200827295 九、發明說明： 【發明所屬之技術領域】 本發明係涉及-種奈米薄膜的製備方法 種由奈米量級賴粒（H)構 :、v 方法。 /丁、未顆粒潯膜的製備 【先前技術】 ❿ 奈米薄膜係尺寸於奈米量級的顆粒 ，者層厚於奈米量級的單層或多層薄膜 二3膜多層薄膜。由於奈米薄膜具有獨特的光 :、力子、電磁學與氣敏特性，其於重1、輕工業、軍 石化等領域呈現了廣泛的應用前 射電子源、光^和生物感測器、透明導電體電t: 料、水#化材料等器件中。目前，較爲常用的製備 二未薄膜財法爲轉—凝膠法、L-B膜法、電化學沈積 心化學乳相沈積、低能團簇沈積、真空蒸發法、藏射沈 二法、分子與原子束外延、分子自組裝等，惟，該等方法 衣備㈣父爲複雜、效率較低；同時，於製備過程中奈来薄 膜的厚度較難控制。 =制有鑒於此，確有必要提供一種奈米薄膜的製備方法， 該衣備方法較爲簡單、效率較高且製備過程中奈米薄膜的 厚度易於控制。 【發明内容】 借了面將藉由實施例進一步詳細說明一種奈米薄膜的製 方法該製備方法較爲簡單、效率較高且製備過程中奈 7 200827295 米薄膜的厚度易於控制。 一種奈米_的製備方法，包括：配製—定濃度的奈 未顆粒制液，懸驗包括有機溶劑及分散於有機溶劑内 的奈米顆粒；及將奈米麵懸驗滴人表面張力大、比奈 米顆粒比重大、且與奈米顆粒不浸潤的液體，於液體表面 形成一奈米顆粒薄膜。 與先前技術相比較，本發明藉由液体表面悬浮技术制 备厚度可控_大©賴米薄膜，方法较为简单且效率较 高。 【實施方式】 下面將結合附圖對本發明奈米薄膜的製備方法作進一 步之詳細說明。 請參閱圖1，本實施例奈米薄膜的製備方法主要包括 以下步驟： 步驟（-），配製-定濃度的奈米顆粒懸濁液； 其中，奈来顆粒懸濁液包括有機溶劑及分散於有機溶 劑内的奈米顆粒。有機溶於純水中有_定的溶解度或 與純水互溶、密度比純水小、與奈_粒浸賴液體，如， 乙醇丙酮、甲醇、異丙醇、⑽乙酯等。奈米顆粒爲與 水不，潤的奈米材料，優選爲奈米碳管或碳黑，奈米石炭管 可爲單壁奈米碳管、雙壁奈米碳管或多壁奈求碳管。奈米 顆粒的長紐選錢微米至幾十微米。該奈米顆粒懸濁液 的配製過程爲：將-定量的奈米顆粒放入有機溶劑中；超 聲分散至少5分鐘即制奈__勻分散的奈米顆粒懸 8 200827295 濁液。 步驟（〆）’將奈米顆粒懸濁液滴入表面張力大、比奈 米顆粒比重大且與奈米顆粒不浸潤的液體，於液體表面 形成一層奈米顆粒薄膜。 其中，比奈米顆粒比重大且與奈米顆粒不浸潤的液體 優選超純水或者鹽的超純水溶液。 於上述步驟中，藉由改變奈米顆粒懸濁液的濃度，可 控制形成的奈米薄膜的厚度。如，當奈米顆粒懸濁液中奈 _ 米顆粒的質里百刀比》辰度爲〇· 1%〜1 %時，可得到厚度爲幾 十奈米的奈米薄膜，當奈米顆粒懸濁液中奈米顆粒的質量 百分比濃度爲1%〜10%時，可得到厚度爲幾百奈米至幾微米 的奈米薄膜。請參閱圖2及圖3，圖2係由本實施例得到 的多壁奈米碳管薄膜的透射電子顯微鏡照片，圖3係本實 施例得到的單壁奈米碳管薄膜的透射電子顯微鏡照片。以 下爲具體實驗步驟： 實驗一： (1) 取提純後的單壁奈米碳管，其直徑約爲8奈米， 長度約爲幾十微米，將單壁奈米管與無水乙醇配製成質量 百分比濃度約爲〇· 25%的單壁奈米碳管/乙醇懸濁液； (2) 將配製好的奈米碳管/乙醇懸濁液進行超聲振蕩 分散’分散時間約爲5分鐘； 另 (•3)將經過超聲振蕩的奈米碳管/乙醇懸濁液用滴管 滴入超純水中，滴入位置於水面上方、水面、水下均可· (4)隨著奈米碳管/乙醇懸濁液的滴入，懸濁液於超 9 200827295 、、’屯水中發生劇烈擴散運動’最終於水面形成奈来碳管薄 膜’形成的單壁奈米碳管薄膜厚度約爲幾十奈米，透光性 好0 實驗二： (1)取碳黑’與無水乙醇配製成濃度5%的石炭黑/乙 醇懸濁液； (2) 將配製好的碳黑/乙醇懸濁液進行超聲振蕩，時 間約爲10分鐘；200827295 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for preparing a nanofilm which is composed of nanometer-sized granules (H): v method. Preparation of butyl or non-granular ruthenium film [Prior Art] ❿ Nano film is a particle having a size on the order of nanometers, and a layer of a single layer or a multilayer film of a thickness of two or three layers. Because nano film has unique light: force, electromagnetic and gas sensing properties, it presents a wide range of applications in the fields of heavy 1, light industry, military and petrochemical, such as front electron source, light and biosensor, transparent Conductor electricity t: material, water # chemical materials and other devices. At present, the more commonly used methods for preparing the two unfilms are the trans-gel method, the LB film method, the electrochemical deposition of the core chemical emulsion, the low energy cluster deposition, the vacuum evaporation method, the Tibetan sedimentation method, and the molecular and atomic beam epitaxy. , molecular self-assembly, etc., however, the method of preparation of these methods (four) the father is complex, low efficiency; at the same time, the thickness of the film is difficult to control during the preparation process. In view of this, it is indeed necessary to provide a method for preparing a nano film which is simpler, more efficient, and easy to control the thickness of the nano film during the preparation process. SUMMARY OF THE INVENTION A method for preparing a nano film will be further described in detail by way of examples. The preparation method is simple, high in efficiency, and the thickness of the film of the 200827295295 meter is easy to control during the preparation process. The invention discloses a preparation method of nanometer, comprising: preparing a liquid solution of a constant concentration of naifei particles, the suspension comprises an organic solvent and a nanoparticle dispersed in an organic solvent; and suspending the surface of the nanometer surface to have a large surface tension and a specific nanometer A liquid having a large particle ratio and not infiltrating with the nanoparticle forms a nanoparticle film on the surface of the liquid. Compared with the prior art, the present invention prepares a thickness controllable film by a liquid surface suspension technique, which is simpler and more efficient. [Embodiment] Hereinafter, a method for preparing a nano film of the present invention will be further described in detail with reference to the accompanying drawings. Referring to FIG. 1, the preparation method of the nano film of the embodiment mainly comprises the following steps: Step (-), preparing a constant concentration of the nano particle suspension; wherein the Nailai particle suspension comprises an organic solvent and is dispersed in Nanoparticles in an organic solvent. Organic soluble in pure water has a certain solubility or miscibility with pure water, a density lower than pure water, and a liquid immersed in nai granules, such as ethanol acetone, methanol, isopropanol, (10) ethyl ester and the like. The nanoparticle is a nanomaterial which is not wet with water, preferably a carbon nanotube or carbon black, and the nanocarbon carbon nanotube can be a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-wall carbon nanotube. . Nanoparticles are selected from micron to tens of microns. The preparation of the nanoparticle suspension is carried out by placing the -quantized nanoparticle in an organic solvent; supersonic dispersing for at least 5 minutes to prepare a neatly dispersed nanoparticle suspension 8 200827295 turbid liquid. Step (〆)' The nanoparticle suspension is dropped into a liquid having a large surface tension, a large specific particle ratio and a non-wetting of the nanoparticle, and a nanoparticle film is formed on the surface of the liquid. Among them, the liquid having a larger ratio of the nanoparticle particles and not infiltrating with the nanoparticle is preferably an ultrapure aqueous solution of ultrapure water or salt. In the above steps, the thickness of the formed nanofilm can be controlled by changing the concentration of the nanoparticle suspension. For example, when the nano-particle ratio of the nano-particles in the nanoparticle suspension is 〇·1%~1%, a nano-film having a thickness of several tens of nanometers can be obtained, when the nano-particles are used. When the mass percentage concentration of the nanoparticles in the suspension is from 1% to 10%, a nano film having a thickness of several hundred nanometers to several micrometers can be obtained. 2 and FIG. 3, FIG. 2 is a transmission electron micrograph of the multi-walled carbon nanotube film obtained in the present embodiment, and FIG. 3 is a transmission electron micrograph of the single-walled carbon nanotube film obtained in the present embodiment. The following are the specific experimental steps: Experiment 1: (1) The purified single-walled carbon nanotubes, which have a diameter of about 8 nm and a length of about several tens of micrometers, are made of single-walled nanotubes and anhydrous ethanol. The mass percentage concentration is about 5%·25% of the single-walled carbon nanotube/ethanol suspension; (2) The prepared carbon nanotube/ethanol suspension is ultrasonically shaken and dispersed, and the dispersion time is about 5 minutes; (3) The ultrasonically oscillated carbon nanotube/ethanol suspension is dropped into ultrapure water with a dropper, and the dropping position is above the water surface, on the water surface or under water. (4) With the nanometer The dripping of the carbon tube/ethanol suspension, the thickness of the single-walled carbon nanotube film formed by the suspension in the super 9 200827295, the 'deep diffusion movement in the 'salt water' and finally the formation of the carbon nanotube film on the water surface is about Dozens of nanometers, good light transmission 0 Experiment 2: (1) Take carbon black 'with anhydrous ethanol to make a concentration of 5% carbon black / ethanol suspension; (2) will be prepared carbon black / ethanol suspension The turbid liquid is ultrasonically shaken for about 10 minutes;
(3) 將經過超聲振蕩的碳黑/乙醇懸濁液用滴管滴入 超純水中； (4) &著碳黑/乙醇懸濁液的滴入，懸濁液於超純水 中的劇烈擴散運動，最終於水面形祕黑薄膜，形成的碳 黑薄膜厚度約幾百奈米。 下面以單壁奈米碳管顆粒及乙醇爲例，對本發明實施 例形成奈料朗原理進行單說明： “山將單壁奈米碳管顆粒放入乙醇中，由於乙醇對單壁奈 ΐ碳管Ϊ浸潤的’於經過超聲處理後，單壁奈米碳管與! 醇形成單壁奈米碳管懸驗。於將單壁奈米碳管懸濁液滴 入超純水巾時，乙醇帶鱗壁奈米碳管運動並由滴入點向 =擴散。於擴散過財，由於單壁奈米碳管的比重小於 二==碳管浮在超純水的表面，又由於單壁奈 :二於超純水中不浸潤，於乙醇中分散的單壁奈米碳管 取隹。的擴散失去了原有的紐後重新聚集在-起，重新 〜的單壁奈米碳管因超純水的表面張力形成—單壁奈米 200827295 碳管薄膜。 綜上所述，本發明確已符合發明專利之要件，遂依法 提出專利申請。.准，以上所述者僅為本發明之較佳實施例， 自不能以此_本案之申料利麵。舉凡熟悉本案技藝 之人士援依本發明之精神所作之等效修飾或變化，皆應涵 蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1係本發明實施例奈米薄膜的製備方法的流程示音 響圖。 〜 圖2係本發明實施例獲得的多壁奈米碳管薄膜的透射 電子顯微鏡照片。 圖3係本發明實施例獲得的單壁奈米碳管薄膜的透射 電子顯微鏡照片。 【主要元件符號說明】 11(3) The ultrasonically oscillated carbon black/ethanol suspension is dropped into ultrapure water with a dropper; (4) & a carbon black/ethanol suspension is dropped, and the suspension is in ultrapure water. The intense diffusion movement ends with a black film on the surface of the water, forming a carbon black film with a thickness of about several hundred nanometers. In the following, the single-walled carbon nanotube particles and ethanol are taken as an example to describe the principle of forming the Nai-Lang in the embodiment of the present invention: "Mountain single-walled carbon nanotube particles are placed in ethanol, because of the ethanol to single-walled naphthene carbon. After sonication, the single-walled carbon nanotubes and the alcohol form a single-walled carbon nanotube suspension. When the single-walled carbon nanotubes are suspended into the ultrapure water towel, the ethanol The scaled-walled carbon nanotubes move and diffuse from the point of instillation to = diffusion. Because the specific gravity of the single-walled carbon nanotubes is less than two == the carbon tube floats on the surface of ultrapure water, and :Second in ultra-pure water, it is not infiltrated, and the single-walled carbon nanotubes dispersed in ethanol take the enthalpy. The diffusion loses the original nucleus and re-aggregates in the -, re-~ single-walled carbon nanotubes due to super The surface tension of pure water is formed - single-walled nano 200827295 carbon tube film. In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. The above is only the comparison of the present invention. The best example, you can't use this _ the application of this case, the person who is familiar with the skill of this case Equivalent modifications or variations in accordance with the spirit of the present invention are intended to be included in the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing the flow of a method for preparing a nano film according to an embodiment of the present invention. 2 is a transmission electron micrograph of a multi-walled carbon nanotube film obtained in an embodiment of the present invention. Fig. 3 is a transmission electron micrograph of a single-walled carbon nanotube film obtained in an embodiment of the present invention.