Charge Transport In Organic Semiconductors Research Articles

Charge transport in organic semiconductors from the mapping approach to surface hopping.

We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum-classical method, the mapping approach to surface hopping. In contrast to standard fewest-switches surface hopping, this method propagates the classical degrees of freedom deterministically on the most populated adiabatic electronic state. This correctly preserves the equilibrium distribution of a quantum charge coupled to classical phonons, allowing one to time-average along trajectories to improve the statistical convergence of the calculation. We illustrate the method with an application to a standard model for the charge transport in the direction of maximum mobility in crystalline rubrene. Because of its consistency with the equilibrium distribution, the present method gives a time-dependent diffusion coefficient that plateaus correctly to a long-time limiting value. The resulting mobility is somewhat higher than that of the relaxation time approximation, which uses a phenomenological relaxation parameter to obtain a non-zero diffusion coefficient from a calculation with static phonon disorder. However, it is very similar to the mobility obtained from Ehrenfest dynamics, at least in the parameter regimes we have investigated here. This is somewhat surprising because Ehrenfest dynamics overheats the electronic subsystem and is, therefore, inconsistent with the equilibrium distribution.

Effect of Halogen Substituents on Charge Transport Properties of n-type Organic Semiconductors: A Theoretical Study.

Organic semiconductors (OSCs) have received significant attention as promising materials for electronic devices. In this study, we investigate the impact of halogen groups on the charge transport properties of n-type OSC-6,13 bis((triisopropylsilyl)ethynyl)-5,7,12,14-tetraazapentacene (TIPS-TAP). The computed mobilities for TIPS-TAPs substituted with F and Cl exhibit excellent agreement with the experimental values, while the simulation overestimates the electron mobility for TIPS-TAP. Interestingly, the mobility of TIPS-TAP-4F is significantly lower than that of TIPS-TAP-4Cl/Br, despite their similar packing structures. This discrepancy can be attributed to the strong electron-withdrawing effect of fluoride, which reduces the electron transfer integral and increases the reorganization energy. While molecular packing is widely recognized as a dominant factor in charge transport in OSCs, our study highlights the crucial role of electronic effects in charge transport in OSCs. This study provides new insights into the mechanisms underlying charge transport in OSCs.

Statistical analysis of interatomic transfer integrals for exploring high-mobility organic semiconductors

ABSTRACT Charge transport in organic semiconductors occurs via overlapping molecular orbitals quantified by transfer integrals. However, no statistical study of transfer integrals for a wide variety of molecules has been reported. Here we present a statistical analysis of transfer integrals for more than 27,000 organic compounds in the Cambridge Structural Database. Interatomic transfer integrals were used to identify substructures with high transfer integrals. As a result, thione and amine groups as in thiourea were found to exhibit high transfer integrals. Such compounds are considered as potential non-aromatic, water-soluble organic semiconductors.

Crystal structure of 1-{4-[bis(4-methylphenyl)amino]phenyl}ethene-1,2,2-tricarbonitrile

The title compound, C25H18N4, crystallizes in the centrosymmetric orthorhombic space group Pbca, with eight molecules in the unit cell. The main feature noticeable in the structure is the impact of the tricyanovinyl (TCV) group in forcing partial planarity of the portion of the molecule carrying the TCV group and directing the molecular packing in the solid state, resulting in the formation of π-stacks of dimers within the unit cell. Short π–π stack closest atom-to-atom distances of 3.444 (15) Å are observed. Such motif patterns are favorable as they are thought to be conducive for better charge transport in organic semiconductors, which results in enhanced device performance. Intramolecular charge transfer is evident from the shortening in the observed experimental bond lengths. The nitrogen atoms (of the cyano groups) are involved in extensive short contacts, primarily through C—H...NC interactions with distances of 2.637 (17) Å.

Di- and Tricyanovinyl-Substituted Triphenylamines: Structural and Computational Studies.

We report herein on the solid-state structures of three closely related triphenylamine derivatives endowed with tricyanovinyl (TCV) and dicyanovinyl (DCV) groups. The molecules described contain structural features commonly found in the design of functional organic materials, especially donor-acceptor molecular and polymeric architectures. The common feature noticeable in these structures is the impact of these exceptionally strong electron-accepting groups in forcing partial planarity of the portion of the molecule carrying these groups and directing the molecular packing in the solid state, resulting in the formation of π-stacks of dimers within the unit cell of each. Stacks are formed between phenyl groups bearing electron-accepting groups on two adjacent molecules. Short π-π stack distances ranging from 3.283 to 3.671 Å were observed. Such motif patterns are thought to be conducive for better charge transport in organic semiconductors and enhanced device performance. Intramolecular charge transfer is evident from the shortening of the observed experimental bond lengths in all three compounds. The nitrogen atoms (of the cyano groups) have been shown to be extensively involved in short contacts in all three structures, primarily through C-H···NC interactions with distances as short as 2.462 Å. The compounds reported here are (3,3-dicyano-2-(4-(diphenylamino)phenyl)-1λ3-allylidene)amide or tricyanovinyltriphenylamine, Ph3NTCV (1); 2-(4-(diphenylamino)benzylidene)-malononitrile or dicyanovinyltriphenylamine, Ph3NDCV (2); and (3,3-dicyano-2-(4-(di-p-tolylamino)phenyl)-1λ3-allylidene)amide or dimethyltricyanovinyltriphenylamine, Me2Ph3NTCV (3). Results of density functional theory calculations using DFT-B3LYP/6-31G(d,p) indicate the lowering of LUMO levels as a result of the introduction of these groups with band gaps of 3.13, 2.61, and 2.55 eV for compounds 1-3, respectively, compared with 4.65 eV calculated for triphenylamine. This is supported by the electronic and fluorescence spectra of these molecules with absorption λmax of 483, 515, and 545 nm for compounds 1, 2, and 3, respectively.

Gas Phase Ionization Energy of Heptacene.

The ionization energy is a fundamental property that is relevant to charge transport in organic semiconductors. We report adiabatic ionization energies (AIEs) of heptacene at 6.21 and 7.20 eV for the X̃+B2g and Ã+Au states, respectively, as the next larger member of the acene series using mass- and isomer-selective double imaging photoelectron photoion coincidence spectroscopy. The X̃+ state energy decreases monotonically with an increase in size within the homologous series of acenes and approaches an asymptotic limit [AIE(polyacene) = 5.94 ± 0.06 eV] based on a fit with an exponential decay function. As byproducts of heptacene formation from cycloreversion of diheptacenes, 5,18-, 7,16-, and 6,17-dihydroheptacene can be detected, and their AIE is similar to that of their largest acene subunit (anthracene and tetracene, respectively), in very good agreement with computational treatments.

Charge Transport Mechanism of Organic Semiconductors Based on Molecular Dynamics Simulation

The aim of this paper is to investigate the charge transport mechanism in organic semiconductors based on molecular dynamics simulation. Molecular dynamics simulation, as an effective computational method, can reveal the microscopic mechanism of charge transport in organic semiconductors. The basic principles and methods of molecular dynamics simulation will be introduced in the paper, and its application in studying charge transport in organic semiconductors will be discussed. Through the simulation analysis, the effects of key parameters such as intermolecular interactions, carrier mobility and electron transport on the performance of organic semiconductor devices can be revealed, providing guidance for the design and optimization of organic semiconductor devices.

Self‐Limited Epitaxial Growth of Patterned Monolayer Organic Crystals for Polarization‐Sensitive Phototransistor with Ultrahigh Dichroic Ratio

AbstractMonolayer organic crystals provide an unprecedented opportunity for studies on the intrinsic charge transport of organic semiconductors because of their 2D nature that is free of grain boundaries with fewer defects. However, due to the spatially stochastic molecular nucleation and the difficulty in controlling monolayer assembly, large‐scale growth of monolayer organic crystals remains a formidable challenge. Here, a self‐limited epitaxial growth strategy is proposed to realize large‐area patterned growth of monolayer organic crystals via physical vapor deposition process. Specifically, this approach confines the molecular nucleation and crystallization in defined wetting patterns, whose sizes are smaller than the mean free path of the molecules on substrate, enabling the formation of a single nucleus in wetting pattern. Meanwhile, the intermolecular lattice mismatch between 2,7‐dialkyl[1]benzothieno[3,2‐b][1]benzothiophene (Cn‐BTBT, n = 8 and 10) derivatives inhibits vertical molecular stacking, thereby promoting the monolayer assembly of organic molecules. Using this approach, centimeter‐sized patterned growth of mixed Cn‐BTBT monolayer organic crystals is achieved. Polarization‐sensitive phototransistors based on the monolayer organic crystals exhibit ultrahigh dichroic ratio up to 4.6 × 103, on par with the commercial polarizers (103). This work sheds light on large‐scale patterned growth of monolayer organic crystals toward high‐performance optoelectronic devices.

Influence of Traps and Lorentz Force on Charge Transport in Organic Semiconductors.

Charge transport characteristics in organic semiconductor devices become altered in the presence of traps due to defects or impurities in the semiconductors. These traps can lead to a decrease in charge carrier mobility and an increase in recombination rates, thereby ultimately affecting the overall performance of the device. It is therefore important to understand and mitigate the impact of traps on organic semiconductor devices. In this contribution, the influence of the capture and release times of trap states, recombination rates, and the Lorentz force on the net charge of a low-mobility organic semiconductor was determined using the finite element method (FEM) and Hall effect method through numerical simulations. The findings suggest that increasing magnetic fields had a lesser impact on net charge at constant capture and release times of trap states. On the other hand, by increasing the capture time of trap states at a constant magnetic field and fixed release time, the net charge extracted from the semiconductor device increased with increasing capture time. Moreover, the net charge extracted from the semiconductor device was nearly four and eight times greater in the case of the non-Langevin recombination rates of 0.01 and 0.001, respectively, when compared to the Langevin rate. These results imply that the non-Langevin recombination rate can significantly enhance the performance of semiconductor devices, particularly in applications that require efficient charge extraction. These findings pave the way for the development of more efficient and cost-effective electronic devices with improved charge transport properties and higher power conversion efficiencies, thus further opening up new avenues for research and innovation in this area of modern semiconductor technology.

Modeling Charge Transport in Organic Semiconductors Using Neural Network Based Hamiltonians and Forces.

The fewest switches surface hopping method has been widely used for the simulation of charge transport in organic semiconductors. In the present study, we perform nonadiabatic molecular dynamics (NAMD) simulations of hole transport in anthracene and pentacene. The simulations employ neural network (NN) based Hamiltonians in two different nuclear relaxation schemes, which utilize either a precalculated reorganization energy or site energy gradients additionally obtained from NN models. The performance of the NN models is evaluated in reproducing hole mobilities and inverse participation ratios in terms of both quality and computational cost. The results show that charge mobilities and inverse participation ratios obtained by models, which were trained on DFTB or DFT training data, are in very good agreement with the respective QM reference method for implicit relaxation and, where available, also for explicit relaxation. Reasonable agreement with experimental hole mobilities is achieved. Utilizing our models in NAMD simulations of charge transfer amounts to a reduction of the computational cost in a range of 1 to 7 orders of magnitude compared to DFTB and DFT. This proves neural networks as promising tools for the improvement of accuracy and efficiency of charge and potentially also exciton transport simulations in complex and large molecular systems.

Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character.

The charged forms of π-conjugated chromophores are relevant in the field of organic electronics as charge carriers in optoelectronic devices, but also as energy storage substrates in organic batteries. In this context, intramolecular reorganization energy plays an important role in controlling material efficiency. In this work, we investigate how the diradical character influences the reorganization energies of holes and electrons by considering a library of diradicaloid chromophores. We determine the reorganization energies with the four-point adiabatic potential method using quantum-chemical calculations at density functional theory (DFT) level. To assess the role of diradical character, we compare the results obtained, assuming both closed-shell and open-shell representations of the neutral species. The study shows how the diradical character impacts the geometrical and electronic structure of neutral species, which in turn control the magnitude of reorganization energies for both charge carriers. Based on computed geometries of neutral and charged species, we propose a simple scheme to rationalize the small, computed reorganization energies for both n-type and p-type charge transport. The study is supplemented with the calculation of intermolecular electronic couplings governing charge transport for selected diradicals, further supporting the ambipolar character of the investigated diradicals.

Jumping Kinetic Monte Carlo: Fast and Accurate Simulations of Partially Delocalized Charge Transport in Organic Semiconductors.

Developing devices using disordered organic semiconductors requires accurate and practical models of charge transport. In these materials, charge transport occurs through partially delocalized states in an intermediate regime between localized hopping and delocalized band conduction. Partial delocalization can increase mobilities by orders of magnitude compared to those with conventional hopping, making it important for the design of materials and devices. Although delocalization, disorder, and polaron formation can be described using delocalized kinetic Monte Carlo (dKMC), it is a computationally expensive method. Here, we develop jumping kinetic Monte Carlo (jKMC), a model that approaches the accuracy of dKMC for modest amounts of delocalization (such as those found in disordered organic semiconductors), with a computational cost comparable to that of conventional hopping. jKMC achieves its computational performance by modeling conduction using identical spherical polarons, yielding a simple delocalization correction to the Marcus hopping rate that allows polarons to jump over their nearest neighbors. jKMC can be used in regimes of partial delocalization inaccessible to dKMC to show that modest delocalization can increase mobilities by as much as 2 orders of magnitude.

An ordered, self-assembled nanocomposite with efficient electronic and ionic transport.

Mixed conductors-materials that can efficiently conduct both ionic and electronic species-are an important class of functional solids. Here we demonstrate an organic nanocomposite that spontaneously forms when mixing an organic semiconductor with an ionic liquid and exhibits efficient room-temperature mixed conduction. We use a polymer known to form a semicrystalline microstructure to template ion intercalation into the side-chain domains of the crystallites, which leaves electronic transport pathways intact. Thus, the resulting material is ordered, exhibiting alternating layers of rigid semiconducting sheets and soft ion-conducting layers. This unique dual-network microstructure leads to a dynamic ionic/electronic nanocomposite with liquid-like ionic transport and highly mobile electronic charges. Using a combination of operando X-ray scattering and in situ spectroscopy, we confirm the ordered structure of the nanocomposite and uncover the mechanisms that give rise to efficient electron transport. These results provide fundamental insights into charge transport in organic semiconductors, as well as suggesting a pathway towards future improvements in these nanocomposites.

A Green Binary Solvent Method to Control Organic Semiconductor Crystallization

AbstractWhile solution‐processed small‐molecular organic semiconductors have been reported with significant research progress, their random crystal orientations and abundant defects at grain boundaries remain as a major obstacle to achieving high performance in organic electronic devices. In this paper, we demonstrate a binary solvent method that comprises a green solvent to manipulate the crystal alignment, morphology and charge transport of organic semiconductors. 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) was studied as an example to showcase the enlargement of grain width and millimeter‐scale alignment of organic crystals based on the toluene/n‐amyl acetate binary solvents. At an optimized volume ratio of 3 : 1, the toluene/n‐amyl acetate binary solvent gave rise to a 4‐fold reduction in misorientation angle and approximately 40 % increase in the grain width. UV‐visible spectroscopy confirmed strong H‐aggregations with more favorable intrachain interaction and charge transport in TIPS pentacene. X‐ray diffraction showed enhanced peak intensities in (00 l) type of reflections and improved film crystallinity. Finally, thin film transistors were demonstrated to test the charge transport in the TIPS pentacene organic crystals. This work demonstrates the binary green solvent method can effectively regulate the organic semiconductor crystallization and alignment even in the absence of external alignment techniques such as solution shearing, and thereby sheds light on advancing facile organic electronic applications.

Binary solvent engineering for small-molecular organic semiconductor crystallization

This article reviews the synergistic effects of engineering binary solvents on the crystallization, morphology and charge transport of organic semiconductors.

Terahertz Electromodulation Spectroscopy for Characterizing Electronic Transport in Organic Semiconductor Thin Films

Terahertz (THz) spectroscopy is a well-established tool for measuring the high-frequency conductance of inorganic semiconductors. Its application to organic semiconductors, however, is challenging, because of the low carrier mobilities in organic materials, which rarely exceed 10cm2/Vs. Furthermore, low charge carrier densities in organic field-effect devices lead to sheet conductivities that are often far-below the detection limits of conventional THz techniques. In this contribution, we present the application of THz electromodulation spectroscopy for characterizing charge transport in organic semiconductors. Pulses of THz radiation are transmitted through organic field-effect devices and are time-resolved by electro-optic sampling. A differential transmission signal is obtained by modulating the gate voltage of the devices. This controls charge injection into the semiconductors, where the charge carriers reduce the THz transmission by their Drude response. Advantageous is that a nearly noise-free differential transmission can be obtained. Furthermore, electromodulation allows to sense specifically either injected electrons or holes. Because the method exclusively probes transport of mobile carriers, it provides access to fundamental transport properties, which are difficult to access with conventional characterization methods, such as conductance measurements of organic field-effect transistors. The outstanding property that a relative differential signal is measured allows to obtain charge carrier mobilities with high reliability. Mobilities as small as 1cm2/Vs can be probed, which makes THz electromodulation spectroscopy an attractive tool for studying charge transport in most technologically relevant organic semiconductors.

Charge carrier mobilities of organic semiconductors: ab initio simulations with mode-specific treatment of molecular vibrations

The modeling of charge transport in organic semiconductors usually relies on the treatment of molecular vibrations by assuming a certain limiting case for all vibration modes, such as the dynamic limit in polaron theory or the quasi-static limit in transient localization theory. These opposite limits are each suitable for only a subset of modes. Here, we present a model that combines these different approaches. It is based on a separation of the vibrational spectrum and a quantum-mechanical treatment in which the slow modes generate a disorder landscape, while the fast modes generate polaron band narrowing. We apply the combined method to 20 organic crystals, including prototypical acenes, thiophenes, benzothiophenes, and their derivatives. Their mobilities span several orders of magnitude and we find a close agreement to the experimental mobilities. Further analysis reveals clear correlations to simple mobility predictors and a combination of them can be used to identify high-mobility materials.

Pulsed gate voltage measurement for charge mobility extraction of organic transistors

The field-effect mobility of organic semiconductors is an important parameter that describes a physical characteristic of charge carriers and is extracted from the current–voltage characteristics of field-effect transistors. For the parameter to be consistent with its physical definition, charge transport in organic semiconductors should be in a steady state. However, charge transport in organic field-effect transistors is often in a non-steady state because of the occurrence of charge-carrier trapping and the Joule heating effect; therefore, careful attention is required for the extraction of the field-effect mobility in such cases. In this study, the effects of gate pulses on the transport characteristics of organic field-effect transistors are investigated. Consequently, an ideal sequence of gate pulses to minimize the effects of intermediate trap states and Joule-heating during extraction of the field-effect mobility of organic transistors is proposed. Finally, an equation that relates the field-effect mobility to the sequence of gate pulses is derived and experimentally validated. • Systematic study of the effects of pulsed-gate measurements on the device characteristics of organic field-effect transistors. • Analytical model to describe the relationship between the effective mobility and gate pulse characteristics. • Ideal sequence of gate pulses for the extraction of the field-effect mobility of organic semiconductors.

From Amorphous to Polycrystalline Rubrene: Charge Transport in Organic Semiconductors Paralleled with Silicon

AbstractWhile progress has been made in the design of organic semiconductors (OSCs) with improved transport properties, the understanding of the mechanisms involved is still limited, hindering further development. In this study, the interplay between structural order and transport considering one single OSC, analogous to past research on silicon is investigated. Rubrene (C42H28) is selected as it spans transport mechanisms from thermally activated hopping in its amorphous form to band‐like in highly ordered crystals in the orthorhombic polymorph. Transport characterizations including variable temperature conductivity, advanced Hall effect, and magnetoresistance measurements are performed on rubrene films with varying levels of order (polycrystalline vs amorphous), crystal phase (orthorhombic vs triclinic), and morphologies (platelet‐like vs spherulitic grains). A conductivity tuning range over four orders of magnitude between polycrystalline (platelet‐like) orthorhombic and amorphous films is reported. As observed in silicon, transport in polycrystalline orthorhombic rubrene is limited by energy barriers at grain boundaries. Additionally, a gradual transition from predominantly band‐like to predominantly hopping transport with increasing disorder, reminiscent of observations in silicon is shown. Nevertheless, OSCs differ from covalently bonded silicon by their weak intermolecular interaction. This study highlights that molecular packing must be optimized in OSCs to favor advantageous π‐orbital overlap and optimized transport properties.

Mixed-Orbital Charge Transport in N-Shaped Benzene- and Pyrazine-Fused Organic Semiconductors.

The hole-carrier transport of organic semiconductors is widely known to occur via intermolecular orbital overlaps of the highest occupied molecular orbitals (HOMO), though the effect of other occupied molecular orbitals on charge transport is rarely investigated. In this work, we first demonstrate evidence of a mixed-orbital charge transport concept in the high-performance N-shaped decyl-dinaphtho[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene (C10–DNBDT–NW), where electronic couplings of the second HOMO (SHOMO) and third HOMO (THOMO) also contribute to the charge transport. We then present the molecular design of an N-shaped bis(naphtho[2′,3′:4,5]thieno)[2,3-b:2′,3′-e]pyrazine (BNTP) π-electron system to induce more pronounced mixed-orbital charge transport by incorporating the pyrazine moiety. An effective synthetic strategy for the pyrazine-fused extended π-electron system is developed. With substituent engineering, the favorable two-dimensional herringbone assembly can be obtained with BNTP, and the decylphenyl-substituted BNTP (C10Ph–BNTP) demonstrates large electronic couplings involving the HOMO, SHOMO, and THOMO in the herringbone assembly. C10Ph–BNTP further shows enhanced mixed-orbital charge transport when the electronic couplings of all three occupied molecular orbitals are taken into consideration, which results in a high hole mobility up to 9.6 cm2 V–1 s–1 in single-crystal thin-film organic field-effect transistors. The present study provides insights into the contribution of HOMO, SHOMO, and THOMO to the mixed-orbital charge transport of organic semiconductors.