Surface decorated silicon nanowires: a route to high-ZT thermoelectrics

Based on atomistic calculations of electron and phonon transport, we propose to use surface decorated Silicon nanowires (SiNWs) for thermoelectric applications. Two examples of surface decorations are studied to illustrate the underlying deas: Nanotrees and alkyl functionalized SiNWs. For both systems we find, (i) that the phonon conductance is significantly reduced compared to the electronic conductance leading to high thermoelectric figure of merit, $ZT$, and (ii) for ultra-thin wires surface decoration leads to significantly better performance than surface disorder.Comment: Accepted for PR

Ab initio vibrations in nonequilibrium nanowires

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's functions.Comment: 16 pages, to appear in Progress in Nonequilibrium Green's Functions IV (PNGF4), Eds. M. Bonitz and K. Baltzer, Glasgow, August 200

Efficiency of Energy Conversion in Thermoelectric Nanojunctions

Using first-principles approaches, this study investigated the efficiency of energy conversion in nanojunctions, described by the thermoelectric figure of merit $ZT$. We obtained the qualitative and quantitative descriptions for the dependence of $ZT$ on temperatures and lengths. A characteristic temperature: $T_{0}= \sqrt{\beta/\gamma(l)}$ was observed. When $T\ll T_{0}$, $ZT\propto T^{2}$. When $T\gg T_{0}$, $ZT$ tends to a saturation value. The dependence of $ZT$ on the wire length for the metallic atomic chains is opposite to that for the insulating molecules: for aluminum atomic (conducting) wires, the saturation value of $ZT$ increases as the length increases; while for alkanethiol (insulating) chains, the saturation value of $ZT$ decreases as the length increases. $ZT$ can also be enhanced by choosing low-elasticity bridging materials or creating poor thermal contacts in nanojunctions. The results of this study may be of interest to research attempting to increase the efficiency of energy conversion in nano thermoelectric devices.Comment: 2 figure

A Molecular Platinum Cluster Junction: A Single-Molecule Switch

We present a theoretical study of the electronic transport through single-molecule junctions incorporating a Pt6 metal cluster bound within an organic framework. We show that the insertion of this molecule between a pair of electrodes leads to a fully atomically engineered nano-metallic device with high conductance at the Fermi level and two sequential high on/off switching states. The origin of this property can be traced back to the existence of a HOMO which consists of two degenerate and asymmetric orbitals, lying close in energy to the Fermi level of the metallic leads. Their degeneracy is broken when the molecule is contacted to the leads, giving rise to two resonances which become pinned close to the Fermi level and display destructive interference.Comment: 4 pages, 4 figures. Reprinted (adapted) with permission from J. Am. Chem. Soc., 2013, 135 (6), 2052. Copyright 2013 American Chemical Societ

Evidence for Quantum Interference in SAMs of Arylethynylene Thiolates in Tunneling Junctions with Eutectic Ga-In (EGaIn) Top-Contacts

This paper compares the current density (J) versus applied bias (V) of self-assembled monolayers (SAMs) of three different ethynylthiophenol-functionalized anthracene derivatives of approximately the same thickness with linear-conjugation (AC), cross-conjugation (AQ), and broken-conjugation (AH) using liquid eutectic Ga-In (EGaIn) supporting a native skin (~1 nm thick) of Ga2O3 as a nondamaging, conformal top-contact. This skin imparts non-Newtonian rheological properties that distinguish EGaIn from other top-contacts; however, it may also have limited the maximum values of J observed for AC. The measured values of J for AH and AQ are not significantly different (J ≈ 10-1 A/cm2 at V = 0.4 V). For AC, however, J is 1 (using log averages) or 2 (using Gaussian fits) orders of magnitude higher than for AH and AQ. These values are in good qualitative agreement with gDFTB calculations on single AC, AQ, and AH molecules chemisorbed between Au contacts that predict currents, I, that are 2 orders of magnitude higher for AC than for AH at 0 < |V| < 0.4 V. The calculations predict a higher value of I for AQ than for AH; however, the magnitude is highly dependent on the position of the Fermi energy, which cannot be calculated precisely. In this sense, the theoretical predictions and experimental conclusions agree that linearly conjugated AC is significantly more conductive than either cross-conjugated AQ or broken conjugate AH and that AQ and AH cannot necessarily be easily differentiated from each other. These observations are ascribed to quantum interference effects. The agreement between the theoretical predictions on single molecules and the measurements on SAMs suggest that molecule-molecule interactions do not play a significant role in the transport properties of AC, AQ, and AH.

Numerical study of the thermoelectric power factor in ultra-thin Si nanowires

Low dimensional structures have demonstrated improved thermoelectric (TE) performance because of a drastic reduction in their thermal conductivity, {\kappa}l. This has been observed for a variety of materials, even for traditionally poor thermoelectrics such as silicon. Other than the reduction in {\kappa}l, further improvements in the TE figure of merit ZT could potentially originate from the thermoelectric power factor. In this work, we couple the ballistic (Landauer) and diffusive linearized Boltzmann electron transport theory to the atomistic sp3d5s*-spin-orbit-coupled tight-binding (TB) electronic structure model. We calculate the room temperature electrical conductivity, Seebeck coefficient, and power factor of narrow 1D Si nanowires (NWs). We describe the numerical formulation of coupling TB to those transport formalisms, the approximations involved, and explain the differences in the conclusions obtained from each model. We investigate the effects of cross section size, transport orientation and confinement orientation, and the influence of the different scattering mechanisms. We show that such methodology can provide robust results for structures including thousands of atoms in the simulation domain and extending to length scales beyond 10nm, and point towards insightful design directions using the length scale and geometry as a design degree of freedom. We find that the effect of low dimensionality on the thermoelectric power factor of Si NWs can be observed at diameters below ~7nm, and that quantum confinement and different transport orientations offer the possibility for power factor optimization.Comment: 42 pages, 14 figures; Journal of Computational Electronics, 201

Conductance statistics from a large array of sub-10 nm molecular junctions

Devices made of few molecules constitute the miniaturization limit that both inorganic and organic-based electronics aspire to reach. However, integration of millions of molecular junctions with less than 100 molecules each has been a long technological challenge requiring well controlled nanometric electrodes. Here we report molecular junctions fabricated on a large array of sub-10 nm single crystal Au nanodots electrodes, a new approach that allows us to measure the conductance of up to a million of junctions in a single conducting Atomic Force Microscope (C-AFM) image. We observe two peaks of conductance for alkylthiol molecules. Tunneling decay constant (beta) for alkanethiols, is in the same range as previous studies. Energy position of molecular orbitals, obtained by transient voltage spectroscopy, varies from peak to peak, in correlation with conductance values.Comment: ACS Nano (in press

Effect of Thermoelectric Cooling in Nanoscale Junctions

We propose a thermoelectric cooling device based on an atomic-sized junction. Using first-principles approaches, we investigate the working conditions and the coefficient of performance (COP) of an atomic-scale electronic refrigerator where the effects of phonon's thermal current and local heating are included. It is observed that the functioning of the thermoelectric nano-refrigerator is restricted to a narrow range of driving voltages. Compared with the bulk thermoelectric system with the overwhelmingly irreversible Joule heating, the 4-Al atomic refrigerator has a higher efficiency than a bulk thermoelectric refrigerator with the same $ZT$ due to suppressed local heating via the quasi-ballistic electron transport and small driving voltages. Quantum nature due to the size minimization offered by atomic-level control of properties facilitates electron cooling beyond the expectation of the conventional thermoelectric device theory.Comment: 8 figure

Transport in Silicon Nanowires: Role of Radial Dopant Profile

We consider the electronic transport properties of phosphorus (P) doped silicon nanowires (SiNWs). By combining ab initio density functional theory (DFT) calculations with a recursive Green's function method, we calculate the conductance distribution of up to 200 nm long SiNWs with different distributions of P dopant impurities. We find that the radial distribution of the dopants influences the conductance properties significantly: Surface doped wires have longer mean-free paths and smaller sample-to-sample fluctuations in the cross-over from ballistic to diffusive transport. These findings can be quantitatively predicted in terms of the scattering properties of the single dopant atoms, implying that relatively simple calculations are sufficient in practical device modelingComment: Submitted to Journal of Computational Electronics, presented in IWCE-1