1 之74789 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種低溫製備奈米碳管之方法，尤指一 種適用於化學氣相沈積法中使用複合金屬催化的奈米碳管 之製造方法。 【先前技術】 自1991年lijima發現奈米碳管以來，至今已有數十種 合成奈米碳管的方法，例如：高溫電弧法（Arc method)、 雷射燒餘法（Laser ablation)、化學氣相沉積法（Chemical Vapor Deposition)等，其中以化學氣相沉積法公認為最便 利生長奈米碳管的方法，不僅可於大面積基材上均勻成長 奈米碳管且易於純化。 利用化學氣相沉積製備奈米碳管的過程中，須先製備 金屬催化層，再藉由此金屬催化劑催化碳源（曱醇、曱苯、 一氧化碳、乙炔、甲烷等）使其分解，以形成活性碳原子並 固熔於催化劑中。當溶解達過飽和時，碳可由催化劑中析 出，而逐漸堆積形成碳管。 習知有利用旋轉塗佈法（Spin-c〇ating)，將粒徑8nm的 鈷被粒均勻分佈在矽基材上，作為催化用之金屬，最後再 利用化子氣相，儿積法製備奈米碳管。由於僅採用鈷金屬作 =催化金屬，所以奈米碳管之生成溫度須達70(TC以上的高 溫。另有以光刻顯影技術dithogfaphy)，藉由光阻定義之圖 像（patt⑽），在發基板上將需要沉積金屬的地方與不需沉 ⑧ 5 1274789174789 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for preparing a carbon nanotube at a low temperature, and more particularly to a carbon nanotube suitable for chemical vapor deposition using a composite metal catalysis. Production method. [Prior Art] Since the discovery of carbon nanotubes by lijima in 1991, there have been dozens of methods for synthesizing carbon nanotubes, such as: Arc method, Laser ablation, Chemistry. Chemical Vapor Deposition, etc., in which chemical vapor deposition is the most convenient method for growing carbon nanotubes, which not only uniformly grows carbon nanotubes on large-area substrates but also facilitates purification. In the process of preparing a carbon nanotube by chemical vapor deposition, a metal catalyst layer must be prepared, and then the carbon source (sterol, benzene, carbon monoxide, acetylene, methane, etc.) is catalyzed by the metal catalyst to decompose it to form The activated carbon atoms are solid-melted in the catalyst. When the dissolution is oversaturated, carbon can be precipitated from the catalyst and gradually build up to form a carbon tube. It is known to use a spin coating method to uniformly distribute cobalt particles having a particle diameter of 8 nm on a ruthenium substrate as a metal for catalysis, and finally to use a gas phase of a chemistry to prepare a smear. Carbon nanotubes. Since only cobalt metal is used as the catalytic metal, the formation temperature of the carbon nanotubes must reach 70 (high temperature above TC. Also by photolithography development technique dithogfaphy), the image defined by the photoresist (patt(10)), The place where the metal will need to be deposited on the substrate is not required to sink 8 5 1274789
積的地方區隔出來，再利用化學還原法沉積鎳金屬於無光 罩之石夕基板上’並利用微波電漿化學氣相沉積法，製傷具 有規則之奈米碳管。但是此方法不僅製程繁瑣、耗時，且 單一的金屬催化，亦有傳統高溫生成奈米碳管之缺點。再 著，也有建議採用物理乾式法得到催化的金屬薄膜，並在 高溫下靠著氳氣將其還原活化，以利混合碳源可分解成為 活性碳原子，進而產出奈米碳管、碳球與其他碳結構之產 物，但此方法仍使用單一催化劑且其反應溫度甚高。 先础技術將基材金屬化的方法大多使用較昂貴的設 備系統製備金屬薄膜，但基材上之金屬薄膜都需經過高 熱處理:使薄膜裂化收縮在基材上形成奈米金屬顆粒，以 利於後續的奈米碳管的生長，為了達到大量且均_奈来等 級之奈米碳管，此類方式f嚴謹的控制反應條件且:理步 驟繁讀。有建議採用—般化學法製備奈米金屬微粒，但^ 粒易於聚集’所以製程須添加保護劑（例如：SDS、CTAB;、 PVA)使金屬微粒形成穩定的膠體。但是，添加劑對於後碎 碳管生長的步驟，卻造成不良影響。此外，亦有研究者： :其他的載材(例如：多孔性材料、ps微球)使金屬微粒分 於載材上田需要使用載材上的金屬時，將這些載材用 南溫燒除或化學侵餘法將載材去除，而這類製程卻十分繁 …習二，，理，貴金屬元素如把、麵、金、銀等， ;::氫化合物裂解脫氫，形成碳元素時所需之催 片^ 用途在於降低裂解反應之溫度。若生長奈米 1274789 碳管時，金屬催化射另含有貴金屬，崎低碳源反應物 之裂解溫度，促使原子態碳生成溫度降低，則有可能降低 奈米碳管之生成溫度。 因此，本發明人嘗試將過去吾人所研究的非均溫化學 析鍍法，應用在基材上以直接析鍍出分散均勻的金屬催化 微粒，再藉由金屬置換反應，使貴金屬析鍍於催化劑微粒 上二而形成複合金屬(co_catalyst)摧化系統。由此構思吾人 旨忒降低奈米碳官之生成溫度，並同時改善習知金屬微粒 分散不均等問題’亦不受限於基材種類，且 程成本，以解決習知製程繁璃、耗時等問題。 【發明内容】 本發明提供一種低溫製備奈米碳管之方法，包括以下 步驟：提供一第一金屬化學鍍液、一基材、以及一含有一 加熱為與一冷部器之反應器；以加熱器加熱化學鍍液，且 、γ卻器冷卻文熱之化學鍍液；進行一無電鍍反應，使基 材表面形成至少一第一金屬微粒；將基材表面之部分第一 金屬微粒以金屬化學置換方法置換成一第二金屬，以在基 材表面形成至少一含有複合金屬之微粒，·以及在基材表面 上形成奈米碳管。其中，反應器内容置有第一金屬化學鍍 、且將基材反纟又於化學錢液中，並使基材與加熱器之間 保持一間隙。 上述本發明所提及之加熱器，其加熱溫度可不受限 制’較佳加熱溫度可介於約1〇〇至約3〇〇艽之間。另外，冷 1274789The place where the product is separated is then deposited by a chemical reduction method on the base plate of the matte hood and subjected to microwave plasma chemical vapor deposition to produce a regular carbon nanotube. However, this method not only has a cumbersome process, is time consuming, and has a single metal catalysis, but also has the disadvantages of conventional high temperature generation of carbon nanotubes. Furthermore, it is also suggested to use a physical dry method to obtain a catalyzed metal film, and to reduce and activate it at a high temperature by helium gas, so that the mixed carbon source can be decomposed into activated carbon atoms, thereby producing carbon nanotubes and carbon spheres. A product with other carbon structures, but this method still uses a single catalyst and its reaction temperature is very high. The first method of metallizing the substrate mostly uses a relatively expensive equipment system to prepare the metal film, but the metal film on the substrate needs to be subjected to high heat treatment: the film is cracked and shrunk to form nano metal particles on the substrate, so as to facilitate the formation of nano metal particles on the substrate. Subsequent growth of the carbon nanotubes, in order to achieve a large number of carbon nanotubes of the same level, such a way to strictly control the reaction conditions and: the steps are familiar. It is recommended to prepare nano metal particles by a general chemical method, but the particles are easy to aggregate. Therefore, a protective agent (for example, SDS, CTAB; PVA) must be added to form a stable colloid of the metal particles. However, the additive has an adverse effect on the growth of the carbon nanotubes. In addition, there are also researchers:: Other materials (for example, porous materials, ps microspheres), when the metal particles are divided into the carrier material, when the metal on the carrier material is used, the materials are burned off at south temperature or The chemical intrusion method removes the carrier material, and such a process is very complicated... Xi 2, Li, precious metal elements such as handle, surface, gold, silver, etc.;:: Hydrogen compound cracking dehydrogenation, required to form carbon The use of the catalyst ^ is to reduce the temperature of the cracking reaction. If the nanotube 1274789 carbon tube is grown, the metal-catalyzed shot contains a precious metal, and the cracking temperature of the low-carbon source reactant causes the temperature of the atomic carbon to decrease, which may lower the temperature at which the carbon nanotube is formed. Therefore, the inventors attempted to apply the non-average temperature chemical plating method studied by the prior art to a substrate to directly deposit and deposit uniformly dispersed metal catalytic particles, and then deposit a noble metal on the catalyst by a metal displacement reaction. On the particles, a composite metal (co_catalyst) catalyzed system is formed. Therefore, it is conceived that the purpose of reducing the formation temperature of the nanocarbon official, and at the same time improving the problem of uneven dispersion of the conventional metal particles, is not limited to the type of the substrate, and the cost of the process is to solve the conventional process of glazing and time consuming. And other issues. SUMMARY OF THE INVENTION The present invention provides a method for preparing a carbon nanotube at a low temperature, comprising the steps of: providing a first metal electroless plating solution, a substrate, and a reactor containing a heating device and a cold portion; The heater heats the electroless plating solution, and the gamma heater cools the electroless plating solution; and performs an electroless plating reaction to form at least one first metal particle on the surface of the substrate; and the first metal particle on the surface of the substrate is made of metal The chemical replacement method is substituted with a second metal to form at least one composite metal-containing fine particle on the surface of the substrate, and to form a carbon nanotube on the surface of the substrate. Wherein, the reactor is placed with a first metal electroless plating, and the substrate is rutheniumed in the chemical liquid, and a gap is maintained between the substrate and the heater. The above-mentioned heater of the present invention may have a heating temperature not limited to a preferred heating temperature of between about 1 Torr and about 3 Torr. Also, cold 1274789
卻器所設定之冷卻溫度亦不受限，較佳冷卻溫度可介於約 -30至約6(rc之範圍内。在此鍍液同時加熱與冷卻的方法， 乃為提供一非均溫之鍍液，並利用此含有第一金屬之化學 鍍液^行一無電鍍反應（化學析鍍）。再著，本發明基材與 :熱器之間所存在的間隙可不限制其距離，其較佳間隙可 7丨於、、、勺10/z m至約1000 # m。由於本發明之第一金屬鍍液為 :具有溫度梯度之非均溫鍍液，所以當基材與加熱器保持 Γ間隙的距離時’其基材受熱溫度是小於加熱器所加熱之 /、中，第一金屬化學鍍液可不限其組成，較佳可包含 王屬皿類、一還原齊丨、-錯合劑、與- pH調節劑。一態 樣中金屬鹽類可為硫酸鎳、氯化鎳、硫酸鈷、氣化鈷、 U夂鐵或其組合；但是可視製程條件之催化金屬種類，而 Ϊ用其他金屬鹽類。另-態樣中，還原劑可為習知任-種 還原劑，較佳可為次碟酸鈉、硫酸聯氨或其組合。此外， ^月所使用之錯合劑可不限種類’較佳可為胺基醋酸、 鈉或其組合;而pH調節劑可採用習知所使用 試劑即可。 p u 么ντΓ者本發明所提及之第—金屬可不限種類，較佳可 2 1族金屬’更佳可為鐵、始、鎳或其合金，且在此所 之苐―金屬可作為奈米碳管之催化金屬。另外，本發 :所使用之第二金屬不受任何限制，較佳可為貴金屬元 素，3可為金H、或銀等。 樣中本發明之基材可為習知任一種基材，·一較 1274789 佳態樣中，該基材可為多 昨 ,ΛΠ Λ, - ^ ^ 夕日日7非日日矽、早晶矽、氧化鋁 或銦錫乳化玻璃（ITO被殖、，r ^ 肖且可採用夕種材料作為基材亦 為本發明優點之一。The cooling temperature set by the device is also not limited, and the preferred cooling temperature may be in the range of about -30 to about 6 (rc). The method of heating and cooling the plating solution at the same time is to provide a non-uniform temperature. The plating solution is used, and the electroless plating solution containing the first metal is used to perform an electroless plating reaction (chemical plating). Further, the gap between the substrate of the present invention and the heat exchanger is not limited, and the distance is not limited. The gap can be from 10/zm to about 1000 #m. Since the first metal plating solution of the present invention is a non-average temperature plating solution having a temperature gradient, the substrate and the heater maintain a gap therebetween. When the distance is 'the heating temperature of the substrate is less than the heating of the heater, the first metal electroless plating solution may not be composed of any composition, preferably including a royal dish, a reductive, a wrong agent, and - pH adjuster. The metal salt in one aspect may be nickel sulfate, nickel chloride, cobalt sulfate, cobalt hydride, U bismuth iron or a combination thereof; however, depending on the process conditions, the metal species may be used, and other metal salts may be used. In another aspect, the reducing agent may be a conventional reducing agent, preferably a secondary dish. Sodium, sulphate sulphate or a combination thereof. In addition, the compounding agent used in the month may be of any kind, preferably amino acid acetate, sodium or a combination thereof, and the pH adjusting agent may be a reagent which is conventionally used. The first metal mentioned in the present invention may be of any type, preferably a Group 2 metal 'more preferably may be iron, an initial, a nickel or an alloy thereof, and the ruthenium metal may be used as a nanocarbon. The catalytic metal of the tube. In addition, the second metal used is not subject to any limitation, preferably a precious metal element, and 3 may be gold H, or silver, etc. The substrate of the present invention may be a conventional one. A substrate, a better than 1274789, the substrate can be more than yesterday, ΛΠ Λ, - ^ ^ 夕日日日日日日, 矽 矽, alumina or indium tin emulsified glass (ITO is colonized It is also one of the advantages of the present invention that r ^ xiao can be used as a substrate.
本發明之奈米碳管生成反應可不限方式，較佳可為一 ，裂解化學氣相沈敍雜VD)，且其可包含以下步驟： 提供-氣體以作為碳來源、_氬氣以作為反應前後保護該 基材之氣體、以及一高溫爐裝置；將已含有複合金屬微粒 之基材置人高溫爐裝置中，同時通人氬氣；加熱高溫爐至 f應溫度’再依序將-氨氣、作為碳來源之氣體分別通 入南溫爐中，以生成奈米碳管；以及待奈米碳管生長完畢， 通入鼠氣，絲th基材。其巾，本發明奈米碳管生成反應 之溫不P艮，較佳可為赋以上的生成溫度，且本發明 奈米碳管之最低生成溫度可較低於習知化學氣相沈積反應 之生成溫度，所以亦為本發明優點之一。此外，上述本發 明中所適用作為碳來源之氣體可為習用任一氣體，較佳4 為一氧化碳、甲醇、曱苯、乙炔、甲烷或其組合等。 本發明之原理係利用一種吾人過往研究之非均溫無電 鍍沉積法（Non-isothermal Deposition, NITD)，使鍍液局部 區域自然發生均相成核反應，產生大量金屬微粒，而直接 吸附在基材上形成奈米金屬微粒，以作為奈米碳管之催化 金屬。此方法不同於一般化學鍍法使用貴金屬進行前處 理，便可直接在甚多材料的基材上進行析鏡反應。此外， 本舍明所形成之金屬微粒彼此間會自然地排列於基材上， 即同日守解決了奈米金屬微粒在基材上之分散與塗佈等問 1274789 題。更進-步地’本發明使用化學置換金屬的方式 微粒可形成祕、鎳金、仙、餘或是難等複 口五屬微粒，可大幅降低化學氣相沉積法生成奈米碳管之 【實施方式】 本發明主要利用非均溫化學析艘反應的特點，在微小 • 間隙下提高鍍液局部區域溫度，使鍍液在所限制的區間下 發生自發性均相成核反應，並在其中產生大量的奈米微 粒而基材與加熱板之間存在的微小間隙内，因為奈米微 粒表面具有大量未配對電子且加上空間的限制因素，所以 ^ I屬微粒會自然地吸附在基材上，而形成金屬微粒群。如 • 此即形成本發明奈米碳管第一金屬之催化層。 本發明一較佳實施步驟係先利用非均溫無電鍍法先製 備金屬觸媒微粒’並將表面具有金屬觸媒微粒之基材，置 • 入貴金屬鍍液後，再利用均溫化學置換方式將觸媒表面部 /刀置換成貝金屬几素，而形成一複合金屬催化形式。最後， 經由熱裂解化學氣相沉積法以生長奈米碳管，其製程可如 下所示： 首先’提供一基材、與一含有一金屬化學鍍液之非均 溫析鑛反應器。其中化學鍍液之組成包含··金屬鹽類（硫酸 錄或硫酸姑）、還原劑次磷酸鈉或硫酸聯氨）、錯合劑（胺基 醋酸或乳酸鈉）及pH調節劑等。 本實施例之反應器為一套管式反應器（可不限此類之 1274789 反應旬，其外部套管利用恆溫水槽為 ::定 絕。該反應器可;':有一:二二:p;=璃作為隔 哭 J斋（本灵^例為熱電偶感测The carbon nanotube formation reaction of the present invention may be in an unrestricted manner, preferably one, pyrolysis chemical vapor deposition (VD), and may include the following steps: providing - gas as a carbon source, _argon as a reaction a gas for protecting the substrate before and after, and a high-temperature furnace device; placing the substrate containing the composite metal particles in a high-temperature furnace device while passing an argon gas; heating the high-temperature furnace to a temperature of f and then sequentially - ammonia The gas and the gas as the carbon source are respectively introduced into the south temperature furnace to generate the carbon nanotubes; and the carbon nanotubes are grown, and the mouse gas and the silk th substrate are introduced. The towel, the temperature of the carbon nanotube formation reaction of the present invention is not high, preferably the formation temperature of the above, and the minimum formation temperature of the carbon nanotube of the invention can be lower than that of the conventional chemical vapor deposition reaction. The temperature is generated, so it is also one of the advantages of the present invention. Further, the gas used as the carbon source in the above-mentioned invention may be any gas conventionally used, and preferably 4 is carbon monoxide, methanol, toluene, acetylene, methane or a combination thereof. The principle of the present invention utilizes a non-isothermal thermal deposition (NITD) method that has been studied in the past, so that a local nucleation reaction occurs naturally in a local region of the plating solution, and a large amount of metal particles are generated, which is directly adsorbed on the substrate. Nano metal particles are formed on the surface to serve as a catalytic metal for the carbon nanotubes. This method differs from general electroless plating by pretreatment with precious metals, allowing direct spectroscopic reactions on substrates of many materials. In addition, the metal particles formed by Benbenming are naturally arranged on the substrate, that is, the same day, the problem of dispersion and coating of the nano metal particles on the substrate is solved. Further, the method of using the chemical replacement metal in the present invention can form a micro-particle of the five-genus, such as secret, nickel gold, celestial, residual or difficult, which can greatly reduce the formation of carbon nanotubes by chemical vapor deposition. Embodiments The present invention mainly utilizes the characteristics of a non-homogeneous chemical precipitation reaction to increase the temperature of a local region of a plating solution under a small gap, so that a spontaneous homogeneous nucleation reaction occurs in the restricted interval of the plating solution, and is generated therein. A large amount of nano-particles and a small gap between the substrate and the heating plate. Because the surface of the nano-particles has a large number of unpaired electrons and space constraints, the particles are naturally adsorbed on the substrate. And forming a group of metal particles. Thus, the catalytic layer of the first metal of the carbon nanotube of the present invention is formed. A preferred embodiment of the present invention is to first prepare a metal catalyst particle by using a non-average temperature electroless plating method and to place a substrate having a metal catalyst particle on the surface, and then apply it to a noble metal plating solution, and then use a uniform temperature chemical replacement method. The catalyst surface portion/knife is replaced with a shell metal to form a composite metal catalytic form. Finally, the carbon nanotubes are grown by thermal cracking chemical vapor deposition, and the process can be as follows: First, a substrate is provided, and a non-homogeneous deionization reactor containing a metal electroless plating solution is provided. The composition of the electroless plating solution includes a metal salt (sulphuric acid or sulfuric acid), a reducing agent sodium hypophosphite or hydrazine sulfate, a complexing agent (aminoacetic acid or sodium lactate), and a pH adjuster. The reactor of this embodiment is a cannula type reactor (it is not limited to the type 1274789 reaction, and the outer casing is made of a constant temperature water tank:: the reactor can be; ': one: two two: p; = glass as a crying J Zhai (this spirit ^ example for thermocouple sensing
时）係固疋於加熱器中心處，以量測加熱器之加熱溫度， 在本例中加熱器之加熱溫度為2〇〇它。此外，反應器更^設 有一可調式之基材載台，以固定基材，並在載台内部可2 有-組可調節腳座，係用以控制基材與加熱器間的間距， 以形成微小反應區間。在此所提及之非均溫反應器乃為本 灸明之一悲樣，因此本發明所指的非均溫反應器並不受限 於此，其乃為一提供一非均勻溫度之化學鍍液（使鍍液呈現 一溫度梯度），且使基材與加熱器之間保持一間隙之反應器 即可，而本實施例之間隙乃為15〇 # m。 首先，將清潔好的基材以適當方法固定於基材載台 上’並調整載台間隙於所需固定高度。接著，調配第一金 屬化學鑛液之配方並置入反應器中，且調整冷卻水恒溫水 槽溫度與加熱控制器溫度。然後，將固定好基材之載台置 入反應器中，待冷卻水恆溫水槽溫度穩定後，啟動加熱控 制器溫度，最後以獲得非均溫無電鍍沉積法之金屬微粒觸 媒。緊接著，將上述具有金屬微粒觸媒之基材自反應器中 取出後，並置入貴金屬鍍液中，進行貴金屬化學置換，即 可得到複合的金屬催化微粒。 本實施例生成奈米碳管之方法係使用熱裂解化學氣相 沉積法生長奈米碳管，其步驟如下： 11 1274789 - 取非均溫無電鍍沉積法製備金屬觸媒之基板，置入高 溫爐管設備中。利用乙炔為提供碳來源之使用氣體，反應 月ίι後之降溫階段以氬氣當保護氣體。開啟高溫爐加熱器， 當溫度達到反應溫度時，先通入氨氣10分鐘後，再通入乙 炔氣體15分鐘。待奈米碳管成長完畢後，關掉氨氣與乙炔。 通入氬氣10分鐘，以作為保護性氣體，避免高溫時產生不 必要之反應，待爐管溫度降至室溫時取出長好奈米碳管之 $ 基板’並利用SEM進行觀察奈米碳管生成之狀態。 下列係利用上述本發明一較佳實施步驟所進行之諸多 具體實施例，其反應條件可分別如下所示。雖然在此所採 用之基材分別為Ρ型矽晶圓（p-type)及ΙΤ〇玻璃，且使用乙 • 炔作為碳來源之氣體，但是不表示本發明基材與碳來源之 氣體僅受限於此，應以申請專利範圍之範疇為準。 實施例一在具有金-鎳金屬微粒之矽晶圓上生長奈米碳管 將矽晶圓基材以非均溫無電鍍製備鎳金屬微粒觸媒， 再將其置入貴金屬鍍液中，進行貴金屬化學置換，以在基 ^ 材表面獲得金-鎳複合金屬微粒之觸媒。最後，將基材置入 高溫爐管設備中，進行熱裂解化學氣相沉積法生長奈米碳 官。操作溫度分別為800°C與400°C，通入適當流量乙炔氣 體，操作時間為10分鐘，反應後以場發射掃描式電子顯微 鏡（FESEM)觀察矽晶圓基材上奈米碳管生成狀況，而在8〇〇 C與400 C之反應溫度下均可見生成奈米碳管。下列為本實 施例製備鎳金屬微粒之鑛液組成，其中化學鎳鑛液成分可 如下所示。 12 ⑧ 1274789 化學鎳鏡液之成分 成份濃度 硫酸鎳（N i S 0 4 · 6 Η 2 0 ) 0.11M 次磷酸鈉（NaH2P02.H2〇) 0.28M 乳酸鈉（C3H5 03Na) 0.36M 胺基醋酸（c2h5o2n) 0.13 Μ 氨水（nh4oh) 將鍍液ρ Η調整至9 此外，本實施例貴金屬化學置換法之鍍液組成，乃如 下列所示，其中本例之貴金屬為金。 化學置換之金鍍液組成 成份濃度 氰化金鉀（KAu(CN)2) 0.02M ~ 氣化胺（nh4ci) 1.1M 檸檬酸鈉（Na3C6H507) 0.2M 檸檬酸 將鍍液ρ Η調整至6 實施例二在具有鈀-鈷金屬微粒之矽晶圓上生長奈米碳管 將矽晶圓基材以非均溫無電鍍製備鈷金屬微粒觸媒， 再將其置入貴金屬鍍液中，進行貴金屬化學置換，以在基 材表面獲得鈀-鈷複合金屬微粒之觸媒。最後，將基材置入 高溫爐管設備中，進行熱裂解化學氣相沉積法生長奈米碳 官。操作溫度分別為800°C與4001：，通入適當流量乙炔氣 體’操作時間為10分鐘，反應後以叩犯“觀察矽晶圓基材 上奈米碳管生成狀況，而在800°c與4〇(^c之反應溫度下均 可見生成奈米碳管。下列為本實施例製備鈷金屬微粒之鍍 液組成，其中化學鈷鍍液成分可如下所示。 鍍液之成分 一成份濃度 ⑧ 13 1274789 0.07M 0.2M 0.2M 0.55M 將錢液pH調整至9 硫酸鈷（CoS04 · 7H20) 次磷酸鈉（NaH2P02 ·Η2〇) 檸檬酸鈉（Na3C6H507) 氯化胺（NHWl) 氨水（nh4oh) 之鑛液組成，乃如 此外，本實施例貴金屬化學置換法 下列所示，其中本例之貴金屬為銳。The system is fixed at the center of the heater to measure the heating temperature of the heater. In this example, the heating temperature of the heater is 2 〇〇. In addition, the reactor is further provided with an adjustable substrate carrier for fixing the substrate, and a set of adjustable feet on the inside of the stage is used to control the distance between the substrate and the heater. A small reaction interval is formed. The non-equal temperature reactor mentioned herein is a sad example of the moxibustion. Therefore, the non-equal temperature reactor referred to in the present invention is not limited thereto, and is an electroless plating which provides a non-uniform temperature. The liquid (which causes the plating solution to exhibit a temperature gradient) and maintains a gap between the substrate and the heater can be used, and the gap of this embodiment is 15 〇 # m. First, the cleaned substrate is fixed to the substrate stage by an appropriate method' and the stage gap is adjusted to the desired fixed height. Next, the formulation of the first metal chemical mineral liquid is formulated and placed in the reactor, and the temperature of the cooling water constant temperature tank and the temperature of the heating controller are adjusted. Then, the substrate on which the substrate is fixed is placed in the reactor, and after the temperature of the cooling water constant temperature tank is stabilized, the temperature of the heating controller is started, and finally, the metal particle catalyst of the non-average temperature electroless deposition method is obtained. Next, the above-mentioned substrate having the metal particulate catalyst is taken out from the reactor and placed in a precious metal plating solution to carry out chemical substitution of the noble metal, whereby composite metal catalytic fine particles can be obtained. The method for generating a carbon nanotube in this embodiment is to grow a carbon nanotube by pyrolysis chemical vapor deposition, and the steps are as follows: 11 1274789 - A substrate for preparing a metal catalyst by a non-average temperature electroless deposition method, and placing a high temperature In the furnace tube equipment. The acetylene is used as a gas source for supplying carbon, and the cooling phase after the reaction is argon gas as a shielding gas. The high temperature furnace heater is turned on. When the temperature reaches the reaction temperature, the ammonia gas is first introduced for 10 minutes, and then the acetylene gas is introduced for 15 minutes. After the growth of the carbon nanotubes is completed, the ammonia gas and acetylene are turned off. Allow argon gas for 10 minutes to use as a protective gas to avoid unnecessary reaction at high temperature. When the temperature of the tube is lowered to room temperature, take out the substrate of long carbon nanotubes and observe the carbon by SEM. The state of the tube generation. The following are a number of specific examples carried out by using a preferred embodiment of the present invention described above, and the reaction conditions are as follows. Although the substrates used herein are p-type and germanium, respectively, and B-alkyne is used as the carbon source gas, it does not mean that the substrate of the present invention and the carbon source gas are only affected by the gas. In view of this, the scope of the patent application shall prevail. Example 1 Growing a carbon nanotube on a germanium wafer with gold-nickel metal particles. A nickel metal particle catalyst is prepared by non-average temperature electroless plating on a germanium wafer substrate, and then placed in a precious metal plating solution. The noble metal is chemically replaced to obtain a catalyst of gold-nickel composite metal particles on the surface of the substrate. Finally, the substrate is placed in a high temperature furnace tube apparatus for thermal cracking chemical vapor deposition to grow nanocarbon. The operating temperatures were 800 ° C and 400 ° C respectively, and the appropriate flow rate of acetylene gas was passed for 10 minutes. After the reaction, the field emission scanning electron microscope (FESEM) was used to observe the formation of carbon nanotubes on the wafer substrate. At the reaction temperature of 8 ° C and 400 C, carbon nanotubes were formed. The following is a mineral liquid composition for preparing nickel metal particles in the present embodiment, wherein the chemical nickel ore liquid composition can be as follows. 12 8 1274789 Composition of chemical nickel mirror solution Concentration of nickel sulfate (N i S 0 4 · 6 Η 2 0 ) 0.11M sodium hypophosphite (NaH2P02.H2〇) 0.28M sodium lactate (C3H5 03Na) 0.36M Amino acetic acid (c2h5o2n 0.13 Μ Ammonia water (nh4oh) The plating solution ρ Η is adjusted to 9. In addition, the composition of the plating solution for the noble metal chemical replacement method of this embodiment is as follows, wherein the noble metal of this example is gold. Chemical substitution gold plating solution composition concentration potassium cyanide (KAu(CN)2) 0.02M ~ gasified amine (nh4ci) 1.1M sodium citrate (Na3C6H507) 0.2M citric acid adjust the plating solution ρ Η to 6 Example 2: Growing a carbon nanotube on a germanium wafer with palladium-cobalt metal particles. Preparing a cobalt metal particulate catalyst by non-average temperature electroless plating on a germanium wafer substrate, and placing it in a precious metal plating solution to carry out a precious metal. Chemically substituted to obtain a catalyst of palladium-cobalt composite metal particles on the surface of the substrate. Finally, the substrate is placed in a high temperature furnace tube apparatus for thermal cracking chemical vapor deposition to grow nanocarbon. The operating temperatures were 800 ° C and 4001 respectively, and the appropriate flow rate of acetylene gas was operated for 10 minutes. After the reaction, the reaction was observed to observe the formation of the carbon nanotubes on the wafer substrate at 800 ° C. 4〇(^c can be seen to form a carbon nanotube at the reaction temperature. The following is the composition of the plating solution for preparing cobalt metal particles in the present embodiment, wherein the composition of the chemical cobalt plating solution can be as follows. 13 1274789 0.07M 0.2M 0.2M 0.55M Adjust the pH of the liquid to 9 cobalt sulfate (CoS04 · 7H20) sodium hypophosphite (NaH2P02 ·Η2〇) sodium citrate (Na3C6H507) ammonium chloride (NHWl) ammonia water (nh4oh) In addition to the composition of the ore liquid, the noble metal chemical replacement method of the present embodiment is as follows, wherein the noble metal of this example is sharp.
0.001M 將錢液pH調整至10.001M adjust the pH of the money to 1
實施^在具有m金屬微粒切晶圓上生長奈米碳管 將矽晶0基材先以非均溫無電鍍製備鎳金屬微粒觸 媒’接著將其置人貴金屬鍍液中，進行貴金屬化學置換， 以在基材表面獲得！e_錄複合金屬微粒之觸媒。最後，再將 具有把鎳金屬微粒之基材置人高溫爐管設備中，以進行轨 裂解化學氣相沉積法生長奈米碳管。操作溫度分別為議 C與400 C，通入適當流量乙炔氣體，操作時間ι〇分鐘，反 應後以FESEM觀察石夕晶圓基材上奈米碳管生成狀況，不論 800°C或是400°C之反應溫度均可觀察到奈米碳管之生成。 本貫施例製備鎳金屬微粒之鍍液組成係相同於實施例一所 示之化學鎳鍍液成分，且本例貴金屬化學置換法之鍍液組 成係相同於實施例二所列之鈀鍍液組成，以在矽晶圓表面 生成纪-鎳複合金屬微粒。 14 辦年6月修正頁 12747.12删1， 年月： 1施例具有鈀-鎳金屬微粒之ιτο玻璃基材上生長奈 米碳管 將I το玻璃基材先以非均溫無電鍍製備鎳金屬微粒觸 媒後，其結果經由穿透式電子顯微鏡的觀察後，係如圖3 所示··本發明之方法的確在ITO玻璃基材上製備出分散均 勻的鎳催化金屬微粒。接著，將上述基材置入貴金屬鍍液 中，以進行貴金屬化學置換反應，而在基材表面獲得把_ 錄複合金屬微粒之觸媒。再將其置入高溫爐管設備中，進 行熱裂解化學氣相沉積法生長奈米碳管。操作溫度分別為 400°c與800°c，通入適當流量乙炔氣體，操作時間1〇分鐘， 反應後以FESEM觀察該基材上奈米碳管生成狀況。由於 800 C時玻璃已損毀，所以無法觀察；而4〇〇艺之反應溫度 則可觀察到奈米碳管生長情形良好。圖2所示，為使用鈀鎳 複合金屬催化劑以40(TC之製程溫度，在IT〇玻璃基材上所 製備奈米碳官之SEM照片圖。圖3所示即為本實施例奈米碳 管之ΤΕΜ照片目，由圖中可明顯觀察出本實施例所製備完 成的奈米碳管。 本貝施例製備錄金屬微粒之鑛液組成係相同於實施例 所不之化學鎳鍍液成分，且本例責金屬化學置換法之鍍 液組成係相同於實施例二所列德鍍液組成，以在㈤玻 璃基材表面生成鈀-鎳複合金屬微粒。 以下對照例係為本發明實施例之對照組，其中係改變 一製私條件而與本發明作為比較，例如：催化金屬種類、 形成催化金屬之方法等，其結果分別如下所示。 15 1274789 對照例一在無催化金屬之矽晶圓上生長奈米碳管 將清潔過後的矽晶圓基材置入高溫爐管設備中，進行 熱裂解化學氣相沉積法生長奈米碳管。操作溫度分別為8 = c與400 C，通入適當流量乙炔氣體，操作時間丨〇分鐘，反 應後以FESEM觀察，矽晶圓基材上並無奈米碳管生成。 對照例二在具有鎳金屬薄膜之矽晶圓上生長奈米碳管 將矽晶圓基材以濺鍍法沈積鎳金屬薄膜觸媒，在將其 置入高溫爐管設備中，進行熱裂解化學氣相沉積法生長奈 米破管。操作溫度分別為80(rc與40(rc，通入適當流量乙 炔氣體，操作時間1〇分鐘，反應後以FESEM觀察矽晶圓基 材上奈米碳管生成狀況，其中80(rc時可觀察到有奈米碳管 產生’ 400°C時則未見生成奈米碳管。 對照例三在具有鈷金屬薄膜之矽晶圓上生長奈米碳管 將石夕晶圓基材以濺鍍法沈積鈷金屬薄膜觸媒，在將其 置入高溫爐管設備中，進行熱裂解化學氣相沉積法生長奈 米碳管。操作溫度分別為8〇〇。€與400〇c，通入適當流量乙 快氣體’操作時間10分鐘，反應後以FESEM觀察矽晶圓基 材上奈米碳管生成狀況，其中800°C時可觀察到有奈米碳管 產生’ 40〇°C時則未見生成奈米碳管。 對照例四在具有鎳金屬微粒之ITO玻璃基材上生長奈米 碳管 將ITO玻璃基材以濺鍍法沉積金屬鎳薄膜觸媒，在將 其置入兩溫爐管設備中，進行熱裂解化學氣相沉積法生長 奈米碳管。操作溫度分別為800°C與400°C，通入適當流量 16 1274789 乙炔氣體，操作時間10分鐘，反應後以FESEM觀察ΙΤ〇玻 璃基材上奈米碳管生成狀況，其中800°C時基材損毁，400 °C時則未見生成奈米碳管。 表一為對照例與實施例之結果整理與比較。由表一可知， 習知單金屬催化之方法，無法在較低溫度下利用熱裂解化 學氣相沉積法生成出奈米碳管。然而，本發明之複合金屬 催化確實能在較低溫度下以熱裂解化學氣相沉積法生成出 奈米碳管，且在不同種類的基材上均可實施。 表一Implementation ^ Growth of carbon nanotubes on m-metal microparticle-cut wafers. Preparation of niobium 0 substrates by non-average temperature electroless plating of nickel metal microparticle catalysts, then placing them in precious metal plating baths for chemical substitution of noble metals , to get on the surface of the substrate! E_ Record the catalyst of composite metal particles. Finally, the substrate having the nickel metal particles is placed in a high temperature furnace tube apparatus to carry out the ore pyrolysis chemical vapor deposition method for growing the carbon nanotubes. The operating temperatures are respectively C and 400 C, and the appropriate flow rate of acetylene gas is introduced. The operation time is 〇 min. After the reaction, the formation of the carbon nanotubes on the Shixi wafer substrate is observed by FESEM, regardless of 800 ° C or 400 °. The formation of carbon nanotubes can be observed at the reaction temperature of C. The composition of the plating solution for preparing the nickel metal particles in the present embodiment is the same as that of the chemical nickel plating solution shown in the first embodiment, and the plating solution composition of the noble metal chemical replacement method is the same as the palladium plating solution listed in the second embodiment. The composition is to form a nickel-nickel composite metal particle on the surface of the germanium wafer. 14 Year of June Amendment Page 12747.12 Delete 1, Year: 1 Example of palladium-nickel metal particles ιτο grown on a glass substrate, carbon nanotubes, I το glass substrate, non-average temperature electroless nickel plating After the particulate catalyst, the results were observed by a transmission electron microscope, as shown in Fig. 3. The method of the present invention did produce uniformly dispersed nickel-catalyzed metal fine particles on the ITO glass substrate. Next, the substrate is placed in a precious metal plating solution to carry out a chemical substitution reaction of the noble metal, and a catalyst for recording the composite metal particles is obtained on the surface of the substrate. Then, it is placed in a high-temperature furnace tube apparatus, and a carbon nanotube is grown by thermal cracking chemical vapor deposition. The operating temperatures were 400 ° C and 800 ° C, respectively, and an appropriate flow rate of acetylene gas was passed for 1 minute. After the reaction, the formation of the carbon nanotubes on the substrate was observed by FESEM. Since the glass was damaged at 800 C, it could not be observed; while the reaction temperature of the 4 〇〇 art was observed, the growth of the carbon nanotubes was good. Figure 2 is a SEM photograph of a nanocarbon prepared on a glass substrate of IT using a palladium-nickel composite metal catalyst at a process temperature of 40 (TC). Figure 3 shows the carbon of the present embodiment. In the photograph of the tube, the carbon nanotube prepared in this example can be clearly observed. The composition of the mineral liquid prepared by the present embodiment is the same as that of the chemical nickel plating solution of the embodiment. And the composition of the plating solution of the metal chemical replacement method is the same as that of the German plating solution listed in the second embodiment, to form palladium-nickel composite metal particles on the surface of the (f) glass substrate. The following comparative examples are examples of the present invention. The control group, which is a comparison with the present invention, is a comparison with the present invention, for example, a catalytic metal species, a method of forming a catalytic metal, etc., and the results are as follows. 15 1274789 Comparative Example 1 Twinning in a non-catalytic metal The carbon nanotubes on the circle are placed in the high-temperature furnace tube equipment after the cleaned silicon carbide substrate, and the carbon nanotubes are grown by thermal cracking chemical vapor deposition. The operating temperatures are 8 = c and 400 C, respectively. Into the appropriate flow The alkyne gas was operated for a few minutes, and after the reaction, it was observed by FESEM, and no carbon nanotubes were formed on the silicon wafer substrate. Comparative Example 2: Growth of carbon nanotubes on a silicon wafer with a nickel metal film. The substrate is deposited by sputtering on a nickel metal film catalyst, and placed in a high temperature furnace tube apparatus to carry out thermal cracking chemical vapor deposition to grow a nanotube. The operating temperatures are 80 (rc and 40, respectively). The appropriate flow rate of acetylene gas was introduced, and the operation time was 1 minute. After the reaction, the formation of the carbon nanotubes on the wafer substrate was observed by FESEM, and 80 (when rc was observed, the carbon nanotubes were produced at 400 ° C). No carbon nanotubes were formed. Comparative Example 3: Carbon nanotubes were grown on a silicon wafer with a cobalt metal film. The cobalt metal film substrate was deposited by sputtering on the stone substrate. In the high-temperature furnace tube equipment, the carbon nanotubes are grown by thermal cracking chemical vapor deposition. The operating temperatures are 8 〇〇, respectively, and 400 〇c, and the appropriate flow rate of B fast gas is used for 10 minutes. After the reaction, FESEM observation of the formation of carbon nanotubes on enamel wafer substrates At 800 ° C, it can be observed that there is no carbon nanotube produced when the carbon nanotubes are produced at 40 ° C. Comparative Example 4: Growing carbon nanotubes on an ITO glass substrate with nickel metal particles will The ITO glass substrate is deposited by sputtering method to deposit a nickel-nickel film catalyst, and is placed in a two-temperature furnace tube apparatus for thermal cracking chemical vapor deposition to grow carbon nanotubes. The operating temperatures are 800 ° C and 400, respectively. °C, pass the appropriate flow rate 16 1274789 acetylene gas, operation time 10 minutes, after reaction, observe the formation of carbon nanotubes on the glass substrate by FESEM, where the substrate is damaged at 800 °C, and not at 400 °C. See the generation of carbon nanotubes. Table 1 shows the comparison and comparison of the results of the comparative examples and the examples. It can be seen from Table 1 that the conventional single metal catalysis method cannot be produced by pyrolysis chemical vapor deposition at a lower temperature. Carbon nanotubes. However, the composite metal catalysis of the present invention can indeed produce a carbon nanotube by pyrolysis chemical vapor deposition at a relatively low temperature and can be carried out on different kinds of substrates. Table I
製程溫度 基材 類別 催化劑類 別 有無形成碳管 實施例一 800 °C 400°C 與 石夕晶圓 金-鎳 複合金屬 均有 實施例二 800 °C 400°C 與 碎晶圓 #巴-鎳 複合金屬 均有 實施例三 800 °C 400°C 與 砍晶圓 4巴-鎳 複合金屬 均有 實施例四 800 °C 400°C 與 ITO玻璃 1巴-鎳 複合金屬 800°C基材毀壞 400°C 有 對照例一 800 °C 400°C 與 碎晶圓 無 均無 對照例二 800 °C 400°C 與 砍晶圓 錄 800〇C 有 400〇C 無 對照例三 800 °C 400°C 與 碎晶圓 鈷 800〇C 有 400°C 無 對照例四 800 °C 400°C 與 ITO玻璃 鎳 800°C基材毁壞 400。。無 17 上述貫施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自應以申請專利範圍所述為準，而非僅限 於上述實施例。 【圖式簡單說明】 圖1係本發明一較佳實施例在ITO玻璃基材上製備鈀鎳複 合金屬催化微粒之SEM照片圖。 圖2係本發明一較佳實施例在IT0玻璃基材上製備奈米碳 管之SEM照片圖。 圖3係本發明一較佳實施例在ΙΤΟ玻璃基材上製備奈米碳 管之ΤΕΜ照片圖。 【主要元件符號說明】 「益丨Process temperature Substrate type Catalyst category with or without carbon tube Example 1 800 °C 400 °C and Shixi wafer gold-nickel composite metal are both Example 2 800 °C 400 °C with shredded wafer #巴-nickel composite The metal has Example 3 800 °C 400 °C and chopped wafer 4 bar-nickel composite metal has Example 4 800 °C 400 °C with ITO glass 1 bar-nickel composite metal 800 ° C substrate destroyed 400 ° C There is a control example of 800 ° C 400 ° C and wafers without uniforms. No. 2 800 ° C 400 ° C and chopped wafers recorded 800 〇 C 400 〇 C No control Example 3 800 ° C 400 ° C with Crushed wafer cobalt 800 〇 C has 400 ° C No control Example 4 800 ° C 400 ° C with ITO glass nickel 800 ° C substrate destroyed 400. . The above-mentioned embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited to the above embodiments. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a SEM photograph of a palladium-nickel composite metal catalytic particle prepared on an ITO glass substrate in accordance with a preferred embodiment of the present invention. Figure 2 is a SEM photograph of a carbon nanotube prepared on an IT0 glass substrate in accordance with a preferred embodiment of the present invention. Fig. 3 is a photograph showing the preparation of a carbon nanotube on a bismuth glass substrate in accordance with a preferred embodiment of the present invention. [Main component symbol description]
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