1324897 玖、發明說明： 【發明所屬之技術領域】 本發明是有關於一種電致色變材料（Electr〇chr〇mic Material)的備製方法及其材製品，特別是有關一種低溫 氧化備製電致色變材料的方法及其製品。 【先前技術】 電致色變材料一般經常被應用在圖案或數字顯示器 (Electrochromic Display Device)、可調節室内陽光入 射量的智慧型窗戶（Smart Wind〇w)、反強光後視鏡 (Antiglare Rearview Mirror)、汽車之頂窗（Sun R〇〇f)， 以及安全眼鏡等領域。 一般習知的電致色變材料’通常包含：一透明基材、 一形成在該基材上的透明導電薄膜，以及一形成在該透明 導電薄臈上的金屬氧化物薄膜（圖未示）。其中，該金屬氧 化物薄膜，例如氧化鎳（Nickel 〇xide)薄膜在被施加一電 壓時，會產生電致色變特性。 該金屬氧化物薄膜是藉由先將一金屬薄膜沉積在該 透明導電薄膜上，接著將該金屬薄膜予以氧化而形成。在 此習知技術中，形成該金屬薄膜的方法一般有兩種： 疋藉由濕製程：例如電鐘法（Electrode position)電化學沈積法（Electrochemical Dep〇sltlon)、溶膠-凝膠技術（SM_Gel 與旋 轉塗佈技術（Spin-Coating Techniques)等。該電鍍法則 疋再現性（Cyclic Ability)較差且所製得的金屬氧化物薄 5 1324897 膜老化（Aging)速率快（只有約3〇〇次的色變壽命）。該溶 膠-凝膠技術則因在移除溶劑時加熱而可能得到品質較差 的金屬薄膜。 二、疋错由一乾製程：例如物理氣相沉積法（Physical VaP〇r Deposition ; PVD)中的真空蒸鍍法（“⑶⑽1324897 发明, the invention description: [Technical field of the invention] The present invention relates to a preparation method of an electrochromic material (Electr〇chr〇mic Material) and a material thereof, in particular to a low temperature oxidation preparation A method of producing a color change material and an article thereof. [Prior Art] Electrochromic materials are often used in patterns or digital displays (Electrochromic Display Devices), smart windows that can adjust the amount of sunlight incident in the room (Smart Wind〇w), and anti-glare rearview mirrors (Antiglare Rearview) Mirror), the roof window of the car (Sun R〇〇f), and safety glasses. A commonly known electrochromic material generally includes: a transparent substrate, a transparent conductive film formed on the substrate, and a metal oxide film formed on the transparent conductive thin film (not shown). . Among them, the metal oxide film, such as a nickel oxide film, produces an electrochromic property when a voltage is applied. The metal oxide film is formed by first depositing a metal thin film on the transparent conductive film and then oxidizing the metal film. In this prior art, there are generally two methods for forming the metal thin film: 疋 by a wet process: for example, Electrode position electrochemical deposition (Electrochemical Dep〇sltlon), sol-gel technique (SM_Gel) And Spin-Coating Techniques, etc. The plating method has poor Cyclic Ability and the produced metal oxide is thin. 5 1324897 The film aging rate is fast (only about 3 times) The color change life). The sol-gel technique may result in a poor quality metal film due to heating when the solvent is removed. 2. The fault is caused by a dry process: for example, physical vapor deposition (Physical VaP〇r Deposition; PVD) Vacuum evaporation method in "(3)(10)
Evaporation)及濺鍍技術（SpuUering Techni(jues)等。 該物理氣相沉積法需要昂貴的設備與一相當大的製程言 矣 備容置空間。 ίο 由上所述，熟知此技術領域的相關人士皆知，對於製 鲁 作大面積電致色變材料所待解決的缺點，不是因為物理氣 相沉積法所使用的真空設備昂貴，就是因為使用溶膠_凝 膠技術或電鍍法所製得的電致色變材料品質不佳且老化 速率快。 15 如美國專利第5708523號所揭露之一種習知用於智慧 型囪戶的輔助電極（C〇unterelectrode)，其中，說明書内 揭露其所使用的電致色變材_(w〇3)是由氣相沉積製得。 20 同樣地，如美國專利第5724176號所揭露之另一種習 鲁 知用於智慧型窗戶的輔助電極，其中，在製作電致色變材 . 料（恥3)的製程是使用如電子束蒸鍍法（EIectr〇n Beam Evaporation)及濺鍍法等氣相沉積法備製而得。 上述兩美國專利所使用的氣相沉積法，皆須利用到真 工5又備。此種方法不但設備昂貴，且在製作過程中由於抽 真空過程耗時，因此時間成本也相對提高。另外，欲藉材 料由固態昇華至氣態而備製電致色變材料所需消耗的能 6 1324897 量高因此也有耗費能源的缺點。 又如美國專利第6297900號揭露出另一種習知光控電 致色變智慧型窗戶及其製作方法（Electr〇ph〇t〇chr〇inic Smart Windows And Method)。其中，在製作電致色變材 料（W〇3)的製程是使用溶膠-凝膠法備製而得。此種備製方 法容易在移除溶劑時因加熱而導致電致色變材料的品質 下降。 此外，申請人前所申請專利（申請案號：090129634; 以下簡稱習知一）之用以備製一電致色變材料的方法，揭 露出該電致色變材料（氧化鎳；Ni0)的備製方法，是利用 一無電鍍法（Electroless Plating Technologies)在一透 明導電基板上沉積一金屬鎳，繼而將此金屬鎳在大氣中於 150至400 C溫度下鍛燒（Calcining)氧化歷時30至120 分鐘。之後，再藉由退火（Anneaiing)處理，使該透明導 電基板上形成一氧化鎳薄膜。此種備製電致色變的方法雖 然解決了氣相沉積法之真空設備昂貴的問題，也沒有溶膠 一凝膠法及電鍍法造成電致色變材料品質不佳及再現性低 等缺點。但仍然具有昇溫氧化消耗能源，以及耗費時間等 缺失。 因此’如何降低使用設備的成本及減少製作電致色變 材料所消耗的時間，並備製出品質佳且再現性好的電致色 變材料’是當前研究開發電致色變材料業者不斷努力的方 向。 【發明内容】 7 1324897 因此，本發明之第-目的，即在提供—種低溫氧化備 製電致色變材料的方法。 另外，本發明之第二目的，即在提供—種電致色變材 料。 本發明低溫氧化備製電致色變材料的方法，包含下列 步驟： (a) 在透明基材上形成一透明導電薄膜； (b) 藉由一無電鍍步驟使一金屬薄膜形成於該透明 導電薄臈上；及 (〇將該金屬薄膜浸泡在一氧化劑中維持一氧化時 間予以一氧化，以在該透明導電薄膜上形成一金 屬氧化物薄膜。 其中，當施加一電壓至該金屬氧化物薄膜時，該金屬 氧化物薄膜會產生電致色變特性。 本發明之電致色變材料，包含：一透明基材、一形成 在該透明基材上的透明導電薄膜，及__形成在該透明導電 薄膜上的金屬氧化物薄膜。 該金屬氧化物薄膜是藉由在該透明導電薄膜上以一 無電鍍形成一金屬薄膜，並接著將該金屬薄膜浸泡在一氧 化劑中，維持一氧化時間而製得。當該金屬氧化物薄膜被 施加一電壓時，會產生電致色變特性。 本發明之功效在於方法簡單、製程省時且設備成本 低，以及可得到品質佳的電致色變材料。 【實施方式】 8 1324897 參閱圖1，本發明低溫備製電致色轡鉍 匕跫柯枓的方法，包 含下列步驟： (a) 在一透明基材上形成一透明導電薄膜； (b) 藉由一無電鍍步驟使該透明導電薄瞑上形成一金 屬薄膜；及 (c) 將該金屬薄膜浸泡在一氧化劑中維持— 予以一氧化，以在該透明導電薄膜上形成一金屬 氧化物薄膜。 ίο 其中’當施加-電壓至該金屬氧化物薄膜時，該金屬 氧化物薄膜會產生電致色變特性。 適用於本發明之該氧化劑是選自於下列群組中的氧 化劑：過氧化氫（H2〇2)、次氣化鈉（Na〇cl)、氣胺 (Ch1〇ramine)及臭氧（⑹。在—較佳具體例中，該氧化劑 15 是過氧化氫（以下簡稱H2〇2)。在另一較佳具體例中，該氧 化劑是次氯化鈉（以下簡稱Na〇cl)。 較佳地，該金屬薄膜浸泡在該氧化劑令的處理溫度是 介於4°C到4(TC，且該氧化時間是介於5至6〇分鐘。夂 20 該金屬薄膜是由鎳所構成。在該透明導電薄膜上的金 屬薄膜之無電鑛’是藉由使用—具有—組成物的鑛浴 (Plating Bath)來進行。該組成物包含一水溶性鎳鹽、一 還原劑’以及選擇性地’—螯合劑（_州叫心⑴與 一緩衝劑（Buf fer)。 物 過用於本發明之該鎳鹽是選自於下列群組 酸鎳（Nickel Sulfate)、氯化鎳（Nic 9 1324897Evaporation) and sputtering technology (SpuUering Techni (jues), etc. This physical vapor deposition method requires expensive equipment and a considerable process to accommodate the space. ίο From the above, people familiar with this technical field It is well known that the shortcomings to be solved for making large-area electrochromic materials are not because the vacuum equipment used in physical vapor deposition is expensive, but also because of the electricity produced by sol-gel technology or electroplating. The color-changing material has a poor quality and a fast aging rate. 15 A conventional auxiliary electrode (C〇unterelectrode) for a smart household is disclosed in U.S. Patent No. 5,085,253, the disclosure of which is incorporated herein by reference. The color-changing material _(w〇3) is produced by vapor deposition. 20 Similarly, another auxiliary electrode disclosed in U.S. Patent No. 5,724,176 is used for an auxiliary window of a smart window, in which electricity is produced. Color-changing material. The material (shame 3) process is prepared by vapor deposition such as electron beam evaporation (EIectr〇n Beam Evaporation) and sputtering. The gas phase used in the above two US patents. sink The method of accumulation must be used in both the real work and the 5th. This method is not only expensive, but also consumes time in the process of vacuuming, so the time cost is relatively increased. In addition, the material is sublimated from the solid state to the gaseous state. The energy required to prepare the electrochromic material is 6 1324897, which is also a disadvantage of energy consumption. Another example is the conventional light-controlled electrochromic intelligent window and its manufacturing method (Electr〇). Ph〇t〇chr〇inic Smart Windows And Method). Among them, the process of making electrochromic material (W〇3) is prepared by using a sol-gel method. This preparation method is easy to remove. In the case of the solvent, the quality of the electrochromic material is lowered due to the heating. In addition, the method of preparing an electrochromic material for the preparation of an electrochromic material by the applicant's previously applied patent (application number: 090129634; hereinafter referred to as the conventional one) is disclosed. The preparation method of the electrochromic material (nickel oxide; Ni0) is to deposit a metal nickel on a transparent conductive substrate by using an electroless plating method (Electroless Plating Technologies). The nickel is calcined for oxidation in the atmosphere at a temperature of 150 to 400 C for 30 to 120 minutes, and then a nickel oxide film is formed on the transparent conductive substrate by annealing (Anneaiing). Although the method of electrochromicization solves the problem of expensive vacuum equipment of vapor deposition method, and there is no disadvantage of poor quality and reproducibility of electrochromic material caused by sol-gel method and electroplating method, Oxidation consumes energy, and time is missing. Therefore, 'how to reduce the cost of using equipment and reduce the time it takes to make electrochromic materials, and to produce high-quality and reproducible electrochromic materials' is the current research and development of electrochromic materials. The direction. SUMMARY OF THE INVENTION 7 1324897 Accordingly, a first object of the present invention is to provide a method for preparing an electrochromic material by low temperature oxidation. Further, a second object of the present invention is to provide an electrochromic material. The method for preparing an electrochromic material by low-temperature oxidation according to the present invention comprises the steps of: (a) forming a transparent conductive film on a transparent substrate; (b) forming a metal film on the transparent conductive layer by an electroless plating step; And immersing the metal film in an oxidizing agent for maintaining an oxidation time to be oxidized to form a metal oxide film on the transparent conductive film. wherein, when a voltage is applied to the metal oxide film When the metal oxide film produces electrochromic properties, the electrochromic material of the present invention comprises: a transparent substrate, a transparent conductive film formed on the transparent substrate, and __ formed thereon a metal oxide film on the transparent conductive film. The metal oxide film is formed by electrolessly forming a metal film on the transparent conductive film, and then immersing the metal film in an oxidant to maintain an oxidation time. When the metal oxide film is applied with a voltage, an electrochromic property is generated. The effect of the invention is that the method is simple, the process is time-saving, and the device is The invention has the advantages of low cost and good quality electrochromic material. [Embodiment] 8 1324897 Referring to Fig. 1, the method for preparing a low-temperature electrochromic enamel according to the present invention comprises the following steps: (a) Forming a transparent conductive film on a transparent substrate; (b) forming a metal film on the transparent conductive thin layer by an electroless plating step; and (c) immersing the metal film in an oxidizing agent to maintain oxidation And forming a metal oxide film on the transparent conductive film. ίο where the metal oxide film produces an electrochromic property when a voltage is applied to the metal oxide film. The oxidizing agent suitable for use in the present invention Is an oxidant selected from the group consisting of hydrogen peroxide (H2〇2), sodium subgas (Na〇cl), nitroamine (Ch1〇ramine), and ozone ((6). In a preferred embodiment, The oxidizing agent 15 is hydrogen peroxide (hereinafter referred to as H2〇2). In another preferred embodiment, the oxidizing agent is sodium hypochlorite (hereinafter referred to as Na〇cl). Preferably, the metal film is immersed in the oxidizing agent. The processing temperature is between 4 ° C To 4 (TC, and the oxidation time is between 5 and 6 minutes. 夂20 The metal film is composed of nickel. The electroless ore of the metal film on the transparent conductive film is made by using - having - The material is carried out by a plating bath. The composition comprises a water-soluble nickel salt, a reducing agent 'and optionally a chelator (_State called (1) and a buffer (Buf fer). The nickel salt used in the present invention is selected from the group consisting of Nickel Sulfate and nickel chloride (Nic 9 1324897).
Chloride)，以及此等之一組合。適用於本發明之該還原 劑是選自於下列群組中的化合物：次磷酸鹽 (Hypophosphite Salt)、聯胺（Hydrazine)及棚氬化納 (Sodium Borohydride)。適用於本發明之該螯合劑是選自於 5 下列群組中的化合物：檸檬酸鈉水合物（TrisodiumChloride), and a combination of these. The reducing agent suitable for use in the present invention is a compound selected from the group consisting of Hypophosphite Salt, Hydrazine, and Sodium Borohydride. The chelating agent suitable for use in the present invention is a compound selected from the group consisting of sodium citrate hydrate (Trisodium)
Citrate Dihydrate，分子式為 Na3C6〇7H5.H2〇)、酒石酸 (Tartaric Acid)、酒石酸納、檸檬酸（Citric Acid)、氯 化敍（Ammon ium Chloride)，以及此等之一組合。適用於 本發明之該緩衝劑是選自於下列群組中的化合物：硼酸 10 (Boric Acid)、馬來酸（Maleic Acid)、衣康酸（ItaconicCitrate Dihydrate, the formula is Na3C6〇7H5.H2〇), Tartaric Acid, sodium tartrate, Citric Acid, Ammonium Chloride, and a combination of these. Suitable buffers for use in the present invention are those selected from the group consisting of Boric Acid, Maleic Acid, and Itaconic.
Ac i d)，以及此等之一組合。 較佳地，該水溶性鎳鹽是硫酸鎳，該還原劑為次磷酸 鈉，而該螯合劑是檸檬酸鈉水合物，該緩衝劑為硼酸。 適用於本發明之該透明基材是由一選自於下列群組 15 中的材料所製成：玻璃、聚氣乙稀（Pol yvinyl Chloride)、 聚乙稀（Polyethylene)、聚碳酸酯（Polycarbonate)，以 及聚對苯二甲酸乙二醋（Polyethylene Ter ephtha late)。 在一較佳具體例中，該透明基材是由玻璃所製成。 適用於本發明之該透明導電薄膜是由一選自於下列 20 群組中的材料所製成：氧化銦錫（Indium Tin Oxide，簡 稱 ITO)、氧化錄錫（Antimony Tin Oxide，簡稱 ΑΤΟ)、氧 化氣錫（Fluorine-Doped Tin Oxide，簡稱 FTO)，以及氧 化錶錫（Iridium Tin Oxide，簡稱IRTO)。在一較佳具體 例中，該透明導電薄膜是由ITO所製成β 10 1324897 由於該金屬薄膜與透明導電薄膜之間的表面吸附性 質不同，因此為了增加該金屬薄膜與透明導電薄膜之間的 結合強度，較佳地，在進行該無電鍍步驟之前，可對該透 明基材上的透明導電薄膜進行一表面處理。該表面處理依 5 序包含下列步驟：（1)使用一包含一界面活性劑 (surfactant)的清潔溶液，以提供該透明基材上的透明導 電薄膜一去脂（Degreasing)步驟。（2)使用一包含一敏化 劑（Sensitizing Agent)的敏化液，給予該透明導電薄膜 一敏化步驟。（3)藉由使用一包含一活化劑的活化溶液， 10 給予該透明導電薄膜一活化步戰。 適用於本發明之該敏化劑是選自於下列群組中的化 合物.氯化錫（Tin Chloride)、氣化鈦（Titanium Chloride)，以及此等之一組合。適用於本發明之該活化 劑是選自於下列群組中的化合物：氯化鈀（PaUadium 15 Chloride)、氣化鉑（Platinuni Chl〇ride)，以及此等之一 組合。較佳地，前面所提及的敏化與活化步驟是在1 至 4 0 °C之間的溫度下進行。例如當使用氯化錫（s n c h)與氯化 鈀（PdCh)分別來作為該敏化劑與活化劑時，在該敏化步驟 操作期間，該敏化液中的錫離子（Sn2+)會滲入該透明導電 2〇 薄膜表面的微孔中，而在該活化步驟操作期間，該鈀離子 (Pd2+)會與錫離子產生氧化還原，被還原的鈀會取代錫離 子而植入微孔中。 較佳地，該敏化劑是氣化錫，而該敏化液是藉由將氣 化錫溶在一鹽酸（HC1)溶液中而製成。 11 1324897 較佳地，該活化劑是氣化鈀，而該活化液是藉由將氯 化鈀溶在一鹽酸溶液中而製成。 參閱圖2,利用本發明之方法，可備製成一電致色變 材料。該電致色變材料包含：一透明基材5、一形成在該 透明基材5上的透明導電薄膜6,及一形成在該透明導電 薄膜6上的金屬氧化物薄膜7。 該金屬氧化物薄膜7是利用本發明的方法，藉由在該 透明導電薄膜6上以一無電鍍形成一金屬薄膜，並接著將 該金屬薄膜浸泡在一氧化劑中，維持一氧化時間而製得。 當該金屬氧化物薄膜7被施加一電壓時，會產生電致 特性。 下面的各實施例將說明該電致色變材料如何根據本 發明的方法來製得。 〈實施例一〉 本實施例中使用玻璃基材與IT〇透明導電薄膜來製成 一透明導電基板。 利用超音波震盪在一包含一非離子型界面活性劑的 清潔溶液中將該基板？以去冑。該清潔溶液是透過將一預 疋罝的非離子型界面活性劑溶解在5〇ml的去離子水 (de-i0nized water)中備製而得。接著再以去離子水洗滌 該基板。 使用一包含0.5g氯化錫（SnCl2)、〇5ral鹽酸與5〇ml 去離子水的組成物之敏化液，對該已祕過的透明導電基 板進行-敏化步驟。該敏化步驟是在呢至4代的溫度 12 下進行5至50分鐘》後續再以去離子水洗滌該已敏化後 的基板。 接著使用一包含0. 025g氣化鈀（PdClO、0· 5ml鹽酸 與50ml去離子水的組成物之活化液，對該基板進行一活 化步驟。該活化步驟是在HTC至4(TC的溫度下進行2至 20分鐘。之後’以去離子水洗滌該已活化的基板。 接者將該透明導電基板浸泡入一包含3g硫酸鎳 (NiS〇4_6H2〇)、6g檸檬酸納水合物、4g硼酸（h3B〇3)與2g 次磷酸鈉（NathPOrfibO)的組成物之鍍浴中，以進行一無電 鍍步驟，並在該透明導電基板上形成一錦金屬薄膜。該無 電鍍步驟是在45。〇至85。(：的溫度下進行〇.5至1〇分鐘。 後續，再使用去離子水洗滌該已被無電鍍的基材，並且接 著予以乾燥。另外，再使用鹽酸將該基板之一侧的—非導 電面之金屬（鎳）薄膜移除。 之後，使無電锻有該錦金屬薄膜的基板浸泡在一氧化 劑中維持一氧化時間。該氧化劑是使用濃度介於25 v〇1% 至40 vol.%的H2〇2水溶液，且在至室溫下維持5至 6〇分鐘，使該IT0導電薄膜上5上之鎳金屬薄膜反應形成 一氧化鎳薄膜（Niz〇3)。當施加一電壓至該氧化鎳薄獏時， 該氧化鎳薄膜會產生電致色變特性。 〈實施例二〉 本實施例與該實施例一大致相同，不同的處在於，該 敏化步驟及活化步驟的處理溫度是28〇c的溫度。該無電鍍 浴中的組成物包含：1.6g硫酸鎳、3 61g檸檬酸鈉水合物、 13 1324897 2.7g氯化銨（Ni^Cl)與〇.75g次磷酸鈉，且該無電鑛過程 是維持在酸驗值等於9的條件下進行。 〈實施例三〉 本實施例與該實施例一大致相同，不同的處在於，該 5 氧化劑是使用6. 0M的NaOCl水溶液。 〈實施例四〉 本實施例與該實施例二大致相同，不同的處在於：該 氧化劑是使用NaOCl水溶液。 〈電致色變反應測試〉 10 使用如圖3所示的一循環伏安計（CyclicAc i d), and a combination of these. Preferably, the water-soluble nickel salt is nickel sulfate, the reducing agent is sodium hypophosphite, and the chelating agent is sodium citrate hydrate, and the buffer is boric acid. The transparent substrate suitable for use in the present invention is made of a material selected from the group consisting of glass, polyvinyl hydride, polyethylene, polycarbonate (Polycarbonate). ), as well as Polyethylene Ter ephtha late. In a preferred embodiment, the transparent substrate is made of glass. The transparent conductive film suitable for use in the present invention is made of a material selected from the group consisting of: Indium Tin Oxide (ITO), Antimony Tin Oxide (abbreviated as ΑΤΟ), Fluorine-Doped Tin Oxide (FTO), and Iridium Tin Oxide (IRTO). In a preferred embodiment, the transparent conductive film is made of ITO, and the surface adsorption property between the metal film and the transparent conductive film is different, so in order to increase the relationship between the metal film and the transparent conductive film. The bonding strength, preferably, the surface of the transparent conductive film on the transparent substrate may be subjected to a surface treatment before the electroless plating step. The surface treatment comprises the following steps: (1) using a cleaning solution comprising a surfactant to provide a transparent conductive film-degreasing step on the transparent substrate. (2) A sensitizing step comprising a sensitizing agent is applied to the transparent conductive film. (3) By using an activation solution containing an activator, 10 is given an activation step to the transparent conductive film. The sensitizer suitable for use in the present invention is a compound selected from the group consisting of tin chloride (Titanium), titanium oxide (Titanium Chloride), and a combination thereof. The activator suitable for use in the present invention is a compound selected from the group consisting of palladium chloride (PaUadium 15 Chloride), platinumated platinum (Platinuni Chlride), and combinations of these. Preferably, the aforementioned sensitization and activation steps are carried out at a temperature between 1 and 40 °C. For example, when tin sulphate and palladium chloride (PdCh) are used as the sensitizer and activator, respectively, tin ions (Sn2+) in the sensitizing solution may permeate during the sensitization step operation. The transparent conductive film is in the micropores on the surface of the film, and during the operation of the activation step, the palladium ions (Pd2+) are redoxed with tin ions, and the reduced palladium is substituted for tin ions and implanted in the micropores. Preferably, the sensitizer is vaporized tin, and the sensitizing solution is prepared by dissolving a vaporized tin in a hydrochloric acid (HC1) solution. 11 1324897 Preferably, the activator is vaporized palladium, and the activation liquid is prepared by dissolving palladium chloride in a hydrochloric acid solution. Referring to Figure 2, an electrochromic material can be prepared by the method of the present invention. The electrochromic material comprises: a transparent substrate 5, a transparent conductive film 6 formed on the transparent substrate 5, and a metal oxide film 7 formed on the transparent conductive film 6. The metal oxide film 7 is obtained by using the method of the present invention by forming a metal film on the transparent conductive film 6 by electroless plating, and then immersing the metal film in an oxidizing agent to maintain an oxidation time. . When the metal oxide film 7 is applied with a voltage, electrical characteristics are generated. The following examples will illustrate how the electrochromic material can be made in accordance with the method of the present invention. <Example 1> In this example, a glass substrate and an IT〇 transparent conductive film were used to form a transparent conductive substrate. Using ultrasonic waves to oscillate the substrate in a cleaning solution containing a nonionic surfactant? To go. The cleaning solution was prepared by dissolving a pre-formed nonionic surfactant in 5 〇ml of de-i0nized water. The substrate is then washed with deionized water. The secreted transparent conductive substrate was subjected to a sensitization step using a sensitizing solution containing a composition of 0.5 g of tin chloride (SnCl 2 ), 〇 5 ral hydrochloric acid and 5 〇 ml of deionized water. The sensitization step is carried out for 5 to 50 minutes at a temperature of 12 to 4, and the sensitized substrate is subsequently washed with deionized water. The substrate is then subjected to an activation step using an activation solution comprising 0.025 g of vaporized palladium (PdClO, 0.5 ml of hydrochloric acid and 50 ml of deionized water. The activation step is at a temperature of HTC to 4 (TC). It is carried out for 2 to 20 minutes. Then, the activated substrate is washed with deionized water. The transparent conductive substrate is immersed in a solution containing 3 g of nickel sulfate (NiS〇4_6H2〇), 6 g of sodium citrate, 4 g of boric acid ( h3B〇3) in a plating bath with a composition of 2 g of sodium hypophosphite (NathPOrfibO) to perform an electroless plating step and forming a ruthenium metal film on the transparent conductive substrate. The electroless plating step is at 45. 85. (: at a temperature of 〇. 5 to 1 〇 minutes. Subsequently, the electroless plated substrate is washed with deionized water, and then dried. Further, one side of the substrate is further treated with hydrochloric acid. - removing the metal (nickel) film of the non-conductive surface. Thereafter, the substrate for electroless forging the ruthenium metal film is immersed in an oxidizing agent for maintaining an oxidation time. The oxidizing agent is used at a concentration of between 25 v〇1% and 40 vol. .% of H2〇2 aqueous solution, and at Maintaining for 5 to 6 minutes at a temperature, reacting a nickel metal film on the IT0 conductive film to form a nickel oxide film (Niz〇3). When a voltage is applied to the nickel oxide thin film, the nickel oxide film The electrochromic property is produced. <Embodiment 2> This embodiment is substantially the same as the first embodiment except that the processing temperature of the sensitizing step and the activation step is a temperature of 28 〇c. The composition comprises: 1.6 g of nickel sulfate, 3 61 g of sodium citrate hydrate, 13 1324897 2.7 g of ammonium chloride (Ni^Cl) and 〇.75 g of sodium hypophosphite, and the electroless ore process is maintained at the acid value equal to <Example 3> This example is substantially the same as the first embodiment except that the 5 oxidizing agent is a 6.0 M aqueous solution of NaOCl. <Example 4> This example and the embodiment Example 2 is roughly the same except that the oxidizing agent is an aqueous solution of NaOCl. <Electrochromic reaction test> 10 A cyclic voltammeter as shown in Fig. 3 is used (Cyclic
Voltammeter)301 ’對該實施例一中所製得的電致色變材 料進行電致色變反應測試。將製得的電致色變材料置於一Voltammeter) 301 'The electrochromic reaction material prepared in the first embodiment was subjected to an electrochromic reaction test. Place the prepared electrochromic material in one
檢測槽（cell)302中以進行測試。該檢測槽302包括一 K0H 電解質溶液4本體，以及沉浸在該溶液4中的一·對極 15 Kcounter electrode)、一參考電極2(白金電極）與一工 作電極3(working electrode，使用該電致色變材料在 測試期間’藉由施加+1. 5V至-1. 5V的電壓方波 (square-wave)輸出與輸入伏特’該工作電極3的電致色 變材料會進行一下列電致色變的可逆反應： 20 Ni2〇3 + 40Η'㈠ 4Ni00H + 〇2 + e* 參閱圖4，該習知一藉該循環伏安計3〇1分析而得的 一循環伏安曲線圖，具有一最高電流密度（current density)值約0.00038 Amps/cm2的表面氣化電流密度，及 一約1000次的上色（(：〇1〇]：丨112)壽命。參閱圖5，本發明之 14 1324897 5 該電致色變材枓藉該循環 — + 301分析而得的一循環伏 、有最问電流费度值約為〇.001 Amps/cm2 的表面氧化電流密度’及'約讓次的上色壽命。比較 "及^的循環伏安曲線圖，可得藉由低溫氧化製程的 最商電流密度值及上色壽命明顯高於高溫氧化製程的最 高電流密度值及上色壽命。 〈表面均勻性分析〉 10 15 參閱圖6及圖7’分別為高溫（該習知一）及低溫（本發 明）氧化製程之掃描式電子顯微鏡（Scanning Electr〇n MiCr〇spectroscopy ;簡稱 SEM)表面形貌（surface morphology)圖。由圖6中的金屬氧化物粒徑較大顯示出 排列較鬆散，因此表面均勻性較差。由圖7中的金屬氧化 物粒徑較小顯示出排列緊密度較高，因此表面均勻性較 高。藉由排列較緻密的金屬氧化物，可提高電致色變反應 特性的品質。 〈X射線繞射分析〉The cell 302 is tested for testing. The detecting tank 302 includes a body of a K0H electrolyte solution 4, and a counter electrode 15 immersed in the solution 4, a reference electrode 2 (platinum electrode) and a working electrode 3 (working electrode). The color-changing material is subjected to the following electrochromic material by applying a voltage of +1.5 volt to -1.5 V to the square-wave output and input volts of the electrochromic material of the working electrode 3 during the test. Reversible reaction: 20 Ni2〇3 + 40Η'(1) 4Ni00H + 〇2 + e* Referring to Figure 4, the conventional cyclic voltammetry chart obtained by the cyclic voltammeter 3〇1 has one The highest current density value is about 0.00038 Amps/cm2 of surface gasification current density, and a color of about 1000 times ((:1〇::丨112) lifetime. Referring to Figure 5, the present invention 14 1324897 5 The electrochromic material 枓 by the cycle - + 301 analysis of a cyclic volt, the most current rate value is about 001.001 Amps / cm2 surface oxidation current density 'and 'about the time Color lifetime. Comparing the cyclic voltammograms of " and ^, can be obtained by low temperature oxidation process The most common current density value and color life is significantly higher than the highest current density value and color life of the high temperature oxidation process. <Surface uniformity analysis> 10 15 Refer to Fig. 6 and Fig. 7 respectively for high temperature (the first one) Scanning Electron Microscope (Scanning Electr〇n MiCr〇spectroscopy; SEM) surface morphology diagram of the low temperature (invention) oxidation process. The larger the metal oxide particle size in Figure 6 shows that the arrangement is looser. Therefore, the surface uniformity is poor. The smaller the metal oxide particle size in Fig. 7 shows that the alignment is higher, so the surface uniformity is higher. By arranging the denser metal oxide, the electrochromic change can be improved. The quality of the reaction characteristics. <X-ray diffraction analysis>
20 參閲圖8，由X射線繞射（X-Ray Diffraction ;簡稱 φ XRD)圖譜可得，利用南溫氧化所形成之金屬氧化物（該習 -知一）的結晶結構具有非常明顯的N i 0訊號；而經低溫氧 化所形成之金屬氧化物（本發明）的結晶結構則出現了很 強之Niz〇3訊號。因此’以低溫氧化所得的金屬氧化物具有 較佳之結晶性（crystallinity)，以致於本發明之電致色 變材料具有較佳的電致色變特性。 由上面所述’本發明之低溫氧化備製電致色變材料的 15 1324897 方法及其製品具有方法簡單、製程省時、節省設備成本、 電致色變特性品質佳及上色壽命較長等特點，確實達到本 發明之目的。 惟以上所述者’僅為本發明之較佳實施例而已，+ w 田+ 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明書内容所作之簡單的等效變化與修飾，皆 應仍屬本發明專利涵蓋之範圍内。 【囷式簡單說明】 圖1是一流程圖，說明本發明之低溫氧化備製電致色 變材料的方法； 圖2是一側視示意圖，說明本發明之電致色變材料； 圖3是一循環伏安特性檢測裝置圖； 圖4是一循環伏安曲線圖，說明使用一高溫氧化一無 電鑛錄金屬薄膜所備製成的電致色變材料之循環伏純 性； 圖5疋循J衣伏安曲線圖，說明由本發明之低溫氧化 備製電致色變材料的方法所備製成的電致色變材料之循 環伏安特性； 圖6疋-掃描式電子顯微鏡相片，說明使用該高溫氧 化該無電鍍鎳金屬薄膜所備製成的電致色變材料之表面 形貌； 圖7疋一掃描式電子顯微鏡相片，說明由本發明之低 氧化備製電致色變材料的方法所備製成的電致色變材 料之表面形貌；及 16 1324897 圖8是X射線繞射圖譜，說明由高溫及低溫氧化所備 製成的兩種電致色變材料之晶體結構。 17 1324897 【圖式之主要元件代表符號簡單說明】 2......... …··參考電極 4..............KOH電解質溶液 3......... …-·工作電極 5..............透明基材 301 …·. ······循環伏安計 6..............透明導電薄膜 302 …·. ……檢測槽 7..............金屬氧化物薄膜 1820 Referring to Fig. 8, the X-ray diffraction (XRD) spectrum can be obtained, and the crystal structure of the metal oxide formed by the oxidation of the south temperature has a very obvious N. The i 0 signal; and the crystal structure of the metal oxide (the present invention) formed by low temperature oxidation exhibits a strong Niz〇3 signal. Therefore, the metal oxide obtained by low temperature oxidation has a preferable crystallinity, so that the electrochromic material of the present invention has better electrochromic properties. The method of the 15 1324897 method and the article thereof for the low-temperature oxidation preparation of the electrochromic material of the present invention has the advantages of simple method, time saving process, equipment cost saving, good electrochromic property quality and long color life. Features that do achieve the objectives of the present invention. However, the above description is only a preferred embodiment of the present invention, and + w field + can limit the scope of implementation of the present invention, that is, the simple equivalent change made by the patent application scope and the description of the invention. And modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart illustrating a method for preparing an electrochromic material by low temperature oxidation according to the present invention; FIG. 2 is a side view showing the electrochromic material of the present invention; FIG. Figure 5 is a cyclic volt-ampere curve showing the cyclic volatility of an electrochromic material prepared by using a high temperature oxidation-electroless metal film; Figure 5 J clothing voltammogram, illustrating the cyclic voltammetric characteristics of the electrochromic material prepared by the method for preparing the electrochromic material by low temperature oxidation of the present invention; FIG. 6 扫描-scanning electron microscope photograph illustrating use The surface morphology of the electrochromic material prepared by the high temperature oxidation of the electroless nickel metal film; FIG. 7 is a scanning electron microscope photograph illustrating the method for preparing an electrochromic material by low oxidation of the present invention. The surface morphology of the prepared electrochromic material; and 16 1324897 Figure 8 is an X-ray diffraction pattern illustrating the crystal structure of two electrochromic materials prepared by high temperature and low temperature oxidation. 17 1324897 [Simplified description of the main components of the drawing] 2...............Reference electrode 4.............. KOH electrolyte solution 3... ............-Working electrode 5..............Transparent substrate 301 ...·········································· ........transparent conductive film 302 ...........detecting groove 7..............metal oxide film 18