技术领域technical field
本发明涉及透明电极领域，更具体的说，涉及一种碳基复合材料的透明电极及其制备方法。The invention relates to the field of transparent electrodes, in particular to a transparent electrode of carbon-based composite material and a preparation method thereof.
背景技术Background technique
随着全球能源需求逐年增加，有机光电研究成为世界关注的热点课题。在此背景下，透明电极以其独特的优异性能引起人们的广泛关注，为了进行工业大规模生产，必须实现柔性印刷制备有机光电器件。柔性大面积光电器件具有成本低廉、制备工艺简单、可任意弯曲、质量轻、便于携带、易于建筑一体化和高功率重量比的优点。然而，基于柔性衬底的制备工艺还很不成熟，印刷电极墨水工艺落后、ITO材料昂贵造成的制作成本较高、器件性能也相对较低，限制其进一步商业化应用的发展。因此，研究和开发可用于大面积柔性衬底的透明导电薄膜替代ITO成为新型透明电极，降低制作成本，成为真正聚合物薄膜太阳能电池实现商业化应用的关键科学技术问题。With the increasing global energy demand year by year, organic optoelectronic research has become a hot topic in the world. In this context, transparent electrodes have attracted widespread attention due to their unique and excellent properties. In order to carry out large-scale industrial production, it is necessary to achieve flexible printing to prepare organic optoelectronic devices. Flexible large-area optoelectronic devices have the advantages of low cost, simple fabrication process, arbitrary bending, light weight, portability, easy building integration, and high power-to-weight ratio. However, the preparation process based on flexible substrates is still very immature, the printing electrode ink process is backward, the production cost is high due to the expensive ITO material, and the device performance is relatively low, which limits the development of its further commercial application. Therefore, the research and development of transparent conductive films that can be used on large-area flexible substrates to replace ITO as new transparent electrodes and reduce production costs has become a key scientific and technical issue for the commercial application of real polymer thin film solar cells.
为了替代ITO，制备更为复合柔性印刷的透明导电薄膜，目前的科学研究主要集中在新型透明金属氧化物(如：铝掺杂的氧化锌(AZO)、氟掺杂的氧化锡(FTO)等)、透明纳米金属材料（银纳米线、金纳米粒子等、导电高分子碳材料(如聚(3,4-乙撑二氧噻吩):(聚苯乙烯磺酸盐)，PEDOT:PSS)、和功能碳材料(碳纳米管、石墨烯等)。In order to replace ITO and prepare more composite flexible printing transparent conductive films, current scientific research mainly focuses on new transparent metal oxides (such as: aluminum-doped zinc oxide (AZO), fluorine-doped tin oxide (FTO), etc. ), transparent nano-metal materials (silver nanowires, gold nanoparticles, etc., conductive polymer carbon materials (such as poly(3,4-ethylenedioxythiophene): (polystyrene sulfonate), PEDOT:PSS), And functional carbon materials (carbon nanotubes, graphene, etc.).
在这些材料中，AZO和FTO材料其制备工艺仍然十分复杂其耗费的成本较高，且在柔性基底上的性能较差。透明纳米金属材料的纳米线节点会产生较大的电阻，影响薄膜的电导率。纳米线网格结构对于薄膜的柔韧性也会产生很大影响，降低薄膜力学稳定性。PEDOT:PSS作为一种优良的导电高分子材料被广泛应用在柔性透明电极中，但目前仍然存在无法避免的问题，如PEDOT:PSS薄膜呈现一种偏蓝的颜色会影响透光性能。PEDOT:PSS耐酸性、加工性不好和较低导电率吸湿性等缺点也不同程度限制了PEDOT:PSS导电薄膜的进一步发展。Among these materials, the preparation process of AZO and FTO materials is still very complicated, the cost is high, and the performance on flexible substrates is poor. The nanowire nodes of the transparent nanometal material will generate a large resistance, which affects the conductivity of the film. The nanowire grid structure will also have a great impact on the flexibility of the film, reducing the mechanical stability of the film. As an excellent conductive polymer material, PEDOT:PSS is widely used in flexible transparent electrodes, but there are still unavoidable problems, such as the bluish color of PEDOT:PSS film will affect the light transmission performance. The disadvantages of PEDOT:PSS acid resistance, poor processability, low conductivity and hygroscopicity also limit the further development of PEDOT:PSS conductive films to varying degrees.
碳基材料自身透光性很高、力学性能稳定。采用碳纳米管、石墨烯等碳基材料应用柔性透明电极因其存在着富电子的π体系，具有高效的电荷传输路径。为了进一步满足大面积商业化应用，仍需解决π-π堆叠效应导致的墨水溶液很难实现高度分散，热处理对界面层的形貌影响，导致载流子的传输通道遭到破坏两大问题。Carbon-based materials have high light transmittance and stable mechanical properties. The use of carbon-based materials such as carbon nanotubes and graphene to apply flexible transparent electrodes has an efficient charge transport path due to the existence of an electron-rich π system. In order to further meet the large-area commercial application, it is still necessary to solve the two major problems that the ink solution caused by the π-π stacking effect is difficult to achieve high dispersion, and the impact of heat treatment on the morphology of the interface layer leads to the destruction of the carrier transport channel.
发明内容Contents of the invention
本发明的目的是提供一种碳基复合透明电极及制备方法。The object of the present invention is to provide a carbon-based composite transparent electrode and a preparation method thereof.
本发明是通过以下技术方案实现的。The present invention is achieved through the following technical solutions.
一种碳基复合透明电极，由透明衬底和透明导电薄膜层构成。其特征是所述的透明导电薄膜为功能化碳材料掺杂PEDOT:PSS[聚(3,4-乙撑二氧噻吩):(聚苯乙烯磺酸盐)]水溶液得到。A carbon-based composite transparent electrode is composed of a transparent substrate and a transparent conductive film layer. It is characterized in that the transparent conductive film is obtained by doping PEDOT:PSS [poly(3,4-ethylenedioxythiophene):(polystyrene sulfonate)] aqueous solution with functionalized carbon material.
本发明所述的功能化碳材料为酸化碳纳米管CNTs、酸化石墨烯Graphene、磺化碳纳米管CNTs或磺化石墨烯Graphene中的一种。The functionalized carbon material of the present invention is one of acidified carbon nanotubes CNTs, acidified graphene Graphene, sulfonated carbon nanotubes CNTs or sulfonated graphene Graphene.
本发明所述的功能化碳材料掺杂PEDOT:PSS的过程是：将功能化碳材料分散液与PEDOT:PSS水溶液共混，然后超声处理得到复合PEDOT:PSS水溶液。其中，功能化碳材料掺杂浓度为质量百分比浓度0.3-1.0%。The process of doping the functionalized carbon material with PEDOT:PSS in the present invention is: blending the functionalized carbon material dispersion with the PEDOT:PSS aqueous solution, and then ultrasonically treating it to obtain a composite PEDOT:PSS aqueous solution. Wherein, the doping concentration of the functionalized carbon material is 0.3-1.0% by mass.
本发明所述的功能化碳材料分散液是将功能化碳材料分散在极性溶剂中，其浓度为0.5 mg/ml。所述的极性溶剂为水、醇和二甲基亚砜。优选二甲基亚砜。The functionalized carbon material dispersion liquid of the present invention is to disperse the functionalized carbon material in a polar solvent, and its concentration is 0.5 mg/ml. Described polar solvent is water, alcohol and dimethyl sulfoxide. Dimethylsulfoxide is preferred.
本发明所述的透明衬底采用透明玻璃衬底或柔性聚合物衬底。所述的透明衬底在制膜之前表面依次经过丙酮、洗洁精和去离子水超声清洗以及plasma等离子体清洗。The transparent substrate of the present invention adopts a transparent glass substrate or a flexible polymer substrate. The surface of the transparent substrate is sequentially cleaned by ultrasonic cleaning with acetone, detergent and deionized water and plasma cleaning before film formation.
本发明所述的透明导电薄膜的制备工艺为小面积旋涂或大面积柔性印刷。The preparation process of the transparent conductive film of the present invention is small-area spin coating or large-area flexographic printing.
本发明所述的透明导电薄膜厚度为70 nm-200 nm。The thickness of the transparent conductive film of the present invention is 70 nm-200 nm.
采用碳材料与PEDOT:PSS结合制备复合透明导电薄膜，可以有效结合二者优点制备出高性能透明导电薄膜。Combining carbon materials and PEDOT:PSS to prepare composite transparent conductive films can effectively combine the advantages of both to prepare high-performance transparent conductive films.
本发明将高度分散的碳基材料分散液掺杂PEDOT:PSS水溶液，制备碳纳米管(CNTs)和石墨烯(Graphene)改性的PEDOT:PSS复合透明电极，实现高电导率以及高透光性电极材料，从而取代ITO，大幅降低电极制备成本。In the present invention, the highly dispersed carbon-based material dispersion liquid is doped with PEDOT:PSS aqueous solution to prepare carbon nanotubes (CNTs) and graphene (Graphene) modified PEDOT:PSS composite transparent electrodes to achieve high electrical conductivity and high light transmittance Electrode materials, thereby replacing ITO, greatly reducing the cost of electrode preparation.
附图说明Description of drawings
图1为本发明的实施方案的透明电极结构。其中，1为透明衬底，2为碳基复合透明导电薄膜。FIG. 1 is a structure of a transparent electrode according to an embodiment of the present invention. Among them, 1 is a transparent substrate, and 2 is a carbon-based composite transparent conductive film.
图2为本发明一个旋涂制备的小面积透明电极的透光率图示。Fig. 2 is a graphic representation of the light transmittance of a small-area transparent electrode prepared by spin coating according to the present invention.
图3为本发明一个大面积柔性卷对卷工艺制备的透明电极的透光率图示。Fig. 3 is a graphic representation of the light transmittance of a transparent electrode prepared by a large-area flexible roll-to-roll process of the present invention.
具体实施方式Detailed ways
本发明将通过以下实施例作进一步说明。应该理解，这样的描述仅用于举例说明本发明，而不用于限制。The invention will be further illustrated by the following examples. It should be understood that such descriptions are made by way of illustration only and not limitation of the invention.
本实施例所用的PEDOT:PSS为德国贺利氏公司生产的Clevios PH 1000型号PEDOT:PSS水溶液。The PEDOT:PSS used in this embodiment is the Clevios PH 1000 model PEDOT:PSS aqueous solution produced by Heraeus, Germany.
实施例1。Example 1.
采用在常温经过酸化处理的单壁碳纳米管按照0.5%质量比加入PEDOT:PSS PH1000水溶液中，经过6小时的超声处理后待用。在薄膜沉积衬底之前，应对基底进行预处理，目的用于提高衬底表面的亲水性。经过plamsa预处理30分钟的透明玻璃基底，放置在匀胶机支撑架中心。将PEDOT:PSS:CNTs滴在玻璃基底上，旋涂制备厚度为75 nm的透明导电薄膜。在120℃条件下热退火20分钟，待冷却后分别通过紫外可见分光光度计和四点探针测试仪测试透明电极的透光率和导电特性。如图2所示为薄膜的透光性。薄膜的平均方块电阻为40.51 Ω sq-1。Single-walled carbon nanotubes that have been acidified at room temperature were added to PEDOT:PSS PH1000 aqueous solution at a mass ratio of 0.5%, and were subjected to ultrasonic treatment for 6 hours before use. Before the thin film is deposited on the substrate, the substrate should be pretreated to improve the hydrophilicity of the substrate surface. The transparent glass substrate that has been pretreated by plamsa for 30 minutes is placed in the center of the support frame of the homogenizer. PEDOT:PSS:CNTs were dropped on a glass substrate and spin-coated to prepare a transparent conductive film with a thickness of 75 nm. Thermal annealing was performed at 120° C. for 20 minutes, and after cooling, the light transmittance and electrical conductivity of the transparent electrode were tested by a UV-visible spectrophotometer and a four-point probe tester. Figure 2 shows the light transmittance of the film. The average sheet resistance of the film is 40.51 Ω sq-1.
实施例2。Example 2.
采用如实施例1一样条件的酸化碳纳米管制备的PEDOT:PSS:CNTs导电墨水。通过深圳市善营自动化设备有限公司的GTB150B-0602E多功能涂布机，进行涂布。在宽度为12 cm基材上均匀涂布五条宽度为1 cm的电极薄膜。滚轮张力控制在30-40N。通过控制滚轮速度与走带速度的涂速比控制薄膜的厚度。实验设定涂速比为1.1。采用将经过超声30分钟以上的PEDOT:PSS:CNTs导电墨水放入凹版印刷墨槽内，设定好预设的涂速比与辊轮张力后，开启机器进行涂布即可。涂布的工艺包括，放卷单元，基材清洗，电晕处理，干燥单元，涂布单元，以及后退火干燥单元和收卷单元。所述清洗单元采用丙酮溶剂进行清洗。干燥单元为热红外烘干。后退火干燥温度为130℃。经过整个卷对卷涂布流程后，薄膜厚度为150 nm。通过紫外可见分光光度计和四点探针测试仪测试透明电极的透过性和导电特性。如图3所示为薄膜的透光性。薄膜的平均方块电阻为17 Ω sq-1。The PEDOT:PSS:CNTs conductive ink prepared by using acidified carbon nanotubes under the same conditions as in Example 1. Coating is carried out by the GTB150B-0602E multifunctional coating machine of Shenzhen Shanying Automation Equipment Co., Ltd. Five electrode films with a width of 1 cm were uniformly coated on a substrate with a width of 12 cm. Roller tension is controlled at 30-40N. The thickness of the film is controlled by controlling the coating speed ratio of the roller speed and the belt speed. The experiment set the coating speed ratio as 1.1. Put the PEDOT:PSS:CNTs conductive ink that has been ultrasonicated for more than 30 minutes into the gravure printing ink tank. After setting the preset coating speed ratio and roller tension, turn on the machine for coating. The coating process includes unwinding unit, substrate cleaning, corona treatment, drying unit, coating unit, post-annealing drying unit and winding unit. The cleaning unit is cleaned with acetone solvent. The drying unit is thermal infrared drying. The post-annealing drying temperature is 130°C. After the entire roll-to-roll coating process, the film thickness was 150 nm. The permeability and conductivity of the transparent electrode were tested by a UV-vis spectrophotometer and a four-point probe tester. Figure 3 shows the light transmittance of the film. The average sheet resistance of the film was 17 Ω sq-1 .
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| CN201410587978.2ACN104465993A (en) | 2014-10-28 | 2014-10-28 | Carbon-based composite transparent electrode and manufacturing method thereof |
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| CN201410587978.2ACN104465993A (en) | 2014-10-28 | 2014-10-28 | Carbon-based composite transparent electrode and manufacturing method thereof |
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| CN201410587978.2APendingCN104465993A (en) | 2014-10-28 | 2014-10-28 | Carbon-based composite transparent electrode and manufacturing method thereof |
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