201215653 , . I WOJUOI^A 1 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種氧化物薄膜，且特別是有關於一 種金屬氧化物薄膜。 【先前技術】 氧化物薄膜已廣泛應用於傳統產業、半導體製程、光 電產業等。目前氧化物薄膜的製備方法可概分為氣相法與 I 溶液法。然而，氣相法例如蒸鍍或濺鍍製備方法需要使用 昂貴的設備，真空系統抽真空的速度限制製程速度，且反 應腔體的尺寸也使得製程難以大面積化。 溶液法例如凝膠或其他水溶液製備方法則有製程繁 瑣費時與氧化物薄膜之特性不容易控制的問題。舉例來 說，一種水溶液製備氧化鎢薄膜的方法係先將鎢粉與雙氧 水攪拌6小時以均勻混合並移除過多的雙氧水，然後將醋 酸加入溶液後迴流12小時，接著對溶液抽真空以移除溶 φ 劑，接著加入介面活性劑至溶液後攪拌約1小時，然後離 心分離溶液中的雜質而留下澄清液體，接著將得到的澄清 液體塗佈在基材上並進行加熱步驟以得到氧化鎢薄膜。此 外，一般溶液法的製程步驟需要精確地控制才能具有再現 性，否則，製程參數稍有誤差，例如溶液攪拌的時間不同 或溶液置放的時間不同就無法得到相同性質的氧化物薄 膜。 【發明内容】 201215653201215653, .I WOJUOI^A 1 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to an oxide film, and more particularly to a metal oxide film. [Prior Art] Oxide films have been widely used in traditional industries, semiconductor processes, and photovoltaic industries. At present, the preparation method of the oxide film can be roughly classified into a gas phase method and an I solution method. However, gas phase processes such as evaporation or sputtering preparation methods require the use of expensive equipment, the speed at which the vacuum system is evacuated limits the process speed, and the size of the reaction chamber also makes the process difficult to enlarge. Solution methods such as gels or other aqueous solution preparation methods have problems in that the process is complicated and time-consuming and the characteristics of the oxide film are not easily controlled. For example, an aqueous solution for preparing a tungsten oxide film is firstly stirred with tungsten water and hydrogen peroxide for 6 hours to uniformly mix and remove excess hydrogen peroxide, then acetic acid is added to the solution and refluxed for 12 hours, and then the solution is evacuated to remove Dissolving the φ agent, followed by adding the surfactant to the solution, stirring for about 1 hour, then centrifuging the impurities in the solution to leave a clear liquid, then coating the obtained clear liquid on the substrate and performing a heating step to obtain tungsten oxide film. In addition, the process steps of the general solution method require precise control to be reproducible. Otherwise, the process parameters may be slightly inaccurate, such as different stirring times of the solution or different time of solution placement, and an oxide film of the same nature may not be obtained. [Abstract] 201215653
I WO^UKPA f ：,. 本發明之貫施例提供一種應用於智慧型窗戶之氧化 鶴薄膜。氧化鶴薄膜的形成方法包括以下步驟。製備塗 料。塗料包括第一前驅物、燃料與溶劑。第一前驅物包ς 鎢粉末、硝酸鎢、硫酸鎢、醋酸鎢或上述之組合。燃料包 括硫脲、尿素、氨基乙酸、擰檬酸或上述之組合。溶劑^ 括水、雙乳水、酒精、或上述之組合。將塗料施加至基材 上以形成塗層。進行退火步驟，以使塗層變成氧化鶴薄膜。 【實施方式】 本發明之實施例提供一種氧化物薄膜及其形成方 法。於實施例中，氧化物薄膜可包括金屬氧化物，其金屬 可例如包括鶴、鎳、鈦、辞、銅、銀或上述之组合。 氧化物薄膜的形成方法包括以下步驟。製備塗料，塗 料包括第-前驅物、燃料與溶劑。將塗料施加至基材上以 开^成塗層。進行退火步驟，以使塗層變成氧化物薄膜。本 發明㈣狀氧化㈣糾形心法簡單、快轻具再現 性。乳化物溥膜的形成方法不需使用昂貴或複雜的設備， 成本低另外可適用於大面積的基材。氧化物薄膜 的形貌與性質可藉由調變製程之參數來控制。 、 燃料包括硫腺、尿素、氨基乙酸、棒樣酸或上述之组 二過程中或在退火步驟中，燃料會釋放熱 體，因卿月之實施例的方法能以較低的退火溫 又幵/成乳化物㈣，或使氧化物薄膜具有孔洞。 ?劑包括水、雙氧水、酒精、或上述之組合。 弟一則驅物包括第—金屬粉末、第一金屬石肖酸鹽、第 201215653I WO^UKPA f :,. The embodiment of the present invention provides a oxidized crane film applied to a smart window. The method for forming an oxidized crane film includes the following steps. A coating is prepared. The coating includes a first precursor, a fuel, and a solvent. The first precursor comprises tungsten powder, tungsten nitrate, tungsten sulfate, tungsten acetate or a combination thereof. The fuel includes thiourea, urea, glycine, citric acid or a combination thereof. Solvents include water, double emulsions, alcohol, or a combination of the above. A coating is applied to the substrate to form a coating. An annealing step is performed to cause the coating to become an oxide crane film. [Embodiment] Embodiments of the present invention provide an oxide film and a method of forming the same. In an embodiment, the oxide film may comprise a metal oxide, the metal of which may, for example, comprise crane, nickel, titanium, rhodium, copper, silver or a combination thereof. The method of forming an oxide film includes the following steps. The coating is prepared and includes a first precursor, a fuel and a solvent. A coating is applied to the substrate to form a coating. An annealing step is performed to cause the coating to become an oxide film. The (four) shape oxidation method of the invention is simple, fast and lightly reproducible. The method of forming the emulsion ruthenium film does not require the use of expensive or complicated equipment, and is low in cost and can be applied to a large-area substrate. The morphology and properties of the oxide film can be controlled by the parameters of the modulation process. The fuel includes sulfur gland, urea, glycine, rod-like acid or the above two groups or in the annealing step, the fuel will release the hot body, and the method of the embodiment can be cooled at a lower annealing temperature. / into the emulsion (four), or to make the oxide film have holes. The agent includes water, hydrogen peroxide, alcohol, or a combination thereof. A disciple of the younger brother, including the first metal powder, the first metal silicate, the first 201215653
* . I w〇jU6rM 一金屬硫酸鹽、第一金屬醋酸趟 金屬可例如包括鶴、鎳、妖、^ _述之、、且合’其中第一 舉例來說，於一些實施例中 ^銀或上述之組合。 用的第一前驅物可包括鋅粉末糸开^氧化鎳薄臈，其中使 或上述之組合。於一些實施例中，成：酸鎳、醋酸鎳 醋酸鶴或上述之組:例如鶴粉末、石肖酸鶴、硫酸鶴、 基材可包括玻璃或透明導電 (ITO)、氧化錫氟(FT〇)等等。 ，列如氧化銦錫 第一前驅物的重量：燃料的重量可 -則驅物的重量：燃料的重量 二中使用的第 施例中係形成氧化n _ 1二;^·64。於-些實 量：燃料的重量可為1:0.3〜U中使用的第-前顧物的重 燃料的重量：溶劑的重量可為】:0 01〜100 於一些形成氧化鎳薄膜的實施例中牛例來說， 重量係一於-些形成氧化鎮薄膜 =二溶劑的 的重量二溶劑的重量可為1:0.03〜40#、的“例中，燃料 於實施例中，塗料可更包括第二摻雜 雜=可例如包括第二金梅、第二金屬:酸= :::鹽、第二金屬醋酸鹽或上述之組 ::包括r鎳、鈦、鋅、銅、銀或上述之组合。第:二 的重量係。使用包括第二推夂==物 可形成摻雜的咖ed)金屬氧化物薄膜，例如撐雜的氧t 5 201215653 薄膜或推雜的氧化鎢薄膜等等。 於實施例中，製備塗料的方法係將材料例如第一前驅 以均=容劑(及第二前驅物)放置在-容器中，並撥拌 入：之。讀料放置在—㈣始算起至㈣均勻混 ㈣間可少於—小時，於—些具體實施例中 法係快途的!1里即可製得塗料，因此氧化物薄膜的形成方 料即使。此外’塗料具有極佳的穩定性，製傷好的塗 ;Π广段長時間’例如超過24小時以上的時間之 後用來形成氧化物仍能展現再現性。 兴制=施例中，退火步驟的溫度可為3G(rc至別。C。 些形成氧化錄薄膜的實施例中，退火步驟 的實二J ° 350c至45(rc。於—些形成氧化鎢薄膜 貫把例中，退火步驟的溫度可例如為3G(TC至5坑 ，佳中’退火步驟的時間可為1〇分鐘至6小時， 季乂佳為1〇分鐘至60分鐘。 氧化鶴缚膜 於-些實施例中，當第一前驅物係鎢粉末，溶劑係雔 二’燃料係硫脲，第一前驅物的重量：燃料的重量係 力.4〜2’燃料的重量：溶劑的重量 ：、 的溫度係425t至550〇Γ Β、Ρ ·15 25 ’退火步驟 60八铲日洋1 步鄉的時間係10分鐘至 化鶴薄膜為—具有裂縫的氧化鹤薄膜。 、I貫施例中，當。第—前驅物係鎢 料係硫服’第一前驅物的重量:燃料= °.4’燃料的重量:溶劑的重量係、比〜25,退火二 6 201215653 驟的溫度係425¾至550。(：，且退火牛 至60分鐘時，氧化鶏薄膜為ϋ孔 =；t間係分鐘 或者氧化鶴_具有結晶相。 ，减鎮缚膜， 於二貫轭例中，當第一前驅物係鶴於 氧水’燃料係硫服，第一前驅物的重量 0.^0-4 1:15： 5 ΪΗ'1： 的溫度係_至425t，退火步驟的時=步驟 分鐘時，氧化物為一平整的氧化鵁薄膜，〇 ;= 薄膜具有非結晶相。 、或者乳化鎢 於些貫施例中，當第一前驅物係鶴於古〜 氧水，燃料係展素，第一前驅物的重量 ㈤〜0.4’燃料的重量：溶劑的重量係科的重1 驟的溫度係425〇C至55(TC，退火步 退火步 ⑼分鐘…薄膜為-平分鐘至 於些只施例中，當第一前驅物係 氧水，燃料係氨基乙酸，第-前驅物的重Γ 谷祕雙 1 non , 别职物的重1 :燃料的重量 係1:0.2〜0.4，燃料的重量：溶劑的重量係' 1: 步驟的溫度係4坑至5耽，退火步驟的時間传i〇j 至6〇/鐘t，氧化嫣薄膜為一具有孔洞的氧化鎢薄膜刀。，里 於一i貫施例中，當第一前驅物係鹤粉末，溶劑係雙 乳水，燃枓係擰檬酸’第一前驅物的重量：燃料的、 1:0.2〜0.4’燃料的重量：溶劑的重量係Hu 驟的溫度係靴至简，退火步驟的時間係1〇分魅 6〇分鐘時’氧化鶴薄膜為—具有孔洞的氧化嫣薄膜。 本發明之實施例的氧化鎮薄膜具有優異的電致色變 7 201215653 I wojuor/Λ , t 性質，適用於各種電致色變元件如智慧型窗戶、電致色變 玻璃、變色太陽眼鏡、變色汽車後視鏡、顯示看板、電子 紙顯示器等等’此外，也能應用在太陽能電池、半導體等 產業。以下例舉一些形成氧化鶴薄膜的具體實施例，並說 明氧化鎢薄膜的分析結果。 實施例1 氧化鎢薄膜的形成方法包括以下步驟。首先，將15g 鎢粉(Merk)溶解於9m卜30%雙氧水(Sigma-AMdch)與lml 去離子水（雙氧水的體積：水的體積係9:1)中，然後將〇 45g 硫脲（Sigma)加入上述溶液中（鎢粉的重量：水加雙氧水的 重量：硫脲的重量係1:6:0.3)，接著攪拌溶液直到溶劑揮 發至溶液的重量係4_5g，藉此得到塗料。將塗料旋轉塗佈 在 ITO 或 FTO 基材（ITO coated glass 或 FTO coated glass (Solarnix;片電阻：8Q/sq))上而形成一塗層。然後對基材 進行退火步驟以使塗層變成氧化鎢薄膜，其中加熱的參數 係設定第一升溫速率為從室溫升溫至35(rc/1〇分鐘；第二 升溫速率為從35〇t升溫至450。(：/5分鐘；恆溫加熱條件 為450°C維持30分鐘；以及降溫至室溫。 從掃描式電子顯微鏡（SEM)(JE0L JSM-6700或 JSM-7000)的結果（附件丨）可知，實施例丨之氧化鎢薄膜（形 成在FT0基材上）為具有孔洞的薄膜。 實施例2 氧化鎢薄膜的形成方法與實施例1相似，其中係以尿 201215653* I w〇jU6rM a metal sulfate, the first metal barium acetate metal may, for example, include crane, nickel, demon, ^, _, and 'in which, for example, in some embodiments, silver or Combination of the above. The first precursor used may include zinc powder splitting, nickel oxide thin, or a combination thereof. In some embodiments, the composition is: nickel acid, nickel acetate acetate or the above group: for example, crane powder, tartaric acid crane, sulphate crane, the substrate may comprise glass or transparent conductive (ITO), tin oxide fluoride (FT 〇 )and many more. The weight of the first precursor such as indium tin oxide: the weight of the fuel - then the weight of the precursor: the weight of the fuel. In the first example used in the second embodiment, the formation of oxidation n _ 1 2; ^ 64. The amount of the fuel: the weight of the fuel may be 1:0.3~U of the weight of the heavy fuel used in the first precursor: the weight of the solvent may be: 0 01~100 in some examples of forming a nickel oxide film In the case of medium cattle, the weight of the solvent may be 1:0.03~40#, and the fuel may be included in the examples. The second doping impurity may, for example, comprise a second gold plum, a second metal: acid = ::: salt, a second metal acetate or a group of the above: comprising r nickel, titanium, zinc, copper, silver or the like Combination: The weight system of the second: using a second push 夂 = = can form a doped ed) metal oxide film, such as a doped oxygen t 5 201215653 film or a doped tungsten oxide film and the like. In an embodiment, the method of preparing the coating is to place a material such as a first precursor with a volume (and a second precursor) in a container, and stir it in. The reading is placed at - (4) To (4) evenly mixed (four) can be less than - hour, in some specific examples, the French system is fast! Even if the coating material has excellent stability and good scratching, it can still exhibit reproducibility when used for forming oxides for a long period of time, for example, more than 24 hours. In the embodiment, the temperature of the annealing step may be 3G (rc to other. C. In some examples of forming an oxide film, the annealing step is actually two J ° 350c to 45 (rc. In the example, the temperature of the annealing step may be, for example, 3G (TC to 5 pits, the time of the annealing process may be 1 minute to 6 hours, and the time of the season is preferably 1 minute to 60 minutes. In some embodiments, when the first precursor is tungsten powder, the solvent is 雔2' fuel system thiourea, the weight of the first precursor: the weight of the fuel. 4~2' the weight of the fuel: the weight of the solvent :, the temperature is 425t to 550〇Γ Β, Ρ · 15 25 'annealing step 60 eight shovel yinyang 1 step township time is 10 minutes to the crane film is - cracked oxidized crane film. Medium, when. - Precursor system tungsten material sulfur service 'the weight of the first precursor: fuel = °.4'The weight of the fuel: the weight of the solvent, the ratio ~25, the annealing temperature of 6 201215653 The temperature is 4253⁄4 to 550. (:, and the annealed ore is 60 minutes, the yttrium oxide film is the pupil =; t Between the minute or the oxidized crane _ has a crystalline phase. The damper is bonded to the film. In the second yoke case, when the first precursor is in the oxygen water 'fuel system sulfur suit, the weight of the first precursor is 0.^0 -4 1:15: 5 ΪΗ'1: Temperature _ to 425t, annealing step = step minutes, the oxide is a flat yttria film, 〇; = film has an amorphous phase. In some embodiments, when the first precursor is in the ancient ~ oxygen water, the fuel system exhibits the weight of the first precursor (5) ~ 0.4' the weight of the fuel: the weight of the solvent is the weight of the branch 425 〇C to 55 (TC, annealing step annealing step (9) minutes... film is - flat minutes for some examples, when the first precursor is oxygen water, the fuel is glycine, the first precursor is the heavy valley Secret double 1 non, the weight of the other object 1: the weight of the fuel is 1:0.2~0.4, the weight of the fuel: the weight of the solvent is '1: the temperature of the step Delays pit train 4 to 5, the annealing step is time to transfer i〇j 6〇 / bell t, Yan oxide thin film is a thin film of tungsten oxide having a blade hole. In the first example, when the first precursor is a crane powder, the solvent is a double emulsion, and the weight of the first precursor of the sulphuric acid sulphuric acid: fuel, 1:0.2~0.4' fuel Weight: The weight of the solvent is Hu. The temperature of the shoe is simple. The time of the annealing step is 1 minute. The oxidized crane film is a yttria film with holes. The oxidized film of the embodiment of the invention has excellent electrochromic properties, and is suitable for various electrochromic components such as smart windows, electrochromic glass, discolored sunglasses, and discoloration. Automotive rearview mirrors, display panels, electronic paper displays, etc. 'In addition, it can also be applied to solar cells, semiconductors and other industries. Specific examples of forming an oxidized crane film are exemplified below, and analysis results of the tungsten oxide film are described. Embodiment 1 A method of forming a tungsten oxide film includes the following steps. First, 15 g of tungsten powder (Merk) was dissolved in 9 m of 30% hydrogen peroxide (Sigma-AMdch) and 1 ml of deionized water (volume of hydrogen peroxide: volume of water: 9:1), and then 45 g of thiourea (Sigma). It was added to the above solution (weight of tungsten powder: weight of water plus hydrogen peroxide: weight of thiourea 1:6:0.3), and then the solution was stirred until the solvent was volatilized to a weight of 4 to 5 g of the solution, whereby a coating material was obtained. The coating was spin-coated on an ITO or FTO substrate (ITO coated glass or FTO coated glass (Solarnix; sheet resistance: 8Q/sq)) to form a coating. The substrate is then annealed to form the coating into a tungsten oxide film, wherein the heating parameter sets the first heating rate to rise from room temperature to 35 (rc/1 〇 minutes; the second heating rate is from 35 〇t) To 450. (: 5 minutes; constant temperature heating condition is maintained at 450 ° C for 30 minutes; and cooling to room temperature. Results from scanning electron microscope (SEM) (JE0L JSM-6700 or JSM-7000) (Attachment 丨) It can be seen that the tungsten oxide film of the example (formed on the FT0 substrate) is a film having pores. Example 2 The method for forming a tungsten oxide film is similar to that of Example 1, in which urine 201215653
, -i wo^uorA 素取代硫脲。SEM的分析結果（附件2)顯示實施例2之氧 化鎢薄膜為平整的薄膜。 實施例3 氧化鎢薄膜的形成方法與實施例1相似，其中係以氨 基乙酸取代硫脲。SEM的分析結果（附件3)顯示實施例3 之氧化鎢薄膜為具有孔洞的薄膜。 φ 實施例4 氧化鎢薄膜的形成方法與實施例1相似，其中係以檸 檬酸取代硫脲。SEM的分析結果（附件4)顯示實施例4之 氧化鎢薄膜為具有孔洞的薄膜。 實施例5 氧化鎢薄膜的形成方法與實施例1相似，其中鎢粉的 重量：水加雙氧水的重量：硫腺的重量係改成1:6:0.81。 • SEM的分析結果（附件5)顯示實施例5之氧化鎢薄膜為具 有裂縫的薄膜。 實施例6 氧化鎢薄膜的形成方法與實施例1相似，其中鎢粉的 重量：水加雙氧水的重量：硫脲的重量係改成1:6:0.4。SEM 的分析結果（附件6)顯示實施例6之氧化鎢薄膜為為具有 孔洞的薄膜。 201215653 實施例7 ' 1 氧化鎢薄膜的形成方法與實施例丨相似，其中退火步 驟的溫度係改成40(TC，亦即，參數係設定第一升溫速$ 為從室溫升溫至35G°C/1G分鐘；第二升溫速率為從3筑 升溫至400Ϊ/5分鐘；恆溫加熱條件為4〇〇(t維持分 鐘；以及降溫至室溫。SEM的分析結果（附件7)顯示實方刀包 例7之氧化鎢薄膜為為平整的薄膜。 實施例8 氧化鎢薄膜的形成方法與實施例丨相似，其中退火步 驟的溫度係改成50(TC。SEM的分析結果（附件8)顯示實 施例8之氧化鎢薄膜為具有孔洞的薄膜。 比較例 氧化鎢薄膜的形成方法與實施例1相似，其中塗料中 並未添加硫脲。SEM的分析結果（附件9)顯示比較例之氧 化鶴薄膜為平整的薄膜。 薄膜結構性質分析 第1圖顯示單斜晶系氧化鎢（W03)的繞射資料 (ICDD-PDF No. 01-072-0677)，與 ITO 基材、實施例卜實 施例7與比較例之試片（氧化鎢薄膜形成在ITO基材上）的 X-光繞射（XRD)(Rigaku DMAX-2000/PC)圖譜。第 2 圖顯 示實施例1、實施例7與比較例之試片的拉曼（JEOL JEM-2100F)圖譜。 201215653 , · I Wt?JWO厂/Λ 從第1圖可知，實施例1與比較例的氧化鶴薄膜具有 多晶結構，並含有單斜晶相的氧化鹤薄膜。實施例7㈣ 片僅出現ΙΤΟ基材的波峰。從第2圖可知，拉曼圖譜在8仍 cm·1、714 cm.1、327 cm.1與272 位置出現的散射波峰 驗證了實施例1與比較例的氧化鎢薄膜含有單斜晶相。相 較於實施例1與比較例的拉曼光譜，實施例7試片的拉曼 光譜在805 cm·1、714 cm—1、位置出現的波峰較弱且更寬二 實施例7之試片也以TEM分析（附件1〇)。選區電子 φ 繞射（selected area electron diffraction; SAED)圖案的結果 顯示’實施例7之試片並不具有整齊排列的結晶結構 (well-ordered crystalline structure)，這與 xrd 圖譜及拉曼 圖譜的結果相符。明視野影像(bright-field image; BFI)、暗 視野影像(dark-field image; Dn)與高解析度穿透式電子顯 微鏡(HRTEM)影像皆顯示實施例7的氧化物薄膜含有奈米 晶體氧化鎢（nanocrystalline tungsten oxide)，其平均直徑約 為5nm’且係埋在非結晶氧化鶴基體（arn〇rphous tungsten • 〇xide matrix)中。此外，從SAED圖案與HRTEM影像皆得 到晶格面距（d-spacing)約 0.37〜0.38nm。 薄膜光學性質分析 試片的光學性質可使用三極式系統（three-electrode system)、電致變色（electrochromic; EC)裝置（二電極系統) 與紫外光可見光近紅外光光譜儀（US-VIS-NIR spectrophotometer)(JASCO V-670)進行分析。 三極式系統使用恆壓器（p〇tentiostat)(Autolab， 201215653 I WOJUOTM ；i PGSTAT302N)’ 電解液為 1M 過氣酸链（lithium perchlorate; LiCl〇4)(Sigma-Aldrich)溶液，其中溶劑係丙烯碳酸鹽 (propylene carbonate; PC)(Alfa Aesar)。試片（FTO 基材上形 成有氧化鎢薄膜）、Pt線與Ag/AgCl係分別作為工作 (working)電極、辅助（counter)電極與參考（reference)電極。 電致變色裝置係將ITO相對電極（counter electrode) 與試片（FTO基材上形成有氧化鎢薄膜，氧化鎢薄膜朝向 ITO相對電極）之間設置60μιη厚的融熔性(hot-melt)樹脂間 隔物（Surlyn spacer)(Solaronix，SA)而彼此隔開，並藉由毛 細作用將上述LiC104/PC電解液導入試片與ITO相對電極 之間的空隙中。 在三極式系統或電致變色裝置中，當對試片施加負的 偏壓時’電解液中的Li離子會嵌入透明的氧化鶴（w〇3)薄 膜（附件11)中而變成彩色的氧化鎢（LixW03)薄膜（附件 12)，如以下化學方程式所示： WO, + xLf + LiJVO^ 當對试片施加正的偏壓時，Li離子會從氧化嫣薄膜脫出， 使得彩色的氧化鎢薄膜褪色。 苐3圖、第4圖與第5圖分別顯不實施例1、實施例 7與比較例之試片的光穿透率與穿透率變化 (modulation)。圖中的“初始製備”表示初始製備之試片的光 穿透率曲線。“彩色態，，表示初始製備之試片的氧化鎢薄膜 在藉由三極式系統變色之後的光穿透率曲線。“褪色態，，表 示彩色的氧化鶴薄膜在藉由三極式系統褪色之後的光穿 透率曲線。“穿透率變化，，表示“褪色態，，曲線扣掉“彩色態，， 201215653 曲線之後的結果。 請參考第3圖至第5圖，實施例1、實施例7與比較 例之初始製備的試片對可見光的穿透率皆約80%左右。 請參考第3圖至第5圖，在初始製備之試片的氧化鎢 薄膜與20 mC cnT2的Li離子嵌合而變色之後，光穿透率 下降。舉例來說，比較例之試片對波長632nm之光線的穿 透率下降至25%，實施例1之試片下降至20%，實施例7 之試片甚至下降至10%以下。 φ 請參考第3圖至第5圖，實施例7之試片在彩色的氧 化鎢薄膜褪色之後的光穿透率與初始製備時的結果相 似。實施例1之試片在彩色的氧化鎢薄膜褪色之後的光穿 透率稍微低於初始製備時的結果。而比較例之試片光穿透 率下降的程度又比實施例1更大。因此，舉例來說，在波 長632nm位置之穿透率變化的結果中，實施例7之氧化鎢 薄膜具有最大的量，約70%。 第6圖顯示實施例1、實施例7與比較例之試片藉由 φ 電致變色裝置在10 pAcm_2的固定電流密度下與Li離子反 應過程中的電荷密度（charge density)與光學密度（optical density; 0D)的關係曲線。從曲線的斜率可求得實施例j、 貫施例7與比較例之试片的變色效率（c〇i〇rati〇n ; CE)分別為 6 cri^C·1、37 試片的變色效率明顯高於士私化 與7 cn^C1。實施例7之 向於比較例的試片。, -i wo^uorA replaces thiourea. The analysis result of SEM (Attachment 2) showed that the tungsten oxide film of Example 2 was a flat film. Example 3 A tungsten oxide film was formed in the same manner as in Example 1, in which thiourea was substituted with aminoacetic acid. The analysis result of SEM (Attachment 3) shows that the tungsten oxide film of Example 3 is a film having pores. φ Example 4 A method of forming a tungsten oxide film was similar to that of Example 1, in which thiourea was replaced by citric acid. The analysis result of SEM (Attachment 4) shows that the tungsten oxide film of Example 4 is a film having pores. Example 5 A tungsten oxide film was formed in the same manner as in Example 1, in which the weight of the tungsten powder: the weight of water plus hydrogen peroxide: the weight of the sulfur gland was changed to 1:6:0.81. • The results of the SEM analysis (Attachment 5) show that the tungsten oxide film of Example 5 is a film having cracks. Example 6 A tungsten oxide film was formed in the same manner as in Example 1, in which the weight of the tungsten powder: the weight of water plus hydrogen peroxide: the weight of the thiourea was changed to 1:6:0.4. The analysis result of SEM (Attachment 6) shows that the tungsten oxide film of Example 6 is a film having pores. 201215653 Example 7 '1 The formation method of the tungsten oxide film is similar to that of the embodiment ,, wherein the temperature of the annealing step is changed to 40 (TC, that is, the parameter is set to the first heating rate: the temperature is raised from room temperature to 35 G ° C /1G minutes; the second heating rate is from 3 building temperature to 400 Ϊ / 5 minutes; constant temperature heating condition is 4 〇〇 (t is maintained for minutes; and cooling to room temperature. SEM analysis results (Attachment 7) shows the real knife package The tungsten oxide film of Example 7 was a flat film. Example 8 The method of forming a tungsten oxide film was similar to that of Example ,, in which the temperature of the annealing step was changed to 50 (TC. The analysis result of SEM (Attachment 8) shows an example. The tungsten oxide film of 8 is a film having pores. The formation method of the tungsten oxide film of the comparative example is similar to that of Example 1, in which thiourea is not added to the coating. The analysis result of SEM (Annex 9) shows that the oxide film of the comparative example is Flat film. Analysis of film structure properties Figure 1 shows diffraction data for monoclinic tungsten oxide (W03) (ICDD-PDF No. 01-072-0677), with ITO substrate, Example 7 and Comparative test piece (tungsten oxide film) X-ray diffraction (XRD) (Rigaku DMAX-2000/PC) pattern formed on an ITO substrate. Fig. 2 shows Raman (JEOL JEM- of the test pieces of Example 1, Example 7 and Comparative Example) 2100F) Atlas, 201215653, · I Wt? JWO Plant / Λ As can be seen from Fig. 1, the oxidized crane film of Example 1 and Comparative Example has a polycrystalline structure and contains a monoclinic phase of an oxidized crane film. Example 7 (4) Only the peak of the ruthenium substrate appeared. As can be seen from Fig. 2, the scattering peaks of the Raman spectrum at 8 cm1, 714 cm.1, 327 cm.1 and 272 verify the oxidation of Example 1 and the comparative example. The tungsten film contains a monoclinic phase. Compared with the Raman spectra of Example 1 and the comparative example, the Raman spectrum of the sample of Example 7 is weaker and more at the position of 805 cm·1, 714 cm-1. The test piece of the second embodiment was also analyzed by TEM (Attachment 1〇). The result of the selected area electron diffraction (SAED) pattern showed that the test piece of Example 7 did not have a neatly arranged crystal structure. (well-ordered crystalline structure), which is consistent with the results of the xrd and Raman spectra. (bright-field image; BFI), dark-field image (Dn) and high-resolution transmission electron microscope (HRTEM) images show that the oxide film of Example 7 contains nanocrystalline tungsten oxide (nanocrystalline). Tungsten oxide) has an average diameter of about 5 nm' and is buried in an arn〇rphous tungsten • 〇xide matrix. In addition, the lattice spacing (d-spacing) is about 0.37~0.38 nm from both the SAED pattern and the HRTEM image. The optical properties of the thin film optical property test piece can be measured using a three-electrode system, an electrochromic (EC) device (two-electrode system) and an ultraviolet visible near-infrared spectrometer (US-VIS-NIR). Spectrophotometer) (JASCO V-670) for analysis. The three-pole system uses a constant pressure device (p〇tentiostat) (Autolab, 201215653 I WOJUOTM; i PGSTAT302N)' electrolyte is a 1M lithium perchlorate (LiCl〇4) (Sigma-Aldrich) solution, in which the solvent system Propylene carbonate (PC) (Alfa Aesar). A test piece (a tungsten oxide film is formed on the FTO substrate), a Pt line, and an Ag/AgCl system are used as a working electrode, a counter electrode, and a reference electrode, respectively. The electrochromic device is provided with a 60 μm thick hot-melt resin between an ITO counter electrode and a test piece (a tungsten oxide film is formed on the FTO substrate, and the tungsten oxide film is oriented toward the ITO opposite electrode). Separate spacers (Solaronix, SA) were separated from each other, and the LiC104/PC electrolyte was introduced into the space between the test piece and the opposite electrode of the ITO by capillary action. In a three-pole system or electrochromic device, when a negative bias is applied to the test piece, Li ions in the electrolyte are embedded in a transparent oxide crane (w〇3) film (Attachment 11) and become colored. A tungsten oxide (LixW03) film (Attachment 12), as shown in the following chemical equation: WO, + xLf + LiJVO^ When a positive bias is applied to the test piece, Li ions are removed from the yttrium oxide film, causing color oxidation. The tungsten film fades. Fig. 3, Fig. 4 and Fig. 5 show the light transmittance and transmittance of the test pieces of Example 1, Example 7 and Comparative Example, respectively. The "initial preparation" in the figure indicates the light transmittance curve of the initially prepared test piece. "Color state, which represents the light transmittance curve of the tungsten oxide film of the initially prepared test piece after discoloration by a three-pole system. "Fad color state, indicating that the colored oxide crane film is discolored by a three-pole system. After the light transmittance curve. "Transmission rate change, indicating "faded state, curve deduction" color state, results after 201215653 curve. Please refer to Figures 3 to 5, the initial preparation of Example 1, Example 7 and the comparative example The transmittance of the test piece to visible light is about 80%. Please refer to Fig. 3 to Fig. 5, after the tungsten oxide film of the initially prepared test piece is mixed with 20 mC cnT2 Li ion, the light is worn. The transmittance is decreased. For example, the transmittance of the test piece of the comparative example to the light having a wavelength of 632 nm is lowered to 25%, the test piece of the embodiment 1 is lowered to 20%, and the test piece of the embodiment 7 is even lowered to 10% or less. φ Please refer to Figures 3 to 5, the light transmittance of the test piece of Example 7 after fading of the colored tungsten oxide film is similar to that at the time of initial preparation. The test piece of Example 1 is colored tungsten oxide. The light transmittance after fading of the film was slightly lower than that at the time of initial preparation, and the degree of light transmittance of the test piece of the comparative example was decreased to be greater than that of Example 1. Therefore, for example, it was worn at a wavelength of 632 nm. As a result of the change in permeability, the tungsten oxide film of Example 7 has the most A large amount, about 70%. Fig. 6 shows the charge density of the test piece of Example 1, Example 7 and the comparative example during the reaction with Li ion at a fixed current density of 10 pAcm 2 by a φ electrochromic device ( The relationship between the charge density and the optical density (0D). The color change efficiency of the test piece of Example j, Example 7 and Comparative Example can be obtained from the slope of the curve (c〇i〇rati〇n; CE The color change efficiency of the test pieces of 6 cri^C·1 and 37, respectively, was significantly higher than that of 7 cn^C1. The test piece of the comparative example of Example 7 was used.
1、實施例7與比較例之 電壓持續2〇〇秒以褪色並彩色試片。 的電遂為-3 V時，試片係彩色的。當 * i 201215653 I VVUJUOr/Λ 施加的電/1為3 V g寺’試片係褚色的。第7圆顯示試片在 第一個測試循環中（50秒時施加電壓3 V #色持續200 秒，然後在250秒時施加電壓_3 v彩色）對波長為632 nm 之光線的穿透率。請參照第7圖，結果顯示， 實施例7之 3式片具有最大的穿透率變化，約6〇%，這樣的趨勢與第3 圖至第5圖的結果相符。實施例7的彩色時間與褪色時間 (以穿透率改變40%的時間做定義）分別為8秒與π秒。比 較例之s式片的穿透率變化小於4〇%。 電致變色材料除了變色效率與反應時間，耐久性 (durability)也是需要考量的重要因素。第8圖顯示試片在 50個測試循環期間對波長為632 nm之光線的穿透率。實 施例7之試片在30次彩色/褪色的循環之後，其穿透率變 化仍有40%。實施例1與比較例之試片在少數彩色/褪色的 循環之後，其穿透率變化僅剩約1〇%。這樣的結果顯示實 施例7之試片的耐久性比比較例好。 第9圖、第10圖與第n圖分別顯示實施例〗、實施 例7與比較例之試片藉由三極式系統在（第2次、第ι〇次、 第100次、第500次與第1000次）彩色/褪色循環中被施加 之電壓（voltage)與在此電壓下量測得的電流密度（^^^以 density)的關係（CV曲線）。請參照第.9圖，實施例t之試 片的cv曲線的改變程度不大。請參照第1〇圖，實施例7 之試片的CV曲線雖有改變，然其圍住的面積沒有太大的 變化，這表示實施例7之試片具有良好的可靠性 (reliability)。請參照第11圖，在彩色/掩色循環之後，比 較例之試片的CV曲線圍住的面積有逐漸辯小的趨勢，這 14 2012156531. The voltages of Example 7 and Comparative Example were continued for 2 sec seconds to fade and color test pieces. When the power is -3 V, the test piece is colored. When * i 201215653 I VVUJUOr / 施加 applied electricity / 1 is 3 V g temple 'slices system color. The 7th circle shows the penetration of the test piece in the first test cycle (applying a voltage of 3 V for 50 seconds, color for 200 seconds, then applying voltage _3 v at 250 seconds) to light with a wavelength of 632 nm. . Referring to Fig. 7, the results show that the pattern of Example 7 3 has the largest change in transmittance, about 6 %, which is consistent with the results of Figs. 3 to 5. The color time and fading time of Example 7 (defined by the time when the transmittance was changed by 40%) were 8 seconds and π seconds, respectively. The transmittance of the s-slice of the comparative example was less than 4%. In addition to the color change efficiency and reaction time, the durability of the electrochromic material is also an important factor to be considered. Figure 8 shows the penetration of the test piece with light at a wavelength of 632 nm during 50 test cycles. The test piece of Example 7 had a change in transmittance of 40% after 30 cycles of color/fading. The test pieces of Example 1 and Comparative Example showed only about 1% change in transmittance after a few color/fading cycles. As a result, the durability of the test piece of Example 7 was better than that of the comparative example. Fig. 9, Fig. 10 and Fig. n show the test pieces of the examples, the examples 7 and the comparative examples, respectively, by the three-pole system (the second, the iv, the 100th, the 500th). The relationship between the voltage applied in the 1000th color/fade cycle and the current density measured at this voltage (^^^density) (CV curve). Referring to Fig. 9, the cv curve of the test piece of Example t is not changed to a large extent. Referring to Fig. 1, the CV curve of the test piece of Example 7 was changed, but the area enclosed therein did not change much, which indicates that the test piece of Example 7 had good reliability. Please refer to Fig. 11. After the color/color masking cycle, the area enclosed by the CV curve of the test piece of the comparative example has a tendency to gradually become smaller. This 14 201215653
, - i wojuorA 表示比較例之試片的可靠性不佳。 智慧型窗戶 第12圖繪不應用氧化鎢薄膜之智慧型窗戶的示意 圖。第13圖顯不應用氧化鎢薄膜之智慧型窗戶亮態的j_v 曲線。第14圖顯不應用氧化鎢薄膜之智慧型窗戶在短路 狀悲下，被父替地照光（light〇n)與不照光(light〇f〇時的穿 透率變化。請參照第12圖，智慧型窗戶包括相對的IT0 •基板2與FT〇基板4。氧化鎢薄膜6與Pt薄膜8設置在 FTO基板4上。Pt薄獏8環繞住氧化鎢薄膜6。由Ti〇2 奈米顆粒10構成的薄獏設置在IT〇基板2上。Ti〇2奈米 顆粒10吸附有染料12(N719 dye)。電解液14(含有0.5 Μ Lil與5 mM I!的丙烯碳酸鹽溶液）設置在ΙΤ〇基板2與ft〇 基板4之間。智慧型窗戶係應用染料敏化型太陽能電池。 從第13圖的結果可知’智慧型窗戶的開路電壓（v〇c)係〇 22 V。短路電流密度（Jsc)係2.13 mA。填充因子（f ρ)係0.27。 • 轉換效率（efficiency)係0.12(%)。從第14圖的結果可知， 智慧型窗戶在照光的情況下具有低的光穿透率。在沒有照 光的情況下具有高的光穿透率。 實施例9 此例係形成氧化鎳薄膜。氧化鎳薄膜的形成方法與實 施例1相似’其中塗料中的第一前驅物係醋酸鎳，燃料係 尿素。醋酸鎳的重量：水加雙氧水的重量：尿素的重量係 1:0.1.5.66。SEM的分析結果（附件13、14)顯示實施例9, - i wojuorA indicates that the test piece of the comparative example is not reliable. Smart Window Figure 12 depicts a schematic of a smart window that does not use a tungsten oxide film. Figure 13 shows the j_v curve of the smart window bright state of the tungsten oxide film. Figure 14 shows that the smart window with no tungsten oxide film is under the short-circuited sadness, and the light transmittance is changed by the light (n) and the light (the light transmittance is changed. Please refer to Figure 12, The smart window includes an opposite IT0 • substrate 2 and FT 〇 substrate 4. The tungsten oxide film 6 and the Pt film 8 are disposed on the FTO substrate 4. The Pt thin layer 8 surrounds the tungsten oxide film 6. From the Ti 2 nanoparticle 10 The thin crucible is disposed on the IT crucible substrate 2. The Ti 2 nanoparticle 10 is adsorbed with a dye 12 (N719 dye). The electrolyte 14 (a propylene carbonate solution containing 0.5 Μ Lil and 5 mM I!) is placed in the crucible. Between the substrate 2 and the ft substrate 4. The smart window uses a dye-sensitized solar cell. From the results of Fig. 13, the open circuit voltage (v〇c) of the smart window is 〇22 V. Short-circuit current density (Jsc) is 2.13 mA. The fill factor (f ρ) is 0.27. • The conversion efficiency (efficiency) is 0.12 (%). From the results of Fig. 14, the smart window has low light penetration in the case of illumination. Rate. Has high light transmittance without illumination. Example 9 This example forms thin nickel oxide The nickel oxide film is formed in a similar manner to that of Example 1 wherein the first precursor in the coating is nickel acetate, and the fuel is urea. The weight of nickel acetate: the weight of water plus hydrogen peroxide: the weight of urea is 1:0.1.5.66. The analysis results of SEM (Annex 13, 14) show Example 9.
' I 201215653 之氧化鎳薄膜為平整的薄膜。 實施例10 氧化鎳薄膜的形成方法與實施例丨相似，其中塗料中 的第一前驅物係硝酸鎳。硝酸鎳的重量：水加雙氧水的重 量：硫脲的重量係1:0.1:3.44。 第15圖顯示使用電致變色裝置對實施例】〇之試片反 覆施加正、負電壓持續600秒以褪色並彩色試片。第Μ 圖顯示實施例10之試片藉由電致變色裝置在5〇 pAcm·2 的固定電流密度下與OH離子反應過程中的電荷密度與光 學密度的關係曲線。從曲線的斜率可求得實施例1(^之試 片的變色效率為28 cn^CT1。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟悉此項技藝者，在不脫離本發明之精 2和範圍内，當可做些許更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 第1圖顯示單斜晶系氧化鎢的繞射資料，與Ιτ〇基 材、實施例卜實施例7與比較例之試片的χ.·光繞射圖譜。 第2圖顯示實施例1、實施例7與比較例之試片的拉 曼圖譜。 第3圖顯示實施例1之试片的光穿透率與穿透率變 化。 弟4圖顯示貫施例7之試片的光穿透率與穿透率變 201215653The nickel oxide film of '201215653 is a flat film. Example 10 A nickel oxide film was formed in a similar manner to Example ,, in which the first precursor in the coating was nickel nitrate. Weight of nickel nitrate: weight of water plus hydrogen peroxide: The weight of thiourea is 1:0.1:3.44. Fig. 15 shows the use of an electrochromic device to apply a positive and negative voltage to the test piece of Example 反 for 600 seconds to fade and color the test piece. Fig. 1 is a graph showing the relationship between the charge density and the optical density in the reaction of the test piece of Example 10 with an OH ion at a fixed current density of 5 〇 pAcm·2 by an electrochromic device. From the slope of the curve, the color change efficiency of the test piece of Example 1 can be determined to be 28 cn^CT1. Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention, and any skill is familiar to the art. The scope of protection of the present invention is subject to the definition of the scope of the appended claims, without departing from the spirit and scope of the invention. The figure shows the diffraction data of monoclinic tungsten oxide, the 绕τ〇 substrate, the sample of Example 7 and the test piece of the comparative example, the light diffraction pattern. The second figure shows the embodiment 1, the embodiment 7: Raman spectrum of the test piece of the comparative example. Fig. 3 shows the change of the light transmittance and the transmittance of the test piece of Example 1. The figure 4 shows the light transmittance of the test piece of Example 7. Penetration rate change 201215653
. r l W03U6KA 化。 第5圖顯示比較例之試片的光穿透率與穿透率變化。 第6圖顯示實施例1、實施例7與比較例之試片的電 荷密度與光學密度的關係曲線。 第7圖顯示實施例1、實施例7與比較例之試片在第 一個測試循環中對波長為632 nm之光線的穿透率。 第8圖顯示實施例1、實施例7與比較例之試片在5〇 個測試循環期間對波長為632 nm之光線的穿透率。 鲁第9圖顯示實施例1之試片在彩色/褪色循環中電壓與 電流密度的關係。 第10圖顯示實施例7之試片在彩色/褪色循環中電壓 與電流密度的關係。 第Π圖顯示比較例之試片在彩色/褪色循環中電壓與 電>’IL也、度的關係。 第12圖繪示應用氧化鎢薄膜之智慧型窗戶的示意圖。 第13圖顯示應用氧化鎢薄膜之智慧型窗戶於亮態的 鲁 J-V曲線。 第14圖顯示應用氧化鎢薄膜之智慧型窗戶在短路狀 態下，被交替地照光與不照光時的穿透率變化。 第15圖顯示實施例10在測試循環中對光線的穿透 坪t 〇 學密度 第16圖顯示實施例10之試片的電荷密度與光 的關係曲線。 【主要元件符號說明】 201215653 1 wcuuor/\ 2 : ITO基板 4 : FTO基板 6 :氧化鎢薄膜 8 : Pt薄膜 10 : Ti02奈米顆粒 12 :染料 14 :電解液. r l W03U6KA. Fig. 5 shows changes in light transmittance and transmittance of the test piece of the comparative example. Fig. 6 is a graph showing the relationship between the charge density and the optical density of the test pieces of Example 1, Example 7 and Comparative Example. Fig. 7 shows the transmittance of the test pieces of Example 1, Example 7 and Comparative Example in the first test cycle for light having a wavelength of 632 nm. Fig. 8 shows the transmittance of the test pieces of Example 1, Example 7 and Comparative Example for light having a wavelength of 632 nm during 5 测试 test cycles. Lu Figure 9 shows the relationship between voltage and current density in the color/fade cycle of the test piece of Example 1. Fig. 10 is a graph showing the relationship between voltage and current density in the color/fading cycle of the test piece of Example 7. The figure shows the relationship between the voltage and the electric >' IL in the color/fading cycle of the test piece of the comparative example. Figure 12 is a schematic view showing a smart window using a tungsten oxide film. Figure 13 shows the Lu J-V curve of a smart window using a tungsten oxide film in a bright state. Fig. 14 shows the change in the transmittance of the smart window using the tungsten oxide film in the short-circuit state when it is alternately illuminated and not illuminated. Fig. 15 is a view showing the penetration of light in the test cycle in Example 10. The density of the test piece shows the relationship between the charge density and the light of the test piece of Example 10. [Main component symbol description] 201215653 1 wcuuor/\ 2 : ITO substrate 4 : FTO substrate 6 : Tungsten oxide film 8 : Pt film 10 : Ti02 nano particle 12 : Dye 14 : Electrolyte