Stavros Athanasopoulos

Influence of intermolecular vibrations on the electronic coupling in organic semiconductors: the case of anthracene and perfluoropentacene.

We have performed classical molecular dynamics simulations and quantum-chemical calculations on molecular crystals of anthracene and perfluoropentacene. Our goal is to characterize the amplitudes of the room-temperature molecular displacements and the corresponding thermal fluctuations in electronic transfer integrals, which constitute a key parameter for charge transport in organic semiconductors. Our calculations show that the thermal fluctuations lead to Gaussian-like distributions of the transfer integrals centered around the values obtained for the equilibrium crystal geometry. The calculated distributions have been plugged into Monte-Carlo simulations of hopping transport, which show that lattice vibrations impact charge transport properties to various degrees depending on the actual crystal structure.

How do disorder, reorganization, and localization influence the hole mobility in conjugated copolymers?

In order to unravel the intricate interplay between disorder effects, molecular reorganization, and charge carrier localization, a comprehensive study was conducted on hole transport in a series of conjugated alternating phenanthrene indenofluorene copolymers. Each polymer in the series contained one further comonomer comprising monoamines, diamines, or amine-free structures, whose influence on the electronic, optical, and charge transport properties was studied. The series covered a wide range of highest occupied molecular orbital (HOMO) energies as determined by cyclovoltammetry. The mobility, inferred from time-of-flight (ToF) experiments as a function of temperature and electric field, was found to depend exponentially on the HOMO energy. Since possible origins for this effect include energetic disorder, polaronic effects, and wave function localization, the relevant parameters were determined using a range of methods. Disorder and molecular reorganization were established first by an analysis of absorption and emission measurements and second by an analysis of the ToF measurements. In addition, density functional theory calculations were carried out to determine how localized or delocalized holes on a polymer chain are and to compare calculated reorganization energies with those that have been inferred from optical spectra. In summary, we conclude that molecular reorganization has little effect on the hole mobility in this system while both disorder effects and hole localization in systems with low-lying HOMOs are predominant. In particular, as the energetic disorder is comparable for the copolymers, the absolute value of the hole mobility at room temperature is determined by the hole localization associated with the triarylamine moieties.

Theoretical Characterization of Charge Transport in One‐Dimensional Collinear Arrays of Organic Conjugated Molecules

A great deal of interest has recently focused on host-guest systems consisting of one-dimensional collinear arrays of conjugated molecules encapsulated in the channels of organic or inorganic matrices. Such architectures allow for controlled charge and energy migration processes between the interacting guest molecules and are thus attractive in the field of organic electronics. In this context, we characterize here at a quantum-chemical level the molecular parameters governing charge transport in the hopping regime in 1D arrays built with different types of molecules. We investigate the influence of several parameters (such as the symmetry of the molecule, the presence of terminal substituents, and the molecular size) and define on that basis the molecular features required to maximize the charge carrier mobility within the channels. In particular, we demonstrate that a strong localization of the molecular orbitals in push-pull compounds is generally detrimental to the charge transport properties.

Efficient Charge Separation of Cold Charge-Transfer States in Organic Solar Cells Through Incoherent Hopping

We demonstrate that efficient and nearly field-independent charge separation of electron-hole pairs in organic planar heterojunction solar cells can be described by an incoherent hopping mechanism. Using kinetic Monte Carlo simulations that include the effect of on-chain delocalization as well as entropic contributions, we simulate the dissociation of the charge-transfer state in polymer-fullerene bilayer solar cells. The model further explains experimental results of almost field independent charge separation in bilayers of molecular systems with fullerenes and provides important guidelines at the molecular level for maximizing the efficiencies of organic solar cells. Thus, utilizing coherent phenomena is not necessarily required for highly efficient charge separation in organic solar cells.

Does supramolecular ordering influence exciton transport in conjugated systems? Insight from atomistic simulations

We have developed a theoretical platform for modelling temperature-dependent exciton transport in organic materials, using indenofluorene trimers as a case study. Our atomistic molecular dynamics simulations confirm the experimentally observed occurrence of a liquid crystalline smectic phase at room temperature and predict a phase transition to the isotropic phase between 375 and 400 K. Strikingly, the increased orientational disorder at elevated temperatures barely affects the ability of excitons to be transported over large distances, though disorder influences the directionality of the energy diffusion process. Detailed quantum-chemical calculations show that this result arises from a trade-off between reduced excitonic couplings and increased spectral overlap at high temperatures. Our results suggest that liquid crystalline oligomeric materials could be promising candidates for engineering optoelectronic devices that require stable and controlled electronic properties over a wide range of temperatures and supramolecular arrangements.

Modelling exciton diffusion in disordered conjugated polymers

We present a combined quantum-chemical and Monte Carlo approach for calculating exciton transport properties in disordered organic materials starting from the molecular scale. We show that traps and energetic disorder are the main limitations for exciton diffusion in conjugated polymers. An analytical model for exciton hopping in a medium of sites with uncorellated energetic disorder gives a quantitative description on the dependence of the diffusion length to both the energetic disorder strength and temperature. We demonstrate how traps and energetic disorder can pin down the diffusion length in conjugated polymers to values below 10 nm.

Analytic Model of Hopping Transport in Organic Semiconductors Including Both Energetic Disorder and Polaronic Contributions

We developed an analytical model to describe hopping conductivity and mobility in organic semiconductors including both energetic disorder and polaronic contributions. The model is based on the Marcus jump rates with a Gaussian energetic disorder, and it is premised upon a generalized Effective Medium approach yet avoids shortcoming involved in the effective transport energy or percolation concepts. The carrier concentration dependence becomes considerably weaker when the polaron energy increases relative to the disorder energy, indicating the absence of universality that is at variance with recent publications.

Increasing Photovoltaic Performance of an Organic Cationic Chromophore by Anion Exchange

Abstract A symmetrical cyanine dye chromophore is modified with different counteranions to study the effect on crystal packing, polarizability, thermal stability, optical properties, light absorbing layer morphology, and organic photovoltaic (OPV) device parameters. Four sulfonate‐based anions and the bulky bistriflylimide anion are introduced to the 2‐[5‐(1,3‐dihydro‐1,3,3‐trimethyl‐2H‐indol‐2‐ylidene)‐1,3‐pentadien‐1‐yl]‐1,3,3‐trimethyl‐3H‐indolium chromophore using an Amberlyst A26 (OH− form) anion exchanger. Anionic charge distribution clearly correlates with device performance, whereby an average efficiency of 2% was reached in a standard bilayer organic solar. Evidence is given that the negative charge of the anion distributed over a large number of atoms is significantly more important than the size of the organic moieties of the sulfonate charge carrying group. This provides a clear strategy for future design of more efficient cyanine dyes for OPV applications.

Global Equilibrium and Non-Equilibrium Theory of Hopping Exciton Transport in Disordered Semiconductors

We develop a temperature dependent theory for singlet exciton hopping transport in disordered semiconductors. It draws on the transport level concept within a Förster transfer model and bridges the gap in describing the transition from equilibrium to non-equilibrium time dependent spectral diffusion. We test the validity range of the developed model using kinetic Monte Carlo simulations and find agreement over a broad range of temperatures. It reproduces the scaling of the diffusion length and spectral shift with the dimensionless disorder parameter and describes in a unified manner the transition from equilibrium to non-equilibrium transport regime. We find that the diffusion length in the non-equilibrium regime does not scale with the the third power of the Förster radius. The developed theory provides a powerful tool for interpreting time-resolved and steady state spectroscopy experiments in a variety of disordered materials, including organic semiconductors and colloidal quantum dots.