Predicting the Electrical, Mechanical, and Geometric Contributions to Soft Electroadhesives through Fracture Mechanics.

Electroadhesion is the modulation of adhesive forces through electrostatic interactions and has potential applications in a number of next-generation technologies. Recent efforts have focused on using electroadhesion in soft robotics, haptics, and biointerfaces that often involve compliant materials and nonplanar geometries. Current models for electroadhesion provide limited insight on other contributions that are known to influence adhesion performance, such as geometry and material properties. This study presents a fracture mechanics framework for understanding electroadhesion that incorporates geometric and electrostatic contributions for soft electroadhesives. We demonstrate the validity of this model with two material systems that exhibit disparate electroadhesive mechanisms, indicating that this formalism is applicable to a variety of electroadhesives. The results show the importance of material compliance and geometric confinement in enhancing electroadhesive performance and providing structure-property relationships for designing electroadhesive devices.

Geometry-controlled instabilities for soft-soft adhesive interfaces.

Soft materials interfaces can develop complex morphologies, such as cavities or finger-like features, during separation as a result of a mechanical instability. While the onset and growth of these instabilities have been investigated previously for interfaces between rigid and soft materials, no existing predictive model provides insight for controlling the separation morphology associated with these instabilities when both "sides" of the interface are soft. Here, we expand previous models to account for the geometry and materials properties of two soft materials that form an interface. The total compliance of the system, which depends nonlinearly on the thickness of each contacting soft material, plays a primary role in governing the morphology of the separating interface. We validate this model with experimental measurements using a series of soft elastomers with varying layer thicknesses and fixed materials properties, in order to emphasize the geometry alone can give rise to the observed differences in the interface separation process. This model also demonstrates that the degree of geometric asymmetry, or the ratio of the layer thicknesses that form an interface, influences the stress experienced in either layer, thus providing a rich means of controlling how unstable interface separations develop and propagate. This framework is a powerful tool to understand and control adhesion mechanisms in fields ranging from biology to soft robotics, and provides intuition for engineering a separation mode for a desired end result.

Branched Side Chains Govern Counterion Position and Doping Mechanism in Conjugated Polythiophenes.

Predicting the interactions between a semiconducting polymer and dopant is not straightforward due to the intrinsic structural and energetic disorder in polymeric systems. Although the driving force for efficient charge transfer depends on a favorable offset between the electron donor and acceptor, we demonstrate that the efficacy of doping also relies on structural constraints of incorporating a dopant molecule into the semiconducting polymer film. Here, we report the evolution in spectroscopic and electrical properties of a model conjugated polymer upon exposure to two dopant types: one that directly oxidizes the polymeric backbone and one that protonates the polymer backbone. Through vapor phase infiltration, the common charge transfer dopant, F4-TCNQ, forms a charge transfer complex (CTC) with the polymer poly(3-(2'-ethyl)hexylthiophene) (P3EHT), a conjugated polymer with the same backbone as the well-characterized polymer P3HT, resulting in a maximum electrical conductivity of 3 × 10-5 S cm-1. We postulate that the branched side chains of P3EHT force F4-TCNQ to reside between the π-faces of the crystallites, resulting in partial charge transfer between the donor and the acceptor. Conversely, protonation of the polymeric backbone using the strong acid, HTFSI, increases the electrical conductivity of P3EHT to a maximum of 4 × 10-3 S cm-1, 2 orders of magnitude higher than when a charge transfer dopant is used. The ability for the backbone of P3EHT to be protonated by an acid dopant, but not oxidized directly by F4-TCNQ, suggests that steric hindrance plays a significant role in the degree of charge transfer between dopant and polymer, even when the driving force for charge transfer is sufficient.

Morphology controls the thermoelectric power factor of a doped semiconducting polymer.

The electrical performance of doped semiconducting polymers is strongly governed by processing methods and underlying thin-film microstructure. We report on the influence of different doping methods (solution versus vapor) on the thermoelectric power factor (PF) of PBTTT molecularly p-doped with F n TCNQ (n = 2 or 4). The vapor-doped films have more than two orders of magnitude higher electronic conductivity (σ) relative to solution-doped films. On the basis of resonant soft x-ray scattering, vapor-doped samples are shown to have a large orientational correlation length (OCL) (that is, length scale of aligned backbones) that correlates to a high apparent charge carrier mobility (µ). The Seebeck coefficient (α) is largely independent of OCL. This reveals that, unlike σ, leveraging strategies to improve µ have a smaller impact on α. Our best-performing sample with the largest OCL, vapor-doped PBTTT:F4TCNQ thin film, has a σ of 670 S/cm and an α of 42 µV/K, which translates to a large PF of 120 µW m-1 K-2. In addition, despite the unfavorable offset for charge transfer, doping by F2TCNQ also leads to a large PF of 70 µW m-1 K-2, which reveals the potential utility of weak molecular dopants. Overall, our work introduces important general processing guidelines for the continued development of doped semiconducting polymers for thermoelectrics.

Sub-particle reaction and photocurrent mapping to optimize catalyst-modified photoanodes.

The splitting of water photoelectrochemically into hydrogen and oxygen represents a promising technology for converting solar energy to fuel. The main challenge is to ensure that photogenerated holes efficiently oxidize water, which generally requires modification of the photoanode with an oxygen evolution catalyst (OEC) to increase the photocurrent and reduce the onset potential. However, because excess OEC material can hinder light absorption and decrease photoanode performance, its deposition needs to be carefully controlled--yet it is unclear which semiconductor surface sites give optimal improvement if targeted for OEC deposition, and whether sites catalysing water oxidation also contribute to competing charge-carrier recombination with photogenerated electrons. Surface heterogeneity exacerbates these uncertainties, especially for nanostructured photoanodes benefiting from small charge-carrier transport distances. Here we use super-resolution imaging, operated in a charge-carrier-selective manner and with a spatiotemporal resolution of approximately 30 nanometres and 15 milliseconds, to map both the electron- and hole-driven photoelectrocatalytic activities on single titanium oxide nanorods. We then map, with sub-particle resolution (about 390 nanometres), the photocurrent associated with water oxidation, and find that the most active sites for water oxidation are also the most important sites for charge-carrier recombination. Site-selective deposition of an OEC, guided by the activity maps, improves the overall performance of a given nanorod--even though more improvement in photocurrent efficiency correlates with less reduction in onset potential (and vice versa) at the sub-particle level. Moreover, the optimal catalyst deposition sites for photocurrent enhancement are the lower-activity sites, and for onset potential reduction the optimal sites are the sites with more positive onset potential, contrary to what is obtainable under typical deposition conditions. These findings allow us to suggest an activity-based strategy for rationally engineering catalyst-improved photoelectrodes, which should be widely applicable because our measurements can be performed for many different semiconductor and catalyst materials.