Rocking motion induced charging of C60 on h-BN/Ni(111)

One monolayer of C60 on one monolayer of hexagonal boron nitride on nickel is investigated by photoemission. Between 150 and 250 K the work function decreases and the binding energy of the highest occupied molecular orbital (HOMO) increases by approx. 100 meV. In parallel, the occupancy of the, in the cold state almost empty, lowest unoccupied molecular orbital (LUMO) changes by 0.4 electrons. This charge redistribution is triggered by onset of molecular rocking motion, i.e. by orientation dependent tunneling between the LUMO of C60 and the substrate. The magnitude of the charge transfer is large and cannot be explained within a single particle picture. It is proposed to involve electron-phonon coupling where C60- polaron formation leads to electron self-trapping.Comment: 15 pages, 4 figure

Effect of bonding of a CO molecule on the conductance of atomic metal wires

We have measured the effect of bonding of a CO molecule on the conductance of Au, Cu, Pt, and Ni atomic contacts at 4.2 K. When CO gas is admitted to the metal nano contacts, a conductance feature appears in the conductance histogram near 0.5 of the quantum unit of conductance, for all metals. For Au, the intensity of this fractional conductance feature can be tuned with the bias voltage, and it disappears at high bias voltage (above $\sim$ 200 mV). The bonding of CO to Au appears to be weakest, and associated with monotomic Au wire formation.Comment: 6 figure

Observation of Magnetic Edge State and Dangling Bond State on Nanographene in Activated Carbon Fibers

The electronic structure of nanographene in pristine and fluorinated activated carbon fibers (ACFs) have been investigated with near-edge x-ray absorption fine structure (NEXAFS) and compared with magnetic properties we reported on previously. In pristine ACFs in which magnetic properties are governed by non-bonding edge states of the \pi-electron, a pre-peak assigned to the edge state was observed below the conduction electron {\pi}* peak close to the Fermi level in NEXAFS. Via the fluorination of the ACFs, an extra peak, which was assigned to the \sigma-dangling bond state, was observed between the pre-peak of the edge state and the {\pi}* peak in the NEXAFS profile. The intensities of the extra peak correlate closely with the spin concentration created upon fluorination. The combination of the NEXAFS and magnetic measurement results confirms the coexistence of the magnetic edge states of \pi-electrons and dangling bond states of \sigma-electrons on fluorinated nanographene sheets.Comment: 4 figures, to appear in Phys. Rev.

Highly Conducting pi-Conjugated Molecular Junctions Covalently Bonded to Gold Electrodes

We measure electronic conductance through single conjugated molecules bonded to Au metal electrodes with direct Au-C covalent bonds using the scanning tunneling microscope based break-junction technique. We start with molecules terminated with trimethyltin end groups that cleave off in situ resulting in formation of a direct covalent sigma bond between the carbon backbone and the gold metal electrodes. The molecular carbon backbone used in this study consist of a conjugated pi-system that has one terminal methylene group on each end, which bonds to the electrodes, achieving large electronic coupling of the electrodes to the pi-system. The junctions formed with the prototypical example of 1,4-dimethylenebenzene show a conductance approaching one conductance quantum (G0 = 2e2/h). Junctions formed with methylene terminated oligophenyls with two to four phenyl units show a hundred-fold increase in conductance compared with junctions formed with amine-linked oligophenyls. The conduction mechanism for these longer oligophenyls is tunneling as they exhibit an exponential dependence of conductance with oligomer length. In addition, density functional theory based calculations for the Au-xylylene-Au junction show near-resonant transmission with a cross-over to tunneling for the longer oligomers.Comment: Accepted to the Journal of the American Chemical Society as a Communication

Evidence for Quantum Interference in SAMs of Arylethynylene Thiolates in Tunneling Junctions with Eutectic Ga-In (EGaIn) Top-Contacts

This paper compares the current density (J) versus applied bias (V) of self-assembled monolayers (SAMs) of three different ethynylthiophenol-functionalized anthracene derivatives of approximately the same thickness with linear-conjugation (AC), cross-conjugation (AQ), and broken-conjugation (AH) using liquid eutectic Ga-In (EGaIn) supporting a native skin (~1 nm thick) of Ga2O3 as a nondamaging, conformal top-contact. This skin imparts non-Newtonian rheological properties that distinguish EGaIn from other top-contacts; however, it may also have limited the maximum values of J observed for AC. The measured values of J for AH and AQ are not significantly different (J ≈ 10-1 A/cm2 at V = 0.4 V). For AC, however, J is 1 (using log averages) or 2 (using Gaussian fits) orders of magnitude higher than for AH and AQ. These values are in good qualitative agreement with gDFTB calculations on single AC, AQ, and AH molecules chemisorbed between Au contacts that predict currents, I, that are 2 orders of magnitude higher for AC than for AH at 0 < |V| < 0.4 V. The calculations predict a higher value of I for AQ than for AH; however, the magnitude is highly dependent on the position of the Fermi energy, which cannot be calculated precisely. In this sense, the theoretical predictions and experimental conclusions agree that linearly conjugated AC is significantly more conductive than either cross-conjugated AQ or broken conjugate AH and that AQ and AH cannot necessarily be easily differentiated from each other. These observations are ascribed to quantum interference effects. The agreement between the theoretical predictions on single molecules and the measurements on SAMs suggest that molecule-molecule interactions do not play a significant role in the transport properties of AC, AQ, and AH.

The number of transmission channels through a single-molecule junction

We calculate transmission eigenvalue distributions for Pt-benzene-Pt and Pt-butadiene-Pt junctions using realistic state-of-the-art many-body techniques. An effective field theory of interacting $\pi$-electrons is used to include screening and van der Waals interactions with the metal electrodes. We find that the number of dominant transmission channels in a molecular junction is equal to the degeneracy of the molecular orbital closest to the metal Fermi level.Comment: 9 pages, 8 figure

Effect of Thermoelectric Cooling in Nanoscale Junctions

We propose a thermoelectric cooling device based on an atomic-sized junction. Using first-principles approaches, we investigate the working conditions and the coefficient of performance (COP) of an atomic-scale electronic refrigerator where the effects of phonon's thermal current and local heating are included. It is observed that the functioning of the thermoelectric nano-refrigerator is restricted to a narrow range of driving voltages. Compared with the bulk thermoelectric system with the overwhelmingly irreversible Joule heating, the 4-Al atomic refrigerator has a higher efficiency than a bulk thermoelectric refrigerator with the same $ZT$ due to suppressed local heating via the quasi-ballistic electron transport and small driving voltages. Quantum nature due to the size minimization offered by atomic-level control of properties facilitates electron cooling beyond the expectation of the conventional thermoelectric device theory.Comment: 8 figure

Effect of Impurities on Pentacene Thin Film Growth for Field-Effect Transistors

Pentacenequinone (PnQ) impurities have been introduced into a pentacene source material at number densities from 0.001 to 0.474 to quantify the relative effects of impurity content and grain boundary structure on transport in pentacene thin-film transistors. Atomic force microscopy (AFM) and electrical measurements of top-contact pentacene thin-film transistors have been employed to directly correlate initial structure and final film structures, with the device mobility as a function of added impurity content. The results reveal a factor four decrease in mobility without significant changes in film morphology for source PnQ number fractions below ~0.008. For these low concentrations, the impurity thus directly influences transport, either as homogeneously distributed defects or by concentration at the otherwise-unchanged grain boundaries. For larger impurity concentrations, the continuing strong decrease in mobility is correlated with decreasing grain size, indicating an impurity-induced increase in the nucleation of grains during early stages of film growth.Comment: 18 pages, 4 Figures, 1 Tabl