Vibrational piezoelectric energy harvesters are being investigated to replace batteries in embedded sensor systems. The energy density that can be harvested depends on the figure of merit, d₃₃g₃₃, where d₃₃ and g₃₃ are the piezoelectric charge and voltage coefficient. Commonly used piezoelectric materials are based on inorganic ceramics, such as lead zirconium titanate (PZT), as they exhibit high piezoelectric coefficients. However, ceramics are brittle, leading to mechanical failure under large cyclic strains and, furthermore, PZT is classified as a Substance of Very High Concern (SVHC). To circumvent these drawbacks, we fabricated quasi 1–3 potassium sodium lithium niobate (KNLN) ceramic fibers in a flexible polydimethylsiloxane (PDMS) matrix. The fibers were aligned by dielectrophoresis. We demonstrate for the structured composites values of d₃₃g₃₃ approaching 18 pm³ J⁻¹, comparable to that of state-of-the-art ceramic PZT. This relatively high value is due to the reduced inter-particle distance in the direction of the electric field. As a confirmation, the stored electrical energy for both material systems was measured under identical mechanical loading conditions. The similar values for KNLN/PDMS and PZT demonstrate that environmentally friendly, lead-free, mechanically compliant materials can replace state-of-the-art environmentally-less-desirable ceramic materials in piezoelectric vibrational energy harvesters.

@en

Depolarization in ferroelectric materials has been studied since the 1970s, albeit quasi-statically. The dynamics are described by the empirical Merz law, which gives the polarization switching time as a function of electric field, normalized to the so-called activation field. The Merz law has been used for decades; its origin as domain-wall depinning has recently been corroborated by molecular dynamics simulations. Here we experimentally investigate domain-wall depinning by measuring the dynamics of depolarization. We find that the boundary between thermodynamically stable and depolarizing regimes can be described by a single constant, P_r/ε₀ε_ferroE_c. Among different multidomain ferroelectric materials the values of coercive field, E_c, dielectric constant, ε_ferro, and remanent polarization, P_r, vary by orders of magnitude; the value for P_r/ε₀ε_ferroE_c however is comparable, about 15. Using this extracted universal value, we show that the depolarization field is similar to the activation field, which corresponds to the transition from creep to domain-wall flow.

@en

Solution-processed memory diodes based on phase separated blends of ferroelectric and semiconducting polymers in the low resistance on-state operate similar to a vertical field-effect transistor at the pinch-off. Numerical simulations have shown that the performance of the diode is dominated by the conduction of charge carriers at the interface between the semiconductor and ferroelectric phases. Here, we present an unambiguous experimental demonstration of the charge injection process in the diodes. We employ a modified diode structure, wherein the electrode in contact with the semiconductor phase has been intentionally removed. Even in the absence of an electrical contact with the semiconductor phase, the diode still shows resistance switching. We provide numerical simulations that reproduce the experimentally measured I-V characteristics and therefore confirm interfacial conduction in the diodes. Furthermore, we discuss the implications of the proposed memory structure particularly in the performance of light-emitting diodes with built-in memory functionality, i.e., MEMOLEDs.

@en

Piezoelectric energy harvesters are at the front of scientific research as enablers of renewable, sustainable energy for autonomous wireless sensor networks. Crucial for this disruptive technology is the achievable output power. Here we show, analytically, that the maximum output energy per unit volume, under a single sinusoidal excitation, is equal to 1/(4 - 2k²) × 1/2dgX², where k² is the electromechanical coupling coefficient, d and g are the piezoelectric charge and voltage coefficient, respectively, and X is the applied stress. The expression derived is validated by the experimentally measured output energy for a variety of piezoelectric materials over an unprecedented range of more than five orders of magnitude. As the prefactor 1/(4 - 2k²) varies only between 1/2 and 1/4 the figure of merit for piezoelectric materials for energy harvesters is not k², as commonly accepted for vibrational harvesters, but dg. The figure of merit does not depend on the compliance, or Young's modulus. Hence we argue that commonly used brittle inorganic piezoelectric ceramics can be replaced by soft, mechanically flexible polymers and composite films, comprising inorganic piezoelectric materials embedded in a polymer matrix.

@en

It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm² V^-1 s^-1. The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.

@en

Diatoms are photosynthetic microalgae, a group with a major environmental role on the planet due to the biogeochemical cycling of silica and global fixation of carbon. However, they can evolve into harmful blooms through a resourceful communication mechanism, not yet fully understood. Here, we demonstrate that a population of diatoms under darkness show quasi-periodic electrical oscillations, or intercellular waves. The origin is paracrine signaling, which is a feedback, or survival, mechanism that counteracts changes in the physicochemical environment. The intracellular messenger is related to Ca²⁺ ions since spatiotemporal changes in their concentration match the characteristics of the intercellular waves. Our conclusion is supported by using a Ca²⁺ channel inhibitor. The transport of Ca²⁺ ions through the membrane to the extracellular medium is blocked and the intercellular waves disappear. The translation of microalgae cooperative signaling paves the way for early detection and prevention of harmful blooms and an extensive range of stress-induced alterations in the aquatic ecosystem.

@en

Re-establishment of electrical conductivity in graphene oxide (GO), the insulating form of graphene, is (partially) accomplished by reduction through high temperature treatments in a reducing atmosphere, or using strongly reducing chemicals or electrolytic processes. The reduction methods are suited for bulk graphene oxide. Spatially resolved reduction of thin films of graphene oxide is important for a wide range of applications such as in microelectronics, where an electrolyte-free, room temperature reduction process is needed. Here, we present spatially resolved solid-state reduction of graphene oxide thin films. We demonstrate that the reduction mechanism is based on electrolysis of water that is adsorbed on the graphene oxide thin film. The reduced graphene oxide thin-films show sheet resistance of only several kOhm, with weak temperature dependence. Graphene oxide can be produced on a large scale and processed using low-cost solution casting techniques. Spatially resolved re-establishment of conductivity in GO can be used in electrically controlled water permeation or in micro- and nanoelectronic applications for instance as an anti-fuse.

@en

Recently reported piezoresponse force microscopy (PFM) measurements have proposed that porcine aortic walls are ferroelectric. This finding may have great implications for understanding biophysical properties of cardiovascular diseases such as arteriosclerosis. However, the complex anatomical structure of the aortic wall with different extracellular matrices appears unlikely to be ferroelectric. The reason is that a prerequisite for ferroelectricity, which is the spontaneous switching of the polarization, is a polar crystal structure of the material. Although the PFM measurements were performed locally, the phase-voltage hysteresis loops could be reproduced at different positions on the tissue, suggesting that the whole aorta is ferroelectric. To corroborate this hypothesis, we analyzed entire pieces of porcine aorta globally, both with electrical and electromechanical measurements. We show that there is no hysteresis in the electric displacement as well as in the longitudinal strain as a function of applied electric field and that the strain depends on the electric field squared. By using the experimentally determined quasi-static permittivity and Young's modulus of the fixated aorta, we show that the strain can quantitatively be explained by Maxwell stress and electrostriction, meaning that the aortic wall is neither piezoelectric nor ferroelectric, but behaves as a regular dielectric material.

@en

In this work, the macroscopic polarization of a ferroelectric capacitor is correlated with the local domain morphology. To this end, a ferroelectric capacitor of the random copolymer poly(vinylidenefluoride-trifluoroethylene) [P(VDF-TrFE)] is poled to a set polarization state in a Sawyer-Tower setup. After chemically removing the top electrode, the exposed ferroelectric is locally probed with piezoresponse force microscopy. The domains without the top electrode are thermodynamically stable for weeks in ambient environment, as proven by comparing the remanent polarization measured before etching away and after re-depositing the top electrode. Out-of-plane PFM phase images show a random distribution of domains with up and down polarity. We unambiguously demonstrate a linear correlation between the mean PFM phase and the macroscopic polarization. As a demonstration of the insights that the global excitation and local probing method can provide, we show how thermal and electrical depoling can result in identical macroscopic polarization yet completely different domain morphologies.

@en

Semiconducting polymer based X-ray detectors doped with high-Z nanoparticles hold the promise to combine mechanical flexibility and large-area processing with a high X-ray stopping power and sensitivity. Currently, a lack of understanding of how nanoparticle doping impacts the detector dynamics impedes the optimization of such detectors. Here, we study direct X-ray radiation detectors based on the semiconducting polymer poly(9,9-dioctyfluorene) blended with Bismuth(III)oxide (Bi₂O₃) nanoparticles (NPs). Pure polymer diodes show a high mobility of 1.3 × 10^-5 cm²/V s, a low leakage current of 200 nA/cm² at -80 V, and a high rectifying factor up to 3 × 10⁵ that allow us to compare the X-ray response of a polymer detector in charge-injection conditions (forward bias) and in charge-collection conditions (reverse bias), together with the impact of NP-loading in the two operation regimes. When operated in reverse bias, the detectors reach the state of the art sensitivity of 24 μC/Gy cm², providing a fast photoresponse. In forward operation, a slower detection dynamics but improved sensitivity (up to 450 ± 150 nC/Gy) due to conductive gain is observed. High-Z NP doping increases the X-ray absorption, but higher NP loadings lead to a strong reduction of charge-carrier injection and transport due to a strong impact on the semiconductor morphology. Finally, the time response of optimized detectors showed a cut-off frequency up to 200 Hz. Taking advantage of such a fast dynamic response, we demonstrate an X-ray based velocity tracking system.

@en

Non-volatile memories—providing the information storage functionality—are crucial circuit components. Solution-processed organic ferroelectric memory diodes are the non-volatile memory candidate for flexible electronics, as witnessed by the industrial demonstration of a 1 kbit reconfigurable memory fabricated on a plastic foil. Further progress, however, is limited owing to the lack of understanding of the device physics, which is required for the technological implementation of high-density arrays. Here we show that ferroelectric diodes operate as vertical field-effect transistors at the pinch-off. The tunnelling injection and charge accumulation are the fundamental mechanisms governing the device operation. Surprisingly, thermionic emission can be disregarded and the on-state current is not space charge limited. The proposed model explains and unifies a wide range of experiments, provides important design rules for the implementation of organic ferroelectric memory diodes and predicts an ultimate theoretical array density of up to 1012 bit cm 2. @en

Poly(vinylidene fluoride) (PVDF) has long been regarded as an ideal piezoelectric ‘plastic’ because it exhibits a large piezoelectric response and a high thermal stability. However, the realization of piezoelectric PVDF elements has proven to be problematic due to, amongst other reasons, the lack of industrially scalable methods to process PVDF into the appropriate polar crystalline forms. Here, we show that fully piezoelectric PVDF films can be produced via a single-step process that exploits the fact that PVDF can be molded at temperatures below its melting temperature, i.e. via solid-stateprocessing. We demonstrate that we thereby produce d-PVDF, the piezoelectric charge coefficient of which is comparable to that of biaxially stretched b-PVDF. We expect that the simplicity and scalability of solid-state processing combined with the excellent piezoelectric properties of our PVDF structures will provide new opportunities for this commodity polymer and will open a range of possibilities for future, large-scale, industrial production of plastic piezoelectric films. @en

Ultraviolet photoelectron spectroscopy (UPS) is a key technique to determine the work function (Φ) of surfaces by measuring the secondary-electron cut-off (SECO). However, the interpretation of SECO spectra as obtained by UPS is not straightforward for multicomponent surfaces, and it is not comprehensively understood to what extent the length scale of inhomogeneity impacts the SECO. Here, this study unravels the physics governing the energy distribution of the SECO by experimentally and theoretically determining the electrostatic landscape above surfaces with defined patterns of Φ. For such samples, the measured SECO spectra exhibit actually two cut-offs, one representing the high Φ surface component and the other one corresponding to an area-averaged Φ value. By combining Kelvin probe force microscopy and electrostatic modeling, it is quantitatively demonstrated that the electrostatic potential of the high Φ areas leads to an additional energy barrier for the electrons emitted from the low Φ areas. Theoretical predictions of the induced energy barrier dependence on the Φ-pattern length scale and sample bias are further experimentally verified. These findings establish a solid base for reliable SECO interpretation of heterogeneous surfaces and improved reliability of interfacial energy-level diagrams from UPS experiments.

@en

A highly sensitive, lead-free, and flexible piezoelectric touch sensor is reported based on composite films of alkaline niobate K_0.485Na_0.485Li_0.03NbO₃ (KNLN) powders aligned in a polydimethylsiloxane (PDMS) matrix. KNLN powder is fabricated by solid-state sintering and consists of microcubes. The particles are dispersed in uncured PDMS and oriented by application of an oscillating dielectrophoretic alignment field. The dielectric constant of the composite film is almost independent of the microstructure, while upon alignment the piezoelectric charge coefficient increases more than tenfold up to 17 pC N^-1. A quantitative analysis shows that the origin is a reduction of the interparticle distance to under 1.0 μm in the aligned bicontinuous KNLN chains. The temperature stable piezoelectric voltage coefficient exhibits a maximum value of 220 mV m N^-1, at a volume fraction of only 10%. This state-of-the-art value outperforms bulk piezoelectric ceramics and composites with randomly dispersed particles, and is comparable to the values reported for the piezoelectric polymers polyvinylidenefluoride and its random copolymer with trifluoroethylene. Optimized composite films are incorporated in flexible piezoelectric touch sensors. The high sensitivity is analyzed and discussed. As the fabrication technology is straightforward and easy to implement, applications are foreseen in flexible electronics such as wireless sensor networks and biodiagnostics.

@en

We demonstrate that ferroelectric memory diodes can be utilized as switching type positive temperature coefficient (PTC) thermistors. The diode consists of a phase separated blend of a ferroelectric and a semiconducting polymer stacked between two electrodes. The current through the semiconducting polymer depends on the ferroelectric polarization. At the Curie temperature the ferroelectric polymer depolarizes and consequently the current density through the semiconductor decreases by orders of magnitude. The diode therefore acts as switching type PTC thermistor. Unlike their inorganic counterparts, the PTC thermistors presented here are thin film devices. The switching temperature can be tuned by varying the Curie temperature of the ferroelectric polymer. @en

A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O3. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention was measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage. @en

Glioma patients often suffer from epileptic seizures because of the tumor’s impact on the brain physiology. Using the rat glioma cell line C6 as a model system, we performed long-term live recordings of the electrical activity of glioma populations in an ultrasensitive detection method. The transducer exploits large-area electrodes that maximize double-layer capacitance, thus increasing the sensitivity. This strategy allowed us to record glioma electrical activity. We show that although glioma cells are nonelectrogenic, they display a remarkable electrical burst activity in time. The low-frequency current noise after cell adhesion is dominated by the flow of Na+ ions through voltage-gated ion channels. However, after an incubation period of many hours, the current noise markedly increased. This electric bursting phenomenon was not associated with apoptosis because the cells were viable and proliferative during the period of increased electric activity. We detected a rapid cell culture medium acidification accompanying this event. By using specific inhibitors, we showed that the electrical bursting activity was prompted by extracellular pH changes, which enhanced Na+ ion flux through the psalmotoxin 1–sensitive acidsensing ion channels. Our model of pH-triggered bursting was unambiguously supported by deliberate, external acidification of the cell culture medium. This unexpected, acidosis-driven electrical activity is likely to directly perturb, in vivo, the functionality of the healthy neuronal network in the vicinity of the tumor bulk and may contribute to seizures in glioma patients. @en