On the role of intrinsic disorder in the structural phase transition of magnetoelectric EuTiO3

Up to now the crystallographic structure of the magnetoelectric perovskite EuTiO3 was considered to remain cubic down to low temperature. Here we present high resolution synchrotron X-ray powder diffraction data showing the existence of a structural phase transition, from cubic Pm-3m to tetragonal I4/mcm, involving TiO6 octahedra tilting, in analogy to the case of SrTiO3. The temperature evolution of the tilting angle indicates a second-order phase transition with an estimated Tc=235K. This critical temperature is well below the recent anomaly reported by specific heat measurement at TA\sim282K. By performing atomic pair distribution function analysis on diffraction data we provide evidence of a mismatch between the local (short-range) and the average crystallographic structures in this material. Below the estimated Tc, the average model symmetry is fully compatible with the local environment distortion but the former is characterized by a reduced value of the tilting angle compared to the latter. At T=240K data show the presence of local octahedra tilting identical to the low temperature one, while the average crystallographic structure remains cubic. On this basis, we propose intrinsic lattice disorder to be of fundamental importance in the understanding of EuTiO3 properties.Comment: 13 pages, 8 figures, 2 table

Structural and dynamic disorder, not ionic trapping, controls charge transport in highly doped conducting polymers

Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counter-ions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique, we find the conductivity of several classes of high-mobility conjugated polymers to be strongly correlated with paracrystalline disorder but poorly correlated with ionic size, suggesting that Coulomb traps do not limit transport. A general model for interacting electrons in highly doped polymers is proposed and carefully parameterized against atomistic calculations, enabling the calculation of electrical conductivity within the framework of transient localisation theory. Theoretical calculations are in excellent agreement with experimental data, providing insights into the disordered-limited nature of charge transport and suggesting new strategies to further improve conductivities

Structural and dynamic disorder, not ionic trapping, controls charge transport in highly doped conducting polymers

Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counter-ions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique, we find the conductivity of several classes of high-mobility conjugated polymers to be strongly correlated with paracrystalline disorder but poorly correlated with ionic size, suggesting that Coulomb traps do not limit transport. A general model for interacting electrons in highly doped polymers is proposed and carefully parameterized against atomistic calculations, enabling the calculation of electrical conductivity within the framework of transient localisation theory. Theoretical calculations are in excellent agreement with experimental data, providing insights into the disordered-limited nature of charge transport and suggesting new strategies to further improve conductivities

Elastic and anelastic relaxations associated with phase transitions in EuTiO3

Elastic and anelastic properties of single crystal samples of EuTiO3 have been measured between 10 and 300 K by resonant ultrasound spectroscopy at frequencies in the vicinity of 1 MHz. Softening of the shear elastic constants C44 and 12(C11−C12) by ∼20–30% occurs with falling temperature in a narrow interval through the transition point, Tc=284 K, for the cubic-tetragonal transition. This is accounted for by classical coupling of macroscopic spontaneous strains with the tilt order parameter in the same manner as occurs in SrTiO3. A peak in the acoustic loss occurs a few degrees below Tc and is interpreted in terms of initially mobile ferroelastic twin walls, which rapidly become pinned with further lowering of temperature. This contrasts with the properties of twin walls in SrTiO3, which remain mobile down to at least 15 K. No further anomalies were observed that might be indicative of strain coupling to any additional phase transitions above 10 K. A slight anomaly in the shear elastic constants, independent of frequency and without any associated acoustic loss, was found at ∼140 K. It marks a change from elastic stiffening to softening with falling temperature and perhaps provides evidence for coupling between strain and local fluctuations of dipoles related to the incipient ferroelectric transition. An increase in acoustic loss below ∼80 K is attributed to the development of dynamical magnetic clustering ahead of the known antiferromagnetic ordering transition at ∼5.5 K. Detection of these elastic anomalies serves to emphasize that coupling of strain with tilting, ferroelectric, and magnetic order parameters is likely to be a permeating influence in determining the structure, stability, properties, and behavior of EuTiO3

Magnetic field and in situ stress dependence of elastic behavior in EuTiO3 from resonant ultrasound spectroscopy

Magnetoelectric coupling phenomena in EuTiO3 are of considerable fundamental interest and are also understood to be key to reported multiferroic behavior in strained films, which exhibit distinctly different properties to the bulk. Here, the magnetoelastic coupling of EuTiO3 is investigated by resonant ultrasound spectroscopy with in situ applied magnetic field and stress as a function of temperature ranging from temperatures above the structural transition temperature Ts to below the antiferromagnetic ordering temperature Tn. One single crystal and two polycrystalline samples are investigated and compared to each other. Both paramagnetic and diamagnetic transducer carriers are used, allowing an examination of the effect of both stress and magnetic field on the behavior of the sample. The properties are reported in constant field/variable temperature and in constant temperature/variable field mode where substantial differences between both data sets are observed. In addition, elastic and magnetic poling at high fields and stresses at low temperature has been performed in order to trace the history dependence of the elastic constants. Four different temperature regions are identified, characterized by unusual elastic responses. The low-temperature phase diagram has been explored and found to exhibit rich complexity. The data evidence a considerable relaxation of elastic constants at high temperatures, but with little effect from magnetic field alone above 20 K, in addition to the known low-temperature coupling

Dynamic self-stabilization in the electronic and nanomechanical properties of an organic polymer semiconductor.

The field of organic electronics has profited from the discovery of new conjugated semiconducting polymers that have molecular backbones which exhibit resilience to conformational fluctuations, accompanied by charge carrier mobilities that routinely cross the 1 cm2/Vs benchmark. One such polymer is indacenodithiophene-co-benzothiadiazole. Previously understood to be lacking in microstructural order, we show here direct evidence of nanosized domains of high order in its thin films. We also demonstrate that its device-based high-performance electrical and thermoelectric properties are not intrinsic but undergo rapid stabilization following a burst of ambient air exposure. The polymer's nanomechanical properties equilibrate on longer timescales owing to an orthogonal mechanism; the gradual sweating-out of residual low molecular weight solvent molecules from its surface. We snapshot the quasistatic temporal evolution of the electrical, thermoelectric and nanomechanical properties of this prototypical organic semiconductor and investigate the subtleties which play on competing timescales. Our study documents the untold and often overlooked story of a polymer device's dynamic evolution toward stability.Royal Society, National Science Foundatio

Effects of Processing-Induced Contamination on Organic Electronic Devices

Organic semiconductors are a family of pi-conjugated compounds used in many applications, such as displays, bioelectronics, and thermoelectrics. However, their susceptibility to processing-induced contamination is not well understood. Here, it is shown that many organic electronic devices reported so far may have been unintentionally contaminated, thus affecting their performance, water uptake, and thin film properties. Nuclear magnetic resonance spectroscopy is used to detect and quantify contaminants originating from the glovebox atmosphere and common laboratory consumables used during device fabrication. Importantly, this in-depth understanding of the sources of contamination allows the establishment of clean fabrication protocols, and the fabrication of organic field effect transistors (OFETs) with improved performance and stability. This study highlights the role of unintentional contaminants in organic electronic devices, and demonstrates that certain stringent processing conditions need to be met to avoid scientific misinterpretation, ensure device reproducibility, and facilitate performance stability. The experimental procedures and conditions used herein are typical of those used by many groups in the field of solution-processed organic semiconductors. Therefore, the insights gained into the effects of contamination are likely to be broadly applicable to studies, not just of OFETs, but also of other devices based on these materials.info:eu-repo/semantics/publishe