A new aberration-corrected, energy-filtered LEEM/PEEM instrument II. Operation and results.

In Part I we described a new design for an aberration-corrected Low Energy Electron Microscope (LEEM) and Photo Electron Emission Microscope (PEEM) equipped with an in-line electron energy filter. The chromatic and spherical aberrations of the objective lens are corrected with an electrostatic electron mirror that provides independent control of the chromatic and spherical aberration coefficients Cc and C3, as well as the mirror focal length. In this Part II we discuss details of microscope operation, how the microscope is set up in a systematic fashion, and we present typical results.

Direct measurement of the growth mode of graphene on SiC(0001) and SiC(0001¯).

We have determined the growth mode of graphene on SiC(0001) and SiC(0001¯) using ultrathin, isotopically labeled Si(13)C "marker layers" grown epitaxially on the Si(12)C surfaces. Few-layer graphene overlayers were formed via thermal decomposition at elevated temperature. For both surface terminations (Si face and C face), we find that the (13)C is located mainly in the outermost graphene layers, indicating that, during decomposition, new graphene layers form underneath existing ones.

Atomic-scale transport in epitaxial graphene.

The high carrier mobility of graphene is key to its applications, and understanding the factors that limit mobility is essential for future devices. Yet, despite significant progress, mobilities in excess of the 2×10(5) cm(2) V(-1) s(-1) demonstrated in free-standing graphene films have not been duplicated in conventional graphene devices fabricated on substrates. Understanding the origins of this degradation is perhaps the main challenge facing graphene device research. Experiments that probe carrier scattering in devices are often indirect, relying on the predictions of a specific model for scattering, such as random charged impurities in the substrate. Here, we describe model-independent, atomic-scale transport measurements that show that scattering at two key defects--surface steps and changes in layer thickness--seriously degrades transport in epitaxial graphene films on SiC. These measurements demonstrate the strong impact of atomic-scale substrate features on graphene performance.

A new aberration-corrected, energy-filtered LEEM/PEEM instrument. I. Principles and design.

We describe a new design for an aberration-corrected low energy electron microscope (LEEM) and photo electron emission microscope (PEEM), equipped with an in-line electron energy filter. The chromatic and spherical aberrations of the objective lens are corrected with an electrostatic electron mirror that provides independent control over the chromatic and spherical aberration coefficients C(c) and C(3), as well as the mirror focal length, to match and correct the aberrations of the objective lens. For LEEM (PEEM) the theoretical resolution is calculated to be approximately 1.5 nm (approximately 4 nm). Unlike previous designs, this instrument makes use of two magnetic prism arrays to guide the electron beam from the sample to the electron mirror, removing chromatic dispersion in front of the mirror by symmetry. The aberration correction optics was retrofitted to an uncorrected instrument with a base resolution of 4.1 nm in LEEM. Initial results in LEEM show an improvement in resolution to approximately 2 nm.

Thermodynamics and kinetics of graphene growth on SiC(0001).

The formation of surface phases on the Si-terminated SiC(0001) surface, from the Si-rich (3x3) structure, through the intermediate (1x1) and (sqrt[3]xsqrt[3])-R30 degrees structures, to the C-rich (6sqrt[3]x6sqrt[3]) phase, and finally epitaxial graphene, has been well documented. But the thermodynamics and kinetics of these phase formations are poorly understood. Using in situ low energy electron microscopy, we show how the phase transformation temperatures can be shifted over several hundred degrees Celsius, and the phase transformation time scales reduced by several orders of magnitude, by balancing the rate of Si evaporation with an external flux of Si. Detailed insight in the thermodynamics allows us to dramatically improve the morphology of the final C-rich surface phases, including epitaxial graphene.

A simple energy filter for low energy electron microscopy/photoelectron emission microscopy instruments.

Addition of an electron energy filter to low energy electron microscopy (LEEM) and photoelectron emission microscopy (PEEM) instruments greatly improves their analytical capabilities. However, such filters tend to be quite complex, both electron optically and mechanically. Here we describe a simple energy filter for the existing IBM LEEM/PEEM instrument, which is realized by adding a single scanning aperture slit to the objective transfer optics, without any further modifications to the microscope. This energy filter displays a very high energy resolution ΔE/E = 2 × 10(-5), and a non-isochromaticity of ∼0.5 eV/10 µm. The setup is capable of recording selected area electron energy spectra and angular distributions at 0.15 eV energy resolution, as well as energy filtered images with a 1.5 eV energy pass band at an estimated spatial resolution of ∼10 nm. We demonstrate the use of this energy filter in imaging and spectroscopy of surfaces using a laboratory-based He I (21.2 eV) light source, as well as imaging of Ag nanowires on Si(001) using the 4 eV energy loss Ag plasmon.

Spontaneous formation and growth of a new polytype on SiC(0001).

Using in situ electron microscopy, we have measured the structure of SiC(0001)-4H during annealing in vacuum. Above 1000 degrees C, an additional SiC bilayer forms on the surface that changes the polytype from hexagonal (4H) to cubic (3C). The interaction with surface steps prevents the cubic layer from growing thicker: the new phase does not wet the steps of the underlying 4H substrate. Instead, the cubic layer expands laterally, accelerating step bunching in the surrounding hexagonal regions. During SiC homoepitaxy, this lack of step edge wetting leads to the growth of 3C twins separated by deep grooves.

Metastability in 2D self-assembling systems.

We show that 2D self-assembled domains can remain trapped in a large variety of long-lived and metastable shapes that arise from an interplay of crystalline anisotropy and relaxation of elastic strain. On commonly used cubic (111) substrates, these shapes include extended or stacked structures made up of triangular domains connected at their corners, compact shapes with both convex and concave curvatures and others with narrow and elongated arms. We show that all of these distinct experimentally observed shapes can be explained within a unified framework and present a phase diagram that systematically classifies the metastable shapes as a function of their size.

Anomalous spiral motion of steps near dislocations on silicon surfaces.

We have used low-energy electron microscopy to measure step motion on Si(111) and Si(001) near dislocations during growth and sublimation. Steps on Si(111) exhibit the classic rotating Archimedean spiral motion, as predicted by Burton, Cabrera, and Frank. Steps on Si(001), however, move in a strikingly different manner. The strain-relieving anomalous behavior can be understood in detail by considering how the local step velocity is affected by the nonuniform strain field arising from the dislocation. We show how the dynamic step-flow pattern is related to the dislocation slip system.

Origins of nanoscale heterogeneity in ultrathin films.

A key challenge in thin-film growth is controlling structure and composition at the atomic scale. We have used spatially resolved electron scattering to measure how the three-dimensional composition profile of an alloy film evolves with time at the nanometer length scale. We show that heterogeneity during the growth of Pd on Cu(001) arises naturally from a generic step-overgrowth mechanism relevant in many growth systems.

The influence of the surface migration of gold on the growth of silicon nanowires.

Interest in nanowires continues to grow, fuelled in part by applications in nanotechnology. The ability to engineer nanowire properties makes them especially promising in nanoelectronics. Most silicon nanowires are grown using the vapour-liquid-solid (VLS) mechanism, in which the nanowire grows from a gold/silicon catalyst droplet during silicon chemical vapour deposition. Despite over 40 years of study, many aspects of VLS growth are not well understood. For example, in the conventional picture the catalyst droplet does not change during growth, and the nanowire sidewalls consist of clean silicon facets. Here we demonstrate that these assumptions are false for silicon nanowires grown on Si(111) under conditions where all of the experimental parameters (surface structure, gas cleanliness, and background contaminants) are carefully controlled. We show that gold diffusion during growth determines the length, shape, and sidewall properties of the nanowires. Gold from the catalyst droplets wets the nanowire sidewalls, eventually consuming the droplets and terminating VLS growth. Gold diffusion from the smaller droplets to the larger ones (Ostwald ripening) leads to nanowire diameters that change during growth. These results show that the silicon nanowire growth is fundamentally limited by gold diffusion: smooth, arbitrarily long nanowires cannot be grown without eliminating gold migration.

Selective placement of carbon nanotubes on metal-oxide surfaces.

We describe a method to selectively position carbon nanotubes on Al2O3 and HfO2 surfaces. The method exploits the selective binding of alkylphosphonic acids to oxide surfaces with large isoelectric points (i.e. basic rather than acidic surfaces). We have patterned oxide surfaces with acids using both microcontact printing and conventional lithography. With proper choice of the functional end group (e.g., -CH3 or -NH2), nanotube adhesion to the surface can be either prevented or enhanced.

Critical role of surface steps in the alloying of Ge on Si(001).

Using low-energy electron microscopy, we show that intermixing of Ge on Si(001) during growth is enhanced on stepped surfaces and is hindered on terraces where step flow does not occur. On large terraces we have identified a dramatic and unanticipated structural rearrangement that facilitates intermixing: Pairs of steps spontaneously form and migrate over the surface, leaving alloyed regions in their wake. The driving force for step formation is the entropy gain associated with the enhanced intermixing of Ge.

Shape and stability of self-assembled surface domains.

The shapes of two-dimensional (2D) nanostructures on surfaces are determined by their boundary energies as well as by long-range elastic, electrostatic or magnetic interactions. Although it is well known that long-range interactions can give rise to shape bifurcation-an abrupt change in shape symmetry at a critical size-a general description of the evolution of shape with size, systematically incorporating both the azimuthal dependence of the boundary energy and long-range interactions, has been lacking. Here we show that unconstrained shape relaxation, including previously ignored boundary curvature, leads to a novel, continuous shape change from convex at small size to concave at large size. In addition to demonstrating a method to quantitatively determine the azimuthal dependence of the boundary energy, we show that the energy gain associated with boundary curvature relaxation is a key factor in stabilizing surface nanostructures. For 7 x 7 domains on Si(111), boundary curvature reduces the formation free-energy by up to 50%.

Influence of supersaturation on surface structure.

Using low-energy electron microscopy, we have investigated the influence of an external flux on the structure of the Si(111) surface during growth and etching at elevated temperatures. We find that varying the adatom supersaturation effectively changes the surface free energies of coexisting 7 x 7 and '1 x 1' regions of the surface. In response, the boundaries separating the phases adopt a new steady-state configuration. The measured configuration can be used to quantitatively determine the difference in free energy between the phases, Deltagamma. The change in Deltagamma provides a measure of the local supersaturation at the surface, and can be interpreted as a change in the phase-transition temperature.

Surface stress and thermodynamic nanoscale size selection.

Using the Si(111) surface as an example, we show how temperature can be used to tune the size of domains during a surface phase transition. From analysis of the measured stable domain sizes, we determine key material parameters and clarify the close relationship between nucleation and thermodynamic size selection. More generally, the model we developed describes nanoscale self-assembly processes in contact with a reservoir (for example, liquid- or vapor-phase epitaxy).

Diffusion kinetics in the Pd/Cu(001) surface alloy.

We use atom-tracking scanning tunneling microscopy to study the diffusion of Pd in the Pd/Cu(001) surface alloy as a function of temperature. By following the motion of individual Pd atoms incorporated in the surface, we show that Pd diffuses by a vacancy-exchange mechanism. We measure an activation energy for the diffusion of incorporated Pd atoms of 0.88 eV, which is in good agreement with our ab initio calculated energy of 0.94 eV.

Phase coexistence during surface phase transitions.

In contrast to standard thermodynamic models, we observe phase coexistence over an extended temperature range at a first-order surface phase transition. We have measured the domain evolution of the Si(111)-( 7x7) to ( 1x1) phase transition with temperature, using low-energy electron microscopy. Comparison with detailed, quantitative theoretical predictions shows that coexistence is due to long-range elastic and electrostatic domain interactions. Phase coexistence is predicted to be a universal feature of surface phase transitions.