Effect of dihydropyrazine on structures and charge transport properties of N-heteropentacenes matters: A theoretical investigation

A family of N-heteropentacenes acted as promising candidates for organic semiconductor materials is of immense interest. It should be attributed to the following reasons that (1) the positions, numbers and valence-states of N atom in N-heteropentacenes can effectively tune their electronic structure, stability, solubility, and molecular stacking; (2) diverse intermolecular interaction and π-stacking motifs appear in their crystals. The effect of the position and number of the 6-π-pyrazine on their structures and charge-transport properties has been systematically investigated in our previous work (J. Phys. Chem. C 115 (2011) 21416). Therefore, in this work, the study on the role of 8-π-dihydropyrazine with another valence-state N atoms is our focus. Density functional theory, Marcus electron transfer theory and Brownian diffusion assumption coupled with kinetic Monte-Carlo simulation are applied into this investigation. Our theoretical results indicate that in contrast with pyrazine, dihydropyrazine introduced is more helpful for promoting p-type organic semiconductor materials. For molecule 4, hole mobility of its single crystal theoretically reach 0.71 cm² V⁻¹ s⁻¹, and coupled with its fine hole-injection ability, it should be a promising candidate for p-type organic semiconductor materials. Although the lowest triplet-state energies of the molecules studied are very small, introduction of dihydropyrazine is very helpful for increasing the energies.     

Understanding electron-withdrawing substituent effect on structural, electronic and charge transport properties of perylene bisimide derivatives

A series of n-type perylene bisimide (PBI) derivatives with electron-withdrawing substituents at both bay and imide nitrogen positions were investigated. The effects of these substituents on internal energy relaxation, molecular orbitals, air stability, electronic properties and charge transport behaviors were systematically discussed with density functional theory (DFT) which has been demonstrated reliable for organic semiconductor study. The investigated derivatives with electron-withdrawing substituents show favorable performances in terms of these properties. The LUMO levels are greatly stabilized by at least 0.3 eV and these derivatives show the strong absorption from 400 to 700 nm which match with the solar spectra very well. The charge transport mainly happens between molecules in the same organic molecular layer and electronic couplings between layer-to-layer molecules are very weak, thus the mobility along layer-to-layer direction is less efficient. The variation of molecular packings and intermolecular interactions produce the highly anisotropic mobilities. The derivative with two fluorine atoms at bay positions and –CH₂C₃F₇ at imide group has broad and strong absorption in the UV-Visible region and the electron mobility could get to 0.514 cm² V⁻¹ s⁻¹ which is greatly encouraging for molecular and material design in organic solar-cell devices. These calculated results are in good agreement with the experimental data. However, not all the functionalization with halogen substituents would induce the increase of the electronic coupling and electron mobility. The derivatives with four halogen substituents at the bay positions could not show advantages in terms of electron mobility which is induced by the distorted conjugated structures. The theoretical understanding of these n-type organic semiconductors figures out the importance of tuning the molecular geometry to get high performance semiconductor materials.     

Charge transport and optical properties of cross-conjugated organic molecules: A theoretical study

The structure, charge transport and optical properties of two-dimensional cruciform molecules 1,4-distyryl-2,5-bis(arylethynyl)benzenes, 1,4-distyryl-2,5-bis(arylethynyl)pyridines and 1,4-bis(ethylenediyl)dipyridine-2,5-bis(benzene) have been studied using density functional theory methods. The effective charge transfer integral and site energy corresponding to hole and electron transports in the above molecules were calculated directly from the matrix elements of Kohn–Sham Hamiltonian. The charge carrier mobility on the cruciform molecules was calculated using Monte Carlo simulation based on the Marcus rate theory and the results show that these cruciform molecules are the p-type organic semiconductors. The excited state calculations were performed using the time-dependent density functional theory method in gas phase, hexane and dichloromethane mediums. The trifluoromethyl substituted 1,4-distyryl-2,5-bis(arylethynyl)benzenes molecule possesses the maximum absorption and emission wavelength of 443 and 504 nm, respectively in dichloromethane medium.     

Effects of disorder on charge transport in semico++ nducting polymers

Polaron transport process in semiconducting polymers with disordered structure and morphology is simulated using a nonadiabatic evolution method. The simulations are performed within the framework of an extended version of the Su–Schrieffer–Heeger model modified to include diagonal disorder, off-diagonal disorder and an external electric field. It is found that the polaron transport mechanism is determined by the competition between the disorder and the electric field. For the case of pure diagonal disorder, the polaron transport undergoes a crossover from adiabatic drift to nonadiabatic hopping under a large scope of electric field (E < 2.0 mV/Å), whereas the field-assisted tunneling dominates charge transport for a higher electric field. For the combined disorder, it is demonstrated that the competition effects and the synergetic effects between the diagonal and off-diagonal disorder are equally important. The effects of diagonal disorder are negative in most cases, and the energetically easier pathways for charge transport are mainly opened by the off-diagonal disorder.     

Modeling of charge transport across disordered organic heterojunctions

Organic electronic devices often consist of a sandwich structure containing several layers of disordered organic semiconductors. In the modeling of such devices it is essential that the charge transport across the organic heterojunctions is properly described. The presence of energetic disorder and of strong gradients in both the charge density and the electric field at the heterojunction complicates the use of continuum drift-diffusion approaches to calculate the electrical current, because of the discrete positions of the sites involved in the hopping transport of charges. We use the results of three-dimensional Monte Carlo simulations to construct boundary conditions in a one-dimensional continuum drift-diffusion approach that accurately describe the charge transport across the junction. The important effects of both short- and long-range Coulomb interactions at the junction are fully accounted for. The developed approach is expected to have a general validity.     

The role of local potential minima on charge transport in thin organic semiconductor layers

We have performed a systematic study of dependence of time-resolved photocurrent on the point of charge excitation within the organic semiconductor channel formed by two coplanar metal electrodes. The results confirm that spatial variation of electric field between the electrodes crucially determines transport of photogenerated charge carriers through the organic layer. Time-of-flight measurements of photocurrent demonstrate that the transit time of photogenerated charge carrier packets drifting between the two electrodes decreases with increasing travelling distance. Such counterintuitive result cannot be reconciled with the spatial distribution of electric field between coplanar electrodes, alone. It is also in contrast to expected role of space-charge screening of external electric field. Supported by Monte Carlo simulations of hopping transport in disordered organic semiconductor layer, we submit that the space-charge screens the external electric field and captures slower charge carriers from the photogenerated charge carrier packet. The remaining faster carriers, exhibit velocity distribution with significantly higher mean value and shorter transit time.     

Charge transport in poly(p-phenylene vinylene) at low temperature and high electric field

Charge transport in poly(2-methoxy, 5-(2′-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV)-based hole-only diodes is investigated at high electric fields and low temperatures using a novel diode architecture. Charge carrier densities that are in the range of those in a field-effect transistor are achieved, bridging the gap in the mobility versus charge carrier density plot between polymer-based light-emitting diodes and field-effect transistors. The extended field range that is accessed allows us to discuss the applicability of current theoretical models of charge transport, using numerical simulations. Finally, within a simple approximation, we extract the hopping length for holes in MEH-PPV directly from the experimental data at high fields, and we derive a value of 1.0 ± 0.1 nm.     

The substituent effect on charge transport property of triisopropylsilylethynyl anthracene derivatives

The charge transport property of two triisopropylsilylethynyl anthracene (TIPSAnt) derivatives TIPSAntBt and TIPSAntNa (bithiophene and naphthalene are introduced at the 2, 6-positions of the TIPSAnt core) were explored through quantum chemical method. To gain a better understanding of the substituent effect on the charge transport property, the results of the parent molecule TIPSAnt was also provided here for comparison. The substituent effect on the molecular geometry, reorganization energy, frontier orbitals, ionization potential (IP) and electronic affinity (EA), crystal property, transfer integrals and charge mobility, band structure and effective mass of the two compounds were investigated to establish the relationship between structures and properties. The introduced bulky TIPS groups made the two compounds adopt two-dimensional, face-to-face, π-stacking structures. The efficient overlaps of π-orbital and smaller π-stacking distance are proved to be the main reason for the high charge mobility of TIPSAntBt and TIPSAntNa. The hole mobilities of TIPSAntBt and TIPSAntNa are 0.88 and 3.60 cm² V⁻¹ s⁻¹, respectively, which is well consistent with experiment values (0.2 and 3.7 cm² V⁻¹ s⁻¹, respectively). For TIPSAntBt, the electron mobility (1.29 cm² V⁻¹ s⁻¹) is a little higher than that of hole due to the more effective transfer integrals of electron. On the contrary, the hole mobility of TIPSAntNa is 20 times larger than that of electron because of the smaller reorganization energy and larger transfer integral of hole, indicating that TIPSAntNa could be used as p-type semiconductor. For TIPSAntBt, the transfer integral is smaller than the reorganization energy, so the hopping mechanism plays a key role in the charge transport property. While the bandwidths and effective mass of TIPSAntNa agreed well with the calculated transfer integrals and charge mobility results. The introduced small substituents to TIPSAnt core contributed to the dramatically different charge transport property from an n-type semiconductor of TIPSAntBt to p-type semiconductor of TIPSAntNa, which shed light on molecular design for an n-type semiconductor through simple chemical structural modification.     

Influence of equilibrium charge reservoir formation on photo generated charge transport in TiO2/organic devices

Charge transport measurements have been performed using the photo induced charge extraction by linearly increasing voltage (photo-CELIV) technique on indium tin oxide/titanium dioxide/poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester/copper (ITO/TiO₂/P3HT:PCBM/Cu) devices. By adjusting the offset voltage such that holes are accumulated at the ITO/TiO₂ contact we obtain space charge limited current (SCLC) extraction in the dark. Using photo-generation the current response is limited by SCLC extraction at low carrier concentrations but becomes purely recombination limited at high photo-generated carrier concentration. A 1-D drift diffusion model has been developed to simulate our results and we show that the hole blocking ITO/TiO₂ contact is responsible for the SCLC behavior. The highly reduced recombination of charges seen in P3HT:PCBM devices is necessary to obtain the large extraction current transients that are seen in the experimental measurements. By comparing the simulated dark CELIV and photo-CELIV we show that photo-generated extraction is more sensitive towards changes in the surface recombination velocity.     

Transverse charge transport in inkjet printed poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)

Transverse (z) alignment of PEDOT grains was demonstrated in inkjet printed PEDOT:PSS. This explained the superior transverse charge conduction mode in inkjet printed PEDOT:PSS films, best fitted by the Efros-Shklovskii 1D-VRH (variable range hopping) model in this study compared with spin coated PEDOT:PSS films, which have demonstrated layers of generally in-plane aligned PEDOT:PSS grains. The findings of this study, regarding the microstructure of inkjet printed PEDOT:PSS films and their transverse charge transport model, justify measurements of the transverse conductivity of inkjet printed films in this study being 600 times higher than that of spin coated films. In addition, it was found that the addition of 5 wt% DMSO in the printing PEDOT:PSS ink lowers the workfunction by 3% approximately.     

Theoretical study on charge transport properties of cyanovinyl-substituted oligothiophenes

When the oligothiophene is substituted by dicyanovinyl (DCV) or tricyanovinyl (TCV) group, how does its transport property change? Here, we will mainly focus on exploring the influence on charge transport properties of introducing a strong electron-withdrawing DCV/TCV group to the thiophene units within Marcus–Levich–Jortner formalism at the level of density functional theory. The results show that the introduction of cyanovinyl-substituents improves the molecular π-stacking, decreases the frontier molecular orbital energy levels and reorganization energies, and increases the transfer integrals and mobilities, comparing with their parent thiophene molecules. It is interesting to find the phenomenon that enriching intermolecular interactions can be favorable for controlling the transport channel and thus get high mobility, which would be shown by the angular resolution anisotropic mobilities analysis. Besides, the simulated packing motifs of dimers for 3a and 3b without crystal structures reported indicate that their packing may form the slip π–π stacking, and that 3b may be a good ambipolar material. In a word, compared with corresponding thiophene analogues and tetracyanoquinodimethane, these compounds may become the candidates for the n-type or ambipolar organic semiconductor materials.     

Chemical synthesis and charge transport mechanism in solution processed flexible polypyrrole films

Polypyrrole (PPy) has been synthesized by a chemical oxidation method using ammonium persulfate to obtain a solution processable PPy powder. The resultant PPy powder was then solution processed to deposit flexible thin films of PPy over flexible substrates. PPy film samples were then characterized using UV–vis spectroscopy, FTIR spectroscopy and X-ray diffraction. It was found that conductivity of PPy (σ=2.4×10⁻² S/cm) reduces by an order of magnitude after solution processing in the form of films. The temperature dependent conductivity of PPy pellet and flexible films of PPy were measured in the temperature range of 80–300 K. It was observed that PPy films show stronger temperature dependence than pelletized samples. Charge transport in PPy samples has been investigated using Kivelson׳s and Mott׳s variable range hopping models. Mott׳s parameters such as density of states at the Fermi level N(E_F), average hopping distance (R) and average hopping energy (W) have been estimated for PPy samples. The results showed that at room temperature average hopping distance for PPy film was about 22.3 Å and average hopping energy was 128.6 meV.     

Unlocking the full potential of light emitting field-effect transistors by engineering charge injection layers

Light emitting field-effect transistors (LEFETs) are a class of next generation devices which combine the switching properties of field-effect transistors (FETs) with light emitting capabilities of organic light-emitting diodes (OLEDs) in a single device architecture. Current LEFET architectures suffer from inefficient charge injection of electrons and holes from the source and drain electrodes, leading to unbalanced charge transport and hence poor device performance. Here we report a simple fabrication method for LEFETs that delivers asymmetric source and drain electrodes comprised of low and high work function materials. The interdigitated low and high work function source–drain electrodes consist of combinations of organic materials, salts, metal oxides and metals. Using this method we were able to obtain a maximum EQE of up to 1.2% in a single layer device with Super Yellow as the active material.     

Transient space-charge-perturbed currents in organic materials: A Monte Carlo study

The transient current holds rich information about carrier transport and is used to derive charge mobility in the time-of-flight (TOF) measurement. Because carriers have finite charge, all transient currents are space-charge-perturbed (SCP). Previous theories of transient SCP currents are derived by neglecting diffusion and assuming a constant mobility, which is unfit for organic materials because of the hopping behavior of carriers. Due to the lack of knowledge, we do not fully understand the results from TOF experiments, which hinders the understanding of the charge transport mechanisms. Here, we perform Monte Carlo simulations of multi-particle carrier movement to study the transient SCP currents in organic materials. Coulomb interactions are calculated, and it is assumed that multiple carriers cannot occupy the same site simultaneously. Our results show that space-charge perturbation has two opposite effects on charge transport. In most cases, the net result is slower carrier movement, which suggests that TOF measurements under SCP conditions underestimate the charge mobility of organic materials.     

A review of some charge transport properties of silicon

This paper reviews the present knowledge of charge transport properties in silicon, with special emphasis on their application in the design of solid-state devices. Therefore, most attention is devoted to experimental findings in the temperature range around 300 K and to high-field properties. Phenomenological expressions are given, when possible, for the most important transport quantities as functions of temperature, field or impurity concentration. The discussion is limited to bulk properties, with only a few comments on surface transport.     

The modification of electrophotographic and mechanical properties of organic photoconductors by ultra-violet irradiation

Experiments have shown that UV treatment has a hardening effect on the surface of a drum-based organic photoconductor (OPC) and improves the retentivity. The dark decay and the photoinduced discharge rates were reduced linearly with the increase of time of UV irradiation. The dark decay rate and photoinduced discharge rates were reduced to 60% and more than 70% of the initial rate, respectively, while there was an increase of the activation energy of the charge transport layer. An initial increase in the residual potential was also observed from 20 to about 70 V. After 40 min of UV irradiation, the residual potential was seen to drop to 50 V again, and at the same time a slight increase of the hardness of the photoreceptor surface was detected from 13 to 16 in Vickers scale (Hv). The phenomena is most likely explained by a photochemical change which reduces the density of charge transport sites, builds up the number of deep traps and changes the molecular distribution. The decrease in charge transport site density and buildup of deep traps reduces the conductivity and hence the dark decay and photoinduced discharge rates. The fragmentation of charge transport molecules may result in a change of activation energy as well as the increase in the residue potential. Moreover, the redistribution of molecules leads to the change in molecular density and hardness.     

基于量子模型的碳纳米管场效应晶体管电子输运特性

采用量子输运模型和NEGF理论,自洽求解薛定谔方程和泊松方程,对类MOS-碳纳米管场效应晶体管的电子输运特性建模。考察了沟道长度Lg为5~25 nm时,其对器件的导通电流、阈值电压、关态泄漏电流、电流开关比、亚阈值摆幅等性质的影响。结果表明:当Lg≥15 nm时,MOS-CNTFET没有量子尺寸效应;当Lg<15 nm时,器件出现短沟道效应;Lg<10 nm时短沟道效应更加明显。     

Photophysical and charge-transporting properties of the copolymer SuperYellow

Conjugated copolymers are important materials for organic light-emitting diodes. Here, an investigation of the photophysical and charge-transporting properties of the prototypical poly(p-phenylene vinylene) based copolymer SuperYellow (SY) is reported. The study also investigated the effect of processing conditions by comparing the properties of spin-coated and solution-cast films. For both types of films, the results of time-resolved fluorescence and photoluminescence quantum yield measurements are similar. The high photoluminescence quantum yield of 60% and its independence of processing conditions shows the effectiveness of the bulky side groups in preventing concentration quenching of fluorescence. Time of flight measurements of charge mobility in both spin-coated and solution-cast films also showed similar results, with mobilities in the range 10^?6–10^?7 cm²/V s for both films. These results provide important information about a widely used copolymer and show that a good polymer light-emitting diode material can have low mobility.     

Temperature and field-dependence of hopping conduction in organic semiconductors

Electrical characteristics of the hopping transport in organic semiconductors are studied theoretically. Based on percolation theory of hopping between localized states, an analytical mobility model is obtained. This model is applied to the analysis of both the electric field dependence and the temperature dependence of the mobility. The results agree quantitatively with recent experimental data.