200804612 ： 九、發明說明： 【發明所屬之技術領域】 本發明係涉及一種奈米碳管的生長方法，尤其涉及一 種低溫生長單壁奈米碳管的方法。 【先前技術】200804612: IX. Description of the Invention: [Technical Field] The present invention relates to a method for growing a carbon nanotube, and more particularly to a method for growing a single-walled carbon nanotube at a low temperature. [Prior Art]
單壁奈米碳管係廣泛應用於微電子、奈米器件、材料 合成、儲氫等許多領域。另，因單壁奈米碳管的埸發射域 值電壓大大低於多壁奈米碳管的埸發射域值電壓，故而採 用單壁奈米碳管作爲埸發射陰極的埸發射器件，可於較低 的電壓下工作，其功耗大大低於採用多壁奈米石炭管作爲場 發射陰極的埸發射器件。 按，先前技術中生長單壁奈米碳管的方法主要有電3 法、鐳射蒸發法、太陽能法以及催化熱解法等。其中，4 為適a大規模生長奈米碳管的方法係催化熱解法，惟，言 類催化熱解法的反應溫度普遍較高。Single-walled carbon nanotubes are widely used in many fields such as microelectronics, nanodevices, material synthesis, and hydrogen storage. In addition, since the 埸 emission domain voltage of a single-walled carbon nanotube is much lower than the 埸 emission domain voltage of a multi-walled carbon nanotube, a single-walled carbon nanotube is used as a ruthenium emission device of a ruthenium emission cathode. Operating at lower voltages, the power consumption is much lower than that of a multi-walled carboniferous tube as a field emission cathode. According to the prior art, the method for growing a single-walled carbon nanotube is mainly an electric 3 method, a laser evaporation method, a solar energy method, and a catalytic pyrolysis method. Among them, 4 is a method for catalyzing pyrolysis of a large-scale growth of carbon nanotubes. However, the reaction temperature of the catalytic pyrolysis method is generally high.
有鑒於此，確有必要提供一種低溫生長單壁奈米碳广 的方法。 ’、/、火E 【發明内容】 下面將藉由實施例進一步詳細說明一種單壁奈米碳管 的生長方法，該生長方法可於較低溫度下進行。 一種單壁奈米碳管的生長方法，該生長方 下步驟： 丁 提供一基底； 於基底上形成-魏鱗電極，魏化銦錫電極的厚 7 200804612 度爲5奈米〜100奈米； 於氧化銦錫電極上沈積一鋁過渡層，該鋁過渡層的厚 度爲5奈米〜40奈米； 於鋁過渡層上沈積一催化劑層，該催化劑層的厚度爲 3奈米〜10奈米； 將沈積有催化劑層、銘過渡層及氧化銦錫電極的基底 放置於空氣中，於300°C〜500°C下熱處理1〇分鐘〜12小"0寺， 該催化劑層經退火後形成氧化顆粒； 將基底放置於反應裝置中，向反應裝置内通入保護氣 體’於保護氣體的保護下加熱至640°C〜900°C ;以及 通入碳源氣與保護氣體的混合氣體，加熱至 640 C〜900°C反應30分鐘〜60分鐘生長出單壁奈米碳管。 與先前技術相較，本發明的單壁奈米碳管的生長方法 係於氧化銦錫電極及鋁過渡層上直接生長，且生長溫度較 低。 【實施方式】 下面將結合附圖對本發明單壁奈米碳管的生長方法作 進一步的詳細說明。 本發明單壁奈米碳管的生長方法主要包括町步驟： (一） 提供一矽或二氧化矽材料的基底10，如矽基底、 石英基底或者玻璃基底； (二） 於基底10上形成氧化銦錫電極20，該氧化铜 錫電極20的厚度爲5奈米〜100奈米； 氧化銦錫電極20可藉由光刻技術、電子束光刻技術結 200804612 合反應離子刻滅術、幹法_技術或麵法_技術於 基底10上形成，但不以此爲限。 藉由光刻技術形成氧化銦錫電極20的方法包括以下 步驟： 首先將基底10置於真空腔内，以氧化辞（Ζη〇χ)、銳 酸鐘（Li_x)、鈦酸鐘（LiTi0x)或者叙酸鐘（LiTa〇x) 爲雜乾材，以氬氣（Ar)與紅氣爲賤鏡氣體，於該基底 10的表面麟-壓電薄膜層，濺鏡的方法可爲反應性直流 藏鏡（DC Reaetive Sputtering)歧舰射賴鐘（RF Reactive Sputtering) ’控制反應參數使得壓電薄膜層的 厚度約爲0.02〜5微米；於壓電薄膜層表面塗覆一光阻層； 然後將-光罩罩於細層表面，該鮮的賴與所需金屬 電極相對應；用雷射光或料光照賴鮮，於光阻表面 形成一曝光區；取下光罩後，將曝光的光阻層置於顯影液 内，去除曝光區的曝光光阻，露出部分壓電薄膜層；藉由 濺鍍法於剩餘光阻及露出的部分壓電薄膜層表面鍍一氧化 銦錫層，該氧化銦錫層的厚度約爲5奈米〜1〇〇奈米；洗去 剩餘光阻及附著於光阻上的金屬膜層，剩餘的氧化銦錫層 即形成所需的氧化銦錫電極2〇。 藉由濕法刻餘技術形成氧化銦錫電極2〇的方法包括 以下步驟： 首先於基底10上藉由蒸鍍或濺射的方法形成一氧化 姻錫層’該氧化銦錫層的厚度約爲5奈米〜1〇〇奈米；將如 光致抗触劑的刻飯保護材料塗覆到氧化銦錫層的表面形成 200804612 去除職保護射選定的部分， rt 錫層；_的氧化銦錫層與刻 :劑其去除，其中，刻_以電解液的形式施 加，電化學或化學地職露出的氧化銦錫層，電解液中包 括==職的方式與氧化銦錫層反應射性鹽、酸或域 以^ 財式與露出的氧化銦錫層反應的化學氧化 成刀藉由有機物4劑如純丙財機物溶劑去除剩餘的刻In view of this, it is indeed necessary to provide a method for low temperature growth of single-walled nanocarbon. ', /, fire E [Summary of the Invention] Hereinafter, a single-walled carbon nanotube growth method will be described in further detail by way of examples, which can be carried out at a lower temperature. A method for growing a single-walled carbon nanotube, the step of growing: a substrate is provided; a Wei scale electrode is formed on the substrate, and the thickness of the indium tin electrode is 7 200804612 degrees is 5 nm to 100 nm; Depositing an aluminum transition layer on the indium tin oxide electrode, the aluminum transition layer having a thickness of 5 nm to 40 nm; depositing a catalyst layer on the aluminum transition layer, the catalyst layer having a thickness of 3 nm to 10 nm The substrate deposited with the catalyst layer, the interlayer transition layer and the indium tin oxide electrode is placed in the air, and heat-treated at 300 ° C to 500 ° C for 1 〇 minutes to 12 small "0 temple, the catalyst layer is annealed to form Oxidizing particles; placing the substrate in the reaction device, introducing a protective gas into the reaction device to be heated to 640 ° C to 900 ° C under the protection of the shielding gas; and introducing a mixed gas of the carbon source gas and the shielding gas, heating The reaction was carried out at 640 C to 900 ° C for 30 minutes to 60 minutes to grow a single-walled carbon nanotube. Compared with the prior art, the growth method of the single-walled carbon nanotube of the present invention is directly grown on the indium tin oxide electrode and the aluminum transition layer, and the growth temperature is low. [Embodiment] The growth method of the single-walled carbon nanotube of the present invention will be further described in detail below with reference to the accompanying drawings. The method for growing a single-walled carbon nanotube of the present invention mainly comprises the steps of: (1) providing a substrate 10 of a tantalum or ruthenium dioxide material, such as a tantalum substrate, a quartz substrate or a glass substrate; (2) forming an oxidation on the substrate 10 Indium tin electrode 20, the thickness of the copper oxide tin electrode 20 is 5 nm to 100 nm; the indium tin oxide electrode 20 can be etched by photolithography, electron beam lithography, 200804612, reactive ion etching, dry method The technique or method is formed on the substrate 10, but is not limited thereto. The method for forming the indium tin oxide electrode 20 by photolithography comprises the steps of: first placing the substrate 10 in a vacuum chamber to oxidize (Ζη〇χ), sharp acid clock (Li_x), titanic acid clock (LiTi0x) or LiTa〇x is a dry material with argon (Ar) and red gas as 贱 mirror gas. On the surface of the substrate 10, the piezoelectric film layer can be a reactive DC. DC Reaetive Sputtering RF Reactive Sputtering 'Controls the reaction parameters so that the thickness of the piezoelectric film layer is about 0.02~5 microns; coating a photoresist layer on the surface of the piezoelectric film layer; The reticle is covered on the surface of the fine layer, and the fresh ray is corresponding to the desired metal electrode; an exposure area is formed on the surface of the photoresist by laser light or light illumination; and the exposed photoresist layer is removed after removing the reticle Disposed in the developing solution to remove the exposure photoresist of the exposed area to expose a portion of the piezoelectric film layer; the indium tin oxide layer is plated on the surface of the remaining photoresist and the exposed portion of the piezoelectric film layer by sputtering The thickness of the layer is about 5 nm to 1 〇〇 nanometer; the residual photoresist is washed away and A metal film layer on the photoresist layer remaining i.e., indium tin oxide, indium tin oxide to form the desired electrode 2〇. The method for forming an indium tin oxide electrode 2 by a wet etching technique comprises the steps of: first forming a tin oxide layer on the substrate 10 by evaporation or sputtering; the thickness of the indium tin oxide layer is about 5 nm ~ 1 〇〇 nano; apply a photo-protective material such as photo-anti-contact agent to the surface of the indium tin oxide layer to form the selected part of the 200804612 removal protective radiation, rt tin layer; _ indium tin oxide Layer and engraving: the removal of the agent, wherein, in the form of an electrolyte, an indium tin oxide layer exposed by an electrochemical or chemical job, the electrolyte includes a method of reacting with an indium tin oxide layer. , acid or domain chemically oxidized with the exposed indium tin oxide layer to remove the remaining engraving by organic matter 4 agent such as pure propylene solvent
姓保護材料，職賴材料下覆蓋_餘氧化銦錫層即形 成所需的氧化銦錫電極20。 (三） 於氧化銦錫電極2G上藉由驗或者雜的方法 瓜成！呂層30作爲過渡層’該紹過渡層％的厚度爲5奈 米~40奈米，最優地’該銘過渡層3〇的厚度爲4〇奈米； (四） 於ί呂過渡層3〇上开)成催化劑層4〇，催化劑可 鐵⑽、録⑽、鎳⑹或者其任意組合的合金 之該催化別層40的厚度與選擇的催化劑麵相對應， 當選用鐵作爲催化劑時，鐵催化劑層的厚度爲3奈米〜1〇 奈米，優選地，鐵催化劑層的厚度爲5奈米； (五） 將沈積有催化劑層4〇、鋁過渡層3〇及金屬電 極20的基底1〇放置於空氣中，於3〇(rc〜5〇(rc下熱處理 10分鐘〜12小時，催化劑層4〇經退火後形成氧化顆粒； (/、）將基底10放置於適於化學氣相沈積（ChemicalThe surname protection material, under the responsibility of the material, covers the remaining indium tin oxide layer to form the desired indium tin oxide electrode 20. (3) On the 2G of indium tin oxide electrode, by means of inspection or miscellaneous method! Lu layer 30 as a transition layer '% of the thickness of the transition layer is 5 nm ~ 40 nm, the optimal thickness of the transition layer 3 为 is 4 〇 nano; (d) ί ί transition layer 3 The thickness of the catalytic layer 40 corresponding to the selected catalyst surface of the catalyst can be iron (10), recorded (10), nickel (6) or any combination thereof. When iron is used as a catalyst, iron is used. The thickness of the catalyst layer is 3 nm to 1 Å nanometer, preferably, the thickness of the iron catalyst layer is 5 nm; (5) The substrate 1 on which the catalyst layer 4 〇, the aluminum transition layer 3 〇 and the metal electrode 20 are deposited The crucible is placed in the air at 3 Torr (rc~5 〇 (heat treatment for 10 minutes to 12 hours under rc, the catalyst layer 4 is annealed to form oxidized particles; (/,) the substrate 10 is placed for chemical vapor deposition) (Chemical
Vapor Deposition，CVD)反應的反應裝置（圖中未顯示） 中，向反應裝置内通入保護氣體，於保護氣體的保護下加 熱到-預定溫度，通人碳喊與保護氣體的混合氣體，加 200804612 * 熱至_ G〜9GQ G反應3G分鐘，分鐘從而生長出奈米碳 管50。 其中，預先通入保護氣體加熱到一預定溫度的作用係 防止催化劑層形成的氧化顆粒於奈米石炭管5〇的生長過程 中進-步被氧化觀影響奈米碳f 5G的生長條件，該預定 溫度因使用的催化難_不_不同…般爲侧^ 〜750 C ’當選用鐵作爲催化劑時，預定溫度優選爲咖。c， • #，預先加熱時使用的保護氣體爲惰性氣體或氮氣，優選 地:保，氣體爲氬氣。於預先加熱過程後，可通入氯氣或 者氨氣_催化劑層形成的氧化顆粒從而得到奈米級的催 化1粒410，惟’於通入礙源氣加熱時，碳源氣分解亦 可將氧倾粒還原形成奈米級的催化劑顆粒，故而， 敎4¾或者絲還原的過料是賴，可根據實際情況 選擇。碳源氣與保護氣體的混合氣體中的碳源氣爲碳氯化 合物’可爲乙块、乙烯等，優選地，礙源氣爲乙块；保護 _ _爲姻线體或錢氣，優選地，保魏體爲氯氣。 、請參關2 ’圖2係依據本發明單壁奈米碳管的生長 方法所得_單壁奈米碳管的拉曼散射譜，其中於⑺‘ 與30W之_ —系列波峰是單壁奈米碳管料吸模特往 峰。本實施例獲得拉曼散射譜的單壁奈米後管的具體生長 步驟大致上包括：提供一玻璃基底；於玻璃基底上形成氧 灿鍚層’然後_濕法職技術形成所需的氧化銦錫電 極；於氧化鋪電極上濺射厚度約爲4〇奈米的紹過渡層； 於銘過渡層上譏射厚度約爲5奈米的鐵層作爲催化劑層； 11 200804612 將沈積有鐵催化劑層、氧化銦錫電極及鋁過渡層的基底放 置於空氣中’約30(TC下熱處理約1〇分鐘，退火後鐵催化 劑層形成氧化鐵顆粒；將帶有氧化鐵顆粒的基底放置於石 英反應舟中’將反應舟裝入管狀石英爐中央的反應室内， 通入氬氣加熱至約64(TC;通入氫氣使氧化鐵顆粒還原形 成奈米級的鐵催化劑顆粒；通入乙炔及氬氣的混合氣體， 加熱至約640°C，反應約40分鐘生長出單壁奈米碳管。 清參閱圖3及圖4，圖3係依據本發明實施例單壁奈 米石反官的生長方法得到的單壁奈米碳管的掃描電子顯微鏡 (Scanning Electron Microscope，SEM)照、>1 ;圖 4 係圖 3中單壁奈米碳管的高解析度的透射電子顯微鏡 (Transmission Electron Microscope，TEM)照片。本實 施例獲得的SEM、TEM照片中生長單壁奈米碳管的具體步驟 大致上包括：提供一矽基底；於矽基底上蒸鍍厚度約爲1〇〇 奈米的氧化銦錫層，然後藉由濕法刻蝕技術形成所需的氧 化銦錫電極，於氧化銦錫電極上濺射厚度約爲奈米的鋁 過渡層；於鋁過渡層上濺射厚度約爲5奈米的鐵層作爲催 化劑層，將沈積有鐵催化劑層、氧化銦錫電極及鋁過渡層 的基底放置於空氣中，約30(rc下熱處理約10分鐘，退火 後催化形成氧化鐵顆粒m氧化麵粒的基底 放^於石英反縣巾，將反應舟裝人管狀石碰中央的反 應至内，通入氬氣加熱至、約74(rc;通入氫氣使氧化麵 粒還原形成奈米級的鐵催化劑顆粒；通入乙炔及氬氣的混 合氣體，加熱至約740。〇反應約40分鐘生長出奈米碳管。 12 200804612 於未採用氧化錮錫電極或者銘過渡層而其他生長條件 $發明早壁奈米碳管的生長方法中的生長條件相同的先 别不米碳管的生長方时，僅發現多縣米碳f，而未發 現單壁奈米碳管。 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。惟’社所述者僅為本剌之較佳實施例， 自不能以此限制本案之申請補範圍。舉凡熟悉本案技藝 =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係本發明單壁奈米碳管的生長方法的流程示 意圖。 圖2係依據本發明單壁奈米碳管的生長方法所得 到的單壁奈米碳管的拉曼散射譜。 圖3係依據本發明單壁奈米碳管的生長方法得到 着 的單壁奈米碳管的掃描電子顯微鏡（ScanningIn the reaction device (not shown) of the Vapor Deposition (CVD) reaction, a protective gas is introduced into the reaction device, and heated to a predetermined temperature under the protection of the protective gas, and a mixture of carbon and a shielding gas is introduced. 200804612 * Heat to _ G~9GQ G reacts for 3G minutes, then grows carbon nanotubes 50. Wherein, the function of heating the protective gas to a predetermined temperature in advance prevents the oxidized particles formed by the catalyst layer from being affected by the oxidation process to affect the growth condition of the nanocarbon f 5G during the growth process of the carbon nanotube tube 5,, The predetermined temperature is difficult to catalyze because of the use of _ no _ different ... as the side ^ 750 C 'When iron is selected as the catalyst, the predetermined temperature is preferably coffee. c, • #, the shielding gas used in the preheating is an inert gas or nitrogen, preferably: the gas is argon. After the pre-heating process, the oxidized particles formed by the chlorine gas or the ammonia-catalyst layer may be introduced to obtain a nano-sized catalyzed one-grain 410, but the carbon source gas may also decompose when the heating is caused by the source gas. The decantation reduction forms nanometer-sized catalyst particles, so that the 敎43⁄4 or the silk-reduced over-material is a reliance, and can be selected according to the actual situation. The carbon source gas in the mixed gas of the carbon source gas and the shielding gas is a chlorocarbon compound, which may be a block, an ethylene, or the like. Preferably, the source gas is a block; the protection _ _ is a line of arms or money, preferably , Bao Wei body is chlorine gas. 2, Figure 2 is a Raman scattering spectrum of a single-walled carbon nanotube obtained according to the growth method of the single-walled carbon nanotube of the present invention, wherein the series of peaks of (7)' and 30W are single-walled The carbon carbon tube material sucks the model to the peak. The specific growth step of the single-walled nano-tube obtained by the Raman scattering spectrum in this embodiment generally comprises: providing a glass substrate; forming an oxidized enamel layer on the glass substrate and then forming a desired indium oxide by wet-method technology a tin electrode; a transition layer having a thickness of about 4 nanometers is sputtered on the oxide electrode; a layer of iron having a thickness of about 5 nanometers is sprayed on the transition layer of Yuming as a catalyst layer; 11 200804612 an iron catalyst layer is deposited The indium tin oxide electrode and the aluminum transition layer are placed in the air at about 30 (heat treatment at TC for about 1 minute, the iron catalyst layer forms iron oxide particles after annealing; and the substrate with iron oxide particles is placed on the quartz reaction boat) In the reaction chamber in the center of the tubular quartz furnace, argon gas is heated to about 64 (TC; hydrogen is passed to reduce the iron oxide particles to form nano-sized iron catalyst particles; acetylene and argon are introduced The mixed gas is heated to about 640 ° C, and the reaction is carried out for about 40 minutes to grow a single-walled carbon nanotube. Referring to Figures 3 and 4, Figure 3 is a method for growing a single-walled nano-stone according to an embodiment of the present invention. Single-walled nano Scanning Electron Microscope (SEM) photograph of carbon nanotubes, >1; Fig. 4 is a high-resolution transmission electron microscope (TEM) photograph of a single-walled carbon nanotube in Fig. 3. This embodiment The specific steps of growing the single-walled carbon nanotube in the SEM and TEM photographs obtained by the method generally include: providing a substrate; depositing an indium tin oxide layer having a thickness of about 1 nanometer on the substrate, and then The wet etching technique forms a desired indium tin oxide electrode, and an aluminum transition layer having a thickness of about nanometer is sputtered on the indium tin oxide electrode; and an iron layer having a thickness of about 5 nm is sputtered on the aluminum transition layer as a catalyst a layer, the substrate on which the iron catalyst layer, the indium tin oxide electrode and the aluminum transition layer are deposited is placed in the air, about 30 (heat treatment for about 10 minutes at rc, and the substrate for oxidizing the iron oxide particles m oxidation surface after annealing is placed on the substrate) Quartz anti-county towel, will react to the reaction of the boat-loaded tubular stone to the center, and heated to argon gas to about 74 (rc; hydrogen gas is introduced to reduce the oxidation surface to form nano-sized iron catalyst particles; Mix of acetylene and argon The gas is heated to about 740. The ruthenium reaction is about 40 minutes to grow the carbon nanotubes. 12 200804612 In the growth method of the invention of the early-walled carbon nanotubes, the growth process of the invented early-wall carbon nanotubes is not used. When the growth conditions are the same, the growth of the carbon nanotubes is not found in the multi-county carbon, but the single-walled carbon nanotubes are not found. In summary, the invention has indeed met the requirements of the invention patent, A patent application is filed. However, the description of the application is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the application in this case. Anyone familiar with the skill of the case = the equivalent modification or change of the person in accordance with the spirit of the present invention All should be covered by the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic flow chart showing a method of growing a single-walled carbon nanotube of the present invention. Fig. 2 is a Raman scattering spectrum of a single-walled carbon nanotube obtained by a method for growing a single-walled carbon nanotube according to the present invention. Figure 3 is a scanning electron microscope (Scanning) of a single-walled carbon nanotube obtained by the growth method of a single-walled carbon nanotube according to the present invention.
Electron Microscope，SEM)照片。 圖4係圖3中單壁奈米碳管的高解析度的透射電 子顯微鏡（Transmission Electron Microscope，TEM) 照片。 【主要元件符號說明】 場發射陰極 1〇〇 基底 10 氧化姻锡電極 20 13 200804612 鋁過渡層 30 催化劑層 40 催化劑顆粒 410 單壁奈米碳管 50 _ 14Electron Microscope, SEM) photo. Fig. 4 is a high-resolution transmission electron microscope (TEM) photograph of the single-walled carbon nanotube of Fig. 3. [Main component symbol description] Field emission cathode 1〇〇 Substrate 10 Oxide tin electrode 20 13 200804612 Aluminum transition layer 30 Catalyst layer 40 Catalyst particles 410 Single-walled carbon nanotubes 50 _ 14