Polymer Chemistry for Haptics, Soft Robotics, and Human-Machine Interfaces.

Progress in the field of soft devices-i.e., haptics, robotics, and human-machine interfaces (HRHMIs)-has its basis in the science of polymeric materials and chemical synthesis. However, in examining the relevant literature, we find that most developments have been enabled by off-the-shelf materials used either alone or as components of physical blends and composites. In this Progress Report, we take the position that a greater awareness of the capabilities of synthetic chemistry will accelerate the capabilities of HRHMIs. Conversely, an awareness of the applications sought by engineers working in this area may spark the development of new molecular designs and synthetic methodologies by chemists. We highlight several applications of active, stimuli-responsive polymers, which have demonstrated or shown potential use in HRHMIs. These materials share the fact that they are products of state-of-the-art synthetic techniques. The Progress Report is thus organized by the chemistry by which the materials were synthesized, including controlled radical polymerization, metal-mediated cross-coupling polymerization, ring-opening polymerization, various strategies for crosslinking, and hybrid approaches. These methods can afford polymers with multiple properties (i.e. conductivity, stimuli-responsiveness, self-healing and degradable abilities, biocompatibility, adhesiveness, and mechanical robustness) that are of great interest to scientists and engineers concerned with soft devices for human interaction.

Organic Haptics: Intersection of Materials Chemistry and Tactile Perception.

The goal of the field of haptics is to create technologies that manipulate the sense of touch. In virtual and augmented reality, haptic devices are for touch what loudspeakers and RGB displays are for hearing and vision. Haptic systems that utilize micromotors or other miniaturized mechanical devices (e.g., for vibration and pneumatic actuation) produce interesting effects, but are quite far from reproducing the feeling of real materials. They are especially deficient in recapitulating surface properties: fine texture, friction, viscoelasticity, tack, and softness. The central argument of this Progress Report is that to reproduce the feel of everyday objects requires chemistry: molecular control over the properties of materials and ultimately design of materials which can change these properties in real time. Stimuli-responsive organic materials, such as polymers and composites, are a class of materials which can change their oxidation state, conductivity, shape, and rheological properties, and thus might be useful in future haptic technologies. Moreover, the use of such materials in research on tactile perception could help elucidate the limits of human tactile sensitivity. The work described represents the beginnings of this new area of inquiry, in which the defining approach is the marriage of materials science and psychology.

Stretchable Conjugated Polymers: A Case Study in Topic Selection for New Research Groups.

The field of π-conjugated (semiconducting) polymers has been underwritten largely because of the promise of flexible (and increasingly, stretchable) devices for energy and health care. Our research group has spent much of the past six years studying the mechanical properties of conjugated polymers. Mechanically robust materials can extend the life spans of devices such as solar cells and organic light-emitting diode (OLED) panels and enable high throughput processing techniques such as roll-to-roll printing. Additionally, wearable and implantable devices, including electronic skin, implantable pressure sensors, and haptic actuators, benefit by having moduli and extensibilities close to those of biological tissue. At the time of our laboratory's inception, however, the optoelectronic properties of conjugated polymers were understood in much greater depth than their mechanical properties. We therefore set out, as our laboratory's first research topic, to understand the molecular and microstructural determinants of the mechanical properties of conjugated polymers. This is an Account not only of our scientific findings but also of the pragmatic aspects, including personnel, funding, and time constraints, behind our studies as a nascent research group. We hope that this Account will provide information to newly independent scientists about the process of starting a new research laboratory. We identify three main stages of our scientific growth. (1) We began by conducting proof-of-concept experiments to identify basic correlations between chemical structure and mechanical properties and to determine whether high optoelectronic performance and mechanical robustness were mutually exclusive. (2) We then added new metrological techniques to enable more rapid and robust measurements, such as obtaining full stress-strain curves for conjugated polymer thin films, characterizing modes of thin film failure, and simplified identification of the glass transition temperature. (3) Finally, we incorporated new capabilities, such as organic synthesis and molecular dynamics simulations, into the toolkit of our group. These stages corresponded with increased funding, personnel commitment, and flexibility to take on long-term projects. Our research efforts identified polythiophene-based semiconducting polymers capable of both achieving high power conversion efficiencies and accommodating high degrees of strain. Additionally, we identified several chemical and microstructural determinants of the mechanical properties of conjugated polymer films, such as the chemical composition and structure of side chains and a high degree of dependence on amorphous packing structure. While the field has not yet produced stretchable materials that retain state-of-the-art electronic properties with high elastic range and repeated deformation, we hope that our work and the work of others in the field has provided a foundation for future advances.

Mechanical Properties of Organic Semiconductors for Stretchable, Highly Flexible, and Mechanically Robust Electronics.

Mechanical deformability underpins many of the advantages of organic semiconductors. The mechanical properties of these materials are, however, diverse, and the molecular characteristics that permit charge transport can render the materials stiff and brittle. This review is a comprehensive description of the molecular and morphological parameters that govern the mechanical properties of organic semiconductors. Particular attention is paid to ways in which mechanical deformability and electronic performance can coexist. The review begins with a discussion of flexible and stretchable devices of all types, and in particular the unique characteristics of organic semiconductors. It then discusses the mechanical properties most relevant to deformable devices. In particular, it describes how low modulus, good adhesion, and absolute extensibility prior to fracture enable robust performance, along with mechanical "imperceptibility" if worn on the skin. A description of techniques of metrology precedes a discussion of the mechanical properties of three classes of organic semiconductors: π-conjugated polymers, small molecules, and composites. The discussion of each class of materials focuses on molecular structure and how this structure (and postdeposition processing) influences the solid-state packing structure and thus the mechanical properties. The review concludes with applications of organic semiconductor devices in which every component is intrinsically stretchable or highly flexible.

Healable Thermoplastic for Kinesthetic Feedback in Wearable Haptic Devices.

The word "haptics" refers to technologies designed to stimulate the tactile and kinesthetic senses. Kinesthesia-the sense of motion-is triggered by imposing forces upon the joints, tendons, and muscles to recreate the geometry and stiffness of objects, as may be useful in physical therapy or virtual reality. Here, we introduce a form of kinesthetic feedback by manipulating the mechanical properties of spandex impregnated with a thermoplastic polymer. Heating or cooling this textile-thermoplastic composite just above or below its glass transition temperature (T g) dramatically changes its mechanical properties (corresponding to a decrease in storage modulus from 36 MPa to 0.55 MPa). In the form of a glove, the composite can also be healed after inadvertent overextension in its stiffened state by heating it above its T g. When fitted with thermoelectric devices for active heating and cooling, the flexible or stiffened state of a glove can be perceived by human subjects. As an example of a human-machine interface, the glove is used to control a robotic finger. When the robotic finger makes contact with a wall, a signal is sent to thermoelectric devices in the glove to cool (stiffen the finger) and thus provide kinesthetic feedback to the user.

Optics-Free, Non-Contact Measurements of Fluids, Bubbles, and Particles in Microchannels Using Metallic Nano-Islands on Graphene.

Despite the apparent convenience of microfluidic technologies for applications in healthcare, such devices often rely on capital-intensive optics and other peripheral equipment that limit throughput. Here, we monitored the transit of fluids, gases, particles, and cells as they flowed through a microfluidic channel without the use of a camera or laser, i.e., "optics-free" microfluidics. We did this by monitoring the deformation of the side walls caused by the analyte passing through the channel. Critically, the analyte did not have to make contact with the channel walls to induce a deflection. This minute deformation was transduced into a change in electrical resistance using an ultrasensitive piezoresitive film composed of metallic nano-islands on graphene. We related changes in the resistance of the sensor to the theoretical deformation of the channel at varying flow rates. Then, we used air bubbles to induce a perturbation on the elastomeric channel walls and measured the viscoelastic relaxation of the walls of the channel. We obtained a viscoelastic time constant of 11.3 ± 3.5 s-1 for polydimethylsiloxane, which is consistent with values obtained using other techniques. Finally, we flowed silica particles and human mesenchymal stem cells and measured the deformation profiles of the channel. This technique yielded a convenient, continuous, and non-contact measurement of rigid and deformable particles without the use of a laser or camera.

Role of fingerprint-inspired relief structures in elastomeric slabs for detecting frictional differences arising from surface monolayers.

The perception of fine texture of an object is influenced by its microscopic topography and surface chemistry-i.e., the topmost layer of atoms and molecules responsible for its surface energy, adhesion, and friction generated when probed by a fingertip. Recently, it has been shown that human subjects can discriminate high-energy (i.e., hydrophilic), oxidized silicon from low-energy (i.e., hydrophobic), fluorinated alkylsilane-coated silicon. The basis of discrimination was consistent with differences between stick-slip friction frequencies generated when sliding the fingertip across the two surfaces. One aspect that was not examined was the presence of surface relief structures on the fingertip. Indeed, papillary ridges-fingerprints-may be involved in enhanced discrimination of fine textures arising from surface roughness, but how (or whether) fingerprints may also be involved in the discrimination of surface chemistry-through its effect on friction-is unknown. Here, using a mock finger made from a slab of silicone rubber shows that relief structures amplify differences in stick-slip friction when slid across either a hydrophilic oxide or a hydrophobic monolayer on silicon. We quantify the similarity between the friction traces of the mock fingers sliding across hydrophilic and hydrophobic surfaces under varying velocities and applied masses using a cross-correlation analysis. We then convert the cross-correlational data into convenient "discriminability matrices." These matrices identify combinations of downward forces and sliding velocities that enhance differences in friction between hydrophilic and hydrophobic monolayers. In addition, a computational model of macroscopic, "rate-and-state" friction confirms that frictional differences in chemistry are amplified when elastic slabs bear a patterned interface. This biomimetic approach to engineering sliding interfaces may inform the development of improved electronic skin and haptic devices and may contribute to understanding the role of relief structure in tactile perception.

Single-Nanowire Strain Sensors Fabricated by Nanoskiving.

This article describes the fabrication of single-nanowire strain sensors by thin sectioning of gold films with an ultramicrotome-i.e., "nanoskiving." The nanowire sensors are transferred to various substrates from the water bath on which they float after sectioning. The electrical response of these single nanowires to mechanical strain is investigated, with the lowest detectable strain determined to be 1.6 × 10-5 with a repeatable response to strains as high as 7 × 10-4. The sensors are shown to have an enhanced sensitivity with a gauge factor of 3.1 on average, but as high as 9.5 in the low strain regime (ε ~ 1 × 10-5). Conventional thin films of gold of the same height as the nanowires are used as controls, and are unable to detect those same strains. The practicality of this sensor is investigated by transferring a single nanowire to polyimide tape, and placing the sensor on the wrist to monitor the pulse pressure waveform from the radial artery. The nanowires are fabricated with simple tools and require no lithography. Moreover, the sensors can be "manufactured" efficiently, as each consecutive section of the film is a quasi copy of the previous nanowire. The simple fabrication of these nanowires, along with the compatibility with flexible substrates, offers possibilities in developing new kinds of devices for biomedical applications and structural health monitoring.

Metallic Nanoislands on Graphene as Highly Sensitive Transducers of Mechanical, Biological, and Optical Signals.

This article describes an effect based on the wetting transparency of graphene; the morphology of a metallic film (≤20 nm) when deposited on graphene by evaporation depends strongly on the identity of the substrate supporting the graphene. This control permits the formation of a range of geometries, such as tightly packed nanospheres, nanocrystals, and island-like formations with controllable gaps down to 3 nm. These graphene-supported structures can be transferred to any surface and function as ultrasensitive mechanical signal transducers with high sensitivity and range (at least 4 orders of magnitude of strain) for applications in structural health monitoring, electronic skin, measurement of the contractions of cardiomyocytes, and substrates for surface-enhanced Raman scattering (SERS, including on the tips of optical fibers). These composite films can thus be treated as a platform technology for multimodal sensing. Moreover, they are low profile, mechanically robust, semitransparent and have the potential for reproducible manufacturing over large areas.

Effect of Broken Conjugation on the Stretchability of Semiconducting Polymers.

Increasing the flexibility of polymer chains is a common method of increasing the deformability of solid polymeric materials. Here, the effects of "conjugation-break spacers" (CBSs)-aliphatic units that interrupt the sp2 -hybridized backbone of semiconducting polymers-on the mechanical and photovoltaic properties of a diketopyrrolopyrrole-based polymer are described. Unexpectedly, the tensile moduli and cracking behavior of a series of polymers with repeat units bearing 0%, 30%, 50%, 70%, and 100% of the CBS are not directly related to the percent incorporation of the flexible unit. Rather, the mechanical properties are a strong function of the order present in the film as determined by grazing-incidence x-ray diffraction. The effect of the CBSs on the photovoltaic performance of these materials, on the other hand, is more intuitive: it decreases with increasing fraction of the flexible units. These studies highlight the importance of solid-state packing structure-as opposed to only the flexibility of the individual molecules-in determining the mechanical properties of a conjugated polymer film for stretchable, ultraflexible, and mechanically robust electronics.

Using the thickness of graphene to template lateral subnanometer gaps between gold nanostructures.

This work demonstrates the use of single-layer graphene as a template for the formation of subnanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a subnanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming subnanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

Metal-assisted exfoliation (MAE): green, roll-to-roll compatible method for transferring graphene to flexible substrates.

Graphene is expected to play a significant role in future technologies that span a range from consumer electronics, to devices for the conversion and storage of energy, to conformable biomedical devices for healthcare. To realize these applications, however, a low-cost method of synthesizing large areas of high-quality graphene is required. Currently, the only method to generate large-area single-layer graphene that is compatible with roll-to-roll manufacturing destroys approximately 300 kg of copper foil (thickness = 25 µm) for every 1 g of graphene produced. This paper describes a new environmentally benign and scalable process of transferring graphene to flexible substrates. The process is based on the preferential adhesion of certain thin metallic films to graphene; separation of the graphene from the catalytic copper foil is followed by lamination to a flexible target substrate in a process that is compatible with roll-to-roll manufacturing. The copper substrate is indefinitely reusable and the method is substantially greener than the current process that uses relatively large amounts of corrosive etchants to remove the copper. The sheet resistance of the graphene produced by this new process is unoptimized but should be comparable in principle to that produced by the standard method, given the defects observable by Raman spectroscopy and the presence of process-induced cracks. With further improvements, this green, inexpensive synthesis of single-layer graphene could enable applications in flexible, stretchable, and disposable electronics, low-profile and lightweight barrier materials, and in large-area displays and photovoltaic modules.

Surface-Grafted Biocompatible Polymer Conductors for Stable and Compliant Electrodes for Brain Interfaces.

Durable and conductive interfaces that enable chronic and high-resolution recording of neural activity are essential for understanding and treating neurodegenerative disorders. These chronic implants require long-term stability and small contact areas. Consequently, they are often coated with a blend of conductive polymers and are crosslinked to enhance durability despite the potentially deleterious effect of crosslinking on the mechanical and electrical properties. Here the grafting of the poly(3,4 ethylenedioxythiophene) scaffold, poly(styrenesulfonate)-b-poly(poly(ethylene glycol) methyl ether methacrylate block copolymer brush to gold, in a controlled and tunable manner, by surface-initiated atom-transfer radical polymerization (SI-ATRP) is described. This "block-brush" provides high volumetric capacitance (120 F cm─3), strong adhesion to the metal (4 h ultrasonication), improved surface hydrophilicity, and stability against 10 000 charge-discharge voltage sweeps on a multiarray neural electrode. In addition, the block-brush film showed 33% improved stability against current pulsing. This approach can open numerous avenues for exploring specialized polymer brushes for bioelectronics research and application.

Conductive block copolymer elastomers and psychophysical thresholding for accurate haptic effects.

Electrotactile stimulus is a form of sensory substitution in which an electrical signal is perceived as a mechanical sensation. The electrotactile effect could, in principle, recapitulate a range of tactile experience by selective activation of nerve endings. However, the method has been plagued by inconsistency, galvanic reactions, pain and desensitization, and unwanted stimulation of nontactile nerves. Here, we describe how a soft conductive block copolymer, a stretchable layout, and concentric electrodes, along with psychophysical thresholding, can circumvent these shortcomings. These purpose-designed materials, device layouts, and calibration techniques make it possible to generate accurate and reproducible sensations across a cohort of 10 human participants and to do so at ultralow currents (≥6 microamperes) without pain or desensitization. This material, form factor, and psychophysical approach could be useful for haptic devices and as a tool for activation of the peripheral nervous system.

Iterative Patient Testing of a Stimuli-Responsive Swallowing Activity Sensor to Promote Extended User Engagement During the First Year After Radiation: Multiphase Remote and In-Person Observational Cohort Study.

BACKGROUND: Frequent sensor-assisted monitoring of changes in swallowing function may help improve detection of radiation-associated dysphagia before it becomes permanent. While our group has prototyped an epidermal strain/surface electromyography sensor that can detect minute changes in swallowing muscle movement, it is unknown whether patients with head and neck cancer would be willing to wear such a device at home after radiation for several months. OBJECTIVE: We iteratively assessed patients' design preferences and perceived barriers to long-term use of the prototype sensor. METHODS: In study 1 (questionnaire only), survivors of pharyngeal cancer who were 3-5 years post treatment and part of a larger prospective study were asked their design preferences for a hypothetical throat sensor and rated their willingness to use the sensor at home during the first year after radiation. In studies 2 and 3 (iterative user testing), patients with and survivors of head and neck cancer attending visits at MD Anderson's Head and Neck Cancer Center were recruited for two rounds of on-throat testing with prototype sensors while completing a series of swallowing tasks. Afterward, participants were asked about their willingness to use the sensor during the first year post radiation. In study 2, patients also rated the sensor's ease of use and comfort, whereas in study 3, preferences were elicited regarding haptic feedback. RESULTS: The majority of respondents in study 1 (116/138, 84%) were willing to wear the sensor 9 months after radiation, and participant willingness rates were similar in studies 2 (10/14, 71.4%) and 3 (12/14, 85.7%). The most prevalent reasons for participants' unwillingness to wear the sensor were 9 months being excessive, unwanted increase in responsibility, and feeling self-conscious. Across all three studies, the sensor's ability to detect developing dysphagia increased willingness the most compared to its appearance and ability to increase adherence to preventive speech pathology exercises. Direct haptic signaling was also rated highly, especially to indicate correct sensor placement and swallowing exercise performance. CONCLUSIONS: Patients and survivors were receptive to the idea of wearing a personalized risk sensor for an extended period during the first year after radiation, although this may have been limited to well-educated non-Hispanic participants. A significant minority of patients expressed concern with various aspects of the sensor's burden and its appearance. TRIAL REGISTRATION: ClinicalTrials.gov NCT03010150; https://clinicaltrials.gov/study/NCT03010150.

Structural transformation by electrodeposition on patterned substrates (STEPS): a new versatile nanofabrication method.

Arrays of high-aspect-ratio (HAR) nano- and microstructures are of great interest for designing surfaces for applications in optics, bio-nano interfaces, microelectromechanical systems, and microfluidics, but the difficulty of systematically and conveniently varying the geometries of these structures significantly limits their design and optimization for a specific function. This paper demonstrates a low-cost, high-throughput benchtop method that enables a HAR array to be reshaped with nanoscale precision by electrodeposition of conductive polymers. The method-named STEPS (structural transformation by electrodeposition on patterned substrates)-makes it possible to create patterns with proportionally increasing size of original features, to convert isolated HAR features into a closed-cell substrate with a continuous HAR wall, and to transform a simple parent two-dimensional HAR array into new three-dimensional patterned structures with tapered, tilted, anisotropic, or overhanging geometries by controlling the deposition conditions. We demonstrate the fabrication of substrates with continuous or discrete gradients of nanostructure features, as well as libraries of various patterns, starting from a single master structure. By providing exemplary applications in plasmonics, bacterial patterning, and formation of mechanically reinforced structures, we show that STEPS enables a wide range of studies of the effect of substrate topography on surface properties leading to optimization of the structures for a specific application. This research identifies solution-based deposition of conductive polymers as a new tool in nanofabrication and allows access to 3D architectures that were previously difficult to fabricate.

Decoupling Planarizing and Steric Energetics to Accurately Model the Rigidity of π-Conjugated Polymers.

The π-conjugated backbone of semiconducting polymers gives rise to both their electronic properties and structural rigidity. However, current computational methods for understanding the rigidity of polymer chains fail in one crucial way. Namely, standard torsional scan (TS) methods do not satisfactorily capture the behavior of polymers exhibiting a high degree of steric hindrance. This deficiency in part stems from the method by which torsional scans decouple energy related to electron delocalization from that related to nonbonded interactions. These methods do so by applying classical corrections of the nonbonded energy to the quantum mechanical (QM) torsional profile for polymers that are highly sterically hindered. These large corrections to the energy from nonbonded interactions can substantially skew the calculated QM energies related to torsion, resulting in an inaccurate or imprecise estimation of the rigidity of a polymer. As a consequence, simulations of the morphology of a highly sterically hindered polymer using the TS method can be highly inaccurate. Here, we describe an alternative, generalizable method by which the delocalization energy can be decoupled from the energy associated with nonbonded interactions─the "isolation of delocalization energy" (DE) method. From torsional energy calculations, we find that the relative accuracy of the DE method is similar to the TS method (within 1 kJ/mol) for two model polymers (P3HT, PTB7) when compared to quantum mechanical calculations. However, the DE method significantly increased the relative accuracy for simulations of PNDI-T, a highly sterically hindered polymer (8.16 kJ/mol). Likewise, we show that comparison of the planarization energy (i.e., backbone rigidity) from torsional parameters is significantly more precise for both PTB7 and PNDI-T when using the DE method as opposed to the TS method. These differences affect the simulated morphology, with the DE method predicting a significantly more planar configuration of PNDI-T.

Solvent-Free Transfer of Freestanding Large-Area Conjugated Polymer Films for Optoelectronic Applications.

Conventional processes for depositing thin films of conjugated polymers are restricted to those based on vapor, liquid, and solution-phase precursors. Each of these methods bear some limitations. For example, low-bandgap polymers with alternating donor-acceptor structures cannot be deposited from the vapor phase, and solution-phase deposition is always subject to issues related to the incompatibility of the substrate with the solvent. Here, a technique to enable deposition of large-area, ultra-thin films (≈20 nm or more), which are transferred from the surface of water, is demonstrated. From the water, these pre-solidified films can then be transferred to a desired substrate, circumventing limitations such as solvent orthogonality. The quality of these films is characterized by a variety of imaging and electrochemical measurements. Mechanical toughness is identified as a limiting property of polymer compatibility, along with some strategies to address this limitation. As a demonstration, the films are used as the hole-transport layer in perovskite solar cells, in which their performance is shown to be comparable to controls formed by spin-coating.

Effect of Additives on the Surface Morphology, Energetics, and Contact Resistance of PEDOT:PSS.

For a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) film employed in a device stack, charge must pass through both the bulk of the film and interfaces between adjacent layers. Thus, charge transport is governed by both bulk and contact resistances. However, for ultrathin films (e.g., flexible devices, thin-film transistors, printed electronics, solar cells), interfacial properties can dominate over the bulk properties, making contact resistance a significant determinant of device performance. For most device applications, the bulk conductivity of PEDOT:PSS is typically improved by blending additives into the solid film. Doping PEDOT:PSS with secondary dopants (e.g., polar small molecules), in particular, increases the bulk conductivity by inducing a more favorable solid morphology. However, the effects of these morphological changes on the contact resistance (which play a bigger role at smaller length scales) are relatively unstudied. In this work, we use transfer length method (TLM) measurements to decouple the bulk resistance from the contact resistance of PEDOT:PSS films incorporating several common additives. These additives include secondary dopants, a silane crosslinker (typically used to stabilize the PEDOT:PSS film), and multi-walled carbon nanotubes (conductive fillers). Using conductive atomic force microscopy, Kelvin probe force microscopy, Raman spectroscopy, and photoelectron spectroscopy, we connect changes in the contact resistance to changes in the surface morphology and energetics as governed by the blended additives. We find that the contact resistance at the PEDOT:PSS/silver interface can be reduced by (1) increasing the ratio of PEDOT to PSS chains, (2) decreasing the work function, (3) decreasing the benzoid-to-quinoid ratio at the surface of the solid film, (4) increasing the film uniformity and contact area, and (5) increasing the phase-segregated morphology of the solid film.