Presolidification in Eutectic Droplets.

Evidence of presolidification, the counterpart to premelting, is reported. Near the eutectic temperature, T_{C}, the propagation direction of thermal gradient driven motion of eutectic Ge-Pt droplets on Ge(110) is determined by presolidification. Well above T_{C}, the micron-sized droplets move towards the hottest location at the substrate, irrespective of crystalline direction. At 90 K above T_{C}, a strong, unanticipated preference for propagation along the substrate [001] azimuth suddenly emerges, which is attributed to presolidification at the liquid-solid interface. The propagation along [001] is accompanied by a distinct change in shape from compact to elongated along [001].

Temperature-Controlled Rotational Epitaxy of Graphene.

When graphene is placed on a crystalline surface, the periodic structures within the layers superimpose and moiré superlattices form. Small lattice rotations between the two materials in contact strongly modify the moiré lattice parameter, upon which many electronic, vibrational, and chemical properties depend. While precise adjustment of the relative orientation in the degree- and sub-degree-range can be achieved via careful deterministic transfer of graphene, we report on the spontaneous reorientation of graphene on a metallic substrate, Ir(111). We find that selecting a substrate temperature between 1530 and 1000 K during the growth of graphene leads to distinct relative rotational angles of 0°, ± 0.6°, ±1.1°, and ±1.7°. When modeling the moiré superlattices as two-dimensional coincidence networks, we can ascribe the observed rotations to favorable low-strain graphene structures. The dissimilar thermal expansion of the substrate and graphene is regarded as an effective compressive biaxial pressure that is more easily accommodated in graphene by small rotations rather than by compression.

Electrochemically Induced Nanobubbles between Graphene and Mica.

We present a new method to create dynamic nanobubbles. The nanobubbles are created between graphene and mica by reducing intercalated water to hydrogen. The nanobubbles have a typical radius of several hundred nanometers, a height of a few tens of nanometers and an internal pressure in the range of 0.5-8 MPa. Our approach paves the way to the realization of nanobubbles of which both size and internal pressure are tunable.

Latent heat induced rotation limited aggregation in 2D ice nanocrystals.

The basic science responsible for the fascinating shapes of ice crystals and snowflakes is still not understood. Insufficient knowledge of the interaction potentials and the lack of relevant experimental access to the growth process are to blame for this failure. Here, we study the growth of fractal nanostructures in a two-dimensional (2D) system, intercalated between mica and graphene. Based on our scanning tunneling spectroscopy data, we provide compelling evidence that these fractals are 2D ice. They grow while they are in material contact with the atmosphere at 20 °C and without significant thermal contact to the ambient. The growth is studied in situ, in real time and space at the nanoscale. We find that the growing 2D ice nanocrystals assume a fractal shape, which is conventionally attributed to Diffusion Limited Aggregation (DLA). However, DLA requires a low mass density mother phase, in contrast to the actual currently present high mass density mother phase. Latent heat effects and consequent transport of heat and molecules are found to be key ingredients for understanding the evolution of the snow (ice) flakes. We conclude that not the local availability of water molecules (DLA), but rather them having the locally required orientation is the key factor for incorporation into the 2D ice nanocrystal. In combination with the transport of latent heat, we attribute the evolution of fractal 2D ice nanocrystals to local temperature dependent rotation limited aggregation. The ice growth occurs under extreme supersaturation, i.e., the conditions closely resemble the natural ones for the growth of complex 2D snow (ice) flakes and we consider our findings crucial for solving the "perennial" snow (ice) flake enigma.

Desorption of oxygen from alloyed Ag/Pt(111).

We have investigated the interaction of oxygen with the Ag/Pt(111) surface alloy by thermal desorption spectroscopy (TDS). The surface alloy was formed during the deposition of sub-monolayer amounts of silver on Pt(111) at 800 K and subsequent cooling to 300 K. The low-temperature phase of the surface alloy is composed of nanometer-sized silver rich stripes, embedded within platinum-rich domains, which were characterized with spot profile analysis low energy electron diffraction. The TDS measurements show that oxygen adsorption is blocked on Ag sites: the saturation coverage of oxygen decreases with increasing Ag coverage. Also, the activation energy for desorption (Edes) decreases with Ag coverage. The analysis of the desorption spectra from clean Pt(111) shows a linear decay of Edes with oxygen coverage, which indicates repulsive interactions between the adsorbed oxygen atoms. In contrast, adsorption on alloyed Ag/Pt(111) leads to an attractive interaction between adsorbed oxygen atoms.

Growth anomalies in supramolecular networks: 4,4'-biphenyldicarboxylic acid on cu(001).

We have used low energy electron microscopy to demonstrate how the interaction of 4,4'-biphenyldicarboxylic acid (BDA) molecules with (steps on) the Cu(001) surface determines the structure of supramolecular BDA networks on a mesoscopic length scale. Our in situ real time observations reveal that steps are permeable to individual molecules but that the change in crystal registry between different layers of the Cu substrate causes them to be completely impermeable to condensed BDA domains. The resulting growth instabilities determine the evolution of the domain shape and include a novel Mullins-Sekerka-type growth instability that is characterized by high growth rates along, instead of perpendicular to, the Cu steps. This growth instability is responsible for the majority of residual defects in the BDA networks.

Formation and decay of a compressed phase of 4,4'-biphenyldicarboxylic acid on Cu(001).

The molecular arrangement of 4,4'-biphenyldicarboxylic acid (BDA) on Cu(001) has been studied at high coverage and relatively high temperature (~400 K) using Low Energy Electron Microscopy, LEEM, and selected area diffraction, µLEED. Next to the previously reported c(8 × 8) structure, we also observe a compressed phase with a [structure: see text] superstructure in matrix notation. All four equivalent (rotational and mirror) domains are equally populated. Both the c(8 × 8) and the compressed phase are confined to the first layer and the latter has a 14% higher density compared to the c(8 × 8) phase. Remarkably, this compressed phase is stable only during deposition and decays after interruption of the deposition. Apparently, the density of physisorbed admolecules on top of the c(8 × 8) layer has to be above a relevant threshold to allow the formation of the compressed phase.

Decoupling of the copper core in a single copperphthalocyanine molecule.

Here, we show how a copper atom in a copperphthalocyanine (CuPc) molecule can be decoupled from its environment. This is realized by trapping the CuPc molecule between two adjacent nanowires that are 1.6 nm apart. Using low-temperature scanning tunnelling microscopy and spectroscopy, the structural and electronic properties of CuPc in the stable "molecular bridge" configuration have been studied. Constant current and differential conductivity maps are recorded to reveal the spatial variation of the electronic structure of the cores and the lobes of CuPc molecules. The core of CuPc molecule is dim at low voltages, but suddenly becomes bright at a voltage of 5 V. Time-resolved scanning tunnelling microscopy measurements show that some of the CuPc lobes are very stable, while other lobes are very dynamic.

Interplay of wrinkles, strain, and lattice parameter in graphene on iridium.

Following graphene growth by thermal decomposition of ethylene on Ir(111) at high temperatures we analyzed the strain state and the wrinkle formation kinetics as function of temperature. Using the moiré spot separation in a low energy electron diffraction pattern as a magnifying mechanism for the difference in the lattice parameters between Ir and graphene, we achieved an unrivaled relative precision of ±0.1 pm for the graphene lattice parameter. Our data reveals a characteristic hysteresis of the graphene lattice parameter that is explained by the interplay of reversible wrinkle formation and film strain. We show that graphene on Ir(111) always exhibits residual compressive strain at room temperature. Our results provide important guidelines for strategies to avoid wrinkling.

Size fluctuations of near critical nuclei and Gibbs free energy for nucleation of BDA on Cu(001).

We present a low-energy electron microscopy study of nucleation and growth of BDA on Cu(001) at low supersaturation. At sufficiently high coverage, a dilute BDA phase coexists with c(8×8) crystallites. The real-time microscopic information allows a direct visualization of near-critical nuclei, determination of the supersaturation and the line tension of the crystallites, and, thus, derivation of the Gibbs free energy for nucleation. The resulting critical nucleus size nicely agrees with the measured value. Nuclei up to 4-6 times larger still decay with finite probability, urging reconsideration of the classic perception of a critical nucleus.

Simulating anisotropic droplet shapes on chemically striped patterned surfaces.

The equilibrium shape of droplets on surfaces, functionalized with stripes of alternating wettability, have been investigated using simulations employing a finite element method. Experiments show that a droplet deposited on a surface with relatively narrow hydrophobic stripes compared to the hydrophilic stripes adopts a strongly elongated shape. The aspect ratio, the length of the droplet divided by the width, decreases toward unity when a droplet is deposited on a surface with relatively narrow hydrophilic stripes. The aspect ratio and the contact angle parallel to the stripes show unique scaling behavior as a function of the ratio between the widths of the hydrophobic and hydrophilic stripes. For a small ratio, the contact angle parallel to the stripes is low and the aspect ratio high, while for a large ratio, the contact angle parallel is high and the aspect ratio low. The simulations exhibit similar scaling behavior, both for the aspect ratio of the droplets and for the contact angles in the direction parallel to the stripes. Two liquids with different surface tensions have been investigated both experimentally and in simulations; similarities and differences between the findings are discussed. Generally, three parameters are needed to describe the droplet geometry: (i) the equilibrium contact angles on the hydrophilic and (ii) hydrophobic areas and (iii) the ratio of the widths of these chemically defined stripes. Furthermore, we derive a simple analytical expression that proves to be a good approximation in the quantitative description of the droplet aspect ratio.

The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM.

The growth of para-sexiphenyl (6P) thin films as a function of substrate temperature on Ir{111} supported graphene flakes has been studied in real-time with Low Energy Electron Microscopy (LEEM). Micro Low Energy Electron Diffraction (µLEED) has been used to determine the structure of the different 6P features formed on the surface. We observe the nucleation and growth of a wetting layer consisting of lying molecules in the initial stages of growth. Graphene defects - wrinkles - are found to be preferential sites for the nucleation of the wetting layer and of the 6P needles that grow on top of the wetting layer in the later stages of deposition. The molecular structure of the wetting layer and needles is found to be similar. As a result, only a limited number of growth directions are observed for the needles. In contrast, on the bare Ir{111} surface 6P molecules assume an upright orientation. The formation of ramified islands is observed on the bare Ir{111} surface at 320 K and 352 K, whereas at 405 K the formation of a continuous layer of upright standing molecules growing in a step flow like manner is observed.

Smooth growth of organic semiconductor films on graphene for high-efficiency electronics.

High-quality thin films of conjugated molecules with smooth interfaces are important to assist the advent of organic electronics. Here, we report on the layer-by-layer growth of the organic semiconductor molecule p-sexiphenyl (6P) on the transparent electrode material graphene. Low energy electron microscopy and micro low energy electron diffraction reveal the morphological and structural evolution of the thin film. The layer-by-layer growth of 6P on graphene proceeds by subsequent adding of {111} layers.

Microscopic Study of the Spinodal Decomposition of Supported Eutectic Droplets During Cooling: PtGe/Ge{110}.

We embarked on an in situ low-energy electron microscopy, photo-electron emission microscopy, and selected area low-energy electron diffraction study during the cooling of huge eutectic droplets through the critical stages of the eutectic transition. On this journey through uncharted waters, we revealed an expected initial shrinking of the exposed area of the droplet, followed by an unanticipated expansion. We attribute this behavior to an initial fast amorphization of the interface between the droplet and surface, followed by the recrystallization of Ge expelled from the droplet at the interface. As a major surprise, we discovered the emergence of extensive "spaghetti"-like patterns, which are rationalized in terms of parallel Ge ripples oriented along, mainly, [-554] and [-55-4] directions. They emerge during spinodal decomposition when passing the eutectic temperature of the system. Their sides are defined by Ge{111} and Ge{11-1} vicinals covered with Pt-modified (√3 × âˆš3) superstructures. The distance between adjacent ripples is about 18 nm.

Anomalous decay of electronically stabilized lead mesas on Ni(111).

With their low surface free energy, lead films tend to wet surfaces. However, quantum size effects (QSE) often lead to islands with distinct preferred heights. We study thin lead films on Ni(111) using low energy electron microscopy and selected area low energy electron diffraction. Indeed, the grown lead mesas show distinct evidence for QSE's. At about 526 K metastable mesas reshape into hemispheres within milliseconds, driven by a huge reduction in interfacial free energy. The underlying diffusion rate is many orders of magnitude faster than expected for lead on bulk lead.

Quantum size effect driven structure modifications of Bi films on Ni(111).

The quantum-size effect (QSE) driven growth of Bi film structures on Ni(111) was studied in situ using low energy electron microscopy and selective area low energy electron diffraction (µLEED). Domains with a (3×3), [(3)(1)(-1)(2)], and (7×7) film structure are found with a height of 3, 5, and 7 atomic layers, respectively. A comparison of I/V-µLEED curves with tensor LEED calculations shows perfectly accommodated Fermi wavelengths, indicative that not only the quantized height, but also the film structure is driven by QSE.

Surface bubble nucleation stability.

Recent research has revealed several different techniques for nanoscopic gas nucleation on submerged surfaces, with findings seemingly in contradiction with each other. In response to this, we have systematically investigated the occurrence of surface nanobubbles on a hydrophobized silicon substrate for various different liquid temperatures and gas concentrations, which we controlled independently. We found that nanobubbles occupy a distinct region of this parameter space, occurring for gas concentrations of approximately 100%-110%. Below the nanobubble region we did not detect any gaseous formations on the substrate, whereas micropancakes (micron wide, nanometer high gaseous domains) were found at higher temperatures and gas concentrations. We moreover find that supersaturation of dissolved gases is not a requirement for nucleation of bubbles.

Smart design of stripe-patterned gradient surfaces to control droplet motion.

The motion of droplets under the influence of lithographically created anisotropic chemically defined patterns is described and discussed. The patterns employed in our experiments consist of stripes of alternating wettability: hydrophobic stripes are created via fluorinated self-assembled monolayers, and for hydrophilic stripes, the SiO(2) substrate is used. The energy gradient required to induce the motion of the droplets is created by varying the relative widths of the stripes in such a way that the fraction of the hydrophilic area increases. The anisotropic patterns create a preferential direction for liquid spreading parallel to the stripes and confine motion to the perpendicular direction, giving rise to markedly higher velocities as compared to nonstructured surface energy gradients. Consequently, the influence of the distinct pattern features on the overall motion as well as suggestions for design improvements from an application point of view are discussed.

The dissociative adsorption of hydrogen on Pt(111): actuation and acceleration by atomic defects.

The dissociation of hydrogen at atomic surface defects is the strongly dominant, if not the decisive, step in the chain of events eventually leading to chemisorbed H-atoms on Pt(111). This holds for perpendicular kinetic energies of the gas phase molecules from 8 to 60 meV, i.e., covering the range relevant to hydrogenation reactions. This insight has been gained in the present study in which we reversibly varied the defect density on one and the same crystal in a controlled way. Information has been derived from measuring the adsorption kinetics as a function of coverage. Two distinct adsorption channels are distinguished. The first, indirect one, prevails at lower H-coverage and involves capture into a non-accommodated molecular precursor state followed by dissociation at step sites as described in our recent paper. The second one, dominant at higher coverage and non-negligible defect densities, obeys second order Langmuir kinetics. Here the dissociative adsorption takes place directly at step sites with a cross section of 0.24 unit cells (initial sticking probability 24% of the step density). These results are consistent with thermally programmed desorption data: the direct channel is responsible for the emergence of the low temperature peak in thermal desorption spectroscopy, usually denoted with ß(1), while the indirect channel is represented by the ß(2) state. The dependence on the perpendicular component of the hydrogen kinetic energy is distinctly different for the two channels: the indirect one shows power law behavior with an exponent 1.9 ± 0.1, while the direct one shows no perpendicular energy dependence at all.

A low energy electron microscopy study of the initial growth, structure, and thermal stability of 4,4'-biphenyldicarboxylic acid domains on Cu(001).

The growth of 4,4(')-biphenyldicarboxylic acid (BDA) on Cu(001) has been studied using low energy electron microscopy and selective area low energy electron diffraction. The emergence of large islands and hydrogen bonding to perpendicularly oriented, adjacent molecules is confirmed. The two benzene rings of adsorbed BDA are twisted along the molecular axis. Unconventional growth of the domains, followed by a second nucleation stage, is observed at room temperature. This unanticipated feature is attributed to the accumulation of stress in the islands. Ostwald ripening in the films and the decay of BDA domains at 448 K exhibits features that are consistent with diffusion limited behavior.