Sara Barja

Self-organization of electron acceptor molecules on graphene

Graphene grown on Ir(111) electronically decouples adsorbed molecules from the metallic substrate and allows the study of their self-organization on surfaces. We study two electron acceptor molecules from the same family. The intermolecular interaction, attractive for TCNQ and repulsive for F(4)-TCNQ, dictates the molecular ordering.

Potential energy landscape for hot electrons in periodically nanostructured graphene.

We explore the spatial variations of the unoccupied electronic states of graphene epitaxially grown on Ru(0001) and observed three unexpected features: the first graphene image state is split in energy; unlike all other image states, the split state does not follow the local work function modulation, and a new interfacial state at +3  eV appears on some areas of the surface. First-principles calculations explain the observations and permit us to conclude that the system behaves as a self-organized periodic array of quantum dots.

Charge density wave order in 1D mirror twin boundaries of single-layer MoSe2

A scanning tunnelling microscopy study demonstrates that one-dimensional charge density waves can form at twin boundaries in a monolayer transition metal dichalcogenide.

Charge percolation pathways guided by defects in quantum dot solids.

Charge hopping and percolation in quantum dot (QD) solids has been widely studied, but the microscopic nature of the percolation process is not understood or determined. Here we present the first imaging of the charge percolation pathways in two-dimensional PbS QD arrays using Kelvin probe force microscopy (KPFM). We show that under dark conditions electrons percolate via in-gap states (IGS) instead of the conduction band, while holes percolate via valence band states. This novel transport behavior is explained by the electronic structure and energy level alignment of the individual QDs, which was measured by scanning tunneling spectroscopy (STS). Chemical treatments with hydrazine can remove the IGS, resulting in an intrinsic defect-free semiconductor, as revealed by STS and surface potential spectroscopy. The control over IGS can guide the design of novel electronic devices with impurity conduction, and photodiodes with controlled doping.

Probing the site-dependent Kondo response of nanostructured graphene with organic molecules.

TCNQ molecules are used as a sensitive probe for the Kondo response of the electron gas of a nanostructured graphene grown on Ru(0001) presenting a moiré pattern. All adsorbed molecules acquired an extra electron by charge transfer from the substrate, but only those adsorbed in the FCC-Top areas of the moiré show magnetic moment and Kondo resonance in the STS spectra. DFT calculations trace back this behavior to the existence of a surface resonance in the low areas of the graphene moiré, whose density distribution strongly depends on the stacking sequence of the moiré area and effectively quenches the magnetic moment for HCP-Top sites.

Molecular Oxygen Induced in-Gap States in PbS Quantum Dots.

Artificial solids composed of semiconductor quantum dots (QDs) are being developed for large-area electronic and optoelectronic applications, but these materials often have defect-induced in-gap states (IGS) of unknown chemical origin. Here we performed scanning probe based spectroscopic analysis and density functional theory calculations to determine the nature of such states and their electronic structure. We found that IGS near the valence band occur frequently in the QDs except when treated with reducing agents. Calculations on various possible defects and chemical spectroscopy revealed that molecular oxygen is most likely at the origin of these IGS. We expect this impurity-induced deep IGS to be a common occurrence in ionic semiconductors, where the intrinsic vacancy defects either do not produce IGS or produce shallow states near band edges. Ionic QDs with surface passivation to block impurity adsorption are thus ideal for high-efficiency optoelectronic device applications.

Elastic Response of Graphene Nanodomes

The mechanical behavior of a periodically buckled graphene membrane has been investigated by noncontact atomic force microscopy in ultrahigh vacuum. When a graphene monolayer is grown on Ru(0001), a regular arrangement of 0.075 nm high nanodomes forming a honeycomb lattice with 3 nm periodicity forms spontaneously. This structure responds in a perfectly reversible way to relative normal displacements up to 0.12 nm. Indeed, the elasticity of the nanodomes is proven by realistic DFT calculations, with an estimated normal stiffness k∼40 N/m. Our observations extend previous results on macroscopic graphene samples and confirm that the elastic behavior of this material is maintained down to nanometer length scales, which is important for the development of new high-frequency (terahertz) electromechanical devices.

Periodically modulated geometric and electronic structure of graphene on Ru(0 0 0 1)

We report here on a method of fabricating and characterizing highly perfect, periodically rippled graphene monolayers and islands, epitaxially grown on single crystal metallic substrates under controlled ultra-high vacuum conditions. The periodicity of the ripples is dictated by the difference in lattice parameters of graphene and substrate, and, thus, it is adjustable. We characterize its perfection at the atomic scale by means of STM and determine its electronic structure in the real space by local tunnelling spectroscopy. There are periodic variations in the geometric and electronic structure of the graphene monolayer. We observe inhomogeneities in the charge distribution, i.e. a larger occupied density of states at the higher parts of the ripples. Periodically rippled graphene might represent the physical realization of an ordered array of coupled graphene quantum dots. The data show, however, that for rippled graphene on Ru(0 0 0 1) both the low and the high parts of the ripples are metallic. The fabrication of periodically rippled graphene layers with controllable characteristic length and different bonding interactions with the substrate will allow a systematic experimental test of this fundamental problem.

Periodic spatial variation of the electron-phonon interaction in epitaxial graphene on Ru(0001)

We have performed low temperature scanning tunnelling spectroscopy measurements on graphene epitaxially grown on Ru(0001). An inelastic feature, related to the excitation of a vibrational breathing mode of the graphene lattice, was found at 360 meV. The change in the differential electrical conductance produced by this inelastic feature, which is associated with the electron-phonon interaction strength, varies spatially from one position to other of the graphene supercell. This inhomogeneity in the electronic properties of graphene on Ru(0001) results from local variations of the carbon–ruthenium interaction due to the lattice mismatch between the graphene and the Ru(0001) lattices.

Highly reproducible low temperature scanning tunneling microscopy and spectroscopy with in situ prepared tips

An in situ tip preparation procedure compatible with ultra-low temperature and high magnetic field scanning tunneling microscopes is presented. This procedure does not require additional preparation techniques such as thermal annealing or ion milling. It relies on the local electric-field-induced deposition of material from the tip onto the studied surface. Subsequently, repeated indentations are performed onto the sputtered cluster to mechanically anneal the tip apex and thus to ensure the stability of the tip. The efficiency of this method is confirmed by comparing the topography and spectroscopy data acquired with either unprepared or in situ prepared tips on epitaxial graphene grown on Ru (0001). We demonstrate that the use of in situ prepared tips increases the stability of the scanning tunneling images and the reproducibility of the spectroscopic measurements.