201035997 六、發明說明： 【發明所屬之技術領域】 本發明係有關於利用奈米溶朦塗佈，並結合熱處理方式在基 材形成透明導電薄膜的製造方法。 【先前技術】 平面顯示器、發光二極體、觸控面板等光電產品皆需要透明 〇 導電膜夾著的設計，目前最常用的透明導電膜為銦鋅氧化物 (indium Zinc 0Xide ’以下簡稱IZ〇)與銦錫氧化物（⑽也201035997 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a transparent conductive film on a substrate by coating with a nano-solvent and a heat treatment. [Prior Art] Photoelectric products such as flat panel displays, light-emitting diodes, and touch panels require a transparent conductive film sandwich. The most commonly used transparent conductive film is indium zinc oxide (indium Zinc 0Xide 'hereinafter referred to as IZ〇). ) with indium tin oxide ((10) also
Qxide’以下簡稱itg)麵透料電薄膜；目前透明導電薄膜在 !產上，大都使用磁控濺鍍或真空蒸鑛等乾式物理方法成膜。物 理方法成膜的主要問題在於成膜設備及乾材都相當昂貴，而且成 膜材料的利用率極低，因此製造成本極高。其間雖有部份作法， 改麵鍍成本醜’如中華民國專利第1295325號，糊一種射 頻共親方式以提高離材料的糊率；巾華民國專鄉16職 © 號’則在包含氬及氧之混合氣體之空氣下進行濺鑛，以提高σ併 進而降低操作成本;但實際成效有限。 有鑑於此’以其它方式形成透明導電薄膜的方法，曰益 重視，包括： (-）無電電鍍法：中華民國專利第121858號，是先在非導電 薄膜上塗討金屬化底漆’如無電化學金屬化浴處理， 使形成導電薄膜’但透光度會較差；中華民國專利第 234885號二則針對此缺點’以金屬膜作成的栅極代替金屬 膜’以提高透光度’但導電性略奸擾；製程複雜且有環 2〇l〇35997 保問題為其最大缺點。 (-)電弧離子蒸鐘法：中華民國專利1228544號、中華民國專 告第2GG54G287號’中華民國專利公告第細5〇〇482 號’皆屬此類；品質良好、材料利用率高為其優點，但設 備投資費用昂貴的問題依舊存在。 (二）導電高分子薄膜法：中華民國專利公告第2〇〇629435號， 所揭橥的是將導電粒子係鱗列或既定驗置固定在高 分子薄膜上或壓入薄膜中，以形成導電薄膜；中華民國專 利公告第200745315號，則直接採用烯丙基醋熱固性樹脂 f成導電高分子薄膜。導電高分子_具妓好附著力及 f曲性’但料其朗上最大瓶頸。 (四）溶膠前驅溶液塗佈法：中華民國專利公告第謂2綱號， 斤揭木的疋將々別將醋酸鋅溶解於異丙醇、硕酸紹溶解於 ^醇’再充分授拌以形成預備覆膜之溶膠前驅溶液，經浸 潰、熱處理’形成導電薄膜；中華民國專利第015602號 ❹ 號所知橥的疋將氯化銦、硝酸銦及高氯酸銦之銦在有機 命劑中此合形成前驅溶液’進行塗佈；所採用溶膠前驅溶 液含多種_ ’這㈣齡塗佈時會包覆在麟中，於熱 處理時，成⑽、結晶缺陷及__，造成膜層結構不 良、附著力差及電阻值（導電度）偏高且變異性大。 ⑴秦^塗佈法.中華民國專利公告第200705065號，針對溶 膠刚驅冷液塗佈法的缺失’改以粒徑數十奈米的導電氧化 物私末與有機溶舰合，繼絲浮液狀的塗佈液，並以 邊式化學成膜法製成細，配合特棘計的紅外線（⑽ 201035997 形稱mm;崎__轉聽溶液 ==_題，但粉末原料中原來所含分散劑及接著 碎t箝、十、叮^播 电顧的電阻值（導電度）偏高。 二Γ:形成透明導電薄臈的方法，仍具有諸多 缺點因此，如何設料—種翁的形成_導鶴 以能有效解決前述諸多問題，即成、 丨攻為♦多業者亟欲達成之-重要Qxide' hereinafter referred to as itg) surface-transparent electric film; at present, transparent conductive films are mostly produced by dry physical methods such as magnetron sputtering or vacuum distillation. The main problem with the physical film formation is that the film forming equipment and the dry material are quite expensive, and the utilization rate of the film forming material is extremely low, so the manufacturing cost is extremely high. In the meantime, although there are some practices, the cost of changing the plating is ugly. For example, the Republic of China Patent No. 1295325, a kind of RF co-parent method to improve the paste rate of the material; the towel of the Republic of China, 16th position, is containing argon and Splashing under the air of oxygen mixed gas to increase σ and thus reduce operating costs; but the actual results are limited. In view of this method of forming a transparent conductive film by other means, the benefits are emphasized, including: (-) electroless plating method: Republic of China Patent No. 121858, which first coats a metallized primer on a non-conductive film. Metallization bath treatment, so that the formation of conductive film 'but the transmittance will be poor; Republic of China Patent No. 234885 2 for this shortcoming 'the gate made of metal film instead of metal film' to improve the transmittance 'but the conductivity is slightly Fraud; the process is complicated and there are loops 2〇l〇35997 to protect the problem as its biggest drawback. (-) Arc ion steaming clock method: Republic of China Patent No. 1228544, Republic of China Special Notice No. 2GG54G287 'Republic of China Patent Notice No. 5〇〇482' are all such; good quality, high material utilization rate is its advantage However, the problem of expensive equipment investment still exists. (2) Conductive polymer film method: No. 2,629,435 of the Republic of China Patent Publication, which discloses that conductive particles are fixed or fixed on a polymer film or pressed into a film to form a conductive film. Film; Republic of China Patent Publication No. 200745315, directly using allyl vinegar thermosetting resin f into a conductive polymer film. Conductive polymer _ has good adhesion and f-flexibility, but it is the biggest bottleneck. (4) Sol-precursor solution coating method: The Republic of China Patent Announcement No. 2 is the title, and the 斤 揭 木 将 将 将 将 将 将 将 将 将 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸 醋酸Forming a pre-coated sol precursor solution, forming a conductive film by dipping and heat-treating; 疋 中 中 中 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 015 In this case, the precursor solution is formed to be coated; the sol precursor solution used contains a plurality of _ 'this (four) age coating will be coated in the lining, in the heat treatment, into (10), crystal defects and __, resulting in the film structure Poor, poor adhesion and high resistance (conductivity) and high variability. (1) Qin ^ coating method. Republic of China Patent Announcement No. 200705065, for the lack of sol-drive liquid cold-coating method, changed to a conductive oxide oxide with a particle size of several tens of nanometers combined with organic solvent, followed by silk float Liquid coating solution, made by edge chemical filming method, with infrared rays ((10) 201035997, called mm; The dispersing agent and the resistance value (conductivity) of the t-clamp, the tenth, and the tweezers are high. Secondly, the method of forming a transparent conductive thin crucible still has many disadvantages. Therefore, how to set up the material-formation _ guide crane can effectively solve the above-mentioned many problems, that is, Cheng Cheng, 丨 attack for ♦ multi-operator 亟 want to achieve - important
【發明内容】 述之·!題與缺點，判人乃根據多年實務經驗及研 開發料出本發明之—種溶膝賴製 膜的方法，以期藉由本發明，能有效解決前述問題。導電4 本發明是_絲健轉塗倾術，將奈米_溶膠粒子 ^鑛或旋魅佈的方式塗佈在透料上，並配合後處理，使 不未粒子形成翻導電薄膜；鍍醜件㈣，產生電阻值^ 至議〇hm/square的導電薄膜；該薄膜具有均勻、緻密、吸附 良好、電阻值變異性低等特性。 内容包括： ―、在清潔完成的透明材料上’以浸鑛或旋轉塗佈的方式，依設 定的操作條件塗佈絲粉體轉，使在透明導輯膜表面形 成一薄而均句的塗佈層（表面塗佈程序）； 7 二、將塗佈完成的透明導電薄膜元件，以設定的溫度程序洪烤， 使传塗佈層轉化成均勻、緻密而吸酿好的導輯膜，達到 具有特定電阻值且電阻值差異性小的目的（後處理程序）。 201035997 ”、’、所述可知本專利申請案是直接以奈米導電氧化物溶膠 =踢林含分散舰接賴）進行賴，由於少了分散劑及接 者4的干擾’不猶特殊設計的紅外線⑽烘乾，即可形成導 電薄膜；因此，本㈣具有：不需抽以、細設備成本較低、 可用浸鍍或旋轉塗佈的方式成膜、材料的利用率高與薄膜電阻值 ，異欧低等躲，且此種直細奈米粉齡雜佈處理形成導電 薄膜的方法，至今則尚無人提出。 Ο 為便貴審查委貞能對本發明目的、技術特徵及其功效，做 更進一步之認識與瞭解，茲舉實施例，詳細說明如下： 【實施方式】 本發明係以浸鍍或旋轉塗佈方式將奈来粉體溶膠粒子塗佈 在透明材料上’並配合後處理’使奈絲子戦透卿電薄膜； ，賴條件關，產生電阻值1G至1_ Qhin/square的導電 缚膜；該薄膜具有均勻、緻密、吸附良好、電JI且值差異性小等特 〇 性。 其中，透明材料包括壓克力、聚碳酸、聚苯乙稀等透明塑膠 材料及其衍生材料'玻璃材料等。表面塗佈所使用的奈米粉體溶 膠為以含氧化銦(I祕）、氧化錫⑽2)、氧化鋅⑽）、四氧化辞 錫(zn2sn〇4)、三氧化辞錫(ZnSn〇3)、氧化鋅銦(Ζη2ίη2〇5)、氧化銦 錫（I祕· SnG2)、氧化銻錫（Sb2G3.Sn〇2)、氧化鋅銘(ZnQ·Al2〇3)、 氧化錫氟⑽2. F)制奈齡雜液，其奈錄體粒子粒 徑分佈為1〜lOOnm，固含量為〇. ho. 〇%，ρΗ=4· 〇〜9· 〇。塗 佈是以浸鍍或旋轉塗佈的方式進行，其中奈米粉體溶膠溶液的溫 201035997 度控制範圍為5〜歡；浸鑛的浸泡暫停時間為5秒至ι〇分鐘， 汉泡後的拉昇速度為1〇〜4〇〇釐米/分鐘（^迅化）；旋轉塗佈 的轉速為600〜3, OOrpn，時間為30秒〜5分鐘。表面塗佈完成 的疋件，即進行烘乾；烘乾的溫度為60〜20(TC、時間為1〇〜60 分鐘。烘乾完成的素材可依導電度需要進行第二種奈米粉體溶膠 塗佈，或直接進行後處理等程序。其中，第二種奈米粉體溶膠塗 佈可為氧化銦（1祕）、氧化鋅⑽)或氧化紹⑴晶）等的奈米 〇 健轉紐。塗雜件翻絲絲制帛-種奈米粉體溶膠 (即最先塗佈的奈米粉體溶膠）塗佈。 後處雖序餘奈綠體翻、麵大械基材射改變條 件；其中，玻璃的煅燒溫度範圍為2〇(rc〜4〇(rc，煅燒時間為 30分鐘〜4小時；透明塑膠材料則以微波處理，所使用的微波頻 率為2. 45GHz，功率為1〇0〜15_，時間為5秒至3〇分鐘，依 奈米粉體種類、顆粒大小及基材性質而定。 經過上述處理的透明導電薄膜，片電阻約在1〇〜 ° l〇〇〇〇hin/square之間’而可見光的平均穿透率在80%以上。所形 成6^透明導電薄膜，亦可再以金屬電製離子源植入技術，在加速 電壓10〜80KeV ’時間分鐘條件下，將铭、氣或嫁等元素 值入薄膜，值入量i〜娜（相對於薄膜質量）以降低電阻值， 所得電阻可在0· 3〜10 ohm/square之間。 以下，舉出實施例以說明本發明内容，但本發明之範圍並不 只限於此等的例子： 【實施例一】： 將洗淨的_浸人HI含量3%，_ 30〜勤的三氧化辞錫 7 201035997 (ZnSn〇3)的溶膠中，靜置60秒後，以100釐米/分鐘（麵/min) 拉昇速度鍍膜；鍍膜後以15(TC / 1〇分鐘進行烘乾。烘乾完成的 玻璃片以28(TC / 60分鐘進行燒結，燒結後的導電玻璃，片電阻 約在50〜100 ohm/square之間，可見光的平均穿透率在85〜9〇%。 【實施例二】： 將洗淨的玻璃浸入固含量3%，粒徑1〇〜40nm的二氧化錫 (Sn〇2)的溶膠中，靜置30秒後，以100釐米/分鐘（mm/min)拉 昇速度鍍膜；鍍膜後以150°c /10分鐘進行烘乾。烘乾完成的玻 璃片以280°C / 60分鐘進行燒結，燒結後以金屬電漿離子源植入 技術，在加速電壓20KeV，時間3分鐘的條件下植入氟元素，值 . 入量2% (相對於二氧化錫薄膜質量），所產出的導電玻璃窗，片 電阻在0.5〜3 ohm/square之間’可見光的平均穿透率在8〇〜 85%。 【實施例三】·· 將洗淨的玻璃浸入固含量3%，粒徑1〇〜4〇薦的二氧化錫 ❹ （Sn〇2)的溶膠中，靜置30秒後，以1〇〇釐米/分鐘（mm/min)拉 昇速度鍍膜；鍍膜後以150。(： / 10分鐘進行烘乾。烘乾完成的玻 璃片再浸入固含量〇· 5%，粒徑30〜70nm的氧化鋅(ZnO)的溶膠 中，靜置60秒後，以50釐米/分鐘（jnm/min)拉昇速度鑛膜； 鍵膜後以150 C / 10分鐘進行烘乾。烘乾完成的玻璃片以3〇〇。〇 /60分鐘進行燒結，燒結後的導電玻璃，片電阻約在1〇〜3〇 ohm/square之間，可見光的平均穿透率在9〇〜。 雖然本發明以二項實施例揭露如上，然其並非用以限定本發 明，任何熟習此應用者，在不脫離本發明之精神和範疇内，當可 8 201035997 作各種更動與應用，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】 【主要元件符號說明】SUMMARY OF THE INVENTION The problems and shortcomings of the present invention are based on years of practical experience and research and development of a method for producing a film of the knee-soled film of the present invention, with the aim of effectively solving the aforementioned problems by the present invention. Conductive 4 The present invention is a _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (4), the conductive film of the resistance value ^ to 〇 hm / square; the film has uniform, dense, good adsorption, low resistance variability and other characteristics. The contents include: ― On the cleaned transparent material, the silk powder is coated by dip or spin coating according to the set operating conditions, so that a thin and uniform coating is formed on the surface of the transparent guide film. Cloth layer (surface coating procedure); 7 2. The coated transparent conductive film element is baked in a set temperature program to convert the transfer coating layer into a uniform, dense and absorbing brewing guide film. It has a specific resistance value and a small difference in resistance value (post-processing program). 201035997 ”, ', It can be seen that the patent application is directly based on nano-conductive oxide sol = Kelly with dispersing ship), because of the lack of dispersant and the interference of the receiver 4 Infrared (10) drying can form a conductive film; therefore, the present (4) has: no need to pump, low cost of equipment, film formation by immersion plating or spin coating, high material utilization rate and film resistance value, The method of forming a conductive film by the treatment of such a straight fine nano-powder miscellaneous cloth has not been proposed so far. Ο For the sake of review, the committee can further improve the purpose, technical features and effects of the present invention. The present invention will be described in detail as follows: [Embodiment] The present invention applies a Neil powder sol particle coated on a transparent material by immersion plating or spin coating method, and is combined with post-treatment to make Nai Nai. Silk 戦 戦 卿 卿 卿 卿 ; , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Among them, transparent materials include transparent plastic materials such as acrylic, polycarbonate, and polystyrene, and their derived materials, such as glass materials. The nano-powder sol used for surface coating is oxidized with indium oxide (I secret). Tin (10) 2), zinc oxide (10)), tin tetraoxide (zn2sn〇4), tin oxide (ZnSn〇3), zinc indium oxide (Ζη2ίη2〇5), indium tin oxide (I secret · SnG2), cerium oxide Tin (Sb2G3.Sn〇2), Zinc Oxide (ZnQ·Al2〇3), Tin Oxide Fluoride (10)2. F) Nai's miscellaneous liquid, whose particle size distribution is 1~100 nm, and the solid content is 〇 Ho. 〇%, ρΗ=4· 〇~9· 〇. Coating is carried out by immersion plating or spin coating, wherein the temperature of the nano-powder sol solution is controlled by the range of 5,035,997 degrees; The soaking pause time is 5 seconds to ι〇 minutes, and the pulling speed after the Han bubble is 1〇~4〇〇cm/min (^Xuhua); the rotating coating speed is 600~3, OOrpn, the time is 30 seconds ~5 minutes. The surface coating is finished, that is, drying; the drying temperature is 60~20 (TC, time is 1〇~60 minutes. The material after drying can be guided. The electric quantity needs to be subjected to a second nano powder sol coating or directly post-treatment, etc. Among them, the second nano powder sol coating may be indium oxide (1 secret), zinc oxide (10) or oxide (1) Nano- 〇 转 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂 涂The surface of the surface is changed by a substrate; wherein the glass has a calcination temperature range of 2 〇 (rc~4 〇 (rc, calcination time is 30 minutes to 4 hours; transparent plastic material is treated by microwave, and the microwave frequency used is 2. 45 GHz, power is 1 〇 0~15 _, time is 5 seconds to 3 〇 minutes, depending on the type of enamel powder, particle size and substrate properties. The transparent conductive film subjected to the above treatment has a sheet resistance of about 1 〇 to ° l〇〇〇〇hin/square' and an average transmittance of visible light of 80% or more. The formed 6^ transparent conductive film can also be implanted into the film by the metal ion source implantation technology, and the value of the element such as Ming, Qi or Marriage is entered into the film under the condition of an accelerating voltage of 10~80KeV. Na (relative to the film quality) to reduce the resistance value, the resulting resistance can be between 0·3~10 ohm/square. Hereinafter, the examples are given to illustrate the contents of the present invention, but the scope of the present invention is not limited to the examples: [Example 1]: The washed _ immersion HI content 3%, _ 30 ~ dilute three-oxidation In the sol of Rexon 7 201035997 (ZnSn〇3), after standing for 60 seconds, the film was coated at a pulling speed of 100 cm/min (face/min); after coating, it was dried at 15 (TC / 1 〇 min. The finished glass piece is sintered at 28 (TC / 60 minutes, the sintered conductive glass, the sheet resistance is between 50~100 ohm/square, and the average transmittance of visible light is 85~9〇%. [Example 2 】: The washed glass is immersed in a sol of tin dioxide (Sn〇2) having a solid content of 3% and a particle size of 1 〇 to 40 nm, and after standing for 30 seconds, it is pulled up at 100 cm/min (mm/min). Speed coating; drying after coating at 150 ° C / 10 minutes. The dried glass sheet is sintered at 280 ° C / 60 minutes, sintered with metal plasma ion source implantation technology, at an accelerating voltage of 20KeV, time Fluorine is implanted under conditions of 3 minutes, with a value of 2% (relative to the quality of the tin dioxide film), the resulting conductive glass window The sheet resistance is between 0.5 and 3 ohm/square. The average transmittance of visible light is between 8 〇 and 85%. [Example 3]·· The immersed glass is immersed in a solid content of 3%, and the particle size is 1〇~4〇. In the sol of tin bismuth (Sn〇2), after standing for 30 seconds, it is coated at a pulling speed of 1 〇〇cm/min (mm/min); after coating, it is baked at 150. (: / 10 minutes) The dried glass flakes are then immersed in a sol of Zn· 5%, zinc oxide (ZnO) having a particle size of 30 to 70 nm, and allowed to stand at 60 cm/min (jnm/min) after standing for 60 seconds. Speed mineral film; After the bond film, it is dried at 150 C / 10 minutes. The dried glass piece is sintered at 3 〇〇 〇 / 60 minutes, and the sintered conductive glass has a sheet resistance of about 1 〇 3 〇. Between ohm/square, the average transmittance of visible light is 9 〇~. Although the present invention is disclosed in the above two embodiments, it is not intended to limit the present invention, and anyone skilled in the art can be without departing from the spirit of the present invention. And within the scope, when the various changes and applications are available, the scope of protection of the present invention is defined by the scope of the patent application attached. Whichever is greater.] [Brief Description of the drawings The main element REFERENCE NUMERALS