Mesoscopic modelling of bipolar charge evolution in CN-PPV LEDs

Since various chances are possible in the molecular structure of the repeat unit, substituted poly(para-phenylenevinylene) (PPV) has ben used as active component in light-emitting diodes (LEDs) to obtain light emission in a wide range of colours.A major aspect determining device performance is the competition between current flow, trapping and recombination within the polymer layer. By suitable Monte Carlo calculations, we have performed computer experiments in which bipolar charge carriers are injected at constant rate in polymer networks made of cyano-substituted PPV chains with variable length and orientation. The intra-molecular electronic properties used in these simulations were calculated by a quantum molecular dynamics method. In order to assess the influence of cyano-substitution on the properties of single-layer PPV LEDs, we have focused our attention on bipolar charge evolution in time. Specifically addressed are the differences in electric field strength needed for intra-molecular charge mobility of electrons and holes and their consequences at mesoscopic scale. (C) 2004 Elsevier B.V. All rights reserved

Computer simulation of electron transfer in molecular electronic devices

The study of electron transfer through individual molecules bound to metal electrodes has become important due to the potential application in molecular electronic devices. Since the electronic and atomic motions in these molecules influence each other they need to be treated self-consistently. We have used self-consistent quantum chemistry molecular dynamics calculations to discuss some of the issues related to electron transfer through a spatially symmetric [9,10-Bis((2′-para-mercaptophenyl)-ethinyl)-anthracene] and an asymmetric [1,4-Bis((2′-para-mercaptophenyl)-ethinyl)-2-acetyl-amino-5-nitro-benzene] molecule bound to metal electrodes. Specifically addressed are the effects of voltage inversion on electron transfer between electrodes through both molecules. Our results show an electron transfer behaviour that reproduces the spatial symmetry of the molecules in agreement with experimental current-voltage data. The change in time of electron density and dimerisation at specific atomic sites is also discussed.Fundação para a Ciência e a Tecnologia (FCT) - Programa Operacional “Ciência , Tecnologia, Inovação” - POCTI/CTM/41574/2001, SFRH/BD/11231/2002.Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER)

Modelling the effects of the anode work function in PPV LED

Transparent conducting oxides are widely used as the transparent electrode in polymer light emitting diodes (PLEDs). The physical properties of these materials and consequently device performance strongly depend on their processing and surface treatment. The injection of charge from the transparent electrode into the polymer layer occurs by tunnelling through a potential barrier from the electrode to molecules close to it. This barrier is influenced by the difference in the relevant energy levels of electrode material and polymer molecules, the external applied potential, the Coulomb potential of the charges present in the polymer layer and the potential of their image charges on the electrodes, and may also be altered by electrode degradation effects. A better understanding of the effect of varying this potential barrier on the functioning of PLED is necessary to achieve further improvements in these applications. Here we present a theoretical study of the influence of changes in the potential barrier at the transparent electrode, on bipolar charge evolution through thin polymer layers, in the absence of defects and impurity states, while the other electrode functions as an ohmic contact. Results of a mesoscopic model provide insight into bipolar charge injection, charge and recombination distribution throughout the polymer layer, and may suggest new materials and processing methods to optimize these optoelectronic devices.FEDER.Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001, CONC-REEQ/443/EEI/2005; SFRH/BD/22143/2005

Quantum molecular dynamics simulations of conjugated polymers

The softness of conjugated polymers leads to strong coupling between polymer's electrons and lattice vibrations. Therefore, it is necessary to perform quantum molecular dynamics computer simulations in order to study their electronic and optical properties at molecular level. We have used self-consistent molecular dynamics calculations with interatomic forces evaluated from quantum mechanical calculations at the complete neglect of differential overlap level to discuss some of the issues relating to the electronic processes involved in polydiacetylene and poly(p-phenylene vinylene). Specifically addressed are the charge induced structural changes of the polymer chains and the intra-molecular charge mobility. The change in the chemical potential of individual polymer strands at zero temperature is also discussed. Our results suggest a geometrical distortion in the bond length distribution relative to the uncharged chains which is accompanied by changes in atomic charges at the distortion site. The charge carrier mobility is predicted to depend on the strength of the electric field, in accordance with experiments

Mesoscopic modelling of the interaction of infrared lasers with composite materials: an application to dental enamel

The mesostructure and composition of composite materials determine their mechanical, optical and thermal properties and, consequently, their response to incident radiation. We have developed general finite element models of porous composite materials under infrared radiation to examine the influence of pore size on one of the determining parameters of the stress distribution in the material: the temperature distribution. We apply them to the specific case of human dental enamel, a material which has nanometer scale pores containing water/organic, and predict the maximum temperature reached after a single 0.35 μs laser pulse of sub-ablative fluence by two lasers: Er:YAG (2.9 μm) and CO2 (10.6 μm). For the Er:YAG laser, the results imply a strong dependence of the maximum temperature reached at the pore on the area-to-volume ratio of the pore, whereas there is little such dependence for CO2 lasers. Thus, CO2 lasers may produce more reproducible results than Er:YAG lasers when it comes to enamel ablation, which may be of significant interest during clinical practice. More generally, when ablating composite materials by infrared lasers researchers should account for the material’s microstructure and composition when designing experiments or interpreting results, since a more simplistic continuum approach may not be sufficient to explain differences observed during ablation of materials with similar optical properties or of the same material but using different wavelengths

Modelling the effect of nonplanarity on charge transport along conjugated polymer chains

Conjugated polymers show interesting properties that make them appropriated for nanoelectronics. Several studies of poly(p-phenylene vinylene) (PPV) have suggested that each polymer chain consists of several planar segments, with conjugation length of nanoscale dimension, linked by twists or kinks. A pronounced twist between two planar segments in a PPV chain not only causes loss of main-chain conjugation but it may also alter electron and hole mobility along the chain, which has further implications for the percolation of charge through the polymer film. We used self-consistent quantum molecular dynamics calculations to provide information on the electric field needed to move the injected charges (either electrons or holes) along the planar segments of PPV and to cross the twist between two planar segments perpendicular to each other. Field-dependent charge mobility was also estimated for conjugated segments of various lengths. Our results suggest that electrons can cross the twist between adjacent planar segments for lower applied electric fields than holes if there is no more than one electronic charge (electron or hole) on the PPV chain, otherwise similar fields are needed.Fundação para a Ciência e a Tecnologia FCT) Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001, CONC-REEQ/443/EEI/2001 e SFRH/BD/11231/200

Intra-molecular properties of DMeOPPV studied by quantum molecular dynamics

Introducing methoxy electron donor groups into a poly(para-phenylene vinylene) (PPV) chain will lead to the appearance of unique electronic properties at the molecular scale which should affect the overall properties of light-emitting diodes based on these polymers. Self-consistent quantum molecular dynamics calculations have been used to provide information on intra-molecular properties of poly(2,5-dimethoxy-para-phenylene vinylene) (DMeOPPV), which are relevant for the modelling and characterization of polymer light-emitting diodes at nanometric length scale. We focus our attention on those properties that have been somewhat neglected in previous literature: the charge distribution associated with positive and negative charge carriers and their intra-molecular mobility when an electric field is applied.Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência, Tecnologia, Inovação” - POCTI/CTM/41574/2001, SFRH/BD/11231/2002.Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER

Modelling the effect of non-planarity on luminescence energy of conjugated polymers

We present theoretical investigations of structural and electronic properties of ground-state and low-lying excited singlet states in isolated chains of conjugated polymers using a self-consistent quantum molecular dynamics method. With this approach, we have determined the energy of both states as function of the twist angle between two planar segments of the same polymer chain, for polymer chains with variable length. The conjugated polymers investigated here are poly(para-phenylene vinylene) (PPV) and polydiacetylene (PDA). Our results show that the energy of the excited-state increases more than that of the ground-state, as the twist angle increases up to 90º degrees. The change in the twist angle of both polymers leads to a blueshift in luminescence transition energy, the effect being stronger in PPV when the planar segments have similar sizes. The predicted blueshift in both polymers is dependent on the chain length, the effect being more pronounced for shorter-chains.Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER)Fundação para a Ciência e a Tecnologia (FCT) - Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001, CONC-REEQ/443/2001 e SFRH/BD/11231/200

Effect of molecular properties on the performance of polymer light-emitting diodes

The performance of a single layer polymer light-emitting diode depends on several interdependent factors, although recombination between electrons and holes within the polymer layer is believed to play an important role. Our aim is to carry out computer experiments in which bipolar charge carriers are injected in polymer networks made of poly(p-phenylene vinylene) chains randomly oriented. In these simulations, we follow the charge evolution in time from some initial state to the steady state. The intra-molecular properties of the polymer molecules obtained from self-consistent quantum molecular dynamics calculations are used in the mesoscopic model. The purpose of the present work is to clarify the effects of intra-molecular charge mobility and energy disorder on recombination efficiency. In particular, we find that charge mobility along the polymer chains has a serious influence on recombination within the polymer layer. Our results also show that energy disorder due to differences in ionization potential and electron affinity of neighbouring molecules affects mainly recombinations that occur near the electrodes at polymer chains parallel to them.Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência, Tecnologia, Inovação” - POCTI/CTM/41574/2001Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER

Mesoscopic modelling of enamel interaction with mid-infrared sub-ablative laser pulses

Using a finite element approach the authors model the influence of enamel's microstructure and water distribution on the temperature and stress at the centre of the laser spot, for a CO2 laser working at 10.6 μm, with 0.35 μs pulse duration and sub-ablative intensity. The authors found that the distribution of water in enamel significantly influences the stress generated at the end of one laser pulse: much lower (two orders of magnitude) stress values occur in models with homogeneously distributed water than in models with 0.27 vol.% water located in pores or 4 vol.% in layers. The amount of water in enamel has a strong influence on the stress distribution, but not on the maximum stress values reached. However, different water contents do not influence the temperature distribution in enamel. These results suggest that adequate modelling of the ablation mechanisms in enamel, as in other highly inhomogeneous materials, must include their structure at the mesoscopic scale