Perylene Diimide Molecular Glass: Investigations of Charge Transport

A new glass-forming organic semiconductor material was synthesized using a known electron transport material, perylene diimide, and attaching it to a molecular glass in order to allow the material to be solution processed. Devices were made using a simple metal-semiconductor-metal structure and electrodes were selected to produce Schottky diodes. Experiments were carried out to characterize this new molecular glass perylene diimide. The new material shows evidence of traps, hysteresis, and other behaviours that are explored in this thesis. The material shows some potential as an electron transport layer with possibilities of memory storage behaviour.

Who is in charge? An L2 Discourse Intonation Study on Four Prosodic Parameters to Exert the Pragmatic Function of Dominance and Control in the Context of L2 Non-specialist Public Speaking

This paper reports the findings from a study of the learning of English intonation by Spanish speakers within the discourse mode of L2 oral presentation. The purpose of this experiment is, firstly, to compare four prosodic parameters before and after an L2 discourse intonation training programme and, secondly, to confirm whether subjects, after the aforementioned L2 discourse intonation training, are able to match the form of these four prosodic parameters to the discourse-pragmatic function of dominance and control. The study designed the instructions and tasks to create the oral and written corpora and Brazil’s Pronunciation for Advanced Learners of English was adapted for the pedagogical aims of the present study. The learners’ pre- and post-tasks were acoustically analysed and a pre / post- questionnaire design was applied to interpret the acoustic analysis. Results indicate most of the subjects acquired a wider choice of the four prosodic parameters partly due to the prosodically-annotated transcripts that were developed throughout the L2 discourse intonation course. Conversely, qualitative and quantitative data reveal most subjects failed to match the forms to their appropriate pragmatic functions to express dominance and control in an L2 oral presentation.

Charge migration induced by attosecond pulses in bio-relevant molecules

After sudden ionization of a large molecule, the positive charge can migrate throughout the system on a sub-femtosecond time scale, purely guided by electronic coherences. The possibility to actively explore the role of the electron dynamics in the photo-chemistry of bio-relevant molecules is of fundamental interest for understanding, and perhaps ultimately controlling, the processes leading to damage, mutation and, more generally, to the alteration of the biological functions of the macromolecule. Attosecond laser sources can provide the extreme time resolution required to follow this ultrafast charge flow. In this review we will present recent advances in attosecond molecular science: after a brief description of the results obtained for small molecules, recent experimental and theoretical findings on charge migration in bio-relevant molecules will be discussed.

Improved Real-time State-of-Charge Estimation of LiFePO4 Battery Based on a Novel Thermoelectric Model

Li-ion batteries have been widely used in electric vehicles, and battery internal state estimation plays an important role in the battery management system. However, it is technically challenging, in particular, for the estimation of the battery internal temperature and state-ofcharge (SOC), which are two key state variables affecting the battery performance. In this paper, a novel method is proposed for realtime simultaneous estimation of these two internal states, thus leading to a significantly improved battery model for realtime SOC estimation. To achieve this, a simplified battery thermoelectric model is firstly built, which couples a thermal submodel and an electrical submodel. The interactions between the battery thermal and electrical behaviours are captured, thus offering a comprehensive description of the battery thermal and electrical behaviour. To achieve more accurate internal state estimations, the model is trained by the simulation error minimization method, and model parameters are optimized by a hybrid optimization method combining a meta-heuristic algorithm and the least square approach. Further, timevarying model parameters under different heat dissipation conditions are considered, and a joint extended Kalman filter is used to simultaneously estimate both the battery internal states and time-varying model parameters in realtime. Experimental results based on the testing data of LiFePO4 batteries confirm the efficacy of the proposed method.

Ultrafast charge-transfer in organic photovoltaic interfaces: geometrical and functionalization effects

Understanding the microscopic mechanisms of electronic excitation in organic photovoltaic cells is a challenging problem in the design of efficient devices capable of performing sunlight harvesting. Here we develop and apply an ab initio approach based on time-dependent density functional theory and Ehrenfest dynamics to investigate photoinduced charge transfer in small organic molecules. Our calculations include mixed quantum–classical dynamics with ions moving classically and electrons quantum mechanically, where no experimental external parameter other than the material geometry is required. We show that the behavior of photocarriers in zinc phthalocyanine (ZnPc) and C60 systems, an effective prototype system for organic solar cells, is sensitive to the atomic orientation of the donor and the acceptor units as well as the functionalization of covalent molecules at the interface. In particular, configurations with the ZnPc molecules facing on C60 facilitate charge transfer between substrate and molecules that occurs within 200 fs. In contrast, configurations where ZnPc is tilted above C60 present extremely low carrier injection efficiency even at longer times as an effect of the larger interfacial potential level offset and higher energetic barrier between the donor and acceptor molecules. An enhancement of charge injection into C60 at shorter times is observed as binding groups connect ZnPc and C60 in a dyad system. Our results demonstrate a promising way of designing and controlling photoinduced charge transfer on the atomic level in organic devices that would lead to efficient carrier separation and maximize device performance.

Manifestation of Colossal Thermoelectric Power by Charge Ordered Small and Intermediate Bandwidth Manganites

Thermoelectric materials are revisited for various applications including power generation. The direct conversion of temperature differences into electric voltage and vice versa is known as thermoelectric effect. Possible applications of thermoelectric materials are in eco-friendly refrigeration, electric power generation from waste heat, infrared sensors, temperature controlled-seats and portable picnic coolers. Thermoelectric materials are also extensively researched upon as an alternative to compression based refrigeration. This utilizes the principle of Peltier cooling. The performance characteristic of a thermoelectric material, termed as figure of merit (ZT) is a function of several transport coefficients such as electrical conductivity (σ), thermal conductivity (κ) and Seebeck coefficient of the material (S). ZT is expressed asκσTZTS2=, where T is the temperature in degree absolute. A large value of Seebeck coefficient, high electrical conductivity and low thermal conductivity are necessary to realize a high performance thermoelectric material. The best known thermoelectric materials are phonon-glass electron – crystal (PGEC) system where the phonons are scattered within the unit cell by the rattling structure and electrons are scattered less as in crystals to obtain a high electrical conductivity. A survey of literature reveals that correlated semiconductors and Kondo insulators containing rare earth or transition metal ions are found to be potential thermoelectric materials. The structural magnetic and charge transport properties in manganese oxides having the general formula of RE1−xAExMnO3 (RE = rare earth, AE= Ca, Sr, Ba) are solely determined by the mixed valence (3+/4+) state of Mn ions. In strongly correlated electron systems, magnetism and charge transport properties are strongly correlated. Within the area of strongly correlated electron systems the study of manganese oxides, widely known as manganites exhibit unique magneto electric transport properties, is an active area of research.Strongly correlated systems like perovskite manganites, characterized by their narrow localized band and hoping conduction, were found to be good candidates for thermoelectric applications. Manganites represent a highly correlated electron system and exhibit a variety of phenomena such as charge, orbital and magnetic ordering, colossal magneto resistance and Jahn-Teller effect. The strong inter-dependence between the magnetic order parameters and the transport coefficients in manganites has generated much research interest in the thermoelectric properties of manganites. Here, large thermal motion or rattling of rare earth atoms with localized magnetic moments is believed to be responsible for low thermal conductivity of these compounds. The 4f levels in these compounds, lying near the Fermi energy, create large density of states at the Fermi level and hence they are likely to exhibit a fairly large value of Seebeck coefficient.

It’s a Trap! Unravelling Reversible Charge Trapping in Nanocrystals Through Single Particle and Ensemble Studies

Thesis (Ph.D.)--University of Washington, 2016-08

Electrodeposited reduced-graphene oxide/cobalt oxide electrodes for charge storage applications

In the present work, electrochemically reduced-graphene oxide/cobalt oxide composites for charge storage electrodes were prepared by a one-step pulsed electrodeposition route on stainless steel current collectors and after that submitted to a thermal treatment at 200 degrees C. A detailed physico-chemical characterization was performed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Raman spectroscopy. The electrochemical response of the composite electrodes was studied by cyclic voltammetry and charge-discharge curves and related to the morphological and phase composition changes induced by the thermal treatment. The results revealed that the composites were promising materials for charge storage electrodes for application in redox supercapacitors, attaining specific capacitances around 430 F g(-1) at 1 A g(-1) and presenting long-term cycling stability. (C) 2016 Elsevier B.V. All rights reserved.

A study of electrochemical transport and diffuse charge dynamics using a Langevin equation

This thesis aims to develop new numerical and computational tools to study electrochemical transport and diffuse charge dynamics at small scales. Previous efforts at modeling electrokinetic phenomena at scales where the noncontinuum effects become significant have included continuum models based on the Poisson-Nernst-Planck equations and atomic simulations using molecular dynamics algorithms. Neither of them is easy to use or conducive to electrokinetic transport modeling in strong confinement or over long time scales. This work introduces a new approach based on a Langevin equation for diffuse charge dynamics in nanofluidic devices, which incorporates features from both continuum and atomistic methods. The model is then extended to include steric effects resulting from finite ion size, and applied to the phenomenon of double layer charging in a symmetric binary electrolyte between parallel-plate blocking electrodes, between which a voltage is applied. Finally, the results of this approach are compared to those of the continuum model based on the Poisson-Nernst-Planck equations.

Le diagnostic anténatal modifie-t-il la prise en charge néonatale et le devenir à 1 an des enfants suivis pour atrésie de l’œsophage de type III ?

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