Thin, Tough, pH-Sensitive Hydrogel Films with Rapid Load Recovery

Stimuli-responsive hydrogels are used as the building blocks of actuators and sensors. Their application has been limited, however, by their lack of mechanical strength and recovery from loading. Here, we report the preparation of pH-sensitive hydrogels as thin as 20 μm. The hydrogels are made of a polyether-based polyurethane and poly­(acrylic acid). A simple method was employed to create hydrogels with thicknesses in the range of 20–570 μm. The hydrogel films volume changed by a factor of ∼2 when the pH was switched around the transition point (pH 4). Tensile extensibilities of up to ∼350% were maintained at each pH, and the average Young’s modulus and tensile strength were in the range of 580–910 and 715–1320 kPa, respectively, depending on the pH. Repeated tensile loading and unloading to 100% extension showed little permanent damage, unlike analogous double-network hydrogels, and with immediate recovery (up to 75–85% of the first loading cycle), unlike hybrid ionic–covalent interpenetrating network hydrogels

Electrically Conductive, Tough Hydrogels with pH Sensitivity

Electrically conductive, mechanically tough hydrogels based on a double network (DN) comprised of poly­(ethylene glycol) methyl ether methacrylate (PPEGMA) and poly­(acrylic acid) (PAA) were produced. Poly­(3,4-ethylenedioxythiophene) (PEDOT) was chemically polymerized within the tough DN gel to provide electronic conductivity. The effects of pH on the tensile and compressive mechanical properties of the fully swollen hydrogels, along with their electrical conductivity and swelling ratio were determined. Compressive and tensile strengths as high as 11.6 and 0.6 MPa, respectively, were obtained for hydrogels containing PEDOT with a maximum conductivity of 4.3 S cm^–1. This conductivity is the highest yet reported for hydrogel materials of high swelling ratios. These hydrogels may be useful as soft strain sensors because their electrical resistance changed significantly when cyclically loaded in compression

Liquid Deposition Patterning of Conducting Polymer Ink onto Hard and Soft Flexible Substrates via Dip-Pen Nanolithography

Ink formulations and protocols that enable the deposition and patterning of a conducting polymer (PEDOT:PSS) in the nanodomain have been developed. Significantly, we demonstrated the ability to pattern onto soft substrates such as silicone gum and polyethylene terephthalate (PET), which are materials of interest for low cost, flexible electronics. The deposition process and dimensions of the polymer patterns are found to be critically dependent on a number of parameters, including the pen design, ink properties, time after inking the pen, dwell time of the pen on the surface, and the nature of material substrate. By assessing these different parameters, an improved understanding of the ability to control the dimensions of individual PEDOT:PSS structures down to 600 nm in width and 10–80 nm in height within patterned arrays was obtained. This applicability of DPN for simple and nonreactive liquid deposition patterning of conducting polymers can lead to the fabrication of organic nanoelectronics or biosensors and complement the efforts of existing printing techniques such as inkjet and extrusion printing by scaling down conductive components to submicrometer and nanoscale dimensions

Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

Some of the most exciting recent advances in conducting polymer synthesis have centered around the method of vapor phase polymerization (VPP) of thin films. However, it is not known whether the VPP process can proceed using significantly reduced volumes of oxidant and therefore be implemented as part of nanolithography approach. Here, we present a strategy for submicrometer scale patterning of the conducting polymer poly­(3,4-ethylenedioxythiophene) (PEDOT) via in situ VPP. Attolitre (10^–18 L) volumes of oxidant “ink” are controllably deposited using dip-pen nanolithography (DPN). DPN patterning of the oxidant ink is facilitated by the incorporation of an amphiphilic block copolymer thickener, an additive that also assists with stabilization of the oxidant. When exposed to EDOT monomer in a VPP chamber, each deposited feature localizes the synthesis of conducting PEDOT structures of several micrometers down to 250 nm in width. PEDOT patterns are characterized by atomic force microscopy (AFM), conductive AFM, two probe electrical measurement, and micro-Raman spectroscopy, evidencing in situ vapor phase synthesis of conducting polymer at a scale (picogram) which is much smaller than that previously reported. Although the process of VPP on this scale was achieved, we highlight some of the challenges that need to be overcome to make this approach feasible in an applied setting

The Role of Unbound Oligomers in the Nucleation and Growth of Electrodeposited Polypyrrole and Method for Preparing High Strength, High Conductivity Films

Polypyrrole is a material with immensely useful properties suitable for a wide range of electrochemical applications, but its development has been hindered by cumbersome manufacturing processes. Here we show that a simple modification to the standard electrochemical polymerization method produces polypyrrole films of equivalently high conductivity and superior mechanical properties in one-tenth of the polymerization time. Preparing the film as a series of electrodeposited layers with thorough solvent washing between layering was found to produce excellent quality films even when layer deposition was accelerated by high current. The washing step between the sequentially polymerized layers altered the deposition mechanism, eliminating the typical dendritic growth and generating nonporous deposits. Solvent washing was shown to reduce the concentration of oligomeric species in the near-electrode region and hinder the three-dimensional growth mechanism that occurs by deposition of secondary particles from solution. As artificial muscles, the high density sequentially polymerized films produced the highest mechanical work output yet reported for polypyrrole actuators

Optical and Electrochemical Methods for Determining the Effective Area and Charge Density of Conducting Polymer Modified Electrodes for Neural Stimulation

Neural stimulation is used in the cochlear implant, bionic eye, and deep brain stimulation, which involves implantation of an array of electrodes into a patient’s brain. The current passed through the electrodes is used to provide sensory queues or reduce symptoms associated with movement disorders and increasingly for psychological and pain therapies. Poor control of electrode properties can lead to suboptimal performance; however, there are currently no standard methods to assess them, including the electrode area and charge density. Here we demonstrate optical and electrochemical methods for measuring these electrode properties and show the charge density is dependent on electrode geometry. This technique highlights that materials can have widely different charge densities but also large variation in performance. Measurement of charge density from an electroactive area may result in new materials and electrode geometries that improve patient outcomes and reduce side effects

Organic Solvent-Based Graphene Oxide Liquid Crystals: A Facile Route toward the Next Generation of Self-Assembled Layer-by-Layer Multifunctional 3D Architectures

We introduce soft self-assembly of ultralarge liquid crystalline (LC) graphene oxide (GO) sheets in a wide range of organic solvents overcoming the practical limitations imposed on LC GO processing in water. This expands the number of known solvents which can support amphiphilic self-assembly to ethanol, acetone, tetrahydrofuran, <i>N</i>-dimethylformamide, <i>N</i>-cyclohexyl-2-pyrrolidone, and a number of other organic solvents, many of which were not known to afford solvophobic self-assembly prior to this report. The LC behavior of the as-prepared GO sheets in organic solvents has enabled us to disperse and organize substantial amounts of aggregate-free single-walled carbon nanotubes (SWNTs, up to 10 wt %) without compromise in LC properties. The as-prepared LC GO-SWNT dispersions were employed to achieve self-assembled layer-by-layer multifunctional 3D hybrid architectures comprising SWNTs and GO with unrivalled superior mechanical properties (Young’s modulus in excess of 50 GPa and tensile strength of more than 500 MPa)

Cation Exchange at Semiconducting Oxide Surfaces: Origin of Light-Induced Performance Increases in Porphyrin Dye-Sensitized Solar Cells

The origin of simultaneous improvements in the short-circuit current density (<i>J</i>_sc) and open-circuit voltage (<i>V</i>_oc) of porphyrin dye-sensitized TiO₂ solar cells following white light illumination was studied by systematic variation of several different device parameters. Reduction of the dye surface loading resulted in greater relative performance enhancements, suggesting open space at the TiO₂ surface expedites the process. Variation of the electrolyte composition and subsequent analysis of the conduction band potential shifts suggested that a light-induced replacement of surface-adsorbed lithium (Li⁺) ions with dimethylpropylimidazolium (DMPIm⁺) ions was responsible for an increased electron lifetime by decreasing the recombination with the redox mediator. Variation of the solvent viscosity was found to affect the illumination time required to generate increased performance, while similar performance enhancements were not replicated by application of negative bias under dark conditions, indicating the light exposure effect was initiated by formation of dye cation molecules following photoexcitation. The substituents and linker group on the porphyrin chromophore were both varied, with light exposure producing increased electron lifetime and <i>V</i>_oc for all dyes; however, increased <i>J</i>_sc values were only measured for dyes containing binding moieties with multiple carboxylic acids. It was proposed that the initial injection limitation and/or fast recombination process in these dyes arises from the presence of lithium at the surface, and the improved injection and/or retardation of fast recombination after light exposure is caused by the Li⁺ removal by cation exchange under illumination

A Nonconjugated Bridge in Dimer-Sensitized Solar Cells Retards Charge Recombination without Decreasing Charge Injection Efficiency

Dye sensitized solar cells (DSSCs) employing a dimer porphyrin, which was synthesised with two porphyrin units connected without conjugation, have shown that both porphyrin components can contribute to photocurrent generation, that is, more than 50 % internal quantum efficiency. In addition, the open-circuit voltage (<i>V</i>_oc) of the DSSCs was higher than that of DSSCs using monomer porphyrins. In this paper, we first optimized cell structure and fabrication conditions. We obtained more than 80% incident photon to current conversion efficiency from the dimer porphyrin sensitized DSSCs and higher <i>V</i>_oc and energy conversion efficiency than monomer porphyrin sensitized solar cells. To examine the origin of the higher <i>V</i>_oc, we measured electron lifetime in the DSSCs with various conditions, and found that the dimer system increased the electron lifetime by improving the steric blocking effect of the dye layer, whilst the lack of a conjugated linker prevents an increase in the attractive force between conjugated sensitizers and the acceptor species in the electrolyte. The results support a hypothesis; dispersion force is one of the factors influencing the electron lifetime in DSSCs

Polymeric Material with Metal-Like Conductivity for Next Generation Organic Electronic Devices

The reduced pressure synthesis of poly­(3,4-ethylenedioxythiophene) (PEDOT) with sheet-like morphology has been achieved with the introduction of an amphiphilic triblock copolymer into the oxidant thin film. Addition of the copolymer not only results in an oxidant thin film which remains liquid-like under reduced pressure but also induces structured growth during film formation. PEDOT films were polymerized using the vacuum vapor phase polymerization (VPP) technique, in which we show that maintaining a liquid-like state for the oxidant is essential. The resulting conductivity is equivalent to commercially available indium tin oxide (ITO) with concomitant optical transmission values. PEDOT films can be produced with a variety of thicknesses across a range of substrate materials from plastics to metals to ceramics, with sheet resistances down to 45 Ω/□ (ca. 3400 S·cm^–1), and transparency in the visible spectrum of >80% at 65 nm thickness. This compares favorably to ITO and its currently touted replacements