We investigate gold-4,4'-bipyridine-gold single-molecule junctions with the mechanically controllable break junction technique at cryogenic temperature ($T=4.2\,\text{K}$). We observe bistable probabilistic conductance switching between the two molecular binding configurations, influenced both by the mechanical actuation, and the applied voltage. We demonstrate that the relative dominance of the two conductance states is tunable by the electrode displacement, whereas the voltage manipulation induces an exponential speedup of both switching times. The detailed investigation of the voltage-tunable switching rates provides an insight into the possible switching mechanisms.
Understanding the formation of metal-molecule contact at the microscopic level is the key towards controlling and manipulating atomic scale devices. Employing two isomers of bipyridine, $4, 4^\prime$ bipyridine and $2, 2^\prime$ bipyridine between gold electrodes, here, we investigate the formation of metal-molecule bond by studying charge transport through single molecular junctions using a mechanically controlled break junction technique at room temperature. While both molecules form molecular junctions during the breaking process, closing traces show the formation of molecular junctions una…
The formation of gold nanowires in vacuum at room temperature reveals a periodic spectrum of exceptionally stable diameters. This is identified as shell structure similar to that which was recently discovered for alkali metals at low temperatures. The gold nanowires present two competing `magic' series of stable diameters, one governed by electronic structure and the other by the atomic packing.
In this paper an experimental study of the interaction of hydrogen molecules with gold nanowires is presented. Our results show, that chains of Au atoms can also be pulled in hydrogen environment, however in this case the conductance of the chain is strongly reduced compared to the perfect transmission of pure Au chains. The comparison of our experiments with recent theoretical prediction for the hydrogen welding of Au nanowires implies that a hydrogen molecule can even be incorporated in the gold nanocontact, and this hydrogen clamp is strong enough to pull a chain of gold atoms.
Molecular dynamics calculations revealed that the temperature of operation and the applied tensile force (f) determine not only the kinetics but also the mode and duration of Au nanowire breaking. In the tensile force range of 0.018 and 0.1 nN/atom, structure transformation of the wire occurs prior to breaking at random positions. The gold wire breaks abruptly when the f is stronger than 0.1nN/atom but no rupture occurs at all when the f is weaker than 0.018 nN/atom. At higher temperatures and under stronger tensile forces, the wire breaks even faster.
We have investigated the stability and conductivity of unsupported, two dimensional infinite gold nanowires using ab-initio density functional theory (DFT). Two dimensional ribbon like nanowires, with 1-5 rows of gold atoms in the non-periodic direction and with different possible structures have been considered. The nanowires with > 2 rows of atoms exhibit dimerization, similar to finite wires, along the non-periodic direction. Our results show that in these zero thickness nanowires, the parallelogram motif is the most stable. A comparison between parallelogram and rectangular shaped nanowire…
The vibrations of gold nanowires and nanorods are investigated numerically in the framework of continuum elasticity using the Rayleigh-Ritz variational method. Special attention is paid to identify the vibrations relevant in Raman scattering experiments. A comprehensive description of the vibrations of nanorods is proposed by determining their symmetry, comparing with standing waves in the corresponding nanowires and estimating their Raman intensity. The role of experimentally relevant parameters such as the anisotropic cubic lattice structure, the presence of faceted lateral surfaces and the …
Carrier dynamics in metallic nanostructures is strongly influenced by their confining dimensions. Gold nanoparticles of size $\sim 2$ nm lie at the boundary separating metallic and non-metallic behavior. In this work, we report carrier dynamics in high aspect ratio ultrathin gold nanowires (Au-UNWs) of average diameter $\sim$2 nm using pump (3.1 eV) and coherent white light continuum as probe in the spectral range of 1.15 eV to 2.75 eV. The transient carrier dynamics in Au-UNWs under extreme excitation regime is slower than predicted by the often used two temperature model. We identify Auger-a…
Nanoscale structuring holds promise to improve thermoelectric properties of materials for energy conversion and photodetection. We report a study of the spatial distribution of the photothermoelectric voltage in thin-film nanowire devices fabricated from single metal. A focused laser beam is used to locally heat the metal nanostructure via a combination of direct absorption and excitation of a plasmon resonance in Au devices. As seen previously, in nanowires shorter than the spot size of the laser, we observe a thermoelectric voltage distribution that is consistent with the local Seebeck coeff…
We extend our previous shell effect observation in gold nanowires at room temperature under ultra high vacuum to the other two noble metals: silver and copper. Similar to gold, silver nanowires present two series of exceptionally stable diameters related to electronic and atomic shell filling. This observation is in concordance to what was previously found for alkali metal nanowires. Copper however presents only electronic shell filling. Remarkably we find that shell structure survives under ambient conditions for gold and silver.
We investigate how the insertion of an oxygen atom in an atomically thin gold nanowire can affect its rupture. We find, using ab initio total energy density functional theory calculations, that O atoms when inserted in gold nanowires form not only stable but also very strong bonds, in such a way that they can extract atoms from a stable tip, serving in this way as a clamp that could be used to pull a string of gold atoms.
Applying ac voltages, we trapped gold nanoparticles between microfabricated electrodes under well-defined conditions. We demonstrate that the nanoparticles can be controllably fused together to form homogeneous gold nanowires with pre-defined diameters and conductance values. Whereas electromigration is known to form a gap when a dc voltage is applied, this ac technique achieves the opposite, thereby completing the toolkit for the fabrication of nanoscale junctions.
We report quantitative electrical admittance measurements of diffusive superconductor--normal-metal--superconductor (SNS) junctions at gigahertz frequencies and millikelvin temperatures. The gold-palladium-based SNS junctions are arranged into a chain of superconducting quantum interference devices. The chain is coupled strongly to a multimode microwave resonator with a mode spacing of approximately 0.6 GHz. By measuring the resonance frequencies and quality factors of the resonator modes, we extract the dissipative and reactive parts of the admittance of the chain. We compare the phase and te…
In this paper the influence of adsorbed hydrogen on the behavior of gold nanojunctions is investigated. It is found, that the hydrogen environment has a strong effect on the conductance of atomic-sized gold junctions, which is markedly reflected by the growth of an additional peak in the conductance histogram at 0.5 quantum unit, 2e^2/h. The statistical analysis of the conductance traces implies that the new peak arises due to the hydrogen-assisted distortion of atomic gold chains.
We show in this paper that it is possible to induce superconducting vortices in a gold nanowire connected to superconducting electrodes. The gold nanowire acquires superconductivity by the proximity effect. The differential magnetoresistance of the nanowire beyond a critical magnetic field shows uniform oscillations with increasing field with a period of \phi0/(2\pir^2) (\phi0 = h/2e is the superconducting flux quantum, r = 35 nm is the radius of the nanowire). We demonstrate that these periodic oscillations are the signatures of the sequential generation and moving of vortices across the gold…
Nanowires of different nature have been shown to self-assemble as a function of stress at the contact between two macroscopic metallic leads. Here we demonstrate for gold wires that the balance between various metastable nanowire configurations is influenced by the microstructure of the starting materials and we discover a new set of periodic structures, which we interpret as due to the atomic discreteness of the contact size for the three principal crystal orientations.
Controlled electromigration of gold nanowires of different cross-sectional areas to form nanogap junctions is studied using a feedback method. A linear correlation between the cross sectional area of the gold nanowires and the power dissipated in the junction during electromigration is observed, indicating that the feedback mechanism operates primarily by controlling the temperature of the junction during electromigration. We also show that the role of the external feedback circuit is to prevent thermal runaway; minimization of series resistance allows controlled electromigration to a signific…
Semiconductor nanowires offer the opportunity to incorporate novel structures and functionality into electronic and optoelectronic devices. A clear understanding of the nanowire growth mechanism is essential for well-controlled growth of structures with desired properties, but the understanding is currently limited by a lack of empirical measurements of important parameters during growth, such as catalyst particle composition. However, this is difficult to accurately determine by investigating post-growth. We report direct measurement of the catalyst composition of individual gold seeded GaAs …
We show in this paper that the heat generated by the optical excitation of resonant plasmonic antennas and diffusing along a simple glass/air interface disturbs the electron transport of a nearby conductive element. By probing the temperature-dependent resistance of a gold nanowire $R_{\rm nw}(T)$, we quantitatively analyze the impact of a resonant absorption of the laser by the antennas. We find that the temperature rise at the nanowire induced by the laser absorption of a distant nanoparticle may exceed that of a direct illumination of the nanowire itself. We also find that a global temperat…
We review recent results on electronic and thermal transport in two different quasi one-dimensional systems: Silicon nanowires (SiNW) and atomic gold chains. For SiNW's we compute the ballistic electronic and thermal transport properties on equal footing, allowing us to make quantitative predictions for the thermoelectric properties, while for the atomic gold chains we evaluate microscopically the damping of the vibrations, due to the coupling of the chain atoms to the modes in the bulk contacts. Both approaches are based on a combination of density-functional theory, and nonequilibrium Green'…
We report comprehensive high-accuracy molecular dynamics simulations using the ReaxFF forcefield to explore the structural changes that occur as Au nanowires are elongated, establishing trends as a function of both temperature and nanowire diameter. Our simulations and subsequent quantitative structural analysis reveal that polytetrahedral structures (e.g., icosahedra) form within the "amorphous" neck regions, most prominently for systems with small diameter at high temperature. We demonstrate that the formation of polytetrahedra diminishes the conductance quantization as compared to systems w…
Molecular-scale components are expected to be central to nanoscale electronic devices. While molecular-scale switching has been reported in atomic quantum point contacts, single-molecule junctions provide the additional flexibility of tuning the on/off conductance states through molecular design. Thus far, switching in single-molecule junctions has been attributed to changes in the conformation or charge state of the molecule. Here, we demonstrate reversible binary switching in a single-molecule junction by mechanical control of the metal-molecule contact geometry. We show that 4,4'-bipyridine…
Using molecular dynamics simulations, we study the impact of physisorbing adsorbates on the structural and mechanical evolution of gold nanowires (AuNWs) undergoing elongation. We used various adsorbate models in our simulations, with each model giving rise to a different surface coverage and mobility of the adsorbed phase. We find that the local structure and mobility of the adsorbed phase remains relatively uniform across all segments of an elongating AuNW, except for the thinning region of the wire where the high mobility of Au atoms disrupts the monolayer structure, giving rise to higher s…
Recent experiments have shown that transport properties of molecular-scale devices can be reversibly altered by the surrounding solvent. Here, we use a combination of first-principles calculations and experiment to explain this change in transport properties through a shift in the local electrostatic potential at the junction caused by nearby conducting and solvent molecules chemically bound to the electrodes. This effect is found to alter the conductance of bipyridine - gold junctions by more than 50%. Moreover, we develop a general electrostatic model that quantitatively predicts the relatio…
Single-molecule break junction measurements deliver a huge number of conductance vs.\ electrode separation traces. Along such measurements the target molecules may bind to the electrodes in different geometries, and the evolution and rupture of the single-molecule junction may also follow distinct trajectories. The unraveling of the various typical trace classes is a prerequisite of the proper physical interpretation of the data. Here we exploit the efficient feature recognition properties of neural networks to automatically find the relevant trace classes. To eliminate the need for manually l…
We introduce scanning-probe-assisted nanowire circuitry (SPANC) as a new method to fabricate electrodes for the characterization of electrical transport properties at the nanoscale. SPANC uses an atomic force microscope (AFM) to manipulate nanowires to create complex and highly conductive nanostructures (paths) that work as nanoelectrodes, allowing connectivity and electrical characterization of other nano-objects. The paths are formed by the spontaneous cold welding of gold nanowires upon mechanical contact, leading to an excellent contact resistance of about 9 Ohms/junction. SPANC is an easy…
Recent experimental realization [J. Am. Chem. Soc., 127 (2005) 7328] of various dithiocarbamate self assembly on gold surface opens the possibility for use of dithiocarbamate linkers to anchor molecular wires to gold electrodes. In this paper, we explore this hypothesis computationally. We computed the electron transport properties of 4,4'-bipyridine (BP), 4,4'-bipyridinium-1,1'-bis(carbodithioate) (BPBC), 4-(4'-pyridyl)-peridium-1-carbodithioate (BPC) molecule junctions based on the density functional theory and non-equilibrium Green's functions. We demonstrated that the stronger molecule-ele…
We report on observation of coherent electron transport in suspended high-quality InAs nanowire-based devices. The InAs nanowires were grown by low-temperature gold-assisted vapor-liquid-solid molecular-beam-epitaxy. The high quality of the nanowires was achieved by removing the typically found stacking-faults and reducing possible Au incorporation. Minimizing substrate-induced scattering in the device was achieved by suspending the nanowires over predefined grooves. Coherent transport involving more than a single one-dimensional mode transport, was observed in the experiment, manifested by Fa…
Understanding the transport characteristics at the atomic limit is the prerequisite for futuristic nano-electronic applications. Among various experimental procedures, mechanically controllable break junction (MCBJ) is one of the well adopted experimental technique to study and control the atomic or molecular scale devices. Here, we present the details of the development of a piezo controlled table top MCBJ set up, working at ambient condition, along with necessary data acquisition technique and analysis of the data. We performed conductance experiment on a macroscopic gold wire, which exhibit…
We examine theoretically the effects of the bonding geometries at the gold-thiol interfaces on the inelastic tunneling spectra of propanedithiolate (PDT) molecules bridging gold electrodes and show that inelastic tunneling spectroscopy combined with theory can be used to determine these bonding geometries experimentally. With the help of density functional theory, we calculate the relaxed geometries and vibrational modes of extended molecules each consisting of one or two PDT molecules connecting two gold nanoclusters. We formulate a perturbative theory of inelastic tunneling through molecules…
Atomic nanowires on semiconductor surfaces induced by the adsorption of metallic atoms have attracted a lot of attention as possible hosts of the elusive, Tomonaga-Luttinger liquid. The Au/Ge(100) system in particular is the subject of controversy as to whether the Au-induced nanowires do indeed host exotic, 1D metallic states. We report on a thorough study of the electronic properties of high quality nanowires formed at the Au/Ge(100) surface. High resolution ARPES data show the low-lying Au-induced electronic states to possess a dispersion relation that depends on two orthogonal directions i…
ZnSe nanowire heterostructures were grown by molecular beam epitaxy in the vapour-liquid-solid growth mode assisted by gold catalysts. Size, shape and crystal structure are found to strongly depend on the growth conditions. Both, zinc-blende and wurtzite crystal structures are observed using transmission electron microscopy. At low growth temperature, cone-shaped nano-needles are formed. For higher growth temperature, the nanowires are uniform and have a high aspect ratio with sizes of 1-2 $μ$m in length and 20-50 nm in width as observed by scanning electron microscopy. Growing a nanowire on t…
Experimental conductance histograms built from several thousand successive breakings of sodium nanowires exhibit peaks up to rather high conductance values (100 x 2e^2/h). In this paper, we present results from a disordered free-electron model of a metallic nanowire, which was previously successful in describing both conductance histograms and shot noise measurements in gold nanocontacts with much lower conductances. We find in particular that, with a modification of the model of disorder, the conductance histogram can be understood as an interplay of conductance quantization and disorder for …
Spin-density-functional calculations of tip-suspended gold chains, with molecular oxygen, or dissociated oxygen atoms, incorporated in them, reveal structural transitions for varying lengths. The nanowires exhibit enhanced strength for both oxygen incorporation modes, and upon stretching tip atoms join the wire. With incorporated molecular oxygen the wire conductance is about 1(2e2/h), transforming to an insulating state beyond a critical length. The nanowire conductance with embedded oxygen atoms is low, 0.2 (2e2/h), and it develops magnetic moments localized on the oxygens and the neighborin…
Gold-Silver (Au-Ag) core-shell nanostructures are gaining importance in stretchable electronics where high tensile and fatigue resistance is of paramount importance. This work proposes the parameterization of a modified embedded atomic model (MEAM) interatomic potential through density functional theory (DFT) calculations for investigating the role of dislocations and defect interaction governing the mechanical behavior of Au-Ag and Ag-Au Core-shell nanostructures under tensile and fatigue loading using molecular dynamics (MD) simulations. A comparative analysis between the Core-shell structur…
Ab-initio total energy calculations reveal benzene-dithiolate (BDT) molecules on a gold surface, contacted by a monoatomic gold STM tip to have two classes of low energy conformations with differing symmetries. Lateral motion of the tip or excitation of the molecule cause it to change from one conformation class to the other and to switch between a strongly and a weakly conducting state. Thus, surprisingly, despite their apparent simplicity these Au/BDT/Au nanowires are shown to be electrically bi-stable switches, the smallest two-terminal molecular switches to date. Experiments with a convent…
Understanding the process of electron tunneling in chirality-induced single-molecule junctions is imperative for the development of nanoscale switching and artificial nanomotors. Based on the combined non-equilibrium Green functions formalism and the ground-state density functional theory, we present here the charge transport behavior of chiral gold (7,3) nanowires (NWs) in comparison with various other chiral and achiral 1D gold nanostructures as the principal leads to form stable single-molecule junctions. For sigma-saturated alkane chains, we find that the contact potential barriers vary wi…
We consider theoretically the spaser excited electrically via a nanowire with ballistic quantum conductance. We show that in the extreme quantum regime, i.e., for a single conductance-quantum nanowire, the spaser with the core made of common plasmonic metals, such as silver and gold, is fundamentally possible. For ballistic nanowires with multiple-quanta or non-quantized conductance, the performance of the spaser is enhanced in comparison with the extreme quantum limit. The electrically-pumped spaser is promising as an optical source, nanoamplifier, and digital logic device for optoelectronic …
Cutting-edge research in the band engineering of nanowires at the ultimate fine scale is related to the minimum scale of a nanowire-based device. The fundamental issue at the subnanometre scale is whether angle-resolved photoemission spectroscopy (ARPES) can be used to directly measure the momentum-resolved electronic structure of a single wire because of the difficulty associated with assembling single wire into an ordered array for such measurements. Here, we demonstrated that the one-dimensional (1D) confinement of electrons, which are transferred from external dopants, within a single subn…
Realizing single photon sources emitting in the telecom band on silicon substrates is essential to reach complementary-metal-oxide-semiconductor (CMOS) compatible devices that secure communications over long distances. In this work, we propose the monolithic growth of needlelike tapered InAs/InP quantum dot-nanowires (QD-NWs) on silicon substrates with a small taper angle and a nanowire diameter tailored to support a single mode waveguide. Such a NW geometry is obtained by a controlled balance over axial and radial growths during the gold-catalyzed growth of the NWs by molecular beam epitaxy. …
The continuing miniaturization of microelectronics raises the prospect of nanometre-scale devices with mechanical and electrical properties that are qualitatively different from those at larger dimensions. The investigation of these properties, and particularly the increasing influence of quantum effects on electron transport, has therefore attracted much interest. Quantum properties of the conductance can be observed when `breaking' a metallic contact: as two metal electrodes in contact with each other are slowly retracted, the contact area undergoes structural rearrangements until it consist…
