Nanoelectronics – theory and simulation


A. Shiotari, H. Okuyama, S. Hatta, T. Aruga, M. Alducin, and T. Frederiksen
Role of valence states of adsorbates in inelastic electron tunneling spectroscopy: A study of nitric oxide on Cu(110) and Cu(001)
Phys. Rev. B 94, 075442 (2016) [ PDF ]

We studied nitric oxide (NO) molecules on Cu(110) and Cu(001) surfaces with low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT). NO monomers on the surfaces are characterized by STM images reflecting 2π* resonance states located at the Fermi level. NO is bonded vertically to the twofold short-bridge site on Cu(110) and to the fourfold hollow site on Cu(001). When NO molecules form dimers on the surfaces the valence orbitals are modified due to the covalent bonding. We measured inelastic electron tunneling spectroscopy (IETS) for both NO monomers and dimers on the two surfaces, and detected characteristic structures assigned to frustrated rotation and translation modes by density functional theory simulations. Considering symmetries of valence orbitals and vibrational modes, we explain the intensity of the observed IETS signals in a qualitative manner.

M. Engelund, N. Papior, P. Brandimarte, T. Frederiksen, A. Garcia-Lekue, and D. Sánchez-Portal
Search for a metallic dangling-bond wire on H-passivated semiconductor surface
J. Phys. Chem. C 120, 20303–20309 (2016) [ PDF ] [arXiv:1609.03842].

We have theoretically investigated the electronic properties of neutral and n-doped dangling bond (DB) quasi-one-dimensional structures (lines) in the Si(001):H and Ge(001):H substrates with the aim of identifying atomic-scale interconnects exhibiting metallic conduction for use in on-surface circuitry. Whether neutral or doped, DB lines are prone to suffer geometrical distortions or have magnetic ground-states that render them semiconducting. However, from our study we have identified one exception – a dimer row fully stripped of hydrogen passivation. Such a DB-dimer line shows an electronic band structure which is remarkably insensitive to the doping level and, thus, it is possible to manipulate the position of the Fermi level, moving it away from the gap. Transport calculations demonstrate that the metallic conduction in the DB-dimer line can survive thermally induced disorder, but is more sensitive to imperfect patterning. In conclusion, the DB-dimer line shows remarkable stability to doping and could serve as a one-dimensional metallic conductor on n-doped samples.

J. N. Ladenthin, T. Frederiksen, M. Persson, J. C. Sharp, S. Gawinkowski, J. Waluk, and T. Kumagai
Force-induced tautomerization in a single molecule
Nature Chemistry 8, 935–940 (2016) [ PDF ]

Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced tautomerization in a single porphycene molecule on a Cu(110) surface at 5 K, which is studied by scanning probe microscopy and density functional theory calculations. Force spectroscopy quantifies the force needed to trigger tautomerization with submolecular spatial resolution. The calculations show how the reaction pathway and barrier of tautomerization are modified in the presence of a copper tip and reveal the atomistic origin of the process. Moreover, we demonstrate that a chemically inert tip whose apex is terminated by a xenon atom cannot induce the reaction because of a weak interaction with porphycene and a strong relaxation of xenon on the tip as contact to the molecule is formed.

M. Engelund, S. Godlewski, M. Kolmer, R. Zuzak, B. Such, T. Frederiksen, M. Szymonski, and D. Sánchez-Portal
The butterfly – a well-defined constant-current topography pattern on Si(001):H and Ge(001):H resulting from current-induced defect fluctuations
Phys. Chem. Chem. Phys. 18, 19309 (2016) [ PDF ]

Dangling bond (DB) arrays on Si(001):H and Ge(001):H surfaces can be patterned with atomic precision and they exhibit complex and rich physics making them interesting from both technological and fundamental perspectives. But their complex behavior often makes scanning tunneling microscopy (STM) images difficult to interpret and simulate. Recently it was shown that low-temperature imaging of unoccupied states of an unpassivated dimer on Ge(001):H results in a symmetric butterfly-like STM pattern, despite that the equilibrium dimer configuration is expected to be a bistable, buckled geometry. Here, based on a thorough characterization of the low-bias switching events, we propose a new imaging model featuring a dynamical two-state rate equation. This model allows us to reproduce the features of the observed symmetric empty-state images which strongly corroborates the idea that the patterns arise due to fast switching events and provides insight into the relation between the tunneling current and switching rates. Our new imaging model is general and can be applied to other systems that exhibit rapid fluctuations during STM experiments.