Flow driven electronic transport in carbon nan otubes

The flow of a liquid on single-walled carbon nanotube bundles induces an electrical signal (voltage/current) in the sample along the direction of the flow. The electrical response is found to be logarithmic in the flow speed over a wide range. The magnitude of the flow induced electrical signal generated depends sensitively on the ionic conductivity and the polar nature of the liquid, and electrical biasing of the nanotubes can control its direction. Our measurements suggest that the dominant mechanism responsible for this highly sub-linear response should involve a direct forcing of the free charge carriers in the nanotubes by the fluctuating Coulombic field of the liquid flowing past it.

Magnetically induced currents and magnetic response properties of molecules

The magnetically induced currents in organic monoring and multiring molecules, in Möbius shaped molecules and in inorganic all-metal molecules have been investigated by means of the Gauge-including magnetically induced currents (GIMIC) method. With the GIMIC method, the ring-current strengths and the ring-current density distributions can be calculated. For open-shell molecules, also the spin current can be obtained. The ring-current pathways and ring-current strengths can be used to understand the magnetic resonance properties of the molecules, to indirectly identify the effect of non-bonded interactions on NMR chemical shifts, to design new molecules with tailored properties and to discuss molecular aromaticity. In the thesis, the magnetic criterion for aromaticity has been adopted. According to this, a molecule which has a net diatropic ring current might be aromatic. Similarly, a molecule which has a net paratropic current might be antiaromatic. If the net current is zero, the molecule is nonaromatic. The electronic structure of the investigated molecules has been resolved by quantum chemical methods. The magnetically induced currents have been calculated with the GIMIC method at the density-functional theory (DFT) level, as well as at the self-consistent field Hartree-Fock (SCF-HF), at the Møller-Plesset perturbation theory of the second order (MP2) and at the coupled-cluster singles and doubles (CCSD) levels of theory. For closed-shell molecules, accurate ring-current strengths can be obtained with a reasonable computational cost at the DFT level and with rather small basis sets. For open-shell molecules, it is shown that correlated methods such as MP2 and CCSD might be needed to obtain reliable charge and spin currents. The basis set convergence has to be checked for open-shell molecules by performing calculations with large enough basis sets. The results discussed in the thesis have been published in eight papers. In addition, some previously unpublished results on the ring currents in the endohedral fullerene Sc3C2@C80 and in coronene are presented. It is shown that dynamical effects should be taken into account when modelling magnetic resonance parameters of endohedral metallofullerenes such as Sc3C2@C80. The ring-current strengths in a series of nano-sized hydrocarbon rings are related to static polarizabilities and to H-1 nuclear magnetic resonance (NMR) shieldings. In a case study on the possible aromaticity of a Möbius-shaped [16]annulene we found that, according to the magnetic criterion, the molecule is nonaromatic. The applicability of the GIMIC method to assign the aromatic character of molecules was confirmed in a study on the ring currents in simple monocylic aromatic, homoaromatic, antiaromatic, and nonaromatic hydrocarbons. Case studies on nanorings, hexaphyrins and [n]cycloparaphenylenes show that explicit calculations are needed to unravel the ring-current delocalization pathways in complex multiring molecules. The open-shell implementation of GIMIC was applied in studies on the charge currents and the spin currents in single-ring and bi-ring molecules with open shells. The aromaticity predictions that are made based on the GIMIC results are compared to other aromaticity criteria such as H-1 NMR shieldings and shifts, electric polarizabilities, bond-length alternation, as well as to predictions provided by the traditional Hückel (4n+2) rule and its more recent extensions that account for Möbius twisted molecules and for molecules with open shells.

Effects of Zr and Ti doping on the dielectric response of CeO2: A comparative first-principles study

Zr doping in ceria (CeO2) results in enhanced static dielectric response compared to pure ceria. On the other hand, Ti doping in ceria keeps its dielectric constant unchanged. We use first-principles density functional theory calculations based on pseudopotentials and a plane wave basis to determine electronic properties and dielectric response of Zr/Ti-doped and oxygen-vacancy-introduced ceria. Softening of phonon modes is responsible for the enhancement in dielectric response of Zr-doped ceria compared to that of pure ceria. The ceria-zirconia mixed oxides should have potential use as high-k materials in the semiconductor industry. (c) 2010 Elsevier Ltd. All rights reserved.

Optical and Electronic Properties of Conjugated Polymer -Nanocluster Semiconductor Hybrid Systems

Conjugated polymers are intensively pursued as candidate materials for emission and detection devices with the optical range of interest determined by the chemical structure. On the other hand the optical range for emission and detection can also be tuned by size selection in semiconductor nanoclusters. The mechanisms for charge generation and separation upon optical excitation, and light emission are different for these systems. Hybrid systems based on these different class of materials reveal interesting electronic and optical properties and add further insight into the individual characteristics of the different components. Multilayer structures and blends of these materials on different substrates were prepared for absorption, photocurrent (Iph), photoluminescence (PL) and electroluminscence (EL) studies. Polymers chosen were derivatives of polythiophene (PT) and polyparaphenylenevinylene (PPV) along with nanoclusters of cadmium sulphide of average size 4.4 nm (CdS-44). The photocurrent spectral response in these systems followed the absorption response around the band edges for each of the components and revealed additional features, which depended on bias voltage, thickness of the layers and interfacial effects. The current-voltage curves showed multi-component features with emission varying for different regimes of voltage. The emission spectral response revealed additive features and is discussed in terms of excitonic mechanisms.

Role of electrolyte chemistry on electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti

The primary objective of the present work was to study the electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti, fabricated independently in various electrolyte solutions consisting of anions such as phosphate (PO43-), borate (B4O72-), citrate (C6H5O73-) and silicate (SiO32-). Further the role of anions on the structural, morphological and compositional properties of the fabricated films was studied. All the titania films were developed by micro-arc oxidation (MAO) technique for a fixed treatment time of 8 min under constant current mode. The surface morphology, elemental distribution, composition and structural characteristics of the films were assessed by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The thermodynamic and kinetic corrosion properties of the films were studied under simulated body fluid (SBF) conditions (pH 7.4 and 37 degrees C) by conducting chronopotentiometric and potentiodynamic polarization tests. Electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit modelling was carried out to analyse the frequency response and Mott-Schottky analysis was performed to study the semiconducting (electronic) properties of the films. Salt spray fog accelerated corrosion test was conducted for 168h as per ASTM B117 standard to corroborate the corrosion and semiconducting properties of the samples based on the visual examination. The XRD results showed that the transformation from the metastable anatase phase to the thermodynamically stable rutile phase and the crystalline growth of the respective phases were strongly influenced by the addition of anions. The SEM-EDS results demonstrated that the phosphorous (P) content in the films varied from 2.4 at% to 5.0 at% indicating that the amount of P in the films could be modified by adding an appropriate electrolyte additive. The electrochemical corrosion test results showed that the film fabricated in citrate (C6H5O73-) containing electrolyte is thermodynamically and kinetically more stable compared to that of all the others. The results of the Mott-Schottky analysis indicated that all the fabricated films showed an n-type semiconducting behaviour and the film developed in citrate (C6H5O73-) containing electrolyte exhibited the lowest donor concentration and the most negative flat band potential that contributed to its highest corrosion resistance in SBF solution. The results of the salt spray accelerated corrosion tests were in agreement with those obtained from the electrochemical and Mott-Schottky analysis.

Multichannel-Emissive V-Shaped Boryl-BODIPY Dyads: Synthesis, Structure, and Remarkably Diverse Response toward Fluoride

Three new V-shaped boryl-BODIPY dyads (1-3) were synthesized and structurally characterized. Compounds 1-3 are structurally close molecular siblings differing only in the number of methyl substituents on the BODIPY moiety that were found to play a major role in determining their photophysical behavior. The dyads show rare forms of multiple-channel emission characteristics arising from different extents of electronic energy transfer (EET) processes between the two covalently linked fluorescent chromophores (borane and BODIPY units). Insights into the origin and nature of their emission behavior were gained from comparison with closely related model molecular systems and related photophysical investigations. Because of the presence of the Lewis acidic triarylborane moiety, the dyads function as highly selective and sensitive fluoride sensors with vastly different response behaviors. When fluoride binds to the tricoordinate borane center, dyad 1 shows gradual quenching of its BODIPY-dominated emission due to the ceasing of the (borane to BODIPY) EET process. Dyad 2 shows a ratiometric fluorescence response for fluoride ions. Dyad 3 forms fluoride-induced nanoaggregates that result in fast and effective quenching of its fluorescence intensity just for similar to 0.3 ppm of analyte (i.e., 0.1 equiv 0.26 ppm of fluoride). The small structural alterations in these three structurally close dyads (1 - 3) result in exceptionally versatile and unique photophysical behaviors and remarkably diverse responses toward a single analyte, i.e., fluoride ion.

Generalized Partial Response Equalization and Data-Dependent Noise Predictive Signal Detection Over Media Models for TDMR

Two-dimensional magnetic recording (2-D TDMR) is an emerging technology that aims to achieve areal densities as high as 10 Tb/in(2) using sophisticated 2-D signal-processing algorithms. High areal densities are achieved by reducing the size of a bit to the order of the size of magnetic grains, resulting in severe 2-D intersymbol interference (ISI). Jitter noise due to irregular grain positions on the magnetic medium is more pronounced at these areal densities. Therefore, a viable read-channel architecture for TDMR requires 2-D signal-detection algorithms that can mitigate 2-D ISI and combat noise comprising jitter and electronic components. Partial response maximum likelihood (PRML) detection scheme allows controlled ISI as seen by the detector. With the controlled and reduced span of 2-D ISI, the PRML scheme overcomes practical difficulties such as Nyquist rate signaling required for full response 2-D equalization. As in the case of 1-D magnetic recording, jitter noise can be handled using a data-dependent noise-prediction (DDNP) filter bank within a 2-D signal-detection engine. The contributions of this paper are threefold: 1) we empirically study the jitter noise characteristics in TDMR as a function of grain density using a Voronoi-based granular media model; 2) we develop a 2-D DDNP algorithm to handle the media noise seen in TDMR; and 3) we also develop techniques to design 2-D separable and nonseparable targets for generalized partial response equalization for TDMR. This can be used along with a 2-D signal-detection algorithm. The DDNP algorithm is observed to give a 2.5 dB gain in SNR over uncoded data compared with the noise predictive maximum likelihood detection for the same choice of channel model parameters to achieve a channel bit density of 1.3 Tb/in(2) with media grain center-to-center distance of 10 nm. The DDNP algorithm is observed to give similar to 10% gain in areal density near 5 grains/bit. The proposed signal-processing framework can broadly scale to various TDMR realizations and areal density points.

Non-enzymatic electronic detection of glucose using aminophenylboronic acid functionalized reduced graphene oxide

We report the non-enzymatic electronic detection of glucose using field effect transistor (FET) devices made of aminophenylboronic acid (APBA) functionalized reduced graphene oxide (RGO). Detection of glucose molecules was carried out over a wide dynamic range of concentration varying from 100 pM to 100 mM with a detection limit of similar to 2 nM using both covalently and non-covalently functionalized APBA-RGO complex. The normalized change in electrical conductance data shows that the FET devices made of non-covalently functionalized APBA-RGO complex (nc-APBA-RGO) exhibited a linear response to glucose aqueous solution of concentrations varying from 1 nM to 10 mM and showed 4 times enhanced sensitivity over the devices made of covalently functionalized APBA-RGO complex (c-APBA-RGO). Specificity of APBA-RGO complex to glucose is confirmed from the observation of negligible change in electrical conductance after exposure to 0.1 mM of lactose and other interfering factors. (C) 2015 Elsevier B.V. All rights reserved.

Studies of response to earthquake ground motion

A study is made of the accuracy of electronic digital computer calculations of ground displacement and response spectra from strong-motion earthquake accelerograms. This involves an investigation of methods of the preparatory reduction of accelerograms into a form useful for the digital computation and of the accuracy of subsequent digital calculations. Various checks are made for both the ground displacement and response spectra results, and it is concluded that the main errors are those involved in digitizing the original record. Differences resulting from various investigators digitizing the same experimental record may become as large as 100% of the maximum computed ground displacements. The spread of the results of ground displacement calculations is greater than that of the response spectra calculations. Standardized methods of adjustment and calculation are recommended, to minimize such errors.

Studies are made of the spread of response spectral values about their mean. The distribution is investigated experimentally by Monte Carlo techniques using an electric analog system with white noise excitation, and histograms are presented indicating the dependence of the distribution on the damping and period of the structure. Approximate distributions are obtained analytically by confirming and extending existing results with accurate digital computer calculations. A comparison of the experimental and analytical approaches indicates good agreement for low damping values where the approximations are valid. A family of distribution curves to be used in conjunction with existing average spectra is presented. The combination of analog and digital computations used with Monte Carlo techniques is a promising approach to the statistical problems of earthquake engineering.

Methods of analysis of very small earthquake ground motion records obtained simultaneously at different sites are discussed. The advantages of Fourier spectrum analysis for certain types of studies and methods of calculation of Fourier spectra are presented. The digitizing and analysis of several earthquake records is described and checks are made of the dependence of results on digitizing procedure, earthquake duration and integration step length. Possible dangers of a direct ratio comparison of Fourier spectra curves are pointed out and the necessity for some type of smoothing procedure before comparison is established. A standard method of analysis for the study of comparative ground motion at different sites is recommended.

Towards a fast electro-thermo-mechanical IGBT/Diode simulation framework for design of reliable power electronic converters

This paper describes a methodology that enables fast and reasonably accurate prediction of the reliability of power electronic modules featuring IGBTs and p-i-n diodes, by taking into account thermo-mechanical failure mechanisms of the devices and their associated packaging. In brief, the proposed simulation framework performs two main tasks which are tightly linked together: (i) the generation of the power devices' transient thermal response for realistic long load cycles and (ii) the prediction of the power modules' lifetime based on the obtained temperature profiles. In doing so the first task employs compact, physics-based device models, power losses lookup tables and polynomials and combined material-failure and thermal modelling, while the second task uses advanced reliability tests for failure mode and time-to-failure estimation. The proposed technique is intended to be utilised as a design/optimisation tool for reliable power electronic converters, since it allows easy and fast investigation of the effects that changes in circuit topology or devices' characteristics and packaging have on the reliability of the employed power electronic modules. © 2012 IEEE.

Electronic energy levels in an asymmetric quantum-dots-in-a-well structure for infrared photodetectors

Theoretical calculation of electronic energy levels of an asymmetric InAs/InGaAS/GaAS quantum-dots-in-a-well (DWELL) structure for infrared photodetectors is performed in the framework of effective-mass envelope-function theory. Our calculated results show that the electronic energy levels in quantum dots (QDs) increase when the asymmetry increases and the ground state energy increases faster than the excited state energies. Furthermore, the results also show that the electronic energy levels in QDs decrease as the size of QDs and the width of quantum well (QW) in the asymmetric DWELL structure increase. Additionally, the effects of asymmetry, the size of QDs and the width of QW on the response peak of asymmetry DWELL photodetectors are also discussed.

Photo-capacitance response of internal tunnelling coupling in quantum-dot-imbedded heterostructures under selective photo-excitation

Under selective photo-excitation, the capacitance response of internal tunnelling coupling in quantum-dots-imbedded heterostructures is studied to clarify the electronic states and the number densities of electrons filling in the quantum dots (QDs). The random nature for both optical transitions and the filling in a QD assembly makes highly resolved capacitance peaks appear in the C-V characteristic after turning off the photo-excitation.

Nonlinear optical response of nc-Si-SiO2 films studied with femtosecond four-wave mixing technique

Nonlinear optical properties of silicon nanocrystals (nc-Si) embedded in SiO2 films are investigated using time-resolved four-wave mixing technique with a femtosecond laser. the off-resonant third-order nonlinear susceptibility chi((3)) is observed to be 1.3 x 10(-10) esu at 800 nm. The relaxation time of the film is fast as short as 50 fs. The off-resonant nonlinearity is predominantly electronic in origin and enhanced due to quantum confinement.

Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules

Successfully predicting the frequency dispersion of electronic hyperpolarizabilities is an unresolved challenge in materials science and electronic structure theory. We show that the generalized Thomas-Kuhn sum rules, combined with linear absorption data and measured hyperpolarizability at one or two frequencies, may be used to predict the entire frequency-dependent electronic hyperpolarizability spectrum. This treatment includes two- and three-level contributions that arise from the lowest two or three excited electronic state manifolds, enabling us to describe the unusual observed frequency dispersion of the dynamic hyperpolarizability in high oscillator strength M-PZn chromophores, where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are connected via an ethyne unit that aligns the high oscillator strength transition dipoles of these components in a head-to-tail arrangement. We show that some of these structures can possess very similar linear absorption spectra yet manifest dramatically different frequency dependent hyperpolarizabilities, because of three-level contributions that result from excited state-to excited state transition dipoles among charge polarized states. Importantly, this approach provides a quantitative scheme to use linear optical absorption spectra and very limited individual hyperpolarizability measurements to predict the entire frequency-dependent nonlinear optical response. Copyright © 2010 American Chemical Society.

Optimization and finite element analysis for reliable electronic packaging

This paper demonstrates a modeling and design approach that couples computational mechanics techniques with numerical optimisation and statistical models for virtual prototyping and testing in different application areas concerning reliability of eletronic packages. The integrated software modules provide a design engineer in the electronic manufacturing sector with fast design and process solutions by optimizing key parameters and taking into account complexity of certain operational conditions. The integrated modeling framework is obtained by coupling the multi-phsyics finite element framework - PHYSICA - with the numerical optimisation tool - VisualDOC into a fully automated design tool for solutions of electronic packaging problems. Response Surface Modeling Methodolgy and Design of Experiments statistical tools plus numerical optimisaiton techniques are demonstrated as a part of the modeling framework. Two different problems are discussed and solved using the integrated numerical FEM-Optimisation tool. First, an example of thermal management of an electronic package on a board is illustrated. Location of the device is optimized to ensure reduced junction temperature and stress in the die subject to certain cooling air profile and other heat dissipating active components. In the second example thermo-mechanical simulations of solder creep deformations are presented to predict flip-chip reliability and subsequently used to optimise the life-time of solder interconnects under thermal cycling.