Nanoelectronics – theory and simulation


Y. Kitaguchi, S. Habuka, H. Okuyama, S. Hatta, T. Aruga, T. Frederiksen, M. Paulsson, and H. Ueba
Controlled switching of single-molecule junctions by mechanical motion of a phenyl ring
Beilstein J. Nanotechnol. 6, 2088-2095 (2015) [ PDF ]

Mechanical methods for single-molecule control have potential for wide application in nanodevices and machines. Here we demonstrate the operation of a single-molecule switch made functional by the motion of a phenyl ring, analogous to the lever in a conventional toggle switch. The switch can be actuated by dual triggers, either by a voltage pulse or by displacement of the electrode, and electronic manipulation of the ring by chemical substitution enables rational control of the on-state conductance. Owing to its simple mechanics, structural robustness, and chemical accessibility, we propose that phenyl rings are promising components in mechanical molecular devices.

M. Engelund, R. Zuzak, S. Godlewski, M. Kolmer, T. Frederiksen, A. García-Lekue, D. Sánchez-Portal, and M. Szymonski
Tunneling spectroscopy of close-spaced dangling-bond pairs in Si(001):H
Scientific Reports 5, 14496 (2015) [ PDF ]

We present a combined experimental and theoretical study of the electronic properties of close- spaced dangling-bond (DB) pairs in a hydrogen-passivated Si(001):H p-doped surface. Two types of DB pairs are considered, called "cross" and "line" structures. Our scanning tunneling spectroscopy (STS) data show that, although the spectra taken over different DBs in each pair exhibit a remarkable resemblance, they appear shifted by a constant energy that depends on the DB-pair type. This spontaneous asymmetry persists after repeated STS measurements. By comparison with density functional theory (DFT) calculations, we demonstrate that the magnitude of this shift and the relative position of the STS peaks can be explained by distinct charge states for each DB in the pair. We also explain how the charge state is modified by the presence of the scanning tunneling microscopy (STM) tip and the applied bias. Our results indicate that, using the STM tip, it is possible to control the charge state of individual DBs in complex structures, even if they are in close proximity. This observation might have important consequences for the design of electronic circuits and logic gates based on DBs in passivated silicon surfaces.

T. Frederiksen
First-principles simulations of electron transport in atomic-scale systems
Book chapter for Handbook of Single-Molecule Electronics edited by K. Moth-Poulsen, Pan Stanford (2015).

An important theoretical challenge in the field of single-molecule electronics is to develop general methods for quantitative simulations of real devices taking into account the atomistic details. This chapter describes an approach toward this goal based on density-functional theory (DFT) for the electronic structure in combination with nonequilibrium Green's functions (NEGF) for the transport. We also address recent developments based on the DFT+NEGF approach to describe electron--vibration interactions in molecular junctions, local heating effects, and inelastic signatures in device current--voltage and shot noise characteristics.

Y. Kitaguchi, S. Habuka, H. Okuyama, S. Hatta, T. Aruga, T. Frederiksen, M. Paulsson, and H. Ueba
Controlling single-molecule junction conductance by molecular interactions
Scientific Reports 5, 11796 (2015) [ PDF ]

For the rational design of single-molecular electronic devices, it is essential to understand environmental effects on the electronic properties of a working molecule. Here we investigate the impact of molecular interactions on the single-molecule conductance by accurately positioning individual molecules on the electrode. To achieve reproducible and precise conductivity measurements, we utilize relatively weak π-bonding between a phenoxy molecule and a STM-tip to form and cleave one contact to the molecule. The anchoring to the other electrode is kept stable using a chalcogen atom with strong bonding to a Cu(110) substrate. These non-destructive measurements permit us to investigate the variation in single-molecule conductance under different but controlled environmental conditions. Combined with density functional theory calculations, we clarify the role of the electrostatic field in the environmental effect that influences the molecular level alignment.

R. B. Christensen, T. Frederiksen, and M. Brandbyge
Identification of pristine and defective graphene nanoribbons by phonon signatures in the electron transport characteristics
Phys. Rev. B 91, 075434 (2015) [ PDF ] [arXiv:1501.02266]

Inspired by recent experiments where electron transport was measured across graphene nanoribbons (GNRs) suspended between a metal surface and the tip of a scanning tunneling microscope [Koch et al., Nat. Nanotechnol. 7, 713 (2012)], we present detailed first-principles simulations of inelastic electron tunneling spectroscopy (IETS) of long pristine and defective armchair and zigzag nanoribbons under a range of charge carrier conditions. For the armchair ribbons we find two robust IETS signals around 169 and 196 mV corresponding to the D and G modes of Raman spectroscopy as well as additional fingerprints due to various types of defects in the edge passivation. For the zigzag ribbons we show that the spin state strongly influences the spectrum and thus propose IETS as an indirect proof of spin polarization.

G. Foti, D. Sánchez-Portal, A. Arnau, and T. Frederiksen
Role of k-point sampling in the supercell approach to inelastic electron tunneling spectroscopy simulations of molecular monolayers
Phys. Rev. B 91, 035434 (2015) [ PDF ]

While the role of sampling of the electron momentum k in supercell calculations of the elastic electron transmission is well understood, its influence in the case of inelastic electron tunneling (IET) has not yet been systematically explored. Here we compare ab initio IET spectra of molecular monolayers in the commonly used Γ-point approximation to rigorously k-converged results. We study four idealized molecular junctions with either alkanedithiolates or benzenedithiolates, and explore variations due to varying molecular tilt angle, density, as well as chemical identity of the monolayer. We show that the Γ-point approximation is reasonable for a range of systems, but that a rigorous convergence is needed for accurate signal amplitudes. We also describe an approximative scheme which reduces the computational cost of the k-averaged calculation in our implementation.

Y. Kim, K. Motobayashi, T. Frederiksen, H. Ueba, and M. Kawai
Action spectroscopy for single-molecules reactions - experiment and theory
Prog. Surf. Sci. 90, 85-143 (2015) [ PDF ] [DOI]

We review several representative experimental results of action spectroscopy (AS) of single molecules on metal surfaces using a scanning tunneling microscope (STM) by M. Kawai's group over last decade. The experimental procedures to observe STM-AS are described. A brief description of a low-temperature STM and experimental setup are followed by key experimental techniques of how to determine an onset bias voltage of a reaction and how to measure a current change associated with reactions and finally how to observe AS for single molecule reactions. The experimental results are presented for vibrationally mediated chemical transformation of trans-2-butene to 1.3-butadiene molecule and rotational motion of a single cis-2-butene molecule among four equivalent orientations on Pd(110). The AS obtained from the motion clearly detects more vibrational modes than inelastic electron tunneling spectroscopy with an STM. AS is demonstrated as a useful and novel single molecule vibrational spectroscopy. The AS for a lateral hopping of water dimer on Pt(111) is presented as an example of novelty. Several distinct vibrational modes are detected as the thresholds in the AS. The assignment of the vibrational modes determined from the analysis of the AS is made from a view of the adsorption geometry of hydrogen-bond donor or acceptor molecules in water dimer.

A generic theory of STM-AS, i.e., a reaction rate or yield as a function of bias voltage, is presented using a single adsorbate resonance model for single molecule reactions induced by the inelastic tunneling current. Formulas for the reaction rate R(V) and Y(V), i.e., reaction yield per electron Y(V) = e R(V)/I are derived. It provides a versatile framework to analyze any vibrationally mediated reactions of single adsorbates on metal surfaces. Numerical examples are presented to demonstrate generic features of the vibrational generation rate and Y(V) at different levels of approximations and to show how the effective broadening of the vibrational density of states (as described by Gaussian or Lorentzian functions) manifest themselves in Y(V) near the threshold bias voltage corresponding to a vibrational excitation responsible for reactions. A prefactor of Y(V) is explicitly derived for various types of elementary processes. Our generic formula of Y(V) also underlines the need to observe Y(V) at both bias voltage polarities, which can provide additional insight into the adsorbate projected density of states near the Fermi level within a span of the vibrational energy.

The theory is applied to analysis of some highlights of the experimental results: Xe transfer, hopping of a single CO molecule on Pd(110), a dissociation of a single dimethyl disulfide (CH3S)2 and a hopping of a dissociated product, i.e., single methyl thiolate CH3S on Cu(111). It underlines that an observation of Y(V) at both bias polarities permits us to certain insight into the molecular alignment with respect to the Fermi level.

K. Smaali, S. Desbief, G. Foti, T. Frederiksen, D. Sánchez-Portal, A. Arnau, J.-P. Nys, P. Leclere, D. Vuillaume, and N. Clement
On the mechanical and electronic properties of thiolated gold nanocrystals
Nanoscale 7, 1809-1819 (2015) [ PDF ] [ Suppl. ] [arXiv:1412.7698]
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We present a quantitative exploration, combining experiment and simulation, of the mechanical and electronic properties, as well as the modifications induced by an alkylthiolated coating, at the single nanoparticle (NP) level. We determined the response of the NPs to external pressure in a controlled manner using an atomic force microscope tip. We found a strong reduction in their Young's modulus, as compared to bulk gold, and a significant influence of strain on the electronic properties of the alkylthiolated NPs. Electron transport measurements of tiny molecular junctions (NP/alkylthiol/CAFM tip) show that the effective tunnelling barrier through the adsorbed monolayer strongly decreases by increasing the applied load, which translates in a remarkable and unprecedented increase in the tunnel current. These observations are successfully explained using simulations based on the finite element analysis (FEA) and first-principles calculations that permit one to consider the coupling between the mechanical response of the system and the electric dipole variations at the interface.