TWI228544B - Method for forming transparent conducting oxide film by arc ion plating - Google Patents
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1228544 五、發明說明（1) 發明所屬之技術領域 本發明係有關於一種开彡A、泰 係-種利用陰極電弧離子^ ，電薄膜之方法，特別 法。 …、鑛法形成透明導電薄膜之方 先前技術 f ! m快速流動、知識***的時代，_、薄、 ^ ^ ^ ^ 』^缺的要素，其中，平面顯干 态被廣泛地應用在各種場人， ^ Τ 卞卸-員不 笙π太〇 门士 每口 如通訊、資訊、消費性電子 寻3Ch口，同％也在辦公室及生產自動化· ··等扮演益 可或缺的角色。由於平面顯干哭比H 、…、 # ^ 'g 'Μ -V' ^ ^ ”、、員不w白疋利用電氣訊號以控制 J之通過或發射，戶斤以需要有一個透光度良好之 電極（透明導電薄膜）來作為調控之用。 /所謂「透明導電電極」係、為高可見光穿透率且低電阻 係數的導電薄膜材料，一般是指在可見光範圍内（波長 380〜7 6 0⑽）具有80%以上的透光率且電阻係數低於工χ 1〇^Ω .cm的薄膜。近年來透明導電薄膜的應用領域及需 求量不斷地擴大，例如平面顯示面板（Fat DispUy Panel)中的液晶顯示器（Liquid Crystal Display)、電致 發光顯示面板（Electro Luminescence Panel)、電漿顯示 面板（Plasma Display Panel)、場發射顯示器（Field Emission Display)、觸控式面板、太陽電池等電子產品 ^使用透明導電薄膜當作電極材料。未來，隨者3 ◦產業的 蓬勃發展及節約能源的全球趨勢，透明導電薄膜的重要性1228544 V. Description of the invention (1) The technical field to which the invention belongs The present invention relates to a Kai-A, Thai-type-a method using a cathode arc ion ^, an electric film, and a special method. …, The method of forming transparent conductive thin films by mining method. In the era of rapid flow and explosion of knowledge, _, thin, ^ ^ ^ ^ ^^ missing elements, among them, the plane dry state is widely used in various fields. Everyone, such as communication, information, consumer electronics, etc., has played an indispensable role in office and production automation. Because the plane is dry and cry than H, ..., # ^ 'g' Μ -V '^ ^ ”, the staff does not use electric signals to control the passage or emission of J, households need to have a good light transmission The electrode (transparent conductive film) is used for regulation. / The so-called "transparent conductive electrode" is a conductive thin film material with high visible light transmittance and low resistivity, which generally refers to the visible light range (wavelength 380 ~ 7 6 0⑽) A thin film having a light transmittance of 80% or more and a resistivity lower than χ 1〇 ^ Ω.cm. In recent years, the application field and demand for transparent conductive films have been continuously expanded, such as liquid crystal displays, electroluminescence panels, and plasma display panels in flat display panels (Fat DispUy Panel). Electronic products such as Plasma Display Panel, Field Emission Display, touch panel, solar cell, etc. ^ use transparent conductive film as the electrode material. In the future, followers 3 ◦ The booming industry and global trends in energy conservation, the importance of transparent conductive films
0178-9962TWF(Nl);05920006;Allen.ptd 第6頁 1228544 五、發明說明（2) 將曰趨重要。表一及表二係分別顯示透明導電薄膜在電學 及光學方面的應用。 表一 電學應用方面 透明導電薄膜 平面發熱膜 抗靜電膜、轷電屏蔽膜 顯示器面板：液晶顯 示器、EL顯示器、 電子彩色顯示器、電 賭·顯示器、觸控面板 太陽能電池：單晶、 非晶碎、光開關、攝 影機照相機器件 防霧防霜用：飛 機、汽車窗玻璃、 屏窗、照相機鏡 頭、暖房用控電盤 加熱器、加熱板烹 調 儀表指示窗、測量儀器 窗、電子顯微鏡窗、顯 像管之顯示器、半導體 器件之封裝帶0178-9962TWF (Nl); 05920006; Allen.ptd page 6 1228544 V. Description of the invention (2) It will become important. Tables 1 and 2 show the electrical and optical applications of transparent conductive films, respectively. Table 1 Electrical application aspects: transparent conductive film, flat heat-generating film, antistatic film, and electric shielding film. Display panels: liquid crystal display, EL display, electronic color display, electronic gaming, display, touch panel, solar cell: single crystal, amorphous, Light switch, camera and camera device anti-fog and anti-frost use: aircraft, automobile window glass, screen window, camera lens, heating control panel heater, heating plate cooking instrument indicator window, measuring instrument window, electron microscope window, display tube display Packaging tape for semiconductor devices
光學應用方面 熱輻射遮斷膜及省能源膜 選擇性透光膜 建築物窗、爐子、烘烤箱的觀 察孔照明燈的外管：低壓鈉光 燈、白熾燈 太陽能集熱器用：平板型樣板玻 璃聚光外管In optical applications, thermal radiation blocking film and energy-saving film. Selective light-transmitting film. Outer tubes of building windows, stoves, and observation holes of baking ovens. Lighting tubes: low-pressure sodium lamps, incandescent solar collectors. Glass condenser tube
在眾多可作為透明電極之材料中（參見表三），氧化 銦錫（Indium Tin Oxide, ITO)薄膜由於具有極佳的導電 特性、高可見光之穿透性及高紅外光之反射性，因此最常Among many materials that can be used as transparent electrodes (see Table 3), Indium Tin Oxide (ITO) thin film is the most suitable for its excellent conductivity, high visible light transmission and high infrared light reflection. often
0178-9962TWF(N1);05920006;A11en.p t d 第7頁 1228544 _ 五、發明說明（3) 被使用。習知用來形成I TO薄膜的技術有電鍍法、化學蒸 鍵法、溶膠-凝膠法、真空蒸鍍法及磁控濺鍍（Magnetr〇n Sputter ing )等方法，其中以磁控濺鍍法最常被使用，但 此技術仍存有不少缺點。首先，（1 )以磁控濺鍍製作透 明導電薄膜之成膜速率相當低，以氧化銦錫薄膜為例，其 成膜速率最高約180〜20 0 nm/min ;再者，（2)磁控濺鐘 製私中使用之錢鍵乾材下方配置有用以產生電漿聚集 (Confinement)之磁鐵，因此在濺鍍一段時間之後，濺鍍 靶表面因特定區域之正離子（Ion)轟擊作用而產生沖蝕= 域（Er〇Slon pr〇file)，使濺鍍靶之材料利 ==成二隨:越=積的心 =越來“，成膜設備也變得龐大複雜，；0178-9962TWF (N1); 05920006; A11en.p t d page 7 1228544 _ V. Description of the invention (3) is used. Conventional techniques used to form I TO films include electroplating, chemical bonding, sol-gel, vacuum evaporation, and magnetron sputtering. Among them, magnetron sputtering This method is most commonly used, but there are still many disadvantages to this technique. First, (1) the film-forming rate of transparent conductive films made by magnetron sputtering is relatively low. Taking indium tin oxide films as an example, the film-forming rate is about 180 ~ 200 nm / min; and (2) magnetic The money key used in the sputter control clock is equipped with a magnet under the dry material to generate plasma concentration. Therefore, after sputtering for a period of time, the surface of the sputtering target is affected by positive ion bombardment in a specific area. = field generated erosion (Er〇Slon pr〇file) the sputtering target material of interest with == into two: the product of heart = = increasingly "film forming apparatus becomes large and complex,;
1228544 五、發明說明（4) 表三一些常用的透明電極材料 材料 用途 性質需求 Sn〇2_F 寒帶建築物低放射(l〇w-E) 玻璃 … ~—1 ~ ====¾¾ 電漿波長w 2 μπι (增加陽光红外 區穿透） Ag、TiN 熱帶建築物低輻射玻璃 — 電漿波長S 1 μηι (反射陽光紅外 區） Sn02：F 太陽電池外表面 熱穩定性、低成本 Sn02：F EC windows 化學穩定性、高透光率、低成本 ΓΓΟ 平面顯示器用電極 易餘刻性、低成膜溫度、低電阻 ΓΓΟ、Ag、 Ag-Cu alloy 除霧玻璃(冰箱、飛機、汽 車） 低成本、耐夂性、低電阻 Sn〇2 烤箱玻璃 高溫穩定性、化學及機械耐夂 性、低成本 Sn〇2 除靜電玻璃 化學及機械耐久性 Sn02 觸控螢幕 低成本、耐久性 Ag、ΓΓΟ 電磁屏蔽(電腦、通訊設備) 低電阻 為了解決上述問題，如第1圖所示，日本專利一特開 平第02 - 213463號（1990年8月24日公開）提出利用陰極電 弧放電製作透明導電薄膜的方法’然而該案中僅以電弧放1228544 V. Description of the invention (4) Table III Some commonly used transparent electrode materials Material application property requirements Sn〇2_F Cold building low emission (l0wE) glass ... ~ -1 ~ === ¾¾ Plasma wavelength w 2 μπι (increased penetration of sunlight infrared region) Ag, TiN tropical building low-emissivity glass-plasma wavelength S 1 μηι (reflected sunlight infrared region) Sn02: F Thermal stability of solar cell outer surface, low cost Sn02: F EC windows chemistry Stability, high light transmittance, low cost ΓΓΟ Electrodes for flat display, low film forming temperature, low resistance ΓΓΟ, Ag, Ag-Cu alloy Defogging glass (refrigerator, airplane, automobile) Low cost, high resistance Resistance, low resistance Sn〇2 oven glass high temperature stability, chemical and mechanical resistance, low cost Sn〇2 static electricity glass chemical and mechanical durability Sn02 touch screen low cost, durability Ag, ΓΓΟ electromagnetic shielding (computer, (Communication equipment) Low resistance In order to solve the above problems, as shown in Figure 1, Japanese Patent Laid-Open No. 02-213463 (published on August 24, 1990) proposed the use of a cathodic arc discharge system. A transparent conductive thin film method 'However, in that case only arc discharge
0l78-9962TW(Nl);05920006;Allen.ptd 第9頁 1228544 五、發明說明（5) 的手段，並未揭露其他可提昇透明導電薄 =(丄Λ 方*，且其所使用之材料僅提及氧化 = τ〇)缚膜’·此外’該案提出之成膜速率也並 優於里產型之磁控濺鍍法。 因此’為了要解決及改進上 種更優良的方法以形成具有低電阻係數展； 膜品質之透明導電薄膜。 -透先性及同溥 發明内容 因此，本 子蒸鍍法形成 本發明之 法形成各種不 氣、氧氣與惰 氣體來與靶材 本發明之 及沉積速率之 負偏壓形成一 板處沉積。 本發明之 性及導電率之 熱，使薄膜之 向，因此提高 本發明之 發明之主要 透明金屬氧 再一目的係 同材質之透 性氣體之混 解離出之離 再一目的係 方法，藉由 較低之電位 再一目的係 方法，藉由 晶格得以重 了薄膜的透 再一目的係 目的係·提供一種利用陰極電弧離 化物導電薄膜之方法。 提供種利用陰極電弧離子蒗錢 ;導電薄膜之方法，藉由通；：氧 i氣體'或可與靶材材料反應之 子反應形成各種薄膜。 ί供Γ種增加透明導電薄膜密度 况積透明導電薄膜時對基板施加 以吸引由靶材解離之離子朝基 提種改善透明導電薄膜透光 :積透明導電薄膜時對基板加 :排列而獲得更完美之晶格配 光性及導電率。 提供一種改善透明導電薄膜均勻0l78-9962TW (Nl); 05920006; Allen.ptd Page 9 1228544 V. The means of the invention description (5) did not disclose other transparent conductive thin film can be improved = (丄 Λ square *, and the materials used only mention And oxidation = τ〇) The film formation rate of the bound film "· In addition" is also superior to the magnetron sputtering method of the domestic type. Therefore, in order to solve and improve the above-mentioned better method to form a transparent conductive thin film with low resistivity spreading and film quality. -Penetration and Peer Summary of the Invention Therefore, the method of the present invention forms a variety of air, oxygen and inert gases to target the target and the negative bias of the deposition rate to form a plate deposition. The heat of the nature and conductivity of the present invention makes the film oriented, so the main purpose of improving the main transparent metal oxygen of the invention of the present invention is a method of dissociating and dissociating with the permeable gas of the same material. The lower potential is another method. The purpose of the thin film through the crystal lattice is to provide a method using a cathode arc ionizing conductive film. Provide a method of using cathode arc ions to save money; a conductive thin film, which can form various thin films by reacting with: oxygen i gas' or reacting with a target material. To increase the density of the transparent conductive film and apply it to the substrate when attracting the dissociated ions from the target to improve the light transmission of the transparent conductive film. Improve the light transmission of the transparent conductive film. Lattice light distribution and conductivity. Provide an improved uniformity of transparent conductive film
12285441228544
五、發明說明（6) 性之方法， 在基板各部 根據上 成透明導電 化物製成之 適量的氣體 弧於靶材表 此基板，並 引導由乾材 電薄膜。 本發明 種不同材質 施加負偏壓 入氧氣、氧 應之氣體等 明性、導電 本發明 之詳細說明 藉由將基板做等速率 份，從而拎4 7 的移動以將薄膜平均沉積 伤仉而增加了薄臈的均勻性。 述目的，本發明提供 薄膜之方法。首先：：種以電弧離子蒸鍵形 靶材；a π先棱供一基板及一由金屬氧 粑材於具有引弧器之直办 ^ ^ ^ ^ i 炙異二设備中，接者，通入 於真空5又備中，然後利用引弧器產生一陰極電 面以解離此靶材，A w楚、Α # 电 n Bi, ^ . 再以專速率運動的方式移動 「口J日$加熱基板。最接 取傻 施加一負偏壓於基板以 解離之離子沉積於基板上，藉此形成一透明導 之優點在於利用陰極電弧離子蒸鍍法來形成各 之透明導電性薄膜，同時，再藉由（1 )對基板 ;(2)加熱基板；（3)等速移動基板；及（4)通 氣與惰性氣體之混合氣體、或可與靶材材料反 方式，從而提高了薄膜的沉積速率、密产、 性及均勻性。 *又、透 之其它目的及諸多優點將藉由下列較佳實施 ’及參照所附圖示，而被完全的揭露。 實施方式 首先，於真空設備中，將基板固定於基板支架上，並 於適當位置設置一靶材，當真空設備溫度為2 5 °C〜4 〇 〇 °C、壓力為O.lPa〜3.0Pa、電弧電流為30安培〜ι〇〇安拉 及基板溫度為100 °C〜400 °C時，從氣體入口處19〇通入適V. Description of the invention (6) The method of the invention, in each part of the substrate, an appropriate amount of gas made of a transparent conductive material is arced on the target surface of the substrate, and the dry film is guided. Different materials of the present invention apply negative bias to inject oxygen, oxygen-responsive gas, and other explicit and conductive materials. The detailed description of the present invention is to increase the thickness of the thin film by averaging the film by making the substrate into equal-rate portions, thereby moving the film to a uniform thickness. The uniformity of the thin cymbals. For this purpose, the present invention provides a method for a thin film. First of all: a kind of arc-ion steam-bonded target; a π first edge for a substrate and a metal oxide material in a direct operation with an arc starter ^ ^ ^ ^ i After being put into vacuum 5 and prepared, an arc striker is used to generate a cathode electrical surface to dissociate the target. A w Chu, A # 电 n Bi, ^. Then move the "port J day $ heating substrate with a special rate of motion" The most suitable method is to apply a negative bias to the substrate to dissociate ions on the substrate, thereby forming a transparent conductor. The advantage is that the cathode arc ion evaporation method is used to form each transparent conductive thin film. By (1) pairing the substrate; (2) heating the substrate; (3) moving the substrate at a constant speed; and (4) a mixed gas of aeration and inert gas, or in the opposite way to the target material, thereby improving the film deposition rate, Dense production, uniformity, and uniformity. * The other purpose and many advantages of the transparent will be fully disclosed by the following preferred implementation and with reference to the attached drawings. Implementation First, in a vacuum device, the substrate It is fixed on the substrate holder, and a Materials, when the temperature of the vacuum equipment is 2 5 ° C ~ 400 ° C, the pressure is 0.1 Pa ~ 3.0 Pa, the arc current is 30 amperes ~ ι〇〇 ampere and the substrate temperature is 100 ° C ~ 400 ° C From the gas inlet at 19〇
1228544 五、發明說明（7) 當氣體，並對基板140施加〇伏特〜3 〇〇伏特之負偏壓，再 利用不同型式之引弧器180接觸靶材16〇以產生陰極電弧放 電及電漿流將靶材160解離，反應時間約為1〇秒〜9〇秒後 沉積出=透明導電薄膜（IT0) 2〇〇於基板14〇之表面。 上述反應過程中，基板尺寸約為5〇〜2〇〇 X _、 基板為玻璃基板，靶材材料係選自金屬氧化物，如丨仏〇3、1228544 V. Description of the invention (7) When the gas is applied, a negative bias voltage of 0 volts to 3,000 volts is applied to the substrate 140, and then different types of arc starters 180 are used to contact the target material 160 to generate a cathodic arc discharge and a plasma. The target material 160 is dissociated by a stream, and the reaction time is about 10 seconds to 90 seconds, and then a transparent conductive film (IT0) is deposited on the surface of the substrate 14 in a thickness of 200. In the above reaction process, the size of the substrate is about 50-200 ×, the substrate is a glass substrate, and the target material is selected from metal oxides, such as 丨 仏 〇3,
sn〇! ' ZnO、CdQ、Cdln2 04、Cd2Sn04、Zn2Sn04、In2Q3 : ZnO (氧化銦鋅燒結體）、！ ％ % : s n〇2 (氧化銦錫燒結體、 indium Tin Oxide， ITO，l〇 wt%) ) &Zn〇:Al2〇3 (氧化 鋅鋁燒結體、Zinc Aluminium Oxide, AZO )，其中並可 摻，適量的Sn、Sb、F、ln、Ga、A1等掺雜物；通入氣體 係選自氧氣、氧氣與惰性氣體之混合氣體、或任何可與靶 材材料反應之氣體；陰極電弧產生方式可為隨機電弧式、 操控式及過濾式。 另外’基板於薄膜沉積時亦可以等速運動方式（相對 材）移動以提高成膜之膜厚均勻性，如第3人圖所示之 仃星式等速迴轉或第3B圖所示之直線式等速移動，其中， ^、Y代表基板中心至靶材之最短直線距離。sn〇! 'ZnO, CdQ, Cdln2 04, Cd2Sn04, Zn2Sn04, In2Q3: ZnO (indium zinc oxide sintered body) ,! %%: Sn〇2 (indium tin oxide sintered body, indium tin oxide, ITO, 10 wt%)) & Zn〇: Al2〇3 (zinc aluminum oxide sintered body, Zinc Aluminium Oxide, AZO), among which Doped with an appropriate amount of dopants such as Sn, Sb, F, ln, Ga, A1; the gas inlet system is selected from the group consisting of oxygen, a mixed gas of oxygen and an inert gas, or any gas that can react with the target material; cathode arc generation The method can be random arc type, control type and filter type. In addition, the substrate can also be moved at a constant speed (opposite material) during the film deposition to improve the uniformity of the film thickness, as shown in the figure 3, the star-shaped constant-speed rotation, or the straight line shown in Figure 3B. The formula moves at a constant speed, where ^ and Y represent the shortest straight line distance from the center of the substrate to the target.
本發明的一些實施例會詳細描述如下，其中，元件的 不同部份並沒有依照實際尺寸繪製。某些尺度與其它部份 ，關的尺度比係被誇張的表示以提供更清楚的描述以幫助 熟，此技藝的相關人士瞭解本發明。同時，下列所述之較 佳貫施例並非用以限定本發明之申請專利範圍，凡其它未 脫離本發明所揭示之精神下所完成之等效改變或修飾，均Some embodiments of the present invention will be described in detail below, in which different parts of elements are not drawn according to actual dimensions. Some scales are related to other parts, and the scales are exaggerated to provide a clearer description to help the person skilled in the art understand the present invention. At the same time, the preferred embodiments described below are not intended to limit the scope of patent application for the present invention. All other equivalent changes or modifications made without departing from the spirit disclosed by the present invention are all
1228544_ 五、發明說明（8) 應包含在下述之申請專利範圍内。 [第一實施例] 如第2圖所示，首先，在一真空設備17〇中，將一尺寸 為50 mm X 50 mm之基板140固定於基板支架150上，基板 材料在此為玻璃基板，並於適當位置設置一靶材160，靶 材材料在此為氧化銦錫燒結體（IndiUII1 Tin Oxide，ITO, In2 03:Sn02， 10 wt°/。）。當真空設備溫度為300 °c、壓力〇.1228544_ V. Description of the invention (8) should be included in the scope of patent application described below. [First Embodiment] As shown in FIG. 2, first, a substrate 140 having a size of 50 mm × 50 mm is fixed on a substrate holder 150 in a vacuum device 170, and the substrate material is a glass substrate here. A target 160 is provided at an appropriate position. The target material is an indium tin oxide sintered body (IndiUII1 Tin Oxide, ITO, In2 03: Sn02, 10 wt ° /.). When the temperature of the vacuum equipment is 300 ° C, the pressure is 0.
5Pa、電弧電流80安培及基板溫度為3〇〇它時，從氣體入口 處1 9 0通入適量氣體，在此為純氧，並分別對基板丨4 〇施加 負偏壓（0伏特及3 00伏特），再利用操控式引弧器18〇接 觸靶材1 6 0以產生陰極電弧放電及電漿流將靶材丨6 〇解離， 反應時間1 0秒後沉積出一透明導電薄膜（丨τ〇 ) 2〇 〇於基板 140之表面。利用X光反射率來測量薄膜2〇〇的厚度，發現 負偏壓為0伏特時薄膜之密度為6·16± 〇 〇6 g/cm3，而負 偏壓為3 0 0伏特日寸氧化姻錫薄膜之密度為6 44 + 〇 〇6 g/cm3 (註：氧化銦錫材料之理論密度為了 ·丨7 g/cm3)，此一 結果顯示施加偏壓確實可以增加薄膜密度。 [第二實施例]5Pa, arc current of 80 amps, and substrate temperature of 300, a suitable amount of gas is introduced from the gas inlet 190, here is pure oxygen, and a negative bias (0 volts and 3 volts) is applied to the substrate 00 volts), and then use the controlled arc starter 180 to contact the target 160 to generate a cathodic arc discharge and plasma flow to dissociate the target 丨 600. A transparent conductive film (丨 is deposited after a reaction time of 10 seconds τ〇) 200 is on the surface of the substrate 140. The X-ray reflectance was used to measure the thickness of the film. It was found that the density of the film was 6 · 16 ± 〇6 g / cm3 when the negative bias was 0 volts, and the negative bias was 300 volts. The density of the tin film is 6 44 + 〇6 g / cm3 (Note: The theoretical density of indium tin oxide material is 7 g / cm3). This result shows that applying a bias voltage can indeed increase the film density. [Second embodiment]
如第2圖所示，首先，靶材材料、基板尺寸及材料、 通入氣體成份、真空設備溫度之條件與反應時間同第一 施例，電弧電流為40〜80安培，對基板14〇施加負偏壓3〇〇 伏特，並分別加溫基板至10(TC及30(rc，再利用操控式引As shown in FIG. 2, first, the conditions and response time of the target material, the size and material of the substrate, the gas composition, and the temperature of the vacuum equipment are the same as in the first embodiment. The arc current is 40 to 80 amps. Negative bias voltage is 300 volts, and warm the substrate to 10 (TC and 30 (rc, respectively, and then use the steering
1228544 五、發明說明（9) 弧器1 8 0接觸乾材1 6 0以產生陰極電弧放電及電漿流將靶材 160解離，最後，沉積出一透明導電薄膜2〇〇於基板14〇之 表面。測量結果顯示當基板溫度為丨〇 〇 t時，所得到的薄 膜電^阻係數為26〜190 X ι〇-4Ω · cm，透光率為78〜9〇% ;而 30 0 °C時所得到的薄膜電阻係數為2•卜4· 2 χ 1〇_4 Q ⑽， 1光率都在8 8%以上。這些結果證明，提高基板溫度對薄 膜電阻及透光性的改善極為明顯，確實可得到性質優於前 案（電阻係數1· 06 X 1〇-3 Ω · cm，透光率8〇%)的透明導電 薄膜。1228544 V. Description of the invention (9) Arc device 180 contacts dry material 160 to generate cathode arc discharge and plasma flow to dissociate target material 160. Finally, a transparent conductive film 200 is deposited on substrate 14 surface. The measurement results show that when the substrate temperature is 〇〇〇t, the electrical resistance coefficient of the obtained film is 26 ~ 190 X ω-4 Ω · cm, the light transmittance is 78 ~ 90%; and at 30 ° C The obtained sheet resistivity is 2 · 4 · 4 2 x 1 0_4 Q ⑽, and the photoresistance is more than 88%. These results prove that increasing the substrate temperature significantly improves the sheet resistance and light transmittance, and it is indeed possible to obtain properties that are superior to the previous case (resistance coefficient 1.06 X 1〇-3 Ω · cm, light transmittance 80%). Transparent conductive film.
[第三實施例] 基板固定不動： ^ a ί ΐ 靶材材料、基板材料、基板溫度、通入氣體成 .ΟΛΠ 你1干Ij弟貫施例，基板140尺寸改 為 ZOO min X 200 mm，其： 土板1 4 0成膜面正對乾材1 6 0且距離 材 X、Υ ηιπι = γ = λ» 丄 ,_ U ) 電弧電流改為8 0安培，對基板 材伏特，再利用操控式引弧器180… \ Λ Λ極Λ弧放電及電|流將㈣16G解離，反應 二=ΓΛ °秒後’沉積出-透明導電薄膜2〇〇 = ,140之表面。以膜厚最大處（基板 測置50mm x 50mmg域之内的薄膜厚度。 丫 基板等速移動：[Third embodiment] The substrate is fixed: ^ a ί 靶 Target material, substrate material, substrate temperature, and gas flow. ΟΛΠ In the example, the size of the substrate 140 is changed to ZOO min X 200 mm, Its: The 1 4 0 film-forming surface of the soil plate is directly opposite to the dry material 1 60 and the distance from the material X, ι ηιπι = γ = λ »丄, _ U) The arc current is changed to 80 Amp, and the base plate voltage is volts, which is then manipulated The arc starter 180 ... \ Λ Λ pole Λ arc discharge and electric | current will dissociate ㈣16G, reaction 2 = Γ Λ ° seconds after the 'deposited-transparent conductive film 2000 =, 140 surface. Where the film thickness is the largest (the substrate thickness is within the range of 50mm x 50mmg). The substrate moves at the same speed:
1228544 五、發明說明（10) 基板運動時必須使用尺寸較小的50 mm χ 50 _其 基板140放置於基板承載盤22〇上，其餘條件與芙^ 動時相同。鍍膜時，電弧開啟時間歷經20秒;、=利用行星 式的傳動方式，等速順時鐘迴轉基板（相對於靶材丨60 ) 使基板140之鍍膜面行經靶材16〇正前方藉以提高成膜 膜f均勻性，所得有效的鍍膜時間約為1〇秒，基板到靶 的最近距離為150 mm (如X所示）也與基板固定不動 同。錢膜元成後，測量基板上的薄膜厚度。 、 定殳可動 固h差運 板偏速 基Q的等 但 出 度持 看％厚維 以3°膜中 可10薄區 ，的但漿 示度，電 所厚低在 四均較板 表平率基 如達速使。 果可膜，性 結差成示句 測偏然顯均 量度雖果的 的厚，結膜 品膜動此薄 樣薄移。加 個的速4°/0增 兩時等1·幅 動板到大 不基降可 表四50x50 mm2區域内ιτο薄膜之厚度量測結果 基板等速 運動 厚度範圍 (nm) 平均厚度 DA(nm) 標準差 δη-ΐ(ηιπ) WDa 無 356 〜437 401 41.2 10.3 % 有 61.3 〜63.0 62.2 0.9 1.4 % [第四實施例] 與第三實施例為同一實驗。對於基板不動的樣品，厚1228544 V. Description of the invention (10) When the substrate is moving, a smaller size 50 mm χ 50 _ must be used. The substrate 140 is placed on the substrate carrier plate 22, and the remaining conditions are the same as when the substrate is moved. During the coating process, the arc opening time elapsed 20 seconds; = the planetary transmission method was used to rotate the substrate clockwise (relative to the target material 60) at a constant speed so that the coating surface of the substrate 140 was passed directly in front of the target material 16 to improve the film formation. The uniformity of the film f, the resulting effective coating time is about 10 seconds, and the closest distance between the substrate and the target is 150 mm (as shown by X), which is also the same as the substrate fixing. After the film is formed, the thickness of the film on the substrate is measured. The fixed-speed base of the movable solid-h-differential plate is equal, but the output is constant. The thickness is 3% in the film, and 10 thin areas can be obtained. However, the thickness of the power plant is lower than that of the board. The rate base is as fast as possible. If the film can be formed, the difference between the results is shown in the sentence. Although the thickness of the fruit is measured, the conjunctival film moves thinly and thinly. Adding a speed of 4 ° / 0, increasing the time by two hours, etc.1. The amplitude of the plate to the large base can be measured in the area of 50x50 mm2, and the thickness of the film is measured. The thickness of the substrate is constant. (Nm) Average thickness DA (nm ) Standard deviation δη-ΐ (ηιπ) WDa None 356 to 437 401 41.2 10.3% 61.3 to 63.0 62.2 0.9 1.4% [Fourth embodiment] The same experiment as the third embodiment. For samples with a stationary substrate, thick
1228544 五、發明說明（11) ' --- a量測、·Ό果顯不在鍛膜的1 〇秒之間’基板中央的膜厚可以 超過4 0 0 nm，基板邊緣的膜厚也達到1〇〇 nm ;換算其成膜 速率’分別為大於2400 nm/min及60 0 nm/min。如果使基、 板等速移動，即使成膜速率較低，也超過3〇〇 nm/min。這 些成膜速率都大於目前量產IT〇磁控濺鍍的最大成膜速率 (約—2 0 0 nm/m丨η)。由此證明，本發明所使用的陰極電弧離 子条錢確實具有極高的成膜速率。 [第五實施例] 貫施設備如第2圖所示。首先，基板尺寸、材料及溫 =、通入氣體成份與真空設備溫度之條件同第一實施例， 材材料改為以氧化鋅鋁燒結體（Zinc Aluminium AZO’ ZnO: Al2〇3 )為靶材，電弧電流改為8〇安培， 板140施加負偏壓30 0伏特，再利用操控式引弧器180 靶材1 6 〇以產生陰極電弧放電及電漿流將靶材1 6 0解 反^日寸間10秒後，沉積出一透明導電薄膜2〇〇於基板 】之 '面。測S結果顯示得到厚度約1 6 0 nm、電阻係數 瞪X Ω · Cm，而透光率為87%的氧化鋅透明導電薄 於J: ^ I ί祖明本發明之陰極電弧離子蒸鍍法也可以適用 莫=材質’用來製作氧化銦錫（I TO )以外的其他透明 等^溥膜。 以m發明已以—較佳實施例揭露如I ’然其並非用 ，任何熟知此技術之人士，在不脫離本發明 之精神及棘圍β ’當可做更動與潤飾，因此本發明之保護1228544 V. Description of the invention (11) '--- a measurement, · fruit display is not within 10 seconds of the forging film' the film thickness in the center of the substrate can exceed 400 nm, and the film thickness at the edge of the substrate can also reach 1 〇nm; the film-forming rates' were greater than 2400 nm / min and 60 nm / min, respectively. If the substrate and the plate are moved at the same speed, even if the film-forming rate is low, it exceeds 300 nm / min. These film-forming rates are greater than the maximum film-forming rates of current mass-produced IT0 magnetron sputtering (about -200 nm / m). This proves that the cathode arc ion coin used in the present invention does have an extremely high film-forming rate. [Fifth embodiment] The application device is shown in Fig. 2. First, the substrate size, material and temperature =, the conditions of the gas composition and the temperature of the vacuum equipment are the same as in the first embodiment, and the material of the substrate is changed to a zinc oxide aluminum sintered body (Zinc Aluminium AZO 'ZnO: Al203) as the target material. The arc current was changed to 80 amperes, the plate 140 was applied with a negative bias of 300 volts, and the controlled arc pilot 180 target 16 was used to generate a cathodic arc discharge and plasma current to reverse the target 160. After 10 seconds, a transparent conductive film 2000 was deposited on the substrate's surface. The results of S measurement show that a zinc oxide having a thickness of about 160 nm, a specific resistance of X Ω · Cm, and a light transmittance of 87% is transparent and thinner than J: ^ I 祖 Zu Ming Cathodic arc ion evaporation method of the present invention Mo = Material can also be applied to make transparent films other than indium tin oxide (I TO). The invention has been disclosed in the m-preferred embodiment. If it is not used, anyone who is familiar with this technology can make changes and retouches without departing from the spirit of the invention and the spine β ′, so the protection of the invention
1228544 五、發明說明（12) 範圍當視後附之申請專利範圍所界定者為準 Φ1228544 V. Description of Invention (12) The scope shall be determined by the scope of the attached patent application Φ
liBI 0178-9962TWF(Nl);05920006;Allen.ptd 第17頁 1228544 __ 圖式簡單說明 第1圖係為習知利用陰極電弧放電製作透明導電薄膜 之不意圖， 第2圖係為根據本發明以電弧離子蒸鍍形成透明導電 薄膜之方法之示意圖； 第3 A及3 B圖係根據本發明第三實施例中，基板設置方 式及運動方向之示意圖； 表一係為透明導電薄膜在電學方面的應用； 表二係為透明導電薄膜在光學方面的應用； 表三係為一些常用的透明電極材料；及 表四係為根據本發明第三實施例所得薄膜之厚度量測 結果。 [符號說明] 1〜真空槽 3〜陰極 4〜靶材 7〜離子蒸鍍用電源 8〜氣體供應入口 11〜支撐座 I 2〜基板 II 0〜電弧電源 1 2 0〜偏壓電源 1 3 0〜幫浦 1 4 0〜基板liBI 0178-9962TWF (Nl); 05920006; Allen.ptd Page 17 1228544 __ Brief description of the diagram. The first diagram is the conventional intention of making a transparent conductive film by using cathodic arc discharge. The second diagram is based on the present invention. Schematic diagram of the method for forming a transparent conductive film by arc ion evaporation; Figures 3 A and 3 B are schematic diagrams of the method of setting the substrate and the direction of movement according to the third embodiment of the present invention; Table 1 shows the electrical aspects of the transparent conductive film Applications; Table 2 is the optical application of transparent conductive films; Table 3 is some commonly used transparent electrode materials; and Table 4 is the thickness measurement results of the film obtained according to the third embodiment of the present invention. [Description of symbols] 1 ~ vacuum tank 3 ~ cathode 4 ~ target 7 ~ power source for ion evaporation 8 ~ gas supply inlet 11 ~ support base I 2 ~ substrate II 0 ~ arc power source 1 2 0 ~ bias power source 1 3 0 ~ Pump 1 4 0 ~ Board
0178-9962TWF(N1);05920006;A11en.p t d 第18頁 1228544_ 圖式簡單說明 1 5 0〜基板支架 1 6 0〜靶材 170〜真空槽 18 0〜引弧器 1 9 0〜氣體入口 200〜透明導電薄膜 22 0〜基板承載盤0178-9962TWF (N1); 05920006; A11en.ptd Page 18 1228544_ Brief description of the drawings 1 0 0 ~ substrate holder 1 6 0 ~ target 170 ~ vacuum tank 18 0 ~ arc starter 1 9 0 ~ gas inlet 200 ~ Transparent conductive film 22 0 ~ substrate carrier
0178-9962TWF(Nl);05920006;Allen.ptd 第19頁0178-9962TWF (Nl); 05920006; Allen.ptd p.19
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