Light-emitting diodes from polyfluorenes: characterisation and stability of performance

This thesis deals with polymer light-emitting diodes (LEDs) containing materials from the polyfluorene family, and investigates their behaviour when employed in device structures. A study of poly(9,9’-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylenediamine) (PFB) by photothermal deflection spectroscopy (PDS) shows that the polymer undergoes a doping reaction with poly(styrene sulphonic acid). This is important because the two materials are found in intimate contact in LED structures. The conditions for reaction are investigated, and it is proposed that the reacted states are directly responsible for the drive-induced degradation of LEDs containing these two materials. LEDs are studied which contain various combinations of poly(9,9’-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) and poly(9,9’-dioctylfluorene-co-benzothiadiazole) (F8BT), using pulsed electroluminescence. A strongly morphology-dependent spike-transient is observed in the electroluminescence at turn-on, and this is investigated by numerical modelling. Although not all features of the system can be well represented in the model, the spike transient is explicitly predicted without the need to impose any special conditions. The origin of this feature is elucidated by repeatedly running the model to a range of end-points and studying the time-evolution of space-charge distributions which result. Finally, F8BT devices are considered on their own, in order to study the evolution of device performance under low-intensity electrical excitation. A phenomenon is investigated in which the quantum efficiency is dramatically increased during the early stages of driving. Ionic motions are ruled out, and the observations are attributed to the trapping of charge in the vicinity of the anode, leading to enhanced hole injection. The reverse-bias behaviour of the effect, in which a further enhancement is seen, is also examined. The analogy is made with polymer LEDs in general which increase in performance following a period of reverse bias, and it is suggested that the causes may be related

Strong ellipticity and spectral properties of chiral bag boundary conditions

We prove strong ellipticity of chiral bag boundary conditions on even dimensional manifolds. From a knowledge of the heat kernel in an infinite cylinder, some basic properties of the zeta function are analyzed on cylindrical product manifolds of arbitrary even dimension.Comment: 16 pages, LaTeX, References adde

Pole structure of the Hamiltonian ζ\zeta-function for a singular potential

We study the pole structure of the $\zeta$-function associated to the Hamiltonian $H$ of a quantum mechanical particle living in the half-line $\mathbf{R}^+$, subject to the singular potential $g x^{-2}+x^2$. We show that $H$ admits nontrivial self-adjoint extensions (SAE) in a given range of values of the parameter $g$. The $\zeta$-functions of these operators present poles which depend on $g$ and, in general, do not coincide with half an integer (they can even be irrational). The corresponding residues depend on the SAE considered.Comment: 12 pages, 1 figure, RevTeX. References added. Version to appear in Jour. Phys. A: Math. Ge

The trace of the heat kernel on a compact hyperbolic 3-orbifold

The heat coefficients related to the Laplace-Beltrami operator defined on the hyperbolic compact manifold H^3/\Ga are evaluated in the case in which the discrete group \Ga contains elliptic and hyperbolic elements. It is shown that while hyperbolic elements give only exponentially vanishing corrections to the trace of the heat kernel, elliptic elements modify all coefficients of the asymptotic expansion, but the Weyl term, which remains unchanged. Some physical consequences are briefly discussed in the examples.Comment: 11 page

Entropy, Dynamics and Instantaneous Normal Modes in a Random Energy Model

It is shown that the fraction f of imaginary frequency instantaneous normal modes (INM) may be defined and calculated in a random energy model(REM) of liquids. The configurational entropy S and the averaged hopping rate among the states R are also obtained and related to f, with the results R~f and S=a+b*ln(f). The proportionality between R and f is the basis of existing INM theories of diffusion, so the REM further confirms their validity. A link to S opens new avenues for introducing INM into dynamical theories. Liquid 'states' are usually defined by assigning a configuration to the minimum to which it will drain, but the REM naturally treats saddle-barriers on the same footing as minima, which may be a better mapping of the continuum of configurations to discrete states. Requirements of a detailed REM description of liquids are discussed

Heat-kernel expansion on non compact domains and a generalised zeta-function regularisation procedure

Heat-kernel expansion and zeta function regularisation are discussed for Laplace type operators with discrete spectrum in non compact domains. Since a general theory is lacking, the heat-kernel expansion is investigated by means of several examples. It is pointed out that for a class of exponential (analytic) interactions, generically the non-compactness of the domain gives rise to logarithmic terms in the heat-kernel expansion. Then, a meromorphic continuation of the associated zeta function is investigated. A simple model is considered, for which the analytic continuation of the zeta function is not regular at the origin, displaying a pole of higher order. For a physically meaningful evaluation of the related functional determinant, a generalised zeta function regularisation procedure is proposed.Comment: Latex, 14 pages, no figures. The version to be published in JM

First GB records of the invasive Asian shore crab, Hemigrapsus sanguineus from Glamorgan, Wales and Kent, England.

The present contribution reports on the capture of two adult male specimens of the Asian/Japanese shore crab, Hemigrapsus sanguineus (de Haan, 1835) from Glamorgan, south Wales and Kent, southern England. These represent the first records of this species from mainland Great Britain