Probing Charge Transport of Ruthenium-Complex-Based Molecular Wires at the Single-Molecule Level

A ruthenium(II) bis(sigma-arylacetylide)-complex-based molecular wire functionalized with thiolacetyl alligator clips at both ends (OPERu) was used to fabricate gold substrate-molecular wire-conductive tip junctions. To elucidate the ruthenium-complex-enhanced charge transport, we conducted a single-molecule level investigation using the technique-combination method, where electronic delay constant, single-molecular conductance, and barrier height were obtained by scanning tunneling microscopy (STM) apparent height measurements, STM break junction measurements, and conductive probe-atomic force microscopy (CP-AFM) measurements, respectively.

Charge Transport Processes of Immobilized Heteropolyanions at Self-assembled Monolayer Modified Gold Electrode by Electrochemical Quartz Crystal Microbalance Measurement

The in situ electrochemical quartz crystal microbalance(EQCM) technique was used to investigate the ion transport of immobilized heteropolyanions at a self-assembled monolayer(SAM) modified gold electrode during electrochemical redox process. A mixed transfer method was presented to analyse the abnormal change of resonant frequency based on the simultaneous insertion/extraction of different ions. The results indicate that the migration of HSO4- anions was indispensable in the redox process of the heteropolyan ions in a I mol/L H2SO4 solution and played a key role in the abnormal change of the resonant frequency. Such a change was attributed to different packing densities derived by means of differently immobilized methods.

From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo(p-phenylene ethynylene)s

The charge transport mechanism of oligo(p-phenylene ethynylene)s with lengths ranging from 0.98 to 5.11 nm was investigated using modified scanning tunneling microscopy break junction and conducting probe atomic force microscopy methods. The methods were based on observing the length dependence of molecular resistance at single molecule level and the current-voltage characteristics in a wide length distribution. An intrinsic transition from tunneling to hopping charge transport mechanism was observed near 2.75 nm. A new transitional zone was observed in the long length molecular wires compared to short ones. This was not a simple transition between direct tunneling and field emission, which may provide new insights into transport mechanism investigations. Theoretical calculations provided an essential explanation for these phenomena in terms of molecular electronic structures.

Conducting probe atomic force microscopy investigation of anisotropic charge transport in solution cast PBD single crystals induced by an external field

2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxdiazole (PBD) is a good electron-transporting material and can form single crystals from solution. In this work, solution cast PBD single crystals with different crystallographic axes (b, c) perpendicular to the Au/S substrates in large area are achieved by controlling the rate of solvent evaporation in the presence and absence of external electrostatic field, respectively. The orientation of these single crystals on Au/S substrate was characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Conducting probe atomic force microscopy (CP-AFM) was used to measure the charge transport characteristics of PBD single crystals grown on Au/S substrates. Transport was measured perpendicular to the substrate between the CP-AFM tip and the Au/S substrate. The electron mobility of 3 x 10(-3) cm(2)/(V s) for PBD single crystal along crystallographic b-axis is determined. And the electron mobility of PBD single crystal along the c-axis is about 2 orders of magnitude higher than that along the b-axis due to the anisotropic charge transport at the low voltage region.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Charge transport in a blue-emitting alternating block copolymer with a small spacer to conjugated segment length ratio

We analyze current versus voltage data obtained using single carrier injection in several metal/polymer/metal sandwich structures. The polymer used in each case is a soluble blue-emitting alternating block copolymer. Our experimental results demonstrate that the electron transport is space-charge limited by the high density of traps having an exponential energy distribution (temperature dependent characteristic energy) in the copolymer. The electron mobility of 8x10(-10) cm(2)/V s is directly determined using space-charge-limited current analytical expressions. Hole transport is also space-charge limited, with a mobility of 2x10(-6) cm(2)/V s. A hole trap with energy 0.17 eV is observed. We compare these results with those obtained for related block copolymers with different spacer and conjugated segment lengths and discuss the influence of spacer length and conjugated segment length on the charge transport properties. (C) 2000 American Institute of Physics. [S0021-8979(00)04501-1].

Charge transport of indigo-carmine doped polypyrrole

Charge transport in polypyrrole doped with indigo-carmine was investigated by the method of electrochemical alternating current impedance. By the nonlinear least square fitting, the equivalent circuit and parameter of each component are obtained. The apparent diffusion coefficients and heterogeneous electron transfer constants are given. It is found that, along with the increasing of film thickness, D-app and k(0) increase also.

Study of charge transport in blends of natural rubber and poly(o-methoxyaniline) based on a resistor network statistical model

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mechanism of charge transport in castor oil-based polyurethane/carbon black composite (PU/CB)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Eumelanin thin films: Solution-processing, growth, and charge transport properties

Eumelanin pigments show hydration-dependent conductivity, broad-band UV-vis absorption, and chelation of metal ions. Solution-processing of synthetic eumelanins opens new possibilities for the characterization of eumelanin in thin film form and its integration into bioelectronic devices. We investigate the effect of different synthesis routes and processing solvents on the growth, the morphology, and the chemical composition of eumelanin thin films using atomic force microscopy and X-ray photoelectron spectroscopy. We further characterize the films by transient electrical current measurements obtained at 50% to 90% relative humidity, relevant for bioelectronic applications. We show that the use of dimethyl sulfoxide is preferable over ammonia solution as processing solvent, yielding homogeneous films with surface roughnesses below 0.5 nm and a chemical composition in agreement with the eumelanin molecular structure. These eumelanin films grow in a quasi layer-by-layer mode, each layer being composed of nanoaggregates, 1-2 nm high, 10-30 nm large. The transient electrical measurements using a planar two-electrode device suggest that there are two contributions to the current, electronic and ionic, the latter being increasingly dominant at higher hydration, and point to the importance of time-dependent electrical characterization of eumelanin films. This journal is © 2013 The Royal Society of Chemistry.

Charge generation, charge transport, and residual charge in the electrospinning of polymers: A review of issues and complications

Electrospinning has become a widely implemented technique for the generation of nonwoven mats that are useful in tissue engineering and filter applications. The overriding factor that has contributed to the popularity of this method is the ease with which fibers with submicron diameters can be produced. Fibers on that size scale are comparable to protein filaments that are observed in the extracellular matrix. The apparatus and procedures for conducting electrospinning experiments are ostensibly simple. While it is rarely reported in the literature on this topic, any experience with this method of fiber spinning reveals substantial ambiguities in how the process can be controlled to generate reproducible results. The simplicity of the procedure belies the complexity of the physical processes that determine the electrospinning process dynamics. In this article, three process domains and the physical domain of charge interaction are identified as important in electrospinning: (a) creation of charge carriers, (b) charge transport, (c) residual charge. The initial event that enables electrospinning is the generation of region of excess charge in the fluid that is to be electrospun. The electrostatic forces that develop on this region of charged fluid in the presence of a high potential result in the ejection of a fluid jet that solidifies into the resulting fiber. The transport of charge from the charge solution to the grounded collection device produces some of the current which is observed. That transport can occur by the fluid jet and through the atmosphere surrounding the electrospinning apparatus. Charges that are created in the fluid that are not dissipated remain in the solidified fiber as residual charges. The physics of each of these domains in the electrospinning process is summarized in terms of the current understanding, and possible sources of ambiguity in the implementation of this technique are indicated. Directions for future research to further articulate the behavior of the electrospinning process are suggested. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3682464]

Study of the Influence of Localized Vibrational Modes in Charge Transport Properties at Nanoscale Systems.

In molecular and atomic devices the interaction between electrons and ionic vibrations has an important role in electronic transport. The electron-phonon coupling can cause the loss of the electron's phase coherence, the opening of new conductance channels and the suppression of purely elastic ones. From the technological viewpoint phonons might restrict the efficiency of electronic devices by energy dissipation, causing heating, power loss and instability. The state of the art in electron transport calculations consists in combining ab initio calculations via Density Functional Theory (DFT) with Non-Equilibrium Green's Function formalism (NEGF). In order to include electron-phonon interactions, one needs in principle to include a self-energy scattering term in the open system Hamiltonian which takes into account the effect of the phonons over the electrons and vice versa. Nevertheless this term could be obtained approximately by perturbative methods. In the First Born Approximation one considers only the first order terms of the electronic Green's function expansion. In the Self-Consistent Born Approximation, the interaction self-energy is calculated with the perturbed electronic Green's function in a self-consistent way. In this work we describe how to incorporate the electron-phonon interaction to the SMEAGOL program (Spin and Molecular Electronics in Atomically Generated Orbital Landscapes), an ab initio code for electronic transport based on the combination of DFT + NEGF. This provides a tool for calculating the transport properties of materials' specific system, particularly in molecular electronics. Preliminary results will be presented, showing the effects produced by considering the electron-phonon interaction in nanoscale devices.

Structure-Property Relationships and Charge Transport Modeling of Organic Molecular Materials

From the perspective of a new-generation opto-electronic technology based on organic semiconductors, a major objective is to achieve a deep and detailed knowledge of the structure-property relationships, in order to optimize the electronic, optical, and charge transport properties by tuning the chemical-physical characteristics of the compounds. The purpose of this dissertation is to contribute to such understanding, through suitable theoretical and computational studies. Precisely, the structural, electronic, optical, and charge transport characteristics of several promising organic materials recently synthesized are investigated by means of an integrated approach encompassing quantum-chemical calculations, molecular dynamics and kinetic Monte Carlo simulations. Particular care is addressed to the rationalization of optical and charge transport properties in terms of both intra- and intermolecular features. Moreover, a considerable part of this project involves the development of a home-made set of procedures and parts of software code required to assist the modeling of charge transport properties in the framework of the non-adiabatic hopping mechanism applied to organic crystalline materials. As a first part of my investigations, I mainly discuss the optical, electronic, and structural properties of several core-extended rylene derivatives, which can be regarded to as model compounds for graphene nanoribbons. Two families have been studied, consisting in bay-linked perylene bisimide oligomers and N-annulated rylenes. Beside rylene derivatives, my studies also concerned electronic and spectroscopic properties of tetracene diimides, quinoidal oligothiophenes, and oxygen doped picene. As an example of device application, I studied the structural characteristics governing the efficiency of resistive molecular memories based on a derivative of benzoquinone. Finally, as a second part of my investigations, I concentrate on the charge transport properties of perylene bisimides derivatives. Precisely, a comprehensive study of the structural and thermal effects on the charge transport of several core-twisted chlorinated and fluoro-alkylated perylene bisimide n-type semiconductors is presented.

Analysis of charge-transport properties in GST materials for next generation phase-change memory devices

The quest for universal memory is driving the rapid development of memories with superior all-round capabilities in non-volatility, high speed, high endurance and low power. The memory subsystem accounts for a significant cost and power budget of a computer system. Current DRAM-based main memory systems are starting to hit the power and cost limit. To resolve this issue the industry is improving existing technologies such as Flash and exploring new ones. Among those new technologies is the Phase Change Memory (PCM), which overcomes some of the shortcomings of the Flash such as durability and scalability. This alternative non-volatile memory technology, which uses resistance contrast in phase-change materials, offers more density relative to DRAM, and can help to increase main memory capacity of future systems while remaining within the cost and power constraints. Chalcogenide materials can suitably be exploited for manufacturing phase-change memory devices. Charge transport in amorphous chalcogenide-GST used for memory devices is modeled using two contributions: hopping of trapped electrons and motion of band electrons in extended states. Crystalline GST exhibits an almost Ohmic I(V) curve. In contrast amorphous GST shows a high resistance at low biases while, above a threshold voltage, a transition takes place from a highly resistive to a conductive state, characterized by a negative differential-resistance behavior. A clear and complete understanding of the threshold behavior of the amorphous phase is fundamental for exploiting such materials in the fabrication of innovative nonvolatile memories. The type of feedback that produces the snapback phenomenon is described as a filamentation in energy that is controlled by electron–electron interactions between trapped electrons and band electrons. The model thus derived is implemented within a state-of-the-art simulator. An analytical version of the model is also derived and is useful for discussing the snapback behavior and the scaling properties of the device.

Simulations of charge transport in organic compounds

To aid the design of organic semiconductors, we study the charge transport properties of organic liquid crystals, i.e. hexabenzocoronene and carbazole macrocycle, and single crystals, i.e. rubrene, indolocarbazole and benzothiophene derivatives (BTBT, BBBT). The aim is to find structure-property relationships linking the chemical structure as well as the morphology with the bulk charge carrier mobility of the compounds. To this end, molecular dynamics (MD) simulations are performed yielding realistic equilibrated morphologies. Partial charges and molecular orbitals are calculated based on single molecules in vacuum using quantum chemical methods. The molecular orbitals are then mapped onto the molecular positions and orientations, which allows calculation of the transfer integrals between nearest neighbors using the molecular orbital overlap method. Thus we obtain realistic transfer integral distributions and their autocorrelations. In case of organic crystals the differences between two descriptions of charge transport, namely semi-classical dynamics (SCD) in the small polaron limit and kinetic Monte Carlo (KMC) based on Marcus rates, are studied. The liquid crystals are investigated solely in the hopping limit. To simulate the charge dynamics using KMC, the centers of mass of the molecules are mapped onto lattice sites and the transfer integrals are used to compute the hopping rates. In the small polaron limit, where the electronic wave function is spread over a limited number of neighboring molecules, the Schroedinger equation is solved numerically using a semi-classical approach. The results are compared for the different compounds and methods and, where available, with experimental data. The carbazole macrocycles form columnar structures arranged on a hexagonal lattice with side chains facing inwards, so columns can closely approach each other allowing inter-columnar and thus three-dimensional transport. When taking only intra-columnar transport into account, the mobility is orders of magnitude lower than in the three-dimensional case. BTBT is a promising material for solution-processed organic field-effect transistors. We are able to show that, on the time-scales of charge transport, static disorder due to slow side chain motions is the main factor determining the mobility. The resulting broad transfer integral distributions modify the connectivity of the system but sufficiently many fast percolation paths remain for the charges. Rubrene, indolocarbazole and BBBT are examples of crystals without significant static disorder. The high mobility of rubrene is explained by two main features: first, the shifted cofacial alignment of its molecules, and second, the high center of mass vibrational frequency. In comparsion to SCD, only KMC based on Marcus rates is capable of describing neighbors with low coupling and of taking static disorder into account three-dimensionally. Thus it is the method of choice for crystalline systems dominated by static disorder. However, it is inappropriate for the case of strong coupling and underestimates the mobility of well-ordered crystals. SCD, despite its one-dimensionality, is valuable for crystals with strong coupling and little disorder. It also allows correct treatment of dynamical effects, such as intermolecular vibrations of the molecules. Rate equations are incapable of this, because simulations are performed on static snapshots. We have thus shown strengths and weaknesses of two state of the art models used to study charge transport in organic compounds, partially developed a program to compute and visualize transfer integral distributions and other charge transport properties, and found structure-mobility relations for several promising organic semiconductors.