Ultrahigh electrical conductivity in solution-sheared polymeric transparent films

With consumer electronics transitioning toward flexible products, there is a growing need for high-performance, mechanically robust, and inexpensive transparent conductors (TCs) for optoelectronic device integration. Herein, we report the scalable fabrication of highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films via solution shearing. Specific control over deposition conditions allows for tunable phase separation and preferential PEDOT backbone alignment, resulting in record-high electrical conductivities of 4,600 ± 100 S/cm while maintaining high optical transparency. High-performance solution-sheared TC PEDOT:PSS films were used as patterned electrodes in capacitive touch sensors and organic photovoltaics to demonstrate practical viability in optoelectronic applications.Conductive films of high optical transparency are required in a myriad of applications, including electromagnetic shielding, antistatic layers, lighting displays, touch sensors, and as electrodes for photovoltaics (1, 2). As flexible, lightweight displays for televisions and portable consumer electronics become closer to reality, emerging transparent conductors (TCs) need to be mechanically robust (3). An ideal TC, therefore, should have a sheet resistance <100 Ω/□, transmissivity greater than 0.90, and be inherently flexible, all while remaining inexpensive to process on a mass scale (4).Indium tin oxide (ITO) is the most widely used TC material due to the combination of low sheet resistance and high transparency when grown on a variety of substrates. Although common to use, ITO is an expensive material due to the requirement for vacuum deposition and a number of postprocessing steps (5). For example, in organic photovoltaic (OPV) modules ITO was estimated to represent 24% of the module cost (6). However, alternative transparent conductor materials, such as poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are estimated to comprise only ∼1% of an OPV module cost. Additionally, ITO is not compatible with flexible applications, because small applied strains of as little as 4.5% lead to an order of magnitude increase in the resistance (7).In recent years there have been a number of emerging TC materials studied in the literature ranging from metal nanowires (Au, Ag, Cu) (8–11), conducting carbon allotropes (graphene, carbon nanotubes) (12–15), conducting polymers (16, 17), and other hybrid approaches (18). Recent attempts using metal nanotroughs by Wu et al. have resulted in superior optoelectronic properties with a sheet resistance of 2 Ω/□ at 90% transmission (19). The use of metal mesoscale grids further enhanced the properties of metal nanowires electrodes to a sheet resistance of 0.36 Ω/□ at 92% transmission (20). Although metal nanowires combine low resistance and high transparency, they have inferior flexibility and stretchability compared with polymer-based TCs (3).PEDOT:PSS consists of insoluble PEDOT that is charge stabilized by PSS (Fig. 1A), which affords good solubility in aqueous formulations. Within these solutions, PEDOT:PSS forms micelles where hydrophilic PSS is in contact with water and hydrophobic PEDOT is located in the micelle core (21). Upon spin-coating from solution, the micelles are deposited as a film and can have conductivities on the order of ∼1 S/cm (22). Subsequent annealing, treatment with cosolvents, and postprocessing steps can increase the conductivity of films to over 3,000 S/cm (23, 24). High-performing spin-cast PEDOT:PSS TCs have reached a sheet resistance of 46 Ω/□ at 90% transmission (25, 26). Furthermore, it is compatible with flexible electronics as films can withstand over 90% applied strain without electrical breakdown (7).Open in a separate windowFig. 1.Schematic of solution shearing process. (A) Chemical structure of PEDOT:PSS. (B) Schematic of the solution shearing design and (C) patterning PEDOT:PSS via selective patterning of solvent wetting and dewetting regions.There is a wide variety of solution processing techniques used to deposit uniform, low-roughness films (27). Spin-casting is a popular laboratory-scale deposition technique due to its simplicity and ability to deposit high-quality films with a variety of materials. However, it is a batch process that is difficult to implement on a continuous mass production scale. Furthermore, it is difficult to use elevated substrate temperatures during spin-coating, a parameter that may play a role in the final film characteristics. Contrarily, scalable fabrication through solution shearing allows for tunable deposition conditions which enable enhanced kinetic control resulting in large impacts on the electrical performance of organic electronics (28–30).In this work we use solution shearing to fabricate high-performance TC PEDOT:PSS films (Fig. 1B). Tunable control of PEDOT backbone orientation, local ordering, and phase separation is demonstrated via precise control of the deposition parameters. Record-high PEDOT:PSS conductivities of 4,600 ± 100 S/cm are obtained and reach a sheet resistance of 17 ± 1 Ω/□ at 97.2 ± 0.4% transmission. A patterning method (Fig. 1C) is also developed which enables the use of high-conductivity transparent conductive films in capacitive pressure sensors and OPV devices.