Falk May

Microscopic Simulations of Charge Transport in Disordered Organic Semiconductors

Charge carrier dynamics in an organic semiconductor can often be described in terms of charge hopping between localized states. The hopping rates depend on electronic coupling elements, reorganization energies, and driving forces, which vary as a function of position and orientation of the molecules. The exact evaluation of these contributions in a molecular assembly is computationally prohibitive. Various, often semiempirical, approximations are employed instead. In this work, we review some of these approaches and introduce a software toolkit which implements them. The purpose of the toolkit is to simplify the workflow for charge transport simulations, provide a uniform error control for the methods and a flexible platform for their development, and eventually allow in silico prescreening of organic semiconductors for specific applications. All implemented methods are illustrated by studying charge transport in amorphous films of tris-(8-hydroxyquinoline)aluminum, a common organic semiconductor.

Electric Field Controlled Magnetic Anisotropy in a Single Molecule

We have measured quantum transport through an individual Fe(4) single-molecule magnet embedded in a three-terminal device geometry. The characteristic zero-field splittings of adjacent charge states and their magnetic field evolution are observed in inelastic tunneling spectroscopy. We demonstrate that the molecule retains its magnetic properties and, moreover, that the magnetic anisotropy is significantly enhanced by reversible electron addition/subtraction controlled with the gate voltage. Single-molecule magnetism can thus be electrically controlled.

Design Rules for Charge-Transport Efficient Host Materials for Phosphorescent Organic Light-Emitting Diodes

The use of blue phosphorescent emitters in organic light-emitting diodes (OLEDs) imposes demanding requirements on a host material. Among these are large triplet energies, the alignment of levels with respect to the emitter, the ability to form and sustain amorphous order, material processability, and an adequate charge carrier mobility. A possible design strategy is to choose a π-conjugated core with a high triplet level and to fulfill the other requirements by using suitable substituents. Bulky substituents, however, induce large spatial separations between conjugated cores, can substantially reduce intermolecular electronic couplings, and decrease the charge mobility of the host. In this work we analyze charge transport in amorphous 2,8-bis(triphenylsilyl)dibenzofuran, an electron-transporting material synthesized to serve as a host in deep-blue OLEDs. We show that mesomeric effects delocalize the frontier orbitals over the substituents recovering strong electronic couplings and lowering reorganization energies, especially for electrons, while keeping energetic disorder small. Admittance spectroscopy measurements reveal that the material has indeed a high electron mobility and a small Poole-Frenkel slope, supporting our conclusions. By linking electronic structure, molecular packing, and mobility, we provide a pathway to the rational design of hosts with high charge mobilities.

Relationship between supramolecular assembly and charge-carrier mobility in perylenediimide derivatives: The impact of side chains

Discotic mesophases are known for their ability to self-assemble into columnar structures which serve as semiconducting molecular wires. Charge-carrier mobility along these wires strongly depends on molecular packing which is controlled by intermolecular interactions. Using solid-state NMR and molecular dynamics simulations we relate how conformations of alkyl and glycol side chains affect helical pitch and angular distribution of molecules within the columnar structures of perylenediimide derivatives. Using the high-temperature limit of Marcus theory we then establish a link between the secondary structure and charge-carrier mobility. Simulation results are compared to pulse-radiolysis time-resolved microwave conductivity measurements. We conclude that for achieving high charge-carrier mobilities in discotics, side chains with specific interactions are required in order to minimize the translational and orientational molecular disorder in the columns.

Challenges for in silico design of organic semiconductors

We outline the objectives of microscopic simulations of charge and energy transport processes in amorphous organic semiconductors, describe the current status of techniques used to achieve them, and list the challenges such methods face when aiming at quantitative predictions.

Interaction of spin and vibrations in transport through single-molecule magnets

Summary We study electron transport through a single-molecule magnet (SMM) and the interplay of its anisotropic spin with quantized vibrational distortions of the molecule. Based on numerical renormalization group calculations we show that, despite the longitudinal anisotropy barrier and small transverse anisotropy, vibrational fluctuations can induce quantum spin-tunneling (QST) and a QST-Kondo effect. The interplay of spin scattering, QST and molecular vibrations can strongly enhance the Kondo effect and induce an anomalous magnetic field dependence of vibrational Kondo side-bands.

Modeling of organic light emitting diodes: from molecular to device properties(Conference Presentation)

We will review the progress in modeling of charge transport in disordered organic semiconductors on various length-scales, from atomistic to macroscopic. This includes evaluation of charge transfer rates from first principles, parametrization of coarse-grained lattice and off-lattice models, and solving the master and drift-diffusion equations. Special attention is paid to linking the length-scales and improving the efficiency of the methods. All techniques will be illustrated on an amorphous organic semiconductor, DPBIC, a hole conductor and electron blocker used in state of the art organic light emitting diodes (OLEDs). The outlined multiscale scheme can be used to predict OLED properties without fitting parameters, starting from chemical structures of compounds.

Modeling of organic light emitting diodes: From molecular to device properties (Presentation Recording)

We review the progress in modeling of charge transport in disordered organic semiconductors on various length-scales, from atomistic to macroscopic. This includes evaluation of charge transfer rates from first principles, parametrization of coarse-grained lattice and off-lattice models, and solving the master and drift-diffusion equations. Special attention is paid to linking the length-scales and improving the efficiency of the methods. All techniques are illustrated on an amorphous organic semiconductor, DPBIC, a hole conductor and electron blocker used in state of the art organic light emitting diodes (OLEDs). The outlined multiscale scheme can be used to predict OLED properties without fitting parameters, starting from chemical structures of compounds. Reference: Advanced Functional Materials, 2015, doi: 10.1002/adfm.201403004