200815121 九、發明說明： 【發明所屬之技術領域】 本發明涉及-種微孔模具，尤其涉及一種奈米級微孔 *模具。 【先前技術】 隨著量子物理與量子化學的完善以及世界奈米技術的 研究與進步，構造物質的基本模組可達到單個原子的水 • 平，原子可以按照一定的路徑組裝成奈米級的材料，這種 類型的製造稱爲奈米製造。目前模具製造向大型與超精微 加工兩方面發展：在大型加工方面，例如製造汽車、飛機 用大型整體壁板的扁擠壓模具，已經形成比較成熟的製造 工藝；而在超精微加工方面，奈米産品需求成幾何級上升， 如何應用先進的奈米製造技術於模具製造，使得超精微加 工形成産業化並與全球模具先進技術同步係帛具行業的發 展趨勢。 _ 理論上，奈米技術可廣泛應用於加工方面。目前已經 提出基於奈米組裝的奈米加工方式，以實現奈米産品自動 化、産業化。這種加工方式設想按照産品的形狀進行分子 排列，從而實現無模生產方式。然而，該方法實際上並不 可行，因爲目前對分子的排列採用的主要係掃描隧道顯微 鏡（Scanmng Tunnelling Microscopy，STM)或原子力顯微 鏡(Atomic Force Microscopy, AFM)，其操作精細，成本 太咼’難以實現大規模製造奈米產品。 有鑒於此，提供一種適用於大規模製造奈米產品的奈 6 200815121 米級微孔模具實為必要。 【發明内容】 以下，將以若干實施例說明一種適用於大規模製 造奈米産品的奈米級微孔模具。 一種奈米級微孔模具，其包括一基體及分佈於基 體中的多個奈米級通孔，該基體包括相對的第一表面 及第二表面，該通孔從基體的第一表面向第二表面延 伸並貫穿整個基體，該多個通孔彼此平行且垂直於基 底的兩個表面。 該基體爲一薄膜。 該通孔的半徑爲10〜100奈米。 該多個通孔之間的間距爲20〜200奈米。 該奈米級微孔模具的厚度爲0.1〜1毫米。 該基體材料爲聚四氟乙烯、矽橡膠、聚酯、聚氯 乙烯、聚乙烯醇、聚乙烯、聚丙烯、環氧樹脂、聚碳 酸酯、聚曱醛或聚縮醛。 相較於先前技術，所述的奈米級微孔模具具有以 下優點：其一，通孔的尺寸較小，長徑比很大，且奈 米級微孔模具的厚度最大可以到毫米量級，擴大了應 用範圍；其二，由於該通孔具有高定向性，提高了模 具的有序性和可控制性。 【實施方式】 下面將結合附圖對本發明作進一步的詳細說明。 請參閱圖1，本發明實施例製造的奈米級微孔模具 7 200815121 10，包括一基體18，該基體18爲一薄膜，其進一步 包括一第一表面182及與第一表面182相對的第二表 面184。該基體18内分佈有複數相互平行排布的奈米 級的通孔186。該複數通孔186基本垂直於基體18的 第一表面182及第二表面184，且沿第一表面182向 第二表面184延伸貫穿整個基體18。本實施例中，該 通孔186的孔洞半徑爲10〜100奈米，通孔186之間 的間距爲20〜200奈米，該奈米級微孔模具10的厚度 爲0. 1〜1毫米。 請參閱圖2，本發明實施例奈米級微孔模具10的 製造方法主要包括以下幾個步驟： (一）提供複數奈米碳管14。 本實施例中複數奈米碳管14可選擇爲多壁或單壁 奈米碳管陣列，其可採用化學氣相沈積法、電漿辅助 化學氣相沈積法或電漿輔助熱絲化學氣相沈積法制 得，因而，複數奈米碳管14通常形成於襯底12上， 且該襯底12可輕易揭掉，而不影響奈米碳管的陣列 性。 本實施例奈米碳管陣列生長方法包括：首先在一 矽襯底12表面塗覆一約5奈米厚度的金屬鐵催化劑 層；在300°C溫度下在空氣中進行熱處理；然後在 700°C溫度下，在矽襯底12上化學氣相沈積生長奈米 碳管陣列，該陣列中奈米碳管14的直徑範圍爲1〜100 奈米。 8 200815121 (二）在所述奈米碳管14至少一末端形成一保護 層16 〇 首先在一承載基底162上均勻塗抹一層壓敏膠 164 ;然後將壓敏膠164壓在遠離矽襯底12的複數奈 米碳管14末端，即形成一端覆蓋有保護層16(包括承 載基底162與壓敏膠164)的奈米碳管14，此時，矽 襯底12本身可作爲奈米碳管14的另一保護層。另， 本實施例中也可在奈米碳管14兩端均形成保護層 16，具體地，可進一步將矽襯底12揭掉之後，再重 復上述步驟，使矽襯底12揭掉後露出的奈米碳管14 的末端也覆蓋保護層16，該保護層16同樣包括壓敏 膠164與承載基底162，從而形成兩末端分別覆蓋保 護層16的奈米碳管14。本實施例中，上述承載基底 162可採用聚酯片，壓敏膠164可採用由撫順輕工業 所生産的YM881型壓敏膠。另，本實施例中保護層16 厚度優選爲0. 05毫米。 (三）在所述形成有保護層16的複數奈米碳管14 間注入基體18溶液或熔融液，並使其固化。 將經過步驟（二）處理的奈米碳管14浸入基體18 溶液或熔融液中，或將基體溶液或基體熔融液注入兩 端形成有保護層16的奈米碳管14中，然後將其在真 空下固化或凝固24小時，獲得注有基體18的奈米碳 管14。其中，基體18選擇爲能耐強酸腐蝕的高分子 化合物，具體可選自聚四氟乙烯、矽橡膠、聚酯、聚 9 200815121 氯乙烯、聚乙烯醇、聚乙烯、聚丙烯、環氧樹脂、聚 碳酸酯、聚曱醛、聚縮醛等高分子材料。本實施例中 優選爲聚四氟乙烯。 另，本實施例步驟（三）可進一步包括一預先抽 真空的步驟，可通過預先將該形成有保護層16的複 數奈米碳管14做抽真空處理約30分鐘，以排出複數 奈米碳管14間的空氣，有利於基體18溶液或熔融液 注入。 (四） 除去保護層16。 保護層16中的承載基底162可直接揭去，壓敏膠 164可以溶解去除，如採用二曱苯、乙酸乙脂或石油 醚溶解。另，本實施例中以生長奈米碳管14的矽襯 底12作爲的保護層可直接揭去。此時，露出基體18 的第一表面182與與其相對的第二表面184，而且原 來被保護層16所覆蓋的奈米碳管14的兩末端也露 出，並分別伸出基體18的兩表面182、184。因而， 除去保護層16後所形成的係兩末端露出基體18表面 的奈米碳管14與基體18的複合結構。 (五） 腐蝕去掉上述複合結構中的奈米碳管14。 本實施例採用強酸性或強氧化性的溶劑腐蝕去除 上述複合結構中的奈米碳管14。優選地，本實施例採 用質量百分比濃度比爲3:1的濃硫酸與濃硝酸的混合 溶液，在環境溫度60攝氏度時回流於上述奈米碳管 14與基體18的複合結構約30分鐘至2小時，利用強 200815121 酸溶劑的腐蝕作用去除複合結構中的奈米碳管14。腐 蝕掉奈米碳管以後，具有耐強酸腐蝕的基體18留下 來形成一奈米級微孔模具10，該微孔模具10中微孔 的直徑範圍爲1〜100奈米。 本技術領域技術人員應明白，本實施例奈米級微 孔模具10的製造方法可通過控制奈米碳管催化劑的 排列，得到不同排列規則的通孔，達到精確控制通孔 位置的目的，提高了奈米級微孔模具10的有序性和 可控制性。 請參閱圖3，爲本實施例製造的奈米級微孔模具 10的應用示意圖。本實施例的奈米級微孔模具1〇可 用於製造其他材料的奈米級陣列。 首先’在上述奈米級微孔权具10中填充一待形成 奈米級陣列的材料，本實施例以金爲例。 其次’去除上述奈米級微孔模具10，即形成該材 料的奈米級的陣列2〇。 本實施例中，該奈米級微孔模具10爲高分子材 料，可通過化學腐蝕、高溫煆燒等方法去除該奈米級 微孔模具10，形成奈米級的金陣列20。 另，本實施例奈米級微孔模具1〇還可應用於壓印 技術’在材料表面形成奈米級的表面凸起結構。 相較於先前技術，本實施例奈米級微孔模具1〇具 有以下優點：其一，通孔186的尺寸較小，如果使用 單壁奈米碳管，可以控制通孔186的半徑在20奈米 π 200815121 以下，其二，通孔186的長徑比彳艮大，且奈米级微孔 模具10的厚度可根據所選奈米;ε炭管陣列的厚度炱少 在幾十微米以上，最多可以到毫米量級，擴大了應用 範圍；其三，由於使用了奈米碳管陣列來作爲母板， 奈米碳管的高定向性得到了保留，並且通過控制奈米 碳管催化劑的排列’可以得到不同排列規則的孔洞， 達到精確控制孔洞位置的㈣，提高了模具的有序性200815121 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a microporous mold, and more particularly to a nano-scale micro-hole mold. [Prior Art] With the improvement of quantum physics and quantum chemistry and the research and advancement of nanotechnology in the world, the basic modules of structural materials can reach the water level of a single atom, and atoms can be assembled into nanometers according to certain paths. Materials, this type of manufacturing is called nanofabrication. At present, mold manufacturing is developing in both large and ultra-fine processing: in large-scale processing, for example, flat extrusion dies for manufacturing large-sized integral siding for automobiles and aircraft, a relatively mature manufacturing process has been formed; and in terms of ultra-fine processing, The demand for rice products has risen geometrically. How to apply advanced nano-manufacturing technology to mold manufacturing, making ultra-fine processing industrialized and synchronizing with the global advanced technology of molds to develop the industry. _ In theory, nanotechnology can be widely used in processing. Nano-processing methods based on nano-assembly have been proposed to realize the automation and industrialization of nano products. This type of processing envisages molecular alignment according to the shape of the product, thereby achieving a mode-free production method. However, this method is actually not feasible because the current array of molecules is mainly Scanmng Tunnelling Microscopy (STM) or Atomic Force Microscopy (AFM), which is delicate in operation and costly. Achieve large-scale manufacturing of nano products. In view of this, it is necessary to provide a Nai 6 200815121 meter microporous mold suitable for large-scale production of nano products. SUMMARY OF THE INVENTION Hereinafter, a nano-scale micropore mold suitable for mass production of nano products will be described in several embodiments. A nano-scale micro-hole mold comprising a substrate and a plurality of nano-level vias distributed in the substrate, the substrate comprising opposing first and second surfaces, the through-holes from the first surface of the substrate The two surfaces extend through the entire substrate, the plurality of through holes being parallel to each other and perpendicular to both surfaces of the substrate. The substrate is a film. The through hole has a radius of 10 to 100 nm. The spacing between the plurality of through holes is 20 to 200 nm. The nano-scale microporous mold has a thickness of 0.1 to 1 mm. The base material is polytetrafluoroethylene, ruthenium rubber, polyester, polyvinyl chloride, polyvinyl alcohol, polyethylene, polypropylene, epoxy resin, polycarbonate, polyacetal or polyacetal. Compared with the prior art, the nano-scale micro-hole mold has the following advantages: first, the size of the through-hole is small, the aspect ratio is large, and the thickness of the nano-scale micro-hole mold can be up to the order of millimeters. The application range is expanded; secondly, due to the high orientation of the through hole, the order and controllability of the mold are improved. [Embodiment] Hereinafter, the present invention will be further described in detail with reference to the accompanying drawings. Referring to FIG. 1, a nano-scale micro-hole mold 7 200815121 10 manufactured in accordance with an embodiment of the present invention includes a substrate 18, which is a film, further comprising a first surface 182 and a first surface 182 opposite to the first surface 182. Two surfaces 184. A plurality of nano-sized through holes 186 arranged in parallel with each other are disposed in the base 18. The plurality of through holes 186 are substantially perpendicular to the first surface 182 and the second surface 184 of the base 18 and extend along the first surface 182 toward the second surface 184 throughout the base 18. 1〜1毫米。 The thickness of the nano-hole micro-mold 10 is 0. 1~1 mm, the thickness of the nano-hole micro-mold 10 is 0. 1~1 mm . Referring to FIG. 2, the manufacturing method of the nano-scale micro-hole mold 10 of the embodiment of the present invention mainly comprises the following steps: (1) providing a plurality of carbon nanotubes 14. In this embodiment, the plurality of carbon nanotubes 14 may be selected as a multi-wall or single-walled carbon nanotube array, which may be a chemical vapor deposition method, a plasma-assisted chemical vapor deposition method or a plasma-assisted hot filament chemical vapor phase. The deposition method is performed, and thus, the plurality of carbon nanotubes 14 are usually formed on the substrate 12, and the substrate 12 can be easily removed without affecting the array of the carbon nanotubes. The carbon nanotube array growth method of the present embodiment comprises: first coating a surface of a ruthenium substrate 12 with a metal iron catalyst layer having a thickness of about 5 nm; heat treatment at 300 ° C in air; then at 700 ° At a temperature of C, a carbon nanotube array is grown by chemical vapor deposition on the tantalum substrate 12, and the diameter of the carbon nanotube 14 in the array ranges from 1 to 100 nm. 8 200815121 (2) Forming a protective layer 16 on at least one end of the carbon nanotube 14 〇 First, uniformly applying a layer of pressure sensitive adhesive 164 on a carrier substrate 162; then pressing the pressure sensitive adhesive 164 away from the ruthenium substrate 12 The end of the plurality of carbon nanotubes 14 is formed with a carbon nanotube 14 covered at one end with a protective layer 16 (including the carrier substrate 162 and the pressure sensitive adhesive 164). At this time, the ruthenium substrate 12 itself can serve as the carbon nanotube 14 Another protective layer. In addition, in this embodiment, the protective layer 16 may be formed on both ends of the carbon nanotube tube 14. Specifically, after the ruthenium substrate 12 is further removed, the above steps are repeated to expose the ruthenium substrate 12 to be exposed. The end of the carbon nanotube 14 is also covered with a protective layer 16, which also includes a pressure sensitive adhesive 164 and a carrier substrate 162 to form a carbon nanotube 14 that covers the protective layer 16 at both ends. In this embodiment, the carrier substrate 162 may be a polyester sheet, and the pressure sensitive adhesive 164 may be a YM881 pressure sensitive adhesive produced by Fushun Light Industry. 5毫米。 The thickness of the protective layer 16 is preferably 0.05 mm. (3) The substrate 18 solution or the melt is injected between the plurality of carbon nanotubes 14 on which the protective layer 16 is formed, and is solidified. The carbon nanotube 14 treated in the step (2) is immersed in the base 18 solution or the melt, or the base solution or the matrix melt is injected into the carbon nanotube 14 having the protective layer 16 formed at both ends, and then placed in The carbon nanotubes 14 impregnated with the substrate 18 were obtained by solidification or solidification under vacuum for 24 hours. The substrate 18 is selected to be a polymer compound resistant to strong acid corrosion, and specifically selected from the group consisting of polytetrafluoroethylene, ruthenium rubber, polyester, poly 9 200815121 vinyl chloride, polyvinyl alcohol, polyethylene, polypropylene, epoxy resin, poly Polymer materials such as carbonate, polyacetal, and polyacetal. In the present embodiment, polytetrafluoroethylene is preferred. In addition, step (3) of the embodiment may further include a pre-vacuum step, which may be performed by vacuuming the plurality of carbon nanotubes 14 formed with the protective layer 16 for about 30 minutes to discharge the plurality of carbons. The air between the tubes 14 facilitates the injection of the matrix 18 solution or melt. (4) The protective layer 16 is removed. The carrier substrate 162 in the protective layer 16 can be directly removed, and the pressure sensitive adhesive 164 can be dissolved and removed, such as by dissolving with diphenylbenzene, ethyl acetate or petroleum ether. Further, in the present embodiment, the protective layer as the base 12 of the growth carbon nanotube 14 can be directly removed. At this time, the first surface 182 of the substrate 18 is exposed and the second surface 184 opposite thereto, and both ends of the carbon nanotube 14 originally covered by the protective layer 16 are also exposed and protrude from the two surfaces 182 of the substrate 18, respectively. 184. Therefore, the composite structure of the carbon nanotube 14 and the substrate 18 on the surface of the substrate 18 exposed at both ends of the protective layer 16 is removed. (5) Corrosion removes the carbon nanotubes 14 in the above composite structure. In this embodiment, the carbon nanotubes 14 in the above composite structure are removed by solvent etching with strong acidity or strong oxidizing property. Preferably, in this embodiment, a mixed solution of concentrated sulfuric acid and concentrated nitric acid having a mass percentage ratio of 3:1 is used, and the composite structure of the above carbon nanotube 14 and the substrate 18 is refluxed at an ambient temperature of 60 ° C for about 30 minutes to 2 In hours, the carbon nanotubes 14 in the composite structure were removed by the corrosive action of a strong 200815121 acid solvent. After etching the carbon nanotubes, the substrate 18 having strong acid corrosion resistance is left to form a nanometer-scale microporous mold 10, and the micropores in the microporous mold 10 have a diameter ranging from 1 to 100 nm. It should be understood by those skilled in the art that the manufacturing method of the nano-scale micro-hole mold 10 of the present embodiment can obtain the through-holes with different arrangement rules by controlling the arrangement of the carbon nanotube catalysts, thereby achieving the purpose of accurately controlling the position of the through-holes and improving the position. The order and controllability of the nano-scale micro-hole mold 10 is obtained. Please refer to FIG. 3, which is a schematic diagram of the application of the nano-scale micro-hole mold 10 manufactured in the present embodiment. The nano-scale micro-hole mold 1 of this embodiment can be used to fabricate nanoscale arrays of other materials. First, a material to be formed into a nano-scale array is filled in the above-mentioned nano-scale microporous weighting device 10. This embodiment takes gold as an example. Next, the above-mentioned nano-scale microporous mold 10 is removed, i.e., a nano-sized array 2〇 of the material is formed. In the present embodiment, the nano-scale micro-hole mold 10 is a polymer material, and the nano-scale micro-hole mold 10 can be removed by chemical etching, high-temperature simmering or the like to form a nano-scale gold array 20. Further, the nano-scale microporous mold 1 of the present embodiment can also be applied to an imprint technique to form a nano-scale surface convex structure on the surface of the material. Compared with the prior art, the nano-scale micro-hole mold 1 of the present embodiment has the following advantages: First, the size of the through-hole 186 is small, and if a single-walled carbon nanotube is used, the radius of the through-hole 186 can be controlled to be 20 Nano π 200815121 hereinafter, secondly, the through-hole 186 has a larger aspect ratio, and the thickness of the nano-scale micro-hole mold 10 can be selected according to the selected nanometer; the thickness of the ε carbon tube array is less than several tens of micrometers. , up to the order of millimeters, to expand the scope of application; third, due to the use of carbon nanotube arrays as a mother board, the high directionality of the carbon nanotubes is retained, and by controlling the carbon nanotube catalyst Arrangement 'can obtain holes with different arrangement rules, to achieve precise control of hole position (4), improve the order of the mold
和可控制，M：。 ’丁、π π u付子货听寻利之要件， ，法提出專利申請。惟’以上所述者僅為本發明之 佳實施例，自不能以此限制本案之申請專利範圍ι 凡熟悉本案技藝之人域依本發明之精神所’ ，修飾或變化，皆應涵蓋於以下申請 之 【圖式簡單說明】 内。 圖1係本發明實施例奈米級微孔模具的結構； 圖。 Κ ( 圖2係本發明實施例奈米級微孔模具的製造 的流程示意圖。 、' 圖3係本發明實施例奈米級微孔模具的應用示音And controllable, M:. 'Ding, π π u pays for goods and listens to the elements of profit, and the law proposes a patent application. However, the above description is only a preferred embodiment of the present invention, and the scope of the patent application of the present invention is not limited thereto. Any person skilled in the art of the present invention should be modified or changed according to the spirit of the present invention. Within the [simplified description of the application]. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a view showing the structure of a nano-scale micro-hole mold according to an embodiment of the present invention; Κ ( FIG. 2 is a schematic flow chart showing the manufacture of a nano-scale micro-hole mold according to an embodiment of the present invention. FIG. 3 is an application sound of a nano-scale micro-hole mold according to an embodiment of the present invention.
【主要元件符號說明】 奈米級微孔模具 1〇 奈米碳管 14 承載基底 1R 概底 保護層 壓敏膠 12 16 164 12 200815121 基體 18 第一表面 182 第二表面 184 通孔 186 陣列 20 13[Main component symbol description] Nano-scale micro-hole mold 1〇 Nano carbon tube 14 Carrier substrate 1R Basic protective layer Pressure sensitive adhesive 12 16 164 12 200815121 Base 18 First surface 182 Second surface 184 Through hole 186 Array 20 13