1306833 九、發明說明 【發明所屬之技術領域】 本發明係關於一種生產奈米碳管之方法。 【先前技術】 丄奈米碳管具有奇異之物理化學性能，如獨特之金屬或半導體導電性、極 巧⑼械強度、儲氫能力、吸附能力與較強之微波吸收能力等，9〇年代初一 經發現即刻受到物理、化學與材料科學界以及高新技術產業部n之極 ，奈米碳管要實現工業顧，首先必綱決奈米碳管之贼本大量製 題。奈米碳管自1991年被發現以來，其製備卫藝得到廣泛研究。目前，有 4主要之製備方法’即電敝電法、雷機歸與化學氣概積法。電弧 放電法與雷機#法鱗之絲巾，絲碳t均盤他雜之韻物共存， 2純化曝，收率較低，且難以麵化。第三種化學氣概積法，由天缺 ^製，之奈米石炭管具有卫藝簡便、成本低、奈米細莫易控制、長度大;1306833 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing a carbon nanotube. [Prior Art] The carbon nanotubes have strange physical and chemical properties, such as unique metal or semiconductor conductivity, excellent (9) mechanical strength, hydrogen storage capacity, adsorption capacity and strong microwave absorption capacity, etc., early 9th Once discovered, it is immediately accepted by the physics, chemistry and materials science community and the high-tech industry department. The carbon nanotubes must realize the industrial considerations, and the first must be the thief of the carbon nanotubes. Since the discovery of the carbon nanotubes in 1991, the preparation of the satellite has been widely studied. At present, there are four main preparation methods, namely, electro-electricity, lightning, and chemical gas accumulation. The arc discharge method and the lightning machine #法鳞的丝巾, silk carbon t are all mixed with his mixed rhyme, 2 purification exposure, low yield, and difficult to face. The third chemical gas accumulation method, which is made up of days, is a simple, low-cost, low-cost, nano-money-controlled and long-length;
=較问等優點’有重要之研究價值。可應職場發射顯示器件、電真空器件、 不米電子學、以及高強度複合材料等方面。 D 惟，目前任何—種大量生產之方法皆不能控制產物中奈来碳管之長度， i生產出，米碳管喷細，瓣綠，不利於奈#碳 增強材料等領域之實際應用。有鑑於此，提供一種生產長度一致，長度可控。， 無糾結易於錄之奈米碳管之方法實為必要。 工 【發明内容】 、為解決先前技術中不能控制奈米碳管之長度，且生產出之奈米碳管糾結 成團難於力政之μ題，本發日月提供一種生產長度一致，長度可控，益糾结 易於分散之奈米碳管之方法。 ’’、'、，° 為解決此技綱題’本個提供—触產奈米碳管之綠，其包括步驟 ⑴提供一基底； (2)沈積催化劑薄膜於基底； π⑶於溫度3GG°〇5GG°C下’對催化劑薄膜進行8〜12小時之退该理， 使得薄膜魏; ⑷於溫度_”c下，使催化劑顆粒麟源氣接觸至少15秒使得 6 1306833 謂飞日修錄).¾.顯j 不木兔音陣列基本垂直於基底長出； (5)將所得之奈米碳管從基底取下。 溶液ί^ΐ:嫩驗述步)後將所得之奈米碳管置於雜 與先前技術相比，本發明利用化學氣相 石^ *長度可控、無糾結易於錄之單根奈米碳管。另，本發明生長夺米 基底可重複使用從而降低奈米碳管之生長成本。 … 方式】 長产ΪΓΓΓ學氣相沈積法，以奈米碳管陣列方式實現生產長度一致， 長度可控，無糾結容易綠之奈米碳管。製備過程如下： 又 S 圖’提供一矽片或石英片作為可反復使用之基底3; 錄、ίί 之金屬催化劑薄膜11，催化劑1可選擇鐵、 U 碗靴儒，職奸，__ 進仃8〜12小時退讀理，使其收縮為分立之奈米觸粒12 ; 爐4 ;4)請參閱第三圖，將帶有催化劑顆粒12之多片基底3同時放織 2 m體(未標示)，同時將錢爐4加熱至_，00。。； 等，嫌），峨㈣氬、識 S =!=度-定的奈米碳管陣列於基底表面長出； 可用:9):ιί圖，取出基底3 ’奈米碳管5可用刀片6刮下，同樣亦 ， 鐵咐髮嫌製蝴槪、再次賴備 碳管5置於乙醇、卜2二氣淡嫩溶液中進 1306833 由於陣列中之秦来舜〜 好之單根奈米碳管。如第五、為平彳^列’無糾結，可輕轉到綠極 可易峨顧單根之奈：=;:米德已縣無糾結， 長所需要之 度，如奸、人、奈核fr 5將具_要續確長 實施方式一： =劑二:==:=== :==ϊ^τ;：=，保護 卻到室溫，得長度㈣鄉的奈;:^。，蘭15秒，然後將麟爐冷 實施方式二： 生長長度為100 _之奈米碳管陣列：於一多似夕基底上缝上_厚 狀基獻线t 。㈣幻Q小時， 然後將基底置於石英μ舟裏送705英管麟爐之中央麟室中，於氮氣保 護下’將魏爐加熱至69GX後，通入乙稀氣，聽5分鐘，然後將缝爐 冷卻至室溫’得長度為100鄉之奈米碳管陣列。 實施方式三： 生長長度為500 之奈米碳管陣列：於一多孔石夕基底上沈積上5nm厚 之鐵催化劑膜，然後將沈積有鐵催化劑之基底於空氣中4〇〇°c退火1〇小時， 然後將基底置於石英舟裏送英管爐之中央^^室中，於氬氣保 護下’將反應爐加熱至710T後，通入乙烯氣，反應10分鐘，然後將反應 爐冷卻至室溫，得長度為500/zm之奈米碳管陣列。 經過實驗確證，奈米碳管陣列之密度可達〇. lg/cm3。以生長looym高 度之陣列計算’能夠同時放置30片4-inch(25.4mm)矽片基底（單面鐘催化 劑）之反應爐可一次生產約2.4克長度為i〇〇ym之奈米碳管，一次生長過 程耗時約5分鐘左右。 綜上所述，本發明確已符合發明專利要件，爰依法提出專利申請。惟， 1306833 以上所述者僅為本之較佳實藏两丁舉冗ni案技藝之人士，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: ί圖式簡單說明】 第一圖係本發明沈積催化劑於基底之示意圖，· 第二圖係本發明之催化劑經退火處理後之示意圖，· 第二圖係本發明將帶有催化劑之基底置於反應爐中通入反應氣體生 奈米碳管之示意圖； 第四圖係本發明將奈米碳管從基底刮下之示意圖； 第五圖係本發日月之奈米碳管陣列於分散溶 後之透射電子 顯微鏡照片； 發明之奈米碳管陣列於錄溶液中超聲作用後之透射電子 ’ μ祕繼恤物崎来碳管·， 【主要元糊爛㈣純管陣列。 催化劑膜 11 基底 3 奈米碳管 5 催化劑 1= Advantages such as asking questions have important research value. It can be used in the workplace to display display devices, electric vacuum devices, non-electronics, and high-strength composite materials. D However, at present, any method of mass production cannot control the length of the carbon nanotubes in the product. i produces, the carbon nanotubes are sprayed finely, and the valve green is not conducive to the practical application in the field of carbon reinforcement. In view of this, a production length is consistent and the length is controllable. It is necessary to have a method of tangling the carbon nanotubes that are easy to record. [Invention] In order to solve the problem that the length of the carbon nanotubes cannot be controlled in the prior art, and the produced carbon nanotubes are entangled into a group, it is difficult to solve the problem. A method of entanglement of carbon nanotubes that are easy to disperse. '', ',, ° to solve this technical problem 'this provides - touch the carbon nanotube green, which includes step (1) to provide a substrate; (2) deposit a catalyst film on the substrate; π (3) at a temperature of 3GG ° At 5GG °C, the catalyst film is subjected to 8 to 12 hours of retreat to make the film Wei; (4) at temperature _"c, the catalyst particles are contacted with the source gas for at least 15 seconds so that 6 1306833 is said to be a fly-by-day repair). 3⁄4. 显j 不木兔音Array grows substantially perpendicular to the substrate; (5) Remove the obtained carbon nanotubes from the substrate. Solution ί^ΐ: After the step of the test, the obtained carbon nanotubes are placed Compared with the prior art, the present invention utilizes a chemical vapor phase stone with a length controllable and entangled to easily record a single carbon nanotube. In addition, the growth rice substrate of the present invention can be reused to reduce the carbon nanotubes. The growth cost. ... Method] The long-term production of vapor deposition method, the carbon nanotube array method to achieve consistent production length, length controllable, no entangled easy green carbon nanotubes. The preparation process is as follows: Provide a cymbal or quartz plate as a reusable substrate 3; recorded, ίί It belongs to catalyst film 11, catalyst 1 can choose iron, U bowl boots, traitor, __ enter 8~12 hours to retreat, so that it shrinks into discrete nano-touch particles 12; furnace 4; 4) see the first In the three figures, the plurality of substrates 3 with the catalyst particles 12 are simultaneously woven into a 2 m body (not shown), while the money furnace 4 is heated to _, 00, etc., etc., argon, argon, and S = !=degree-determined carbon nanotube array grows on the surface of the substrate; Available: 9): ιί图, remove the substrate 3 'Nanocarbon tube 5 can be scraped off with the blade 6, also the shovel is suspected of making a butterfly Once again, the carbon tube 5 is placed in the ethanol, and the 2 2 gas in the tender solution into the 1306833. Because of the Qinlai 舜 in the array ~ the good single carbon nanotube. If the fifth, the flat 彳 ^ column 'no tangles, can Lightly turn to the green pole can easily care for the single root of the Nai:=;: Meide has no entanglement in the county, the degree of long-term needs, such as rape, people, Nai nuclear fr 5 will have _ to continue to be a long way to implement one: = Agent 2: ==:=== :==ϊ^τ;:=, protection is to room temperature, the length (four) township Nai;: ^., blue 15 seconds, then the furnace cooling method 2: growth Carbon nanotube array of length 100 _: More than one eve of the base is sewed on the _ thick base line t. (4) phantom Q hours, and then placed in the quartz μ boat into the central chamber of the 705 British tube furnace, under the protection of nitrogen 'will After heating to 69GX, pass through the ethylene gas, listen for 5 minutes, and then cool the seaming furnace to room temperature to obtain a carbon nanotube array with a length of 100. Embodiment 3: Array of carbon nanotubes with a growth length of 500 : depositing a 5 nm thick iron catalyst film on a porous stone substrate, and then annealing the substrate on which the iron catalyst is deposited in air at 4 ° C for 1 hour, and then placing the substrate in a quartz boat for sending the tube In the central chamber of the furnace, under the protection of argon, the reactor is heated to 710T, then ethylene gas is introduced, reacted for 10 minutes, and then the reactor is cooled to room temperature to obtain a nanocarbon having a length of 500/zm. Tube array. It has been experimentally confirmed that the density of the carbon nanotube array can reach 〇. lg/cm3. A reactor capable of simultaneously placing 30 4-inch (25.4 mm) ruthenium substrates (single-faced catalyst) with an array of growing lookm heights can produce about 2.4 grams of carbon nanotubes of length i〇〇ym at a time. A growth process takes about 5 minutes. 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-mentioned patents are only included in the following patents: 1306833 The above is only the best of the two people who are skilled in the case of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a schematic diagram of the deposition catalyst of the present invention on a substrate, the second figure is a schematic diagram of the catalyst of the present invention after annealing, and the second figure is a substrate with a catalyst placed in the present invention. The schematic diagram of the reaction gas into the raw carbon nanotubes is introduced into the reaction furnace; the fourth figure is a schematic diagram of the present invention for scraping the carbon nanotubes from the substrate; the fifth figure is the dispersion of the carbon nanotube array of the present day and the moon. After transmission electron micrograph; the invention of the carbon nanotube array in the recording solution after the ultrasonic transmission of the electrons 'μ secrets of the Suzuki carbon tube ·, [main element paste (four) pure tube array. Catalyst film 11 substrate 3 carbon nanotubes 5 catalyst 1
奈米催化劑顆粒U 4 6 &Μ爐 刀片Nano catalyst particles U 4 6 &