200521623 尤其係關於200521623 Especially about
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去 種奈米粒子之製備方法。 先前技術】 奈米粒子亦叫超微顆粒，一般是指粒徑在卜丨〇 〇奈米 間之粒子’處在原子簽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。V. Description of the invention (1) The technical field to which the invention belongs] The present invention relates to a method for preparing a nano material and a method for preparing nano particles. [Previous technology] Nano particles are also called ultrafine particles, which generally refers to particles with a particle size between 1000 nanometers at the transition area of the atomic signature and the boundary of macroscopic objects. It is a typical mesoscopic system with a surface Effect, 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（Chemical Reduction Method)，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 until the alloying target is reached and nano-sized particles are produced; the third type is the chemical reduction method ( Chemical Reduction Method), is a chemical solution of various metal ions with oxidation state 'reduced metal ions
200521623 五、發明說明（2) 成零價金屬奈米 惟，上述方 之方式獲得，其 從亦係隨機分布 有鑒於此， 備方法實為必要 [内容】 為解決先前 問題，本發明之 子之製備方法。 為實現本發 備方法，其包括 一犧牲層；於該 層’·於該材質層 印於光阻劑層； ^劑層及犧牲層 相較於先前 術製備奈米粒子 &刻所控制，故 + ’且其形狀及 【貫施方式】 乂丈 ^曰 奈^仔之奈米粒子，由於係通過隨機成長 粒子形狀不確定且難以制， 、 獲侍預定之大小及形狀。 >(i£ _ $ 壬 /、 種大小及形狀可控之奈米粒子之製 技術之奈米粒子之大小及形狀隨機分布之 目的係提供一種大小及形狀可控之奈米粒 明之目 下列步 犧牲層 上形成 將材質 ’過渡 技術， ，由於 可確保 大小之 的，本發明提供一種奈米粒子之製 驟：提供一基底；於該基底上形成 上形成一欲製備成奈米粒子之材質 一光阻劑層；將所需之奈米圖樣轉 層姓刻出所需之奈米圖樣；除去光 出奈米粒子。 本發明係利用深次微米微影蝕刻技 該方法所獲得之奈米粒子係由微影 該奈米粒子具有預定之形狀及大 單一性亦非常高。 I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 私圖，其包括以下步驟：步驟u，提供一基底6;步驟200521623 V. Description of the invention (2) The zero-valent metal nanometer is obtained by the above method, which is also randomly distributed. In view of this, the preparation method is necessary. [Content] To solve the previous problem, the preparation of the son of the present invention method. In order to realize the preparation method, it includes a sacrificial layer; the layer is printed on the photoresist layer on the material layer; the agent layer and the sacrificial layer are controlled compared with the nanometer particles prepared by the prior art, and Therefore + 'and its shape and [performing method] The size of the nano particles of the 乂 ^ ^ 奈 奈 ^ 仔 仔, due to the random shape of the particles is uncertain and difficult to make, the size and shape of the predetermined. > (i £ _ $ //, the technology of making nano particles with controllable size and shape) The purpose of the random distribution of the size and shape of nano particles is to provide a controllable size and shape of nano particles. The material transition technology is formed on the sacrificial layer. Because the size can be ensured, the present invention provides a method for preparing nano particles: providing a substrate; forming a material on the substrate to form nano particles. Photoresist layer; transfer the required nano pattern to the last name to engrav the required nano pattern; remove the nano particles out of the light. The present invention is the nano particles obtained by deep submicron lithography etching method. The lithography of the nano particles has a predetermined shape and a large unity. The surface is further described in detail with reference to the drawings. Please refer to the first figure for the flow of the preparation method of the nano particles of the present invention. The private image includes the following steps: step u, providing a substrate 6; steps
五、發明說明（3) U，於基底6上形成一犧牲層5 ,·牛 成一欲製備成奈米粒子之材所7 · 衣犧牲層5上形 形成-光阻劑層3 ;步驟】5，將曰所：】4 ’於材質層4上 阻劑層3 ;步驟]6，將材寳声/而示米圖樣轉印於光 驟Η，除去光阻劑層3及刻出所需之奈米圖樣，·步 請-併參閱第二圖至犧第牲五層H5’：遽出奈米粒子。 粒子之製備方法進一步詳細說明。 棱供之示未 步驟11，提供-基底6。本實施例中使用 e，其直徑為5·08爱米，厚35〇微米。 f為基底 步‘12 ’於基底6上形成—犧牲層5。犧牲層5可選用 熱塑性㈣樹脂、A活化性化合物或環化膠添加芳香族 (Phenol Base)等光阻劑材料，其厚度為數十到數百太、 米，本實施例中選用光活化性化合物。纟係將光活化不性化 合物灑在基底6上，經旋轉塗覆法（Spin c〇ating)，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可選用矽、金、銀、鋁、銅、鐵、鋅、 鉻、鎳、鈷等材料，本實施例中選用鋁，其厚度為數十到 數百奈米，其形成可採用蒸鍍法或分子束磊晶成長法。. 步驟1 4 ’於材質層4上形成光阻劑層3。光阻劑層3可 远用熱塑性齡酸樹脂、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。 200521623 五、發明說明（4) f驟1 5將所需之奈米圖樣轉印於光阻劑層3。首 先藉由相^位光柵自我干涉（Self Interference/Tabl〇t )或罙’外光掃描步進機（DUV Scanner/Stepper)對 光阻劑層3進行。農伞 /4； M ^ y 、、 *先’使預先設計好的奈米圖樣（如長方線 I : 準方形及三角形等）完整的傳遞到光阻劑層3 、在匕乂驟中，要球保光罩2高精度且無缺陷。光罩2由 平坦且透明之石英板21及其表面所覆蓋之鉻膜22(厚度約 奈米）構成。然後，藉由顯影定影製程，將該= 圖樣成像於光阻劑層3。 ’、 步驟1 6，將材質層4蝕刻出所需之奈米圖樣。對應於 不同的材貝層4材料，選用不同的蝕刻劑。在本實施例 中，係使用磷酸、硝酸、乙酸及水作為蝕 wet btchmg)、或使用四氣化碳或三氣化硼及氯 四氣化矽作為蝕刻劑的幹式蝕刻法（Dry Etchmg)將二L 層4钱刻出所需之奈米圖樣。 貝 步驟1 7，除去光阻劑層3及犧牲層5，過濾出奈米粒 ，。/將基底6 (含光阻劑層3、材質層4及犧牲層5 )放入壯 顯影劑8之清洗容器7中，顯影劑8可選用氫氧化四甲基1 安 (TMAH)或氫氧化四乙基銨（TEAH)等，本實施例中選用 化四曱基銨，清洗容器7帶有閥門9，閥門9還設有過遽乳穿氣 置（圖未示）以容許溶液流過而限制其中之奈米粒子通…過夜， 要確保顯影劑8之液面高過犧牲層5，藉由氫氧化四甲夷# 除去光阻劑層3及犧牲層5後，打開閥門9，將溶液導入'"接、女 收容器1 0中，從而，在清洗容器7中便可獲得預定形狀及V. Description of the invention (3) U, forming a sacrificial layer 5 on the substrate 6, Niu Chengyi, a material to be prepared into nano-particles 7, a sacrificial layer 5 is formed on the photoresist layer 3; step] 5 , Will be said:] 4 'on the material layer 4 on the resist layer 3; Step] 6, the material Baosheng / Semi pattern is transferred to the photoburst, remove the photoresist layer 3 and engraving the required Nano pattern, please follow the steps-and refer to the second picture to the fifth layer H5 ': spit out nano particles. The preparation method of the particles is further explained in detail. The confession is shown in step 11, providing-substrate 6. In this embodiment, e is used, which has a diameter of 5.08 μm and a thickness of 35 μm. f is the substrate Step '12' is formed on the substrate 6-the sacrificial layer 5. The sacrificial layer 5 can be made of a thermoplastic resin, an A-activating compound, or a cyclic rubber with a photoresist material such as aromatic base (Phenol Base). Compounds. The system is formed by spraying a photoactivatable compound on the substrate 6 and spin coating it to uniformly coat the photoactivatable 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 made of silicon, gold, silver, aluminum, copper, iron, zinc, chromium, nickel, cobalt and other materials. In this embodiment, aluminum is used. Its thickness is tens to hundreds of nanometers. Plating or molecular beam epitaxial growth. Step 1 4 ′ forms a photoresist layer 3 on the material layer 4. The photoresist layer 3 can be made of a thermoplastic aging acid resin, a photoactive compound, or a cyclized rubber to add an aromatic material. In this embodiment, a photoactive 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. 200521623 V. Description of the invention (4) f Step 15 Transfer the desired nano pattern to the photoresist layer 3. First, the photoresist layer 3 is performed by using a phase grating self-interference (Self Interference / Tablot) or a 罙 'external light scanning stepper (DUV Scanner / Stepper). Agricultural Umbrella / 4; M ^ y, * Firstly, the pre-designed nano pattern (such as rectangular line I: quasi-square and triangle, etc.) is completely transferred to the photoresist layer 3. In the step, The ball protection mask 2 is required to be highly accurate and defect-free. The photomask 2 is composed of a flat and transparent quartz plate 21 and a chrome film 22 (thickness about nanometer) covered by the surface. Then, the = pattern is imaged on the photoresist layer 3 by a developing and fixing process. ′, Steps 16 and 6 etch the material layer 4 into a desired nano pattern. Corresponding to different materials and layers 4 materials, different etching agents are used. In this embodiment, a dry etching method (Dry Etchmg) using phosphoric acid, nitric acid, acetic acid, and water as an etchant is used, or carbon tetrachloride or boron trioxide and silicon tetrachloride are used as an etchant. Carve the desired nano pattern from the two L layers and 4 dollars. Step 17: Remove the photoresist layer 3 and the sacrificial layer 5 and filter out the nano particles. / Place the substrate 6 (containing the photoresist layer 3, the material layer 4 and the sacrificial layer 5) into a cleaning container 7 of a strong developer 8. The developer 8 can be selected from tetramethyl hydroxide 1 amp (TMAH) or hydroxide Tetraethylammonium (TEAH), etc. In this embodiment, tetramethylammonium is selected. The cleaning container 7 is provided with a valve 9 and the valve 9 is also provided with a permeation pump (not shown) to allow the solution to flow through. Limit the nano particles in it ... overnight, make sure that the liquid level of the developer 8 is higher than the sacrificial layer 5. After removing the photoresist layer 3 and the sacrificial layer 5 with tetramethylhydroxide #, open the valve 9 and place the solution Introduced into the "" female receiving container 10, so that the predetermined shape and
第8頁 200521623 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 200521623 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 200521623 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嗪光之示意 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 器 7 顯 影 劑 8 閥 門 9 接 收 容器 10Page 9 200521623 Brief description of the diagram The first diagram is a flowchart of a method for preparing nano particles according to the present invention. The second diagram is a schematic diagram of the photoresist layer subjected to azine light 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 symbols of main components] Stone board 21 chrome film 22 photomask 2 photoresist layer. 3 material layer 4 sacrificial layer 5 base 6 cleaning container 7 developer 8 valve 9 receiving container 10