Organic Mixed Conductors Research Articles

Role of the Anion on the Transport and Structure of Organic Mixed Conductors

AbstractOrganic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium‐ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte‐mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.

Benchmarking organic mixed conductors for transistors

Organic mixed conductors have garnered significant attention in applications from bioelectronics to energy storage/generation. Their implementation in organic transistors has led to enhanced biosensing, neuromorphic function, and specialized circuits. While a narrow class of conducting polymers continues to excel in these new applications, materials design efforts have accelerated as researchers target new functionality, processability, and improved performance/stability. Materials for organic electrochemical transistors (OECTs) require both efficient electronic transport and facile ion injection in order to sustain high capacity. In this work, we show that the product of the electronic mobility and volumetric charge storage capacity (µC*) is the materials/system figure of merit; we use this framework to benchmark and compare the steady-state OECT performance of ten previously reported materials. This product can be independently verified and decoupled to guide materials design and processing. OECTs can therefore be used as a tool for understanding and designing new organic mixed conductors.

Controlling the mode of operation of organic transistors through side-chain engineering

Electrolyte-gated organic transistors offer low bias operation facilitated by direct contact of the transistor channel with an electrolyte. Their operation mode is generally defined by the dimensionality of charge transport, where a field-effect transistor allows for electrostatic charge accumulation at the electrolyte/semiconductor interface, whereas an organic electrochemical transistor (OECT) facilitates penetration of ions into the bulk of the channel, considered a slow process, leading to volumetric doping and electronic transport. Conducting polymer OECTs allow for fast switching and high currents through incorporation of excess, hygroscopic ionic phases, but operate in depletion mode. Here, we show that the use of glycolated side chains on a thiophene backbone can result in accumulation mode OECTs with high currents, transconductance, and sharp subthreshold switching, while maintaining fast switching speeds. Compared with alkylated analogs of the same backbone, the triethylene glycol side chains shift the mode of operation of aqueous electrolyte-gated transistors from interfacial to bulk doping/transport and show complete and reversible electrochromism and high volumetric capacitance at low operating biases. We propose that the glycol side chains facilitate hydration and ion penetration, without compromising electronic mobility, and suggest that this synthetic approach can be used to guide the design of organic mixed conductors.

The influence of spatial disorder of the ion distribution on the surface morphology in thin films of blend based organic mixed ionic-electronic conductors

We report on investigations of the morphology of spin-coated thin films of an organic mixed ionic-electronic conductor consisting of the conjugated polymer methyl substituted ladder type poly(para- phenylene) (mLPPP) blended with a solid state electrolyte (Dicyclohexano18crown6 (DCH18C6), complexed with lithium trifluoromethanesulfonate (LiCF 3SO 3)). This blend system was successfully applied as active layer in light-emitting electrochemical cells (LECs). While thin films blends of the conjugated polymer and the pristine crown ether show a very smooth surface, the addition of LiCF 3SO 3 causes a pronounced surface roughening. Since such a distinct surface roughness can be the reason for a device failure mechanism that limits the device lifetime, this attitude is investigated by tapping mode atomic force microscopy (AFM). These studies are complemented with X-ray analysis by means of energy dispersive X-ray spectrometry (EDXS), in the scanning electron microscope (SEM), in order to get a better insight into the ion distribution within the blend layer and its influence on the surface roughness formed.