2019

Recent scanning tunnelling microscopy (STM) experiments reported single-molecule fluorescence induced by tunneling currents in the nanoplasmonic cavity formed by the STM tip and the substrate.The electric field of the cavity mode couples with the current-induced charge fluctuations of the molecule, allowing the excitation of the mode. We investigate theoretically this system for the experimentally relevant limit of large damping rate \kappa for the cavity mode and arbitrary coupling strength to a single-electronic level. We find that for bias voltages close to the first inelastic threshold of photon emission, the emitted light displays anti-bunching behavior with vanishing second-order photon correlation function. At the same time, the current and the intensity of emitted light display Franck--Condon steps at multiples of the cavity frequency \omega_c with a width controlled by kappa rather than the temperature T. For large bias voltages, we predict strong photon bunching of the order of the \kappa/\Gamma where \Gamma is the electronic tunneling rate. Our theory thus predicts that strong coupling to a single level allows current-driven non-classical light emission.

The shot noise of the current I through junctions to single trioxatriangulenium cations (TOTA+) on Au(111) is measured with a low temperature scanning tunneling microscope using Au tips. The noise is significantly reduced compared to the Poisson noise power of 2eI and varies linearly with the junction conductance. The data are consistent with electron transmission through a single spin-degenerate transport channel and show that TOTA+ in a Au contact does not acquire an unpaired electron. Ab initio calculations reproduce the observations and show that the current involves the lowest unoccupied orbital of the molecule and tip states close to the Fermi level.

Miniaturization of electronic circuits into the single-atom level requires novel approaches to characterize transport properties. Due to its unrivaled precision, scanning probe microscopy is regarded as the method of choice for local characterization of atoms and single molecules supported on surfaces. Here we investigate electronic transport along the anisotropic germanium (001) surface with the use of two-probe scanning tunneling spectroscopy and first-principles transport calculations. We introduce a method for the determination of the transconductance in our two-probe experimental setup and demonstrate how it captures energy-resolved information about electronic transport through the unoccupied surface states. The sequential opening of two transport channels within the quasi-one-dimensional Ge dimer rows in the surface gives rise to two distinct resonances in the transconductance spectroscopic signal, consistent with phase-coherence lengths of up to 50 nm and anisotropic electron propagation. Our work paves the way for the electronic transport characterization of quantum circuits engineered on surfaces.

The conductances of molecules physisorbed to Au(111) via an extended π system are probed with the tip of a low-temperature scanning tunneling microscope to maximize the control of the junction geometry. Inert hydrogen, methyl, and reactive propynyl subunits were attached to the platform and stand upright. Because of their different reactivities, either non-bonding (hydrogen and methyl) or bonding (propynyl) tip-molecule contacts are formed. The conductances exhibit little scatter between different experimental runs on different molecules, display distinct evolutions with the tip-subunit distance, and reach contact values of 0.003-0.05 G₀. For equal tip-platform distances the contact conductance of the inert methyl is close to that of the reactive propynyl. Under further compression, the inert species, hydrogen and methyl, are found to be better conductors. This shows that the current flow is not directly correlated with the chemical interaction. Atomistic calculations for the methyl case reproduce the conductance evolution and reveal the role of the junction geometry, forces and orbital symmetries at the tip-molecule interface. The current flow is controlled by orbital symmetries at the electrode interfaces rather than by the energy alignment of the molecular orbitals and electrode states. Functionalized molecular platforms thus open new ways to control and engineer electron conduction through metal-molecule interfaces at the atomic level.

Turning graphene magnetic is a promising challenge to make it an active material for spintronics. Predictions state that graphene structures with specific shapes can spontaneously develop magnetism driven by Coulomb repulsion of π-electrons, but its experimental verification is demanding. Here, we report on the observation and manipulation of individual magnetic moments in graphene open-shell nanostructures on a gold surface. Using scanning tunneling spectroscopy, we detect the presence of single electron spins localized around certain zigzag sites of the carbon backbone via the Kondo effect. We find near-by spins coupled into a singlet ground state and quantify their exchange interaction via singlet-triplet inelastic electron excitations. Theoretical simulations picture how electron correlations result in spin-polarized radical states with the experimentally observed spatial distributions. Extra hydrogen atoms bound to radical sites quench their magnetic moment and switch the spin of the nanostructure in half-integer amounts. Our work demonstrates the intrinsic π-paramagnetism of graphene nanostructures.

Electrons in graphene can show diffraction and interference phenomena fully analogous to light thanks to their Dirac-like energy dispersion. However it is not clear how this optical analogy persists in nanostructured graphene, e.g. with pores. Nanoporous graphene (NPG) consisting of linked graphene nanoribbons has recently been fabricated using molecular precursors and bottom-up assembly [Moreno et al, Science 360, 199 (2018)]. We predict that electrons propagating in NPG exhibit the interference Talbot effect, analogous to photons in coupled waveguides. Our results are obtained by parameter-free atomistic calculations of rea l-sized NPG samples, based on seamlessly integrated density functional theory and tight-binding regions. We link the origins of this interference phenomenon to the band structure of the NPG. Most importantly, we demonstrate how the Talbot effect may be detected experimentally using dual-probe scanning tunneling microscopy. Talbot interference of electron waves in NPG or other related materials may open up new opportunities for future quantum electronics, computing or sensing.