First-principles calculations of anisotropic charge-carrier mobilities in organic semiconductor crystals (original) (raw)
Related papers
A unified theory for charge-carrier transport in organic crystals
The Journal of chemical physics, 2008
To characterize the crossover from bandlike transport to hopping transport in molecular crystals, we study a microscopic model that treats electron-phonon interactions explicitly. A finite-temperature variational method combining Merrifield's transformation with Bogoliubov's theorem is developed to obtain the optimal basis for an interacting electron-phonon system, which is then used to calculate the bandlike and hopping mobilities for charge carriers. Our calculations on the one dimensional ͑1D͒ Holstein model at T = 0 K and finite temperatures show that the variational basis gives results that compared favorably to other analytical methods. We also study the structures of polaron states at a broad range of parameters including different temperatures. Furthermore, we calculate the bandlike and hopping mobilities of the 1D Holstein model in different parameters and show that our theory predicts universal power-law decay at low temperatures and an almost temperature independent behavior at higher temperatures, in agreement with experimental observations. In addition, we show that as the temperature increases, hopping transport can become dominant even before the polaron state changes its character. Thus, our result indicates that the self-trapping transition studied in conventional polaron theories does not necessarily correspond to the bandlike to hopping transition in the transport properties in organic molecular crystals. Finally, a comparison of our 1D results with experiments on ultrapure naphthalene crystals suggests that the theory can describe the charge-carrier mobilities quantitatively across the whole experimental temperature range.
Role of Correlation on Charge Carrier Transport in Organic Molecular Semiconductors
We have investigated the charge carrier transport in organic molecular semiconductors. It has been found that mobility is a function of electric field and temperature due to hopping conduction. Several theoretical models for charge transport in disordered solids have been debated over the role of spatial and energetic correlation in these systems and such correlations have been recently shown to explain the universal electric field dependence of mobility. We have compared and evaluated the applicability of different theoretically proposed models using very simple experimental results and based on our extensive analysis, we have found that correlation is important to explain the electrical transport in these systems.
Carrier concentration dependence of the mobility in organic semiconductors
Synthetic Metals, 2007
Charge transport in organic materials as a function of carrier concentration is investigated. An analytical model of the concentration dependent mobility based on the variable hopping range theory is formulated. This model is applied to analyze the discrepancy between the experimental mobilities extracted from FETs and LEDs. The result shows that an exponential density of states (DOS) is a good approximation of the tail states for describing the charge transport in FETs. When applied to the low carrier concentration regime, for example to the LEDs regime, a Gaussian DOS should be assumed.
2024
We present a first-principles numerical study of charge transport in a realistic two-dimensional tightbinding model of organic molecular semiconductors. We use the hybrid Monte Carlo (HMC) algorithm to simulate the full quantum dynamics of phonons and either single or multiple charge carriers without any tunable parameters. We introduce a number of algorithmic improvements, including efficient Metropolis updates for phonon fields based on analytical insights, which lead to negligible autocorrelation times and allow sub-per-mille precisions to be reached at a low computational cost of O (1) CPU hours. Our simulations produce charge-mobility estimates that are in good agreement with experiments and that also justify the phenomenological transient localization approach.
Charge Transport in Organic Semiconductors
Chemical Reviews, 2007
Modern optoelectronic devices, such as light-emitting diodes, fieldeffect transistors and organic solar cells require well controlled motion of charges for their efficient operation. The understanding of the processes that determine charge transport is therefore of paramount importance for designing materials with improved structure-property relationships. Before discussing different regimes of charge transport in organic semiconductors, we present a brief introduction into the conceptual framework in which we interpret the relevant photophysical processes. That is, we compare a molecular picture of electronic excitations against the Su-Schrieffer-Heeger semiconductor band model. After a brief description of experimental techniques needed to measure charge mobilities, we then elaborate on the parameters controlling charge transport in technologically relevant materials. Thus, we consider the influences of electronic coupling between molecular units, disorder, polaronic effects and space charge. A particular focus is given to the recent progress made in understanding charge transport on short time scales and short length scales. The mechanism for charge injection is briefly addressed towards the end of this chapter. Keywords Charge carrier mobility Á Charge transport Á Organic semiconductors Á Molecular model Á Gaussian disorder model Á SSH model Á Organic optoelectronics Contents
Physical Review B, 2013
We developed an analytical model to describe hopping transport in organic semiconductors including both energetic disorder and polaronic contributions due to geometric relaxation. The model is based on a Marcus jump rate in terms of the small-polaron concept with a Gaussian energetic disorder, and it is premised upon a generalized effective medium approach yet avoids shortcomings involved in the effective transport energy or percolation concepts. It is superior to our previous treatment [Phys. Rev. B 76, 045210 ] since it is applicable at arbitrary polaron activation energy E a with respect to the energy disorder parameter σ . It can be adapted to describe both charge-carrier mobility and triplet exciton diffusion. The model is compared with results from Monte Carlo simulations. We show (i) that the activation energy of the thermally activated hopping transport can be decoupled into disorder and polaron contributions whose relative weight depend nonlinearly on the σ /E a ratio, and (ii) that the choice of the density of occupied and empty states considered in configurational averaging has a profound effect on the results of calculations of the Marcus hopping transport. The σ /E a ratio governs also the carrier-concentration dependence of the charge-carrier mobility in the large-carrier-concentration transport regime as realized in organic field-effect transistors. The carrier-concentration dependence becomes considerably weaker when the polaron energy increases relative to the disorder energy, indicating the absence of universality. This model bridges a gap between disorder and polaron hopping concepts.
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.