Improvement of luminescence efficiency by electrical annealing in single-layer organic light-emitting diodes based on a conjugated dendrimer

In this paper, we study the effects of electrical annealing at different voltages on the performance of organic light-emitting diodes. The light-emitting diodes studied here are single-layer devices based on a conjugated dendrimer doped with 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole as the emissive layer. We find that these devices can be annealed electrically by applying a voltage. This process reduces the turn-on voltage and enhances the brightness and efficiency. We obtained an external electroluminescence quantum efficiency of 0.07% photon/electron and a brightness of 2900 cd m(-2) after 12.4 V electrical annealing, which are about 6 times and 9 times higher than un-annealing devices, respectively. The improved luminance and efficiency are attributed to the presence of a space charge field near the electrodes caused by charging of traps.

Determination of electron mobility in a blue-emitting alternating block copolymer by space-charge-limited current measurements

In this communication we analyse current versus voltage data obtained using one carrier injection at metal/polymer/metal structures, The used polymer is a soluble blue-emitting alternating block copolymer, Our experimental results demonstrate that the electron current is limited by a large amount of traps with exponential energy distribution in the copolymer. The electron ;mobility of 5.1 x 10(-10) cm(2)/V s is directly determined by space-charge-limited current measurements. The electron mobility is at least three orders of magnitude smaller than that for holes in the copolymer. (C) 1999 Elsevier Science Ltd. All rights reserved.

Electrochemical, SEM/EDS and quantum chemical study of phthalocyanines as corrosion inhibitors for mild steel in 1 mol/l HCl

The inhibition effect of metal-free phthalocyanine (H2Pc), copper phthalocyanine (CuPc) and copper phthalocyanine tetrasulfuric tetrasodium salt (CuPc center dot S(4)center dot Na-4) on mild steel in I mol/l HCl in the concentration range of 1.0 X 10(-5) to 1.0 X 10(-3) mol/l was investigated by electrochemical test, scanning electron microscope with energy dispersive spectrometer (SEM/EDS) and quantum chemical method. The potentiodynamic polarization curves of mild steel in hydrochloric acid containing these compounds showed both cathodic and anodic processes of steel corrosion were suppressed, and the Nyquist plots of impedance expressed mainly as a capacitive loop with different compounds and concentrations. For all these phthalocyanines, the inhibition efficiency increased with the increase in inhibitor concentration, while the inhibition efficiencies for these three phthalocyanines with the same concentration decreased in the order Of CuPc center dot S(4)center dot Na-4 > CuPc > H2Pc according to the electrochemical measurement results. The SEM/EDS analysis indicated that there are more lightly corroded and oxidative steel surface for the specimens after immersion in acid solution containing 1.0 x 10(-3) mol/l phthalocyanines than that in blank. The quantum chemical calculation results showed that the inhibition efficiency of these phthalocyanines increased with decrease in molecule's LUMO energy, which was different from the micro-cyclic compounds. (c) 2005 Elsevier B.V. All rights reserved.

Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1 M HCl solution

The purines and its derivatives, such as, guanine, adenine, 2,6-diaminopurine, 6-thioguanine and 2,6-dithiopurine, were investigated as corrosion inhibitors for mild steel in 1 M HCl solution by weight loss measurements, electrochemical tests and quantum chemical calculations. The polarization curves of mild steel in the hydrochloric acid solutions of the purines showed that both cathodic and anodic processes of steel corrosion were suppressed. The Nyquist plots of impedance expressed mainly as a depressed capacitive loop with different compounds and concentrations. For all these purines, the inhibition efficiency increased by increasing the inhibitor concentration, and the inhibition efficiency orders are 2,6-dithiopurine > 6-thioguanine > 2,6-diaminopurine > adenine > guanine with the highest inhibiting efficiency of 88.0% for 10(-3) M 2,6-dithiopurine. The optimized structures of purines, the Mulliken charges, molecular orbital densities and relevant parameters were calculated by quantum chemical calculations. The quantum chemical calculation results inferred that the adsorption belong to physical adsorption, which might arise from the pi stacking between the pi electron of the purines and the metal surface. (C) 2008 Elsevier Ltd. All rights reserved.

Dynamical Instabilities and Deterministic Chaos in Ballistic Electron Motion in Semiconductor Superlattices

We consider the motion of ballistic electrons within a superlattice miniband under the influence of an alternating electric field. We show that the interaction of electrons with the self-consistent electromagnetic field generated by the electron current may lead to the transition from regular to chaotic dynamics. We estimate the conditions for the experimental observation of this deterministic chaos and discuss the similarities of the superlattice system with the other condensed matter and quantum optical systems.

Experimental study of quantum dot and dash lasers

Quantum dashes are elongated quantum dots. Polarized edge-photovoltage and spontaneous emission spectroscopy are used to study the anisotropy of optical properties in 1.5μm InGaAsP and AlGaInAs-based quantum dash lasers. Strain, which causes TM-polarized transitions to be suppressed at the band edge, coupled with carrier confinement and dash shape leads to an enhancement of the optical properties for light polarized along the dash long axis, in excellent agreement with theoretical results. An analysis of the integrated facet and spontaneous emission rate with total current and temperature reveals that, in both undoped and p-doped InGaAsP-based quantum dash lasers at room temperature, the threshold current and its temperature dependence remain dominated by Auger recombination. We also identify two processes which can limit the output power and propose that the effects of the dopant in p-doped InGaAsP-based lasers dominate at low temperature but decrease with increasing temperature. A high threshold current density in undoped AlGaInAs-based quantum dash laser samples studied, which degrade rapidly at low temperature, is not due to intrinsic carrier recombination processes. 1.3μm GaAs-based quantum dots lasers have been widely studied, but there remains issues as to the nature of the electronic structure. Polarized edge-photovoltage spectroscopy is used to investigate the energy distribution and nature of the energy states in InAs/GaAs quantum dot material. A non-negligible TM-polarized transition, which is often neglected in calculations and analyses, is measured close to the main TE-polarized ground state transition. Theory is in very good agreement with the experimental results and indicates that the measured low-energy TM-polarized transition is due to the strong spatial overlap between the ground state electron and the light-hole component of a low-lying excited hole state. Further calculations suggest that the TM-polarized transition reduces at the band edge as the quantum dot aspect ratio decreases.

Techniques for engineering quantum states

In this thesis I theoretically study quantum states of ultracold atoms. The majority of the Chapters focus on engineering specific quantum states of single atoms with high fidelity in experimentally realistic systems. In the sixth Chapter, I investigate the stability and dynamics of new multidimensional solitonic states that can be created in inhomogeneous atomic Bose-Einstein condensates. In Chapter three I present two papers in which I demonstrate how the coherent tunnelling by adiabatic passage (CTAP) process can be implemented in an experimentally realistic atom chip system, to coherently transfer the centre-of-mass of a single atom between two spatially distinct magnetic waveguides. In these works I also utilise GPU (Graphics Processing Unit) computing which offers a significant performance increase in the numerical simulation of the Schrödinger equation. In Chapter four I investigate the CTAP process for a linear arrangement of radio frequency traps where the centre-of-mass of both, single atoms and clouds of interacting atoms, can be coherently controlled. In Chapter five I present a theoretical study of adiabatic radio frequency potentials where I use Floquet theory to more accurately model situations where frequencies are close and/or field amplitudes are large. I also show how one can create highly versatile 2D adiabatic radio frequency potentials using multiple radio frequency fields with arbitrary field orientation and demonstrate their utility by simulating the creation of ring vortex solitons. In the sixth Chapter I discuss the stability and dynamics of a family of multidimensional solitonic states created in harmonically confined Bose-Einstein condensates. I demonstrate that these solitonic states have interesting dynamical instabilities, where a continuous collapse and revival of the initial state occurs. Through Bogoliubov analysis, I determine the modes responsible for the observed instabilities of each solitonic state and also extract information related to the time at which instability can be observed.

Quantum chemical study of the effect of precursor stereochemistry on dissociative chemisorption and surface redox reactions during the atomic layer deposition of the transition metal copper

Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu(II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu(II)/Cu(I)/Cu(0) intermediate complexes from the respective Cu(II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu55 cluster. Cu(I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu(II) versus Cu(I) compounds. A pair of CuEt intermediates or the dimer Cu2Et2 reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu(I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface.

Toward autonomous measurements of photosynthetic electron transport rates: An evaluation of active fluorescence-based measurements of photochemistry

This study presents a methods evaluation and intercalibration of active fluorescence-based measurements of the quantum yield ( inline image) and absorption coefficient ( inline image) of photosystem II (PSII) photochemistry. Measurements of inline image, inline image, and irradiance (E) can be scaled to derive photosynthetic electron transport rates ( inline image), the process that fuels phytoplankton carbon fixation and growth. Bio-optical estimates of inline image and inline image were evaluated using 10 phytoplankton cultures across different pigment groups with varying bio-optical absorption characteristics on six different fast-repetition rate fluorometers that span two different manufacturers and four different models. Culture measurements of inline image and the effective absorption cross section of PSII photochemistry ( inline image, a constituent of inline image) showed a high degree of correspondence across instruments, although some instrument-specific biases are identified. A range of approaches have been used in the literature to estimate inline image and are evaluated here. With the exception of ex situ inline image estimates from paired inline image and PSII reaction center concentration ( inline image) measurements, the accuracy and precision of in situ inline image methodologies are largely determined by the variance of method-specific coefficients. The accuracy and precision of these coefficients are evaluated, compared to literature data, and discussed within a framework of autonomous inline image measurements. This study supports the application of an instrument-specific calibration coefficient ( inline image) that scales minimum fluorescence in the dark ( inline image) to inline image as both the most accurate in situ measurement of inline image, and the methodology best suited for highly resolved autonomous inline image measurements.

Quantum manifestations of scattering orbits in the scaled spectrum of a non-hydrogenic atom in crossed fields

Evidence for scattering closed orbits for the Rydberg electron of the singly excited helium atom in crossed electric and magnetic fields at constant scaled energy and constant scaled electric field strength has been found through a quantum calculation of the photo-excitation spectrum. A particular 3D scattering orbit in a mixed regular and chaotic region has been investigated and the hydrogenic 3D closed orbits composing it identified. To the best of our knowledge, this letter reports the first quantum calculation of the scaled spectrum of a non- hydrogenic atom in crossed fields.

Electron impact ionization of He above the threshold

Near-threshold ionization of He has been studied by using a uniform semiclassical wavefunction for the two outgoing electrons in the final channel. The quantum mechanical transition amplitude for the direct and exchange scattering derived earlier by using the Kohn variational principle has been used to calculate the triple differential cross sections. Contributions from singlets and triplets are critically examined near the threshold for coplanar asymmetric geometry with equal energy sharing by the two outgoing electrons. It is found that in general the tripler contribution is much smaller compared to its singlet counterpart. However, at unequal scattering angles such as theta (1) = 60 degrees, theta (2) = 120 degrees the smaller peaks in the triplet contribution enhance both primary and secondary TDCS peaks. Significant improvements of the primary peak in the TDCS are obtained for the singlet results both in symmetric and asymmetric geometry indicating the need to treat the classical action variables without any approximation. Convergence of these cross sections are also achieved against the higher partial waves. Present results are compared with absolute and relative measurements of Rosel et al (1992 Phys. Rev. A 46 2539) and Selles et al (1987 J. Phys. B. At. Mel. Phys. 20 5195) respectively.

Correlated electron transport in molecular electronics

Theoretical and experimental values to date for the resistances of single molecules commonly disagree by orders of magnitude. By reformulating the transport problem using boundary conditions suitable for correlated many-electron systems, we approach electron transport across molecules from a new standpoint. Application of our correlated formalism to benzene-dithiol gives current-voltage characteristics close to experimental observations. The method can solve the open system quantum many-body problem accurately, treats spin exactly, and is valid beyond the linear response regime.

Independent particle descriptions of tunneling using the many-body quantum transport approach

Currents across thin insulators are commonly taken as single electrons moving across classically forbidden regions; this independent particle picture is well-known to describe most tunneling phenomena. Examining quantum transport from a different perspective, i.e., by explicit treatment of electron-electron interactions, we evaluate different single particle approximations with specific application to tunneling in metal-molecule-metal junctions. We find maximizing the overlap of a Slater determinant composed of single-particle states to the many-body current-carrying state is more important than energy minimization for defining single-particle approximations in a system with open boundary conditions. Thus the most suitable single particle effective potential is not one commonly in use by electronic structure methods, such as the Hartree-Fock or Kohn-Sham approximations.

Correlated electron-ion dynamics with open boundaries: formalism

We extend a new formalism, which allows correlated electron-ion dynamics to be applied to the problem of open boundary conditions. We implement this at the first moment level (allowing heating of ions by electrons) and observe the expected cooling in the classical part of the ionic kinetic energy and current-induced heating in the quantum contribution. The formalism for open boundaries should be easily extended to higher moments of the correlated electron-ion fluctuations.

Correlated electron-ion dynamics: the excitation of atomic motion by energetic electrons

Correlated electron-ion dynamics (CEID) is an extension of molecular dynamics that allows us to introduce in a correct manner the exchange of energy between electrons and ions. The formalism is based on a systematic approximation: small amplitude moment expansion. This formalism is extended here to include the explicit quantum spread of the ions and a generalization of the Hartree-Fock approximation for incoherent sums of Slater determinants. We demonstrate that the resultant dynamical equations reproduce analytically the selection rules for inelastic electron-phonon scattering from perturbation theory, which control the mutually driven excitations of the two interacting subsystems. We then use CEID to make direct numerical simulations of inelastic current-voltage spectroscopy in atomic wires, and to exhibit the crossover from ionic cooling to heating as a function of the relative degree of excitation of the electronic and ionic subsystems.