Phonon interference effects in molecular junctions

We study coherent phonon transport through organic, \pi-conjugated molecules. Using first principles calculations and Green's function methods, we find that the phonon transmission function in cross-conjugated molecules, like meta-connected benzene, exhibits destructive quantum interference features very analogous to those observed theoretically and experimentally for electron transport in similar molecules. The destructive interference features observed in four different cross-conjugated molecules significantly reduce the thermal conductance with respect to linear conjugated analogues. Such control of the thermal conductance by chemical modifications could be important for thermoelectric applications of molecular junctions.Comment: 10 pages, 10 figure

Quantifying Transition Voltage Spectroscopy of Molecular Junctions

Transition voltage spectroscopy (TVS) has recently been introduced as a spectroscopic tool for molecular junctions where it offers the possibility to probe molecular level energies at relatively low bias voltages. In this work we perform extensive ab-initio calculations of the non-linear current voltage relations for a broad class of single-molecule transport junctions in order to assess the applicability and limitations of TVS. We find, that in order to fully utilize TVS as a quantitative spectroscopic tool, it is important to consider asymmetries in the coupling of the molecule to the two electrodes. When this is taken properly into account, the relation between the transition voltage and the energy of the molecular orbital closest to the Fermi level closely follows the trend expected from a simple, analytical model.Comment: 5 pages, 4 figures. To appear in PR

Improving Transition Voltage Spectroscopy of Molecular Junctions

Transition voltage spectroscopy (TVS) is a promising spectroscopic tool for molecular junctions. The principles in TVS is to find the minimum on a Fowler-Nordheim plot where $\ln(I/V^2)$ is plotted against $1/V$ and relate the voltage at the minimum, $V_{\rm min}$, to the closest molecular level. Importantly, $V_{\rm min}$, is approximately half the voltage required to see a peak in the $dI/dV$ curve. Information about the molecular level position can thus be obtained at relatively low voltages. In this work we show that the molecular level position can be determined at even lower voltages, $V_{\rm min}^{(\alpha)}$ by finding the minimum of $\ln(I/V^\alpha)$ with $\alpha<2$. On the basis of a simple Lorentzian transmission model we analyze theoretical {\it ab initio} as well as experimental $I-V$ curves and show that the voltage required to determine the molecular levels can be reduced by $\sim 30$ as compared to conventional TVS. As for conventional TVS, the symmetry/asymmetry of the molecular junction needs to be taken into account in order to gain quantitative information. We show that the degree of asymmetry may be estimated from a plot of $V_{\rm min}^{(\alpha)}$ vs. $\alpha$.Comment: 6 pages, 8 figure

Inelastic vibrational signals in electron transport across graphene nanoconstrictions

We present calculations of the inelastic vibrational signals in the electrical current through a graphene nanoconstriction. We find that the inelastic signals are only present when the Fermi-level position is tuned to electron transmission resonances, thus, providing a fingerprint which can link an electron transmission resonance to originate from the nanoconstriction. The calculations are based on a novel first-principles method which includes the phonon broadening due to coupling with phonons in the electrodes. We find that the signals are modified due to the strong coupling to the electrodes, however, still remain as robust fingerprints of the vibrations in the nanoconstriction. We investigate the effect of including the full self-consistent potential drop due to finite bias and gate doping on the calculations and find this to be of minor importance

First-principles method for electron-phonon coupling and electron mobility: Applications to 2D materials

We present density functional theory calculations of the phonon-limited mobility in n-type monolayer graphene, silicene and MoS$_2$. The material properties, including the electron-phonon interaction, are calculated from first-principles. We provide a detailed description of the normalized full-band relaxation time approximation for the linearized Boltzmann transport equation (BTE) that includes inelastic scattering processes. The bulk electron-phonon coupling is evaluated by a supercell method. The method employed is fully numerical and does therefore not require a semi-analytic treatment of part of the problem and, importantly, it keeps the anisotropy information stored in the coupling as well as the band structure. In addition, we perform calculations of the low-field mobility and its dependence on carrier density and temperature to obtain a better understanding of transport in graphene, silicene and monolayer MoS$_2$. Unlike graphene, the carriers in silicene show strong interaction with the out-of-plane modes. We find that graphene has more than an order of magnitude higher mobility compared to silicene. For MoS$_2$, we obtain several orders of magnitude lower mobilities in agreement with other recent theoretical results. The simulations illustrate the predictive capabilities of the newly implemented BTE solver applied in simulation tools based on first-principles and localized basis sets

Controlling the transmission line shape of molecular t-stubs and potential thermoelectric applications

Asymmetric line shapes can occur in the transmission function describing electron transport in the vicinity of a minimum caused by quantum interference effects. Such asymmetry can be used to increase the thermoelectric efficiency of molecular junctions. So far, however, asymmetric line shapes have been only empirically found for just a few rather complex organic molecules where the origins of the line shapes relation to molecular structure were not resolved. In the present work we introduce a method to analyze the structure dependence of the asymmetry of interference dips from simple two site tight-binding models, where one site corresponds to a molecular $\pi$ orbital of the wire and the other to an atomic $p_z$ orbital of a side group, which allows us to analytically characterize the peak shape in terms of just two parameters. We assess our scheme with first-principles electron transport calculations for a variety of {\it t-stub} molecules and also address their suitability for thermoelectric applications.Comment: 11 pages, 5 figures; J. Chem. Phys., in print (2011

Efficient first-principles calculation of phonon assisted photocurrent in large-scale solar cell devices

We present a straightforward and computationally cheap method to obtain the phonon-assisted photocurrent in large-scale devices from first-principles transport calculations. The photocurrent is calculated using nonequilibrium Green's function with light-matter interaction from the first-order Born approximation while electron-phonon coupling (EPC) is included through special thermal displacements (STD). We apply the method to a silicon solar cell device and demonstrate the impact of including EPC in order to properly describe the current due to the indirect band-to-band transitions. The first-principles results are successfully compared to experimental measurements of the temperature and light intensity dependence of the open-circuit voltage of a silicon photovoltaic module. Our calculations illustrate the pivotal role played by EPC in photocurrent modelling to avoid underestimation of the open-circuit voltage, short-circuit current and maximum power. This work represents a recipe for computational characterization of future photovoltaic devices including the combined effects of light-matter interaction, phonon-assisted tunneling and the device potential at finite bias from the level of first-principles simulations

Electrochemical control of quantum interference in anthraquinone-based molecular switches

Using first-principles calculations we analyze the electronic transport properties of a recently proposed anthraquinone based electrochemical switch. Robust conductance on/off ratios of several orders of magnitude are observed due to destructive quantum interference present in the anthraquinone, but absent in the hydroquinone molecular bridge. A simple explanation of the interference effect is achieved by transforming the frontier molecular orbitals into localized molecular orbitals thereby obtaining a minimal tight-binding model describing the transport in the relevant energy range in terms of hopping via the localized orbitals. The topology of the tight-binding model, which is dictated by the symmetries of the molecular orbitals, determines the amount of quantum interference.Comment: 6 pages, 6 figure

Multiterminal single-molecule--graphene-nanoribbon thermoelectric devices with gate-voltage tunable figure of merit ZT

We study thermoelectric devices where a single 18-annulene molecule is connected to metallic zigzag graphene nanoribbons (ZGNR) via highly transparent contacts that allow for injection of evanescent wave functions from ZGNRs into the molecular ring. Their overlap generates a peak in the electronic transmission, while ZGNRs additionally suppress hole-like contributions to the thermopower. Thus optimized thermopower, together with suppression of phonon transport through ZGNR-molecule-ZGNR structure, yield the thermoelectric figure of merit ZT ~ 0.5 at room temperature and 0.5 < ZT < 2.5 below liquid nitrogen temperature. Using the nonequilibrium Green function formalism combined with density functional theory, recently extended to multiterminal devices, we show how the transmission resonance can also be manipulated by the voltage applied to a third ZGNR electrode, acting as the top gate covering molecular ring, to tune the value of ZT.Comment: 5 pages, 4 figures, PDFLaTe