Application of Numerical Methods to Study Arrangement and Fracture of Lithium-Ion Microstructure

The focus of this work is to develop and employ numerical methods that provide characterization of granular microstructures, dynamic fragmentation of brittle materials, and dynamic fracture of three-dimensional bodies.

We first propose the fabric tensor formalism to describe the structure and evolution of lithium-ion electrode microstructure during the calendaring process. Fabric tensors are directional measures of particulate assemblies based on inter-particle connectivity, relating to the structural and transport properties of the electrode. Applying this technique to X-ray computed tomography of cathode microstructure, we show that fabric tensors capture the evolution of the inter-particle contact distribution and are therefore good measures for the internal state of and electronic transport within the electrode.

We then shift focus to the development and analysis of fracture models within finite element simulations. A difficult problem to characterize in the realm of fracture modeling is that of fragmentation, wherein brittle materials subjected to a uniform tensile loading break apart into a large number of smaller pieces. We explore the effect of numerical precision in the results of dynamic fragmentation simulations using the cohesive element approach on a one-dimensional domain. By introducing random and non-random field variations, we discern that round-off error plays a significant role in establishing a mesh-convergent solution for uniform fragmentation problems. Further, by using differing magnitudes of randomized material properties and mesh discretizations, we find that employing randomness can improve convergence behavior and provide a computational savings.

The Thick Level-Set model is implemented to describe brittle media undergoing dynamic fragmentation as an alternative to the cohesive element approach. This non-local damage model features a level-set function that defines the extent and severity of degradation and uses a length scale to limit the damage gradient. In terms of energy dissipated by fracture and mean fragment size, we find that the proposed model reproduces the rate-dependent observations of analytical approaches, cohesive element simulations, and experimental studies.

Lastly, the Thick Level-Set model is implemented in three dimensions to describe the dynamic failure of brittle media, such as the active material particles in the battery cathode during manufacturing. The proposed model matches expected behavior from physical experiments, analytical approaches, and numerical models, and mesh convergence is established. We find that the use of an asymmetrical damage model to represent tensile damage is important to producing the expected results for brittle fracture problems.

The impact of this work is that designers of lithium-ion battery components can employ the numerical methods presented herein to analyze the evolving electrode microstructure during manufacturing, operational, and extraordinary loadings. This allows for enhanced designs and manufacturing methods that advance the state of battery technology. Further, these numerical tools have applicability in a broad range of fields, from geotechnical analysis to ice-sheet modeling to armor design to hydraulic fracturing.

Trasporte eléctrico y magnetismo en sistemas electrodo - aislante - electrodo: hacia el desarrollo de dispositivos del tipo juntura tunel.

La presente tesis es un estudio dedicado a la optimización y desarrollo de sistemas del tipo juntura túnel. La metodología utilizada para la realización de la tesis consistió, en primer lugar, en la optimización de las componentes independientes de la juntura túnel: electrodo y barrera aislante. Posteriormente se optimizaron los procesos de fabricación para el desarrollo y caracterización de dispositivos del tipo juntura túnel en su forma final. En la primera parte de la tesis se analizan detalladamente los resultados obtenidos de la caracterización eléctrica y topografica de barreras aislantes en sistemas electrodo - barrera. Los sistemas bicapas estudiados, GdBa_2Cu_3_7/SrTiO_3, Nb/Ba_0,05Sr_0,95TiO_3 y YBa_2Cu_3O_7/SrTiO_3, fueron caracterizados utilizando un microscopio de fuerza atómica en modo conductor. Se propuso un modelo fenomenológico basado en los resultados experimentales, que permitió la obtención de parámetros críticos para el desarrollo de dispositivos del tipo juntura túnel con nuevas funcionalidades. La información obtenida de la caracterización de los sistemas bicapas (homogeneidad de crecimiento, baja densidad de defectos y de pinholes) indican un muy buen control de los parámetros de crecimiento de las barreras. Por otro lado, se obtuvo un buen comportamiento aislante para espesores mayores a 2 nm sin la presencia de pinholes en la barrera. La similitud en la estequiometría de las barreras (SrTiO_3) permitió comparar los distintos sistemas estudiados en términos de conductividad eléctrica. Se verificó que el modelo fenomenológico permite comparar la conductividad eléctrica de los sistemas mediante uno de los parámetros definidos en el modelo fenomenológico (obtenido de los ajustes lineales de las curvas I(V)). De los 3 sistemas estudiados, las bicapas GdBa_2Cu_3O_7/SrTiO_3 presentaron un mayor valor de longitud de atenuación de los portadores de carga a través de la barrera y una muy baja densidad de defectos superficiales. Las bicapas YBa_2Cu_3O_7/SrTiO_3 y Nb/Ba_0,05Sr_0,95TiO_3 permitieron validar el modelo fenomenológico propuesto para el análisis de la respuesta corriente - voltaje obtenida con el microscopio de fuerza atómica en modo conductor. La segunda parte de la tesis abarca conceptos de magnetismo y microfabricación para el desarrollo de junturas túnel magnéticas. Durante la caracterización de las películas ferromagnéticas individuales de Co_90Fe_10 (CoFe) se logró aumentar valor del campo coercitivo de films de 10 nm de espesor al incrementar la temperatura de depósito. Esto se debe a un aumento del tamaño de grano de los films. El aumento de la temperatura del sustrato durante el crecimiento influye en la morfología y las propiedades magnéticas de los films de CoFe favoreciendo la formación de granos y la pérdida del eje preferencial de magnetización. Estos resultados permitieron la fabricación de sistemas Co_90Fe_10/M_gO/Co_90Fe_10 con distintas orientaciones relativas accesibles con campo magnético para el estudio del acople magnético entre los films de CoFe. La caracterización eléctrica de estos sistemas, particularmente la respuesta corriente - voltaje obtenida con el microscopio de fuerza atómica en modo conductor, indicó que las propiedades de transporte eléctrico de las junturas presentan un alto grado de reproducibilidad. Se analizó además la inuencia del sustrato utilizado en la corriente túnel que atraviesa la barrera aislante. Por otro lado, se discuten los fenómenos relacionados a la optimización de las propiedades magnéticas de electrodos ferromagnéticos para la fabricación de junturas túnel Co_90Fe_10/MgO/Co_90Fe_10 y Co_90Fe_10/MgO /Fe_20Ni_80. En particular, se estudió el acople magnético entre capas ferromagnéticas y la inuencia del sustrato utilizado para el crecimiento de las tricapas. La optimización de los electrodos magnéticos involucró el análisis de la inuencia de la presencia de un aislante entre dos capas magnéticas en el acople de los electrodos. Se logró el desacople de films de 10 nm de Co_90Fe_10 y Fe_20Ni_80 separados por un espaciador de MgO de 2 nm. Finalmente se detallan los pasos para la fabricación de una red de junturas túnel magnéticas y su caracterización eléctrica a bajas temperaturas. El sistema estudiado fue la tricapa Co_90Fe_10 (10 nm)/M_gO (8 nm)/ Fe_20Ni_80 (10 nm) crecido sobre un sustrato de M_gO. La caracterización eléctrica confirmó la buena calidad de la junturas fabricadas. Las junturas obtenidas presentaron un comportamiento altamente resistivo (~ MΩ). Las mediciones de la corriente túnel en función de la temperatura permitieron descartar la presencia de pinholes en la barrera. El transporte de los portadores de carga es por efecto túnel a través de la barrera aislante. Las curvas de conductancia diferencial permitieron calcular el valor medio de la altura de la barrera de potencial (φ = 3.1 eV) a partir del modelo de Brinkman. Los resultados obtenidos en cada uno de los capítulos se complementan y son relevantes para la optimización de junturas túnel, debido a que brindan información crítica para su correcto funcionamiento. En la presente tesis se lograron obtener los primeros avances para la fabricación de arreglos de junturas túnel que permitan el desarrollo de dispositivos.

Trasporte eléctrico y magnetismo en sistemas electrodo - aislante - electrodo: hacia el desarrollo de dispositivos del tipo juntura tunel.

La presente tesis es un estudio dedicado a la optimización y desarrollo de sistemas del tipo juntura túnel. La metodología utilizada para la realización de la tesis consistió, en primer lugar, en la optimización de las componentes independientes de la juntura túnel: electrodo y barrera aislante. Posteriormente se optimizaron los procesos de fabricación para el desarrollo y caracterización de dispositivos del tipo juntura túnel en su forma final. En la primera parte de la tesis se analizan detalladamente los resultados obtenidos de la caracterización eléctrica y topografica de barreras aislantes en sistemas electrodo - barrera. Los sistemas bicapas estudiados, GdBa_2Cu_3_7/SrTiO_3, Nb/Ba_0,05Sr_0,95TiO_3 y YBa_2Cu_3O_7/SrTiO_3, fueron caracterizados utilizando un microscopio de fuerza atómica en modo conductor. Se propuso un modelo fenomenológico basado en los resultados experimentales, que permitió la obtención de parámetros críticos para el desarrollo de dispositivos del tipo juntura túnel con nuevas funcionalidades. La información obtenida de la caracterización de los sistemas bicapas (homogeneidad de crecimiento, baja densidad de defectos y de pinholes) indican un muy buen control de los parámetros de crecimiento de las barreras. Por otro lado, se obtuvo un buen comportamiento aislante para espesores mayores a 2 nm sin la presencia de pinholes en la barrera. La similitud en la estequiometría de las barreras (SrTiO_3) permitió comparar los distintos sistemas estudiados en términos de conductividad eléctrica. Se verificó que el modelo fenomenológico permite comparar la conductividad eléctrica de los sistemas mediante uno de los parámetros definidos en el modelo fenomenológico (obtenido de los ajustes lineales de las curvas I(V)). De los 3 sistemas estudiados, las bicapas GdBa_2Cu_3O_7/SrTiO_3 presentaron un mayor valor de longitud de atenuación de los portadores de carga a través de la barrera y una muy baja densidad de defectos superficiales. Las bicapas YBa_2Cu_3O_7/SrTiO_3 y Nb/Ba_0,05Sr_0,95TiO_3 permitieron validar el modelo fenomenológico propuesto para el análisis de la respuesta corriente - voltaje obtenida con el microscopio de fuerza atómica en modo conductor. La segunda parte de la tesis abarca conceptos de magnetismo y microfabricación para el desarrollo de junturas túnel magnéticas. Durante la caracterización de las películas ferromagnéticas individuales de Co_90Fe_10 (CoFe) se logró aumentar valor del campo coercitivo de films de 10 nm de espesor al incrementar la temperatura de depósito. Esto se debe a un aumento del tamaño de grano de los films. El aumento de la temperatura del sustrato durante el crecimiento influye en la morfología y las propiedades magnéticas de los films de CoFe favoreciendo la formación de granos y la pérdida del eje preferencial de magnetización. Estos resultados permitieron la fabricación de sistemas Co_90Fe_10/M_gO/Co_90Fe_10 con distintas orientaciones relativas accesibles con campo magnético para el estudio del acople magnético entre los films de CoFe. La caracterización eléctrica de estos sistemas, particularmente la respuesta corriente - voltaje obtenida con el microscopio de fuerza atómica en modo conductor, indicó que las propiedades de transporte eléctrico de las junturas presentan un alto grado de reproducibilidad. Se analizó además la inuencia del sustrato utilizado en la corriente túnel que atraviesa la barrera aislante. Por otro lado, se discuten los fenómenos relacionados a la optimización de las propiedades magnéticas de electrodos ferromagnéticos para la fabricación de junturas túnel Co_90Fe_10/MgO/Co_90Fe_10 y Co_90Fe_10/MgO /Fe_20Ni_80. En particular, se estudió el acople magnético entre capas ferromagnéticas y la inuencia del sustrato utilizado para el crecimiento de las tricapas. La optimización de los electrodos magnéticos involucró el análisis de la inuencia de la presencia de un aislante entre dos capas magnéticas en el acople de los electrodos. Se logró el desacople de films de 10 nm de Co_90Fe_10 y Fe_20Ni_80 separados por un espaciador de MgO de 2 nm. Finalmente se detallan los pasos para la fabricación de una red de junturas túnel magnéticas y su caracterización eléctrica a bajas temperaturas. El sistema estudiado fue la tricapa Co_90Fe_10 (10 nm)/M_gO (8 nm)/ Fe_20Ni_80 (10 nm) crecido sobre un sustrato de M_gO. La caracterización eléctrica confirmó la buena calidad de la junturas fabricadas. Las junturas obtenidas presentaron un comportamiento altamente resistivo (~ MΩ). Las mediciones de la corriente túnel en función de la temperatura permitieron descartar la presencia de pinholes en la barrera. El transporte de los portadores de carga es por efecto túnel a través de la barrera aislante. Las curvas de conductancia diferencial permitieron calcular el valor medio de la altura de la barrera de potencial (φ = 3.1 eV) a partir del modelo de Brinkman. Los resultados obtenidos en cada uno de los capítulos se complementan y son relevantes para la optimización de junturas túnel, debido a que brindan información crítica para su correcto funcionamiento. En la presente tesis se lograron obtener los primeros avances para la fabricación de arreglos de junturas túnel que permitan el desarrollo de dispositivos.

Electrical and optical studies on carbon nanotube arrays

Single-walled carbon nanotubes (SWNTs) have been studied as a prominent class of high performance electronic materials for next generation electronics. Their geometry dependent electronic structure, ballistic transport and low power dissipation due to quasi one dimensional transport, and their capability of carrying high current densities are some of the main reasons for the optimistic expectations on SWNTs. However, device applications of individual SWNTs have been hindered by uncontrolled variations in characteristics and lack of scalable methods to integrate SWNTs into electronic devices. One relatively new direction in SWNT electronics, which avoids these issues, is using arrays of SWNTs, where the ensemble average may provide uniformity from device to device, and this new breed of electronic material can be integrated into electronic devices in a scalable fashion. This dissertation describes (1) methods for characterization of SWNT arrays, (2) how the electrical transport in these two-dimensional arrays depend on length scales and spatial anisotropy, (3) the interaction of aligned SWNTs with the underlying substrate, and (4) methods for scalable integration of SWNT arrays into electronic devices. The electrical characterization of SWNT arrays have been realized by polymer electrolyte-gated SWNT thin film transistors (TFTs). Polymer electrolyte-gating addresses many technical difficulties inherent to electrical characterization by gating through oxide-dielectrics. Having shown polymer electrolyte-gating can be successfully applied on SWNT arrays, we have studied the length scaling dependence of electrical transport in SWNT arrays. Ultrathin films formed by sub-monolayer surface coverage of SWNT arrays are very interesting systems in terms of the physics of two-dimensional electronic transport. We have observed that they behave qualitatively different than the classical conducting films, which obey the Ohm’s law. The resistance of an ultrathin film of SWNT arrays is indeed non-linear with the length of the film, across which the transport occurs. More interestingly, a transition between conducting and insulating states is observed at a critical surface coverage, which is called percolation limit. The surface coverage of conducting SWNTs can be manipulated by turning on and off the semiconductors in the SWNT array, leading to the operation principle of SWNT TFTs. The percolation limit depends also on the length and the spatial orientation of SWNTs. We have also observed that the percolation limit increases abruptly for aligned arrays of SWNTs, which are grown on single crystal quartz substrates. In this dissertation, we also compare our experimental results with a two-dimensional stick network model, which gives a good qualitative picture of the electrical transport in SWNT arrays in terms of surface coverage, length scaling, and spatial orientation, and briefly discuss the validity of this model. However, the electronic properties of SWNT arrays are not only determined by geometrical arguments. The contact resistances at the nanotube-nanotube and nanotube-electrode (bulk metal) interfaces, and interactions with the local chemical groups and the underlying substrates are among other issues related to the electronic transport in SWNT arrays. Different aspects of these factors have been studied in detail by many groups. In fact, I have also included a brief discussion about electron injection onto semiconducting SWNTs by polymer dopants. On the other hand, we have compared the substrate-SWNT interactions for isotropic (in two dimensions) arrays of SWNTs grown on Si/SiO2 substrates and horizontally (on substrate) aligned arrays of SWNTs grown on single crystal quartz substrates. The anisotropic interactions associated with the quartz lattice between quartz and SWNTs that allow near perfect horizontal alignment on substrate along a particular crystallographic direction is examined by Raman spectroscopy, and shown to lead to uniaxial compressive strain in as-grown SWNTs on single crystal quartz. This is the first experimental demonstration of the hard-to-achieve uniaxial compression of SWNTs. Temperature dependence of Raman G-band spectra along the length of individual nanotubes reveals that the compressive strain is non-uniform and can be larger than 1% locally at room temperature. Effects of device fabrication steps on the non-uniform strain are also examined and implications on electrical performance are discussed. Based on our findings, there are discussions about device performances and designs included in this dissertation. The channel length dependences of device mobilities and on/off ratios are included for SWNT TFTs. Time response of polymer-electrolyte gated SWNT TFTs has been measured to be ~300 Hz, and a proof-of-concept logic inverter has been fabricated by using polymer electrolyte gated SWNT TFTs for macroelectronic applications. Finally, I dedicated a chapter on scalable device designs based on aligned arrays of SWNTs, including a design for SWNT memory devices.

Strong quantum memory at resonant Fermi edges revealed by shot noise

Studies of non-equilibrium current fluctuations enable assessing correlations involved in quantum transport through nanoscale conductors. They provide additional information to the mean current on charge statistics and the presence of coherence, dissipation, disorder, or entanglement. Shot noise, being a temporal integral of the current autocorrelation function, reveals dynamical information. In particular, it detects presence of non-Markovian dynamics, i.e., memory, within open systems, which has been subject of many current theoretical studies. We report on low-temperature shot noise measurements of electronic transport through InAs quantum dots in the Fermi-edge singularity regime and show that it exhibits strong memory effects caused by quantum correlations between the dot and fermionic reservoirs. Our work, apart from addressing noise in archetypical strongly correlated system of prime interest, discloses generic quantum dynamical mechanism occurring at interacting resonant Fermi edges.

Room temperature photo-response of titanium supersaturated silicon at energies over the bandgap

Silicon samples were implanted with high Ti doses and subsequently processed with the pulsed-laser melting technique. The electronic transport properties in the 15–300 K range and the room temperature spectral photoresponse at energies over the bandgap were measured. Samples with Ti concentration below the insulator-metal (I-M) transition limit showed a progressive reduction of the carrier lifetime in the implanted layer as Ti dose is increased. However, when the Ti concentration exceeded this limit, an extraordinary recovery of the photoresponse was measured. This result supports the theory of intermediate band materials and is of utmost relevance for photovoltaic cells and Si-based detectors.

Insulator-to-metal transition in vanadium supersaturated silicon: variable-range hopping and Kondo effect signatures

We report the observation of the insulator-to-metal transition in crystalline silicon samples supersaturated with vanadium. Ion implantation followed by pulsed laser melting and rapid resolidification produce high quality single-crystalline silicon samples with vanadium concentrations that exceed equilibrium values in more than 5 orders of magnitude. Temperature-dependent analysis of the conductivity and Hall mobility values for temperatures from 10K to 300K indicate that a transition from an insulating to a metallic phase is obtained at a vanadium concentration between 1.1 × 10^(20) and 1.3 × 10^(21) cm^(−3) . Samples in the insulating phase present a variable-range hopping transport mechanism with a Coulomb gap at the Fermi energy level. Electron wave function localization length increases from 61 to 82 nm as the vanadium concentration increases in the films, supporting the theory of impurity band merging from delocalization of levels states. On the metallic phase, electronic transport present a dispersion mechanism related with the Kondo effect, suggesting the presence of local magnetic moments in the vanadium supersaturated silicon material.

Procesos hopping a través del modelo difusional en materiales nanocristalinos usados para aplicaciones fotovoltaicas

Se presentan los modelos de hopping de rango variable (variable range hopping; VRH), vecinos cercanos (nearest neighbor hopping; NNH) y barreras de potencial presentes en las fronteras de grano; como mecanismos de transporte eléctrico predominantes en los materiales semiconductores para aplicaciones fotovoltaicas. Las medidas de conductividad a oscuras en función de temperatura fueron realizadas para región de bajas temperaturas entre 120 y 400 K con Si y compuestos Cu3BiS2 y Cu2ZnSnSe4. Siguiendo la teoría de percolación, se obtuvieron parámetros hopping y la densidad de estados cerca del nivel de Fermi, N(EF), para todas las muestras. A partir de los planteamientos dados por Mott para VRH, se presentó el modelo difusional, que permitió establecer la relación entre la conductividad y la densidad de estados de defecto o estados localizados en el gap del material. El análisis comparativo entre modelos, evidenció, que es posible obtener mejora hasta de un orden de magnitud en valores para cada uno de los parámetros hopping que caracterizan el material.

Electronic, structural, and transport properties of Ni-doped graphene nanoribbons

We have investigated the electronic and transport properties of zigzag Ni-adsorbed graphene nanoribbons (Ni/GNRs) using ab initio calculations. We find that the Ni adatoms lying along the edge of zigzag GNRs represent the energetically most stable configuration, with an energy difference of approximately 0.3 eV when compared to the adsorption in the middle of the ribbon. The carbon atoms at the ribbon edges still present nonzero magnetic moments as in the pristine GNR even though there is a quenching by a factor of almost five in the value of the local magnetic moments at the C atoms bonded to the Ni. This quenching decays relatively fast and at approximately 9 A from the Ni adsorption site the magnetic moments have already values close to the pristine ribbon. At the opposite edge and at the central carbon atoms the changes in the magnetic moments are negligible. The energetic preference for the antiparallel alignment between the magnetization at the opposite edges of the ribbon is still maintained upon Ni adsorption. We find many Ni d-related states within an energy window of 1 eV above and below the Fermi energy, which gives rise to a spin-dependent charge transport. These results suggest the possibility of manufacturing spin devices based on GNRs doped with Ni atoms.

Technologies applied to the transport sector: electronic fare collection systems

Electronic transactions are becoming increasingly commonplace in the countries of Latin America and the Caribbean, despite the collapse of many dotcom firms and the failure of e-commerce to make inroads in the region. In the transport sphere, the gradual incorporation of technology in support of processes and the exchange of money flows between players has brought greater versatility, security and flexibility. In public transport, such initiatives take the form of automatic ticket machines and prepaid card dispensing machines. In urban transit, electronic purses used for the supervision and payment of parking time, and in road pricing, electronic toll systems streamline the process of collecting money; this is especially the case with motorways and urban concessions. And in shipping, electronic transfers are increasingly being used for the payment of customs dues and port charges.In view of the importance of the topic and the interest expressed in it, the Transport Unit has begun a study of these issues, and recently published a paper entitled Sistemas de cobro electrónico de pasajes en el transporte público, ("Electronic systems for payment of tickets in public transport") LC/L.1752-P/E, July 2002, on which this issue of the Bulletin is based.

Electronic energy transfer processes and charge carrier transport in pi-conjugated polymers

Conjugated polymers have attracted tremendous academical and industrial research interest over the past decades due to the appealing advantages that organic / polymeric materials offer for electronic applications and devices such as organic light emitting diodes (OLED), organic field effect transistors (OFET), organic solar cells (OSC), photodiodes and plastic lasers. The optimization of organic materials for applications in optoelectronic devices requires detailed knowledge of their photophysical properties, for instance energy levels of excited singlet and triplet states, excited state decay mechanisms and charge carrier mobilities. In the present work a variety of different conjugated (co)polymers, mainly polyspirobifluorene- and polyfluorene-type materials, was investigated using time-resolved photoluminescence spectroscopy in the picosecond to second time domain to study their elementary photophysical properties and to get a deeper insight into structure-property relationships. The experiments cover fluorescence spectroscopy using Streak Camera techniques as well as time-delayed gated detection techniques for the investigation of delayed fluorescence and phosphorescence. All measurements were performed on the solid state, i.e. thin polymer films and on diluted solutions. Starting from the elementary photophysical properties of conjugated polymers the experiments were extended to studies of singlet and triplet energy transfer processes in polymer blends, polymer-triplet emitter blends and copolymers. The phenomenon of photonenergy upconversion was investigated in blue light-emitting polymer matrices doped with metallated porphyrin derivatives supposing an bimolecular annihilation upconversion mechanism which could be experimentally verified on a series of copolymers. This mechanism allows for more efficient photonenergy upconversion than previously reported for polyfluorene derivatives. In addition to the above described spectroscopical experiments, amplified spontaneous emission (ASE) in thin film polymer waveguides was studied employing a fully-arylated poly(indenofluorene) as the gain medium. It was found that the material exhibits a very low threshold value for amplification of blue light combined with an excellent oxidative stability, which makes it interesting as active material for organic solid state lasers. Apart from spectroscopical experiments, transient photocurrent measurements on conjugated polymers were performed as well to elucidate the charge carrier mobility in the solid state, which is an important material parameter for device applications. A modified time-of-flight (TOF) technique using a charge carrier generation layer allowed to study hole transport in a series of spirobifluorene copolymers to unravel the structure-mobility relationship by comparison with the homopolymer. Not only the charge carrier mobility could be determined for the series of polymers but also field- and temperature-dependent measurements analyzed in the framework of the Gaussian disorder model showed that results coincide very well with the predictions of the model. Thus, the validity of the disorder concept for charge carrier transport in amorphous glassy materials could be verified for the investigated series of copolymers.

Electronic tuning effects via cyano substitution of a fused tetrathiafulvalene–benzothiadiazole dyad for ambipolar transport properties

Electronic tuning effects of substituents at the 4- and 8-positions of benzothiadiazole (BTD) within the fused tetrathiafulvalene–BTD donor–acceptor dyad have been studied. The electron acceptor strength of BTD is greatly increased by replacing Br with CN groups, extending the optical absorption of the small dyad into the near-IR region and importantly, the charge transport can be switched from p-type to ambipolar behaviour.

Emergence of half-metallicity in suspended NiO chains: Ab initio electronic structure and quantum transport calculations

Contrary to the antiferromagnetic and insulating character of bulk NiO, one-dimensional chains of this material can become half metallic due to the lower coordination of their atoms. Here we present ab initio electronic structure and quantum transport calculations of ideal infinitely long NiO chains and of more realistic short ones suspended between Ni electrodes. While infinite chains are insulating, short suspended chains are half-metallic minority-spin conductors that displays very large magnetoresistance and a spin-valve behavior controlled by a single atom.

Electronic structure and transport properties of atomic NiO spinvalves

Ab initio quantum transport calculations show that short NiO chains suspended in Ni nanocontacts present a very strong spin-polarization of the conductance.The generalized gradient approximation we use here predicts a similar polarization of the conductance as the one previously computed with non-local exchange, confirming the robustness of the result. Their use as nanoscopic spinvalves is proposed.