We investigate the direct-current response of crystalline organic semiconductors in the presence of finite external electric fields by the quantum-classical Ehrenfest dynamics complemented with instantaneous decoherence corrections (IDC). The IDC is carried out in the real-space representation with the energy-dependent reweighing factors to account for both intermolecular decoherence and energy relaxation by which conduction occurs. In this way, both the diffusion and drift motion of charge carriers are described in a unified framework. Based on an off-diagonal electron-phonon coupling model for pentacene, we find that the drift velocity initially increases with the electric field and then decreases at higher fields due to the Wannier-Stark localization, and a negative electric-field dependence of mobility is observed. The Einstein relation, which is a manifestation of the fluctuation-dissipation theorem, is found to be restored in electric fields up to ~$10^5$ V/cm for a wide temperature region studied. Furthermore, we show that the incorporated decoherence and energy relaxation could explain the large discrepancy between the mobilities calculated by the Ehrenfest dynamics and the full quantum methods, which proves the effectiveness of our approach to take back these missing processes.
We elucidate the crystalline nature and the three-dimensional orientation of isolated organic nanocrystals embedded in a sol-gel matrix, using a polarized nonlinear microscopy technique that combines two-photon fluorescence and second harmonic generation. This technique allows the distinction between mono-crystalline structures and nano-scale poly-crystalline aggregates responsible for incoherent second harmonic signals.
Molecular organic materials offer the promise of novel electronic devices but also present challenges for understanding charge transport in narrow band systems. Low temperature studies elucidate fundamental transport processes. We report the lowest temperature field effect transport results on a crystalline oligomeric organic material, rubrene. We find field effect switching with on-off ratio up to 10^7 at temperatures down to 10 K. Gated transport shows a factor of ~10 suppression of the thermal activation energy in 10-50 K range and nearly temperature independent resistivity below 10 K.
We consider different structures, which can be obtained by polymerization of aromatic organic molecules under high pressures. These 2D and 3D covalently bonded organic polymers and their functionalization can pave the way to production of energy storage and conversion devices. High-pressure synthesis might serve as a useful hint for production of these structures and their functionalized analogs by means of wet chemical synthesis.
The consequences of several microscopic interactions on the photoemission spectra of crystalline organic semiconductors (OSC) are studied theoretically. It is argued that their relative roles can be disentangled by analyzing both their temperature and their momentum/energy dependence. Our analysis shows that the polaronic thermal band narrowing, that is the foundation of most theories of electrical transport in OSC, is inconsistent in the range of microscopic parameters appropriate for these materials. An alternative scenario is proposed to explain the experimental trends.
We show that the thermal stability of thin films of the organic semiconductor diindenoperylene (DIP) can be strongly enhanced by aluminum oxide capping layers. By thermal desorption spectroscopy and in-situ X-ray diffraction we demonstrate that organic films do not only stay on the substrate, but even remain crystalline up to 460C, i.e. 270 deg. above their desorption point for uncapped films (190C). We argue that this strong enhancement of the thermal stability compared to uncapped and also metal-capped organic layers is related to the very weak diffusion of aluminum oxide and the structurall…
We report a detailed comparison on the role of a self-assembled monolayer (SAM) of dipolar molecules on the threshold voltage and charge carrier mobility of organic field-effect transistor (OFET) made of both amorphous and polycrystalline organic semiconductors. We show that the same relationship between the threshold voltage and the dipole-induced charges in the SAM holds when both types of devices are fabricated on strictly identical base substrates. Charge carrier mobilities, almost constant for amorphous OFET, are not affected by the dipole in the SAMs, while for polycrystalline OFET (pent…
Understanding the charge carrier transport in the disordered organic molecular semiconductors is a fascinating and still unresolved problem in modern condensed-matter physics, yet has an extremely important bearing on their application in ``plastic'' based field effect transistor, light emitting diodes and lasers. The most contentious issue in this subject is the nature of the charge carriers i.e. whether they are bare electrons or dressed electrons, known as polarons. Here we show for the first time, by means of simple experiments that polaron moving in static disorder is responsible for char…
By comparing photoemission spectroscopy with a non-perturbative dynamical mean field theory extension to many-body ab initio calculations, we show in the prominent case of pentacene crystals that an excellent agreement with experiment for the bandwidth, dispersion and lifetime of the hole carrier bands can be achieved in organic semiconductors provided that one properly accounts for the coupling to molecular vibrational modes and the presence of disorder. Our findings rationalize the growing experimental evidence that even the best band structure theories based on a many-body treatment of elec…
Covalent-organic frameworks (COFs) are intriguing platforms for designing functional molecular materials. Here, we present a computational study based on van der Waals dispersion-corrected hybrid density functional theory calculations to analyze the material properties of boroxine-linked and triazine-linked intercalated-COFs. The effect of Fe atoms on the electronic band structures near the Fermi energy level of the intercalated-COFs have been investigated. The density of states (DOSs) computations have been performed to analyze the material properties of these kind of intercalated-COFs. We pr…
For a class of 2D hybrid organic-inorganic perovskite semiconductors based on $π$-conjugated organic cations, we predict quantitatively how varying the organic and inorganic component allows control over the nature, energy and localization of carrier states in a quantum-well-like fashion. Our first-principles predictions, based on large-scale hybrid density-functional theory with spin-orbit coupling, show that the interface between the organic and inorganic parts within a single hybrid can be modulated systematically, enabling us to select between different type-I and type-II energy level alig…
The exciton transport in the prototypical organic semiconductor Di-Indeno-Perylene (DIP) has been investigated by means of photoluminescence (PL) quenching and interpreted by an advanced exciton diffusion model including interference effects, quencher penetration as well as non-perfect exciton quenching. X-ray difraction revealed a correlation between the exciton diffusion length of about 90 nm and the structural coherence length of the DIP layers. Temperature dependent studies in a range of 5 - 300 K indicated an incoherent exciton transport above 80 K at activation energies of 10 - 20 meV re…
Monte Carlo simulation was carried out to understand the influence of morphological inhomogeneity on carrier diffusion in organic thin films. The morphological inhomogeneity was considered in the simulation by incorporating the regions of low energetic disorder in a host lattice of high energetic disorder which decreases the overall energetic disorder of the system. For the homogeneous films, the carrier diffusion was found to decrease upon decreasing the energetic disorder. In contrast to this, in the case of inhomogeneous films the carrier diffusion enhanced upon decreasing the overall energ…
A large number of non-adiabatic dynamical studies have been applied to reveal the nature of carrier transport in organic semiconductors with different approximations. We present here a "nearly exact" graphical process unit (GPU) based finite temperature TD-DMRG method to evaluate the carrier mobility in organic semiconductors as described by electron-phonon model, in particular to rubrene crystal, one of the prototypical organic semiconductors, with parameters derived from first-principles. We find that (i) TD-DMRG is a general and robust method that can bridge the gap between hopping and band…
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…
The power conversion efficiency of organic solar cells based on donor--acceptor blends is governed by an interplay of polaron pair dissociation and bimolecular polaron recombination. Both processes are strongly dependent on the charge carrier mobility, the dissociation increasing with faster charge transport, with raised recombination losses at the same time. Using a macroscopic effective medium simulation, we calculate the optimum charge carrier mobility for the highest power conversion efficiency, for the first time accounting for injection barriers and a reduced Langevin-type recombination.…
Finite-bandwidth effects on the temperature dependence of the mobility of injected carriers in pure organic crystals are explored for a simplifed case of impurity scattering. Temperature-dependent bandwidth effects are discussed briefly through a simplified combination of band and polaronic concepts.
A model describing the low density carrier state in an organic single crystal FET with high-$κ$ gate dielectrics is studied. The interplay between charge carrier coupling with inter-molecular vibrations in the bulk of the organic material and the long-range interaction induced at the interface with a polar dielectric is investigated. This interplay is responsible for the stabilization of a polaronic state with an internal structure extending on few lattice sites, at much lower coupling strengths than expected from the polar interaction alone. This effect could give rise to polaron self-trappin…
The kinetics of the charge carrier recombination in dye molecule-doped multilayer organic light-emitting diodes (OLEDs) was quantified by transient electroluminescence (EL). Three sets of dye molecules, such as derivatives of naphthalimide and stilbene, were used as dopants in light-emission layer. Although the devices show almost the same EL spectra for each set of molecules, they show very different EL efficiency. The difference in EL efficiency was attributed to the difference in charge carrier recombination, as revealed by transient EL. The recombination coefficient (γ) was determined from…
In addition to electronic polarization or charge redistribution, the shape of neutral conjugated molecules yields position-dependent ionization potentials and electron affinities in organic thin films. Self-consistent I(n) and A(n) are computed in each layer n of 10-layer films of prototypical organics on a metal. The depth dependence of I(n) is discussed at surfaces of anthracene, C60 and PTCDA. The shape contribution can be substantial, up to 0.5 eV, and comes primarily from charge-quadrupole interactions.
The effect of thermal structural fluctuations on the modulation of the transfer integrals between close molecules is studied using a combination of molecular dynamics simulations and quantum chemical calculations of the transfer integral. We have found that the fluctuations of the transfer integrals are of the same order of magnitude of their average value for two common organic semiconductors an observation that puts into question the currently adopted models for charge transport in organic semiconductors and identifies in the dynamic electronic disorder the limiting factor for the charge car…
We report the observation of carrier mediated decrease in the stiffness of crystalline (c)-Si(100) under nanoindentation. The apparent elastic modulii of heavily dopes (1E21 cm-3) p- and n-type c-Si are observed to be lower by 5.-7.5 percent that the estimated value for intrinsic (1E14 cm-3) c-Si. The deviation observed with respect to elastic modulus remarkably matches with the estimated value while considering the electronic elastic strain effect on carrier concentration as an influence of negative pressure coefficient of band gap for Si. The value is predominantly higher than the reported v…
The influence of film morphology induced carrier diffusion on the broadening of the time-of-flight transient photo-current pulse was investigated using Monte Carlo simulation in organic thin films. Assuming the Gaussian Disorder Model for the charge transport the simulation of the time-of-flight photo-current pulse shape was carried out for homogeneous and inhomogeneous films by varying the overall energetic disorder of the system. In the case of homogeneous system, the value of the tail broadening parameter (W) of the photocurrent pulse is found to decrease upon decreasing the energetic disor…
Charge transport in crystalline organic semiconductors is intrinsically limited by the presence of large thermal molecular motions, which are a direct consequence of the weak van der Waals inter-molecular interactions. These lead to an original regime of transport called \textit{transient localization}, sharing features of both localized and itinerant electron systems. After a brief review of experimental observations that pose a challenge to the theory, we concentrate on a commonly studied model which describes the interaction of the charge carriers with inter-molecular vibrations. We present…
The open circuit voltage Voc and the corresponding charge carrier density were measured in dependence of temperature and illumination intensity by current-voltage and charge extraction measurements for P3HT:PCBM and P3HT:bisPCBM solar cells. At lower temperatures a saturation of Voc was observed which can be explained by energetic barriers at the contacts (metal-insulator-metal model). Such injection barriers can also influence Voc at room temperature and limit the performance of the working solar cell, as was assured by macroscopic device simulations on temperature-dependent IV characteristic…
We consider the non-radiative resonant energy transfer from a two-dimensional Wannier exciton (donor) to a Frenkel exciton of a molecular crystal overlayer (acceptor). We characterize the effect of the optical anisotropy of the organic subsystem on this process. Using realistic values of material parameters, we show that it is possible to change the transfer rate within typically a factor of two depending on the orientation of the crystalline overlayer. The resonant matching of donor and acceptor energies is also partly tunable via the organic crystal orientation.
The rise of organic electronics calls for versatile modeling tools. In this context, we develop a semiclassical Boltzmann theory that describes transport and excitonic processes in crystalline organic semiconductors on equal footing. The generation of singlet and triplet excitons out of the ground state, their formation from free electrons and holes, the reverse processes, as well as the fusion and fission of excitons are included. The corresponding scattering integrals respect spin conservation, which requires matrix-valued distribution functions. They also include fermionic and bosonic many-…
Free electron laser-powered pulsed electron paramagnetic resonance (EPR) experiments performed at 240 GHz / 8.56 T on the crystalline organic radical BDPA reveal a tip-angle dependent resonant frequency. Frequency shifts as large as 11 MHz (45 ppm) are observed during a single Rabi oscillation. We attribute the frequency shifts to a "dressing" of the nutation by spin-spin interactions. A nonlinear semi-classical model which includes a temperature- and sample-geometry-dependent demagnetizing field reproduces experimental results. Because experiments are performed without a cavity, radiation dam…
The long charge carrier lifetime of the hybrid organic-inorganic perovskites (HOIPs) is the key for their remarkable performance as a solar cell material. The microscopic mechanism for the long lifetime is still in debate. Here, by using muon spin relaxation technique that probes the fluctuation of local magnetic fields, we show that the muon depolarization rate ($Δ$) of a prototype HOIP methylammonium lead iodide (MAPbI$_3$) shows a sharp decrease with increasing temperature in two steps above 120 K and 190 K across the structural transition from orthorhombic to tetragonal structure at 162 K.…
In order to provide an accurate theoretical description of current density voltage (J-V) characteristics of an organic heterojunction device over a wide range of electric fields at various temperatures, it is proposed that an accumulation of charge carriers at the heterojunction will lead to a reduction in the barrier height across the heterojunction. Two well-known hole transporting materials, 4,4,4-Tris(N-3-methylphenyl-N-phenyl-amino) triphenylamine (MTDATA) and N,N-diphenyl-N,N-bis(1-naphthyl)(1,1-biphenyl)-4,4diamine (NPB) were used to fabricate unipolar heterojunction devices. It is foun…
A relation derived from the Kubo formula shows that optical conductivity measurements below the gap frequency in doped semiconductors can be used to probe directly the time-dependent quantum dynamics of charge carriers. This allows to extract fundamental quantities such as the elastic and inelastic scattering rates, as well as the localization length in disordered systems. When applied to crystalline organic semiconductors, an incipient electron localization caused by large dynamical lattice disorder is unveiled, implying a breakdown of semiclassical transport.
Hall effect measurements are important for elucidating the fundamental charge transport mechanisms and intrinsic mobility in organic semiconductors. However, Hall effect studies frequently reveal an unconventional behavior that cannot be readily explained with the simple band-semiconductor Hall effect model. Here, we develop an analytical model of Hall effect in organic field-effect transistors in a regime of coexisting band and hopping carriers. The model, which is supported by the experiments, is based on a partial Hall voltage compensation effect, occurring because hopping carriers respond …
Martensitic-like transition between liquid crystalline and crystalline phases of prototypical discotic organic semiconductor
Rice University（莱斯大学）；Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory（斯坦福同步辐射光源，SLAC国家加速器实验室）；Prairie View A & M University（普雷里维尤A&M大学）
Perovskite solar cells have shown remarkable efficiencies beyond 22%, through organic and inorganic cation alloying. However, the role of alkali-metal cations is not well-understood. By using synchrotron-based nano-X-ray fluorescence and complementary measurements, we show that when adding RbI and/or CsI the halide distribution becomes homogenous. This homogenization translates into long-lived charge carrier decays, spatially homogenous carrier dynamics visualized by ultrafast microscopy, as well as improved photovoltaic device performance. We find that Rb and K phase-segregate in highly conce…
For topological insulators and topological crystalline insulators (TCIs), their exotic surface states are promising for fundamental condensed matter physics research as well as future electronics such as low-dissipation electronics and spintronics. However, the high bulk carrier density that often dominates the transport property is the major materials challenge, critically hindering our ability to study and manipulate the surface states. In this manuscript, we demonstrate an alloying strategy, SnSexTe1-x, to effectively reduce the bulk carrier density. As long as SnSexTe1-x remains in the cub…
We developed a novel method for obtaining the distribution of trapped carriers over their degree of localization in organic transistors, based on the fine analysis of electron spin resonance spectra at low enough temperatures where all carriers are localized. To apply the method to pentacene thin-film transistors, we proved through continuous wave saturation experiments that all carriers are localized at below 50 K. We analyzed the spectra at 20 K and found that the major groups of traps comprise localized states having wave functions spanning around 1.5 and 5 molecules and a continuous distri…
The tunable properties of molecular materials place them among the favorites for a variety of future generation devices. In addition, to maintain the current trend of miniaturization of those devices, a departure from the present top-down production methods may soon be required and self-assembly appears among the most promising alternatives. On-surface synthesis unites the promises of molecular materials and of self-assembly, with the sturdiness of covalently bonded structures: an ideal scenario for future applications. Following this idea, we report the synthesis of functional extended nanowi…
Computer simulation of the hopping charge transport in disordered organic materials has been carried out explicitly taking into account charge-charge interactions. This approach provides a possibility to take into account dynamic correlations that are neglected by more traditional approaches like mean field theory. It was found that the effect of interaction is no less significant than the usually considered effect of filling of deep states by non-interacting carriers. It was found too that carrier mobility generally increases with the increase of carrier density, but the effect of interaction…
Crystallization is a key for ferroelectricity which is a collective behavior of microscopic electric dipoles. On the other hand, uncontrolled crystallization leads to uneven morphology and random crystal orientations, which undermines the application potential of ferroelectric thin films. In this work, we introduce a film fabrication method of low-temperature physical vapor deposition followed by restrained crystallization, with electrical properties monitored in real-time by in situ measurements. This method was adopted to fabricate films of 2-methylbenzimidazole (MBI), whose molecule crystal…
The transport properties at finite temperature of crystalline organic semiconductors are investigated, within the Su-Schrieffer-Heeger model, by combining exact diagonalization technique, Monte Carlo approaches, and maximum entropy method. The temperature-dependent mobility data measured in single crystals of rubrene are successfully reproduced: a crossover from super- to sub-diffusive motion occurs in the range $150 \leq T \leq 200$ K, where the mean free path becomes of the order of the lattice parameter and strong memory effects start to appear. We provide an effective model which can succe…
Predicting charge transport in organic molecular crystals is notoriously challenging. Carrier mobility calculations in organic semiconductors are dominated by quantum chemistry methods based on charge hopping, which are laborious and only moderately accurate. We compute from first principles the electron-phonon scattering and the phonon-limited hole mobility of naphthalene crystal in the framework of ab initio band theory. Our calculations combine GW electronic bandstructures, ab initio electron-phonon scattering, and the Boltzmann transport equation. The calculated hole mobility is in very go…
Many crystals in nature exhibit fascinating mechanical, optical, magnetic and other characteristics. One of the reasons for this phenomenon has to do with the presence of specific organic molecules that are tightly associated with the mineral. Over the years, some organic crystals have been found to be located within the lattices of their singlecrystalline biogenic hosts. A number of questions remain unanswered: for example, how do these molecules become incorporated and what is their function? In this review we survey the gradual refinement of the above mentioned finding in biogenic crystals,…
Energetic disorder in disordered organic solids has been found to alter their physical parameters. Here, we have demonstrated, by means of Monte-Carlo simulation and experiments, that the electroluminescence (EL) spectrum is dependent on energetic disorder. This dependence has been attributed to the charge carrier relaxation during hopping process. The dependence of EL spectrum on energetic disorder makes it temperature dependent and temperature dependence has been found to vary with energetic disorder in a variety of materials. The simulation has been performed by taking the relaxation of cha…
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 organic 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 is applied for this model to determine the waiting time and thus the diffusion coefficient. We …
We have used an electro-optic technique to measure the position-dependent infrared absorption of holes injected into a thin crystal of the organic semiconductor, 6,13-bis(triisopropylsilylethynyl)-pentacene incorporated in a field-effect transistor. By applying square-wave voltages of variable frequency to the gate or drain, one can measure the time it takes for charges to accumulate on the surface, and therefore determine their mobility.
We develop an analytical method for the processing of electron spin resonance (ESR) spectra. The goal is to obtain the distributions of trapped carriers over both their degree of localization and their binding energy in semiconductor crystals or films composed of regularly aligned organic molecules [Phys. Rev. Lett. v. 104, 056602 (2010)]. Our method has two steps. We first carry out a fine analysis of the shape of the ESR spectra due to the trapped carriers; this reveals the distribution of the trap density of the states over the degree of localization. This analysis is based on the reasonabl…
We consider the bimolecular charge carrier recombination in amorphous organic semiconductors having a special kind of energetic disorder where energy levels for electrons and holes at a given transport site move in the same direction with the variation of some disorder governing parameter (the parallel disorder). This particular kind of disorder could be found in materials where the dominant part of the energetic disorder is provided by the conformational disorder. Contrary to the recently studied case of electrostatic disorder, the conformational disorder, if spatially correlated, leads to th…
It was shown in the recent experiments that the hybrid organic/inorganic resonant structures can provide a flexible materials platform aimed at the design of novel light emitting devices. The applications of hybrid structures for photovoltaic solar cell can also be useful. We pay attention in this note that the resonant energy transfer in hybrid structure from the organic thin layer to the semiconductor nanostructures can drastically increase the intensity of the free carrier generation. To demonstrate this idea we use the results of recently published paper by Zhang et al., Nature Nanotechnol…
The theoretical effects of phase separation on encounter-limited charge carrier recombination in organic semiconductor blends are investigated using kinetic Monte Carlo (KMC) simulations of pump-probe experiments. Using model bulk heterojunction morphologies, the dependence of the recombination rate on domain size and charge carrier mobility are quantified. Unifying competing models and simulation results, we show that the mobility dependence of the recombination rate can be described using the power mean of the electron and hole mobilities with a domain size dependent exponent. Additionally, …
It is textbookly regarded that phonons, i.e., an energy quantum of propagating lattice waves, are the main heat carriers in perfect crystals. As a result, in many crystals, e.g., bulk silicon, the temperature-dependent thermal conductivity shows the classical 1/T relationship because of the dominant Umklapp phonon-phonon scattering in the systems. However, the thermal conductivity of many crystalline metal-organic frameworks is very low and shows no, a weakly negative and even a weakly positive temperature dependence (glass-like thermal conductivity). It has been in debate whether the thermal …
We present a simple model of the bimolecular charge carrier recombination in polar amorphous organic semiconductors where the dominant part of the energetic disorder is provided by permanent dipoles and show that the recombination rate constant could be much smaller than the corresponding Langevin rate constant. The reason for the strong decrease of the rate constant is the long range spatial correlation of the random energy landscape in amorphous dipolar materials, without spatial correlation even strong disorder does not modify the Langevin rate constant. Our study shows that the significant…
Monte Carlo simulation of the charge carrier transport in disordered nonpolar organic materials has been carried out. As a suitable model we considered the model of quadrupolar glass. A general formula for the temperature and field dependence of the mobility was suggested. A comparison with experimental data has been carried out.
We have experimentally tested the hypothesis of free charge carrier mediated spin-transport in the small molecule organic semiconductor Alq3 at room temperature. A spin current was pumped into this material by pulsed ferromagnetic resonance of an adjacent NiFe layer, while a charge current resulting from this spin current via the inverse spin-Hall effect (ISHE) was detected in a Pt layer adjacent on the other side of the Alq3 layer, confirming a pure spin current through the Alq3 layer. Charge carrier spin states in Alq3, were then randomized by simultaneous application of electron paramagneti…
We have observed the Hall effect in the field-induced accumulation layer on the surface of small-molecule organic semiconductor. The Hall mobility mu_H increases with decreasing temperature in both the intrinsic (high-temperature) and trap-dominated (low-temperature) conduction regimes. In the intrinsic regime, the density of mobile field-induced charge carriers extracted from the Hall measurements, n_H, coincides with the density n calculated using the gate-channel capacitance, and becomes smaller than n in the trap-dominated regime. The Hall data are consistent with the diffusive band-like m…
Simulations of charge transport in amorphous semiconductors are often performed in microscopically sized systems. As a result, charge carrier mobilities become system-size dependent. We propose a simple method for extrapolating a macroscopic, nondispersive mobility from the system-size dependence of a microscopic one. The method is validated against a temperature-based extrapolation [Phys. Rev. B 82, 193202 (2010)]. In addition, we provide an analytic estimate of system sizes required to perform nondispersive charge transport simulations in systems with finite charge carrier density, derived f…
