200424130 玖"發明說明 (發明說明鍾明··發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） 【發明所屬之技術領域】 本發明係與薄膜製程有關，特別是指一種製備二氧化 欽膜<万法’其可於室溫下迅速形成奈米結構之銳鈦礦相 (anatase)二氧化鈦膜，且可應用於同質基材或異質基材上。 【先前技術】 奈米結構之銳鈦礦相二氧化鈦由於具有優異之光觸 媒、超親水性等特性，已成為業界爭相研發之產品，傳統 上以電化學陽極氧化法製備二氧化鈦（Ti〇2)，大都使用鈦 10塊材做為基材’其應用範園有限；其他製造方法如將鈦塊 材直接浸泡在強鹼溶液(如5M Na0H)中，可形成多孔結構 之二氧化鈥膜，然該結構屬微米級，且其結晶相屬NaTi03+ 金紅石相（rutile)Ti〇2 ’或金紅石+銳鈥礦相（anatase)Ti〇2i 混雜相，該製程之浸泡時間一般至少需要數小時，且常須 15 加溫至60°C以上。 銳鈦礦相二氧化鈦雖具有極佳之光觸媒特性，然實際 應用時仍有許多技術上之問題有待克服，特別如何將二氧 化鈦與基材結合在一起而不會脫落，此結合技術一直未臻 成熟，再者，由於二氧化鈇具有強大的活性，因此有機物 20製成之基材很容易被分解，此為另一待克服之技術問題。 【發明内容】 有鑑於上述缺失，本發明之主要目的即在提供一種製 備二氧化鈦膜之方法，其可於室溫下迅速形成奈米結構之 ^續次頁（發明說明頁不敷使用時，請註記並使用續頁） 200424130 發明說明，續頁 銳数礦相^一乳化钦膜。 本發明之另一目的在於提供一種製備二氧化鈦膜之方 法，其可應用於同質基材或異質基材上。 本發明之又一目的在於提供一種製備二氧化鈦膜之方 5 法，可生成性質均一之二氧化鈥膜。 本發明之再一目的在於提供一種製備二氧化鈦膜之方 法，可將二氧化鈦膜與一基材穩固地結合在一起。 緣是為達成前揭目的，本發明所提供製備二氧化鈦膜 之方法係包含有以下步驟：首先於一基材表面鐘上一献 10 膜，接著將鍍有鈦膜之基材置於一電解液中，以該鈦膜作 為陽極，該電解液可採用強鹼或強酸溶液，以電化學陽極 氧化法於該鈥膜表面合成一銳鈇礦相之二氧化欽膜。 【實施方式】 15 為了詳細說明本發明之特點所在，茲舉以下二較佳實 施例並配合圖式說明如后，其中： 第一圖係本發明第一較佳實施例所製造產品之表面顯 微照片。 第二圖係本發明第一較佳實施例所製造產品之剖面顯 20 微照片。 第三圖係本發明第一較佳實施例所製造產品之拉曼光 譜。 第四圖係本發明第一較佳實施例所製造產品於大氣下 以500°C加熱二小時後之表面顯微照片。 -5 - 200424130 發明說明續頁200424130 发明 " Explanation of the invention (Instruction of the invention Zhong Ming ·· A brief description of the technical field, prior art, contents, embodiments and drawings of the invention) [Technical field to which the invention belongs] The present invention relates to the film manufacturing process, and particularly refers to An ammonium dioxide film <Wanfa 'can rapidly form anatase phase titanium dioxide film with a nano structure at room temperature, and can be applied to a homogeneous substrate or a heterogeneous substrate. [Previous technology] Nanostructured anatase titanium dioxide has become a competitive product in the industry due to its excellent photocatalyst and super hydrophilic properties. Traditionally, titanium dioxide (TiO2) is prepared by electrochemical anodization. Most use 10 blocks of titanium as the base material. Its application range is limited; other manufacturing methods, such as directly immersing the titanium block in a strong alkaline solution (such as 5M Na0H), can form a porous structured oxide film. The structure is micron grade, and its crystalline phase is NaTi03 + rutile Ti02 'or rutile + anatase Ti02i mixed phase. The soaking time of this process generally requires at least several hours, and It is often necessary to warm up to above 60 ° C. Although the anatase titanium dioxide has excellent photocatalytic properties, there are still many technical problems to be overcome in practical application. In particular, how to combine titanium dioxide with the substrate without falling off, this bonding technology has not yet matured. Moreover, because of the strong activity of thorium dioxide, the substrate made of the organic substance 20 can be easily decomposed, which is another technical problem to be overcome. [Summary of the Invention] In view of the above-mentioned shortcomings, the main purpose of the present invention is to provide a method for preparing a titanium dioxide film, which can quickly form a nanostructure at room temperature. ^ Continued pages (Insufficient invention pages, please use Note and use continuation sheet) 200424130 Description of the invention, continuation sheet sharp number mineral phase ^ an emulsified film. Another object of the present invention is to provide a method for preparing a titanium dioxide film, which can be applied to a homogeneous substrate or a heterogeneous substrate. It is still another object of the present invention to provide a method for preparing a titanium dioxide film, which can form a film with uniform properties. Another object of the present invention is to provide a method for preparing a titanium dioxide film, which can firmly combine the titanium dioxide film with a substrate. In order to achieve the purpose of pre-disclosure, the method for preparing a titanium dioxide film provided by the present invention includes the following steps: firstly presenting 10 films on a surface clock of a substrate, and then placing the substrate coated with the titanium film in an electrolyte Using the titanium film as an anode, the electrolyte can use a strong alkali or a strong acid solution, and an electrochemical anodization method is used to synthesize an anatase phase on the surface of the film. [Embodiment] 15 In order to explain the features of the present invention in detail, the following two preferred embodiments are illustrated in conjunction with the drawings as follows, wherein: The first diagram is a surface display of a product manufactured by the first preferred embodiment of the present invention. Micro photo. The second figure is a micrograph of a cross section of a product manufactured in the first preferred embodiment of the present invention. The third figure is a Raman spectrum of a product manufactured according to the first preferred embodiment of the present invention. The fourth figure is a photomicrograph of the surface of a product manufactured by the first preferred embodiment of the present invention after being heated at 500 ° C for two hours in the atmosphere. -5-200424130 Description of the Invention Continued
第五圖係本發明第一較佳實施例各階段產品之拉曼光 譜。 第六圖係本發明第二較佳實施例所製造產品之表面顯 微照片。 θ 5 第七圖係本發明第二較佳實施例各階段產品之拉曼光 譜。 本發明第一較佳實施例所提供者，乃是一種可於同質 基材（鈦）或異質基材（例如半導體如矽、金屬、玻璃、陶瓷 或高分子材料）上製備二氧化鈦膜之方法，為說明方便起 10見，兹舉於-石夕基材上製備二氧化鈥膜之方法為例。 本發明所提供之方法包含有破i及電化學陽極氧化沉 積二氧化鈥膜兩個階段，第一階段係以賤鍍方式將鈥膜鐘 2矽晶片上，當然亦可鍍於鈦塊材或其他材質之基材上， 第二階段之電化學陽極氧化係選用氫氧化却㈣印的強驗 μ性電解液，可以在相當短的時間内形成具有奈米網狀結構 心二氧化鈥膜，換言之，本發明係先在—基材上形成欽晶 種層（seeding layer)，再用此晶種層做為底材，以電化學陽 極氧化法於該基材上形成二氧化鈦薄膜。 兹將本實施例所提供之方法詳述如下，同時請參閱第 —圖首先，於碎晶片10表面錢上―欽膜，該 鈦膜12係用非平衡磁控濺射沉積於4吋p型（1〇〇 )矽晶 片1〇(電阻度為4〜7 ncm)上，鏟著參數分別為：乾電流 〇·9 A，工作壓力：i mtorr，背景壓力：8χι〇·6 _，偏壓： -50 V ’基材溫度：25°C，沉積時間：8〇分鐘，形成之献 -6- 200424130 發明說明$賣頁 膜厚度約〇.5μπι，實際製造時，使用其他的鍍著方式如蒸 鍍（evaporation)亦應可行，膜厚並無太大限制。 接著，將鍍有鈦膜12之矽晶片10置於一電解液中， 以該鈦膜12作為陽極，以濃度1M之KOH溶液作為電解 5 液，以電化學陽極氧化法在室溫下於該鈦膜12表面合成 一銳鈦礦相之二氧化鈦膜14，其中，電化學電解槽的工 作電極面積固定在1 cm2，陰極採用鉑（Pt)，陽極與陰極的 距離為11 cm，參考電極為Ag/AgCl，用以量測陽極表面 電壓，參考電極尖端與陽極的距離為3 mm，該電化學系. 10 統為二極的系統，電源供應器之電壓範圍為〇〜100 V，電 流範圍為0〜1 A，鍍著模式則可選擇以掃描電壓或定電壓 之方式。 利用場發射掃描式電子顯微鏡之觀察結果顯示，掃描 電壓由0 V開始，以掃描速率10 mV/s掃描至3 V時，即 15 在鈦膜12表面發現奈米網狀結構之二氧化鈦膜14，耗時 約5分鐘；掃描截止電壓為10 V時(耗時約17分鐘)之二 氧化鈦膜14表面形貌係如第一圖所示，其網狀結構已相 當均勻完整，網環直徑約50 nm，網線寬約10nm以下， 二氧化鈦膜14之橫截面則如第二圖所示，二氧化鈦膜14 20 厚度為60 nm，且二氧化鈦膜14/鈦膜12/矽基材10之間 的附著性極佳，不易發生脫落情形，可有效解決以二氧化 鈦作為光觸媒時與基材間之結合問題；若進一步將掃描電 壓增加至70 V時，二氧化鈦膜14之膜厚可達250 nm。 進一步利用拉曼光譜分析二氧化鈦之成分，結果如第 -7- 200424130 發明說明續頁 三圖所示，其中p曲線、q曲線、r曲線分別是以掃描電 壓模式(掃描速率為l〇mV/s)，掃描至10V、20V、30V(掃 描截止電壓）時所產生之二氧化鈦膜14拉曼光譜，均具有 銳鈦礦相之特徵能峰，表示以上三種狀況下均已有單一銳 5 鈦礦相之二氧化鈦晶體結構生成，其中，s曲線係尚未經 陽極氧化處理之鍍鈦矽晶片之拉曼光譜，用以供對比之 用。 依本發明方法所製成之奈米網狀結構二氧化鈦，若於 大氣下500°C進行熱處理，升溫時間為每分鐘5°C，持溫 10 2小時，則二氧化鈦膜之表面將如第四圖所示，可見其網 狀結構並未改變，但由拉曼光譜的分析發現在此溫度下， 銳鈦礦相將完全轉變為金紅石相（rutile)，如第五圖所示， 其中a曲線係未經陽極氧化之鍍鈥梦晶片，b曲線係以陽 極氧化法在鍍鈥秒晶片上形成銳鈇礦相之二氧化鈥膜，c 15 曲線則為在大氣下於500°C加熱二小時後產生之金紅石相 二氧化鈦，且奈米結構二氧化鈦至少可維持至600°C而不 會被破壞，更具有極佳之生醫應用價值。 實際操作時本發明第二階段時，各項參數均可依需要 變更，經過實際測試均可達到預期效果，如氫氧化鉀溶液 20 可由其他含有鹼金屬離子之溶液代替，例如氫氧化鈉 NaOH，電解液之濃度可以介於0.1〜5 Μ之間，氫氧化鉀 溶液之濃度則以1 Μ為最佳，電壓掃描速率可介於OmV/s 至100 mV/s之間，掃描截止電壓則可介於3 V至85 V之 間，電化學陽極氧化法進行之時間以5分鐘〜10小時均可， -8- 發明說明續頁 操作溫度則以t為最佳，甚u =:進行陽極氧化亦可產生奈米網狀結構銳鈇= …，谷欣如硫酸作為電解液亦可達成本發 明之目的，如第六圖所示，係 _ 達成本發 切晶片上，们mh2S〇4電=極氧化法於室溫下在鍍 描速率為lOmWs)，掃描至 T私麵式（知 的表面形貌，由照片中 可以看出，二氧化鈥係形成顆粒狀，表面性質相當均―， 且顆粒之粒徑大小約為1Gnm，屬料米結構；進一步利 用拉曼光譜分析二氧化鈥之成分，結果如第七圖所示，其 中e曲線、；f曲線、g曲線 h "崎h曲線及i曲線分別是以掃描 逮率為 iOmWs，掃描至 7ν、1〇ν、2〇ν、3〇ν·ν^ 描截止電壓）時所產生之二氧缝膜拉曼光譜，由圖中可 15 看出除e曲線外，均具有銳欽礦相之特徵能峰，表示掃描 截止電壓在K) V以上時即有單—銳欽礦相之二氧化欽晶 體結構生成。 依本發明所提供方法，不僅能於室溫下快速地形成奈 米結構銳飲礦相二氧化鈇，且可應用於同質基材或異質基 材上，應用上更具有極佳之光觸媒特性，且二氧化鈥/飲 20膜/基材 < 結構可有效防止基材被分解破壞，與習知技術 比較明顯具有增進功效，同時由於本方法製成之二氧化处 結構係屬奈米級，更有極佳之太陽電池（銳鈦礦相）及生醫 (金紅石相）上之應用，產業利用之價值潛力無窮。 200424130 【圖式簡單說明】 第一圖係本發明第一較佳實施例所製造產品之表面顯 微照片。 第二圖係本發明第一較佳實施例所製造產品之剖面顯 5 微照片。 第三圖係本發明第一較佳實施例所製造產品之拉曼光 譜。 第四圖係本發明第一較佳實施例所製造產品於大氣下 以500°C加熱二小時後之表面顯微照片。 10 第五圖係本發明第一較佳實施例各階段產品之拉曼光 譜。 第六圖係本發明第二較佳實施例所製造產品之表面顯 微照片。 第七圖係本發明第二較佳實施例各階段產品之拉曼光 15 譜。 【圖式符號說明】 10矽晶片 12鈦膜 14二氧化鈦膜 -10-The fifth diagram is the Raman spectrum of the product at each stage of the first preferred embodiment of the present invention. The sixth figure is a microphotograph of the surface of a product manufactured by the second preferred embodiment of the present invention. The seventh graph of θ 5 is the Raman spectrum of the product at each stage of the second preferred embodiment of the present invention. The first preferred embodiment of the present invention provides a method for preparing a titanium dioxide film on a homogeneous substrate (titanium) or a heterogeneous substrate (for example, a semiconductor such as silicon, metal, glass, ceramic, or polymer material). For the convenience of explanation, the method of preparing dioxide film on Shi Xi substrate is taken as an example. The method provided by the present invention includes two stages, i.e., breaking and electrochemical anodizing deposition of a dioxide film. The first stage is to deposit the film on a silicon wafer by means of a base plating method. Of course, it can also be plated on a titanium bulk On the substrate of other materials, the second-stage electrochemical anodic oxidation system uses the strong μ-electrolyte solution of hydroxide but imprint, which can form a core dioxide film with a nano-network structure in a relatively short time. In other words, the present invention first forms a seeding layer on a substrate, and then uses the seed layer as a substrate to form a titanium dioxide film on the substrate by electrochemical anodization. The method provided in this embodiment is described in detail below. Please also refer to FIG. 1. First, a film on the surface of the broken wafer 10 is a chin film, and the titanium film 12 is deposited on a 4-inch p-type by unbalanced magnetron sputtering. (100) On the silicon wafer 10 (resistance 4 ~ 7 ncm), the shovel parameters are: dry current 0.9 A, working pressure: imtorr, background pressure: 8 × 0.6, bias : -50 V 'substrate temperature: 25 ° C, deposition time: 80 minutes, formation of -6-200424130 Description of the invention The thickness of the film is about 0.5 μm. In actual manufacture, other plating methods such as Evaporation should also be feasible, and there is not much restriction on film thickness. Next, the silicon wafer 10 coated with the titanium film 12 is placed in an electrolytic solution, the titanium film 12 is used as an anode, and a KOH solution having a concentration of 1M is used as an electrolytic 5 solution. An anatase titanium dioxide film 14 is synthesized on the surface of the titanium film 12, wherein the working electrode area of the electrochemical cell is fixed at 1 cm2, the cathode is platinum (Pt), the distance between the anode and the cathode is 11 cm, and the reference electrode is Ag. / AgCl is used to measure the anode surface voltage. The distance between the reference electrode tip and the anode is 3 mm. This electrochemical system is a two-pole system. The voltage range of the power supply is 0 ~ 100 V and the current range is 0 ~ 1 A, the plating mode can be selected by scanning voltage or constant voltage. Observation results using a field emission scanning electron microscope show that when the scanning voltage starts from 0 V and is scanned at a scanning rate of 10 mV / s to 3 V, that is, a titanium dioxide film 14 having a nano-network structure is found on the surface of the titanium film 12, It takes about 5 minutes; the surface morphology of the titanium dioxide film 14 at the scan cut-off voltage of 10 V (about 17 minutes) is shown in the first figure, and its network structure is quite uniform and complete, and the diameter of the ring is about 50 nm. The width of the network line is less than about 10 nm. The cross section of the titanium dioxide film 14 is as shown in the second figure. The thickness of the titanium dioxide film 14 20 is 60 nm, and the adhesion between the titanium dioxide film 14 / titanium film 12 / silicon substrate 10 is extremely low. It is not easy to fall off, which can effectively solve the problem of bonding with the substrate when titanium dioxide is used as a photocatalyst; if the scanning voltage is further increased to 70 V, the film thickness of the titanium dioxide film 14 can reach 250 nm. The composition of titanium dioxide was further analyzed by Raman spectroscopy. The results are shown in Figure 7-200424130 of the third page of the description of the invention. The p-curve, q-curve, and r-curve are in the scanning voltage mode (the scanning rate is 10mV / s). ), The Raman spectrum of the titanium dioxide film 14 generated when scanning to 10V, 20V, 30V (scanning cut-off voltage), all have the characteristic energy peak of the anatase phase, indicating that there is already a single anatase phase in the above three conditions The titanium dioxide crystal structure was generated. Among them, the s-curve is the Raman spectrum of a titanium-plated silicon wafer that has not been anodized for comparison. The nano-titanium dioxide prepared by the method of the present invention, if heat-treated at 500 ° C in the atmosphere, with a heating time of 5 ° C per minute and a holding temperature of 10 2 hours, the surface of the titanium dioxide film will be as shown in the fourth figure As shown, it can be seen that the network structure has not changed, but analysis of the Raman spectrum reveals that at this temperature, the anatase phase will completely change into a rutile phase, as shown in the fifth figure, where a curve It is a non-anodized “Dream-plated wafer”. The curve “b” is anodized to form an anatase phase on the plated wafer. The curve “c 15” is heated at 500 ° C for two hours in the atmosphere. The later produced rutile titanium dioxide, and the nano-structured titanium dioxide can be maintained at least to 600 ° C without being destroyed, and has excellent biomedical application value. In actual operation, in the second stage of the present invention, various parameters can be changed as required, and the expected results can be achieved after actual tests. For example, the potassium hydroxide solution 20 can be replaced by other solutions containing alkali metal ions, such as sodium hydroxide NaOH, The concentration of the electrolyte can be between 0.1 and 5 Μ, and the concentration of the potassium hydroxide solution is preferably 1 Μ. The voltage scan rate can be between 0 mV / s and 100 mV / s, and the scan cutoff voltage can be Between 3 V and 85 V, the electrochemical anodizing process can be performed for 5 minutes to 10 hours. -8- Description of the invention The operation temperature on the next page is t, which is the best, even u =: Anodizing Can also produce nano-mesh structure sharp 鈇…, Gu Xin such as sulfuric acid as an electrolyte can also achieve the purpose of the invention, as shown in the sixth figure, the system is up to the cost of cutting chips, mh2S〇4 电 = Polar oxidation method at room temperature at a plating rate of 10mWs), scanning to the T private surface type (known surface morphology, as can be seen from the photos, the dioxide's form particles, and the surface properties are quite uniform-and The particle size is about 1Gnm, which belongs to the material structure; Raman spectroscopy was used to analyze the composition of the dioxide, and the results are shown in the seventh figure, where the e curve, f curve, g curve h " 崎 h curve, and i curve are scanned at a scan rate of iOmWs, respectively. The Raman spectra of the two oxygen slit membranes generated at 7ν, 1〇ν, 2〇ν, 3〇ν · ν ^ trace cut-off voltage) can be seen from the figure 15 except for the e curve, all of which have sharp Qin ore facies. The characteristic energy peak indicates that when the scan cut-off voltage is above K) V, a single-acrylic acid phase crystal structure is formed. According to the method provided by the present invention, not only the nanostructured sharp drinking mineral phase rhenium dioxide can be quickly formed at room temperature, but also can be applied to homogeneous substrates or heterogeneous substrates, and has excellent photocatalytic properties in application. In addition, the structure of the “dioxide / film 20 substrate / substrate” can effectively prevent the substrate from being decomposed and damaged, which has obvious enhancement effect compared with the conventional technology. At the same time, the structure of the dioxide site made by this method belongs to the nanometer class. There are also excellent solar cells (anatase phase) and biomedical (rutile phase) applications, and the value potential of industrial utilization is endless. 200424130 [Brief description of the drawings] The first figure is a microphotograph of the surface of a product manufactured by the first preferred embodiment of the present invention. The second figure is a micrograph showing a cross-section of a product manufactured by the first preferred embodiment of the present invention. The third figure is a Raman spectrum of a product manufactured according to the first preferred embodiment of the present invention. The fourth figure is a photomicrograph of the surface of a product manufactured by the first preferred embodiment of the present invention after being heated at 500 ° C for two hours in the atmosphere. 10 The fifth graph is the Raman spectrum of the product at each stage of the first preferred embodiment of the present invention. The sixth figure is a microphotograph of the surface of a product manufactured by the second preferred embodiment of the present invention. The seventh diagram is the Raman spectrum of the product at each stage of the second preferred embodiment of the present invention. [Illustration of Symbols] 10 silicon wafer 12 titanium film 14 titanium dioxide film -10-