TW201432718A - 碳奈米管透明複合電極的製備方法 - Google Patents
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Abstract
本發明涉及一種碳奈米管透明複合電極的製備方法；本發明以超順排碳奈米管薄膜為導電基體，導電高分子為載體，形成一種或多種層狀結構。所形成的透明CNT電極薄膜顯示出優異的導電性，可以在室溫條件下，利用機械的工藝按照經濟且簡單的方式大面積製造該透明CNT複合電極，並且該透明CNT複合電極可應用於柔性OLED顯示器件、太陽能電池、液晶顯示，觸控式螢幕面板等器件。
Description
本發明涉及一種透明複合電極，特別是涉及一種碳奈米管透明複合電極的製備方法。
液晶面板、OLED面板、觸控式螢幕、電子紙、太陽能電池等顯示器件和光伏器件，透明電極都是不可缺少的部分。傳統透明電極性能要求主要包括透過率和電阻率，其中要求透過率達到80%以上，電阻率低於500Ω/sqm以下。但隨著科技的發展及需求的增加，透明電極除了透過率和電阻率的要求外，正朝柔性、可彎曲方面發展。氧化銦錫(ITO)在玻璃基底上形成ITO薄膜顯示出優異的透光性和導電性，目前商業化的ITO電極在透明電極的應用領域裡佔有主導地位。然而隨著透明電極應用領域的多元化，透明電極必須具備低方阻，可見光範圍內良好的透過率、柔性、可實現大面積精細塗布成膜的簡單操作的工藝等要求，這使得ITO薄膜的拓展應用中存在技術上難以克服的問題，如ITO電極高溫的製備工藝條件（蒸鍍法或濺鍍法）、易破碎、難以降低方阻、均勻性差、顏色泛黃、藍光難以透射等，並且如果將ITO薄膜配合熔點低的柔性基底，只能在低溫下沉積，所製備的ITO導電薄膜電阻率高、透明度差，與柔性基底之間的附著力差，在彎曲時易折裂，造成器件失效。並且常用的高分子柔性襯底材料與ITO的熱膨脹係數相反，在器件工作中會因為器件熱效應而導致ITO 導電薄膜脫落而失效。再者ITO薄膜所用的銦元素資源匱乏，導致ITO薄膜製備成本增高，這也成為開發新型透明導電電極材料的推動力。
碳奈米管（Carbon Nanotube，以下簡稱CNT）是一種具有典型的層狀中空結構特徵的碳材料，構成碳奈米管的管身由六邊形石墨碳環結構單元組成， 是一種具有特殊結構（徑向尺寸為奈米量級，軸向尺寸為微米量級）的一維量子材料。它的管壁構成主要為數層到數十層的同軸圓管。層與層之間保持固定的距離，約為0.34nm，直徑一般為2～20nm 。碳奈米管上碳原子的P電子形成大範圍的離域π鍵，由於共軛效應顯著，碳奈米管具有一些特殊的電學性質。由於碳奈米管的結構與石墨的片層結構相同，所以具有很好的電學性能。 碳奈米管材料因為其高電子遷移率，低電阻率及高透明度，已被科研和產業界認定為可代替ITO的透明電極。
目前製備碳奈米管透明電極的方法較多，大致分為濕法和乾法製備。濕法合成主要指採用碳奈米管粉體均勻分散在溶液進行薄膜製備，包含真空抽濾轉移法[Green A A, Hersam M C. Colored Semitransparent Conductive Coatings Consisting of Monodisperse Metallic Single -Walled Carbon Nanotubes[J]. Nano Lett., 2008, 8(5): 1417-1422.]、噴塗法[Kang S J, Song Y, Yi Y, et al. Work-Function Engineering of Carbon Nanotube Transparent Conductive Films[J]. Carbon, 2010, 48(2):520-524.]、旋塗法[Meitl M A, Zhou Y X, Gaur A, et al. Solution Casting and Transfer Printing Single-Walled Carbon Nanotube Films [J]. Nano. Lett., 2004, 4(9):1643-1647.]、提拉法[Ng M H A, Hartadi L T, Tan H , et al. Efficient Coating of Transparent and Conductive Carbon Nanotube Thin Films on Plastic Substrates[J]. Nanotechnology, 2008, 19: 205703.]、LB法[Li X L, Zhang L, Wang X R, et al. Langmuir-Blodgett Assembly of Densely Aligned Single-Walled Carbon Nanotubes from Bulk Materials[J]. J. Am. Chem. Soc., 2007, 129(16): 4890-4891.]、電泳法[Pei S F, Du J H, Zeng Y, et al. The Fabrication of a Carbon Nanotube Transparent Conductive Film by Electrophoretic Deposition and Hot-Pressing Transfer[J]. Nanotechnology, 2009, 20:235707.]等；乾法製備包括氣溶膠直接合成法[Fraser I S, Motta M S, Schmidt R K, et al. Continuous Production of Flexible Carbon Nanotube-Based Transparent Conductive Films[J]. Sci. Technol. Adv. Mater., 2010, 11(4), 045004.]，超陣列提拉法[Feng C, Liu K, Wu J S, et al. Flexible, Stretchable, Transparent Conducting Films Made from Superaligned Carbon Nanotubes [J]. Adv. Funct. Mater., 2010, 20(6):885-891.]等。
採用濕法製備的碳奈米管透明電極由於存在碳奈米管分散不均勻的問題，所製備電極會由於局部缺陷會導致電極失效，目前的研究局限於實驗室研究，在大面積應用方面還存在很大的技術挑戰。
採用乾法-氣溶膠直接合成法碳奈米管透明電極的工藝，是將氣相沉積爐中生成的碳奈米管氣溶膠打在透明聚合膠帶上後由柱狀瓦解為平坦的膜狀。該方法製備的碳奈米管透明電極的形貌及品質受到反應過程中諸多因素的影響，如化學氣相沉積爐的溫度、載氣氫的流速、柔性基底的繞行速度等。沉積膜的寬度受到反應爐出口處直徑的限制，進而也限制了製備大面積碳奈米管透明電極。
超陣列提拉法利用碳奈米管的可伸展性，可將碳奈米管拉伸為無限長的薄膜。超順排碳奈米管陣列在經過退火處理後，CNT的陣列方向由垂直變為水平。在拉伸時，將其置於柔性基底和拉伸膜之間，通過兩個滾輪將其壓緊。此超陣列提拉法與濕法合成法相比，工藝簡單，CNT 利用率高，費用低，成膜品質高，可用於工業化批量生產。但碳奈米管與柔性基底的結合只是通過機械擠壓的方法附著在柔性基底的表面，相對而言，其工藝操作過程中由於碳奈米管膜層的不牢固會導致電極品質受限。並且此工藝方法不易在同一基底上進行多次操作。
本發明開發了一種新型的透明碳奈米管複合電極的製備工藝方法。本發明以超順排碳奈米管薄膜[Feng C, Liu K, Wu J S, et al. Flexible, Stretchable, Transparent Conducting Films Made from Superaligned Carbon Nanotubes [J]. Adv. Funct. Mater., 2010, 20(6):885-891.]為導電基體，導電高分子為載體，形成一種一層或多層的層狀結構，所形成的透明CNT複合電極薄膜顯示出優異的導電性，可以在室溫條件下，利用機械擠壓工藝，可大面積製備碳奈米管透明複合電極。該透明CNT複合電極可應用於柔性OLED顯示器件、太陽能電池、液晶顯示，觸控式螢幕面板等器件。
碳奈米管透明複合電極，包括透明高分子基底和在透明基底的表面上形成的CNT複合薄膜，所述CNT複合薄膜由CNT薄膜和導電高分子膜組成，其製備方法包括如下步驟：（1）在透明高分子基底上鋪放超順排的碳奈米管薄膜，由引膜件在矽片上生長的超順排碳奈米管的邊緣抽出一定寬度的碳奈米管膜層，然後將此膜層平鋪在透明高分子基底表面至鋪滿所需區域，採用鐳射切割方法或者採用乙醇收縮的方法切斷碳奈米管薄膜；(2)將鋪有碳奈米管薄膜的基板通過一對相對旋轉的輥筒之間，使碳奈米管薄膜的表面上粘附一層導電高分子膜，所述一個或兩個輥筒表面塗刷有導電高分子溶液。
所述輥筒表面粗糙度Ra0.02~0.01μm。
所述輥筒之間的夾縫最小距離為基板厚度。
所述導電高分子溶液的粘度為1-10×10-3PaS。
所述導電高分子水溶液主要組成成分為：1）聚苯胺、聚3， 4-乙撐二氧噻吩、聚乙炔或/和聚吡咯， 2）助溶劑：聚苯乙烯磺酸鹽、樟腦磺酸、十二烷基苯磺酸及鹽、十六烷基苯磺酸及鹽或/和萘磺酸及鹽，3）改性助劑：丙二醇，山梨醇，二甲基亞碸或/和N-N二甲基甲醯胺，乙二醇， 4）其餘為水。
所述導電高分子水溶液為的1.8%PEDOT：PSS水溶液，其具體組成如下： 聚3， 4-乙撐二氧噻吩PEDOT 0.5-1%， 聚苯乙烯磺酸鹽PSS 0.8-1.3%， 十二烷基苯磺酸鈉 0.01%-0.05%， 乙二醇 0.37%-0.44%， 水 加至100%。
所述輥筒內部設有加熱部件。
本發明公開了一種利用碳奈米管（CNT）薄膜製備的透明導電複合電極的方法。該透明CNT薄膜電極包括透明高分子基底和在透明基底的表面上形成的CNT複合薄膜，其中，CNT導電薄膜由包含CNT薄膜和導電高分子膜組成。本發明是採用與基底附著力良好的碳奈米管陣列薄膜與液相的導電高分子在機械擠壓時形成一個CNT複合薄膜。該透明CNT複合電極顯示出優異的導電性，可以在室溫條件下利用機械擠壓的濕法工藝製備透明的CNT複合電極。高分子導電膜是採用溶液的形式粘附在碳奈米管薄膜表面的，高分子導電膜與碳奈米管拉伸膜及基底之間有良好的結合力，適合於多層工藝操作。本發明形成的膜是一層或多層複合薄膜。由於CNT膜層本比較薄，單層CNT膜層厚度是幾個或幾十個奈米，這樣膜層在鋪放的過程中會出現局部破壞，為了保證CNT導電層的平面或三維的導電性，可多層鋪設。此工藝方法製備成本低廉，可實現大面積透明電極的製備。該透明CNT電極可應用於製造需要具有透光性和導電性的各種裝置如柔性有機電致發光顯示器件（OLED）、太陽能電池、液晶顯示器件、等離子顯示器件（PDP）、圖像感測器、觸控式螢幕面板等。
該透明CNT複合電極可應用於製造需要具有透光性和導電性的各種裝置如柔性有機電致發光顯示器件（OLED）、太陽能電池、液晶顯示器件、等離子顯示器件（PDP）、圖像感測器、觸控式螢幕面板等的電極材料。
透明碳奈米管複合電極的製備的主要技術分為兩個部分：(1)碳奈米管薄膜與基底之間的附著是通過碳奈米管薄膜2表面與透明基底1之間的表面分子間力結合。具體的成膜示意圖見圖1。為保證碳奈米管薄膜2與透明基底1之間附著力，可將形如圖2的碳奈米管薄膜2平放於乙醇噴霧的環境中進行收縮。單次拉膜後形成的碳奈米管薄膜2在乙醇的蒸汽環境中，會自動收縮形成穩定的線狀的碳奈米管束所組成的結構。乙醇分子會吸附在其表面，修飾其表面極性，同時也增強了碳奈米管薄膜2與透明基體1襯底的結合力，所得碳奈米管薄膜2不會輕易在環境運輸及放置過程中破壞。(2)將圖2中所示鋪有碳奈米管薄膜的透明基底4通過一對相對旋轉的輥筒5。要求輥筒5表面粗糙度Ra0.02~0.01μm。輥筒5之間的夾縫最小距離為透明基底1厚度。在輥筒5表面塗刷粘度在1-10×10-3PaS的導電高分子水溶液。如果需要可添加一定的加熱附件以實現輥筒溫度的控制，以確保高分子體的粘度。從輥筒5上方出來基板表面形成了帶有碳奈米管的導電高分子複合薄膜3，圖3是複合薄膜3的製備示意圖。形成的薄膜結構如圖4。可根據需要將圖4中的碳奈米管高分子薄膜重複鋪一次碳奈米管膜後接著粘附導電高分子層，還可以多次操作。
導電高分子水溶液成分：1）聚苯胺、聚3,4-乙撐二氧噻吩、聚乙炔或/和聚吡咯， 2）助溶劑：聚苯乙烯磺酸鹽、樟腦磺酸、十二烷基苯磺酸及鹽、十六烷基苯磺酸及鹽或/和萘磺酸及鹽，3）改性助劑：丙二醇，山梨醇，二甲基亞碸或/和N-N二甲基甲醯胺，乙二醇， 4）其餘為水。
製備方法：是將所有組分按比例混合溶解在一定的溶劑中，其濃度可通過添加水或相應的溶劑來調整。
如：導電高分子水溶液為的1.8%PEDOT：PSS水溶液。 聚3， 4-乙撐二氧噻吩PEDOT 0.5-1% 聚苯乙烯磺酸鹽PSS 0.8- 1.3% 十二烷基苯磺酸鈉 0.01%-0.05% 乙二醇 0.37%-0.44% 水 加至100%。
製備得到透明碳奈米管複合電極：(1)在高分子透明基底1上鋪放超順排的碳奈米管薄膜2，由引膜件7在矽片6上生長的超順排碳奈米管的邊緣抽出一定寬度的碳奈米管膜層，然後將此膜層平鋪在高分子透明基底1表面至鋪滿所需區域，採用鐳射切割方法或者採用乙醇收縮的方法切斷碳奈米管薄膜2；(2)將鋪有碳奈米管薄膜的基底4通過一對相對旋轉的輥筒5之間，其中，導電高分子水溶液塗於輥筒5上，使碳奈米管薄膜2的表面上粘附一層導電高分子膜，形成複合薄膜3。
1．．．透明基底
2．．．碳奈米管薄膜
3．．．碳奈米管複合薄膜
4．．．鋪有碳奈米管薄膜的透明基底
5．．．輥筒
6．．．矽片
7．．．引膜件
[圖1]係本發明之矽片上碳奈米管薄膜的製備； [圖2]係本發明之透明基體上碳奈米管薄膜示意圖； [圖3]係本發明之碳奈米管高分子複合薄膜的製備示意圖； [圖4]係本發明之碳奈米管高分子複合薄膜示意圖；以及 [圖5]係本發明之多層碳奈米管高分子複合薄膜示意圖。
1．．．透明基底
2．．．碳奈米管薄膜
6．．．矽片
7．．．引膜件
Claims (7)
- 一種碳奈米管透明複合電極的製備方法，所述碳奈米管透明複合電極包括透明高分子基底和在透明基底的表面上形成的碳奈米管複合薄膜，所述碳奈米管複合薄膜由碳奈米管薄膜和導電高分子膜組成，其製備方法包含如下步驟：(1)在透明高分子基底上鋪放超順排的碳奈米管薄膜，由引膜件在矽片上生長的超順排碳奈米管的邊緣抽出一定寬度的碳奈米管膜層，然後將此膜層平鋪在透明高分子基底表面至鋪滿所需區域，採用鐳射切割方法或者採用乙醇收縮的方法切斷碳奈米管薄膜；(2)將鋪有碳奈米管薄膜的基板通過一對相對旋轉的輥筒之間，使碳奈米管薄膜的表面上粘附一層導電高分子膜，所述一個或兩個輥筒表面塗刷有導電高分子水溶液。
- 如申請專利範圍第1項所述的碳奈米管透明複合電極的製備方法，其中所述輥筒表面粗糙度Ra0.02~0.01μm。
- 如申請專利範圍第1項所述的碳奈米管透明複合電極的製備方法，其中所述輥筒之間的夾縫最小距離為基板厚度。
- 如申請專利範圍第1項所述的碳奈米管透明複合電極的製備方法，其中所述導電高分子水溶液的粘度為1-10×10-3PaS。
- 如申請專利範圍第1項所述的碳奈米管透明複合電極的製備方法，其中所述導電高分子水溶液主要組成成分為：1）聚苯胺、聚3，4-乙撐二氧噻吩、聚乙炔或/和聚吡咯， 2）助溶劑：聚苯乙烯磺酸鹽、樟腦磺酸、十二烷基苯磺酸及鹽、十六烷基苯磺酸及鹽或/和萘磺酸及鹽，3）改性助劑：丙二醇，山梨醇，二甲基亞碸或/和N-N二甲基甲醯胺，乙二醇， 4）其餘為水。
- 如申請專利範圍第1項所述的碳奈米管透明複合電極的製備方法，其中所述導電高分子水溶液為的1.8%PEDOT：PSS水溶液，其具體組成如下： 聚3，4-乙撐二氧噻吩 0.5-1%， 聚苯乙烯磺酸鹽 0.8-1.3%， 十二烷基苯磺酸鈉 0.01%-0.05%， 乙二醇 0.37%-0.44%， 水 加至100%。
- 如申請專利範圍第1項所述的碳奈米管透明複合電極的製備方法，所述輥筒內部設有加熱部件。
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| US11121341B2 (en) | 2017-08-30 | 2021-09-14 | Tsinghua University | Organic light emitting diode including electron transport layer including carbon nanotubes |
| TWI773640B (zh) * | 2015-02-23 | 2022-08-11 | 美商美國琳得科股份有限公司 | 黏著薄片 |
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| CN105361977B (zh) * | 2014-08-26 | 2018-08-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | 电阻式柔性透明关节部位电子皮肤及其制备方法和应用 |
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| US10374158B2 (en) | 2017-08-30 | 2019-08-06 | Tsinghua University | Method for making organic light emitting diode |
| TWI689119B (zh) * | 2017-08-30 | 2020-03-21 | 鴻海精密工業股份有限公司 | 有機發光二極體 |
| US11121341B2 (en) | 2017-08-30 | 2021-09-14 | Tsinghua University | Organic light emitting diode including electron transport layer including carbon nanotubes |
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| DE112013006416T5 (de) | 2015-10-15 |
| CN103928637B (zh) | 2016-05-04 |
| TWI553662B (zh) | 2016-10-11 |
| KR20150118583A (ko) | 2015-10-22 |
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