Molecular Electron Transport Research Articles

Molecular stacking character and charge transport properties of tetrabenzoheptacenes derivatives: the effects of nitrogen doping and phenyl substitution.

The nitrogen doping and phenyl substitution effects on the geometries, molecular stacking character, electronic, and charge transport properties of tetrabenzoheptacene (TTBH) have been investigated by means of density functional theory (DFT) calculation and incoherent charge hopping model. Our results indicate that the nitrogen doping (TTH) at the 6,8,15,17 positions improves its stability in air and the ability of electron injection and in the meantime slightly changes the molecular stacking due to the C-H···N interaction. For both TTBH and TTH, large hole transport mobility (μh) and electron transport mobility (μe), which are on the same order of magnitude, are given rise by their dense displaced π-stacking in crystal. Comparatively, the phenyl substitution (Ph-TTBH) at the 6,8,15,17 positions adopts a non-planar conformation, adverse to close packing and therefore leads to smaller electron/hole transport mobility (μ) than those of TTBH and TTH. The calculations suggest TTBH and TTH are promising candidates for excellent ambipolar OFET materials.

Odd-even effect in molecular electronic transport via an aromatic ring.

A distinct odd-even effect on the electrical properties, induced by monolayers of alkyl-phenyl molecules directly bound to Si(111), is reported. Monomers of H2C═CH-(CH2)n-phenyl, with n = 2-5, were adsorbed onto Si-H and formed high-quality monolayers with a binding density of 50-60% Si(111) surface atoms. Molecular dynamics simulations suggest that the binding proximity is close enough to allow efficient π-π interactions and therefore distinctly different packing and ring orientations for monomers with odd or even numbers of methylenes in their alkyl spacers. The odd-even alternation in molecular tilt was experimentally confirmed by contact angle, ellipsometry, FT-IR, and XPS with a close quantitative match to the simulation results. The orientations of both the ring plane and the long axis of the alkyl spacer are more perpendicular to the substrate plane for molecules with an even number of methylenes than for those with an odd number of methylenes. Interestingly, those with an even number conduct better than the effectively thinner monolayers of the molecules with the odd number of methylenes. We attribute this to a change in the orientation of the electron density on the aromatic rings with respect to the shortest tunneling path, which increases the barrier for electron transport through the odd monolayers. The high sensitivity of molecular charge transport to the orientation of an aromatic moiety might be relevant to better control over the electronic properties of interfaces in organic electronics.

Molecular modeling and electron transport in polyethylene

Polyethylene is commonly used as an insulator for AC power cables. However it is known to undergo chemical and physical change which can lead to dielectric breakdown. Despite almost eighty years of experimental characterization of its electrical properties, very little is known about the details of the electrical behaviour of this material at the molecular level. An understanding of the mechanisms of charge trapping and transport could help in the development of materials with better insulating properties required for the next generation of high voltage AC and DC cables. Molecular simulation techniques provide a unique tool with which to study dielectric processes at the atomic and electronic level. Here we summarise simulation methodologies which have been used to study the properties of PE at the molecular level, elucidating the role of morphology in the trapping of excess electrons. We find that polyethylene has localised states due to conformational trapping extending below the mobility edge (above which the electrons are delocalised), at -0.1±0.1eV with respect to the vacuum level. These trap states with localisation lengths between 0.3 and 1.2nm have energies as low as -0.4±0.1eV in the amorphous and interfacial regions of polyethylene with more positive values in lamella structures. Crystalline regions have a mobility edge at +0.46 ±0.1eV, so we would expect transport by electrons excited above the mobility edge to delocalised states to be predominantly through amorphous regions if they percolate the sample.

Cesium carbonate-doped 1,4,5,8-naphthalene-tetracarboxylic-dianhydride used as efficient electron transport material in polymer solar cells

The use of appropriate charge carrier transport materials in organic solar cells strongly influences the device performance. In this work, we focused on the molecular electron transport material 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) doped by cesium carbonate (Cs2CO3). We first investigated the electrical properties of such n-type doped material as a function of the doping concentration before using it as electron transport layer (ETL) in polymer solar cells. The doped transparent ETL reduces the series resistance leading to an increased open circuit voltage. A power conversion efficiency of 3.8% was finally achieved in a device with a blend of poly(3-hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as the active layer and a 5nm-thick NTCDA:Cs2CO3 film with a molar ratio of 30% as ETL.

Conformation‐Controlled Electron Transport in Single‐Molecule Junctions Containing Oligo(phenylene ethynylene) Derivatives

Understanding the relationships between the molecular structure and electronic transport characteristics of single-molecule junctions is of fundamental and technological importance for future molecular electronics. Herein, we report a combined experimental and theoretical study on the single-molecule conductance of a series of oligo(phenylene ethynylene) (OPE) molecular wires, which consist of two phenyl-ethynyl-phenyl π units with different dihedral angles. The molecular conductance was studied by scanning tunneling microscopy (STM)-based break-junction techniques under different conditions, including variable temperature and bias potential, which suggested that a coherent tunneling mechanism takes place in the OPE molecular wires with a length of 2.5 nm. The conductance of OPE molecular junctions are strongly affected by the coupling strength between the two π systems, which can be tuned by controlling their intramolecular conformation. A cos(2)θ dependence was revealed between the molecular conductance and dihedral angles between the two conjugated units. Theoretical investigations on the basis of density functional theory and nonequilibrium Green's functions (NEGF) gave consistent results with the experimental observations and provided insights into the conformation-dominated molecular conductance.

L‐Tryptophan‐Induced Electron Transport across Supported Lipid Bilayers: an Alkyl‐Chain Tilt‐Angle, and Bilayer‐Symmetry Dependence

Molecular orientation-dependent electron transport across supported 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayers (SLBs) on semiconducting indium tin oxide (ITO) is reported with an aim towards potential nanobiotechnological applications. A bifunctional strategy is adopted to form symmetric and asymmetric bilayers of DPPC that interact with L-tryptophan, and are analyzed by surface manometry and atomic force microscopy. Polarization-dependent real-time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) analysis of these SLBs reveals electrostatic, hydrogen-bonding, and cation-π interactions between the polar head groups of the lipid and the indole side chains. Consequently, a molecular tilt arises from the effective interface dipole, facilitating electron transport across the ITO-anchored SLBs in the presence of an internal Fe(CN)(6)(4-/3-) redox probe. The incorporation of tryptophan enhances the voltammetric features of the SLBs. The estimated electron-transfer rate constants for symmetric and asymmetric bilayers (k(s) = 2.0×10(-2) and 2.8×10(-2) s(-1)) across the two-dimensional (2D) ordered DPPC/tryptophan SLBs are higher compared to pure DPPC SLBs (k(s) = 3.2×10(-3) and 3.9×10(-3) s(-1)). In addition, they are molecular tilt-dependent, as it is the case with the standard apparent rate constants k(app)(0), estimated from electrochemical impedance spectroscopy and bipotentiostatic experiments with a Pt ultramicroelectrode. Lower magnitudes of k(s) and k(app)(0) imply that electrochemical reactions across the ITO-SLB electrodes are kinetically limited and consequently governed by electron tunneling across the SLBs. Standard theoretical rate constants (k(th)(0)) accrued upon electron tunneling comply with the potential-independent electron-tunneling coefficient β = 0.15 Å(-1). Insulator-semiconductor transitions moving from a liquid-expanded to a condensed 2D-phase state of the SLBs are noted, adding a new dimension to their transport behavior. These results highlight the role of tryptophan in expediting electron transfer across lipid bilayer membranes in a cellular environment and can provide potential clues towards patterned lipid nanocomposites and devices.

Controlled formation of charge depletion zones by molecular doping in organic pin-diodes and its description by the Mott-Schottky relation

Molecular doping of organic semiconductors is a key technology for highly efficient organic light-emitting diodes. Nevertheless, the underlying fundamental mechanisms are under discussion. This is because of the complex situation of structural disorder and strong polaronic coupling in such systems. We provide for the first time a systematic study of the formation of charge depletion zones in organic pin-diodes comprising molecular doped hole and electron transport layers. Impedance spectroscopy is employed to study the capacitance of these depletion zones. In particular, we show that the voltage dependent capacitance function obeys the Mott-Schottky relation concerning the influence of doping and the effect of an additional depletion zone given by the intrinsic interlayer. From temperature dependent measurements of the depletion capacitance, we can deduce the amount of active dopant states, their activation energy, and the spatial field distribution within the junction. The measured activation energy of the dopant states and the overall value of active dopant molecules suggest a highly efficient doping process, where dopant molecules act as shallow acceptor states.

Organic pin-diodes approaching ultra-high-frequencies

Organic pin-diodes employing molecular doped hole and electron transport layers working at ultra-high-frequencies (UHF) are presented. In comparison to undoped organic Schottky diodes reported for ultra-high-frequency applications, the pin-concept is superior since the doping concentration and the intrinsic interlayer thickness can be adjusted in order to control the performance of such pin-diodes. We investigate the influence of both parameters on basic diode parameters like forward resistance and rectification ratio. In particular, we discuss the role of molecular doping and its influence on the AC signal response and we present an optimized doping ratio in order to accomplish highest charge carrier mobility and conductivity. Optimized devices are working as rectifiers up to 300MHz at a small operating voltage of 2V. The frequency limit is estimated to be at 1GHz.

Reply to “Comment on ‘Critical analysis of a variational method used to describe molecular electron transport’”

We show that the failure of the Delaney-Greer (DG) variational ansatz for transport demonstrated by us in Phys.\ Rev.\ B {\bf 80}, 165301 (2009) (I) is not related to an unsuitable constraint that prevents a broken time-reversal symmetry or to real orbitals, as DG incorrectly claim. The complex orbitals suggested by them as a way-out solution merely represent a particular case of the general case considered by us in I, which do not in the least affect our conclusion.

Comment on “Critical analysis of a variational method used to describe molecular electron transport”

B\^aldea and K\"oppel [Phys. Rev. B 80, 165301 (2009)] have generalized our correlated transport formalism [P. Delaney and J. C. Greer, Phys. Rev. Lett. 93, 036805 (2004)] to constrain the occupancies of single-electron orbitals, and then claimed that zero conductivity $G=0$ in linear response follows and that our method is invalid. We show here that it was their incorrect choice to constrain the occupancies of real orbitals that resulted in $G=0$. In a scattering state incident to a barrier with values at $\ifmmode\pm\else\textpm\fi{}\ensuremath{\infty}$ differing by $\mathit{eV}$, only the incoming plane wave component has the bias-independent amplitude of 1, while the outgoing has $r$ which depends on the voltage $V$ and the barrier geometry. Thus, if occupancies are to be constrained to bias-independent values in transport, those of complex orbitals such as an incoming plane wave on each side are suitable, while real orbitals such as sines are not. This is true whether constant current constraints are additionally imposed or not.

Orbital Views of Molecular Conductance Perturbed by Anchor Units

Site-specific electron transport phenomena through benzene and benzenedithiol derivatives are discussed on the basis of a qualitative Hückel molecular orbital analysis for better understanding of the effect of anchoring sulfur atoms. A recent work for the orbital control of electron transport through aromatic hydrocarbons provided an important concept for the design of high-conductance connections of a molecule with anchoring atoms. In this work the origin of the frontier orbitals of benzenedithiol derivatives, the effect of the sulfur atoms on the orbitals and on the electron transport properties, and the applicability of the theoretical concept on aromatic hydrocarbons with the anchoring units are studied. The results demonstrate that the orbital view predictions are applicable to molecules perturbed by the anchoring units. The electron transport properties of benzene are found to be qualitatively consistent with those of benzenedithiol with respect to the site dependence. To verify the result of the Hückel molecular orbital calculations, fragment molecular orbital analyses with the extended Hückel molecular orbital theory and electron transport calculations with density functional theory are performed. Calculated results are in good agreement with the orbital interaction analysis. The phase, amplitude, and spatial distribution of the frontier orbitals play an essential role in the design of the electron transport properties through aromatic hydrocarbons.

Solution-processed small molecular electron transport layer for multilayer polymer light-emitting diodes

Solution-processed electron transport layers (ETL) have been fabricated by solution process and applied in multilayer polymer light-emitting diodes with tris[2-(p-tolyl)pyridine]iridium(III) blended in poly(vinylcarbazole) as the emissive layer. Three kinds of small molecular electron transport materials,including 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), 3-(4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ), and 4,7-diphenyl-1,10-phenanthroline (BPhen), are tested and dissolved in methanol to form electron transport layers by blade coating. Such electron transport layer provides efficient electron injection and electron transport ability in the devices. The efficiency of the devices with the combination of ETL and LiF/Al cathode reaches 21.5 cd/A at 10 V (4050 cd/m 2). The efficiency of the devices without ETL are 3.5 cd/A (13 V) for LiF/Al cathode and 17 cd/A (7 V) for CsF/Al cathode at 1000 cd/m 2. The aggregation of the solution-processed ETL can be controlled by annealing temperature to further optimize the device performance to maximal efficiency of 53 cd/A.

A theoretical discussion on the relationships among molecular packings, intermolecular interactions, and electron transport properties for naphthalene tetracarboxylic diimide derivatives

Three naphthalene tetracarboxylic diimide derivatives 1–3 with high electron mobilities and long-term ambient stabilities were investigated employing Marcus–Levich–Jortner formalism at the density functional theory (DFT) level. The complicated relationships among molecular packings, intermolecular interactions, and transport properties for these compounds were focused on and analyzed through investigating the sensitivities of transfer integrals to intermolecular relative orientations, the optimizations of the major transport pathways and the calculations of intermolecular interaction energies by using dispersion-corrected DFT. The results show that the transfer integrals are sensitive to the subtle changes of relative orientations of molecules, especially for core-chlorinated compounds, and there is an interplay between intermolecular interaction and molecular packing. It is found that the transfer integrals associated with the molecular packing motifs of these systems determine their electron mobilities. Interestingly, further discussions on band structures, the anisotropies and temperature dependences of mobilities, and the comparisons of mobilities before and after optimization indicate that the intermolecular packing motifs in the film state may be different from those in the crystalline state for 2. Finally, we hope that our conjecture would facilitate the future design and preparation of high-performance charge-transport materials.

Temperature effects on the atomic arrangement and conductance of atomic-size goldnanowires generated by mechanical stretching

We have studied the changes induced by thermal effects in the structural and transportresponse of Au nanowires generated by mechanical elongation. We have usedtime-resolved atomic resolution transmission electron microscopy imaging andquantum conductance measurement using a mechanically controllable break junction.Our results showed remarkable differences in the NW evolution for experimentsrealized at 150 and 300 K, which modifies drastically the conductance responseduring elongation. Molecular dynamics and electronic transport calculations wereused to consistently correlate the observed structural and conductance behavior.These results emphasize that it is essential to take into account the precise atomicarrangement of nanocontacts generated by mechanical stretching to understand electricaltransport properties. Also, our study shows that much care must be taken whencomparing results obtained in different experimental conditions, mainly differenttemperatures.

Differential conductance as a promising approach for rapid DNA sequencing with nanopore-embedded electrodes

We propose an approach for nanopore-based DNA sequencing using characteristic transverse differential conductance. Molecular dynamics and electron transport simulations show that the transverse differential conductance during the translocation of DNA through the nanopore is distinguishable enough for the detection of the base sequence and can withstand electrical noise caused by DNA structure fluctuation. Our findings demonstrate several advantages of the transverse conductance approach, which may lead to important applications in rapid genome sequencing.

Rigid adamantane tripod linkage for well-defined conductance of a single-molecule junction

We present a systematic analysis of molecular level alignments and electron transport characteristics based on the non-equilibrium Green's function (NEGF) approach combined with density functional theory (DFT) for phenyl dithiol (PDT) derivatives with two different linkages, simple thiol (ST) and tripod-shaped adamantane trithiol (ATT). The substantial adamantane-metal bonds afford a rigid contact structure and well-defined conductance of a single-molecule junction irrespective of interfacial phenomena, which accordingly allows us to utilize the intrinsic nature of the molecule for designing molecular devices with prescribed transport characteristics. We suggest a feasible application of the ATT linkage embedded single-molecule junction to a molecular transistor based on the practical feature of the ATT linkage, which is the unsusceptible behavior of transmission under the applied bias voltage. The present result may serve as an important reference point for designing molecular devices with prescribed transport properties.

Erratum: Critical analysis of a variational method used to describe molecular electron transport [Phys. Rev. B80, 165301 (2009)

Received 21 October 2009DOI:https://doi.org/10.1103/PhysRevB.80.209902©2009 American Physical Society

Critical analysis of a variational method used to describe molecular electron transport

In a recent paper [I.\ B\^aldea and H.\ K\"oppel, \prb {\bf 78}, 115315 (2008)], we showed that a variational approach [P.\ Delaney and J.\ C.\ Greer, \prl {\bf 93}, 036805 (2004)] proposed to compute the electron transport through molecules, which is based on boundary constraints of the Wigner function, is unable to correctly describe the zero-bias conductance of the simplest uncorrelated and correlated systems. In the present paper, we extend our previous analysis of the linear response limit of that approach, by considering, instead of the Wigner function, general constraints. We demonstrate that, if, as usual in transport theories, the quasi-particle distributions in electrodes are constrained, this method yields the completely unphysical result that the zero-bias conductance vanishes. Therefore, we conclude that the variational approach itself is defective.

Decoupling of the processes of molecular oxygen synthesis and electron transport in Ca2+-depleted PSII membranes

Extraction of Ca(2+) from the O(2)-evolving complex (OEC) of photosystem II (PSII) membranes with 2 M NaCl in the light (PSII(-Ca/NaCl)) results in 90% inhibition of the O(2)-evolution reaction. However, electron transfer from the donor to acceptor side of PSII, measured as the reduction of the exogenous acceptor 2,6-dichlorophenolindophenol (DCIP) under continuous light, is inhibited by only 30%. Thus, calcium extraction from the OEC inhibits the synthesis of molecular O(2) but not the oxidation of a substrate we term X, the source of electrons for DCIP reduction. The presence of electron transfer across PSII(-Ca/NaCl) membranes was demonstrated using fluorescence induction kinetics, a method that does not require an artificial acceptor. The calcium chelator, EGTA (5 mM), when added to PSII(-Ca/NaCl) membranes, does not affect the inhibition of O(2) evolution by NaCl but does inhibit DCIP reduction up to 92% (the reason why electron transport in Ca(2+)-depleted materials has not been noticed before). Another chelator, sodium citrate (citrate/low pH method of calcium extraction), also inhibits both O(2) evolution and DCIP reduction. The role of all buffer components (including bicarbonate and sucrose) as possible sources of electrons for PSII(-Ca/NaCl) membranes was investigated, but only the absence of chloride anions strongly inhibited the rate of DCIP reduction. Substitution of other anions for chloride indicates that Cl(-) serves its well-known role as an OEC cofactor, but it is not substrate X. Multiple turnover flash experiments have shown a period of four oscillations of the fluorescence yield (both the maximum level, F(max), and the fluorescence level measured 50 s after an actinic flash in the presence of DCMU) in native PSII membranes, reflecting the normal function of the OEC, but the absence of oscillations in PSII(-Ca/NaCl) samples. Thus, PSII(-Ca/NaCl) samples do not evolve O(2) but do transfer electrons from the donor to acceptor sides and exhibit a disrupted S-state cycle. We explain these results as follows. In Ca(2+)-depleted PSII membranes, obtained without chelators, the oxidation of the OEC stops after the absorption of three quanta of light (from the S1 state), which should convert the native OEC to the S4 state. An one-electron oxidation of the water molecule bound to the Mn cluster then occurs (the second substrate water molecule is absent due to the absence of calcium), and the OEC returns to the S3 state. The appearance of a sub-cycle within the S-state cycle between S3-like and S4-like states supplies electrons (substrate X is postulated to be OH(-)), explains the absence of O(2) production, and results in the absence of a period of four oscillation of the normal functional parameters, such as the fluorescence yield or the EPR signal from S2. Chloride anions probably keep the redox potential of the Mn cluster low enough for its oxidation by Y(Z)(*).

A meshless, spectrally accurate, integral equation solver for molecular surface electrostatics

The need to determine electrostatic fields in domains bounded by molecular surfaces arises in a number of nanotechnology applications including: biomolecule design, carbon nanotube simulation, and molecular electron transport analysis. Molecular surfaces are typically smooth, without the corners common in electrical interconnect problems, but are often so geometrically complicated that numerical evaluation of the associated electrostatic fields is extremely time-consuming. In this paper we describe and demonstrate a meshless spectrally-accurate integral equation method that only requires a description of the molecular surface in the form of a collection of surface points. Our meshless method is a synthesis of techniques, suitably adapted, including: spherical harmonic surface interpolation, spectral-element-like integral equation discretization, integral desingularization via variable transformation, and matrix-implicit iterative matrix solution. The spectral accuracy of this combined method is verified using analytically solvable sphere and ellipsoid problems, and then its accuracy and efficiency is demonstrated numerically by solving capacitance and coupled Poisson/linearized Poisson-Boltzmann problems associated with a commonly used model of a molecule in solution. The results demonstrate that for a tolerance of 10 −3 this new approach reduces the number of unknowns by as much as two orders of magnitude over the more commonly used flat panel methods.