Electric Field Directed Growth of Molecular Wires of Charge Transfer Molecules on Prefabricated Metal Electrodes

Molecular wires of charge transfer molecules were formed by co-evaporating the 7 7 8 8-Tetracyanoquinodimethane [TCNQ] (acceptor) and Tetrathiafulvalene [TTF] (donor) molecules across prefabricated metal electrodes. Molecular wires of TTF TCNQ were also formed by evaporating single complex of TTF:TCNQ across prefabricated metal electrodes The prefabricated metal electrodes were made using electron beam lithography on SiO2 and glass cover slip substrates. Even though TTF: TCNQ wires grown from both co-evaporation and evaporation techniques show semiconductor like behavior in temperature dependence of resistance they show different activation energies due the difference in stoichiometry of TTF and TCNQ.

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.

A novel nanometer-scale "gold electrode-molecular wires-silver" junction: An efficient test bed for electrochemical investigation of electron transportation through molecular wires in self-assembled monolayers

A novel "gold electrode-molecular wires-silver" junction was facilely fabricated for electrochemical study on the electron transportation through molecular wires. Rapid electron transportation through this sandwich-like structure was indeed observed by cyclic voltammograms and ac impedance measurements. Since rather reproducible and reliable results are easily available by electrochemical techniques, it would be an efficient and reliable test bed for electrochemical investigation of charge transportation through molecular wires in self-assembled monolayers on electrodes.

Column chromatographic purification free synthesis of long-chain monodisperse oligo(1,4-phenyleneethynylene)s: towards large-scale automatic synthesis of molecular wires

A facile, mild and rapid solid phase synthetic route free of column chromatographic purification to the synthesis of soluble monodisperse long-chain oligo(1,4-phenyleneethynylene)s is presented.

A rapid solid-phase synthesis to soluble oligothiophene molecular wires

A novel method for the preparation of oligothiophene molecular wires is described via a bi-directional solid-phase synthesis. Using an alternating sequence of bromination and Stille coupling reactions, oligomers were obtained up to the heptamer in excellent yield and purity.

Metal-containing molecular wires and their electron transportation properties

Metal-containing conjugated bisthioester 1 was synthesized. It was fabricated into "gold electrode - molecular wires monolayers - gold nanoparticles" junction using self-assembly and nanoparticles deposition techniques. The junction is suitable for investigating the electron transportation property of molecular wires.

Redox control of thermopower and figure of merit in phase-coherent molecular wires

We demonstrate how redox control of intra-molecular quantum interference in phase-coherent molecular wires can be used to enhance the thermopower (Seebeck coefficient) S and thermoelectric figure of merit ZT of single molecules attached to nanogap electrodes. Using first principles theory, we study the thermoelectric properties of a family of nine molecules, which consist of dithiol-terminated oligo (phenylene-ethynylenes) (OPEs) containing various central units. Uniquely, one molecule of this family possesses a conjugated acene-based central backbone attached via triple bonds to terminal sulfur atoms bound to gold electrodes and incorporates a fully conjugated hydroquinonecentral unit. We demonstrate that both S and the electronic contribution Z el T to the figure of merit ZT can be dramatically enhanced by oxidizing the hydroquinone to yield a second molecule, which possesses a cross-conjugated anthraquinone central unit. This enhancement originates from the conversion of the pi-conjugation in the former to cross-conjugation in the latter, which promotes the appearance of a sharp anti-resonance at the Fermi energy. Comparison with thermoelectric properties of the remaining seven conjugated molecules demonstrates that such large values of S and Z el T are unprecedented. We also evaluate the phonon contribution to the thermal conductance, which allows us to compute the full figure of merit ZT = Z el T/(1 + κ p/κ el), where κ p is the phonon contribution to the thermal conductance and κ el is the electronic contribution. For unstructured gold electrodes, κ p/κ el Gt⃒ 1 and therefore strategies to reduce κ p are needed to realize the highest possible figure of merit.

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.

Molecular conduction: Do time-dependent simulations tell you more than the Landauer approach?

A dynamical method for simulating steady-state conduction in atomic and molecular wires is presented which is both computationally and conceptually simple. The method is tested by calculating the current-voltage spectrum of a simple diatomic molecular junction, for which the static Landauer approach produces multiple steady-state solutions. The dynamical method quantitatively reproduces the static results and provides information on the stability of the different solutions. (c) 2006 American Institute of Physics.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.

The calcite(10-14) surface: a versatile substrate for molecular self-assembly

This thesis presents a detailed and successful study of molecular self-assembly on the calcite CaCO3(10-14) surface. One reason for the superior applicability of this particular surface is given by reflecting the well-known growth modes. Layer-by-layer growth, which is a necessity for the formation of templated two-dimensional (2D) molecular structures, is particularly favoured on substrates with a high surface energy. The CaCO3(10-14) surface is among those substrates and, thus, most promising. rnrnAll experiments in this thesis were performed using the non-contact atomic force microscope (NC-AFM) under ultra-high vacuum conditions. The acquisition of drift-free data became in this thesis possible owing to the herein newly developed atom-tracking system. This system features a lateral tip-positioning precision of at least 50pm. Furthermore, a newly developed scan protocol was implemented in this system, which allows for the acquisition of dense three-dimensional (3D) data under room-temperature conditions. An entire 3D data set from a CaCO3(10-14) surface consisting of 85x85x500 pixel is discussed. rnrnThe row-pairing and (2x1) reconstructions of the CaCO3(10-14) surface constitute most interesting research subjects. For both reconstructions, the NC-AFM imaging was classified to a total of 12 contrast modes. Eight of these modes were observed within this thesis, some of them for the first time. Together with literature findings, a total of 10 modes has been observed experimentally to this day. Some contrast modes presented themselves as highly distance-dependent and at least for one contrast mode, a severe tip-termination influence was found. rnrnMost interestingly, the row-pairing reconstruction was found to break a symmetry element of the CaCO3(10-14) surface. With the presence of this reconstruction, the calcite (10-14) surface becomes chiral. From high-resolution NC-AFM data, the identification of the enantiomers is here possible and is presented for one enantiomer in this thesis. rnrnFive studies of self-assembled molecular structures on calcite (10-14) surfaces are presented. Only for one system, namely HBC/CaCO3(10-14), the formation of a molecular bulk structure was observed. This well-known occurence of weak molecule-insulator interaction hinders the investigation of two-dimensional molecular self-assembly. It was, however, possible to force the formation of an island phase for this system upon following a variable-temperature preparation. rnFor the C60/CaCO3(10-14) system it is most notably that no branched island morphologies were found. Instead, the first C60 layer appeared to wet the calcite surface. rnrnIn all studies, the molecules arranged themselves in ordered superstructures. A templating effect due to the underlying calcite substrate was evident for all systems. This templating strikingly led either to the formation of large commensurate superstructures, such as (2x15) with a 14 molecule basis for the C60/CaCO3(10-14) system, or prevented the vast growth of incommensurate molecular motifs, such as the chicken-wire structure in the trimesic acid (TMA)/CaCO3(10-14) system. rnrnThe molecule-molecule and the molecule-substrate interaction was increased upon choosing molecules with carboxylic acid moieties in the third, fourth and fifth study, using terephthalic acid, TMA and helicene molecules. In all these experiments, hydrogen-bonded assemblies were created. rnrnDirected hydrogen bond formation combined with intermolecular pi-pi interaction is employed in the fifth study, where the formation of uni-directional molecular "wires" from single helicene molecules succeeded. Each "wire" is composed of heterochiral helicene pairs, well-aligned along the [01-10] substrate direction and stabilised by pi-pi interaction.

Quantum transport in a single molecular junction

The craze for faster and smaller electronic devices has never gone down and this has always kept researchers on their toes. Following Moore’s law, which states that the number of transistors in a single chip will double in every 18 months, today “30 million transistors can fit into the head of a 1.5 mm diameter pin”. But this miniaturization cannot continue indefinitely due to the ‘quantum leakage’ limit in the thickness of the insulating layer between the gate electrode and the current carrying channel. To bypass this limitation, scientists came up with the idea of using vastly available organic molecules as components in an electronic device. One of the primary challenges in this field was the ability to perform conductance measurements across single molecular junctions. Once that was achieved the focus shifted to a deeper understanding of the underlying physics behind the electron transport across these molecular scale devices. Our initial theoretical approach is based on the conventional Non-Equilibrium Green Function(NEGF) formulation, but the self-energy of the leads is modified to include a weighting factor that ensures negligible current in the absence of a molecular pathway as observed in a Mechanically Controlled Break Junction (MCBJ) experiment. The formulation is then made parameter free by a more careful estimation of the self-energy of the leads. The calculated conductance turns out to be atleast an order more than the experimental values which is probably due to a strong chemical bond at the metal-molecule junction unlike in the experiments. The focus is then shifted to a comparative study of charge transport in molecular wires of different lengths within the same formalism. The molecular wires, composed of a series of organic molecules, are sanwiched between two gold electrodes to make a two terminal device. The length of the wire is increased by sequentially increasing the number of molecules in the wire from 1 to 3. In the low bias regime all the molecular devices are found to exhibit Ohmic behavior. However, the magnitude of conductance decreases exponentially with increase in length of the wire. In the next study, the relative contribution of the ‘in-phase’ and the ‘out-of-phase’ components of the total electronic current under the influence of an external bias is estimated for the wires of three different lengths. In the low bias regime, the ‘out-of-phase’ contribution to the total current is minimal and the ‘in-phase’ elastic tunneling of the electrons is responsible for the net electronic current. This is true irrespective of the length of the molecular spacer. In this regime, the current-voltage characteristics follow Ohm’s law and the conductance of the wires is found to decrease exponentially with increase in length which is in agreement with experimental results. However, after a certain ‘off-set’ voltage, the current increases non-linearly with bias and the ‘out-of-phase’ tunneling of electrons reduces the net current substantially. Subsequently, the interaction of conduction electrons with the vibrational modes as a function of external bias in the three different oligomers is studied since they are one of the main sources of phase-breaking scattering. The number of vibrational modes that couple strongly with the frontier molecular orbitals are found to increase with length of the spacer and the external field. This is consistent with the existence of lowest ‘off-set’ voltage for the longest wire under study.

Electron transport in molecular systems

The remarkable advances in nanoscience and nanotechnology over the last two decades allow one to manipulate individuals atoms, molecules and nanostructures, make it possible to build devices with only a few nanometers, and enhance the nano-bio fusion in tackling biological and medical problems. It complies with the ever-increasing need for device miniaturization, from magnetic storage devices, electronic building blocks for computers, to chemical and biological sensors. Despite the continuing efforts based on conventional methods, they are likely to reach the fundamental limit of miniaturization in the next decade, when feature lengths shrink below 100 nm. On the one hand, quantum mechanical efforts of the underlying material structure dominate device characteristics. On the other hand, one faces the technical difficulty in fabricating uniform devices. This has posed a great challenge for both the scientific and the technical communities. The proposal of using a single or a few organic molecules in electronic devices has not only opened an alternative way of miniaturization in electronics, but also brought up brand-new concepts and physical working mechanisms in electronic devices. This thesis work stands as one of the efforts in understanding and building of electronic functional units at the molecular and atomic levels. We have explored the possibility of having molecules working in a wide spectrum of electronic devices, ranging from molecular wires, spin valves/switches, diodes, transistors, and sensors. More specifically, we have observed significant magnetoresistive effect in a spin-valve structure where the non-magnetic spacer sandwiched between two magnetic conducting materials is replaced by a self-assembled monolayer of organic molecules or a single molecule (like a carbon fullerene). The diode behavior in donor(D)-bridge(B)-acceptor(A) type of single molecules is then discussed and a unimolecular transistor is designed. Lastly, we have proposed and primarily tested the idea of using functionalized electrodes for rapid nanopore DNA sequencing. In these studies, the fundamental roles of molecules and molecule-electrode interfaces on quantum electron transport have been investigated based on first-principles calculations of the electronic structure. Both the intrinsic properties of molecules themselves and the detailed interfacial features are found to play critical roles in electron transport at the molecular scale. The flexibility and tailorability of the properties of molecules have opened great opportunity in a purpose-driven design of electronic devices from the bottom up. The results that we gained from this work have helped in understanding the underlying physics, developing the fundamental mechanism and providing guidance for future experimental efforts.

Spectroscopic investigation of the polymerisation of pyrrole and thiophene within zeolite channels

The reaction of pyrrole and thiophene monomers with copper- or nickel-exchanged mordenite has been investigated using X-ray photoelectron (XPS) and photoacoustic infrared (PAIRS) spectroscopies. Because of the differing oxidising powers of the cations studied, polymerisation occurred only with copper-exchanged mordenite. PAIRS and XPS data indicated that both polypyrrole and polythiophene were partially oxidised when synthesised within the zeolite structure. IR spectra of polythiophene and polythiophene and polypyrrole showed intense bands typical of ring vibrations which could couple to the large dipole change induced by charges moving along the polythiophene chain. In addition it was noted that only vibrations typical of oxidised polymer structures were recorded, suggesting that the charge carrier was located within these segments. Furthermore, N 1s spectra contained a high binding energy peak at 402.5 eV which was attributed to a positively charged nitrogen species, in agreement with IR data. Significantly, C 1s spectra confirmed that molecular wires were formed within the confines of the zeolite lattice. Depth-profiling experiments suggested that polypyrrole was distributed throughout the entire zeolite host. By contrast, polythiophene may have been restricted to the uppermost zeolite channels owing to the ability of sulfur species to bond to CuI sites [produced by reduction of copper(II) ions during the polymerisation process], thus obstructing movement along the channels.

Dynamics of quantum dissipation systems interacting with fermion and boson grand canonical bath ensembles: Hierarchical equations of motion approach

A hierarchical equations of motion formalism for a quantum dissipation system in a grand canonical bath ensemble surrounding is constructed on the basis of the calculus-on-path-integral algorithm, together with the parametrization of arbitrary non-Markovian bath that satisfies fluctuation-dissipation theorem. The influence functionals for both the fermion or boson bath interaction are found to be of the same path integral expression as the canonical bath, assuming they all satisfy the Gaussian statistics. However, the equation of motion formalism is different due to the fluctuation-dissipation theories that are distinct and used explicitly. The implications of the present work to quantum transport through molecular wires and electron transfer in complex molecular systems are discussed. (c) 2007 American Institute of Physics.