The mechanism of light emission from a scanning tunnelling microscope operating in air.

The scanning tunnelling microscope (STM) may be used as a low-energy, electrical nanosource of surface plasmon polaritons and light. In this article, we demonstrate that the optimum mode of operation of the STM for maximum photon emission is completely different in air than in vacuum. To this end, we investigate the emission of photons, the variation in the relative tip-sample distance and the measured current as a function of time for an STM operating in air. Contrary to the case of an STM operating in vacuum, the measured current between the tip and sample for an STM in air is very unstable (rapidly fluctuating in time) when the applied voltage between the tip and sample is in the ∼1.5-3 V range (i.e., in the energy range of visible photons). The photon emission occurs in short (50 µs) bursts when the STM tip is closest to the sample. The current instabilities are shown to be a key ingredient for producing intense light emission from an STM operating in air (photon emission rate several orders of magnitude higher than for stable current). These results are explained in terms of the interplay between the tunnel current and the electrochemical current in the ubiquitous thin water layer that exists when working in air.

Plasmon scattering from holes: from single hole scattering to Young's experiment.

In this paper, the scattering of surface plasmon polaritons (SPPs) into photons at holes is investigated. A local, electrically excited source of SPPs using a scanning tunneling microscope (STM) produces an outgoing circular plasmon wave on a thick (200 nm) gold film on glass containing holes of 250, 500 and 1000 nm diameter. Fourier plane images of the photons from hole-scattered plasmons show that the larger the hole diameter, the more directional the scattered radiation. These results are confirmed by a model where the hole is considered as a distribution of horizontal dipoles whose relative amplitudes, directions, and phases depend linearly on the local SPP electric field. An SPP-Young's experiment is also performed, where the STM-excited SPP wave is incident on a pair of 1 µm diameter holes in the thick gold film. The visibility of the resulting fringes in the Fourier plane is analyzed to show that the polarization of the electric field is maintained when SPPs scatter into photons. From this SPP-Young's experiment, an upper bound of ≈200 nm for the radius of this STM-excited source of surface plasmon polaritons is determined.

STM imaging, spectroscopy and manipulation of a self-assembled PTCDI monolayer on epitaxial graphene.

Scanning Tunneling Microscopy (STM), Scanning Tunneling Spectroscopy (STS), and manipulation studies were performed on an ordered self-assembled monolayer (SAM) of N,N'-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) molecules on epitaxial graphene on hexagonal silicon carbide - SiC(0001). Four novel aspects of the molecular SAM on graphene are presented. Molecules adsorb in both armchair and zig-zag configurations, giving rise to six orientations of the molecular layer with respect to the underlying substrate. The interaction between the molecules and the graphene surface shifts the LUMO towards the Fermi level, inducing a charge transfer and the opening of a band gap in the graphene, with the LUMO inside. This decouples the LUMO from the surface rendering it invisible in the dI/dV spectroscopy. The HOMO only becomes visible at short tip-surface distances, as its energy lies within the band gap of the SiC substrate. Finally, the observed molecular defects are very particular, being composed exclusively of molecular dimers. These molecular dimers have a stronger interaction with the graphene than other molecules.

The paradox of an insulating contact between a chemisorbed molecule and a wide band gap semiconductor surface.

Controlling the intrinsic optical and electronic properties of a single molecule adsorbed on a surface requires electronic decoupling of some molecular orbitals from the surface states. Scanning tunneling microscopy experiments and density functional theory calculations are used to study a perylene molecule derivative (DHH-PTCDI), adsorbed on the clean 3 × 3 reconstructed wide band gap silicon carbide surface (SiC(0001)-3 × 3). We find that the LUMO of the adsorbed molecule is invisible in I(V) spectra due to the absence of any surface or bulk states and that the HOMO has a very low saturation current in I(z) spectra. These results present a paradox that the molecular orbitals are electronically isolated from the surface of the wide band gap semiconductor even though strong chemical bonds are formed.

Excitation of propagating surface plasmons with a scanning tunnelling microscope.

Inelastic electron tunnelling excitation of propagating surface plasmon polaritons (SPPs) on a thin gold film is demonstrated. This is done by combining a scanning tunnelling microscope (STM) with an inverted optical microscope. Analysis of the leakage radiation in both the image and Fourier planes unambiguously shows that the majority (up to 99.5%) of the detected photons originate from propagating SPPs with propagation lengths of the order of 10  µm. The remaining photon emission is localized under the STM tip and is attributed to a tip-gold film coupled plasmon resonance as evidenced by the bimodal spectral distribution and enhanced emission intensity observed using a silver STM tip for excitation.

Manipulation of cadmium selenide nanorods with an atomic force microscope.

We have used an atomic force microscope (AFM) to manipulate and study ligand-capped cadmium selenide nanorods deposited on highly oriented pyrolitic graphite (HOPG). The AFM tip was used to manipulate (i.e., translate and rotate) the nanorods by applying a force perpendicular to the nanorod axis. The manipulation result was shown to depend on the point of impact of the AFM tip with the nanorod and whether the nanorod had been manipulated previously. Forces applied parallel to the nanorod axis, however, did not give rise to manipulation. These results are interpreted by considering the atomic-scale interactions of the HOPG substrate with the organic ligands surrounding the nanorods. The vertical deflection of the cantilever was recorded during manipulation and was combined with a model in order to estimate the value of the horizontal force between the tip and nanorod during manipulation. This horizontal force is estimated to be on the order of a few tens of nN.

Theoretical simulations of the tip-induced configuration changes of the 4,4(')-diacetyl-p-terphenyl molecule chemisorbed on Si(001).

We have investigated from a theoretical point of view modifications of the 4,4(')-diacetyl-p-terphenyl molecule chemisorbed on Si(001) induced by the scanning tunneling microscope (STM). In previous experiments, these modifications were observed to occur preferentially at the end of the molecule after a +4.0 V voltage pulse and at the center after a +4.5 V voltage pulse. In the framework of ab initio simulations, we have realized a systematic energetic study of the dissociative chemisorption of one, two, or three phenyl rings of the substituted p-terphenyl molecule. Charge densities were then calculated for the investigated configurations and compared to the STM topographies. Before manipulation with the STM tip, the substituted p-terphenyl molecule is preferentially adsorbed without phenyl ring dissociation, allowing a partial rotation of the central phenyl ring. Our results show that the STM induced modifications observed at the end of the molecule might originate from the dissociation of two phenyl rings (one central and one external ring), while the modifications occurring at the central part of the molecule can be interpreted as a dissociation of the two external rings.

Active drift compensation applied to nanorod manipulation with an atomic force microscope.

We have developed a simple algorithm to overcome the problem of thermal drift in an atomic force microscope (AFM) operating under ambient conditions. Using our method, we demonstrate that the AFM tip remains above a 5-nm-high and 50-nm-long CdSe nanorod for more than 90 min despite the thermal drift present (6 nm/min). We have applied our drift compensation technique to the AFM manipulation of CdSe colloidal nanorods lying horizontally on a highly oriented pyrolytic graphite surface. Since we have precise control over the position of the AFM tip relative to the nanorod, we can choose to either translate or rotate the rod by changing the location of the tip-rod interaction point.

Difficulty for oxygen to incorporate into the silicon network during initial O2 oxidation of Si(100)-(2x1).

First principles calculations and scanning tunneling microscopy studies of the oxidation of Si(100)-(2x1) surfaces by molecular oxygen reveal that the surface silanone (O)(Si=O) species is remarkably stable, constituting the key intermediate for initial oxidation. The propensity for oxygen to remain within the top surface layer as opposed to incorporating within Si-Si backbonds is surprisingly high. This resistance to incorporation into a cubic lattice even at higher coverages could be a factor to facilitate surface amorphization in subsequent steps.

Picometer-scale electronic control of molecular dynamics inside a single molecule.

Tunneling electrons from a low-temperature (5 kelvin) scanning tunneling microscope were used to control, through resonant electronic excitation, the molecular dynamics of an individual biphenyl molecule adsorbed on a silicon(100) surface. Different reversible molecular movements were selectively activated by tuning the electron energy and by selecting precise locations for the excitation inside the molecule. Both the spatial selectivity and energy dependence of the electronic control are supported by spectroscopic measurements with the scanning tunneling microscope. These experiments demonstrate the feasibility of controlling the molecular dynamics of a single molecule through the localization of the electronic excitation inside the molecule.

Atomic-scale STM experiments on semiconductor surfaces: towards molecular nanomachines.

The electronic or quantum control of individual molecules with the scanning tunnelling microscope offers exciting perspectives on operating molecular nanomachines. This implies the use of semiconductor surfaces rather than metallic surfaces which would rapidly quench the electronic excitations. We review recent results illustrating the state of the art and the main problems which need to be solved: the choice, design and properties of functionalized organic molecules on semiconductor surfaces; the control of the inelastic electronic channels through a single molecule; and the search for well-controlled atomic-scale wide-band-gap semiconductor surfaces.

Electronic structure of partially hydrogenated Si(100)-( 2 x 1) surfaces prepared by thermal and nonthermal desorption.

The electronic structure of partially hydrogenated Si(100)- (2 x 1) surfaces, prepared by controlled thermal annealing and nonthermal photon stimulated desorption of fully hydrogenated Si(100) surfaces, has been investigated by using valence band photoemission. Thermal and nonthermal desorption are found to produce very specific electronic surface structures. This led us to the discovery of two specific surface states having binding energies of 1.0 and 0.7 eV associated with the isolated Si dimers and single Si dangling bonds, respectively.

Selective photon-stimulated desorption of hydrogen from GaAs surfaces.

Photon-stimulated desorption of H(+) from hydrogenated GaAs (110) and (100) surfaces was studied as a function of photon energy. Distinct peaks, observed around As 3d core-level binding energy for desorption from the GaAs (100) surface and in the As 3d and Ga 3p region for desorption from the GaAs (110) surface, show a striking similarity with the fine structure (spin-orbit splitting) measured in the photoemission from As 3d and Ga 3p levels. These results provide clear evidence for direct desorption processes and represent a basis for selective modification of hydrogenated GaAs surfaces.