200913073 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種銦錫氧化物膜制、木 為兩段式結晶成膜製程，主要藉以 衣&方法，稱之 佳、阻值變化率較*，以及更^ ^耐候性及均勻性較 氧化物膜層及具有特定阻值及/式 用上更耐久的銦錫 結構，尤其適用於觸控螢幕結構中〜之銦錫氧化物膜層 【先前技術】 =化：(Indium Tin 〇xide，ιτ〇)透明導_ 為目刖具有研九與經濟價值的熱門產物之— 、： 2圍包括有：車用液晶顯示器、觸控面板、隔磁 玻璃、液晶手錶、家電用品液晶面板、太陽電池、攜帶式 液晶電玩、量測儀器用之顯示器、液晶彩色電視、筆記〇 個士電腦、攜帶型個人電腦、電漿顯示器(pDp)、EL、液晶 顯示益（LCD) ’以及彩色渡鏡用之電極等等。 至於，ιτο本身係為氧化銦中換混（d〇pe)少量的氧化 錫而組成，使錫原子取代氧化銦結構中部分的錮原子，所-以就其整體結構組成還是以氧化銦GmO3)為主，屬於一種 氧化物半導體材料，不但有高的能隙（bandgapEgg2. 9#) 讓可見光穿透，更有尚濃度的導電載子（carrier)及移動率 (mobility);當然，依照其本身的導電性不同，所應用的 範圍也跟著有所差異。ΙΤ0膜層的導電特性主要來自於錫 摻混（tin doping)及氧空缺（〇xygeri vacancy)兩種帶電 載子（charge carrier) ’而若控制在固定的錫摻混量的狀 200913073 所⑽氧空缺在讓層中， &自m卜真補，使得鍵結之兩個電子釋出形 方犬m 缺亦以n型施體（n,e d_r)的 氧化物之導電性。氧空缺濃度會擔鍍 製私條件所影響，例如真空程度及 影響整體™薄膜的帶電程度及電^ 曰 加：二場針對IT0透明導電膜層的需求曰漸增 當務之急Cr:性優良的製備方式已成為 層的既有習知方法前-種用以製造1το膜 習知方法主要先將透二又式結晶成膜製程。此既有 高溫下加熱貝璃基板以200〜說的 (一)内進行再:^ 玻璃基板上形成結晶ΙΤ0膜層。接者瞻一 ’- 曰ΠΌ膜習用技術係彻高溫频的方式獲得之結 二電性佳，導致若欲達到特 且其表面粗輪度之太薄僅可達約5至2〇, 因此導致不耐刮、不耐二為0.2〜0.5nm，不夠粗糙， 受到高溫高濕環境影二:::使== =觸=於觸控螢幕時會形成發散現象，:法】 迷S用技術係利用一段式έ士晶成膜贺敍的古 =!:用:形成低電阻值之_層= 犯圍’尤其適用於形成約2GG歐姆者，但是若欲形成 200913073 較高阻值的ΙΤ0膜層則遭遇困難。 尤其，上述習用技術係必須先將玻璃基板於高溫快速 加熱及濺鍍之後，再快速降溫冷卻，使得玻璃基板的強度 經過高溫後的快速降溫而變弱，而且高溫濺鍍的溫度超過 塑膠基材可以容忍範圍，因此更不剌於塑膠基材，反而 使其適用範圍受到嚴重限制。 【發明内容】 一本發明係之主要目的即在提供一種用以獲致耐候性及 均勻性較佳、電阻值變化率較低，以及更刺，使用上更 耐久的ΙΤ0膜層的製造方法，尤其是適用於觸控式螢幕之 ΙΤ0膜層，為達上揭目的，主要係將基板以不預熱方式處理 之後，再於濺鍍艙體（Chamber)内以不加熱的製程條件下 (或低於前述習知200〜40(TC的溫度）進行ΙΤ0濺鍍處理令 IT0膜層成為非結晶狀態，之後再以熱處理方式，使ΙΤ0膜 層轉成為結晶狀態，稱之為兩段式結日日日成膜製程。 、本發明之功效之一 ’在於本發明不需將基板高溫加熱 且’賤錢處理及快速冷卻’因此無改變強度的問題，當然能 夠保持基板原有的強度。 本發明之功效之二，在於本發明所形成的ΙΤ〇膜層於濺 錢艙體不加熱的製程條件下雜處理後先為非結晶狀態， ^後再以熱處理使其成為結晶狀態 ，因此氧空缺濃度比一 ^式結晶成膜製程的ΙΤ0膜層為低，因此較不受溼熱影響 k耐候性較佳）’整體ΙΤ0膜層均勻性較佳（即改善ΙΤ0膜層 均句性）、電阻值變化率較小。 200913073 μ ίίΐί功效之三，在於本發明所形成的1TQ膜.士曰 程度較為：全且緻密，晶粒的大小相對較大，ιτ〇膜；：： ^相對較為粗f造，當然耐磨較好，因此更耐刮，使^ = 【實施方式】 而獲可參閱本案圖式及實施例之詳細說明 本發明主·露—㈣以獲致耐候性 層W方法，㈣時配合參照第二圖所示 ^ 臈層製造方法係依序包括有下列程序： 月之1το a. 製備-基板，該基板可為—透明基板，而 ,可選㈣璃基板或塑膠基板；該玻璃基板係以鈉驗= U〇daLimeGlass)或石英玻璃為佳；該塑膠基板 係選自聚碳酸S旨樹脂類（PC ’ pQlycarb_te)、聚 酸甲酷（眶）、聚對苯二甲酸乙二醇醋⑽），尤 碟酸醋樹賴為佳；麵基板部分係先將㈣好的*璃= 材用洗劑清洗，以清除玻璃基材表面的油潰及灰塵—玻$ 基材以去離子水洗淨，將殘留在玻璃基材表面的洗劑與不 純物清除4將清洗後之玻璃基材以乾燥清潔之空氣（&Α) 吹乾’避免玻璃基材上有「水潰」的殘留，同時也可清除 基材表面的灰塵—以熱風刀烘乾，再次確保水氣不會殘留 S將吹乾之玻璃基板妥為保存，以備使用。 b. 在基板表面進行錮錫氧化物（indium Tin Oxide， 200913073 ΙΤ0)膜層之建構處理；於實施時，係於濺鍍艙體（Chamber) 不加熱的製程條件下（或低於前述習知200〜400°C的溫 度），採用濺鍍（sputter)的方式在基板表面上建構ΙΤ0膜 層，形成一半成品’此時之ΙΤ0膜層是為非結晶狀態。其 中’基板於進行銦錫氧化物（Indium Tin Oxide，ΙΤ0)膜 層之建構處理之前可不預熱。 c.熱處理’將該半成品置入或經過一加熱裝置（例如 烘箱）於一預特定溫度下處理’此時可依據上述不同的基 板進行不同的加熱條件，而形成不同結晶方式的IT〇膜 層：（1)於玻璃基板形成一結晶狀態的ΙΤ〇膜層，係並以 150〜40(TC，尤其以300〜400°C為佳，進行〇. 5〜3小時的熱 處理；（2)於塑膠基板形成另一結晶狀態IT〇膜層，係以低 於2〇(rc，尤其以100〜160。(；為佳，進行1〇分鐘~2小時的 熱處理；經過以上兩種方式（1)或（2)的方式熱處理後，即 可獲致具有特定導電性的結晶狀態IT〇膜層，此為一成 品；如前所述’此兩段式結晶成膜製程之成品比一段式结 f成膜製程產品氧空缺濃度較低，因此受外界環境例如高 :、及座氣的影響小，财候性及耐久性佳；進而電阻值變化 率小，導致整片ΙΤ0薄膜之均勻性佳。爯去 成品規格條件下，與習知-段式結晶成臈製程 =結晶成㈣狀™膜層結晶㈣較騎密，晶粒大 小相對較大，表面也相對較為粗輪，絲面粒糙 可達為0.4〜1.2nm，因此更耐刮，使用上更耐久: 由於’習知採用-段式結晶賴製財 層，需將玻璃基板以德高溫加熱並於^賤二膜 200913073 快速降溫冷卻，造成玻璃基板歷麵高溫後的快速泠卻f 序，因此玻璃的強度變弱；而且高趨加熱溫度超過一基 材可以容忍範圍’因此不適用於塑膠基材。至於，本新發 明所採用之兩段式結晶成膜方式，是ς濺鍍後，、缓慢且穩 處理使ITQ膜結晶，因此μ將基板高溫雜及快 速降’因此無改變強度的問題。 知用兩段式結晶成膜製程所備製的IT0膜層，1⑽ 膜層的電阻值範圍可達到約調至咖歐姆的範圍，，、尤立 更可適用約400至600歐姆的範圍。再者，本發明所形^ 之ιτο膜層之膜厚範圍可達約15至5〇nm ’尤其更可適用 約20至35nm的範圍。 依據本發明之兩段式結晶成膜製程所形成之一具ιτ〇 膜層之結構體，是於玻璃基板上形成ιτ〇膜層，而兮ιτο 膜層具有電阻值約200至1500歐姆及/或膜厚約15至 50mn。而該結構體可進一步應用於觸控螢幕結構中。 本發明之技術内容及技術特點巳揭示如上，然而熟系 本項技術之人士仍可能基於本發明之揭示而作各種不背離 本案發明精神之替換及修飾。因此，本發明之保護範^應 不限於實施例所揭示者，而應包括各種不背離本發^之替 換及修飾，並為以下之申請專利範圍所涵蓋。 曰 200913073 【圖式簡單說明】 第一圖係為習知利用一段式結晶成膜製造銦錫氧化物透明 導電薄膜之製造流程。 第二圖係為本發明之製造流程。 【主要元件代表符號說明】 無200913073 IX. Description of the invention: [Technical field of the invention] The present invention relates to an indium tin oxide film system and a two-stage crystal film forming process, which is mainly referred to by the clothing & method, which is said to be good and the rate of change of resistance Compared with *, and more than the weathering and uniformity of the oxide film layer and the indium tin structure with a specific resistance and / / more durable, especially suitable for the indium tin oxide film layer in the touch screen structure [Prior technology] = (Indium Tin 〇xide, ιτ〇) transparent guide _ for the purpose of witnessing the nine products and economic value of the popular products -,: 2 surrounded by: automotive LCD, touch panel, separated Magnetic glass, liquid crystal watch, home appliance liquid crystal panel, solar cell, portable liquid crystal video game, display instrument for measuring instrument, liquid crystal color TV, note-taking computer, portable personal computer, plasma display (pDp), EL, Liquid crystal display (LCD) 'and electrodes for color mirrors and so on. As for the ιτο itself, it is composed of a small amount of tin oxide in the indium oxide, so that the tin atom replaces a part of the ruthenium atom in the indium oxide structure, so that the overall structural composition is also indium oxide GmO3) Mainly, belonging to an oxide semiconductor material, not only has a high energy gap (bandgapEgg2. 9#), allowing visible light to penetrate, more concentrated conductive carriers and mobility; of course, according to itself The conductivity is different and the range of application is also different. The conductive properties of the ΙΤ0 film layer mainly come from tin doping and oxygen vacancy (charge carrier), and if controlled in a fixed tin blend amount, 200913073 (10) oxygen The vacancy is in the layer, and the sum of the two electrons of the bond is also the conductivity of the oxide of the n-type donor (n, e d_r). The oxygen vacancy concentration will be affected by the plating conditions, such as the degree of vacuum and the degree of electrification of the overall TM film and the addition of electricity: the demand for the IT0 transparent conductive film layer is increasing. The Ur: Cr: Excellent preparation method The prior art method that has become a layer is a conventional method for manufacturing a 1τ film. The heating of the glass substrate at a high temperature is carried out in a 200-degree (1) manner: a film layer of crystallization 形成0 is formed on the glass substrate. The pick-up is a '- 曰ΠΌ 习 习 系 系 系 系 系 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温 高温Not scratch-resistant, not resistant to 0.2~0.5nm, not rough enough, subject to high temperature and high humidity environment 2::: make == = touch = will form divergence when touch screen,: method] Fan S technology department Using a piece of gentleman crystal to form a film of Hexu's ancient =!: Use: to form a low resistance value of _ layer = guilty is especially suitable for the formation of about 2GG ohms, but if you want to form a higher resistance 20090 film layer of 200913073 Then encounter difficulties. In particular, the above-mentioned conventional technology must first rapidly cool and sputter the glass substrate at a high temperature, and then rapidly cool down and cool, so that the strength of the glass substrate is weakened by rapid cooling after high temperature, and the temperature of the high temperature sputtering exceeds the plastic substrate. It can tolerate the range, so it is not confined to the plastic substrate, but its scope of application is severely limited. SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for producing a ΙΤ0 film layer which is excellent in weather resistance and uniformity, has a low rate of change in resistance value, and is more thorny and more durable in use, especially It is suitable for the ΙΤ0 film layer of the touch screen. It is mainly for the purpose of not preheating the substrate, and then in the non-heating process under the sputtering chamber (or low) In the above-mentioned conventional 200 to 40 (temperature of TC), the ΙΤ0 sputtering treatment is performed to make the IT0 film layer amorphous, and then the ΙΤ0 film layer is converted into a crystalline state by heat treatment, which is called a two-stage knot day. The invention has the advantages of the present invention. In the present invention, the substrate does not need to be heated at a high temperature and the 'money treatment and rapid cooling' does not change the strength, and of course the original strength of the substrate can be maintained. The second effect is that the ruthenium film layer formed by the invention is in a non-crystalline state after the miscellaneous treatment under the process condition that the splash chamber is not heated, and then is heat treated to become a crystalline state, so oxygen The vacancy concentration is lower than that of the ΙΤ0 film layer of the crystallization process, so it is less affected by the damp heat, k is more weather resistant.) The overall ΙΤ0 film layer uniformity is better (ie, the ΙΤ0 film layer uniformity), resistance The rate of change of value is small. The third effect of 200913073 μ ίίΐί lies in the 1TQ film formed by the invention. The degree of gentry is relatively: full and dense, the size of the crystal grain is relatively large, and the film is relatively thick, and the wear resistance is relatively high. It is better, so it is more scratch-resistant, so that it can be referred to the drawings and the detailed description of the embodiments. The present invention is mainly disclosed in the present invention to obtain the weather-resistant layer W method, and (4) with reference to the second figure. The method for manufacturing the layer includes the following procedures: 1 το a. Preparation - substrate, the substrate can be a transparent substrate, and optionally a (four) glass substrate or a plastic substrate; the glass substrate is determined by sodium = U〇daLimeGlass) or quartz glass is preferred; the plastic substrate is selected from the group consisting of polycarbonates (PC ' pQlycarb_te), polyacids (眶), and polyethylene terephthalate (10). The sour vinegar tree is preferred; the surface of the substrate is first cleaned with (4) good * glass = material to remove the oil from the surface of the glass substrate and dust - glass $ substrate washed with deionized water, will remain The lotion on the surface of the glass substrate and the removal of impurities 4 will be cleaned The glass substrate is dried with a dry and clean air (&Α) to avoid the residue of “water collapse” on the glass substrate, and also to remove the dust on the surface of the substrate—to dry with a hot air knife to ensure the moisture again. Residual S will dry the glass substrate properly for use. b. The construction of the indium Tin Oxide (200913073 ΙΤ0) film layer on the surface of the substrate; in the implementation process, under the process condition that the sputtering chamber is not heated (or lower than the above-mentioned conventional At a temperature of 200 to 400 ° C, a ΙΤ0 film layer is formed on the surface of the substrate by sputtering to form a half-finished product. At this time, the 膜0 film layer is in an amorphous state. The 'substrate' may not be preheated prior to the construction process of the indium tin oxide (Indium Tin Oxide) layer. c. Heat treatment 'The semi-finished product is placed in or processed by a heating device (for example, an oven) at a pre-specified temperature. At this time, different heating conditions can be performed according to the different substrates described above, and an IT film layer of different crystal forms can be formed. : (1) forming a crystalline film layer on the glass substrate, preferably 150 to 40 (TC, especially 300 to 400 ° C, for 5 to 3 hours of heat treatment; (2) The plastic substrate forms another crystalline state IT film layer, which is less than 2 〇 (rc, especially 100 to 160. (; preferably, heat treatment is performed for 1 ~ to 2 hours; after the above two methods (1) Or after the heat treatment in the manner of (2), the crystalline ruthenium film layer having a specific conductivity can be obtained, which is a finished product; as described above, the finished product of the two-stage crystallized film-forming process is formed into a one-piece type The membrane process product has a low oxygen vacancy concentration, so it is less affected by the external environment, such as high: and seat gas, and has good finance and durability; and the resistance value change rate is small, resulting in good uniformity of the whole film. Under the conditions of the finished product, it is crystallized with the conventional-stage臈Processing = crystallized into (four) shaped TM film layer crystallization (4) is more dense than riding, the grain size is relatively large, the surface is relatively thicker, the surface roughness of the silk surface can be 0.4~1.2nm, so it is more scratch resistant and more used. Durability: Due to the fact that the conventional use of segmental crystallization depends on the financial layer, the glass substrate needs to be heated by the high temperature and cooled rapidly by the high temperature of the film, which causes the rapid deterioration of the glass substrate after the high temperature. The strength of the glass becomes weak; and the high heating temperature exceeds a substrate tolerable range', so it is not suitable for plastic substrates. As for the two-stage crystal film formation method adopted by the new invention, after sputtering, Slow and stable treatment makes the ITQ film crystallize, so μ will high temperature and fast drop of the substrate. Therefore, there is no problem of changing the strength. Knowing the resistance value range of the ICO film layer prepared by the two-stage crystal film forming process, 1(10) film layer It can be adjusted to the range of about 805 ohms, and the erect can be applied to the range of about 400 to 600 ohms. Furthermore, the film thickness of the ιτ film layer of the present invention can reach about 15 to 5 〇 nm. Especially suitable for the range of about 20 to 35 nm According to the two-stage crystal film forming process of the present invention, the structure having the ιτ〇 film layer is formed on the glass substrate, and the 兮ιτο film layer has a resistance value of about 200 to 1500 ohms and/or Or the film thickness is about 15 to 50 mn. The structure can be further applied to the touch screen structure. The technical content and technical features of the present invention are disclosed above, but those skilled in the art may still be based on the disclosure of the present invention. The present invention is not limited to the scope of the invention, and the invention is not limited to the embodiments disclosed, but includes various alternatives and modifications without departing from the scope of the invention. Covered 曰200913073 [Simple description of the diagram] The first diagram is a manufacturing process for manufacturing a transparent conductive film of indium tin oxide by one-stage crystallized film formation. The second figure is the manufacturing process of the present invention. [Main component representative symbol description]