparing carbon nanotubes involves the synthesis of carbon nanotubes doped with isotopes. ^ And [Contents] In summary, in order to overcome the lack of isobaric carbon nanotubes in the prior art, the technical problem to be solved by the present invention is to provide a two-dimensional carbon nanotube. > Η position In order to overcome the absence of a method for preparing carbon nanotubes doped with isotopes in the prior art, the technical problem to be solved by the present invention is to provide a method for preparing carbon nanotubes doped with carbon. The technical solution of the present invention for solving the above technical problem is to provide a nano carbon tube doped with isotopes, which is composed of two or more single isotopes mixed with two, wherein the isotope mixing ratio of the mixed components is along the tube rectangle = ^ Periodic or aperiodic changes. In order to prepare the above-mentioned carbon nanotubes doped with isotopes, the first preparation method provided by the present invention includes the following steps: providing a first carbon source gas, a second carbon source gas, and a third carbon source gas containing a single isotope; A substrate having a catalyst deposited thereon; using a chemical vapor deposition method to 'react the isotopes of carbon provided by the first carbon source gas and deposit the first carbon nanotube fragments generated on the substrate on the substrate; after a predetermined time of reaction, The carbon source is switched to the second carbon source gas, and the chemical isotope of the carbon provided by the second carbon source gas is also reacted, and the generated second nano carbon tube segment is grown on the first carbon. Above the tube segment; after a predetermined reaction time, the carbon source is switched to the third stone 1 source gas, and the third carbon source gas is also provided by chemical vapor deposition.

200538389 五、發明說明（3) -- 碳之同位，發生反應，生成之第三奈米碳管片段生長於第 =奈米碳管片段之上，從而得到摻有複數同位素之奈米碳官。化學氣相沈積法工作溫度為5 〇〇〜丨丨〇〇。C。為製備上述摻有同位素之奈米碳管，本發明提供之第，種製，方=包括如下步驟··提供含有單一同位素之第一石反，第二蛟源及第三碳源，分別作為陽極；提供一與第一碳源、第二碳源及第三碳源相對應設置之陰極；使第一碳源與該陰極發生雷抓铃+，你穿山知王電弧放电，使弟一碳源提供之碳之同位素發生反應亚使反靡卄& 士、膂_太1 1 » 時間後，將碳源切；至第；管片段；反應預定成之第二奈米碳素發生反應，生庫箱宕日* Μ饴長；弟不米碳管片段之上；反陰極發生電弧放電筮- 便弟一反源與該岸，生成之第- ΐ 提供之碳之同位素發生反上，從而得到找女、；第~不米碳管片段之攸而付到摻有同位素之奈米碳管， Λ _借F ’L積於5玄陰極上。马衣備上迹摻有同位素之奈米碳三種製備方法包括如下牛砰·担糾人本發明&供之第碳源、第二碳源及第二冋位素之第一第-碳源、第- 供奈米碳管收集裝置；將入反庫室中源與該奈米碳管收集裝置放碳源及第三碳源之一側；用置於第一碳=第^反，、弟二三碳源另一側之脈衝雷射照射第—碳源:η第之碳之同位素發生反應並使反應生成之第太:t源提供取 < 弟一奈米碳管片200538389 V. Description of the invention (3)-The carbon isotope reacts, and the generated third carbon nanotube segment grows on the first carbon nanotube segment, so as to obtain a carbon nanocarbon doped with a plurality of isotopes. The chemical vapor deposition method has an operating temperature of 500 to 丨丨〇. C. In order to prepare the above-mentioned carbon nanotubes doped with isotopes, the first aspect of the present invention includes the following steps: The first stone counter, the second tritium source, and the third carbon source containing a single isotope are provided as Anode; Provide a cathode corresponding to the first carbon source, the second carbon source, and the third carbon source; make the first carbon source and the cathode generate a lightning strike +, and you arc through the mountain to make the brother a carbon After the carbon isotope provided by the source reacts, the carbon source is cut off after a period of time, and the carbon source is cut; to the first; the tube segment; the second nanocarbon that is scheduled to react reacts, The storage tank is down * Μ 饴 long; the top of the carbon tube segment of the brother; the arc discharge of the counter-cathode 筮-the source of the carbon and the bank, the isotopes of the carbon provided by the-反 are reversed, so Get the female, the first ~ carbon nanotube fragments and pay the carbon nanotubes doped with isotopes, Λ _ by F 'L accumulated on the 5 mysterious cathode. Three methods for preparing nano carbon with isotope doped on horse clothing include the following: the first carbon source, the second carbon source, and the first carbon source of the second carbon isotope; , No.-Nano carbon tube collection device; Place the source in the reverse storage room and the carbon carbon tube collection device at one side of the carbon source and the third carbon source; place the first carbon = the third carbon, Pulse laser irradiation on the other side of the second and third carbon sources—the carbon source: the carbon isotopes of η react and cause the reaction to generate the carbon source: the source of the carbon source

第7頁 200538389 五、發明說明（4) ^ ^應預定時間後，用脈衝雷射照射第二碳源，使第二 =源提供，蛱之同位素發生反應，生成之第二奈米碳管片’ ^ ^長於第一奈米碳管片段之上；反應預定時間後，用脈 ^ ^射照射第f碳源，使第三碳源提供之碳之同位素發生 r t成i第三奈米碳管片段生長於第二奈米碳管片段 =π μ =付到摻有複數同位素之奈米碳管，沈積於該奈木石反官收集裝置上。 ,山η與ΪΪ技術相比較，本發明提供之方法可製備由不同二：：:、:2替生長之奈米碳管’⑯而可用拉曼光譜或二次 4方法記錄碳同位素原位生長之圖案，進而研究 ί = 機理’同時也可用本發明提供之方法合成 3有同位素異質結之一維奈米材料。【實施方式】 I =將結合附圖對本發明作進一步之詳細說明。由‘圖’本發明之摻有同位素之奈米碳管4〇係 nn炭管片段402、由％組成之奈米碳管片段 \〇3及由C組成之奈米碳管片段4〇4混合組成，段40 2、403及404混合比例沿管長方向月细不'、火s 發明之優選實施例中製備之該摻有同位辛之夺米反吕4〇之長度為1〇〜1〇〇〇mm，管之直徑為〇 5 5〇nm。士發:月提供之第一種製備摻有同位素 “二氣相沈積法’請參閱第二圖，其具體步驟如下： (1) 提供分別由12C、13C及uc組成之乙烯氣 (2) 提供基底132，該基底132上表面沈積有二層厚為Page 7 200538389 V. Description of the invention (4) ^ ^ After a predetermined time, the second carbon source is irradiated with a pulsed laser, so that the second source is provided, the isotopes of the tritium react, and the second carbon nanotube chip is generated. ^ ^ Is longer than the first nano carbon tube fragment; after a predetermined time of reaction, the f-th carbon source is irradiated with a pulse ^ ^, so that the isotopes of the carbon provided by the third carbon source are rt to i third nano carbon tube The fragment grows on the second nano carbon tube fragment = π μ = is deposited on the nano carbon tube doped with a plurality of isotopes, and is deposited on the nano-wood stone anti-official collection device. Compared with the technology of ΪΪ and η, the method provided by the present invention can be prepared by different two :::,: 2 instead of growing carbon nanotubes ⑯, and Raman spectroscopy or quadratic 4 methods can be used to record carbon isotope in situ growth The pattern can be further studied. At the same time, the method provided by the present invention can also be used to synthesize one of the three nanomaterials with isotope heterojunction. [Embodiment] I = The present invention will be further described in detail with reference to the accompanying drawings. The 'graph' of the present invention isotope-incorporated carbon nanotube 40-series carbon nanotube segment 402, the carbon nanotube segment composed of% \ 〇3, and the carbon nanotube segment composed of C 404 are mixed. Composition, the mixing ratio of segments 40 2, 403, and 404 along the length of the tube is not fine, and the length of the rice-repellent rice 40 mixed with iso-synthesis prepared in the preferred embodiment of the invention is 10 to 100. 〇mm, the diameter of the tube was 055 nm. Shifa: The first method for preparing "two-phase vapor deposition" with isotope doped in the month. Please refer to the second figure. The specific steps are as follows: (1) Provide ethylene gas consisting of 12C, 13C and uc respectively. (2) Provide A substrate 132 having two layers thick on the upper surface of the substrate 132

第8頁 200538389 五、發明說明（5) 5nm作為催化劑使用之鐵膜1 34，並將該沈積有催化劑鐵膜 134之基底132放入反應室11〇中； (3 )通過排氣通道丨1 6將反應室1 1 〇抽真空後，再通過氣體輸入通道118通入壓強為1個大氣壓之氬氣，同時通過反應爐106加熱反應室丨10至其溫度達7〇〇 ° c ; (4)打開閥門112，由氣體輸入通道102通入流量為 120sccm ’流速為i.2cm/s之由!2C組成之乙烯氣體，反應生成之由C組成之奈米碳管片段（圖未示）沈積於該催化劑鐵膜134上； (5 )反應預定時間後，關閉閥門丨丨2，打開閥門丨丨3，由氣體輸入通道103通入流量為I20sccm，流速為^⑽/^之由 13C組成之乙烯氣體，由i3c組成之奈米碳管片段（圖未示）繼續生長於步驟（4)生成之由i2c組成之奈米碳管片段上； (6 )反應預定時間後，關閉閥門丨丨3，打開閥門丨丨4，由氣體輸入通道104通入流量為120sccn]，流速為12cm/s之由 “C組成之乙烯氣體，由hC組成之奈米碳管片段（圖未示）繼縯生長於步驟（5)生成之由ιγ組成之奈米碳管片段上； (7)繼續反應預定時間後，將反應室丨丨〇冷卻至室溫，在催化劑鐵膜1 34上得到摻有複數同位素之奈米碳管。可以理解之是，本方法中可在步驟（6)後重復步驟（4)、及（6)付到周期性排列之摻有同位素之奈米碳管，或者在步驟（6)後隨機重復步驟（4)、（5)及（6)可得到非周期性排列之摻有同位素之奈米碳管；也可用鈷、鎳及其合金，或苴他合適之催化劑代替鐵作為催化劑使用；也可用其他碳氫Page 8 200538389 V. Description of the invention (5) 5nm iron film 1 34 used as a catalyst, and the substrate 132 on which the catalyst iron film 134 is deposited is placed in the reaction chamber 110; (3) through the exhaust channel 丨 1 6 After the reaction chamber 110 is evacuated, argon gas having a pressure of 1 atmosphere is passed through the gas input channel 118, and the reaction chamber 106 is heated through the reaction furnace 106 to a temperature of 700 ° C; (4 ) Open the valve 112, and pass the gas input channel 102 into the flow of 120sccm 'ethylene flow consisting of! 2C with a flow rate of i.2cm / s, and the carbon nanotube segment (not shown) consisting of C deposited by the reaction is deposited On the catalyst iron film 134; (5) after the reaction is scheduled, close the valve 丨 2 and open the valve 丨 3; the gas input channel 103 flows into I20 sccm and the flow rate is ^ ⑽ / ^, which is composed of 13C Ethylene gas, the nano carbon tube segment (not shown) composed of i3c continues to grow on the nano carbon tube segment composed of i2c generated in step (4); (6) after the predetermined reaction time, the valve is closed 3 , Open the valve 丨丨 4 and the flow rate from the gas input channel 104 is 120scc n], an ethylene gas composed of "C" with a flow rate of 12 cm / s, and a carbon nanotube segment (not shown) composed of hC is subsequently grown in step (5) to produce a carbon nanotube segment composed of ιγ (7) After the reaction is continued for a predetermined time, the reaction chamber is cooled to room temperature, and a carbon nanotube doped with a plurality of isotopes is obtained on the catalyst iron film 134. It can be understood that, in this method, After step (6), repeat steps (4), and (6) to periodically arrange isotope-doped carbon nanotubes, or repeat steps (4), (5), and (6) randomly after step (6) ) Non-periodic carbon nanotubes doped with isotopes can be obtained; cobalt, nickel and its alloys, or other suitable catalysts can be used instead of iron as catalysts; other hydrocarbons can also be used

第9頁 200538389Page 9 200538389

為碳源氣使氩氣作為保化合物，如甲烷、乙炔、丙二烯等代替乙烯作用，也可以採用氦氣、氮氣或者係氫氣等代替護氣使用。 9 本發明提供之第二種製備摻有同位素奈米碳係電狐放電法’請參閱第三圖，其具體步驟如下· 彳 (1)用NU質量百分比濃度〇〜13%)及/或¥2〇3(質濃度0〜48%)之催化劑粉末與直徑為5mm之由％組成之古:^ 粉顆粒在350 0個大氣壓下壓成直徑為1〇隨之碳棒2 了用= 樣之方法製成一個由13C組成之碳棒2〇3及一個由uc組成之石碳棒2 0 4，將碳棒2 0 2、2 0 3及2 0 4用兩絕緣膠2 〇 6粘到一起，分別與電弧放電源之正極2 1 4相連作為陽極使用，另外，’ 可將碳棒2 02、203及2 04近距絕緣放置，分別與電私放電源之正極2 1 4相連作為陽極使用； '、 (2 )用普通純碳棒與電弧放電源之負極2 1 5相連作為阶極208使用； "" (3) 把步驟（1)及（2)所製得之陽極及陰極2〇8相對而置，相距1. 5〜2mm，放進電弧放電反應室210中，並通過排氣通道2 1 6將電弧放電反應室2 1 0抽真空後，再通過氣體輸入通道218通進壓強為100〜5 0 0Torr之氦氣； (4) 將電開關212接通碳棒2 0 2，以100A之電流進行電弧放電，放電電壓為20〜40V，反應生成之由12C組成之奈米碳管片段（圖未示）； (5 )反應預定時間後，將電開關2 1 2接通碳棒2 0 3，以 100A之電流進行電弧放電，放電電壓為20〜40V，由13C組成For carbon source gas, argon gas is used as a holding compound, such as methane, acetylene, propadiene, etc. instead of ethylene, and helium, nitrogen, or hydrogen gas can also be used instead of shielding gas. 9 The second method provided by the present invention for preparing a carbon-based electric fox discharge doped with isotopes is shown in the third figure. The specific steps are as follows: 彳 (1) Use NU mass percentage concentration of 0 ~ 13%) and / or ¥ 203 (mass concentration 0 ~ 48%) of catalyst powder and 5% diameter of the ancient composition consisting of%: ^ powder particles were pressed to a diameter of 10 at 350 atmospheres and the carbon rod 2 was used = the same Method: Make a carbon rod 203 composed of 13C and a stone carbon rod 204 composed of uc, and stick the carbon rods 20, 2, 3, and 2 4 with two insulating glues 2 and 6 together. , Respectively connected to the positive electrode 2 1 4 of the arc discharge power supply as an anode, in addition, 'can be placed close to the carbon rods 02, 203, and 2 04, and separately connected to the positive electrode 2 1 4 of the electric private power supply as an anode use ; ', (2) Use ordinary pure carbon rod to connect to the anode 2 1 5 of the arc discharge power source as the step 208; " " (3) Anode and cathode produced in steps (1) and (2) 2〇8 opposed to each other, 1.5 ~ 2mm apart, put into the arc discharge reaction chamber 210, and evacuated the arc discharge reaction chamber 2 10 through the exhaust channel 2 1 6 and then passed The body input channel 218 is supplied with helium gas with a pressure of 100 ~ 500 Torr; (4) The electric switch 212 is connected to the carbon rod 202, and arc discharge is performed at a current of 100A. The discharge voltage is 20 ~ 40V. A nano carbon tube segment (not shown) composed of 12C; (5) After a predetermined reaction time, the electric switch 2 1 2 is turned on the carbon rod 2 0 3, and arc discharge is performed at a current of 100 A, and the discharge voltage is 20 ~ 40V, composed of 13C

200538389 五、發明說明（7) 之奈米碳管片段（圖夫+ )〇 U禾不）M績生長於步驟（4)生成之由丨2C組成之奈米碳管片段上； (6 )反應預定時間诒，险； Η0Α之電流進行電弧放V:關212接…2°4，以 ^ , 5放電’玫電電壓為20〜40V，由14C組成之奈米碳管片段（圖夫千、繼病二、.,,,^ J 禾不）、禮續生長於步驟（5 )生成之由13 C組二：1又上，反應生成之摻有同位素之奈米碳管沈積於該陰極2 0 8上；續反應預定時間後，不斷消耗之陽極在陰極2〇8 上沈積下來持縯形成摻有同位素之奈米碳管。 ⑷、H理解之广’本方法中可在步驟（6)後重復步驟及6)得到周期性排列之摻有同位素之奈米碳管， :戈：在步驟⑹後隨機重復步驟⑷、⑸及⑷彳得到非周 ,月排列之掺有同位素之奈米碳管；也可用，纯之銘粉或純之錄=或^其他合適之催化劑與碳粉複合壓炭棒；也可以私用氮氣、ll II或者係氫氣等代替氛氣作為保護氣使用；也可將含有不同同位素之陽極以旋轉之方式接通電源；也可於f孤反應室上安有冷水管以免由於電狐放生之熱量過高。 ^本發明提供之第二種製備摻有同位素奈米碳管之方法係田射燒蝕法，請參閱第四圖，其具體步驟如下：、（1)用摻鈷粉（質量百分比濃度2· 8%)及鎳（質量百分比浪度2. 8%)粉與由i2C組成之高純碳粉壓製成複合碳塊作為㊈射燒蝕法之雷射照射靶302，用同樣之方法分別製成一個二 13C組成之靶3 0 3及一個由14C組成之靶3〇4 ;200538389 V. Description of the invention (7) Nano carbon tube fragments (Tuff +) 0U Hebu) M growth on the carbon nanotube fragments composed of 丨 2C generated in step (4); (6) reaction Predetermined time, dangerous; Η0Α current arc discharge V: off 212 connection ... 2 ° 4, ^, 5 discharge 'Mei electric voltage is 20 ~ 40V, composed of 14C nano-carbon tube fragments (Tuf thousand, Following the disease 2, ... ,,, ^ J Wobu), Li continued to grow in step (5), which is formed from 13C group 2: 1, and then, the carbon nanotubes doped with isotopes generated by the reaction are deposited on the cathode 2 After the reaction is continued for a predetermined period of time, the continuously consumed anode is deposited on the cathode 208 to form a carbon nanotube doped with isotopes. ⑷, H is widely understood 'In this method, the steps can be repeated after step (6) and 6) to obtain periodically arranged carbon nanotubes doped with isotopes,: Ge: Steps ⑷, ⑸ and 随机 are randomly repeated after step ⑹ ⑷ 彳 Non-weekly and monthly aligned carbon nanotubes doped with isotopes; also available, pure powder or pure powder = or ^ other suitable catalyst and carbon powder composite carbon pressure rod; you can also use nitrogen, ll II or hydrogen is used instead of the atmosphere as the protective gas; the anode containing different isotopes can be connected to the power supply in a rotating manner; a cold water pipe can be installed on the f-solenium reaction chamber to avoid the heat generated by the electric fox. high. ^ The second method for preparing carbon nanotubes doped with isotopes provided by the present invention is the field ablation method. Please refer to the fourth figure. The specific steps are as follows: (1) Cobalt-doped powder (mass percentage concentration 2 · 8%) and nickel (mass percentage wave range 2. 8%) powder and high purity carbon powder composed of i2C are pressed into a composite carbon block as the laser irradiation target 302 of the radon ablation method, and respectively made by the same method A target 3 03 composed of two 13C and a target 3 04 composed of 14C;

200538389 五、發明說明（8) (2 )提供奈米碳管收集裝置3 0 8 ; (3)把步驟（1 )所製得之靶3 0 2、3 0 3、3 04及步驟（2)之奈米碳管收集裝置3 0 8放入雷射燒蝕反應室3 1 0中，並使奈米碳管收集裝置308置於靶3 0 2、3 0 3、304之一側； (4 )並通過排氣通道3 1 6把雷射燒蝕反應室3 1 0抽真空後，再通過氣體輸入通道318通進壓強為50〜760Torr之氬氣； (5 )用加熱器3 0 6將雷射燒蝕反應室3 1 0中靶3 0 2、3 0 3、 304所在之區域加熱到1〇〇〇〜12〇〇。c ;200538389 V. Description of the invention (8) (2) Provide nano carbon tube collection device 3 0 8; (3) Take the target obtained in step (1) 3 0 2, 3 0 3, 3 04 and step (2) The nano carbon tube collection device 3 0 8 is placed in the laser ablation reaction chamber 3 1 0, and the nano carbon tube collection device 308 is placed on one side of the target 3 2, 3, 3, and 304; (4 ) And evacuate the laser ablation reaction chamber 3 1 0 through the exhaust channel 3 1 6, and then pass argon gas having a pressure of 50 to 760 Torr through the gas input channel 318; (5) the heater 3 6 6 The area where the target 30, 2, 3, 3, and 304 in the laser ablation reaction chamber 3 10 is heated is 100 to 120.00. c;

(6)利用聚焦透鏡312將置於靶3 0 2、303、304另一側之波長為532nm、單個雷射脈衝之能量為250mJ之脈衝雷射光束314聚焦於靶302上，照射點之直徑為5mm，反應生成之由 12C組成之奈米碳管片段（圖未示）；，（7 )照射預定時間後，調節聚焦透鏡3 1 2之位置將雷射光束314聚焦於另一塊靶303上，由nc組成之奈米碳管片段 (圖未示）繼續生長於步驟（6)生成之由〖2C組成之奈米碳管片段上；一（8 )知、射預疋時間後，調節聚焦透鏡3 1 2之位置將雷射光束314聚焦於另一塊靶3〇4上，由M(：組成之奈米碳管片段圖未示）繼續生長於步驟（6)生成之由組成之奈米碳管片 ί ΐ隹反應生成之摻有同位素之奈米碳管沈積於該奈米碳官收集裝置308上；放置(之9):/Λ1η預定時間後’在與雷射光束314相對-端放置之收集裝置308上持續沈積有摻有同位素之奈米碳管。(6) The focusing lens 312 is used to focus the pulsed laser beam 314 with a wavelength of 532 nm and a single laser pulse energy of 250 mJ placed on the other side of the target 3 2, 2, 303, and 304 onto the target 302, and the diameter of the irradiation spot It is 5mm, and a carbon nanotube segment (not shown) composed of 12C is generated by the reaction; (7) After irradiating for a predetermined time, adjust the position of the focusing lens 3 1 2 to focus the laser beam 314 on another target 303 The nano carbon tube segment (not shown) composed of nc continues to grow on the nano carbon tube segment composed of [2C] generated in step (6); one (8) knows and adjusts the focus after the pre-shooting time; The position of the lens 3 1 2 focuses the laser beam 314 on another target 3 04, and M (: the nano-carbon tube fragment diagram of the composition is not shown) continues to grow in the nano-composition of the composition generated in step (6). Carbon tube fragments ί Isotopically doped nano carbon tubes are deposited on the nano carbon official collection device 308; placed (of 9): / Λ1η after a predetermined time 'at the end opposite the laser beam 314 The placed collection device 308 continuously deposits carbon nanotubes doped with isotopes.

第12頁 200538389 五、發明說明（9) ' ' ----- 可以理解之是’本方法中可在步驟（8)後重復步驟 (6)、（7)及（8)得到周期性排列之摻有同位素之奈米碳管，，或者在步驟（8)後隨機重復步驟（6)、（7)及（8)可得到期性排列之摻有同位素之奈米碳營· m 之鎳粉或者其他合適之催化劑與碳粉複合粉壓成乾作$j 射燒钱法之雷射照射乾；也可採用氮氣、氮氣或^ 等代替氬氣作為保護氣使用；也可利、/ ’、氧乱兩個靶位置之方式將雷射源照射到另一塊乾上射原次又換本發明提供之方法可製備由不同之石炭同位辛之奈米碳管，從而可用拉曼光譜或二次離子質碰二錄碳同位素原位生長之圖案，進而研究奈来碳；之= 之-維奈米材料。万法。成含有同位素異質結儘管結合優選實施方案具體展示及介切所屬領域之技術人員應明白，在形式 D —發月，但明做出各種變化，而不會脫籬所蚪描4丨莊丄毛發明之精神及範圍。所附推利要求書所限定之本綜上所述，本發明確已符合發明專利提出專利m，以上所述者僅為本發明之較佳實施法例’自不能以此限制本荦之申—主皇女丨铲、杜範夕人本接化太欢月專耗圍。舉凡熟悉本案 ; = = ί ΐ明之精神所作之等效修飾或變化，皆應涵盍於以下申凊專利範圍内。Page 12 200538389 V. Description of the invention (9) '' ----- It can be understood that 'in this method, steps (6), (7) and (8) can be repeated periodically after step (8) to obtain a periodic arrangement. Isotope-doped carbon nanotubes, or after step (8), repeat steps (6), (7), and (8) randomly to obtain regularly arranged isotope-doped carbon nanotubes · m of nickel Powder or other suitable catalyst and carbon powder composite powder to dry for $ j laser burn method; also use nitrogen, nitrogen or ^ instead of argon as the protective gas; also, The method of irradiating two target positions to irradiate a laser source to another dry source and changing the method provided by the present invention can prepare carbon nanotubes with different carbon isotopes, so that Raman spectroscopy or two The secondary ionic mass touched the pattern of in-situ growth of the two carbon isotope, and then studied the Nile carbon; Wanfa. Although isotopes containing heterotopes are specifically displayed in combination with the preferred embodiments and those skilled in the art should understand that in the form D-the month, various changes will be made without delineation 4 丨 Zhuang Maomao The spirit and scope of the invention. In summary of the above, as defined in the attached request for profit, the present invention has indeed met the invention patent m. The above is only a preferred embodiment of the present invention. 'It cannot be used to restrict this application — The main queen queen 丨 shovel, Du Fanxi's personal connection is too Huan Yue dedicated exclusively to siege. Anyone familiar with this case; = = ί The equivalent of the modification or change made by the spirit of Tong Ming should be covered by the following patents.

第13頁 200538389 圖式簡單說明第一圖係本發明摻有同位素之奈米# μ 灭言之示旁、圖同位素奈米第二圖係利用本發明第一種方法製傷碳管所用裝置示意圖。摻有弟二圖係利用本發明第二種方法噥管所用裝置示意圖。有同位素奈米第四圖係利用本發明第三種方法製借碳管所用裝置示意圖。 ^ 【主要元件符號說明】氣體輸入通道 102, 103, 104, 118 反應爐 106 反應室閥門 112, 113, 114 排氣通道基底 132 鐵膜碳棒 2 0 2, 203, 204 絕緣膠陰極 208 電開關 110, 210, 310 116, 216, 316 134 206 212 正極 214 負極 215 加熱器 306 聚焦透鏡3 1 2 奈米碳管4 0Page 13 200538389 Brief description of the diagram The first diagram is the nanometer with mixed isotope # μ of the present invention, the side picture of the isotope nanometer, the second diagram is a schematic diagram of the device used to make the carbon tube using the first method of the present invention . The second figure is a schematic diagram of the device used for the stern tube using the second method of the present invention. With the isotope nanometer, the fourth diagram is a schematic diagram of a device for making a carbon tube by the third method of the present invention. ^ [Description of main component symbols] Gas input channel 102, 103, 104, 118 Reactor 106 Reactor valve 112, 113, 114 Exhaust channel base 132 Iron film carbon rod 2 0 2, 203, 204 Insulating rubber cathode 208 Electric switch 110, 210, 310 116, 216, 316 134 206 212 Positive 214 Negative 215 Heater 306 Focusing lens 3 1 2 Nano carbon tube 4 0

^ 302, 303, 304 收集裝置 3 Q 8 雷射光束 314 奈米碳管片段40 2,40 3,404^ 302, 303, 304 Collection device 3 Q 8 Laser beam 314 Nano carbon tube segment 40 2,40 3,404

第14頁Page 14

Claims

200538389 六、申請專利範圍 i單 1 · 一種奈米碳管，其特徵在於該奈米碳管係兩種以上 I浪t 一同位素混合組成，其中，該混合成份之同位f 比例沿管長方向呈周期性或非周期性變化。 2 ·如申請專利範圍第1項所述之一奈米碳管，其中所述奈米碳管由12C、13C及14C組成。 3 ·如申請專利範圍第1項所述之奈米碳管，其中所述i α 奈米碳管之長度為10〜1000mm。二 4 ·如申請專利範圍第1項所述之奈米碳管，其中所述之該奈米碳管之直徑為0· 5〜50nm ° 5 · —種奈米碳管之製備方法，其特徵在於包括如下少’第提供含有單一同位素之第一碳源氣、第二碳源氣及三碳源氣；提供其上沈積有催化劑之基底’ 利用化學氣相沈積法，使第一碳源氣提供之碳之同j 素發生反應並使反應生成之第一奈米碳管片段此、於該基底上； / 反應預定時間後，將碳源切換至第二碳源氣上’同木利用化學氣相沈積法，使第二碳源氣提供之碳之f 位素發生反應，生成之第二奈米碳管片段生長於第一奈米碳管片段之上；反應預定時間後，將碳源切換至第三碳源氣上，同樣利用化學氣相沈積法，使第三碳源氣提供之碳之同位素發生反應，生成之第三奈米碳管片段生長於第二奈米碳管片段之上，從而得到摻有複數同位素之200538389 6. Scope of patent application i Single 1 · A carbon nanotube, which is characterized in that the carbon nanotube is composed of two or more isotopes, and the isotopic f ratio of the mixed component is periodic along the length of the tube. Sexual or non-periodic changes. 2 · A nano carbon tube as described in item 1 of the scope of patent application, wherein the nano carbon tube is composed of 12C, 13C and 14C. 3. The nano carbon tube according to item 1 of the scope of patent application, wherein the length of the i α nano carbon tube is 10 to 1000 mm. 24. The nano carbon tube according to item 1 in the scope of the patent application, wherein the diameter of the nano carbon tube is from 0.5 to 50 nm ° 5. A method for preparing a nano carbon tube, and its characteristics The method includes the following steps: providing a first carbon source gas, a second carbon source gas, and a three carbon source gas containing a single isotope; providing a substrate having a catalyst deposited thereon; and using a chemical vapor deposition method to make the first carbon source gas The provided carbon reacts with the same element and causes the first nano carbon tube fragment generated by the reaction to be on the substrate; / After a predetermined time of the reaction, the carbon source is switched to the second carbon source gas. The vapor deposition method causes the f-position of carbon provided by the second carbon source gas to react, and the generated second nano carbon tube segment grows on the first nano carbon tube segment; after a predetermined time of reaction, the carbon source is Switch to the third carbon source gas, and also use the chemical vapor deposition method to react the carbon isotope provided by the third carbon source gas, and the generated third nano carbon tube segment is grown on the second nano carbon tube segment. Up, so as to get a complex isotope

第15頁 200538389 六、申請專利範圍奈米碳管。 6. 如申請專利範圍第5項所述之奈米碳管之製備方法，其中所述之該催化劑包括始、鎳或鐵及其合金。 7. 如申請專利範圍第5項所述之奈米碳管之製備方法，其中所述之化學氣相沈積法工作溫度為5 0 0〜1 1 0 0 ° C。 8. 如申請專利範圍第5項所述之奈米碳管之製備方法，其中所述之該第一碳源氣、第二碳源氣及第三碳源氣為碳氫氣體。 9. 如申請專利範圍第8項所述之奈米碳管之製備方法，其中所述之碳氩氣體包括甲烷、乙烯、乙炔或丙二烯。 1 0.如申請專利範圍第5項所述之奈米碳管之製備方法，其中所述之反應過程中通入保護氣體。 11.如申請專利範圍第1 0項所述之奈米碳管之製備方法，其中所述之該保護性氣體包括氦氣、氬氣、氮氣或氫氣。 1 2. —種奈米碳管之製備方法，其特徵在於包括如下步驟：提供含有單一同位素之第一碳源、第二碳源及第三碳源，分別作為陽極；提供一與第一碳源、第二碳源及第三碳源相對應設置之陰極；使第一碳源與該陰極發生電弧放電，使第一碳源提供之碳之同位素發生反應並使反應並生成第一奈米碳管片段；Page 15 200538389 6. Scope of patent application Nano carbon tube. 6. The method for preparing a nano carbon tube according to item 5 of the scope of the patent application, wherein the catalyst includes starting, nickel or iron and alloys thereof. 7. The method for preparing a nano carbon tube as described in item 5 of the scope of patent application, wherein the chemical vapor deposition method has an operating temperature of 500 to 110 ° C. 8. The method for preparing a nano carbon tube according to item 5 of the scope of the patent application, wherein the first carbon source gas, the second carbon source gas, and the third carbon source gas are hydrocarbon gases. 9. The method for preparing a nano carbon tube according to item 8 of the scope of the patent application, wherein the carbon argon gas includes methane, ethylene, acetylene or propadiene. 10. The method for preparing a nano carbon tube according to item 5 of the scope of the patent application, wherein a protective gas is introduced during the reaction process. 11. The method for preparing a nano carbon tube according to item 10 of the scope of patent application, wherein the protective gas includes helium, argon, nitrogen or hydrogen. 1 2. A method for preparing a nano carbon tube, which is characterized by including the following steps: providing a first carbon source, a second carbon source, and a third carbon source containing a single isotope as anodes; providing one and the first carbon A cathode corresponding to the source, the second carbon source, and the third carbon source; causing an arc discharge between the first carbon source and the cathode to cause the isotopes of carbon provided by the first carbon source to react and cause the reaction to generate the first nanometer Carbon tube fragments

第16頁 200538389 六、申請專利範圍反應預定時間後，將碳源切換至第二碳源，使第一碳源與邊陰極發生電？瓜放電’使第二碳源^提供之碳之同位素發生反應’生成之第二奈米碳營片' $ 生長於第一奈米碳管片段之上；又反應預定時間後，將碳源切換至第三碳源，使第二碳源與該陰極發生電孤放電’使第三碳源提供之碳之同位素發生反應，生成之第三奈米峻營片'段生長於弟一奈米碳管片段之上’從而得到摻有门位素之奈米碳管，沈積於該陰極上。 1 3 ·如申請專利範圍第1 2項所述之奈米碳管之製傷方法，其中所述之第一碳源、第二礙源及第三碳源係由催化劑粉末分別與由單一同位素組成之高純碳粉遷製而成之第一碳棒、第二碳棒及第三碳棒。 1 4 ·如申請專利範圍第1 2項所述之奈米碳管之製備方法，其中所述之於電弧放電之放電電流為10 0A。 1 5 ·如申請專利範圍第1 3項所述之奈米碳管之製備方法，其中所述之該催化劑粉末包括鎳及/或三氧化二紀粉末。 ” 1 6 ·如申請專利範圍第1 3項所述之奈米碳管之製備方法，其中所述之該第一碳棒、第二碳棒及第三碳棒係在 3500大氣壓下壓製而成之直徑為10mm之碳棒。 1 7 ·如申請專利範圍第1 3項戶斤述之奈米碳管之製備方法，其中所述之該第一碳棒、第二碳棒及第三碳源用絕緣膠粘到一起或近距絕緣放置。Page 16 200538389 6. Scope of patent application After a predetermined time of the reaction, the carbon source is switched to the second carbon source, so that the first carbon source and the side cathode generate electricity? The melon discharge 'reacts the carbon isotope provided by the second carbon source ^ to generate a second carbon nano chip' which grows on the first carbon nanotube segment; after a predetermined time, the carbon source is switched To the third carbon source, causing the second carbon source to electrically isolate with the cathode, 'reacting the isotope of the carbon provided by the third carbon source, and the resulting third nano-junction film' grows on the di-nan carbon On top of the tube segment, a nano carbon tube doped with a gate is obtained, which is deposited on the cathode. 1 3 · The method for wounding carbon nanotubes as described in item 12 of the scope of the patent application, wherein the first carbon source, the second interfering source, and the third carbon source are each composed of a catalyst powder and a single isotope. The first carbon rod, the second carbon rod, and the third carbon rod made from the composed high-purity carbon powder. 14 · The method for preparing a nano carbon tube according to item 12 of the scope of the patent application, wherein the discharge current for the arc discharge is 100 A. 15. The method for preparing a nano carbon tube according to item 13 of the scope of the patent application, wherein the catalyst powder includes nickel and / or trioxide powder. "1 6 · The method for preparing a nano carbon tube according to item 13 of the scope of the patent application, wherein said first carbon rod, second carbon rod and third carbon rod are pressed at 3500 atm. A carbon rod with a diameter of 10 mm. 1 7 · The method for preparing a nano carbon tube as described in item 13 of the patent application scope, wherein the first carbon rod, the second carbon rod, and the third carbon source are described. Put together with insulation glue or put it in close distance.

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六、申請專利範圍 1 8 ·如申請專利範圍第1 2項其中所述之反應過程中所述之奈米碳管之製備方中通入保護性氣體。 1 9 ·如申請專利範圍第1 8項所述之=二反了，製備方法，其中所述之該保護性氣體係氦氣、虱氣、氮氣或氫氣。一 20. —種奈米碳管之製備方法，其特徵在於包括如下步提供含有單一同位素之第一破源、第二碳源及第三碳源；提供奈米碳管收集裝置；將第一碳源、第二碳源及第三破源與該奈米碳管收集裝置放入反應室中，並使奈米碳管收集裝置置於第一碳源、第二碳源及第三碳源之一側；用置於第一碳源、第二石炭源及第三碳源另一側之脈衝雷射照射第一碳源，使第一碳源提供之碳之同位素發生反應並使反應生成之第一奈米碳管片反應預定時間後，用脈衝雷射照射第二碳源’使第二碳源提供之碳之同位素發生反應’生成之第二奈米碳管片段生長於第一奈米碳管片段之上；反應預定時間後，用脈衝雷射照射第三碳源，使第三碳源提供之碳之同位素發生反應，生成之第三奈米碳管片段生長於第二奈米碳管片段之上，從而得到摻有複數同位素之奈米碳管，沈積於該奈6. Scope of patent application 1 8 · As described in item 12 of the scope of patent application, the preparation process of the carbon nanotubes described in the reaction process is passed with protective gas. 19 · As described in item 18 of the scope of the patent application, the method of preparation is reversed, the preparation method, wherein the protective gas system is helium, lice, nitrogen or hydrogen. A 20. A method for preparing a carbon nanotube, comprising the steps of providing a first breaking source, a second carbon source, and a third carbon source containing a single isotope; providing a nano carbon tube collecting device; The carbon source, the second carbon source, and the third broken source and the nano carbon tube collection device are placed in the reaction chamber, and the nano carbon tube collection device is placed on the first carbon source, the second carbon source, and the third carbon source. One side; irradiate the first carbon source with a pulsed laser placed on the other side of the first carbon source, the second carbon source and the third carbon source, so that the isotopes of the carbon provided by the first carbon source react and cause the reaction to form After the first nano carbon tube piece reacts for a predetermined time, the second carbon source is irradiated with a pulsed laser to 'react the carbon isotope provided by the second carbon source' to generate a second nano carbon tube segment that grows in the first nano Above the carbon tube segment; after a predetermined time of reaction, the third carbon source is irradiated with a pulse laser, so that the isotopes of the carbon provided by the third carbon source react, and the generated third nano carbon tube segment grows on the second nano Carbon tube fragments, so as to get a complex of isotopes Rice carbon tube, deposited in Chennai

第18頁 200538389 六、申請專利範圍米碳管收集裝置上。 2 1.如申請專利範圍第2 0項所述之奈米碳管之製備方法，其中所述之第一碳源、第二碳源及第三碳源所在區域之溫度為1 0 0 0〜1 2 0 0 ° C。 2 2.如申請專利範圍第2 0項所述之奈米碳管.之製備方法，其中所述之第一碳源、第二碳源及第三碳源係由催化劑粉末分別與由單一同位素組成之高純碳粉壓製而成之第一乾塊、第二乾塊及第三乾塊。Page 18 200538389 6. Scope of patent application On the carbon tube collection device. 2 1. The method for preparing a nano carbon tube according to item 20 of the scope of the patent application, wherein the temperature of the region where the first carbon source, the second carbon source, and the third carbon source are located is 100 0 ~ 1 2 0 0 ° C. 2 2. The method for preparing a nano carbon tube according to item 20 of the scope of the patent application, wherein the first carbon source, the second carbon source, and the third carbon source are composed of a catalyst powder and a single isotope, respectively. The first dry block, the second dry block, and the third dry block are formed by pressing the composed high-purity toner.

2 3.如申請專利範圍第2 2項所述之奈米碳管之製備方法，其中所述之該催化劑粉末包括鎳及/或始粉末。 2 4.如申請專利範圍第20項所述之奈米碳管之製備方法，其中所述之使用之係波長為5 32nm、單個雷射脈衝之能量為250mJ之脈衝雷射。。 2 5.如申請專利範圍第2 0項所述之奈米碳管之製備方法，其中所述之反應過程中通入保護性氣體。 2 6.如申請專利範圍第2 5項所述之奈米碳管之製備方法，其中所述之該保護性氣體包括氦氣、氬氣、氮氣或氫氣。2 3. The method for preparing a nano carbon tube according to item 22 of the scope of patent application, wherein the catalyst powder includes nickel and / or starting powder. 2 4. The method for preparing a nano carbon tube according to item 20 of the scope of the patent application, wherein the pulsed laser with a wavelength of 5 32 nm and a single laser pulse with an energy of 250 mJ is used. . 25. The method for preparing a nano carbon tube according to item 20 of the scope of patent application, wherein a protective gas is introduced during the reaction. 2 6. The method for preparing a nano carbon tube according to item 25 of the scope of the patent application, wherein the protective gas includes helium, argon, nitrogen or hydrogen.

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