Monte Carlo simulation based on dynamic disorder model in organic semiconductors: from coherent to incoherent transport

The dynamic disorder model for charge carrier transport in organic semiconductors has been extensively studied in recent years. Although it is successful on determining the value of bandlike mobility in the organic crystalline materials, the incoherent hopping, the typical transport characteristic in amorphous molecular semiconductors, cannot be described. In this work, the decoherence process is taken into account via a phenomenological parameter, say, decoherence time, and the projective and Monte Carlo method are applied for this model to determine the waiting time and thus the diffusion coefficient. It is obtained that the type of transport is changed from coherent to incoherent with a sufficiently short decoherence time, which indicates the essential role of decoherence time in determining the type of transport in organics. We have also discussed the spatial extent of carriers for different decoherence time, and the transition from delocalization (carrier resides in about 10 molecules) to localization is observed. Based on the experimental results of spatial extent, we estimate that the decoherence time in pentacene has the order of 1 ps. Furthermore, the dependence of diffusion coefficient on decoherence time is also investigated, and corresponding experiments are discussed.     

Characteristics of high efficiency dye-sensitized solar cells

Impedance spectroscopy was applied to investigate the characteristics of dye-sensitized nanostructured TiO2 solar cells (DSC) with high efficiencies of light to electricity conversion of 11.1% and 10.2%. The different parameters, that is, chemical capacitance, steady-state transport resistance, transient diffusion coefficient, and charge-transfer (recombination) resistance, have been interpreted in a unified and consistent framework, in which an exponential distribution of the localized states in the TiO2 band gap plays a central role. The temperature variation of the chemical diffusion coefficient dependence on the Fermi-level position has been observed consistently with the standard multiple trapping model of electron transport in disordered semiconductors. A Tafel dependence of the recombination resistance dependence on bias potential has been rationalized in terms of the charge transfer from a distribution of surface states using the Marcus model of electron transfer. The current-potential curve of the solar cells has been independently constructed from the impedance parameters, allowing a separate analysis of the contribution of different resistive processes to the overall conversion efficiency.     

Charge transport in high mobility molecular semiconductors: classical models and new theories

The theories developed since the fifties to describe charge transport in molecular crystals proved to be inadequate for the most promising classes of high mobility molecular semiconductors identified in the recent years, including for example pentacene and rubrene. After reviewing at an elementary level the classical theories, which still provide the language for the understanding of charge transport in these systems, this tutorial review outlines the recent experimental and computational evidence that prompted the development of new theories of charge transport in molecular crystals. A critical discussion will illustrate how very rarely it is possible to assume a charge hopping mechanism for high mobility organic crystals at any temperature. Recent models based on the effect of non-local electron-phonon coupling, dynamic disorder, coexistence of localized and delocalized states are reviewed. Additionally, a few more recent avenues of theoretical investigation, including the study of defect states, are discussed.     

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.     

有机半导体中载流子迁移率的测量方法*

本文简要地介绍了有机半导体中载流子迁移率的几种模型,着重阐述了测量有机半导体中载流子迁移率的各种方法的测试原理。主要有如下几种：稳态（CW）直流电流-电压特性法（steady-state DC J-V）,飞行时间法（time of flight, TOF）,瞬态电致发光法（transient electroluminescence,transient EL）,瞬态电致发光法的修正方法即双脉冲方波法和线性增压载流子瞬态法（carrier extraction by linearly increasing voltage,CELIV）,暗注入空间电荷限制电流（dark injection space charge limited current, DI SCLC）,场效应晶体管方法（field-effect transistor,FET）,时间分辨微波传导技术（time-resolved microwave conductivity technique,TRMC）,电压调制毫米波谱（voltage-modulated millimeter-wave spectroscopy,VMS）光诱导瞬态斯塔克谱方法（photoinduced transient Stark spectroscopy）,阻抗（导纳）谱法（impedance（admittance）spectroscopy）。说明了各种实验方法的应用范围、使用条件和优缺点。     

Temperature dependence of charge mobility in model discotic liquid crystals

We address the calculation of charge carrier mobility of liquid-crystalline columnar semiconductors, a very promising class of materials in the field of organic electronics. We employ a simple coarse-grained theoretical approach and study in particular the temperature dependence of the mobility of the well-known triphenylene family of compounds, combining a molecular-level simulation for reproducing the structural changes and the Miller-Abrahams model for the evaluation of the transfer rates within the hopping regime. The effects of electric field, positional and energetic disorder are also considered. Simulations predict a low energetic disorder (~0.05 eV), slightly decreasing with temperature within the crystal, columnar and isotropic phases, and fluctuations of the square transfer integral of the order of 0.003 eV(2). The shape of the temperature-dependent mobility curve is however dominated by the variation of the transfer integral and barely affected by the disorder. Overall, this model reproduces semi-quantitatively all the features of experimentally measured mobilities, on one hand reinforcing the correctness of the hopping transport picture and of its interplay with system morphology, and on the other suggesting future applications for off-lattice modeling of organic electronics devices.     

Hopping charge transport in amorphous organic and inorganic materials with spatially correlated random energy landscape

The general properties of the hopping transport of charge carriers in amorphous organic and inorganic materials are discussed. The case where the random energy landscape in the material is strongly spatially correlated is considered. This situation is typical of organic materials with the Gaussian density of states (DOS) and may also be realized in some materials with the exponential DOS. It is demonstrated that the different DOS types can lead to very different functional forms of the mobility field dependence even for the identical correlation function of random energy. Important arguments are provided in favor of the significant contribution of the local orientational order to the total magnitude of energetic disorder in organic materials. A simple but promising model of charge transport in highly anisotropic composites materials is proposed.     

Quantum chemical analysis of electronic structure and n- and p-type charge transport in perfluoroarene-modified oligothiophene semiconductors

Density-functional theory (DFT) is employed to investigate the structural, electronic, and transport properties of several isomeric fluoroarene-oligothiophene-based semiconductors. Three oligothiophene systems varying in the perfluoroarene group positions within the molecule are studied to understand the electronic structure leading to the observed mobility values and to the n- or p-type behavior in these structures. Analyses of both intermolecular interactions in dimers and extended interactions in crystalline structures afford considerable insight into the electronic properties and carrier mobilities of these materials, as well as the polarity of the charge carriers. From the calculated carrier effective masses, we find that sterically governed molecular planarity plays a crucial role in the transport properties of these semiconductors. Our calculations correlate well with experimentally obtained geometries, highest-occupied molecular orbital (HOMO)/lowest-unoccupied molecular orbital (LUMO) energies, and the experimental carrier mobility trends among the systems investigated.     

Techniques for characterization of charge carrier mobility in organic semiconductors

The charge transport characteristics of organic semiconductors are one of the key attributes that impacts the performance of organic electronic and optoelectronic devices in which they are utilized. For improved performance in organic photovoltaic cells, light-emitting diodes, and field-effect transistors (FETs), efficient transport of the charge carriers within the organic semiconductor is especially critical. Characterization of charge transport in these organic semiconductors is important both from scientific and technological perspectives. In this review, we shall mainly discuss the techniques for measuring the charge carrier mobility and not the theoretical underpinnings of the mechanism of charge transport. Mobility measurements in organic semiconductors and particularly in conjugated polymers, using space-charge-limited current, time of flight, carrier extraction by linearly increasing voltage, double injection, FETs, and impedance spectroscopy are discussed. The relative merits, as well as limitations for each of these techniques are reviewed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Charge transport and electronic properties of N-heteroquinones: quadruple weak hydrogen bonds and strong π–π stacking interactions

The charge transport and photophysical properties of N-heteroquinones, which can function as n-type organic semiconductors in organic field-effect transistors (OFETs) with high electron mobility, were systematically investigated using hopping model, band theory, and time-dependent density functional theory (TDDFT). The calculated absorption spectra and electron mobility are in good agreement with experimental results. To the studied compounds, subtle structural modifications can greatly reduce the reorganization energy. There are two main kinds of intermolecular interaction forces of the studied compounds in the crystal, which result from intermolecular π–π and hydrogen bonds interactions, respectively. The results of hopping model show that the electron transport properties are mainly determined by pathways containing intermolecular π–π interactions, and hole transport properties are mainly determined by pathways containing intermolecular hydrogen bonds from the standpoint of transfer integral. Moreover, electronic transfer integral value increases with the enhancement of intermolecular overlap corresponding to the overlap extent of π–π packing. Hole transfer integral value decreases with decreasing the number of hydrogen bonds. This means that charge transport properties can be efficiently tuned by controlling the relative positions of the molecules and the number of hydrogen bonds. The analysis of band structure also supports the conclusion of hopping model.     

Physical electrochemistry of nanostructured devices

This Perspective reviews recent developments in experimental techniques and conceptual methods applied to the electrochemical properties of metal-oxide semiconductor nanostructures and organic conductors, such as those used in dye-sensitized solar cells, high-energy batteries, sensors, and electrochromic devices. The aim is to provide a broad view of the interpretation of electrochemical and optoelectrical measurements for semiconductor nanostructures (sintered colloidal particles, nanorods, arrays of quantum dots, etc.) deposited or grown on a conducting substrate. The Fermi level displacement by potentiostatic control causes a broad change of physical properties such as the hopping conductivity, that can be investigated over a very large variation of electron density. In contrast to traditional electrochemistry, we emphasize that in nanostructured devices we must deal with systems that depart heavily from the ideal, Maxwell-Boltzmann statistics, due to broad distributions of states (energy disorder) and interactions of charge carriers, therefore the electrochemical analysis must be aided by thermodynamics and statistical mechanics. We discuss in detail the most characteristic densities of states, the chemical capacitance, and the transport properties, specially the chemical diffusion coefficient, mobility, and generalized Einstein relation.     

Theoretically Rational Designs of Transport Organic Semiconductors Based on Heteroacenes

A Marcus electron transfer theory coupled with an incoherent polaron hopping and charge diffusion model in combining with first‐principle quantum chemistry calculation was applied to investigating the effects of heteroatom on the intermolecular charge transfer rate for a series of heteroacene molecules. The influences of intermolecular packing and charge reorganization energy were discussed. It was found that the sulphur and nitrogen substituted heteroacenes were intrinsically hole‐transporting materials due to the reduced hole reorganization energy and the enhanced overlap between HOMOs. For the oxygen‐substituted heteroacene, it was found that both the electronic couplings and the reorganization energies for holes and electrons were comparative, indicating the application potential of ambipolar devices. Most interestingly, for the boron‐substituted heteroacenes, theoretical calculations predicted a promising electron‐transport material, which is rare for organic materials. These findings provide insights into rationally designing organic semiconductors with specific properties.     

Charge carrier transport in poly[methyl(phenyl)silylene]: the effect of additives

Poly[methyl(phenyl)silylene], PMPSi, was doped with compounds of the electron acceptor type. The charge carrier mobility increases with increasing electron affinity of the acceptors having zero dipole moments. At the same time the energy distribution of hopping states narrows. On the other hand, the hole drift mobility is influenced by the dipole moment of the dopand. The electrostatic charge carrier‐dipole interaction causes a broadening of the energy distribution of transport states which results in a decrease in the charge carrier mobility. The charge carrier transport can be explained by the disordered polaronic theory, according to which the activation energy of charge carrier mobility has contributions based on the dynamic disorder, i.e. the polaronic barrier, and on the static disorder, i.e. the variation of the energy of transport states as a result of the environment. Copyright © 2001 John Wiley & Sons, Ltd.     

Role of mesoscopic molecular organization in organic-based thin film transistors

Organic-based thin film transistors have been realized from various organic conjugated materials, which can be gathered into two categories, according to the mechanism describing charge transport. In conjugated polymers and amorphous materials, occurrence of a variable range hopping mechanism leads to a direct relationship between doping level, conductivity and carrier mobility, which explains the difficulty for achieving materials possessing, at the same time, a high mobility and a low conductivity. On the other hand, the trap-limited mechanism of charge transport in conjugated oligomers allows a distinct control of carrier mobility and conductivity. Carrier mobility in thin films of conjugated oligomers can be increased by lowering the concentration of grain boundaries, which can be readily achieved by imposing long range structural ordering of oligomer molecules. Thin films of oligomer with a liquid crystal-like structure have thus been realized, using a self-assembly approach, which presents a mobility close to that of a single crystal of this oligomer. On the other hand, conductivity of these oligomers can be decreased by controlling the purity of these materials. High mobility and low conductivity values can thus be achieved with conjugated oligomers, allowing the realization of organic thin-film transistors presenting characteristics close to those of amorphous-silicon based ones.     

强度调制光电流谱研究纳晶薄膜电极过程

用强度调制光电流谱研究半导体纳晶薄膜电极光生电荷的界面转移和输运动力学过程.从测量不同外加电压和不同硫化钠溶液浓度下CdSe纳晶薄膜电极的光电流响应得到了参数:归一化稳态光电流和表面态寿命,分析界面空穴的直接转移和通过表面态的间接转移过程.通过测量不同背景光强下TiO2纳晶薄膜电极的电子扩散系数研究电子输运过程.应用HCl化学处理方法明显增大了电子扩散系数,改善了电子在TiO2纳晶薄膜电极中的输运性能.     

Electrical properties of electrochemically doped organic semiconductors using light-emitting electrochemical cells

We present a study of the electrical properties of electrochemically doped conjugated polymers using polymeric light-emitting electrochemical cells (PLECs) and interpreting the results according to a phenomenological model (PM) which assumes that, above the device turn-on voltage, the bulk transport properties of the doped organic semiconductor are responsible for the main contribution to the whole device conductivity. To confirm the predictions of this model, the dependence of the conductivity of PLECs with different parameters is evaluated and compared with the behavior expected for a doped semiconducting polymeric material. The organic semiconductor doping level, the blend concentration of organic semiconducting molecules, the device thickness, the charge carrier mobility, and the temperature are the parameters varied to perform this analysis. We observed that the device conductivity is independent of the active layer thickness, weakly dependent on the temperature, but strongly dependent on the semiconductor doping level, on the semiconductor fraction in the blend, and on the intrinsic charge carrier mobility. These results were well described by the variable range hopping (VRH) model, which has been widely employed to describe the charge transport in doped semiconducting polymeric materials, confirming the prediction of the phenomenological model. The current analysis demonstrates that PLECs are a suitable system for studying, in situ, the electrochemical doping of semiconducting polymers, permitting the evaluation of material properties as, for instance, the density of electronic charge carriers (and, consequently, the ionic charge carrier concentration) necessary to achieve the maximum electrochemical doping level of the organic semiconductor.     

Influence of polymorphism on charge transport properties in isomers of fluorenone-based liquid crystalline semiconductors

We measured the charge carrier mobilities for two isomers of fluorenone-based liquid crystalline organic semiconductors from their isotropic down to crystalline states through one or two mesophases. Improved charge transport properties of melt-processed crystalline films were obtained for the isomer exhibiting a highly ordered mesophase below its disordered smectic phase.     

Photoconduction in Amorphous Organic Solids

Herein, we focus on the principles of photoconduction in random semiconductors—the key processes being optical generation of charge carriers and their subsequent transport. This is not an overview of the current work in this area, but rather a highlight of elementary processes, their involvement in modern devices and a summary of recent developments and achievements. Experimental results and models are discussed briefly to visualize the mechanism of optical charge generation in pure and doped organic solids. We show current limits of models based on the Onsager theory of charge generation. After the introduction of experimental techniques to characterize charge transport, the hopping concept for transport in organic semiconductors is outlined. The peculiarities of the transport of excitons and charges in disorderd organic semiconductors are highlighted. Finally, a short discussion of ultrafast transport and single chain transport completes the review.     

The role of short-ranged energetic correlations in the mobility field dependence of disordered organic materials

We studied the mobility of charge carriers in a model for disordered organic solids where the energies of the localized states are Gaussianly distributed with short-ranged correlations. We obtained an expression for the mobility as a function of electric field, temperature, energetic variance, and correlation radius. The temperature dependence obtained with short-ranged energetic correlations is different from that obtained with power-law decaying energetic correlations and suggests a possible way to distinguish the two types of correlations from the measured mobility. This work also presents a practical way of computing the mobility, applicable to any transport model based on a linear master equation, directly from the matrix of the hopping rates.