Interpretation of electron diffusion coefficient in organic and inorganic semiconductors with broad distributions of states

The carrier transport properties in nanocrystalline semiconductors and organic materials play a key role for modern organic/inorganic devices such as dye-sensitized (DSC) and organic solar cells, organic and hybrid light-emitting diodes (OLEDs), organic field-effect transistors, and electrochemical sensors and displays. Carrier transport in these materials usually occurs by transitions in a broad distribution of localized states. As a result the transport is dominated by thermal activation to a band of extended states (multiple trapping), or if these do not exist, by hopping via localized states. We provide a general view of the physical interpretation of the variations of carrier transport coefficients (diffusion coefficient and mobility) with respect to the carrier concentration, or Fermi level, examining in detail models for carrier transport in nanocrystalline semiconductors and organic materials with the following distributions: single and two-level systems, exponential and Gaussian density of states. We treat both the multiple trapping models and the hopping model in the transport energy approximation. The analysis is simplified by thermodynamic properties: the chemical capacitance, C(mu), and the thermodynamic factor, chi(n), that allow us to derive many properties of the chemical diffusion coefficient, D(n), used in Fick's law. The formulation of the generalized Einstein relation for the mobility to diffusion ratio shows that the carrier mobility is proportional to the jump diffusion coefficient, D(J), that is derived from single particle random walk. Characteristic experimental data for nanocrystalline TiO(2) in DSC and electrochemically doped conducting polymers are discussed in the light of these models.     

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     

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.     

Naphthodithiophene-based donor materials for solution processed organic solar cells

As an emerging donor building block, naphthodithiophene (NDT) is causing more concerns in the field of organic semiconductors. With the rigid and coplanar molecule structure, NDT will exhibit more application space relying on its own advantage for facilitating the charge carrier transport. In this review article, we have summarized the development progress on the NDT-based donor materials for solution processed organic solar cells. Discussions and comments on those representative NDT type materials about structure and property are also presented.     

Separation and preconcentration phenomena in internally heated poly(dimethylsilicone) capillaries: preliminary modelling and demonstration studies

The concept of achieving low-resolution separations in internally heated capillary membranes is discussed in terms of controlling the diffusion coefficients of volatile organic compounds in poly(dimethylsilicone) membranes in space and time. The behaviour of 1,1,1-trichloroethane in polydimethylsilicone was used in conjunction with a mixed-physics finite element model, incorporating second order partial differential equations, to describe time and spatial variations of mass-flux, membrane temperature and diffusion coefficients. The model, coded with Femlab, predicted highly non-linear diffusion coefficient profiles resulting from temperature programming a 500 [micro sign]m thick membrane, with an increase in the diffusion coefficient of approximately 30% in the last 30% of the membrane thickness. Simulations of sampling hypothetical analytes, with disparate temperature dependent diffusion coefficient relationships, predicted distinct thermal desorption profiles with selectivities that reflected the extent of diffusion through the membrane. The predicted desorption profiles of these analytes also indicated that low resolution separations were possible. An internally heated poly(dimethylsilicone) capillary membrane was constructed from a 10 cm long, 1.5 mm od capillary with 0.5 mm thick walls. Thirteen aqueous standards of volatile organic compounds of environmental significance were studied, and low-resolution separations were indicated, with temperature programming of the membrane enabling desorption profiles to be differentiated. Further, analytically useful relationships in the [micro sign]g cm(-3) concentration range were demonstrated with correlation coefficients >0.96 observed for linear regressions of desorption profile intensities to analyte concentrations.     

高性能双极性聚合物半导体材料与晶体管器件

有机聚合物半导体材料与晶体管器件是融合了化学、材料、半导体以及微电子等学科的前沿交叉研究方向.聚合物半导体材料分子是该领域研究的重要内容,其中双极性聚合物分子半导体材料,兼具了电子和空穴的双重载流子输运能力而受到学术界的广泛关注.本文总结了双极性聚合物半导体材料与器件的研究进展,重点介绍了我们在D-A型双极性聚合物分子半导体材料设计、加工技术与器件制备以及功能应用方面的研究工作,并论述了双极性聚合物分子半导体材料与器件研究过程中存在的科学问题及发展方向.     

On the carrier effect mechanism in relation to mass transport processes in the arc discharge

The time of residence of impurity atoms in the arc discharge is calculated. Diffusion, ion motion in the electric field, and ambipolar diffusion are taken into account. It is shown for the first time that ambipolar diffusion contributes significantly to the total particle flow from the arc discharge zone. The effect of charge exchange on the speed of ion motion in the arc is estimated. The influence of a carrier on the residence time of atoms in the arc discharge zone is calculated. Attention is paid to the peculiarities of the mechanism of the carrier effect associated with halide compounds. An attempt is made to explain the influence of halide compounds on the residence time of atoms in the arc using the considered model of mass transport. The velocities of mass transport and the time of atoms in the discharge zone are calculated for the are with and without halide containing substances. The initial parameters of calculation (discharge temperature, electron density, degree of ionization, and coefficient of atom diffusion) are partly measured and partly taken from the literature. The results of the calculation are compared with experimental data published in the literature. The adopted mass transport model adequately accounts for the influence of a carrier on the residence time of atoms in the arc discharge zone.     

Isolating the effect of torsional defects on mobility and band gap in conjugated polymers

Conjugated polymers represent a promising class of organic semiconductors with potential applications in a variety of molecular devices. Poly(3-alkylthiophene)s, in particular, are garnering interest due to their large charge carrier mobility and band gap in the visible region of the spectrum. Defects play a pivotal role in determining the performance of polymer electronics, and yet the function of specific types of defects is still largely unknown. Density functional theory calculations of alkyl-substituted oligothiophenes are used to isolate the effect of static inter-ring torsion defects on key parameters such as electronic coupling between rings and band gap. Results have potential implications both for the fundamental understanding of intramolecular charge transport and for improving processing in organic devices.     

Induction time in metal permeation processes through supported liquid membranes

The origin of the induction time observed in the permeation process of cadmium species through trilaurylammonium chloride in triethylbenzene supported liquid membranes is discussed. A model for the non-steady state transference process, where aqueous film diffusion coupled to an interfacial chemical reaction are the main rate determining processes, was developed. By comparison with experimental transference data, the rate constant of the interfacial reaction between cadmium chloride aqueous complexes and the membrane carrier, trilaurylammonium chloride, was evaluated. The time evolution of the concentration profiles through the aqueous diffusion film is also described.     

Modeling of diffusive transport of benzoic acid through a liquid membrane

A model of diffusive transport of benzoic acid through a liquid membrane (LM) separating two aqueous solutions, based on diffusion layers and the assumption of a steady state, has been developed and tested using experimental results. It has been found that a model with the apparent partition coefficient dependent on the concentration is able to describe the time dependence of acid concentration in LM with and without a maximum on that dependence. The quality of the model fit with the single apparent diffusion coefficient of benzoic acid is the same as the one which takes into account the diffusion of benzoic acid in different forms (undissociated and dissociated form in aqueous phase, monomer and dimer in organic phase); however, in the second case, the model becomes overparameterized. Assuming that the partition and diffusion coefficients are constant, the diffusion layer model corresponds to the model of reversible consecutive reactions. Analytical solution for such case is given. Apart from the partition equilibrium, also kinetics of partitioning was considered. It was shown that in some basic situations both cases yield identical results.     

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.     

Molecular Aggregation of Naphthalene Diimide(NDI) Derivatives in Electron Transport Layers of Inverted Perovskite Solar Cells and Their Influence on the Device Performance

One of key factors to design applicable electron transport layers (ETLs) for perovskite solar cells is the morphology of ETLs since a good morphology would help to facilitate the carrier transport at two interfaces (perovskite\ETL and ETL\cathode). However, one drawback of most organic ETL small molecules is the internal undesired accumulation, which would cause the formation of inappropriate morphology and rough ETL surface. Here, by elaborately designing the side chains of NDI derivatives, the molecular interaction could be modified to achieve the aggregation in different degrees, which would eventually affect the accumulation of molecules and surface qualities of ETLs. By speculating from the comparison between the absorption spectra of solutions and films, the sequence of extent of molecule interaction and aggregation was built among three NDI derivatives, which is further confirmed by direct evidence of atomic force microscopy (AFM) images. Then, carrier exaction abilities are simply studied by steady‐state photoluminescence spectroscopy. The carrier transport process is also discussed based on cyclic voltammetry, time‐resolved photoluminescence spectroscopy and mobility. NDIF1 are proven to have the appropriate internal aggregation to smooth the contact with cathode and low series resistance, and a device performance of 15.6 % is achieved. With the ability of preventing the thermal diffusion of Ag towards the perovskite surface due to the strong interaction between molecules, NDIF2 at high concentration shows the highest fill factor (80 %).     

Modeling the adsorption kinetics of some priority organic pollutants in water from diffusion and activation energy parameters

The kinetic aspects of adsorption of some priority organic pollutants, viz., phenol (hydroxybenzene), o-hydroxyphenol (1,2-dihydroxybenzene), m-hydroxyphenol (1,3-dihydroxybenzene), and 4-nitrophenol (1-hydroxy-4-nitrobenzene), on fly ash have been studied. The process is found to be of complex nature consisting of both surface adsorption and pore diffusion, the extent being estimated from the diffusion coefficient value. Activation parameter data for the ultimate adsorption as well as the pore diffusion are also evaluated. The data indicate that in the studied solute concentration range, external transport mainly governs the rate-limiting process.     

Modelling charge transport in organic semiconductors: from quantum dynamics to soft matter

The charge carrier dynamics in organic semiconductors has been traditionally discussed with the models used in inorganic crystalline and amorphous solids but this analogy has severe limitations because of the more complicated role of nuclear motions in organic materials. In this perspective, we discuss how a new approach to the modelling of charge transport is emerging from the alliance between the conventional quantum chemical methods and the methods more traditionally used in soft-matter modelling. After describing the conventional limit cases of charge transport we discuss the problems arising from the comparison of the theory with the experimental and computational results. Several recent applications of numerical methods based on the propagation of the wavefunction or kinetic Monte Carlo methods on soft semiconducting materials are reviewed.     

Liquid-supported membranes in chromium(VI) optical sensing: transport modelling

Flat sheet liquid-supported membranes (FSLSM) containing Aliquat 336 as a carrier have been evaluated as sample interface in an optical sensor for Cr(VI) monitoring. A model describing the transport mechanism of Cr(VI) through the membrane is reported. The model considers a diffusion process through a feed aqueous diffusion layer, a fast interfacial chemical reaction and a diffusion of ALQHCrO₄ and (ALQ)₂CrO₄ species through the membrane (Aliquat 336, ALQ). The mathematical equations describing the transport rate are derived and they correlate the membrane permeability coefficient to diffusional and equilibrium parameters as well as to the chemical composition of the system, i.e. extractant concentration in the membrane phase and acidity in the feed phase. The experimental data are explained by the derived equations and the diffusion resistances to mass transfer are evaluated. The influence of other experimental parameters, such as stirring speed in the feed phase and nature of the diluent and stripping agent on the transport is also discussed. Experiments with optical detection demonstrate the suitability of liquid-supported membranes (LSM) containing ALQ as interfaces for optical sensing.     

Theoretical comparative studies on transport properties of pentacene,pentathienoacene, and 6,13‐dichloropentacene

Pentacene derivative 6,13‐dichloropentacene (DCP) is one of the latest additions to the family of organic semiconductors with a great potential for use in transistors. We carry out a detailed theoretical calculation for DCP, with systematical comparison to pentacene, pentathienoacene (PTA, the thiophene equivalent of pentacene), to gain insights in the theoretical design of organic transport materials. The charge transport parameters and carrier mobilities are investigated from the first‐principles calculations, based on the widely used Marcus electron transfer theory and quantum nuclear tunneling model, coupled with random walk simulation. Molecular structure and the crystal packing type are essential to understand the differences in their transport behaviors. With the effect of molecule modification, significant one‐dimensional π‐stacks are found within the molecular layer in PTA and DCP crystals. The charge transport along the a‐axis plays a dominant role for the carrier mobilities in the DCP crystal due to the strong transfer integrals within the a‐axis. Pentacene shows a relatively large 3D mobility. This is attributed to the relatively uniform electronic couplings, which thus provides more transport pathways. PTA has a much smaller 3D mobility than pentacene and DCP for the obvious increase of the reorganization energy with the introduction of thiophene. It is found that PTA and DCP exhibit lower HOMO (highest occupied molecular orbital) levels and better environmental stability, indicating the potential applications in organic electronics. © 2015 Wiley Periodicals, Inc.     

Estimation of the kinetic characteristics of sorption of an organic ion on a heterogeneous crosslinked polymer sorbent within the framework of a bidisperse model

For the sorption of rubomycin, an antitumor athracycline-type antibiotic, on BDM-12 carboxyl-containing heterogeneous crosslinked polymer sorbent, it was shown that the measured time dependences of the extent of process are determined by two characteristic times: τ₁ (in the range of short times) and τ₂ (at long times). A phenomenological theory of the kinetics of sorption on the heterogeneous sorbent was developed on the basis of a biporous sorbent model. The dependences of the characteristic times τ₁ and τ₂ on the sorbent grain radius were obtained. It was concluded that the theory makes predictions in good agreement with experimental data and allows calculating the most important kinetic parameters of sorption of organic ions on polymer sorbents: the time of diffusion of the sorbate into microgranules, the diffusion coefficient of the sorbate in transport pores, the effective coefficient of the sorbate diffusion into the heterogeneous sorbent, etc.     

Charge‐carrier transport in disordered polymers

The general properties of charge‐carrier transport in disordered organic materials are discussed. The spatial correlation between energies of transport sites determined the form of drift‐mobility field dependence. The type of spatial correlation in a disordered material depends on its nature. Mobility field dependences must be different in polar and nonpolar materials. Different methods of mobility calculation from the shape of photocurrent transient were analyzed. A widely used method is very sensitive to the variation of the shape of the transient and sometimes produces results that effectively masquerade the true dependence of the mobility on the electric field or trap concentration. Arguments in favor of the better, more reliable method are suggested. Charge transport in materials containing charged traps was considered without using the isolated trap approximation, and this led to qualitatively different results. The results indicated that the effect of charged traps can hardly be responsible for the experimentally observed transport properties of disordered organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2584–2594, 2003     

Reformulated space-charge-limited current model and its application to disordered organic systems

We have reformulated a traditional model used to describe the current-voltage dependence of low mobility materials sandwiched between planar electrodes by using the quasi-electrochemical potential as the fundamental variable instead of the local electric field or the local charge carrier density. This allows the material density-of-states to enter explicitly in the equations and dispenses with the need to assume a particular type of contact. The diffusion current is included and as a consequence the current-voltage dependence obtained covers, with increasing bias, the diffusion limited current, the space-charge limited current, and the injection limited current regimes. The generalized Einstein relation and the field and density dependent mobility are naturally incorporated into the formalism; these two points being of particular relevance for disordered organic semiconductors. The reformulated model can be applied to any material where the carrier density and the mobility may be written as a function of the quasi-electrochemical potential. We applied it to the textbook example of a nondegenerate, constant mobility material and showed how a single dimensionless parameter determines the form of the I(V) curve. We obtained integral expressions for the carrier density and for the mobility as a function of the quasi-electrochemical potential for a Gaussianly disordered organic material and found the general form of the I(V) curve for such materials over the full range of bias, showing how the energetic disorder alone can give rise, in the space-charge limited current regime, to an I∝V(n) dependence with an exponent n larger than 2.     

Factors influencing the transport of tryptophan hydrochloride through supported liquid membranes containing macrocyclic carriers

Commercially available PTFE membranes were used as a support for liquid membranes in amino acid transport. Using tryptophan as a model amino acid, the influence of the type of organic liquid, kind of macrocyclic carrier and counter-ion on transport efficiency was examined. These studies show the strong influence of the kind of the counter-ion co-transported with amino acid cation, and the type of macrocyclic carrier used on the transport efficiency. The transport efficiency depends also on the pH of the source phase and on the nature of the organic liquid used as a membrane solvent. Liquid membranes supported on commercial porous-PTFE-membranes with hydrophobic solvents are stable for more than two months, while those with more hydrophilic solvents, for more than 30 days. The use of dodecylbenzenesulfonic acid as a counter-ion results in the highest flux of tryptophan, but in this case, the stability of membranes appeared to be five times lower.