TWI237064B - Supported metal catalyst for synthesizing carbon nanotubes by low-temperature thermal chemical vapor deposition and method of synthesizing nanotubes using the same - Google Patents

Supported metal catalyst for synthesizing carbon nanotubes by low-temperature thermal chemical vapor deposition and method of synthesizing nanotubes using the same Download PDF

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TWI237064B
TWI237064B TW091105806A TW91105806A TWI237064B TW I237064 B TWI237064 B TW I237064B TW 091105806 A TW091105806 A TW 091105806A TW 91105806 A TW91105806 A TW 91105806A TW I237064 B TWI237064 B TW I237064B
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metal catalyst
patent application
item
catalyst
metal
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TW091105806A
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Chien-Liang Hwang
Jack Ting
Jih-Shun Chiang
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Ind Tech Res Inst
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Priority to JP2002290290A priority patent/JP3580549B2/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

The present invention discloses a supported metal catalyst useful in synthesizing carbon nanotubes by low-temperature (< 600 DEG C) thermal chemical vapor deposition (CVD), which contains particles of a noble metal having a diameter of 0.01-10 microns as a support and a metal catalyst deposited on the noble metal particles. The metal catalyst is iron, cobalt, nickel or an alloy thereof. The supported metal catalyst has a weight ratio of the metal catalyst to the noble metal particles ranging from 0.1:100 to 10:100. The present invention also discloses a method of synthesizing carbon nanotubes directly on a substrate by low-temperature thermal CVD, wherein the metal support is no need to be removed from the substrate after the growth of carbon nanotubes.

Description

1237064 案&quot;βΐ 91 105806 曰 修正 五、拎明說明（丨） 發明領域 衣發明係有關一種奈米破管（c a r b ο η n a η 〇 t u b e s )的 合成方法，尤其有關一種適用於低溫熱化學氣相沉積合成 奈米碳管的負載金屬觸媒。 發明背景 奈米碳管（carbon nanotubes )具有非常特別的性 質’遠如低岔度、咼強度、而勒性、可撓曲、高表面積、 表面曲度大、高熱導度、導電性特異等等，所以吸引許多 研究工作者專注於開發其可能的應用方式，例如複合材 料、微電子元件、平面顯示器、無線通訊、燃料電池以及 經離子電池等等。以奈米碳管作為電子發射源之場發射顯 示々（carbon nanotube field emission displays ，簡稱 C N T - F E D )為一極具潛力的新型平面顯示器，通常較大型的 CNT-FED製程是以純化研磨後之奈米碳管摻混導電膠體， 經混漿、網印等技術佈植於導電玻璃基板表面，再經攝氏 3 5 0_到2 度之燒結步驟以去除漿料中的高分子物質，以形 ，π二:性良好之電子放射薄膜。這樣的CNT-FED製程除 ===個步驟、技術較為煩項外，而且奈米碳管不易均 勾刀政方；该導電膠體中。 右兩=:旎夠合成具備場發射電子功能的奈米碳管的方法 迅I電法（arc dlscharge)、雷射蒸發法（laser v a = 〇〇；^atl〇n)·和熱化學氣相沉積法（thermal chemical 雷射蒸發法 不 &lt;堇##空制奈米碳管產物之長度及管徑Case No. 1237064 &quot; βΐ 91 105806 Amendment V. 拎 明明 (丨) Field of the Invention The invention of the clothing is related to a method for synthesizing nanometer tube breaks (carb ο η na η 〇tubes), and particularly to a method suitable for low temperature thermochemistry Metal-supported catalyst for synthesis of carbon nanotubes by vapor deposition. BACKGROUND OF THE INVENTION Carbon nanotubes have very special properties, such as low bifurcation, chirp strength, tensile properties, flexibility, high surface area, large surface curvature, high thermal conductivity, specific conductivity, etc. Therefore, it has attracted many researchers to focus on developing its possible applications, such as composite materials, microelectronic components, flat-panel displays, wireless communications, fuel cells, and ion-ion batteries. Carbon nanotube field emission displays (CNT-FED) with nanometer carbon tubes as the electron emission source is a new type of flat display with great potential. Generally, the larger CNT-FED process is based on purified and ground Nano-tubes are mixed with conductive colloids, and they are planted on the surface of conductive glass substrates by mixing, screen printing and other technologies, and then sintered at a temperature of 350 ° to 2 ° C to remove the polymer substances in the slurry. , Π 二: Good electron emission film. Such a CNT-FED manufacturing process is not only equal to === steps, but the technology is more annoying, and the carbon nanotubes are not easy to be uniformly cut; in the conductive colloid. Right two =: Method for synthesizing nano carbon tube with field emission electron function. Arc I dlscharge, laser evaporation (laser va = 〇〇; ^ atl〇n), and thermochemical vapor phase Deposition method (thermal chemical laser evaporation method)

甘=PC)S11lon， thermal CVD )等等。電弧放電法和 案號 91105806 年 月 曰 1237064 修正 五、拎叫說明（2) '&quot;'—'—- 其產毕相S低。另外會產生相當多的非定形碳 (amorphous carbon )，需要進一步純化處理。此外，這 些製程的操作溫度都超過攝氏丨〇 〇 〇度，無法直接在玻璃基 材上合成奈米碳管。因此，一般認為熱化學氣相沉積法最 有潛力成為低溫生產奈米礙管的技術主流。 過去熱化學氣相沉積法合成奈米碳管技術，主要是以 多孔性氧化矽（porous silica )、沸石（ze〇lite )、氧 化紹（a 1 u m i n a )或氧化鎮（m a g n e s丨u m 〇 χ丨d e )為擔體， 並以含浸法（impregnation)製備沉積於該擔體上的活性 金屬觸媒。選用以上擔體的主要原因是因為此類擔體為相 當穩定之惰性氧化物，不易在加溫時與活性金屬觸媒反 應，使得活性金屬觸媒失去活性，而無法進行奈米碳管之 合成反應。選用之活性金屬主要為鐵、鈷或鎳，並加入微 量金屬如銅、錮、锰、鋅或始等加以調節反應活性。使用 該沉積於擔體的活性金屬觸媒在反應器中進行催化積碳反 應生成奈米碳管的反應條件包括：對反應器導入惰性氣體 (氦、氬、氮氣）、氫氣、及竣源氣體，反應溫度通常為 8 5 0至1 0 0 0 t：，壓力為1至2大氣壓，反應時間為1至1 2 〇分 鐘。所使用的碳源包括碳氫化合物或一氧化碳。反應結束 後需以酸液將擔體去除，才能得到較純的奈米碳管，以供 CNT —FED製程使用或其他用途。 一般而言，經鍛燒之耐溫玻璃的形變溫度（strain t e m p e r a t u r e )最高可達6 5 0 °C，較差的鈉玻璃形變溫度約 5 5 0 °C或更低，故若要以熱化學氣相沉積法直接將奈米碳 管生長於基板表面，則其反應溫度不能超過基材的形變溫Gan = PC) S11lon, thermal CVD) and so on. Arc Discharge Method and Case No. 91105806 Date: 1237064 Amended 5. Howling Explanation (2) '&quot;' —'—- Its production phase is low. In addition, a considerable amount of amorphous carbon is generated, which requires further purification. In addition, the operating temperatures of these processes are above 1000 ° C, making it impossible to synthesize carbon nanotubes directly on glass substrates. Therefore, it is generally believed that the thermochemical vapor deposition method has the most potential to become the mainstream of the technology for the production of nanometer obstructive tubes at low temperature. In the past, the technology of synthesizing carbon nanotubes by thermochemical vapor deposition was mainly based on porous silica, zeolite, a 1 umina or magnes 丨 um 〇χ 丨de) is a support, and an active metal catalyst deposited on the support is prepared by an impregnation method. The main reason for choosing the above carriers is that such carriers are relatively stable inert oxides, and it is not easy to react with the active metal catalyst during heating, which makes the active metal catalyst inactive, and it is impossible to synthesize nano carbon tubes. reaction. The active metal used is mainly iron, cobalt or nickel, and a small amount of metal such as copper, hafnium, manganese, zinc or zinc is added to adjust the reactivity. The reaction conditions for using the active metal catalyst deposited on the carrier to catalyze carbon deposition in the reactor to generate carbon nanotubes include introducing an inert gas (helium, argon, nitrogen), hydrogen, and source gas into the reactor. The reaction temperature is usually 850 to 100 t: the pressure is 1 to 2 atmospheres, and the reaction time is 1 to 120 minutes. The carbon sources used include hydrocarbons or carbon monoxide. After the reaction is completed, the carrier needs to be removed with an acid solution to obtain a relatively pure carbon nanotube for use in the CNT-FED process or other purposes. Generally speaking, the strain temperature of the fired temperature-resistant glass can reach a maximum of 6 50 ° C, and the temperature of the poor soda glass is about 5 50 ° C or lower. The phase deposition method directly grows the carbon nanotubes on the substrate surface, and the reaction temperature cannot exceed the deformation temperature of the substrate.

1237064 _ 案號 91 10580R_年月___1 修正 五、铎明說明（:)） &quot; - 度，亦即最好低於6 0 0艽。然而製程溫度太低，觸媒活性 就不足以合成奈米碳管，故需開發—高活性的特殊觸媒系 統，以低於6 0 0 °C之低溫之下進行奈米碳管合成。 歐洲專利申請案EP 1 0 6 1 0 4 1 A1揭示一種低溫熱以^設 仇和利用设備合成奈米碳管的方法，是將該設備中的反應 $ ~成在空間上鄰接氣體輸入部分、用於熱分解輸入氣體 的第一區，和空間上鄰接排氣部分、用於利用前述的分解 氣體合成奈米碳管第二區，並且，保持兩區的溫度，使第 一區的溫度低於第一區的溫度。在奈米碳管之生成反應區 使用兩種不同之觸媒基板，其中一片作為助觸媒使用，主 要作用為加速乙炔裂解，成份為p d、c r及P t等，另一片則 沉積有鐵、鈷、鎳或其合金觸媒膜，是主要生成奈米破管 的觸媒。將具有鐵、鈷、鎳或其合金觸媒膜的觸媒基板用 钱刻氣腐|虫’形成納米級催化性顆粒，利用上述設備先於 第一區高熱分解碳源氣，然後，通過第二區在等於或低於 基片形變溫度的溫度下使用被助觸媒分解的碳源氣，經熱 化學氣相沉積反應，在基板上上每個隔離的納米級催化性 金屬顆粒上生長垂直排列的碳納米管。此前案技術除了使 用攝氏4 5 0至6 5 0度的低溫反應區段外，仍須使用攝氏7 0 0 至1 0 0 0度的高溫進行碳源氣的熱分解（第一區），並非是純 低溫製程，也因此此前案技術必須使用特殊的CVD反應 為。此外於此剷案技術中必須於兩基材上形成兩種不同的 至屬觸媒層，再將此兩種基材以金屬層相對的方式間隔者 一段距離放置於熱CVD反應器中。很明顯的，此前案技術 的製程複雜、成本高、且不容易實施。1237064 _ Case No. 91 10580R_Year Month ___1 Amendment V. Duo Ming's explanation (:)) &quot;-Degree, which is preferably lower than 6 0 0 艽. However, the process temperature is too low, and the catalyst activity is not enough to synthesize carbon nanotubes. Therefore, a special catalyst system with high activity needs to be developed to synthesize carbon nanotubes at a low temperature below 600 ° C. European patent application EP 1 0 6 1 0 4 1 A1 discloses a method of low-temperature heating to synthesize nano-carbon tubes by using a device, which is to react the gas in the device into a space adjacent to the gas input. Part, the first region for thermally decomposing the input gas, and the second region spatially adjacent to the exhaust part, for synthesizing the second carbon nanotube with the aforementioned decomposed gas, and maintaining the temperature of the two regions so that the The temperature is lower than that of the first zone. Two different catalyst substrates are used in the generation reaction zone of the carbon nanotubes. One of them is used as a catalyst to accelerate the acetylene cracking. The components are pd, cr, and P t. The other is deposited with iron, The catalyst film of cobalt, nickel or its alloy is the catalyst that mainly generates nanometer tube breaks. The catalyst substrate with iron, cobalt, nickel or its alloy catalyst film is engraved with cavitation | worms to form nano-scale catalytic particles. The above equipment is used to decompose the carbon source gas in the first zone with high heat, and then pass through the first The second zone uses the carbon source gas decomposed by the catalyst at a temperature equal to or lower than the deformation temperature of the substrate. After thermochemical vapor deposition, the substrate grows vertically on each isolated nanometer-sized catalytic metal particle on the substrate. Aligned carbon nanotubes. In the previous case, in addition to using a low-temperature reaction zone of 450 to 650 degrees Celsius, the carbon source gas must be thermally decomposed using a high temperature of 700 to 100 degrees Celsius (the first zone). It is a pure low temperature process, so the previous technology must use a special CVD reaction. In addition, in this case technology, two different types of subordinate catalyst layers must be formed on the two substrates, and then the two substrates should be placed in the thermal CVD reactor at a distance from each other with the metal layers facing each other. Obviously, the technology of the previous case is complicated, expensive, and difficult to implement.

第8頁 1237064 案號 91105806 A_ 修正 五、發叫說叫（，1) 歐^·ι、|專 々沾飧低溫合 上形成金屬 級催化性金 度的溫度下 片上每個隔 碳納米管。 媒層。於此 屬觸媒層， 段距離放置 改進Ε Ρ 1 0 6 1 加熱系統更 顯之進步性 統。 利申請案ΕΡ 1 0 6 1 0 4 3 Α1揭示一種利用金屬觸 成碳納米管的方法。在該合成方法中，在基材 觸媒層，該金屬觸媒層被钮刻形成隔離的納米 屬顆粒。然後，通過在等於或低於基片形變溫 用被分解的碳源氣，經熱化學汽相沈積，在基 離的納米級催化性金屬顆粒上生長垂直排列的 該被分解的碳源氣係使用一碳源氣分解金屬觸 前案技術中必須於兩基材上形成兩種不同的金 再將此兩種基材以金屬層相對的方式間隔著一 於熱CVD反應器中。很明顯的，此前案技術為 0 4 1 A 1之製程專利，主要的進步性為將兩段式 改為一段式加熱系統，但對於觸媒系統並無明 ，仍需在兩片基板上使用兩種不同之觸媒系 發明要旨 本發明的一主要目的在提供一種適用於低溫熱化學氣 相沉積合成奈米碳管的負載金屬觸媒，其可以容易的被製 備。 本發明的另一目的在提供一種適用於低溫熱化學氣相 沉積合成奈米碳管的負載金屬觸媒，該負載金屬觸媒具有 觸媒組成容易調整及控制的優點。 本發明的另一目的在提供一種直接於基材上低溫合成奈米 碳管的方法，其不具有前述先前技藝的缺點。 本發明的另一目的在提供一種直接於基材上低溫合成奈米Page 8 1237064 Case No. 91105806 A_ Amendment V. Calling (, 1) ou ^ · ι, | specially dipped in low temperature to form a metal-grade catalytic gold temperature at the temperature of each carbon nanotube on the chip. Media layer. This is a catalyst layer, which is placed at a distance to improve the EP 1 0 6 1 heating system. The patent application EP 1 0 6 1 0 4 3 A1 discloses a method for using a metal to form carbon nanotubes. In this synthesis method, a metal catalyst layer is etched on the substrate catalyst layer to form isolated nano particles. Then, by decomposing the carbon source gas for the substrate deformation temperature equal to or lower than the substrate deformation temperature, and by thermochemical vapor deposition, the decomposed carbon source gas system is vertically arranged on the radical nano-sized catalytic metal particles. In the case of using a carbon source gas to decompose a metal, the two technologies must form two different golds on two substrates, and then place the two substrates in a thermal CVD reactor with the metal layers facing each other. Obviously, the technology of the previous case is a process patent of 0 4 1 A 1. The main advancement is to change the two-stage type to a one-stage heating system, but it is not clear about the catalyst system. It is still necessary to use two on two substrates. Summary of the Invention of Different Catalyst Systems A main object of the present invention is to provide a supported metal catalyst suitable for low-temperature thermochemical vapor deposition synthesis of carbon nanotubes, which can be easily prepared. Another object of the present invention is to provide a supported metal catalyst suitable for low-temperature thermochemical vapor deposition synthesis of carbon nanotubes. The supported metal catalyst has the advantage that the catalyst composition is easy to adjust and control. Another object of the present invention is to provide a method for synthesizing a carbon nanotube directly on a substrate at a low temperature, which does not have the disadvantages of the foregoing prior art. Another object of the present invention is to provide a low-temperature synthesis of nanometer directly on a substrate.

第9頁 1237064 案號 91105806 曰 修正 L、發明說叫（5) 碳管的方法，其具有觸媒 為達成上述發明目的 於低溫熱化學氣相沉積合 含： 粒徑介於0 . (H至1 0微 沉積於該貴金屬粒子 係選自鐵、鈷、鎳及其等 觸媒對該貴金屬粒子的重 間。 較佳的，該貴金屬粒 的合金，其中以銀為更佳 較佳的，本發明的負 屬粒子與該金屬觸媒的一 得的混合物中的溶劑，使 子上而製備。該金屬觸媒 硫酸鹽溶液，該硝酸鹽溶 液。 較佳的，本發明的負 步驟的沉積沈澱法而製備 a)將該貴金屬粒子分 b )將該金屬觸媒之一 屬粒子的分散液； c )加入一沈澱劑於步 混合物；以及 d )加入一還原劑於步 系統製備簡易的優點。 ，一種依照本發明而完成的適用 成奈米碳管的負載金屬觸媒包 米的貴金屬粒子；及 上的金屬觸媒，其中該金屬觸媒 之合金所組成之族群，及該金屬 量比介於0 . 1 .· 1 0 0至1 0 : 1 0 0之 子為銀、金、翻、纪及銅或它們 的。 載金屬觸媒，其係藉由將該貴金 鹽類溶液加予混合，再加熱所獲 得該金屬觸媒沉積於該貴金屬粒 的鹽類溶液可以為硝酸鹽溶液及 液及硫酸鹽溶液可為水或醇類溶 載金屬觸媒，其係藉由包括以下 散於一溶劑中； 鹽類溶液加入於步驟a )的該貴金 驟b)的混合物中並加熱所獲得的 驟c )的混合物以還原該金屬觸媒Page 9 1237064 Case No. 91105806 refers to the method of amending L, the invention is called (5) a carbon tube, which has a catalyst for achieving the above-mentioned purpose of the invention at low temperature thermochemical vapor deposition. The particle size is between 0. (H Up to 10 micro-deposited in the precious metal particles is selected from the weight of the precious metal particles of iron, cobalt, nickel, and other catalysts. Preferably, the alloy of the precious metal particles is more preferably silver, The solvent in the obtained mixture of the negative particles of the present invention and the metal catalyst is prepared on the surface of the catalyst. The metal catalyst sulfate solution, the nitrate solution. Preferably, the negative step deposition of the present invention Precipitation method to prepare a) divide the precious metal particles b) disperse a particle of the metal catalyst; c) add a precipitant to the step mixture; and d) add a reducing agent to the step system. . A precious metal particle suitable for nanometer carbon tube-loaded metal catalyst coated rice catalyst; and a metal catalyst thereon, wherein the group of alloys of the metal catalyst and the ratio of the amount of metal From 0.1. · 1 0 to 1 0: 1 0 0 The sons are silver, gold, turn, period and copper or theirs. The metal-bearing catalyst is obtained by adding and mixing the precious gold salt solution, and then heating the salt solution obtained by depositing the metal catalyst on the precious metal particles, which may be a nitrate solution and a liquid and a sulfate solution. Water or alcohol-based metal catalysts are prepared by including the following dispersed in a solvent; a salt solution is added to the mixture of step b) of the precious gold step b) and the mixture obtained by step c) is heated To reduce the metal catalyst

第10頁 1237064 _案號 91 105806_年月日__ 五、發叫說明（6) 的離子而使該金屬觸媒沉積於該貴金屬粒子上。 較佳的，步·驟a )的溶劑為水或醇類。 蛟佳的，步·驟c)的沈殿劑為氨水或碳酸氫鈉。 較佳的，步驟d)的還原劑為聯胺、甲醛、次磷酸鹽或 笨甲醛。 本發明亦提供一種低溫熱化學氣相沉積合成奈米碳管 的方法，包含下列步驟： a )將本發明的負載金屬觸媒分散於一基材上；及 b )使用一碳源氣體藉由熱化學氣相沉積於該負載金屬 觸媒上成長奈米碳管。 較佳的，本發明的低溫熱化學氣相沉積合成奈米碳管 的方法的步驟a)包含將該負載金屬觸媒分散於一含有高分 子及有機溶劑的膠液中，將所獲得分散膠液塗佈於該基材 上，加熱所獲得的塗層以移除其中的高分子及有機溶劑。 更佳的，該加熱所獲得的塗層以移除其中的高分子及有機 溶劑的溫度介於3 5 0〜5 0 0 °C之間。 較佳的，本發明的低.溫熱化學氣相沉積合成奈米碳管 的方法的步驟a)包含將該負載金屬觸媒加入於一有機溶劑 中，經超音波震盪一段時間加予分散，將所獲得的分散液 傾倒於一石英船基板上而於其上形成一薄層，及加熱乾燥 該薄層。 較佳的，本發明的低溫熱化學氣相沉積合成奈米碳管 的方法的步驟a )之基材選自於I T 0導電玻璃、強化玻璃、 納玻璃、石英、氧化石夕、石夕晶圓、銘和金屬薄片所組成的 族群。Page 10 1237064 _Case No. 91 105806_Year_Month__ V. Call the note (6) to deposit the metal catalyst on the precious metal particles. Preferably, the solvent of step a) is water or alcohol. The preferred Shen Dian agent in step c) is ammonia or sodium bicarbonate. Preferably, the reducing agent in step d) is hydrazine, formaldehyde, hypophosphite or benzaldehyde. The present invention also provides a method for synthesizing carbon nanotubes by low-temperature thermochemical vapor deposition, including the following steps: a) dispersing the supported metal catalyst of the present invention on a substrate; and b) using a carbon source gas to borrow Nano-carbon tubes are grown by thermochemical vapor deposition on the supported metal catalyst. Preferably, step a) of the method for synthesizing carbon nanotubes by low-temperature thermochemical vapor deposition of the present invention comprises dispersing the supported metal catalyst in a glue solution containing a polymer and an organic solvent, and dispersing the obtained dispersion. The glue solution is coated on the substrate, and the obtained coating is heated to remove the polymers and organic solvents therein. More preferably, the temperature of the coating obtained by heating to remove the polymers and organic solvents therein is between 3500 and 500 ° C. Preferably, step a) of the method for synthesizing nano-carbon tubes of the low-temperature thermal chemical vapor deposition of the present invention comprises adding the supported metal catalyst to an organic solvent, and dispersing it by ultrasonic vibration for a period of time, The obtained dispersion was poured onto a quartz ship substrate to form a thin layer thereon, and the thin layer was dried by heating. Preferably, the substrate of step a) of the method for synthesizing carbon nanotubes of low temperature thermochemical vapor deposition according to the present invention is selected from the group consisting of IT 0 conductive glass, reinforced glass, nano glass, quartz, oxidized stone and stone. A group of wafers, inscriptions, and metal foils.

1237064 _案號 91 105806_年月日__ 五、拎叫說明（7)1237064 _ Case No. 91 105806_ Year Month Day __ Howling Instructions (7)

較佺的，本發明的低溫熱化學氣相沉積合成奈米碳管 的方法的步驟b )的熱化學氣相沉積係於一介於4 0 0至6 0 0 °C 的反應溫度進行。 較佳的，本發明的低溫熱化學氣相沉積合成奈米碳管 的方法的步驟b )的熱化學氣相沉積係於一介於0. 5至2大氣 壓的壓力進行一介於1至1 2 0分鐘的反應時間；及該碳源氣 體包含碳氫化合物或一氧化碳。該碳氫化合物較佳的含有 1到1 2個碳。更佳的，該碳源氣體係指曱烷、乙炔或一氧 化石炭。 較佳的，本發明的低溫熱化學氣相沉積合成奈米碳管 的方法的步驟b )的熱化學氣相沉積係於氫氣存在下進行； 及該碳源氣體包含礙氫化合物或一氧化碳。 較佳具體實施例的詳細說明 本發明揭示一種適用於低溫（低於6 0 0 ° C )熱化學氣相 沉積合成奈米竣管的負載金屬觸媒，有別於前述EP申請案 所揭示的消去性合成奈米金屬觸媒的方式，本發明以加成 性的方法製備觸媒。首先挑選可與奈米碳管一起應用於一 下游產品的擔體，亦即該擔體將不影響下游產品與其製 程。以CNT-FED為例，銀膠中的銀顆粒即可作為觸媒擔 體，因為銀膠為CNT-FED製程中所必需使用的導電表面接 著劑，所以此擔體將不需去除即可直接投入於CNT-FED製 程中◦將活性金屬觸媒以沉積沉澱法或含浸法佈植於此類 擔體表面，再將此負載金屬觸媒分散或塗佈於基材表面， 後經熱化學氣相沉積反應便可生成奈米碳管，而且將反應In comparison, step b) of the method for synthesizing carbon nanotubes in the low-temperature thermochemical vapor deposition method of the present invention is performed at a reaction temperature between 400 and 600 ° C. Preferably, step b) of the method for synthesizing carbon nanotubes of the low-temperature thermochemical vapor deposition method of the present invention is performed at a pressure between 0.5 and 2 atmospheres and a pressure between 1 and 1 2 A reaction time of 0 minutes; and the carbon source gas comprises a hydrocarbon or carbon monoxide. The hydrocarbon preferably contains 1 to 12 carbons. More preferably, the carbon source gas system is pinane, acetylene, or mono-oxygen charcoal. Preferably, step b) of the method for synthesizing carbon nanotubes in the low-temperature thermochemical vapor deposition method of the present invention is performed in the presence of hydrogen; and the carbon source gas includes a hydrogen-blocking compound or carbon monoxide. Detailed description of a preferred embodiment The present invention discloses a supported metal catalyst suitable for low temperature (less than 600 ° C) thermochemical vapor deposition to synthesize nano tubes, which is different from that disclosed in the aforementioned EP application In the manner of eliminating synthetic nano-metal catalysts, the present invention prepares catalysts by an additive method. First, choose a carrier that can be used with a carbon nanotube for a downstream product, that is, the carrier will not affect the downstream product and its process. Taking CNT-FED as an example, the silver particles in the silver glue can be used as a catalyst support. Because the silver glue is a conductive surface adhesive necessary for the CNT-FED process, this support will be directly removed without removing it. Invested in the CNT-FED process.The active metal catalyst is deposited on the surface of such a support by deposition precipitation method or impregnation method, and then the supported metal catalyst is dispersed or coated on the surface of the substrate. Phase deposition reaction can generate carbon nanotubes, and the reaction

第12頁 1237064 案號 91105806 年 月 曰 修正 五、發明說明（8) 溫度控制在6 0 0 ° C以下 本發明的觸媒擔體 他、鉑等，其顆粒大小 性觸媒的方法有兩種， 積沉殿法。這兩種方法 含浸法將銀顆粒水溶液 鐘’然後加入含活性金 液，其中活性金屬包括 鹽類可為硝酸鹽或硫酸 混合溶液加熱濃縮，去 體之上，成為負載金屬 沉積沉澱法則將含 (例如氨水）使溶液p Η值 鐘，將擔體表面改質為 液加入，攪拌均勻後再 屬予以沉澱並還原，沉 然後過濾移去溶劑，即 本發明的一種低温 法，包含將前述的負載 一碳源氣體藉由熱化學 奈米碳管。 將ιΐ述的負 載金屬觸媒分散於一基材上的方式之 下。取一片基材，浸泡 ，然後 在基材 1 0分鐘加予清潔 可增加觸媒系統Page 12 1237064 Case No. 91105806 Amendment V. Description of the invention (8) The catalyst carriers of the present invention, such as platinum, platinum, etc., whose temperature is controlled below 600 ° C, have two methods of particle size catalyst , Accumulate the temple law. In these two methods, the silver particle aqueous solution is impregnated, and then an active gold-containing solution is added. The active metal including salts may be a nitrate or sulfuric acid mixed solution, heated and concentrated, and removed from the body to become a supported metal deposition method. For example, ammonia water), make the solution p 钟 value clock, modify the surface of the support to add liquid, stir and then precipitate and reduce, and then filter to remove the solvent, which is a low temperature method of the present invention, which includes the aforementioned load A carbon source gas is passed through a thermochemical nanocarbon tube. The method of dispersing a metal catalyst as described above on a substrate is dispersed. Take a piece of substrate, soak it, and clean it in 10 minutes to increase the catalyst system

仍可大量合成奈米碳管。 為貴重金屬顆粒，如金、銀、銅、 分佈於0 . 0 1 - 1 0微米之間。製備活 第一種是含浸法，及第二種則是沉 都需先將貴金屬顆粒分散於水中。 以超音波震盪一段時間例如1 0分 屬鹽類溶液，例如硝酸錄的水溶 過渡金屬元素，如鐵、钻、鎳等， 鹽。當兩個溶液混合均勻後，將此 除溶劑，活性金屬觸媒便分佈於擔 觸媒。 銀顆粒之水溶液加入一驗性水溶液 為8〜9再煮沸一段時間例如3 0分 鹼性，再將含活性金屬鹽類之水溶 加入沉澱劑與化學還原劑將活性金 殿劑例如氨水，還原劑例如曱酸， 可得到負載金屬觸媒。 熱化學氣沉積合成奈米碳管的方 金屬觸媒分散於一基材上；及使用 氣相沉積於該負載金屬觸媒上成長 如 於丙酮中，以超音波震盪器震盪約 取出乾燥備用，此步驟為前處理， 表面的附著力。前述的基材可為矽Nanotubes can still be synthesized in large quantities. It is precious metal particles, such as gold, silver, copper, distributed between 0.01 and 10 microns. Preparation The first method is impregnation, and the second method involves dispersing precious metal particles in water. Shock with ultrasound for a period of time such as 10 is a salt solution, such as water-soluble transition metal elements recorded by nitric acid, such as iron, diamond, nickel, etc., salt. When the two solutions are mixed well, the solvent is removed, and the active metal catalyst is distributed in the catalyst. Add an aqueous solution of silver particles to an aqueous solution of 8 to 9 and boil for a period of time, such as 30 minutes alkaline, and then add water containing active metal salts to the precipitating agent and chemical reducing agent. For example, osmic acid can obtain a supported metal catalyst. A square metal catalyst for synthesizing nano-carbon tubes by thermochemical gas deposition is dispersed on a substrate; and vapor-phase deposition is used to grow on the supported metal catalyst, such as in acetone, and it is shaken out with an ultrasonic oscillator to dry out. This step is pretreatment, surface adhesion. The aforementioned substrate may be silicon

第13頁 1237064 _案號 91105806_£ 五、發明說明（9) 曰 修正 晶圓、石英玻璃、強化玻璃、鈉玻璃、IT 0導電玻璃、金 屬薄片或氧化矽。將製備好的負載金屬觸媒與高分子膠液 混合均勻，負載金屬觸媒對高分子膠液的混合比例（重量） 從1 ·丨0到3 · 1 。一合適的南分子膠液包含一纖維素樹脂 (C e H u 1 〇 s e r e s i η ) 3 5 w t %，作為溶劑的d 1 - 1 -對-稀帖醇 (d L - a - t e r p i n e ο 1 ) 5 0 w t %，及作為分散劑（d i s p e r s a n t) 的碟酸鈉（s〇d i u m p h o s p h a t e ) 1 0 w t %及玻璃粉（g i a s s powder ) 1 5 wt%。該玻璃粉的功用為增加接著性。以網印Page 13 1237064 _Case No. 91105806_ £ 5. Description of the invention (9) Revisions Wafer, quartz glass, tempered glass, soda glass, IT 0 conductive glass, metal flakes or silicon oxide. The prepared loaded metal catalyst is mixed with the polymer glue evenly, and the mixing ratio (weight) of the loaded metal catalyst to the polymer glue is from 1 · 丨 0 to 3 · 1. A suitable south molecular gum solution contains a cellulose resin (C e H u 1 〇seresi η) 3 5 wt%, as a solvent of d 1-1 -p-tripineol (d L-a-terpine ο 1) 50 wt%, and sodium phosphate (sodium phosphate) 10 wt% and glass powder (giass powder) 15 wt% as dispersant. The function of the glass frit is to increase adhesion. Screen printing

之方式將混合膠體塗佈於基材表面，經1 1 〇艺烘乾3 〇分鐘 後，再經3 5 0〜5 0 0。(：在空氣氣氛下燒結30分鐘，以去除高 分子膠液。將本發明的負載金屬觸媒分散於一基材上的另 一方式包含將該負載金屬觸媒加入於一有機溶劑例如乙醇 中經超音波震盪一段時間例如1 〇分鐘加予分散，將混合液 傾倒於一石英船基板上經11 〇 °c烘乾3 〇分鐘。In this way, the mixed colloid is coated on the surface of the substrate, dried for 30 minutes in a 110-minute process, and then 350-500. (: Sintering in air for 30 minutes to remove polymer glue. Another method of dispersing the supported metal catalyst of the present invention on a substrate includes adding the supported metal catalyst to an organic solvent such as ethanol After ultrasonic shaking for a period of time, for example, 10 minutes, pre-dispersion is performed. The mixed liquid is poured on a quartz ship substrate and dried at 110 ° C for 30 minutes.

將前述分散有該負載金屬觸媒的基材置於一反應器中 進行熱化學氣相沉積反應即可於該負載金屬觸媒上成長卉 米碳管。反應氣體包括惰性氣體（例如氦、氬、氮氣）^ ^ 氣及碟源氣體，所使用的碳源氣體包括碳氫化合物或一= 化碳，反應溫度為攝氏4〇〇- 6 0 0度，反應時間為卜12Q分平 鐘，壓力為0.5-2大氣壓。反應後在觸媒擔體表面生成奈 米碳管，其管徑分佈於卜2 0 0奈米之間。 不 實施例1 將1克之顆粒大小分佈於卜5微米之間的銀顆粒加入 in 1的水，接著以$音波振盪處理溶液i 0分鐘。將濃度工％的The aforementioned substrate on which the supported metal catalyst is dispersed is placed in a reactor to perform a thermal chemical vapor deposition reaction to grow carbon nanotubes on the supported metal catalyst. The reaction gas includes an inert gas (such as helium, argon, nitrogen) and a gas source. The carbon source gas used includes hydrocarbons or carbon monoxide, and the reaction temperature is from 400 to 600 degrees Celsius. The reaction time is 12 minutes, and the pressure is 0.5-2 atm. After the reaction, carbon nanotubes were formed on the surface of the catalyst carrier, and their diameters were distributed between 200 nanometers. Example 1 1 g of silver particles having a particle size distribution between 5 μm and 1 in water were added, and then the solution was treated with sonication for 0 minutes. The concentration of%

第14頁 1237064 _iM 911Q58nn 年月 B 修生_ 五、發叫說叫（10) 硝酸鎳的水溶液1克加入所獲得的銀水溶液中，並且攪拌 %合之。所獲得的混合液接著被加熱移除其中的溶劑，而 獲得含1 %鎳金屬之銀擔體觸媒1 · 〇 1克的半成品。 實施例2 : 取1 · 0克顆粒大小分佈於0 . 0 5 - 0 · 1微米之間的銀顆粒 粉末加入5 0 m 1去離子水攪拌1 5分鐘後再加入濃度為2 8 %之 氨水0 · 0 5克再攪拌5分鐘，接著加熱迴流3 〇分鐘，再緩慢 加入濃度1 0 %之硝酸鎳水溶液〇 · 5克，再加入濃度為2 8 %之 氨水0 · Q 8克’繼續攪拌煮沸4小時後再加入濃度為3 7%之甲 酸水溶液0.44克，再沸騰3〇分鐘。待冷卻後過濾，取濾餅 經1 1 0 C乾煉4小時，得含5 %鎳金屬之銀擔體觸媒丨.〇 5克。 實施例3 : 將貫施例1製備好的負載金屬觸媒與高分子膠液混合 均勻’負載金屬觸媒對高分子膠液的混合比例（重量）為 1 : 1。一合適的高分子膠液包含一纖維素樹脂（CeUul〇se resin) 35wt%，作為溶劑的dl-卜對—烯帖醇（d^a一 t e r p i n e ο 1 ) 5 0 w t % ’ 一作為分散劑（d i s p e r s a n t)的石粦酸 鈉（sodium phosphate) 10 wt% 及玻璃粉（glass powder) 1 5 w t %。塗佈了觸媒膠液的基板經丨丨〇它烘乾3 〇分鐘後， 置於一熱化學氣相沉積反應器中，然後將反應器内溫度升 南至5 0 0 C ’在空氣氣氛下燒結3 〇分鐘，以去除高分子及 溶劑。將氬氣導入1 0分鐘，流量為1 5 〇 〇 m 1 / m i n，將空氣 趕出反應器。開始反應前將氬氣（500 ml/min)及氫氣（75Page 14 1237064 _iM 911Q58nn Month B Xiusheng_ Five, call (10) 1 g of an aqueous solution of nickel nitrate is added to the obtained silver aqueous solution, and the% is mixed together. The obtained mixed solution was then heated to remove the solvent therein, and a semi-finished product of 1.1 g of a silver-supported catalyst containing 1% nickel metal was obtained. Example 2: Take 1.0 grams of silver particles with a particle size distribution between 0.05 and 0.5 micrometers, add 50 m 1 of deionized water and stir for 15 minutes, then add ammonia water with a concentration of 28% 0.5 g was stirred for another 5 minutes, followed by heating under reflux for 30 minutes, and then slowly added a 10% strength nickel nitrate aqueous solution, 0.5 g, and then a 28% strength ammonia water, 0.Q 8 g. After boiling for 4 hours, add 0.44 g of a formic acid aqueous solution with a concentration of 3 7%, and boil for another 30 minutes. After cooling, it was filtered and the filter cake was dried at 110 ° C for 4 hours to obtain a silver support catalyst containing 5% nickel metal. 0.5 g. Embodiment 3: The uniformly loaded metal catalyst prepared in Example 1 is mixed with the polymer glue liquid, and the mixing ratio (weight) of the loaded metal catalyst to the polymer glue liquid is 1: 1. A suitable polymer gum solution contains 35% by weight of a cellulose resin (CeUulose resin), as a solvent, dl-bu-enetenol (d ^ a-terpine ο 1) 50% by weight-as a dispersant (Dispersant) 10% by weight of sodium phosphate and glass powder (15% by weight). After the substrate coated with the catalyst glue solution was dried for 30 minutes, it was placed in a thermal chemical vapor deposition reactor, and then the temperature in the reactor was raised to 50 ° C in an air atmosphere. Sinter for 30 minutes to remove polymer and solvent. The argon gas was introduced for 10 minutes, and the flow rate was 1500 m 1 / min, and the air was driven out of the reactor. Before starting the reaction, argon (500 ml / min) and hydrogen (75

第15頁 1237064 案號 91 105806 年 月 修正 五、發叫說明（Π) ηι 1 / in i η )混合後通入系統中持續5分鐘，再加入乙炔（2 5 in 1 / ini η )混合後開始進行熱化學氣相沉積反應。俟反應進 行β分鐘後，先將乙炔及氫氣關閉，再將加熱電源關閉， 等系統降溫至1 0 0 °C以下後關閉氬氣，然後將基板取出， 此時基板上塗佈有觸媒處可觀察到黑色沈積物。該黑色沈 積物經電子顯微鏡觀察為管徑20到60奈米之間的奈米碳 管。 實施例4 : 重覆實施例3的步驟，但以實施例2製得擔體金屬觸媒 取代實施例1所製備者。在基材表面長成的奈米碳管管徑 分佈介於2 0到6 0奈米之間。 實施例5 : 將實施例2製得的負載金屬觸媒0. 0 1克散佈於一石英 船基板上。接著該石英船基板置於一熱化學氣相沉積反應 器中以相同於實施例3的條件步驟成長奈米碳管。在基材 表面長成的奈米碳管管徑分佈介於2 0到6 0奈米之間。 與前案相比較，本發明主要優點有：一、本發明的擔 體金屬觸媒可用於低溫（低於6 0 0 ° C)熱化學氣相沉積的奈 米碳管的合成。二、本發明的擔體金屬觸媒可用於於基材 上直接低溫合成奈米碳管的方法，不需去除觸媒擔體。 三、本發明使用單一高活性觸媒系統，而非兩種觸媒系 統，可降低成本。四、本發明使用一段式低溫加熱方式，Page 15 1237064 Case No. 91 Amended in May 105806 5. Calling instructions (Π) ηι 1 / in i η) are mixed into the system for 5 minutes, and then acetylene (2 5 in 1 / ini η) is added after mixing Thermochemical vapor deposition reaction begins. After the β reaction is performed for β minutes, the acetylene and hydrogen are turned off, and then the heating power is turned off. After the system is cooled to below 100 ° C, the argon gas is turned off, and then the substrate is taken out. At this time, the substrate is coated with a catalyst. Black deposits were observed. The black deposit was observed by an electron microscope to be a carbon nanotube having a tube diameter of 20 to 60 nm. Example 4: The steps of Example 3 were repeated, but a support metal catalyst prepared in Example 2 was used instead of the one prepared in Example 1. The diameter distribution of the carbon nanotubes grown on the surface of the substrate is between 20 and 60 nm. Example 5: 0.01 g of the loaded metal catalyst prepared in Example 2 was dispersed on a quartz boat substrate. The quartz ship substrate was then placed in a thermochemical vapor deposition reactor to grow nano carbon tubes in the same conditions as in Example 3. The diameter distribution of the carbon nanotubes grown on the surface of the substrate is between 20 and 60 nm. Compared with the previous case, the main advantages of the present invention are as follows: 1. The support metal catalyst of the present invention can be used for the synthesis of nano-carbon tubes with low temperature (less than 600 ° C) thermochemical vapor deposition. 2. The carrier metal catalyst of the present invention can be used for a method for directly synthesizing a carbon nanotube on a substrate at low temperature without removing the catalyst carrier. 3. The invention uses a single highly active catalyst system instead of two catalyst systems, which can reduce costs. Fourth, the present invention uses a one-stage low-temperature heating method,

第16頁 1237064 案號 91 105806 年 月 修正 五、發明說明（12) 不；需經：段南溫區處理碳源氣體。五、與現有之厚膜 (t lu c k ί' 1 1 ill)製程使用相同導電層為擔體，可直接嵌入 C NT-FED原有之製程，具有完全之相容性。Page 16 1237064 Case No. 91 Month 105806 Amended 5. Explanation of the invention (12) No; need to go through: Duannan temperature zone to deal with carbon source gas. 5. The same conductive layer as the existing thick film (t lu c k ί '1 1 ill) process is used as the support, which can be directly embedded into the original process of C NT-FED, and has complete compatibility.

第17頁 1237064 _案號 91105806_年月日_修正 冏式簡革說明Page 17 1237064 _Case No. 91105806_Year_Month_Amendment

第18頁Page 18

Claims (1)

1237064 案號 91105806 _n_ 修正 ^、屮請專利範圍 1. 一種適用於低溫熱化學氣相沉積合成奈米碳管的負 載金屬觸媒，包含： 粒徑介於0 . 0 1至1 0微米的貴金屬粒子；及 沉積於該貴金屬粒子上的金屬觸媒，其中該金屬觸媒 係選自鐵、鈷、鎳及其等之合金所組成之族群，及該金屬 觸媒對該貴金屬粒子的重量比介於0. 1 : 1 0 0至1 0 : 1 0 0之 間。 2. 如申請專利範圍第1項的負載金屬觸媒，其中該貴金 屬粒子為銀、金、始、把及銅或它們的合金。 3. 如申請專利範圍第2項的負載金屬觸媒，其中該貴金 屬粒子為銀。 4. 如申請專利範圍第1項的負載金屬觸媒，其係藉由將 該貴金屬粒子與該金屬觸媒的一鹽類溶液加予混合，再加 熱所獲得的混合物中的溶劑，使得該金屬觸媒沉積於該貴 金屬粒子上而製備。 5. 如申請專利範圍第4項的負載金屬觸媒，其中的金屬 觸媒的鹽類溶液為硝酸鹽溶液及硫酸鹽溶液。 6. 如申請專利範圍第5項的負載金屬觸媒，其中的金屬 觸媒的鹽類溶液之溶劑為水或醇類溶液。1237064 Case No. 91105806 _n_ Amendment ^, please patent scope 1. A supported metal catalyst suitable for low temperature thermochemical vapor deposition synthesis of carbon nanotubes, comprising: a particle size between 0.01 and 10 microns Noble metal particles; and a metal catalyst deposited on the noble metal particles, wherein the metal catalyst is selected from the group consisting of iron, cobalt, nickel, and alloys thereof, and the weight ratio of the metal catalyst to the noble metal particles Between 0.1: 1 0 0 to 1 0: 1 0 0. 2. If the supported metal catalyst of item 1 of the patent application scope, wherein the precious metal particles are silver, gold, metal, copper and their alloys. 3. For the supported metal catalyst of item 2 of the patent application, wherein the precious metal particles are silver. 4. For the supported metal catalyst of item 1 of the scope of patent application, the precious metal particles are mixed with a salt solution of the metal catalyst, and then the solvent in the obtained mixture is heated to make the metal A catalyst is prepared by depositing the noble metal particles. 5. For the supported metal catalyst in item 4 of the patent application, the salt solution of the metal catalyst is a nitrate solution and a sulfate solution. 6. For the metal catalyst supported in item 5 of the patent application, the solvent of the salt solution of the metal catalyst is water or alcohol solution. 第19頁 1237064 __案號 91 10 5 8 0 6 年 月 曰 修正 六、屮請專利範圍 7. 如申請專利範圍第1項的負載金屬觸媒，其係藉由包 括以下步驟的沉積沈澱法而製備： a )將該貴金屬粒子分散於一溶劑中； b )將該金屬觸媒之一鹽類溶液加入於步驟a)的該貴金 屬粒子的分散液； c )加入一沈澱劑於步驟b)的混合物中並加熱所獲得的 混合物；以及Page 19 1237064 __Case No. 91 10 5 8 0 6 Amendment 6. Patent scope 7. If the metal catalyst supported in the first scope of the patent application is applied, it is by a deposition precipitation method including the following steps And preparing: a) dispersing the precious metal particles in a solvent; b) adding a salt solution of the metal catalyst to the dispersion of the precious metal particles in step a); c) adding a precipitating agent in step b) And the resulting mixture; and d )加入一還原劑於步驟c)的混合物以還原該金屬觸媒 的離子而使該金屬觸媒沉積於該貴金屬粒子上。 8. 如申請專利範圍第7項的負載金屬觸媒，其中步驟a) 的溶劑為水或醇類。 9. 如申請專利範圍第7項的負載金屬觸媒，其中步驟c) 的沈澱劑為氨水或碳酸氫鈉。d) adding a reducing agent to the mixture of step c) to reduce the ions of the metal catalyst so that the metal catalyst is deposited on the precious metal particles. 8. The metal-supported catalyst of item 7 of the patent application, wherein the solvent of step a) is water or alcohol. 9. The metal-supported catalyst as claimed in item 7 of the patent application, wherein the precipitant in step c) is ammonia or sodium bicarbonate. 1 0.如申請專利範圍第7項的負載金屬觸媒，其中步驟 d)的還原劑為聯胺、甲醛、次磷酸鹽或苯甲醛。 1 1. 一種低溫熱化學氣相沉積合成奈米碳管的方法，包 含下列步驟： a )將申請專利範圍第1項的負載金屬觸媒分散於一基材 上；及10. The supported metal catalyst according to item 7 of the scope of the patent application, wherein the reducing agent in step d) is hydrazine, formaldehyde, hypophosphite or benzaldehyde. 1 1. A method for synthesizing carbon nanotubes by low-temperature thermochemical vapor deposition, comprising the following steps: a) dispersing the supported metal catalyst in the patent application item 1 on a substrate; and 第20頁 1237064 _案號 91105806_年月日__ 六、屮請專利範圍 b )使用一碳源氣體藉由熱化學氣相沉積於該負載金屬 觸媒上成長奈米破管。 L 2.如申請專利範圍第1 1項的方法，其中步驟a )包含將 該負、載金屬觸媒分散於一含有高分子及有機溶劑的膠液 中，將所獲得分散膠液塗佈於該基材上，加熱所獲得的塗 層以移除其中的高分子及有機溶劑。 1 3.如申請專利範圍第1 2項的方法，其中去除高分子及 有機溶劑的溫度介於3 5 0〜5 0 0 °C之間。 1 4.如申請專利範圍第1 1項的方法，其中步驟a)包含將 該負載金屬觸媒加入於一有機溶劑中，經超音波震盪一段 時間加予分散，將所獲得的分散液傾倒於一石英船基板上 而於其上形成一薄層，及加熱乾燥該薄層。 1 5.如申請專利範圍第1 1項的方法，其中步驟a)之基材 選自於I T 0導電玻璃、強化玻璃、鈉玻璃、石英、氧化 石夕、石夕晶圓、ί呂和金屬薄片所組成的族群。 16.如申請專利範圍第1 1項的方法，其中步驟b)的熱 化學氣相沉積係於一介於4 0 0至6 0 0 °C的反應溫度進行。 1 7.如申請專利範圍第1 1項的方法，其中步驟b)的熱化Page 20 1237064 _Case No. 91105806_ Year Month__ VI. Patent scope b) Use a carbon source gas to grow a nanometer tube on the supported metal catalyst by thermochemical vapor deposition. L 2. The method according to item 11 of the scope of patent application, wherein step a) comprises dispersing the negative and metal-bearing catalyst in a glue solution containing a polymer and an organic solvent, and applying the obtained dispersion glue solution to On the substrate, the obtained coating is heated to remove the polymers and organic solvents therein. 1 3. The method according to item 12 of the scope of patent application, wherein the temperature for removing the polymer and the organic solvent is between 350 ° C and 500 ° C. 14. The method according to item 11 of the scope of patent application, wherein step a) comprises adding the supported metal catalyst to an organic solvent, adding ultrasonic dispersion for a period of time to disperse, and pouring the obtained dispersion liquid on A quartz ship substrate is used to form a thin layer thereon, and the thin layer is dried by heating. 15. The method according to item 11 of the scope of patent application, wherein the substrate of step a) is selected from the group consisting of IT 0 conductive glass, strengthened glass, soda glass, quartz, oxidized stone, crystalline silicon wafer, aluminum and metal Ethnic group made up of thin slices. 16. The method according to item 11 of the patent application, wherein the thermal chemical vapor deposition of step b) is performed at a reaction temperature between 400 and 600 ° C. 1 7. The method according to item 11 of the patent application, wherein the heating in step b) 第21頁 1237064 案號 flll 05806 年月曰 修正 7、屮請專利範圍 學氣相沉積係於一介於0. 5至2大氣壓的壓力進行一介於1 至1 2 0分鐘的反應時間；及該碳源氣體包含碳氫化合物或 一氣化峻。 1 8.如申請專利範圍第1 7項的方法，其中該碳氫化合物 含有1到1 2個碳。 1 9.如申請專利範圍第1 7項的方法，其中該碳源氣體係 指曱烷、乙炔或一氧化碳。 2 0 .如申請專利範圍第1 1項的方法，其中步驟b)的熱化 學氣相沉積係於氫氣存在下進行；及該碳源氣體包含碳氫 化合物或一氧化碳。Page 21 1237064 Case No. flll Modified in May, 05806 7. Patent scope is requested. Vapor deposition is performed at a pressure between 0.5 and 2 atmospheres for a reaction time between 1 and 120 minutes; and the carbon The source gas contains hydrocarbons or monogas. 18. The method according to item 17 of the scope of patent application, wherein the hydrocarbon contains 1 to 12 carbons. 19. The method according to item 17 of the scope of patent application, wherein the carbon source gas system refers to pinane, acetylene or carbon monoxide. 20. The method according to item 11 of the scope of patent application, wherein the thermochemical vapor deposition of step b) is performed in the presence of hydrogen; and the carbon source gas comprises a hydrocarbon or carbon monoxide. 第22頁 修正 修正本Page 22 Amendments 名稱或 姓名 財團法人工業技術研究院 1. Industrial Technology Research Institute 申請人 (共i人） 名稱或 姓名 /英文）1¾ ||· (中英i)l.中華民國TW 声居所 (營業所） 住居所 (營業所） 代表人 (中文） I新竹縣竹東鎮中興路4段195號（本地址與前向貴局申請者相同） 1. .·翁政義Name or name Industrial Technology Research Institute 1. Industrial Technology Research Institute Applicant (total i) Name or name / English 1¾ || · (Chinese-English i) l. TW Acoustic Residence (Business Office) Residence (Business Office) Representative (Chinese) I. No. 195, Section 4, Zhongxing Road, Zhudong Town, Hsinchu County (this address is the same as the previous applicant to your office) 1.. · Weng Zhengyi
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