TW200925301A - Copper-cobalt-carbon thin film catalyst and preparation method thereof and method for synthesizing carbon nanotube using the catalyst - Google Patents

Abstract

The present invention provides a copper-cobalt-carbon thin film catalyst. A copper-cobalt-carbon target is plated over a substrate to form a copper-cobalt-carbon thin film of nanometer scale thickness. The catalyst metal is copper, cobalt, carbon or an alloy thereof. The catalyst crystal grains are formed by using the immiscible property of copper, cobalt and carbon. The present invention utilizes the feature that copper, cobalt and carbon are not miscible to each other to control the size of the copper-cobalt-carbon thin film catalyst. This invention also plates copper, cobalt, and carbon over a silicon wafer by radio frequency magnetron sputtering to form the copper-cobalt-carbon alloy thin film of nanometer scale thickness. With the feature that copper, cobalt, and carbon are not miscible, catalyst crystal grains with about 10-50 nm may be generated from the alloy thin film via a thermal chemical evaporation process. The carbon nanotube of a size smaller than 50 nm is successfully synthesized at 700 Celcius degree and C2H2 atmosphere. In addition, the present invention also provides a method for preparing a copper-cobalt-carbon thin film catalyst and method for synthesizing a carbon nanotube by utilizing the copper-cobalt-carbon thin film catalyst.

Description

200925301 九、發明說明： 【發明所屬之技術領域】 碳營係;ΐ銅·姑.膜觸媒及以該觸媒合成奈米 尤其疋一種將銅-鈷-碳靶材鍍於-基材上，形 ί lit 合金薄膜，該觸媒金屬為銅、鈷、 觸媒晶粒以及以該觸媒合成奈米碳管之方法。 生 【先前技術】 π自,1991、年日本nec公司之科學家飯島澄男先生 (Surn^o _a)發現奈米碳管後，引起各界注意及研究孰 ❿ 潮。奈米碳管特殊之物理化學性質被預測有革命性用途*，、 可能用途概述如下：奈米碳管擁有金屬至半導體之間的性 質，加上奈米級尺寸，應用於微電子元件深具潛力，包括 奈米導$、場效電晶體，整流二極體、分子電腦等；奈米 碳管具高強度、高韌性、可撓曲性及導電性，適用於精密 的碳針頭，可廣泛應用於化學、生化及生物科技；因為導 $性佳、長度/半徑比夠大，可作為場發射顯示器(FED)、 掃瞒式電子顯微鏡(SEM)或穿透式電子顯微鏡(TEM)之場 發射電極；利用奈米碳管之導電性及強度，可製備好的複 合材料及最強之碳纤維；奈米碳管儲氫能力極佳且量大， 作為燃料電池健氫槽將有助於能源問題的解決；以奈米碳 管取代鐘電池石墨正極，其鋰電子存量更高，可提高電池 儲電量。200925301 IX. Description of the invention: [Technical field of invention] Carbon catalysis; bismuth copper and gu. Membrane catalyst and synthesis of nanoparticle with the catalyst, especially a copper-cobalt-carbon target plated on a substrate , a shape of the alloy film, the catalyst metal is copper, cobalt, catalyst grains and a method of synthesizing a carbon nanotube with the catalyst. [Previous technology] π 自, 1991, the Japanese nec company scientist Mr. Iijima Cheng (Surn^o _a) found the carbon nanotubes, attracted attention and research 孰 潮 tide. The special physicochemical properties of carbon nanotubes are predicted to be revolutionary in use*, and the possible uses are summarized as follows: Nanocarbon tubes possess metal-to-semiconductor properties, plus nanometer dimensions for use in microelectronic components Potential, including nano-conductor, field-effect transistor, rectifying diode, molecular computer, etc.; carbon nanotubes with high strength, high toughness, flexibility and conductivity, suitable for precision carbon needles, can be widely used Used in chemistry, biochemistry and biotechnology; because of its good conductivity and long enough length/radius ratio, it can be used as a field emission display (FED), broom electron microscope (SEM) or transmission electron microscope (TEM). The emitter electrode; using the conductivity and strength of the carbon nanotube, can prepare a good composite material and the strongest carbon fiber; the carbon storage capacity of the carbon nanotube is excellent and large, and the hydrogen tank as a fuel cell will contribute to the energy The solution of the problem; replacing the bell battery graphite cathode with a carbon nanotube, the lithium electron inventory is higher, which can increase the battery storage capacity.

目前用以製備奈米碳管最常用之方法有電弧放電法 (arcdischarge)，雷射爐管法(丨aserfurnace)以及化學氣相 沉積法(chemica丨 vapor deposition，簡稱 CVD)。其中 CVD 法可在常壓及較低溫下合成，因此有經濟上之優勢，此外 200925301 ί 之碳源(氣、液、固）、碳管可長在不同之 為狀之射及最可能i產料色，應 屬太23ncvD法係含碳氣體在高溫下通過金 ’會分解成碳元伽容人金朗媒中， 過飽和時’碳會以富勒辛圓頂(fuHerenedome)方 i i=ϊϊϊ成如倒立試管之中空圓柱，即為奈米碳 ❹ ΐ由ίίf (rftrate)間之作用力較強時，碳 " 置成長，此為底部成長模式(base growth =〇 e) ’备金屬觸媒與基質(substrat 時，位置成長，此為_4#== 。。_絲碳管成長之主要时有魏、金屬觸媒 碳源可以是氣體(C0、Μ、糾4…等）、液體 =、砌咖、巾她如〇丨…等)及固體(cam—、 有細爾換纖才能在金 ㈣屬t C。、啦素，是最被常糊製備奈米 金屬。例如+華民國已核准之第 Ϊί ί^ 低絲姆餘沉積合縣米碳管的 相沉積合 ΐ屬fl氧切粉末’其中該觸媒金屬為鐵、姑、錄或其 等之α金’其中該二氧化雜末的粒#介於Q Q5至5、m、，At present, the most commonly used methods for preparing carbon nanotubes are arcdischarge, laser tube method (chema丨furnace) and chemical vapor deposition (CVD). Among them, the CVD method can be synthesized at normal pressure and lower temperature, so it has economic advantages. In addition, the carbon source (gas, liquid, solid) and carbon tube of 200925301 ί can be different in different types and most likely to be produced. The color of the material should be too 23ncvD. The carbonaceous gas in the system will be decomposed into carbon by the gold at the high temperature. In the case of supersaturation, the carbon will be Fuerin dome (fuHerenedome). For example, if the hollow cylinder of the inverted test tube is a nanocarbon ❹ ΐ when the force between ίίf (rftrate) is strong, the carbon " grows, this is the bottom growth mode (base growth = 〇e) 'preparation of metal catalyst With the substrate (substrat, the position grows, this is _4#== .. _ The main reason for the growth of the carbon tube is Wei, the metal catalyst carbon source can be gas (C0, Μ, 44, etc.), liquid = , bricks, towels, such as 〇丨 ..., etc.) and solid (cam-, there is a fine fiber replacement in gold (four) is t C., vegetarian, is the most commonly prepared nano metal. For example, + Republic of China has Approved Ϊί ί^ Low-Simm deposition sedimentary meter carbon nanotube phase deposits are genus fl oxygen-cut powder 'where the catalyst metal is iron Regardless, the recording or the like gold α 'end wherein the heteroaryl dioxide particles is between Q Q5 to # 5, m ,,

^該f金屬對二氧化石夕粉末的重量比介於，：J 50 ·· 100。惟該專利係使粉末型觸媒，製備時需使用大量 200925301 化學品有污染環境之虞，誠屬美中不足之處。 因此，有必要設計一種銅_鈷_碳薄膜觸媒及其製 =及以該_合絲米鮮之綠，喊服上述=方法 【發明内容】 ^發^的目的在於提供一種銅_鈷_碳薄膜觸媒及其製 ΐ i If係_务碳姆齡—紐上，形成奈米級厚 度之銅-鈷·碳合金薄膜，該觸媒金屬為銅、鈷、碳薄膜或其 ❹ ❹ ，其係利用銅、銘與碳互不相溶之特性以產生銅-姑_ 奴薄膜觸媒晶粒以及以該觸媒合成奈米碳管之方法。 拔人ΐΐϊ ϊί 一目的在於提供一種以該銅-鈷-碳薄膜觸 其仙熱化學氣相沉積設備並以 為了達到上述目的，本發明之銅_銘_碳薄膜觸 方法，其係利用射頻磁控麵機將銅·鈷·碳:材η: ΐΠ成ί米級厚度之銅4碳合金薄膜，再經由熱化學蒸 鍍程f 、銘與碳互不相溶之特性以產生觸媒晶粒、： ”接ίΐίϊ1上述目的，本發明之—種適用於熱化學氣相 成奈米碳管的銅_銘_碳薄膜觸媒，係以奈米級厚度之 二ifΪ形式附著於—基材上，該觸媒金屬為銅、銘、碳 金’其侧贿、絲碳互不相溶之雜以產生觸 媒敎本發明之一種制銅善碳薄膜觸 積以合成一奈米碳管之方法’其係將如上 所t銅善碳薄麵媒置於熱化學氣相沉積設備中，並通 等纽或綠錢11，在-特定溫度下 為使貴審查委員能進一步瞭解本發明之結構、特徵 200925301 及其目的，茲附以圖式及較佳具體實施例之詳細說明如後。 【實施方式】 請參照圖1，其繪示本發明之觸媒製備方法中用以製 備觸媒之射頻磁控錢錄機之示意圖。如圖所示，本^^明之 銅-钻-碳薄膜觸媒製備方法係藉由一射頻磁控減鑛機1所 元成，其中該射頻磁控減鍵機1至少具有一試片交換室 10、一腔至20、一旋轉幫浦30、若干闕40〜42、若干壓 力表50〜51及一渦輪分子幫浦60所組成。 ❹ ❹ 其中’該試片交換室1〇係用以試片與腔體 20(chamber)交換動作，以減少抽真空所需時間。該腔室 =〇係為該射頻磁控濺鍍機1之核心所在，其進一步具有一 試片基座21，其具有旋轉的功能用以放置一基材2土，例 如但不限於為一矽晶圓、載玻片或多孔性氧化鋁，在本實 施例中係以矽晶圓為例加以說明，但並不以此為限。 ^严室2〇中進一步具有一把材a，其例如但不限於 ^一銅/姑/碳姆，可以將銅靶25直接放置於一銘靶以 若再上具有若干貫穿孔251，形成一銅雀無， 鈷-碳穿置於該銅25上，即可形成一銅· 士伽# ’其中’該貫穿孔251之數量例如但不限於為 26，且銘''碳乾23上可具有二個、四個或六個碳“ 於1 η : \旋26係以慢速切割機切割成直裡例如但不限 例如但不限於為1公分之圓柱體。此; 23可以放在—起也可以分開放置。 敍而接圖If!示，該紙材23上钻面積4%記為Cu_C〇#1， 3%記為CU_C0#2 ,鈷面積吼9%記為 放置6個碳旋26 = 在Cu_Co#2再放置4個碳錠26記為 8 200925301^ The weight ratio of the f metal to the dioxide powder is between: J 50 ··100. However, this patent is a powder type catalyst. It is a flaw in the environment that requires a large amount of 200925301 chemicals to be polluted. Therefore, it is necessary to design a copper-cobalt-carbon film catalyst and its system=and the green color of the _hesi rice, shouting the above = method [invention content] ^ hair ^ is to provide a copper _ cobalt _ Carbon film catalyst and its preparation If i If is a carbon-cobalt-carbon alloy film of nanometer thickness, the catalyst metal is copper, cobalt, carbon film or its crucible, It utilizes the incompatibility of copper, imprint and carbon to produce copper-gu-nano film catalyst grains and a method of synthesizing carbon nanotubes using the catalyst. The purpose of the present invention is to provide a copper-cobalt-carbon film contact with a thermal chemical vapor deposition apparatus and to achieve the above object, the copper_ing_carbon film touch method of the present invention utilizes radio frequency magnetic The control machine combines copper, cobalt and carbon: η: into a copper-carbon alloy film with a thickness of 5,000 meters, and then produces a catalyst crystal through the thermochemical vapor deposition process f, the incompatibility between carbon and carbon. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The catalyst metal is copper, inscription, carbon gold, which is incompatible with each other to produce a catalyst. The method for synthesizing a copper carbon film of the present invention to synthesize a carbon nanotube 'The system will place the copper-based thin-faced medium as described above in the thermal chemical vapor deposition equipment, and pass the new or green money 11. At a specific temperature, in order to enable the reviewing committee to further understand the structure of the present invention, Features 200925301 and its purpose are attached to the drawings and detailed description of preferred embodiments such as [Embodiment] Please refer to FIG. 1 , which is a schematic diagram of a radio frequency magnetic control recorder for preparing a catalyst in a method for preparing a catalyst according to the present invention. As shown in the figure, the copper-drill-carbon of the present invention is shown. The method for preparing a thin film catalyst is realized by an RF magnetron reducer 1 having at least one test piece exchange chamber 10, a cavity to 20, a rotary pump 30, and a plurality of阙40~42, several pressure gauges 50~51 and a turbo molecular pump 60. ❹ ❹ where 'the test piece exchange chamber 1 is used to exchange the test piece with the chamber 20 to reduce pumping The time required for the vacuum. The chamber is the core of the RF magnetron sputtering machine 1 and further has a test strip base 21 having a rotating function for placing a substrate 2 soil, for example It is not limited to a single wafer, a glass slide or a porous alumina. In the present embodiment, a germanium wafer is taken as an example, but it is not limited thereto. Material a, which is, for example but not limited to, a copper/gu/carbon, which can be placed directly on a target to be re-attached. There are a plurality of through holes 251, forming a copper fin without a cobalt-carbon penetrating on the copper 25, thereby forming a copper 士 伽# 'where the number of the through holes 251 is, for example but not limited to, 26, and ''Carbon dry 23 may have two, four or six carbons on the 1 η : \ 旋 26 system is cut in a straight speed cutter, for example but not limited to, for example, but not limited to, a cylinder of 1 cm. This; 23 can be placed in - or can be placed separately. Referring to Figure If!, the paper area 23 is marked as 4% Cu_C〇#1, 3% is recorded as CU_C0#2, and the cobalt area is 9% recorded as 6 carbon rotation 26 = in Cu_Co#2 Then place 4 carbon ingots 26 and record them as 8 200925301

Cu-Co-C#2、在Cu-Co#4再放置2個碳錠26 ^u_C〇-C#4,在每-個新的树23麵沉積之前必須^ &gt;月理靶材(pre-sputter)之動作，即將靶材23上之吸附性 因與大氣接觸所形成之氧化物，在本發明中利用一個槽&amp; (shutter)27加在乾材23與基材22中間，使得在清理無材 Ο ❹ (pre-sputter)時檔去沉積之前吸附性物質，清理乾材23 時間通常;11〜2小時，直到錢可赠定的生纽去除無 材23表面之吸附氧或其他物質，基材推進腔體2〇後，乾 材23必須再作一次清理靶材23之動作大約為15分鐘。 當滅鑛時可以使基座21轉動，讓銅-姑-碳薄膜(圖未示） 在成長過成中均分佈於基材20上，在幾鑛時通以氬氣 (Ar)，讓氬原子解離成離子(a「+)撞擊靶材23產生電漿，氮 氣流量控制在20 cc/sccm。 於沉積此銅·鈷-碳薄膜係利用射頻磁控濺鍍機彳其射 頻功率為50〜100 (watts)及氬氣流量之工作壓力為7χ1〇-3 t〇rr (氣體流量為20 cc/sccm)。基材22選用了發晶圓、載 玻片（glass slides)及多孔性氧化鋁，基材22於沉積銅銘_ 碳薄膜時並沒有加熱(室溫），滅鑛之溫度大約為100 t , 係利用熱電偶感測器(thermo couple)測得，它的位置約在 離基材22之4 cm處，本發明之沉積銅-姑-碳薄膜之參數 在表1作概略說明。 ' 表一沉積鎳薄膜之參數 射頻功率(W) 50 ' '— 預滅鍍“間(min) Ί ^ 工作麼力(mTorrj 7 工作距離icm) 15 - 氬氣之流量(seem) 20 ~~~~~~- 基材旋棘速度(rpm) 5 - 薄膜之厚度(nm) 30 - 200925301 該銅老製室20中通入氬氣(八「)及氧氣(〇)， 式朝基材22方向t子、雜子及碳離子將以電裝方 銅-銘碳合金薄膜移利用材22之表面上沉積成一 觸媒晶粒，此即如ϋ賴碳互不相溶之特性以產生 碳合。料該祕 P^e mial'alyfef^ ❹ 學成分分淤夕砝Γ 嶋)進行銅-鈷-碳合金薄膜之化 I C-C°-C#1^ Cu-Co-C#2 2.71at.%。 之碳含量勿別為 2_86at·%、2.80at_%及Cu-Co-C#2, and place 2 carbon ingots 26 ^u_C〇-C#4 in Cu-Co#4, and must be used before the deposition of each new tree 23 surface. -sputter), that is, the oxide formed on the target 23 due to contact with the atmosphere, in the present invention, a groove & (shutter) 27 is applied between the dry material 23 and the substrate 22, so that Clean up the material Ο pre (pre-sputter) when the file is deposited before the deposition of the adsorbent material, clean the dry material 23 time usually; 11~2 hours, until the money can be given to the raw material to remove the adsorbed oxygen or other substances on the surface of the material 23 After the substrate is pushed into the cavity 2, the dry material 23 must be cleaned again for about 15 minutes. When the ore is destroyed, the susceptor 21 can be rotated, and the copper-gu-carbon film (not shown) is distributed on the substrate 20 during growth and formation, and argon (Ar) is used in several ores to allow argon. The atom dissociates into ions (a "+) strikes the target 23 to produce a plasma, and the nitrogen flow rate is controlled at 20 cc/sccm. The copper-cobalt-carbon film is deposited by a radio frequency magnetron sputtering machine with an RF power of 50~ The working pressure of 100 (watts) and argon flow is 7χ1〇-3 t〇rr (gas flow is 20 cc/sccm). The substrate 22 is made of wafer, glass slides and porous alumina. The substrate 22 is not heated (room temperature) when depositing the copper _ carbon film, and the temperature of the ore is about 100 t, which is measured by a thermocouple, and its position is about from the substrate. At 4 cm of 22, the parameters of the deposited copper-gu-carbon film of the present invention are schematically illustrated in Table 1. 'Table 1 Parameters of Deposited Nickel Film RF Power (W) 50 ' '- Pre-de-plating "min" Ί ^Working force (mTorrj 7 working distance icm) 15 - Argon flow rate (seem) 20 ~~~~~~- Substrate spine speed (rpm) 5 - Thickness of film (nm) 30 - 200925301 Argon gas (eight "" and oxygen (〇) are introduced into the copper old chamber 20, and the t-type, hetero and carbon ions in the direction of the substrate 22 are transferred to the electric copper-minor carbon alloy film. The surface is deposited as a catalyst crystal grain, which is such that the carbon is incompatible with each other to produce carbon. The secret P^e mial'alyfef^ ❹ 成分 成分 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行- Carbon alloy film I CC°-C#1^ Cu-Co-C#2 2.71at.%. The carbon content should not be 2_86at·%, 2.80at_% and

Cu-Co#2 Cu-Co#4 Cu-Co-C#iCu-Co#2 Cu-Co#4 Cu-Co-C#i

Cu-Co-C#2 _ 時晶粒t顯、銅：二麵太含量明顯增加(Cu-C0#4 銘·碳觸媒 銘·碳觸媒在銘含量日碳管未明顯變小 乳3重4膜觸媒之氧含量降低可抑制奈: 200925301 =管直赠大’目此銅春碳觸媒可合成較小直徑之奈米破 官0 細謂3(a!r3(b) ’其緣示使用xps進行本發明之 碳、ί金薄膜上氧(0)之化學分析結果示意 =其中，圖3(a)』不鋼-姑合金薄膜銅，钴23 Cu_c〇#4在 ㈣職之氧(〇)_，g 3(b)齡本發明之銅 口金薄膜銅/鈷/碳靶23上使用2個碳鍵24Cu_c〇 c 濺難前麟形成之_)頻譜。比較圖3⑻及圖 ❹ 丄）濺鑛侧前^波峰面積可看_鲁碳雜之氧含量 ϊϋΐ刻後氧即消失，反細·料膜之氧含量較高， 且餘刻後氧尚有殘留。 照圖4⑻〜4(C) ’其分別顯示利用電子顯微鏡 ^進?本發明之⑶·。。·。^絲砂析_得到之微 =片之7F意圖。如騎示，姻電子顯微鏡(SEM)進行 ^發明之+CU-CO-C薄膜表面分析時，可得知本發明之 u Co-C薄膜表面之晶粒分布均勻，且晶粒隨碳含量之增 加而增加，晶粒大小分別為：cu_co_c#1是47±2nm， 是 18±2nm，Cu-Co-C#4 是 14±2nm(另請參照 請參照圖5，其緣示本發明於一熱化學氣相沉積設備 中合成一奈米碳管之示意圖。如圖所示，本發明之一種使 用銅-銘-碳薄膜觸媒熱化學氣相沉積以合成一奈米碳管之 方法將圖1中所製備之含Cu-Co-C薄膜觸媒之基材22放 置=一熱化學氣相沉積設備10〇中，並通入％、h2、c2h2 等氣體或其混合氣體，在一特定溫度下以合成一奈米碳管 110。 其中，該熱化學氣相沉積設備彳〇〇中之操作溫度及何 11 200925301 時可加入&amp;、Η2、(¾¾等氣體或其混合氣體之程序請參 照圖)6。如圖6所示，該熱化學氣相沉積設備100中係在Cu-Co-C#2 _ when the grain t is obvious, copper: the content of the two sides is significantly increased (Cu-C0#4 Ming·carbon catalyst Ming·carbon catalyst in the content of the day, the carbon tube is not obviously small milk 3 The decrease of the oxygen content of the heavy 4 membrane catalyst can inhibit the naphthalene: 200925301 = The tube directly gives the big 'eye. This copper spring carbon catalyst can synthesize the smaller diameter of the nano-breaking official 0. The fineness is 3 (a!r3(b) 'its The chemical analysis results of oxygen (0) on the carbon and ί gold film of the present invention using xps are shown as follows: wherein, FIG. 3(a) is a non-steel-gu alloy thin film copper, and cobalt 23 Cu_c〇#4 is in the (four) position. Oxygen (〇)_, g 3 (b) Age of the copper-copper film of the present invention copper/cobalt/carbon target 23 using two carbon bonds 24Cu_c〇c splashing before the formation of the _) spectrum. Compare Figure 3 (8) and Figure丄) The area of the front peak of the splashing side can be seen. The oxygen content of the ruthenium is disappeared after the sulphur content, and the oxygen content of the anti-fine material film is high, and the oxygen remains after the remaining time. 4(8) to 4(C)' show the (3) of the present invention by an electron microscope. . ·. ^ silk sand analysis _ get the micro = 7F intention of the film. When the surface of the +CU-CO-C film of the invention was analyzed by riding electron microscopy (SEM), it was found that the crystal grain distribution on the surface of the u Co-C film of the present invention was uniform, and the crystal grains were in accordance with the carbon content. Increase and increase, the grain size is: cu_co_c#1 is 47±2nm, is 18±2nm, Cu-Co-C#4 is 14±2nm (Please refer to FIG. 5 for further reference, the invention is shown in FIG. Schematic diagram of synthesizing a carbon nanotube in a thermal chemical vapor deposition apparatus. As shown in the figure, a method of synthesizing a carbon nanotube by using a copper-inscription-carbon thin film catalyst for thermal chemical vapor deposition is illustrated. The substrate 22 containing the Cu-Co-C film catalyst prepared in 1 is placed in a thermal chemical vapor deposition apparatus, and is passed through a gas such as %, h2, c2h2 or a mixed gas thereof at a specific temperature. The following is a synthesis of a carbon nanotube 110. Among them, the operating temperature of the thermal chemical vapor deposition apparatus and the time of 2009 and 200925301 can be added to the procedures of &amp;, Η2, (3⁄43⁄4, etc., or their mixed gases, please refer to Figure 6. As shown in Figure 6, the thermal chemical vapor deposition apparatus 100 is attached to

550°C下先通入％氣體加熱80分鐘後，溫度維持在550°C 並加入氣體加熱30分鐘，接著將溫度提高至7〇〇°c並 ^除Η? $體只通入％氣體後加熱2〇分鐘，然後將溫度固 定於700°c並加入〇此氣體後加熱30分鐘，最後於240 分鐘内將溫度降至室溫，即得於該基材22之Cu_c〇_c薄 膜^長出奈米碳管。其中，該N2氣體之流量為1〇〇SCCM , ❹ ❹After heating at 550 ° C for 80 minutes, the temperature is maintained at 550 ° C and heated by adding gas for 30 minutes, then the temperature is increased to 7 ° ° C and ^ Η $ $ 体 体 体 体 体 体After heating for 2 minutes, the temperature is fixed at 700 ° C, and the gas is added and heated for 30 minutes, and finally the temperature is lowered to room temperature in 240 minutes, that is, the Cu_c〇_c film of the substrate 22 is long. Out of carbon nanotubes. Wherein, the flow rate of the N2 gas is 1 〇〇SCCM, ❹ ❹

Ha氣，之流量為10SCCM’C2H2氣體之流量為100SCCM 請參照圖7(a)〜7(c)，其分別顯示利用電子顯微鏡 (SEM)進行觀察本發明之Cu_c〇_c薄膜觸媒合成之奈米碳 管所得到之微縮影片之示意圖。如圖所示，利用電子顯微 鏡(SEM)進行觀察本發明之Cu_c〇_c觸媒合成之奈米碳管 時，可得知本發明之3種Cu-Co-C觸媒，Cu-Co-C #1， Cu-Co-C #2及Cu-Co-C #4均可成功合成奈米碳管，且該 奈米碳管直徑&lt;50nm。 請參照圖8,其顯示利用利用拉曼光譜分析本發明之 Cu-Co-C觸媒合成之奈米碳管之示意圖。如圖所示，使用 本發明之3種Cu-Co-C觸媒合成之奈米碳管可都可得奈米 碳管之特性振動波峰，分別為D頻帶（band)在 1345-1355cm-1 和 G 頻帶(band)在 1580-1590cm·1。由 拉曼光譜SEM分析結果可確認所合成之產物確為&lt;5〇nm 直徑之奈米碳管。 是以’經由發明之一種鋼_鈷_碳薄膜觸媒及其製備方$ =以該觸合絲米碳管之方法之實施，其可以奈米匆 ^之銅务碳合金_形式_於—基材上，該_金^ 為銅、始、破或其合金，其係_鋼、賴碳互不相溶戈 12 200925301 以熱化學氣相沉積設備即可將該 碳管;=等優點，因此，確可改善習知合成奈米 更或ΪΪΐΐΐί:較佳實施例之—種，舉凡局部之變 易於推知者源俱===:習該項技藝之人所 ❹ 其迥二論就目的、手段與功效，在在顯示 ίϋϊϊ ΐ鱗徵’且其首先發明合於實用，亦在 曰賜會想以查委員明察，並祈早 【圖式之簡單說明】 践德便 製備三㊉意備圏觸二 碳錠、4 之㈣上可以有2個 ❹ 發氧==二=本 設備本發明於-熱化學氣相沉積 備十Ηίί)?;=學序氣之= 觸媒合成之奈米碳管所 13 200925301 明:其顯示糊彻拉曼光譜分析本發 月之Cu-Co-C觸媒合成之奈米碳管之示意圖。 【主要元件符號說明】 。 射頻磁控濺鍍機1 腔室20 基材22 鈷靶24 貫穿孔251 檔板27 ®閥40〜42 渦輪分子幫浦60 奈米碳管110 試片交換室10 試片基座21 靶材23 铜靶25 雙旋26 旋轉幫浦3〇 壓力表50〜51 熱化學氣相沉積設備100Ha gas, the flow rate is 10SCCM 'C2H2 gas flow rate is 100SCCM, please refer to FIG. 7 (a) to 7 (c), which respectively show the Cu_c〇_c film catalyst synthesis of the present invention by electron microscopy (SEM). A schematic representation of a miniature film obtained from a carbon nanotube. As shown in the figure, when observing the carbon nanotubes synthesized by the Cu_c〇_c catalyst of the present invention by an electron microscope (SEM), it is known that the three Cu-Co-C catalysts of the present invention, Cu-Co- Both C #1, Cu-Co-C #2 and Cu-Co-C #4 can successfully synthesize carbon nanotubes, and the diameter of the carbon nanotubes is &lt; 50 nm. Referring to Fig. 8, there is shown a schematic diagram of the analysis of a carbon nanotube synthesized by the Cu-Co-C catalyst of the present invention by Raman spectroscopy. As shown in the figure, the carbon nanotubes synthesized by using the three kinds of Cu-Co-C catalysts of the present invention can obtain the characteristic vibration peaks of the carbon nanotubes, respectively, and the D band is 1345-1355 cm-1. And the G band is at 1580-1590 cm·1. From the results of SEM analysis by Raman spectroscopy, it was confirmed that the synthesized product was a carbon nanotube of &lt;5 〇 nm diameter. It is implemented by the method of a steel_cobalt-carbon film catalyst and its preparation method by the invention, which can be used in the method of contacting the silicon carbon tube, which can be used in the form of copper alloy carbon alloy__ On the substrate, the _金^ is copper, the first, the broken or the alloy thereof, and the _ steel and the lan are mutually incompatible. 12 200925301 The carbon tube can be replaced by a thermal chemical vapor deposition apparatus; Therefore, it is indeed possible to improve the conventional synthetic nano or :ί: the preferred embodiment of the species, the local change is easy to infer the source of the source ===: the person who learns the skill is the second, the purpose, Means and efficacy, in the display of ϋϊϊ ΐ ΐ 征 ' ' and its first invention is practical, but also in the gift will want to check the members of the inspection, and pray early [simple description of the schema] There are 2 ❹ 触 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = 本 本 本Tube Institute 13 200925301 Ming: It shows a schematic diagram of the carbon nanotubes synthesized by Cu-Co-C catalyst synthesis in this month. [Main component symbol description]. RF magnetron sputtering machine 1 chamber 20 substrate 22 cobalt target 24 through hole 251 baffle 27 ® valve 40~42 turbo molecular pump 60 carbon tube 110 test piece exchange chamber 10 test piece base 21 target 23 Copper target 25 double rotation 26 rotary pump 3 pressure gauge 50~51 thermal chemical vapor deposition equipment 100

Claims (1)

200925301 十、申請專利範圍： 祕滅種鋼-鈷-碳薄膜觸媒之製備方法，其係利用射頻磁 :、機將銅-銘-破無材鍍於一基材上，形成奈米級厚度之 銘-碳合金薄膜’再經由熱化學蒸鍍程序，利用銅、鈷與 碳互不相溶之特性以產生觸媒晶粒。 、 制供巾請專利細第1項所述之銅备碳薄賴媒之 巧方法，其巾該基材可為—梦晶圓、載玻片或多孔性氧 化銘。 ❹ 制供m專利範圍第1項所述之銅务碳薄膜觸媒之 氧備，法，其中該銅普碳合金薄膜之厚度約3〇nm。 制偌古Hf利範圍第1項所述之銅钻-破薄膜觸媒之 巧方法’其中該銅·銘.碳練可以將銅乾直接放置於一姑 辆故I* ΐ該蛛上具有若干貫穿孔，再縣干雜放置於 銅乾上中，以形成一銅_銘_碳歡。 贺借圍第4項所述之鋼-姑·韻膜觸媒之 裝備方法’其中該銅-銘-碳乾上可具有2個、4個 赠速蝴細贼直縣g.5公分高為1 製備申4項所述之鋼善碳薄膜觸媒之 =控濺鍍機至少具有-腔室、-旋 壓力表，該銅-鈷-碳靶係置於該腔室中:i通 及:： 銅成於該基材之表面上，即為觸媒 贺備方ϊίίΐί圍第6項所述之觸媒之銅-鈷-碳薄膜 裝備方法，其中該射頻磁控錢鑛機^ 备备少冷县*^土丨If刀馬7mT 作距離為15公分， 虱氟U為絲20立方公分，歸旋觀度為每分鐘5 15 〇 Ο 200925301 轉。 成兹適用於熱化學氣相沉積合成奈米碳管的銅普 =膜觸媒，係以奈米級厚度之銅普碳薄膜形式附著於一 二b上，該觸媒金屬為銅、銘、碳或其合金，其係利用銅、 鈷與碳互不相溶之特性以產生觸媒晶粒。 9_如巾請專利範圍第8項所述之觸媒，其中該基材可 為一矽晶圓、載玻片或多孔性氧化鋁。 *人！申請專利範圍第8項所述之觸媒，其中該銅·銘_ 碳合金薄膜之厚度約30nm。 一太Γ· 一種使用銅始-破薄膜觸媒熱化學氣相沉積以合成 一不米碳管之方法，其係將如申請專利範圍8〜10中任一 項所述之銅鈷_碳薄膜觸媒置於熱化學氣相沉積設備中，並 通入N2、H2、C2H2等氣體或其混合氣體，在一特定溫度 下以合成一奈米碳管。 溫度=7^專利_ 11項所述之方法，其中該特定 13·如申請專利第Ή項所述之方法，其中該熱化 =相沉積補中係在55Q°C下先通人％氣體加熱80分 鐘後，再加入A氣體加熱30分鐘，將溫度提高至7〇〇艺 並移除Η:氣體後加熱20分鐘，然後將溫度固定於7〇〇。〇 並加入(¾¾氣體後加熱30分鐘，最後於24〇分鐘 度降至室溫，即得該奈米碳管。 现 灰14.如申請專利範圍第13項所述之方法，其中該N 氣體之流量為ioosccm，h2氣體之流量為10SCCM，2 C2H2氣體之流量為100SCCM。 破管^第1 W其中該奈米 200925301 16·如申請專利範園第彳 =之振減d_為%mf，，斯該奈米 ^580-1590cm 1 ° 及 G 繽帶為 硝釦如巾請專利細第1項所述之方法ϋ 把材可以放在一起也可以分開放置。 、中該鋼-麵_ 17200925301 X. Patent application scope: The preparation method of the secret-killing steel-cobalt-carbon film catalyst is to use the radio frequency magnetic: machine to plate the copper-ming-breaking material on a substrate to form the nanometer thickness. The Ming-carbon alloy film is then subjected to a thermochemical evaporation process using copper, cobalt and carbon incompatible properties to produce catalyst grains. For the supply of towels, please refer to the patented method for copper-based carbon thinner according to the first item. The substrate of the towel can be a dream wafer, a glass slide or a porous oxide. An oxygen preparation method for a copper carbon film catalyst according to item 1 of the patent scope of the invention, wherein the copper carbon alloy film has a thickness of about 3 〇 nm. The method of making a copper drill-breaking film catalyst according to the first item of the Hf range is the one in which the copper can be placed directly on a scorpion, so that there are several Through the hole, the county is placed in the copper dry to form a copper _ Ming _ carbon Huan. He borrows the equipment method of steel-gu and rhyme membrane catalyst mentioned in Item 4, where the copper-ming-carbon can have 2, 4 free speed thieves straight county g. 5 cm high 1 Preparation of the steel good carbon film catalyst according to Item 4 = The controlled sputtering machine has at least a chamber, a rotary pressure gauge, and the copper-cobalt-carbon target is placed in the chamber: i pass and: : The copper is formed on the surface of the substrate, that is, the copper-cobalt-carbon film assembly method of the catalyst described in the sixth item, wherein the radio frequency magnetic control machine has less preparation Cold County*^Tuyu If Knife 7mT is a distance of 15 cm, 虱Fluorum U is 20 cm cm, and the degree of revolving is 5 15 每 200925301 rpm. Chengz is suitable for the thermal chemical vapor deposition of carbon nanotubes. The copper catalyst is attached to the first and second b in the form of a nano-thick copper film. The catalyst metal is copper, Ming, Carbon or an alloy thereof that utilizes the incompatibility of copper, cobalt, and carbon to produce catalyst grains. The catalyst described in claim 8, wherein the substrate can be a wafer, a glass slide or a porous alumina. *people! The catalyst described in claim 8 wherein the copper alloy metal film has a thickness of about 30 nm. A copper-cobalt-carbon film according to any one of claims 8 to 10, which is a copper-cobalt-carbon film according to any one of claims 8 to 10, which is a method for synthesizing a carbon nanotube by using a copper-starting film-catalyst thermal chemical vapor deposition. The catalyst is placed in a thermal chemical vapor deposition apparatus, and a gas such as N2, H2, C2H2 or the like or a mixed gas thereof is introduced to synthesize a carbon nanotube at a specific temperature. The method of claim 11, wherein the method of claim 13 wherein the heating/phase deposition system is first heated at 55Q°C. After 80 minutes, additional A gas was added for 30 minutes, the temperature was increased to 7 并 and the Η was removed: the gas was heated for 20 minutes and then the temperature was fixed at 7 Torr. 〇 加入 加入 加入 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体The flow rate is ioosccm, the flow rate of h2 gas is 10SCCM, and the flow rate of 2 C2H2 gas is 100SCCM. Breaking pipe ^1 W where the nanometer 200925301 16·If applying for patent Fanyuan 彳=the vibration reduction d_ is %mf, , 斯纳米奈^580-1590cm 1 ° and G ribbon belt for the buckle, such as the towel, please refer to the method described in the first item. ϋ The materials can be placed together or separately. The steel-face _ 17