C60 chain phases on ZnPc/Ag(111) surfaces: Supramolecular organization driven by competing interactions.

Serpentine chain C60 phases were observed in scanning tunneling microscopy (STM) images of C60 layers on zinc phthalocyanine (ZnPc) or pentacene covered Ag(111) and Au(111) surfaces. This low-density, quasi-one-dimensional organization contrasts starkly with the close-packed hexagonal phases observed for C60 layers on bare metal substrates. STM was employed to perform a detailed investigation of these chain structures for C60/ZnPc/Ag(111) heterolayers. Motivated by the similarity of these chain phases, and the chain and stripe organization occurring in dipole-fluid systems, we investigated a model based on competing van der Waals attractions and electrostatic repulsions between C60 molecules as an explanation for the driving force behind these monolayer phases. Density functional theory (DFT) calculations revealed significant charge transfer to C60 from the Ag(111) substrate, through the intervening ZnPc layer, inducing electrostatic interactions between C60 molecules. Molecular dynamics simulations performed with attractive van der Waals interactions plus repulsive dipole-dipole interactions reproduced the C60 chain phases with dipole magnitudes consistent with DFT calculations.

Visualizing the electron scattering force in nanostructures.

In nanoscale metal wires, electrical current can cause structural changes through electromigration, in which the momentum of electrons biases atomic motion, but the microscopic details are complex. Using in situ scanning tunneling microscopy, we examined the effects of thermally excited defects on the current-biased displacement of monatomic islands of radius 2 to 50 nanometers on single-crystal Ag(111). The islands move opposite to the current direction, with velocity varying inversely with radius. The force is thus in the same direction as electron flow and acts on atomic defect sites at the island edge. The unexpectedly large force on the boundary atoms can be decreased by over a factor of 10 by adding a mildly electron-withdrawing adsorbate, C60, which also modifies the step geometry. The low coordination of the identified scattering sites is the likely origin of the large force.

High-fidelity conformation of graphene to SiO2 topographic features.

High-resolution noncontact atomic force microscopy of SiO2 reveals previously unresolved roughness at the few-nm length scale, and scanning tunneling microscopy of graphene on SiO2 shows graphene to be slightly smoother than the supporting SiO2 substrate. A quantitative energetic analysis explains the observed roughness of graphene on SiO2 as extrinsic, and a natural result of highly conformal adhesion. Graphene conforms to the substrate down to the smallest features with nearly 99% fidelity, indicating conformal adhesion can be highly effective for strain engineering of graphene.

Defect scattering in graphene.

Irradiation of graphene on SiO2 by 500 eV Ne and He ions creates defects that cause intervalley scattering as is evident from a significant Raman D band intensity. The defect scattering gives a conductivity proportional to charge carrier density, with mobility decreasing as the inverse of the ion dose. The mobility decrease is 4 times larger than for a similar concentration of singly charged impurities. The minimum conductivity decreases proportional to the mobility to values lower than 4e(2)/pih, the minimum theoretical value for graphene free of intervalley scattering. Defected graphene shows a diverging resistivity at low temperature, indicating insulating behavior. The results are best explained by ion-induced formation of lattice defects that result in midgap states.

Generalized survival in step fluctuations.

The properties of the generalized survival probability, that is, the probability of not crossing an arbitrary location R during relaxation, have been investigated experimentally (via scanning tunneling microscope observations) and numerically. The results confirm that the generalized survival probability decays exponentially with a time constant tau(s) (R). The distance dependence of the time constant is shown to be tau(s) (R) = tau(s0) exp[-R/w (T)], where w2 (T) is the material-dependent mean-squared width of the step fluctuations. The result reveals the dependence on the physical parameters of the system inherent in the prior prediction of the time constant scaling with R/L(alpha), with L the system size and alpha the roughness exponent. The survival behavior is also analyzed using a contrasting concept, the generalized inside survival S(in) (t,R), which involves fluctuations to an arbitrary location R further from the average. Numerical simulations of the inside survival probability also show an exponential time dependence, and the extracted time constant empirically shows (R/w)(lambda) behavior, with lambda varying over 0.6 to 0.8 as the sampling conditions are changed. The experimental data show similar behavior, and can be well fit with lambda = 1.0 for T = 300 K, and 0.5 < lambda < 1 for T = 460 K. Over this temperature range, the ratio of the fixed sampling time to the underlying physical time constant, and thus the true correlation time, increases by a factor of approximately 10(3). Preliminary analysis indicates that the scaling effect due to the true correlation time is relevant in the parameter space of the experimental observations.

Atomic structure of graphene on SiO2.

We employ scanning probe microscopy to reveal atomic structures and nanoscale morphology of graphene-based electronic devices (i.e., a graphene sheet supported by an insulating silicon dioxide substrate) for the first time. Atomic resolution scanning tunneling microscopy images reveal the presence of a strong spatially dependent perturbation, which breaks the hexagonal lattice symmetry of the graphitic lattice. Structural corrugations of the graphene sheet partially conform to the underlying silicon oxide substrate. These effects are obscured or modified on graphene devices processed with normal lithographic methods, as they are covered with a layer of photoresist residue. We enable our experiments by a novel cleaning process to produce atomically clean graphene sheets.

Spatial first-passage statistics of Al/Si(111)-(square root 3 x square root 3) step fluctuations.

Spatial step edge fluctuations on a multicomponent surface of Al/Si(111)-(square root 3 x square root 3) were measured via scanning tunneling microscopy over a temperature range of 720-1070 K, for step lengths of L=65-160 nm. Even though the time scale of fluctuations of steps on this surface varies by orders of magnitude over the indicated temperature range, measured first-passage spatial persistence and survival probabilities are temperature independent. The power law functional form for spatial persistence probabilities is confirmed and the symmetric spatial persistence exponent is measured to be theta=0.498+/-0.062 in agreement with the theoretical prediction theta=1/2. The survival probability is found to scale directly with y/L, where y is the distance along the step edge. The form of the survival probabilities agrees quantitatively with the theoretical prediction, which yields exponential decay in the limit of small y/L. The decay constant is found experimentally to be y(s)/L=0.076+/-0.033 for y/L

Biased surface fluctuations due to current stress.

Direct correlation between temporal structural fluctuations and electron wind force is demonstrated, for the first time, by STM imaging and analysis of atomically resolved motion on a thin film surface under large applied current (10(5) A/cm2). The magnitude of the momentum transfer between current carriers and the geometrically constrained atoms in the fluctuating structure is at least 5x to 15x (+/-1sigma range) larger than for freely diffusing adatoms. Corresponding changes in surface resistivity will contribute significant fluctuation signature to nanoscale electronic properties.

Distinctive fluctuations in a confined geometry.

Spurred by recent theoretical predictions [Phys. Rev. E 69, 035102(R) (2004)10.1103/PhysRevE.69.035102; Surf. Sci. Lett. 598, L355 (2005)10.1016/j.susc.2005.09.023], we find experimentally using STM line scans that the fluctuations of the step bounding a facet exhibit scaling properties distinct from those of isolated steps or steps on vicinal surfaces. The correlation functions go as t0.15 +/- 0.03 decidedly different from the t0.26 +/- 0.02 behavior for fluctuations of isolated steps. From the exponents, we categorize the universality, confirming the prediction that the nonlinear term of the Kardar-Parisi-Zhang equation, long known to play a central role in nonequilibrium phenomena, can also arise from the curvature or potential-asymmetry contribution to the step free energy.

Spiral evolution in a confined geometry.

Supported nanoscale lead crystallites with a step emerging from a noncentered screw dislocation on the circular top facet were prepared by rapid cooling from just above the melting temperature. STM observations of the top facet show a nonuniform rotation rate and shape of the spiral step as the crystallite relaxes. These features can be accurately modeled using curvature driven dynamics, as in classical models of spiral growth, with boundary conditions fixing the dislocation core and regions of the step lying along the outer facet edge.

Sampling-time effects for persistence and survival in step structural fluctuations.

The effects of sampling rate and total measurement time have been determined for single-point measurements of step fluctuations within the context of first-passage properties. Time dependent scanning tunneling microscopy has been used to evaluate step fluctuations on Ag(111) films grown on mica as a function of temperature (300-410 K) , on screw dislocations on the facets of Pb crystallites at 320 K , and on Al-terminated Si(111) over the temperature range 770-970 K . Although the fundamental time constant for step fluctuations on Ag and Al/Si varies by orders of magnitude over the temperature ranges of measurement, no dependence of the persistence amplitude on temperature is observed. Instead, the persistence probability is found to scale directly with t/delta t where delta t is the time interval used for sampling. Survival probabilities show a more complex scaling dependence, which includes both the sampling interval and the total measurement time t(m) . Scaling with t/delta t occurs only when delta t/ t(m) is a constant. We show that this observation is equivalent to theoretical predictions that the survival probability will scale as delta t/ L(z) , where L is the effective length of a step. This implies that the survival probability for large systems, when measured with fixed values of t(m) or delta t , should also show little or no temperature dependence.

Spontaneous breaking of time-reversal symmetry in the pseudogap state of a high-Tc superconductor.

A change in 'symmetry' is often observed when matter undergoes a phase transition-the symmetry is said to be spontaneously broken. The transition made by underdoped high-transition-temperature (high-Tc) superconductors is unusual, in that it is not a mean-field transition as seen in other superconductors. Rather, there is a region in the phase diagram above the superconducting transition temperature Tc (where phase coherence and superconductivity begin) but below a characteristic temperature T* where a 'pseudogap' appears in the spectrum of electronic excitations. It is therefore important to establish if T* is just a cross-over temperature arising from fluctuations in the order parameter that will establish superconductivity at Tc (refs 3, 4), or if it marks a phase transition where symmetry is spontaneously broken. Here we report that, for a material in the pseudogap state, left-circularly polarized photons give a different photocurrent from right-circularly polarized photons. This shows that time-reversal symmetry is spontaneously broken below T*, which therefore corresponds to a phase transition.

Commensurate water monolayer at the RuO2(110)/water interface.

We demonstrate the presence of two types of commensurate, registered water monolayers with different densities at the RuO2(110)/bulk-water (0.1 M NaOH solution) interface with off-specular, oxygen crystal truncation rods. At anodic potentials (close to oxygen evolution), the extraneous water layer and the surface hydroxide layer form a bilayer with O-H-O bond distances similar to that of ice X. At cathodic potentials, the water molecules converted from the bridging OH molecules form a low-density water layer.