Ferroelectric Polarization Induces Electric Double Layer Bistability in Electrolyte-Gated Field-Effect Transistors

The dense surface charges expressed by a ferroelectric polymeric thin film induce ion displacement within a polyelectrolyte layer and vice versa. This is because the density of dipoles along the surface of the ferroelectric thin film and its polarization switching time matches that of the (Helmholtz) electric double layers formed at the ferroelectric/polyelectrolyte and polyelectrolyte/semiconductor interfaces. This combination of materials allows for introducing hysteresis effects in the capacitance of an electric double layer capacitor. The latter is advantageously used to control the charge accumulation in the semiconductor channel of an organic field-effect transistor. The resulting memory transistors can be written at a gate voltage of around 7 V and read out at a drain voltage as low as 50 mV. The technological implication of this large difference between write and read-out voltages lies in the non-destructive reading of this ferroelectric memory

Double-Gate Light-Emitting Electrochemical Transistor: Confining the Organic p–n Junction

In conventional light-emitting electrochemical cells (LECs), an off-centered p–n junction is one of the major drawbacks, as it leads to exciton quenching at one of the charge-injecting electrodes and results in performance instability. To combat this problem, we have developed a new device configuration, the double-gate light-emitting electrochemical transistor (DG-LECT), in which the location of the light-emitting p–n junction can be precisely defined via the position of the two gate terminals. Based on a planar LEC structure, two gate electrodes made from an electrochemically active conducting polymer are employed to predefine the p- and n-doped area of the light-emitting polymer. Thus, a p–n junction is formed in between the p-doped and n-doped regions. We demonstrate a homogeneous and centered p–n junction as well as other predefined junction patterns in these DG-LECT devices. Additionally, we report an electrical model that explains the operation of the DG-LECTs. The DG-LECT device provides a new tool to study the fundamental physics of LECs, as it dissects the key working process of LEC into decoupled p-doping, n-doping, and electroluminescence

Organic Reprogrammable Circuits Based on Electrochemically Formed Diodes

We report a method to construct reprogrammable circuits based on organic electrochemical (EC) p–n junction diodes. The diodes are built up from the combination of the organic conjugated polymer poly­[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] and a polymer electrolyte. The p–n diodes are defined by EC doping performed at 70 °C, and then stabilized at −30 °C. The reversible EC reaction allows for in situ reprogramming of the polarity of the organic p–n junction, thus enabling us to reconfigure diode circuits. By combining diodes of specific polarities dedicated circuits have been created, such as various logic gates, a voltage limiter and an AC/DC converter. Reversing the EC reaction allows in situ reprogramming of the p–n junction polarity, thus enabling reconfiguration of diode circuits, for example, from an AND gate to an OR gate. The reprogrammable circuits are based on p–n diodes defined from only two layers, the electrodes and then the active semiconductor:electrolyte composite material. Such simple device structures are promising for large-area and fully printed reconfigurable circuits manufactured using common printing tools. The structure of the reported p–n diodes mimics the architecture of and is based on identical materials used to construct light-emitting electrochemical cells (LEC). Our findings thus provide a robust signal routing technology that is easily integrated with traditional LECs

Tuning the Thermoelectric Properties of Conducting Polymers in an Electrochemical Transistor

While organic field-effect transistors allow the investigation of interfacial charge transport at the semiconductor–dielectric interface, an electrochemical transistor truly modifies the oxidation level and conductivity throughout the bulk of an organic semiconductor. In this work, the thermoelectric properties of the bulk of the conducting polymer poly­(3,4-ethylenedioxythiophene)–poly­(styrene sulfonate) were controlled electrically by varying the gate voltage. In light of the growing interest in conducting polymers as thermoelectric generators, this method provides an easy tool to study the physics behind the thermoelectric properties and to optimize polymer thermoelectrics

Cross-Linked Nanocellulose Membranes for Nanofluidic Osmotic Energy Harvesting

Osmotic energy generated from the salinity gradient is a kind of clean and renewable energy source, where the ion-exchange membranes play a critical role in its operation. The nanofluidic technique is emerging to overcome the limitations of high resistance and low mass transport of traditional ion-exchange membranes and thus improve osmotic power conversion. However, the currently reported nanofluidic materials suffer from high cost and complicated fabrication processes, which limits their practical application. Here, we report low-cost nanocellulose membranes that can be facilely prepared by a chemical cross-linking approach. The obtained membranes exhibit excellent ion transport characteristics as high-performance nanofluidic osmotic power generators. The control of cross-linker dosage enables the simultaneous tunability of the surface charge density and size of nanofluidic channels created between the interwoven cellulose nanofibrils. The maximum osmotic power generated by the membrane is reached when the cross-linker weight content is 20 wt %. Furthermore, the cross-linked nanocellulose membranes exhibit long-term working stability in osmotic energy harvesting under a wide range of pH values (3.2–9.7). This nanocellulose membrane derived from green and sustainable natural materials demonstrates a promising potential for renewable osmotic energy harvesting

Spatial Control of p–n Junction in an Organic Light-Emitting Electrochemical Transistor

Low-voltage-operating organic electrochemical light-emitting cells (LECs) and transistors (OECTs) can be realized in robust device architectures, thus enabling easy manufacturing of light sources using printing tools. In an LEC, the p–n junction, located within the organic semiconductor channel, constitutes the active light-emitting element. It is established and fixated through electrochemical p- and n-doping, which are governed by charge injection from the anode and cathode, respectively. In an OECT, the electrochemical doping level along the organic semiconducting channel is controlled via the gate electrode. Here we report the merger of these two devices: the light-emitting electrochemical transistor, in which the location of the emitting p–n junction and the current level between the anode and cathode are modulated via a gate electrode. Light emission occurs at 4 V, and the emission zone can be repeatedly moved back and forth within an interelectrode gap of 500 μm by application of a 4 V gate bias. In transistor operation, the estimated on/off ratio ranges from 10 to 100 with a gate threshold voltage of −2.3 V and transconductance value between 1.4 and 3 μS. This device structure opens for new experiments tunable light sources and LECs with added electronic functionality

Electronic Control over Detachment of a Self-Doped Water-Soluble Conjugated Polyelectrolyte

Water-soluble conducting polymers are of interest to enable more versatile processing in aqueous media as well as to facilitate interactions with biomolecules. Here, we report a substituted poly­(3,4-ethylenedioxythiophene) derivative (PEDOT-S:H) that is fully water-soluble and self-doped. When electrochemically oxidizing a PEDOT-S:H thin film, the film detaches from the underlying electrode. The oxidation of PEDOT-S:H starts with an initial phase of swelling followed by cracking before it finally disrupts into small flakes and detaches from the electrode. We investigated the detachment mechanism and found that parameters such as the size, charge, and concentration of ions in the electrolyte, the temperature, and also the pH influence the characteristics of detachment. When oxidizing PEDOT-S:H, the positively charged polymer backbone is balanced by anions from the electrolyte solution and also by the sulfonate groups on the side chains (more self-doping). From our experiments, we conclude that detachment of the PEDOT-S:H film upon oxidation occurs in part due to swelling caused by an inflow of solvated anions and associated water and in part due to chain rearrangements within the film, caused by more self-doping. We believe that PEDOT-S:H detachment can be of interest in a number of different applications, including addressed and active control of the release of materials such as biomolecules and cell cultures

pH Dependence of γ‑Aminobutyric Acid Iontronic Transport

The organic electronic ion pump (OEIP) has been developed as an “iontronic” tool for delivery of biological signaling compounds. OEIPs rely on electrophoretically “pumping” charged compounds, either at neutral or shifted pH, through an ion-selective channel. Significant shifts in pH lead to an abundance of H⁺ or OH^–, which are delivered along with the intended substance. While this method has been used to transport various neurotransmitters, the role of pH has not been explored. Here we present an investigation of the role of pH on OEIP transport efficiency using the neurotransmitter γ-aminobutyric acid (GABA) as the model cationic delivery substance. GABA transport is evaluated at various pHs using electrical and chemical characterization and compared to molecular dynamics simulations, all of which agree that pH 3 is ideal for GABA transport. These results demonstrate a useful method for optimizing transport of other substances and thus broadening OEIP applications

Amphiphilic Poly(3-hexylthiophene)-Based Semiconducting Copolymers for Printing of Polyelectrolyte-Gated Organic Field-Effect Transistors

Polyelectrolytes are promising electronically insulating layers for low-voltage organic field effect transistors. However, the polyelectrolyte–semiconductor interface is difficult to manufacture due to challenges in wettability. We introduce an amphiphilic semiconducting copolymer which, when spread as a thin film, can change its surface from hydrophobic to hydrophilic upon exposure to water. This peculiar wettability is exploited in the fabrication of polyelectrolyte-gated field-effect transistors operating below 0.5 V. The prepared amphiphilic semiconducting copolymer is based on a hydrophobic regioregular poly­(3-hexylthiophene) (P3HT) covalently linked to a hydrophilic poly­(sulfonated)-based random block. Such a copolymer is obtained in a three-step strategy combining Grignard metathesis (GRIM), atom transfer radical polymerization (ATRP) processes, and a postmodification method. The structure of the diblock copolymer was characterized using FT-IR, ¹H NMR spectroscopy, and gel permeation chromatography (GPC)