Internal electric fields and electrode effects in ferroelectric thin films for piezoelectric energy harvesting

The continuing decrease of power requirements of electronic circuits offers the potential to deploy wireless systems as embedded sensors for cars or industrial tools, and implanted medical devices. Harvesting ambient vibrations by an appropriate energy harvesting (EH) device allows to avoid an undesirable battery replacement. At the scale of micro-electromechanical systems, where severe size constraints must be met, microfabricated EH devices with piezoelectric thin films offer the best energy density. Ferroelectric lead zirconate titanate (PZT) thin films with interdigitated electrodes (IDE) appear as the most promising device design for this purpose. Accurate characterization of the thin film response is necessary to determine the PZT composition and doping, the electrode geometry, and the stack design for maximum EH efficiency. Unfortunately, there is no rigorous description of the physical behavior of the IDE system to date. One goal of this thesis was thus to provide a better understanding of the experimental observations made by previous researchers. In addition, only a limited PZT composition and doping range has been investigated in this configuration. It was the second goal of this thesis to widen this range in order to determine the combination that yields the best EH efficiency. Finally, the risk of partial or total depoling over the device lifetime is always present in ferroelectric materials. The phenomena of aging and self-poling are of great interest to ensure proper retention of the poled state and, thus, the reliability of the harvesting device. Neither of the two are well understood. It was the third goal of this thesis to investigate the aging behavior and methods to promote self-poling. In this thesis work, we have have proposed a description of the physical behavior of the IDE system, and we have developed an analytical model for extracting the effective material properties from standard characterization measurements, which is well supported by both finite element (FE) simulations and experimental data. We found that if the substrate is conductive enough, a parasitic capacitance is present in parallel to the material response. We have provided a method to subtract the contribution of the parasitic capacitance, which has an accuracy of better than 4% in a wide range of IDE geometries as determined by FE simulations. We have investigated the performances of doped PZT thin films with IDE for several combinations of dopant and composition. We have improved an existing fabrication route to obtain textured PZT films on an insulating MgO layer. We found that dopants systematically reduced the piezoelectric response and retention capability, and increased the dielectric constant. All three are detrimental for EH. Undoped compositions should be chosen. We have studied methods to improve the stability of the poled state through aging and self-poling. Introducing the latter into the IDE configuration did not provide sufficiently strong effects to be of practical interest. On the contrary, the aging process may allow to tune the extrinsic contributions to the dielectric and piezoelectric response. It is likely caused by polarization discontinuities at grain boundaries. Further work is needed for fully optimizing this phenomenon. Finally, from the previous investigations, we could deduce and propose golden rules for the design of IDE structures, and discuss typical applications where they are advantageous

Analysis of Performance Instabilities of Hafnia-Based Ferroelectrics Using Modulus Spectroscopy and Thermally Stimulated Depolarization Currents

The discovery of the ferroelectric orthorhombic phase in doped hafnia films has sparked immense research efforts. Presently, a major obstacle for hafnia's use in high-endurance memory applications like nonvolatile random-access memories is its unstable ferroelectric response during field cycling. Different mechanisms are proposed to explain this instability including field-induced phase change, electron trapping, and oxygen vacancy diffusion. However, none of these is able to fully explain the complete behavior and interdependencies of these phenomena. Up to now, no complete root cause for fatigue, wake-up, and imprint effects is presented. In this study, the first evidence for the presence of singly and doubly positively charged oxygen vacancies in hafnia–zirconia films using thermally stimulated currents and impedance spectroscopy is presented. Moreover, it is shown that interaction of these defects with electrons at the interfaces to the electrodes may cause the observed instability of the ferroelectric performance

Two-Fold Odd-Even Effect in Self-Assembled Nanowires from Oligopeptide-Polymer-Substituted Perylene Bisimides

Organic nanowires are important building blocks for nanoscopic organic electronic devices. In order to ensure efficient charge transport through such nanowires, it is important to understand in detail the molecular parameters that guide self-assembly of pi-conjugated molecules into one-dimensional stacks with optimal constructive pi-pi overlap. Here, we investigated the subtle relationship between molecular structure and supramolecular arrangement of the chromophores in self-assembled nanowires prepared from perylene bisimides with oligopeptide-polymer side chains. We observed a "two-fold" odd-even effect in circular dichroism spectra of these derivatives, depending on both the number of L-alanine units in the oligopeptide segments and length of the alkylene spacer between chromophore and oligopeptide substituents. Our results indicate that there is a complex interplay between the translation of molecular chirality into supramolecular helicity and the molecules' inherent propensity for well-defined one-dimensional aggregation into beta-sheet-like superstructures in the presence of a central chromophore. Strong excitonic coupling as expressed by the appearance of hypsochromically and bathochromically shifted UV-vis absorptions and strong CD signals was systematically observed for molecules with an odd number of L-alanines in the side chains. The latter derivatives gave rise to nanowires with a significantly higher electron mobility. Our results, hence, provide an important design rule for self-assembled organic nanowires

Two-Fold Odd–Even Effect in Self-Assembled Nanowires from Oligopeptide-Polymer-Substituted Perylene Bisimides

Organic nanowires are important building blocks for nanoscopic organic electronic devices. In order to ensure efficient charge transport through such nanowires, it is important to understand in detail the molecular parameters that guide self-assembly of π-conjugated molecules into one-dimensional stacks with optimal constructive π–π overlap. Here, we investigated the subtle relationship between molecular structure and supramolecular arrangement of the chromophores in self-assembled nanowires prepared from perylene bisimides with oligopeptide-polymer side chains. We observed a “two-fold” odd–even effect in circular dichroism spectra of these derivatives, depending on both the number of l-alanine units in the oligopeptide segments and length of the alkylene spacer between chromophore and oligopeptide substituents. Our results indicate that there is a complex interplay between the translation of molecular chirality into supramolecular helicity and the molecules’ inherent propensity for well-defined one-dimensional aggregation into β-sheet-like superstructures in the presence of a central chromophore. Strong excitonic coupling as expressed by the appearance of hypsochromically and bathochromically shifted UV–vis absorptions and strong CD signals was systematically observed for molecules with an odd number of l-alanines in the side chains. The latter derivatives gave rise to nanowires with a significantly higher electron mobility. Our results, hence, provide an important design rule for self-assembled organic nanowires

Effect of oxygen defects blocking barriers on gadolinium doped ceria (GDC) electro-chemo-mechanical properties

Some oxygen defective metal oxides, such as cerium and bismuth oxides, have recently shown exceptional electrostrictive properties that are even superior to the best performing lead-based electrostrictors, e.g. lead-magnesium-niobates (PMN). Compared to piezoelectric ceramics, electromechanical mechanisms of such materials do not depend on crystalline symmetry but on the concentration of oxygen vacancy (V-(O) over dot ) in the lattice. In this work, we investigate for the first time the role of oxygen defects configuration on the electro-chemo-mechanical properties. This is achieved by tuning the oxygen defects blocking barrier density in polycrystalline gadolinium doped ceria with known oxygen vacancy concentration, Ce0.9Gd0.1O2-delta, delta = 0.05. Nanometric starting powders of ca. similar to 12 nm are sintered in different conditions, including field assisted spark plasma sintering (SPS), fast firing and conventional method at high temperatures. These approaches allow controlling grain size and Gd-dopant diffusion, i.e. via thermally driven solute drag mechanism. By correlating the electro-chemo-mechanical properties, we show that oxygen vacancy distribution in the materials plays a key role in ceria electrostriction, overcoming the expected contributions from grain size and dopant concentration. (C) 2019 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved

Domain Pinning: Comparison of Hafnia and PZT Based Ferroelectrics

Even though many studies on the field cycling behavior of ferroelectric hafnium oxide have recently been published, the issue is still not fully understood. The initial increase of polarization during first cycles is explained by different theoretical and empirical approaches. Field-induced phase changes as well as oxygen vacancy diffusion from interfacial layers toward the bulk are discussed. Trapped charges as well as the mentioned oxygen vacancy diffusion might cause a shift of the hysteresis along the voltage axis called imprint. Even though various studies connect this effect to charge diffusion with progression of cycling, a final experimental proof for the origin of wakeup and imprint is still missing. Based on the comprehensive comparative study of hafnia-zirconia and iron-doped lead zirconate titanate ferroelectrics, it is verified that the diffusion of oxygen vacancies is the main cause for both imprint and wake-up. Moreover, it is shown that a local seed inhibition of ferroelectric domains is most likely responsible for the reduced ferroelectric response in pristine state

Peupler la terre

Il y a 70 000 ans, Homo sapiens sortait d’Afrique pour coloniser le monde. Il y a 6 000 ans, il fondait les premières villes. Aujourd’hui, à l’ère des réseaux de villes, il crée des régions métropolitaines de plus en plus étendues et complexes. De la préhistoire à l’ère des métropoles, l’homme occupe l’espace terrestre selon des modalités d’une infinie variété, sous l’influence d’une multitude de facteurs. Comment les Bantu peuplent-ils un espace déjà occupé par les Pygmées en Afrique équatoriale ? Comment naissent les villes à l’Âge du bronze ? Comment se développe puis disparaît la société des pueblos aux États-Unis ? Quels sont les effets de la romanisation sur le peuplement de Gaule méridionale ? Comment émerge le système villageois aux alentours de l’an Mil en Europe ? Ce livre aborde douze grands changements du peuplement mondial formalisés sous forme de « transitions ». Qu’est-ce qu’une transition ? Comment l’identifier dans le domaine empirique ? Archéologues, historiens, linguistes et géographes unissent leur regard pour construire, analyser et comparer des modèles de transition du peuplement dans l’histoire mondiale. Observant le particulier, ils recherchent l’universel. Ce livre propose une méthode pour comprendre les lois du peuplement humain dans la très longue durée