1241460 五、發明說明（1) 【發明所屬之技術領域】 本發明係關於一種奈米材料之製備方法，尤其係關於 一種奈米粒子之製備方法。 【先前技術】1241460 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a method for preparing a nano material, and more particularly to a method for preparing a nano particle. [Prior art]
奈米粒子亦叫超微顆粒，一般是指粒徑在1〜1 0 0奈米 間之粒子，處在原子簇及宏觀物體交界的過渡區域，係一 種典型的介觀系統，具有表面效應、小尺寸效應及宏觀量 子隧道效應。當宏觀物體被細分為奈米粒子後，其光學、 熱學、電學、磁學、力學及化學方面的性質將會有顯著的 改變，可廣泛應用於電子、醫藥、化工、軍事、航空航太 等眾多領域。Nanoparticles are also called ultrafine particles. Generally, they refer to particles with a particle size between 1 and 100 nanometers. They are located in the transition area between the clusters of atoms and macroscopic objects. They are a typical mesoscopic system with surface effects, Small size effect and macro quantum tunnel effect. When a macroscopic object is subdivided into nano particles, its optical, thermal, electrical, magnetic, mechanical, and chemical properties will change significantly. It can be widely used in electronics, medicine, chemicals, military, aerospace, etc. Many fields.
奈米粒子之製備方法大致可分為三類，第一類係氣相 凝結法（Gas-Condensation Method)，其包括物理氣相沈 積法及化學氣相沈積法，其中，物理氣相沈積法係藉由 熱、電子束、電漿、雷射光束等高密度能量源，將原料於 低壓環境中熔融蒸發，再使其冷凝於低溫基材之表面；化 學氣相沈積法係將反應性氣體通入化學氣相沈積爐中，經 過熱源、電漿區或光源等活化區，使氣體進行反應產生欲 得之元素或化合物奈米粒子；第二類為機械合成法，即以 高能量球磨方式，利用磨球將粗大之原料粉末加以塑性變 形，使原料破裂後再接合，經由不斷的重複同樣的過程直 至達到合金化的目標，並產出奈米尺寸的粒子；第三類為 化學還原法（C h e m i c a 1 R e d u c t i ◦ η M e t h 〇 d )，係將各種具 氧化態之金屬離子之化學溶液，以還原劑將金屬離子還原 1241460 五、發明說明（2) 成零價金屬奈米粒子。 惟，上述方法獲得之奈米粒子，由於係通過隨機成長 之方式獲得，其奈米粒子形狀不確定且難以控制，且其粒 徑亦係隨機分布，無法獲得預定之大小及形狀。 有鑒於此，提供一種大小及形狀可控之奈米粒子之製 備方法實為必要。 【内容】 為解決先前技術之奈米粒子之大小及形狀隨機分布之 問題，本發明之目的係提供一種大小及形狀可控之奈米粒 子之製備方法。 為實現本發明之目的，本發明提供一種奈米粒子之製 備方法，其包括下列步驟：提供一基底；於該基底上形成 一犧牲層；於該犧牲層上形成一欲製備成奈米粒子之材質 層；於該材質層上形成一光阻劑層；將所需之奈米圖樣轉 印於光阻劑層；將材質層蝕刻出所需之奈米圖樣；除去光 阻劑層及犧牲層，過渡出奈米粒子。 相較於先前技術，本發明係利用深次微米微影蝕刻技 術製備奈米粒子，由於該方法所獲得之奈米粒子係由微影 蝕刻所控制，故可確保該奈米粒子具有預定之形狀及大 小，且其形狀及大小之單一性亦非常高。 【實施方式】 下面結合附圖對本發明作進一步詳細說明。 請先參閱第一圖，係本發明之奈米粒子之製備方法流 程圖，其包括以下步驟：步驟11，提供一基底6 ;步驟The preparation methods of nano particles can be roughly divided into three types. The first type is the gas-condensation method, which includes physical vapor deposition and chemical vapor deposition. Among them, the physical vapor deposition method With high-density energy sources such as heat, electron beam, plasma, and laser beam, the raw materials are melt-evaporated in a low-pressure environment, and then condensed on the surface of the low-temperature substrate; chemical vapor deposition method Into a chemical vapor deposition furnace, through the heat source, plasma area or light source activation area, the gas is reacted to produce desired element or compound nano particles; the second type is mechanical synthesis, that is, high energy ball milling, The coarse raw material powder is plastically deformed with a grinding ball, and the raw materials are fractured and then joined. The same process is repeated repeatedly until the goal of alloying is achieved, and nano-sized particles are produced; the third type is the chemical reduction method ( C hemica 1 R educti ◦ η M eth 〇), is a chemical solution of various metal ions with oxidation state, reducing metal ions with reducing agents 1241460 V. Invention Explanation (2) into zero-valent metal nano particles. However, because the nano particles obtained by the above method are obtained by random growth, the shape of the nano particles is uncertain and difficult to control, and the particle diameter is randomly distributed, and the predetermined size and shape cannot be obtained. In view of this, it is necessary to provide a method for preparing nano particles with controllable size and shape. [Content] In order to solve the problem of random size and shape distribution of nano particles in the prior art, the object of the present invention is to provide a method for preparing nano particles with controllable size and shape. In order to achieve the purpose of the present invention, the present invention provides a method for preparing nano particles, which includes the following steps: providing a substrate; forming a sacrificial layer on the substrate; and forming a nano particle to be prepared on the sacrificial layer Material layer; forming a photoresist layer on the material layer; transferring the desired nano pattern to the photoresist layer; etching the material layer to the required nano pattern; removing the photoresist layer and the sacrificial layer , Transition out of nano particles. Compared with the prior art, the present invention uses deep sub-micron lithographic etching technology to prepare nano particles. Since the nano particles obtained by this method are controlled by lithographic etching, it can ensure that the nano particles have a predetermined shape. And size, and the unity of its shape and size is also very high. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. Please refer to the first figure, which is a flowchart of a method for preparing nano particles according to the present invention, which includes the following steps: step 11, providing a substrate 6; steps
1241460 五、發明說明（3) 1 2，於基底6上形成一犧牲層5 ;步驟1 3，於犧牲層5上形 成一欲製備成奈米粒子之材質層4 ;步驟1 4，於材質層4上 形成一光阻劑層3 ;步驟1 5，將所需之奈米圖樣轉印於光 阻劑層3 ;步驟1 6，將材質層3蝕刻出所需之奈米圖樣；步 驟1 7，除去光阻劑層3及犧牲層5，過濾出奈米粒子。 請一併參閱第二圖至第五圖，對本發明所提供之奈米 粒子之製備方法進一步詳細說明。 步驟1 1，提供一基底6。本實施例中使用石英片作為基底 6，其直徑為5. 08釐米，厚350微米。 步驟12，於基底6上形成一犧牲層5。犧牲層5可選用 熱塑性酚醛樹脂、光活化性化合物或環化膠添加芳香族 (P h e η ο 1 B a s e )等光阻劑材料，其厚度為數十到數百奈 米，本實施例中選用光活化性化合物。其係將光活化性化 合物灑在基底6上，經旋轉塗覆法（Spin Coating)，使光 活化性化合物均勻的塗布於基底6表面而形成。 步驟1 3，於犧牲層5上形成一欲製備成奈米粒子之材 質層4。材質層4可選用石夕、金、銀、銘、銅、鐵、鋅、 鉻、鎳、鈷等材料，本實施例中選用鋁，其厚度為數十到 數百奈来，其形成可採用蒸鐘法或分子束蠢晶成長法。 步驟1 4，於材質層4上形成光阻劑層3。光阻劑層3可 選用熱塑性酚醛樹脂、光活化性化合物或環化膠添加芳香 族的材料，本實施例中選用光活化性化合物。其係將光活 化性化合物灑在材質層4上，經旋轉塗覆法，使光活化性 化合物均勻的塗布於材質層4表面而形成。1241460 V. Description of the invention (3) 1 2 to form a sacrificial layer 5 on the substrate 6; Step 13 to form a material layer 4 to be prepared into nano particles on the sacrificial layer 5; Step 14 to the material layer A photoresist layer 3 is formed on step 4; step 15 is to transfer the desired nano pattern to the photoresist layer 3; step 16 is to etch the material layer 3 to the required nano pattern; step 17 , Removing the photoresist layer 3 and the sacrificial layer 5 and filtering out nano particles. Please refer to FIG. 2 to FIG. 5 together to further describe the preparation method of nano particles provided by the present invention. Step 11: Provide a substrate 6. In this embodiment, a quartz plate is used as the substrate 6, and its diameter is 5.08 cm and the thickness is 350 microns. In step 12, a sacrificial layer 5 is formed on the substrate 6. The sacrificial layer 5 can be made of a thermoplastic phenol resin, a photo-activating compound, or a photoresist material such as an aromatic (P he η ο 1 B ase), and has a thickness of tens to hundreds of nanometers. Use light-activating compounds. It is formed by spraying a photoactive compound on the substrate 6 and spin coating to uniformly coat the photoactive compound on the surface of the substrate 6. In step 13, a material layer 4 to be prepared into nano particles is formed on the sacrificial layer 5. The material layer 4 can be selected from materials such as stone, gold, silver, copper, iron, zinc, chromium, nickel, cobalt, etc. In this embodiment, aluminum is selected, and its thickness is tens to hundreds of nanometers. Steamed bell method or molecular beam stupid growth method. Step 14: forming a photoresist layer 3 on the material layer 4. The photoresist layer 3 may be made of a thermoplastic phenol resin, a photoactivatable compound or an aromatic material added to the cyclized rubber. In this embodiment, a photoactivatable compound is used. It is formed by spraying a photoactive compound on the material layer 4 and applying the photoactive compound uniformly on the surface of the material layer 4 by a spin coating method.
1241460 五、發明說明（4) 先，^ 71 5 ’將所需之奈米圖樣轉印於光阻劑層3。首 Effect) 九栅自我干涉（Self Interference/Tablot 光阻劑/3、果备外光掃描步進機（DUV Scanner/Stepper)對 形、^ 進订D暴光’使預先設計好的奈米圖樣（如長方線 上。在此牛t方形及三角形等）完整的傳遞到光阻劑層3 平坦且透^驟中i要確保光罩2高精度且無缺陷。光罩2由 80〜1〇〇太米）之石央板21及其表面所覆蓋之鉻膜22(厚度約 圖樣光二：後’藉由顯影定影製程’將該奈米 不同的材質岸4將材材料貝層f蝕刻出所需之奈米圖樣。對應於 中，係使用不同的勉刻劑。在本實施例 四氯化石夕作為二^三e氣㈣及氯氣或 層“虫刻出所需之奈米圖樣'㈣法(Dry Etch，)將材質 乂驟17，除去光阻劑層3 子。將基底6(含光阻劑層3、材丄曰5=出奈米粒 顯影細之清洗容器7中，顯影劑8;4及犧乂？ ^ (η)或氫氧化四乙基敍（tea 氧匕四甲基銨 化四甲基錢，清洗容器7帶有間門9，匕選㈣ 置（圖未示）以容許溶 過而避過濾裝 要確保顯影劑8之液面高過犧牲層= :子通過， 除去光阻劑層3及犧牲層5後，打開閱：：，虱二 中’從而’在清洗容器7中便可獲得預定形狀及1241460 V. Description of the invention (4) First, ^ 71 5 ′ transfer the desired nano pattern to the photoresist layer 3. First Effect) Nine-gate self-interference (Self Interference / Tablot photoresist / 3, DUV Scanner / Stepper) shape, ^ order D exposure to make the pre-designed nano pattern ( Such as a rectangular line. In this case, square and triangle, etc.) the complete transfer to the photoresist layer 3 is flat and transparent. In order to ensure that the photomask 2 is high-precision and defect-free. The photomask 2 consists of 80 ~ 100. Shimian plate 21 and the chrome film 22 (thickness about pattern light 2) covered by the surface of the material The nanopattern. Corresponding to the medium, different etchants are used. In this example, the tetrachloride stone is used as the second and third e gas scabs and the chlorine gas or layer. Dry Etch,) Step 17 of the material, remove the photoresist layer 3. The substrate 6 (containing the photoresist layer 3, the material is 5 = out of the nano-grain developing container 7, the developer 8; 4 And sacrifice? ^ (Η) or tetraethyl hydroxide (tea oxygen tetramethylammonium tetramethylammonium), cleaning container 7 with compartment door 9 (Shown) To allow dissolution and avoid filtering, make sure that the liquid level of the developer 8 is higher than the sacrificial layer =: sub-pass, after removing the photoresist layer 3 and the sacrificial layer 5, open the reading ::, lice two 'thus' A predetermined shape and shape can be obtained in the cleaning container 7
第8頁 1241460 五、發明說明（5) 大小之奈米粒子。 相較於先前技術，本發明係利用深次微米微影蝕刻技 術製備奈米粒子，由於該方法所獲得之奈米粒子係由微影 蝕刻所控制，故可確保該奈米粒子具有預定之形狀及大 小，且其形狀及大小之單一性亦非常高。 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，以上所述者僅為本發明之較佳實施 例，自不能以此限制本案之申請專利範圍。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。Page 8 1241460 V. Description of the invention (5) Nano-sized particles. Compared with the prior art, the present invention uses deep sub-micron lithographic etching technology to prepare nano particles. Since the nano particles obtained by this method are controlled by lithographic etching, it can ensure that the nano particles have a predetermined shape. And size, and the unity of its shape and size is also very high. In summary, the present invention has indeed met the requirements for an invention patent, and a patent application was filed in accordance with the law. However, the above is only a preferred embodiment of the present invention, and it cannot be used to limit the scope of patent application in this case. All equivalent modifications or changes made by those skilled in the art of the case with the aid of the spirit of the present invention shall be covered by the scope of the following patent applications.
第9頁 1241460 圖式簡單說明 第一圖係本發明奈米粒子之製備方法流程圖。 第二圖係本發明實施例中對光阻劑層進行嗥光之示意 圖。 第三圖係本發明實施例中光阻劑層顯影定影後之示意 圖。 第四圖係本發明實施例中對材質層微影蝕刻後之示意 圖。 第五圖係本發明實施例中除去光觸媒層及犧牲層之裝 置示意圖。 【主要元件符號說明】 石 英 板 21 鉻 膜 22 光 罩 2 光 阻 劑 層 3 材 質 層 4 犧 牲 層 5 基 底 6 清 洗 容 哭 口口 7 顯 影 劑 8 閥 門 9 接 收 容器 101241460 Brief description of the drawings The first diagram is a flowchart of a method for preparing nano particles according to the present invention. The second figure is a schematic view of calendering the photoresist layer in the embodiment of the present invention. The third figure is a schematic view of the photoresist layer after development and fixing in the embodiment of the present invention. The fourth diagram is a schematic diagram after lithographic etching of the material layer in the embodiment of the present invention. The fifth figure is a schematic diagram of a device for removing a photocatalyst layer and a sacrificial layer in the embodiment of the present invention. [Description of main component symbols] Shiying board 21 chrome film 22 photomask 2 photoresist layer 3 material layer 4 sacrificial layer 5 base 6 cleaning capacity cry mouth 7 developer 8 valve 9 receiving container 10
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