We present quantum-based simulations of single grain boundary reflectivity of electrons in metals, Cu and Ag. We examine twin and non-twin grain boundaries using non-equilibrium Green's function and first principles methods. We also investigate the mechanism of reflectivity in grain boundaries by modeling atomic vacancies, disorder, and orientation and find that the change in grain orientation and disorder in the boundary itself both contribute significantly to reflectivity. We find that grain boundary reflectivity may vary widely depending on the grain boundary structure consistent with experimental results. Finally, we examine the reflectivity from multiple grain boundaries and find that grain boundary reflectivity may depend on neighboring grain boundaries. This study based on detailed numerical techniques reveals some potential limitations in the independent grain boundary assumptions of the Mayadas-Shatzkes model.
We have investigated atomic and electronic structure of grain boundaries in monolayer MoS2, where relative angles between two different grains are 0 and 60 degree. The grain boundaries with specific relative angle have been formed with chemical vapor deposition growth on graphite and hexagonal boron nitride flakes; van der Waals interlayer interaction between MoS2 and the flakes restricts the relative angle. Through scanning tunneling microscopy and spectroscopy measurements, we have found that the perfectly stitched structure between two different grains of MoS2 was realized in the case of th…
Despite the structures and properties of tilt grain boundaries of graphite surface and graphene have been extensively studied, their effect on the structures and electronic spectra of graphene layers has not been fully addressed. Here we study effects of one-dimensional tilt grain boundaries on structures and electronic spectra of graphene multilayers by scanning tunneling microscopy and spectroscopy. A tilt grain boundary of a top graphene sheet in graphene multilayers leads to a twist between consecutive layers and generates superstructures (Moiré patterns) on one side of the boundary. Our r…
Molecular dynamics simulations were used to quantify mechanically-induced structural evolution in nanocrystalline Al with an average grain size of 5 nm. A polycrystalline sample was cyclically strained at different temperatures, while a recently developed grain tracking algorithm was used to measure the relative contributions of novel deformation mechanisms such as grain rotation and grain sliding. Sample texture and grain size were also tracked during cycling, to show how nanocrystalline plasticity rearranges overall grain structure and alters the grain boundary network. While no obvious text…
The magnetic and electronic properties of metal phthalocyanines (MPc) and fluorinated metal phthalocyanines (F$_{16}$MPc) are studied by means of spin density functional theory (SDFT). Several metals (M) such as Ca, all first d-row transition metals and Ag are investigated. By considering different open shell transition metals it is possible to tune the electronic properties of MPc, in particular the electronic molecular gap and total magnetic moment. Besides assigning the structural and electronic properties of MPc and F$_{16}$MPc, the vibrational modes analysis of the ScPc\textendash ZnPc se…
The evolution of electronic wave packets (WPs) through grain boundaries (GBs) of various structures in graphene was investigated by the numerical solution of the time-dependent Schroedinger equation. WPs were injected from a simulated STM tip placed above one of the grains. Electronic structure of the GBs was calculated by ab-initio and tight-binding methods. Two main factors governing the energy dependence of the transport have been identified: the misorientation angle of the two adjacent graphene grains and the atomic structure of the GB. In case of an ordered GB made of a periodic repetitio…
Recent experiments suggest that Bi impurities segregate to form bilayer films on Ni and Cu grain boundaries but do not segregate in Fe. To explain these phenomena, we study the total energies of Bi films on transition metal (TM) $Σ$3(111) and $Σ$5(012) GBs using density functional theory. Our results agree with the observed stabilities. We propose a model to predict Bi bilayer stability at Ni GBs which suggests that Bi bilayer is not stable on (111) twist CSL GBs but is stable in most (100) twist CSL GBs. We investigate the interaction and bonding character between Bi and TMs to explain the di…
The embrittlement of metallic alloys by liquid metals leads to catastrophic material failure and severely impacts their structural integrity. The weakening of grain boundaries by the ingress of liquid metal and preceding segregation in the solid are thought to promote early fracture. However, the potential of balancing between the segregation of cohesion-enhancing interstitial solutes and embrittling elements inducing grain boundary decohesion is not understood. Here, we unveil the mechanisms of how boron segregation mitigates the detrimental effects of the prime embrittler, zinc, in a $Σ5\,[0…
Molecular dynamics simulations are used to investigate strain localization in a model nanocrystalline metal. The atomic mechanisms of such catastrophic failure are first studied for two grain sizes of interest. Detailed analysis shows that the formation of a strain path across the sample width is crucial, and can be achieved entirely through grain boundary deformation or through a combination of grain boundary sliding and grain boundary dislocation emission. Pronounced mechanically-induced grain growth is also found within the strain localization region. The effects of testing conditions on st…
We perform a MonteCarlo simulation in order to study the connection between the morphology and the transport properties of grain boundaries (GBs) in graphene. We explore the configurational space of GBs to generate ensembles of realistic models of disordered interfaces between graphene misoriented domains. Among other observables, transmission across GBs has been probed all along the simulation, thus making us able to establish a connection between averaged transmission and the topological invariant of GBs, the misorientation angle. We extend to disordered GBs the remarkable result that the lo…
The success of all-graphene electronics is severely hindered by the challenging realization and subsequent integration of semiconducting channels and metallic contacts. Here, we comprehensively investigate the electronic transport across width-modulated heterojunctions consisting of a graphene quantum dot of varying lengths and widths embedded in a pair of armchair-edged metallic nanoribbons, of the kind recently fabricated via on-surface synthesis. We show that the presence of the quantum dot enables the opening of a width-dependent transport gap, thereby yielding built-in one-dimensional met…
Grain boundary complexions have been observed to affect the mechanical behavior of nanocrystalline metals, improving both strength and ductility. While an explanation for the improved ductility exists, the observed effect on strength remains unexplained. In this work, we use atomistic simulations to explore the influence of ordered and disordered complexions on two deformation mechanisms which are essential for nanocrystalline plasticity, namely dislocation emission and propagation. Both ordered and disordered grain boundary complexions in Cu-Zr are characterized by excess free volume and prom…
Graphene, a two-dimensional honeycomb lattice of carbon atoms, is of great interest in (opto)electronics and plasmonics and can be obtained by means of diverse fabrication techniques, among which chemical vapor deposition (CVD) is one of the most promising for technological applications. The electronic and mechanical properties of CVD-grown graphene depend in large part on the characteristics of the grain boundaries. However, the physical properties of these grain boundaries remain challenging to characterize directly and conveniently. Here, we show that it is possible to visualize and investi…
We calculate the resistivity contribution of tilted grain boundaries with varying parameters in sub-10nm diameter metallic nanowires. The results have been obtained with the Boltzmann transport equation and Fermi's golden rule, retrieving correct state-dependent relaxation times. The standard approximation schemes for the relaxation times are shown to fail when grain boundary tilt is considered. Grain boundaries tilted under the same angle or randomly tilted induce a resistivity decrease.
A modeling approach, based on an analytical solution of the semiclassical multi-subband Boltzmann transport equation, is presented to study resistivity scaling in metallic thin films and nanowires due to grain boundary and surface roughness scattering. While taking into account the detailed statistical properties of grains, roughness and barrier material as well as the metallic band structure and quantum mechanical aspects of scattering and confinement, the model does not rely on phenomenological fitting parameters.
We study the fluctuation conductivity of superconducting granular metals at low temperatures and strong magnetic field destroying the Cooper pairs. Explicit calculations are performed for larger values of the coupling between the grains than those considered in previous works. We show that in a broad region of the coupling constants the superconducting fluctuations still significantly reduce the conductivity leading to a negative magnetoresistance.
We present a theory of mesoscopic fluctuations of g tensors and avoided crossing energies in a small metal grain. The model, based on random matrix theory, contains both the orbital and spin contributions to the g tensor. The two contributions can be experimentally separated for weak spin-orbit coupling while they merge in the strong coupling limit. For intermediate coupling, substantial correlations are found between g factors of neighboring levels.
We study the effect of the exchange interactions in small superconducting grains near the Coulomb blockade regime. We extend the standard description of the grain in terms of a single collective variable, the charge and its conjugated phase, to include the spin degree of freedom. The suppression of spin fluctuations enhances the tendency towards Coulomb blockade. The effective charging energy and conductance are calculated numerically in the regime of large grain-lead coupling.
We study Coulomb blockade effects in the thermodynamic quantities of a weakly disordered metallic grain coupled to a metallic lead by a tunneling contact with a large conductance $g_T$. We consider the case of broken time-reversal symmetry and obtain expressions for both the {\em ensemble averaged} amplitude of the Coulomb blockade oscillations of the thermodynamic potential and the correlator of its {\em mesoscopic fluctuations} for a finite mean level spacing $δ$ in the grain. We develop a novel method which allows for an exact evaluation of the functional integral arising from disorder aver…
Effect of level statistics on local electronic states and local magnetism in nanoscale metallic grains with transition-metal impurity in the ballistic regime is studied. It is shown that the mean occupation of local electron and the local magnetic moment in nanoscale metallic grains with odd conduction electrons are larger than those with even conduction electrons. The effect of even-odd parity on the condition for the occurrence of local magnetic moment is also discussed, it is found that the critical value $ρ_{d}(0)U_{c}$ for the formation of local moment in nanoscale metallic grains is much…
We propose a simple phenomenological model for an ultrasmall ferromagnetic grain, formulated in terms of the grain's discrete energy levels. We compare the model's predictions with recent measurements of the discrete tunneling spectrum through such a grain. The model can qualitatively account for the observed features if we assume (i) that the anisotropy energy varies among different eigenstates of one grain, and (ii) that nonequilibrium spin accumulation occurs.
Grain boundaries (GBs) are structural imperfections that typically degrade the performance of materials. Here we show that dislocations and GBs in two-dimensional (2D) metal dichalcogenides MX2 (M = Mo, W; X = S, Se) can actually improve the material by giving it a qualitatively new physical property: magnetism. The dislocations studied all have a substantial magnetic moment of ~1 Bohr magneton. In contrast, dislocations in other well-studied 2D materials are typically non-magnetic. GBs composed of pentagon-heptagon pairs interact ferromagnetically and transition from semiconductor to half-met…
We study the Kondo effect in an ultrasmall metallic grain, i.e. small enough to have a discrete energy-level spectrum, by calculating the susceptibility chi of the magnetic impurity. Our quantum Monte Carlo simulations, and analytic solution of a simple model, show that the behavior changes dramatically depending on whether the number of electrons in the grain is even or odd. We suggest that the measurements of chi provide an effective experimental way of probing the grain's number parity.
Perturbations of the two dimensional carbon lattice of graphene, such as grain boundaries, have significant influence on the charge transport and mechanical properties of this material. Scanning tunneling microscopy measurements presented here show that localized states near the Dirac point dominate the local density of states of grain boundaries in graphene grown by chemical vapor deposition. Such low energy states are not reproduced by theoretical models which treat the grain boundaries as periodic dislocation-cores composed of pentagonal-heptagonal carbon rings. Using ab initio calculations…
Temperature dependence of electron dephasing time $τ_ϕ(T)$ is calculated for a disordered metal with small concentration of superconductive grains. Above the macroscopic superconducting transition line, when electrons in the metal are normal, Andreev reflection from the grains leads to a nearly temperature-independent contribution to the dephasing rate. In a broad temperature range $1/τ_phi(T)$ strongly exceeds the prediction of the classical theory of dephasing in normal disordered conductors, whereas magnetoresistance is dominated (in two dimensions) by the Maki-Tompson correction and is pos…
In the presence of spin-orbit scattering, the splitting of an energy level in a generic small metal grain due to the Zeeman coupling to a magnetic field B depends on the direction of B, as a result of mesoscopic fluctuations. The anisotropy is described by the eigenvalues g_j^2 (j=1,2,3) of a tensor G, corresponding to the (squares of) g-factors along three principal axes. We consider the statistical distribution of G and find that the anisotropy is enhanced by eigenvalue repulsion between the g_j.
We consider a model for electron tunneling between a pair of ultrasmall metallic grains. Under appropriate circumstances, non-equilibrium final state effects can strongly enhance tunneling and produce electron-hole coherence between the grains. The model displays a quantum phase transition between a Coulomb blockaded state to a coherent state exhibiting subohmic tunneling conductance. The critical state of the junction exhibits a temperature independent resistance of order $h/e^2$. Finally we discuss the possible relevance to granular materials and quantum dots. In particular, similarities bet…
Most materials in available macroscopic quantities are polycrystalline. Graphene, a recently discovered two-dimensional form of carbon with strong potential for replacing silicon in future electronics, is no exception. There is growing evidence of the polycrystalline nature of graphene samples obtained using various techniques. Grain boundaries, intrinsic topological defects of polycrystalline materials, are expected to dramatically alter the electronic transport in graphene. Here, we develop a theory of charge carrier transmission through grain boundaries composed of a periodic array of dislo…
We investigate the electronic transport property of lateral heterojunctions of semiconducting and metallic transition-metal dichalcogenide monolayers, MoSe$_2$ and NbSe$_2$, respectively. We calculate the electronic transmission probability by using a multi-orbital tight-binding model based on the first-principles band structure. The transmission probability depends on the spin and valley degrees of freedom. This dependence qualitatively changes by the interface structure. The heterostructure with a zig-zag interface preserves the spin and the valley of electron in the transmission process. On…
A roller-ball pen enabled direct writing electronics via room temperature liquid metal ink was proposed. With the rolling to print mechanism, the metallic inks were smoothly written on flexible polymer substrate to form conductive tracks and electronic devices. The contact angle analyzer and scanning electron microscope were implemented to probe the inner property of the obtained electronics. An ever high writing resolution with line width and thickness as 200μm and 80μm, respectively was realized. Further, with the administration of external writing pressure, GaIn24.5 droplets embody increasi…
Recent advances in large-scale synthesis of graphene and other 2D materials have underscored the importance of local defects such as dislocations and grain boundaries (GBs), and especially their tendency to alter the electronic properties of the material. Understanding how the polycrystalline morphology affects the electronic properties is crucial for the development of applications such as flexible electronics, energy harvesting devices or sensors. We here report on atomic scale characterization of several GBs and on the structural-dependence of the localized electronic states in their vicini…
The interactions between carbon nanotubes (CNTs) and metal adatoms as well as metal contacts are studied by means of ab initio electronic structure calculations. We show that the electronic properties of a semiconducting (8,4) CNT can be modified by small amounts of Pd adatoms. Such a decoration conserves the piezoelectric properties of the CNT. Besides the electronic influence, the stability of a single adatom, which is of big importance for future technology applications, is investigated as well. We find only small energy barriers for the diffusion of a Pd adatom on the CNT surface. Thus, si…
Semi-metals are characterized by nodal band structures that give rise to exotic electronic properties. The stability of Dirac semi-metals, such as graphene in two spatial dimensions (2D), requires the presence of lattice symmetries, while akin to the surface states of topological band insulators, Weyl semi-metals in three spatial dimensions (3D) are protected by band topology. Here we show that in the bulk of topological band insulators, self-organized topologically protected semi-metals can emerge along a grain boundary, a ubiquitous extended lattice defect in any crystalline material. In add…
We discuss electron transport in individual nanometer-scale metallic grains at dilution refrigerator temperatures. In the weak coupling regime, the grains exhibit Coulomb blockade and discrete energy levels. Electron-electron interactions lead to clustering and broadening of quasiparticle states. Magnetic field dependences of tunneling resonances directly reveal Kramers degeneracy and Lande g-factors. In grains of Au, which have strong spin-orbit interaction, g-factors are strongly suppressed from the free electron value. We have recently studied grains in the strong coupling regime. Coulomb b…
We investigate the low-energy electronic transport across grain boundaries in graphene ribbons and infinite flakes. Using the recursive Green's function method, we calculate the electronic transmission across different types of grain boundaries in graphene ribbons. We show results for the charge density distribution and the current flow along the ribbon. We study linear defects at various angles with the ribbon direction, as well as overlaps of two monolayer ribbon domains forming a bilayer region. For a class of extended defect lines with periodicity 3, an analytic approach is developed to st…
With a reduction in the average grain size in nanostructured films of elemental Nb, we observe a systematic crossover from metallic to weakly-insulating behavior. An analysis of the temperature dependence of the resistivity in the insulating phase clearly indicates the existence of two distinct activation energies corresponding to inter-granular and intra-granular mechanisms of transport. While the high temperature behavior is dominated by grain boundary scattering of the conduction electrons, the effect of discretization of energy levels due to quantum confinement shows up at low temperatures…
We introduce a model for amorphous grain boundaries in graphene, and find that stable structures can exist along the boundary that are responsible for local density of states enhancements both at zero and finite (~0.5 eV) energies. Such zero energy peaks in particular were identified in STS measurements [J. Červenka, M. I. Katsnelson, and C. F. J. Flipse, Nature Physics 5, 840 (2009)], but are not present in the simplest pentagon-heptagon dislocation array model [O. V. Yazyev and S. G. Louie, Physical Review B 81, 195420 (2010)]. We consider the low energy continuum theory of arrays of disloca…
We demonstrate electronic cooling of a suspended AuPd island using superconductor-insulator-normal metal tunnel junctions. This was achieved by developing a simple fabrication method for reliably releasing narrow submicron sized metal beams. The process is based on reactive ion etching and uses a conducting substrate to avoid charge-up damage and is compatible with e.g. conventional e-beam lithography, shadow-angle metal deposition and oxide tunnel junctions. The devices function well and exhibit clear cooling; up to factor of two at sub-kelvin temperatures.
Post-deposition CdCl$_2$ treatment of polycrystalline CdTe is known to increase photovoltaic efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this study, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries. In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl$_2$ treatment and ambient oxyg…
We have investigated by means of first principles calculations the structural and electronic properties of hydrogenated graphene structures with distinct grain boundary defects. Our total energy results reveal that the adsorption of a single H is more stable at grain boundary defect. The electronic structure of the grains boundaries upon hydrogen adsorption have been examined. Further total energy calculations indicate that the adsorption of two H on two neighbor carbons, forming a basic unit of graphane, is more stable at the defect region. Therefore, we expect that these extended defects wou…
Based on first principles calculation, the electronic properties of graphene on metal (Ti, Ca, Ni, Mn, Co, Fe, Cr, K) modified SiO2 substrate have been studied. The results of binding energies supported graphene indicate that the metal atoms are adsorbed more stably on O surface than on Si surface of SiO2 substrate, and graphene is adsorbed very stably on metal modified substrate. The band structures of supported graphene are similar with that of suspending graphene when deposited on Co modified SiO2 surface, but change obviously with the effect of decorated Fe atoms. Interesting, a semi-metal…
After making a cold weld by pressing two clean metal surfaces together, upon gradually separating the two pieces a metallic nanowire is formed, which progressively thins down to a single atom before contact is lost. In previous experiments [1,2] we have observed that the stability of such nanowires is influenced by electronic shell filling effects, in analogy to shell effects in metal clusters [3]. For sodium and potassium at larger diameters there is a crossover to crystalline wires with shell-closings corresponding to the completion of additional atomic layers. This observation completes the…
We investigate the competition between pairing correlations and ferromagnetism in small metallic grains in the presence of a Zeeman field. Our analysis is based on the universal Hamiltonian, valid in the limit of large Thouless conductance. We show that the coexistence regime of superconducting and ferromagnetic correlations can be made experimentally accessible by tuning an external Zeeman field. We compare the exact solution of the model with a mean-field theory and find that the latter cannot describe pairing correlations in the intermediate regime. We also study the occurrence of spin jump…
We study the finite-temperature optical conductivity, sigma(omega,T), of a granular metal using a simple model consisting of a array of spherical metallic grains. It is necessary to include quantum tunneling and Coulomb blockade effects to obtain the correct temperature dependence of sigma(omega, T), and to consider polarization oscillations to obtain the correct frequency dependence. We have therefore generalized the Ambegaokar-Eckern-Schoen (AES) model for granular metals to obtain an effective field theory incorporating the polarization fluctuations of the individual metallic grains. In con…
The interplay of quantum fluctuations and dissipation in chains of mesoscopic superconducting grains is analyzed, and the results are also applied to nanowires. It is shown that in 1-d arrays of resistively shunted Josephson junctions, the superconducting-normal charge relaxation within the grains plays an important role. At zero temperature, two superconducting phases can exist, depending primarily on the strength of the dissipation. In the fully superconducting phase (FSC), each grain acts superconducting, and the coupling to the dissipative conduction is important. In the SC* phase, the dis…
We study the impact of the valence and the geometry on the electronic structure and transport properties of different transition metal-benzene sandwich molecules bridging the tips of a Cu nanocontact. Our density-functional calculations show that the electronic transport properties of the molecules depend strongly on the molecular geometry which can be controlled by the nanocontact tips. Depending on the valence of the transition metal center certain molecules can be tuned in and out of half-metallic behaviour facilitating potential spintronics applications. We also discuss our results in the …
In this work we present a detailed study and derivation of the thermopower and thermoelectric coefficient of nano-granular metals at large tunneling conductance between the grains, g_T>> 1. An important criterion for the performance of a thermoelectric device is the thermodynamic figure of merit which is derived using the kinetic coefficients of granular metals. All results are valid at intermediate temperatures, E_c>>T/g_T>δ, where δis the mean energy level spacing for a single grain and E_c its charging energy. We show that the electron-electron interaction leads to an increase of the thermo…
We investigate nonradiative emission and absorption rates of two-level quantum emitters embedded in a metal at low temperatures. We obtain the expressions for both nonradiative transition rates and identify a unique, experimentally accessible way to obtain the nonradiative decay rates via electronic transport in the host metallic system. Our findings not only provide a microscopic description of nonradiative decay channels in metals, but they also allows one to identify and differentiate them from other decay channels, which is crucial to understand and control light-matter interactions at the…
