Thomas Lenz

The negative piezoelectric effect of the ferroelectric polymer poly(vinylidene fluoride)

Piezoelectricity describes interconversion between electrical charge and mechanical strain. As expected for lattice ions displaced in an electric field, the proportionality constant is positive for all piezoelectric materials. The exceptions are poly(vinylidene fluoride) (PVDF) and its copolymers with trifluoroethylene (P(VDF-TrFE)), which exhibit a negative longitudinal piezoelectric coefficient. Reported explanations exclusively consider contraction with applied electric field of either the crystalline or the amorphous part of these semi-crystalline polymers. To distinguish between these conflicting interpretations, we have performed in situ dynamic X-ray diffraction measurements on P(VDF-TrFE) capacitors. We find that the piezoelectric effect is dominated by the change in lattice constant but, surprisingly, it cannot be accounted for by the polarization-biased electrostrictive contribution of the crystalline part alone. Our quantitative analysis shows that an additional contribution is operative, which we argue is due to an electromechanical coupling between the intermixed crystalline lamellae and amorphous regions. Our findings tie the counterintuitive negative piezoelectric response of PVDF and its copolymers to the dynamics of their composite microstructure.

Quantum tunnelling and charge accumulation in organic ferroelectric memory diodes

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.

Open-circuit voltage loss in annealed P3HT:perylene diimide bulk heterojunction solar cells

Solar cells based on blends of regioregular poly(3-hexylthiophene) as a donor and a commercial perylene diimide derivative as a acceptor are investigated. Thermal annealing of the devices results in increased photocurrent generation but is simultaneously accompanied by a loss in open-circuit voltage. It is shown that the decreased open-circuit voltage is caused by the formation of a cathode barrier, as evidenced by injection-limited electron currents, a reduced built-in voltage, and a weaker light-intensity dependence of the open-circuit voltage. Device simulations show that the increased photocurrent after annealing is the result of an increased electron mobility.

Solid-state-processing of δ-PVDF

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-state-processing. We demonstrate that we thereby produce δ-PVDF, the piezoelectric charge coefficient of which is comparable to that of biaxially stretched β-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.

Ferroelectricity and piezoelectricity in soft biological tissue: Porcine aortic walls revisited

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.

Thin film thermistor with positive temperature coefficient of resistance based on phase separated blends of ferroelectric and semiconducting polymers

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.

Interfacial conduction in organic ferroelectric memory diodes

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.