Disorder-driven doping activation in organic semiconductors

Conductivity doping of organic semiconductors is an essential prerequisite for many organic devices, but the specifics of dopant activation are still not well understood. Using many-body simulations that include Coulomb interactions and dopant ionization/de-ionization events explicitly we here show significant doping efficiency even before the electron affinity of the dopant exceeds the ionization potential of the organic matrix (p-doping), similar to organic salts. We explicitly demonstrate that the ionization of weak molecular dopants in organic semiconductors is a disorder-, rather than thermally induced process. Practical implications of this finding are a weak dependence of the ionized dopant fraction on the electron affinity of the dopant, and an enhanced ionization of the weak dopants upon increasing dopant molar fraction. As a result, strategies towards dopant optimization should aim for presently neglected goals, such as the binding energy in host-dopant charge-transfer states being responsible for the number of mobile charge carriers. Insights into reported effects are provided from the analysis of the density of states, where two novel features appear upon partial dopant ionization. The findings in this work can be used in the rational design of dopant molecules and devices

Magnetic anisotropy of graphene quantum dots decorated with a ruthenium adatom

The creation of magnetic storage devices by decoration of a graphene sheet by magnetic transition-metal adatoms, utilizing the high in-plane versus out-of-plane magnetic anisotropy energy (MAE), has recently been proposed. This concept is extended in our density-functional-based modeling study by incorporating the influence of the graphene edge on the MAE. We consider triangular graphene flakes with both armchair and zigzag edges in which a single ruthenium adatom is placed at symmetrically inequivalent positions. Depending on the edge-type, the graphene edge was found to influence the MAE in opposite ways: for the armchair flake the MAE increases close to the edge, while the opposite is true for the zigzag edge. Additionally, in-plane pinning of the magnetization direction perpendicular to the edge itself is observed for the first time

Ab initio modeling of steady-state and time-dependent charge transport in hole-only α-NPD devices

We present an ab initio modeling study of steady-state and time-dependent charge transport in hole-only devices of the amorphous molecular semiconductor α–NPD [N,N ′ −Di(1–naphthyl)−N,N ′ −diphenyl−(1,1 ′ −biphenyl)−4,4 ′ −diamine] α–NPD [N,N′-Di(1–naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine]. The study is based on the microscopic information obtained from atomistic simulations of the morphology and density functional theory calculations of the molecular hole energies, reorganization energies, and transfer integrals. Using stochastic approaches, the microscopic information obtained in simulation boxes at a length scale of ∼10 nm is expanded and employed in one-dimensional (1D) and three-dimensional (3D) master-equation modeling of the charge transport at the device scale of ∼100 nm. Without any fit parameter, predicted current density-voltage and impedance spectroscopy data obtained with the 3D modeling are in very good agreement with measured data on devices with different α-NPD layer thicknesses in a wide range of temperatures, bias voltages, and frequencies. Similarly good results are obtained with the computationally much more efficient 1D modeling after optimizing a hopping prefacto

Effects of energy correlations and superexchange on charge transport and exciton formation in amorphous molecular semiconductors:an ab initio study

In this study, we investigate on the basis of ab initio calculations how the morphology, molecular on-site energies, reorganization energies, and charge transfer integral distribution affect the hopping charge transport and the exciton formation process in disordered organic semiconductors. We focus on three materials applied frequently in organic light-emitting diodes: α-NPD, TCTA, and Spiro-DPVBi. Spatially correlated disorder and, more importantly, superexchange contributions to the transfer integrals, are found to give rise to a significant increase of the electric field dependence of the electron and hole mobility. Furthermore, a material-specific correlation is found between the HOMO and LUMO energy on each specific molecular site. For α-NPD and TCTA, we find a positive correlation between the HOMO and LUMO energies, dominated by a Coulombic contribution to the energies. In contrast, Spiro-DPVBi shows a negative correlation, dominated by a conformational contribution. The size and sign of this correlation have a strong influence on the exciton formation rate