Hexagonal Islands Research Articles

Graphene-like monolayer low-buckled honeycomb germanium film

Molecular dynamics simulations have been performed to study the cooling process of two-dimensional liquid germanium under nanoslit confinement. The results clearly indicates that the liquid germanium undergoes an obvious liquid-solid phase transition to a monolayer honeycomb film with the decrease of temperature, accompanying the rapid change in potential energy, atomic volume, coordination number and lateral radial distribution function. During the solidification process, some hexagonal atomic islands first randomly emerge in the disordered liquid film and then grow up to stable crystal grains which keep growing and finally connect together to form a honeycomb polycrystalline film. It is worth noting that the honeycomb germanium film is low-buckled, quite different from the planar graphene.

Hexagonal mesoporous silica islands to enhance photovoltaic performance of planar junction perovskite solar cells

Wormhole-like hexagonal mesoporous silica (HMS) can modify the perovskite morphology and increase the light path length in a planar junction perovskite solar cell to improve the average PCE to 17.6% over 30 devices.

Closing the superconducting gap in small Pb nanoislands with high magnetic fields

Superconducting properties change in confined geometries. Here we study the effects of strong confinement in nanosized Pb islands on Si(111) $7\ifmmode\times\else\texttimes\fi{}7$. Small hexagonal islands with diameters less than 50 nm and a uniform height of seven atomic layers are formed by depositing Pb at low temperature and annealing at 300 K. We measure the tunneling spectra of individual Pb nanoislands using a low-temperature scanning tunneling microscope operated at 0.6 K and follow the narrowing of the superconducting gap as a function of magnetic field. We find the critical magnetic field, at which the superconducting gap vanishes, reaches several Tesla, which represents a greater than 50-fold enhancement compared to the bulk value. By independently measuring the size of the superconducting gap, and the critical magnetic field that quenches superconductivity for a range of nanoislands, we can correlate these two fundamental parameters and estimate the maximal achievable critical field for 7 ML Pb nanoislands to be 7 T.

Structural analysis of ultra-thin Pd films on W(110)

We report on a scanning tunneling microscopy (STM) growth study of ultra-thin Pd films on W(110) in the thickness range up to about three atomic layers. At a substrate temperature of (573±20)K during deposition the initial growth at submonolayer coverages takes place in the step-flow mode, whereby the Pd step edges are preferentially oriented along 〈11¯1〉 directions leading to a pronounced saw-tooth–like appearance. It is found that the Pd monolayer is not smooth but instead exhibits a one-dimensional pattern consisting of alternating straight and zigzag lines along the [001] direction with a periodicity of (7.3±0.5)nm. Atomic resolution STM images reveal that these stripes mark transition regions between two different three-fold–coordinated adsorption sites, i.e. left (L) or right (R) triangular. A structural model is presented which explains the straight and zigzag lines as vacancy rows and Pd grown in the Kurdjumov-Sachs configuration, respectively. In a transition regime between 0.93AL–1.03AL the one-dimensional character converts into triangularly shaped L and R domains up to 100nm in size which are separated by short straight segments approximatelly oriented along 〈11¯1〉 and [001] directions. Growth of the second Pd layer occurs via the nucleation of hexagonal islands and at Pd coverages beyond 2AL the growth mode changes from layer-by-layer to island growth, probably due to the structural transition from the bcc to the fcc crystal structure.

Tip-assisted directional growth of atomically thin Ag islands

The growth and decay of metal nanostructures are important in many areas of physical science and catalytic chemistry. Here, we show the directional growth of Ag island stripes at room temperature via tip-assisted coarsening of hexagonal islands on Ag(111) using scanning tunneling microscope (STM). The mechanism of this process is attributed to the alignment of the adatom and vacancy islands along the scanning direction via tip-sample interaction during the process of the intrinsic decay of the metastable Ag islands. We find that this tip-assisted island growth is not directly related to the tunneling current and the bias voltage. Experiments performed using Ag tips and W tips show similar coarsening effects. The chamber pressure and the O2 exposure also do not have systematic effects on the rate of island growth. The tip-assisted coarsening strongly depends on the tip morphology.

Controlled growth of high-quality graphene using hot-filament chemical vapor deposition

High-quality graphene was grown on polycrystalline copper (Cu) foils (1 cm x 1 cm) using hot-filament chemical vapor deposition method. The role of process parameters such as gas flow rates (methane and hydrogen), growth temperatures (filament and substrate) and durations on the growth of graphene was studied. The process parameters were also optimized to grow monolayer, bilayer and multilayer graphene in a controlled manner, and a growth mechanism was deduced from the experimental results. The presence of graphene on Cu foils was confirmed using X-ray photoelectron spectroscopy, microRaman spectroscopy, field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) techniques. FESEM micrographs clearly showed that the graphene starts nucleating as hexagonal islands and later evolves as dendritic lobe-shaped islands with an increase in supersaturation. The TEM images substantiate the growth of monolayer, bilayer and multilayer graphene. The I-2D/I-G ratio = 2 confirmed the presence of the monolayer graphene and the absence of `D' peak in the Raman spectrum indicated the high purity of graphene grown on Cu foils. These results also show that the polycrystalline copper foil morphology has negligible effect on the growth of monolayer graphene.

Evidence for multi-polymorphic islands during epitaxial growth of ZnO on Ag(1 1 1)

A range of models of free standing and Ag(1 1 1)-supported stoichiometric ZnO films with coverages between 2–3 monolayers are studied using density functional calculations. Following experimental observations we focus on stoichiometric hexagonal and triangular ad-layer islands grown on top of two complete ZnO monolayers. The adlayer islands display distinct edge and corner reconstructions and are found to induce a structural transition extending from the island core to the layered phase below. Based on our results we propose a general model of ad-layer triangular island structure based on seven regions exhibiting four distinct polymorphs.

Hetero-epitaxy of ε-Ga2O3 layers by MOCVD and ALD

Growth of gallium oxide thin films was carried out by Metalorganic Chemical Vapor Deposition (MOCVD) at different temperatures. Pure ε-phase epilayers of Ga2O3, with good morphology and structural properties, were obtained, for the first time with this technique, on sapphire at the temperature of 650°C. XRD analysis performed by high-resolution diffractometry confirmed the good crystallographic quality of the grown layers. At temperatures higher than 700°C the usual stable β-Ga2O3 phase was obtained. The ε-films were successfully deposited also on (0001)-oriented GaN and (111)- and (001)-oriented 3C–SiC templates, provided that the appropriate temperature was chosen. This indicates that the temperature, rather than substrate structure, is the growth parameter which decides what phase actually forms. The growth proceeds via coalescence of hexagonal islands and is favored when a substrate with an in-plane hexagonal arrangement of the atoms is employed. By applying Atomic Layer Deposition (ALD), epitaxial growth of the ε-phase was achieved at lower temperature, while the overall uniformity resulted improved, even on large sapphire substrates.

Multilayer hexagonal silicon forming in slit nanopore.

The solidification of two-dimensional liquid silicon confined to a slit nanopore has been studied using molecular dynamics simulations. The results clearly show that the system undergoes an obvious transition from liquid to multilayer hexagonal film with the decrease of temperature, accompanied by dramatic change in potential energy, atomic volume, coordination number and lateral radial distribution function. During the cooling process, some hexagonal islands randomly appear in the liquid first, then grow up to grain nuclei, and finally connect together to form a complete polycrystalline film. Moreover, it is found that the quenching rate and slit size are of vital importance to the freezing structure of silicon film. The results also indicate that the slit nanopore induces the layering of liquid silicon, which further induces the slit size dependent solidification behavior of silicon film with different electrical properties.

Characterization of PTCDA nanocrystals on Ge(0 0 1):H-(2 × 1) surfaces

We analyze self-assembled nanocrystals of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on hydrogen passivated Ge(001) surfaces with use of scanning tunneling microscopy (STM) and spectroscopy (STS). At 0.7ML coverage, 2.1nm high, elongated, hexagonal islands inclined at 37° with respect to the substrate row are mostly observed. By measuring the differential tunneling conductance, we observe an effect of electronic decoupling of the nanocrystals due to the introduced passivating layer. Finally, we shortly discuss the stability of the islands and their interaction with the scanning probe in the ultra-high vacuum environment.

Step energies and equilibrium shape of strained monolayer islands

Using a simple atomistic model of anharmonic nearest-neighbors interaction, we have calculated the step energies of strained hexagonal monolayer islands. These have been found to decrease with the absolute value of the misfit due to the strain relaxation at steps. The effect is significantly more pronounced in the case of positive misfit owing to the stronger repulsive interatomic forces. Furthermore, (111)-faceted steps are favored at positive misfit (compressed islands) and, to a lesser extent, (100)-faceted steps at negative misfits (tensile islands). The result is rationalized in terms of the different bonding geometries at step edges and a comparison with experiments is included. Thus, the equilibrium shape transforms from regular hexagons at zero misfit to threefold symmetric hexagons with increasing misfit.

Design and characterization of ultra-stretchable monolithic silicon fabric

Stretchable electronic systems can play instrumental role for reconfigurable macro-electronics such as distributed sensor networks for wearable and bio-integrated electronics. Typically, polymer composite based materials and its deterministic design as interconnects are used to achieve such systems. Nonetheless, non-polymeric inorganic silicon is the predominant material for 90% of electronics. Therefore, we report the design and fabrication of an all silicon based network of hexagonal islands connected through spiral springs to form an ultra-stretchable arrangement for complete compliance to highly asymmetric shapes. Several design parameters are considered and their validation is carried out through finite element analysis. The fabrication process is based on conventional microfabrication techniques and the measured stretchability is more than 1000% for single spirals and area expansions as high as 30 folds in arrays. The reported method can provide ultra-stretchable and adaptable electronic systems for distributed network of high-performance macro-electronics especially useful for wearable electronics and bio-integrated devices.

Real time observation of ZnO nanostructure formation via the solid-vapor and solid-solid-vapor mechanisms.

We report in situ transmission electron microscopy studies of the formation of ZnO nanostructures--nanoscale depressions, nanoholes, nanoribbons, and nanosheets--and the phase stability and kinetics of Au catalysts on ZnO. During annealing, the ZnO layer produces hexagonally shaped, vertical nanoscale depressions, which increase in size along the 〈 0001 〉 growth direction through preferential dissociation from the {101[combining macron]0} facet and which subsequently form hexagonal islands at their six-fold junctions. Real time observations of the annealing of Au deposited on ZnO show that the catalysts remain solid up to 900 °C, an observation that has implications regarding ZnO nanowire growth via the vapor-solid-solid mechanism (VSS). The Au also creates hexagonal nanoscale holes only at the location of solid Au catalysts, via the solid-solid-vapor (SSV) mechanism. Importantly, coarsening of the Au particles is negligible due to limited Au diffusion on the side facets of the nanoscale depressions, suggesting an approach to the growth of uniform hybrid nanowires with control over both diameter and location. Furthermore, we directly monitor the evolution of the transformation of a nanoribbon into a nanosheet with {101[combining macron]0} facets. This process takes place through a periodic, kinetic roughening transition of the surface, which is controlled by the kinetic competition between surface growth and the transfer of evaporated gases. In total, these observations give new insights into multiple growth processes occurring in this important materials system.

Dynamics of dysprosium silicide nanostructures on Si(001) and (111) surfaces

The growth and coarsening dynamics of dysprosium silicide nanostructures are observed in real-time using photoelectron emission microscopy. The annealing of a thin Dy film to temperatures in the range of 700–1050 °C results in the formation of epitaxial rectangular silicide islands and nanowires on Si(001) and triangular and hexagonal silicide islands on Si(111). During continuous annealing, individual islands are observed to coarsen via Ostwald ripening at different rates as a consequence of local variations in the size and relative location of the surrounding islands on the surface. A subsequent deposition of Dy onto the Si(001) surface at 1050 °C leads to the growth of the preexisting islands and to the formation of silicide nanowires at temperatures above where nanowire growth typically occurs. Immediately after the deposition is terminated, the nanowires begin to decay from the ends, apparently transferring atoms to the more stable rectangular islands. On Si(111), a low continuous flux of Dy at 1050 °C leads to the growth of kinked and jagged island structures, which ultimately form into nearly equilateral triangular shapes.

Simultaneous Formation of AlB2-Type and ThSi2-Type Nanoislands of Er Silicide by Using a Prepatterned Si(001) Substrate

We report the simultaneous growth of hexagonal AlB2-phase and tetragonal ThSi2-phase nanoislands of erbium silicide on the same silicon substrate. As a new technique, the patterned Si(001) surface with pits in a reverse-pyramid shape and {111} sidewalls is taken as the substrate template. The distribution of nanoislands reveals that the upward diffusion over surface steps plays an influential role on the location of islands. Si {111} facets on the pit sidewalls actually provide growth symmetry for the hexagonal islands. This work paves the way for exploring the intrinsic electrical transport properties of metal-semiconductor nanocontacts.

Growth morphology of Pb films on Ni3Al(111)

Scanning tunnelling microscopy (STM) and Auger electron spectroscopy (AES) have been used to investigate the growth morphology of ultra-thin Pb films on the Ni3Al(111) face at room temperature. A previous study [K. Miśków and A. Krupski Appl Surf Sci 273, 2013, 554] using low-energy electron diffraction (LEED) and real time Auger intensity recording has demonstrated that an initial two-dimensional growth of the first Pb monolayer thick ‘wetting layer’ takes place. With further deposition and for T = 300 K, flat three atomic-layer-high islands are grown. Above 350 K, the Stranski–Krastanov growth mode was observed. In the current study, the analysis of STM measurements indicate and confirm that for coverage θ = 1.0 ML two-dimensional growth of the first Pb monolayer took place. Above θ > 1.0 ML, a three-dimensional growth of the Pb islands was observed with a strongly preferred atomic-scale ‘magic height (N),’ hexagonal shape and flat-tops. At coverage θ = 3.5 ML, only islands containing N = 3, 5, 7 and 11 atomic layers of Pb are observed. At the higher coverage θ = 5.5 ML, three types of regular hexagonal islands with side lengths of 25, 30 and 45 nm are observed. Furthermore, three different island adsorption configurations rotated by 10° ± 1° and 30° ± 6° with respect to each other were observed. After an annealing at T = 400 K of 5.5 ML of lead deposited at RT on the Ni3Al(111) the morphology of the surface changes. Post-anneal, islands of Pb are observed above the ‘wetting layer’ with an estimated average size and diameter of 768 ± 291 nm2 and 38.17 ± 6.56 nm and constant uniform height of two atomic layers (N = 2).

Scanning tunneling microscopy study of molecular growth structures of Gd@C82 on Cu(111)

The coverage and temperature-dependent nucleation behaviors of the Gd@C82 metallofullerenes on Cu(111) have been studied by low-temperature scanning tunneling microscopy (LT-STM) in detail. Upon molecular deposition at low temperature, Gd@C82 molecules preferentially decorate the steps and nucleate into single layer islands with increasing coverage. Further annealing treatment leads some of the Gd@C82 molecules to assemble into bright and dim patches, which are correlated to the adsorption induced substrate reconstruction. Upon sufficient thermal activation, Gd@C82 molecules sink into the Cu(111) surface one-copper-layer-deep, forming hexagonal close-packed molecular islands with intra-molecular details observed as striped patterns. By considering the commensurability between the Gd@C82 nearest-neighbor distance and the lattice of the underlying Cu(111), we clearly identified two kinds of in-plane molecular arrangements as (√19 × √19)R23.4° and (√19 × √19)R36.6° with respect to Cu(111). Within the assembled Gd@C82 molecular, island molecules with dim—bright contrast are spatially distributed, which may be modulated by the preexisted species on Cu(111).

Effect of High NH3 Input Partial Pressure on Hydride Vapor Phase Epitaxy of InN Using Nitrided (0001) Sapphire Substrates

The influence of the source gas supply sequence prior to growth and the NH3 input partial pressure (PoNH3) on the nucleation of InN islands during the initial stages of hydride vapor phase epitaxy on a nitrided (0001) sapphire substrate was investigated. The crystalline quality of the InN layer after subsequent lateral growth was also examined. When NH3 was flowed prior to growth, single-crystal hexagonal InN islands formed. When InN was grown with a higher PoNH3, the number of InN islands decreased remarkably while their diameter increased. The crystalline quality of InN grown on the hexagonal islands with a high PoNH3 significantly improved with increasing growth time. A strong PL spectrum was observed only from InN layers grown with a high PoNH3. It was thus revealed that an NH3 preflow and a high PoNH3 are effective for producing InN with high crystalline quality and good optical and electrical properties.

Stepwise self-assembly of C60 mediated by atomic scale moiré magnifiers

Self-assembly of atoms or molecules on a crystal surface is considered one of the most promising methods to create molecular devices. Here we report a stepwise self-assembly of C₆₀ molecules into islands with unusual shapes and preferred sizes on a gold-indium-covered Si(111) surface. Specifically, 19-mer islands prefer a non-compact boomerang shape, whereas hexagonal 37-mer islands exhibit extraordinarily enhanced stability and abundance. The stepwise self-assembly is mediated by the moiré interference between an island with its underlying lattice, which essentially maps out the adsorption-energy landscape of a C₆₀ on different positions of the surface with a lateral magnification factor and dictates the probability for the subsequent attachment of C₆₀ to an island's periphery. Our discovery suggests a new method for exploiting the moiré interference to dynamically assist the self-assembly of particles and provides an unexplored tactic of engineering atomic scale moiré magnifiers to facilitate the growth of monodispersed mesoscopic structures.

Influence of Gas Phase Equilibria on the Chemical Vapor Deposition of Graphene

We have investigated the influence of gas phase chemistry on the chemical vapor deposition of graphene in a hot wall reactor. A new extended parameter space for graphene growth was defined through literature review and experimentation at low pressures (≥0.001 mbar). The deposited films were characterized by scanning electron microscopy, Raman spectroscopy, and dark field optical microscopy, with the latter showing promise as a rapid and nondestructive characterization technique for graphene films. The equilibrium gas compositions have been calculated across this parameter space. Correlations between the graphene films grown and prevalent species in the equilibrium gas phase revealed that deposition conditions associated with a high acetylene equilibrium concentration lead to good quality graphene deposition, and conditions that stabilize large hydrocarbon molecules in the gas phase result in films with multiple defects. The transition between lobed and hexagonal graphene islands was found to be linked to the concentration of the monatomic hydrogen radical, with low concentrations associated with hexagonal islands.