Direct Observation of Structural Phase Transformations during Phosphorene Formation on Cu(111).

Blue phosphorene, a two-dimensional, hexagonal-structured, semiconducting phosphorus, has gained attention as it is considered easier to synthesize on metal surfaces than its allotrope, black phosphorene. Recent studies report different structures of phosphorene, for example, on Cu(111), but the underlying mechanisms of their formation are not known. Here, using a combination of in situ ultrahigh vacuum low-energy electron microscopy and in vacuo scanning tunneling microscopy, we determine the time evolution of the surface structure and morphology during the deposition of phosphorus on single-crystalline Cu(111).

Growth of Highly Oriented (VNbMoTaW)S Layers.

Compositional tunability, an indispensable parameter for modifying the properties of materials, can open up new applications for van der Waals (vdW) layered materials such as transition-metal dichalcogenides (TMDCs). To date, multielement alloy TMDC layers are obtained via exfoliation from bulk polycrystalline powders. Here, we demonstrate direct deposition of high-entropy alloy disulfide, (VNbMoTaW)S, layers with controllable thicknesses on free-standing graphene membranes and on bare and hBN-covered AlO(0001) substrates via ultra-high-vacuum reactive dc magnetron sputtering of the VNbMoTaW target in Kr and HS gas mixtures.

Borazine Promoted Growth of Highly Oriented Thin Films.

We report on a phenomenon, where thin films sputter-deposited on single-crystalline AlO(0001) substrates exposed to borazine─a precursor commonly used for the synthesis of hexagonal boron nitride layers─are more highly oriented than those grown on bare AlO(0001) under the same conditions. We observed this phenomenon in face-centered cubic Pd, body-centered cubic Mo, and trigonal TaC thin films grown on AlO(0001). Interestingly, intermittent exposure to borazine during the growth of TaC thin films on TaC yields better crystallinity than direct deposition of monolithic TaC.

Self-Organized Growth of 111-Oriented (VNbTaMoW)N Nanorods on MgO(001).

Refractory high-entropy alloy nitride, (VNbTaMoW)N, layers are grown on single-crystalline MgO(001) via ultrahigh vacuum direct current magnetron sputtering of a VNbTaMoW target in Kr/N gas mixtures at 1073 K. X-ray diffraction, scanning and transmission electron microscopy, and energy dispersive X-ray spectroscopy characterizations revealed the formation of B1-structured, 111-textured (VNbTaMoW)N with lattice parameter = 0.4249 nm.

Ultra-high vacuum dc magnetron sputter-deposition of 0001-textured trigonal α-TaC/AlO(0001) thin films.

We report on the effects of substrate temperature (1073 K ≤ ≤ 1373 K) and deposition time (= 3 ~ 30 min.) on the crystallinity of TaC/AlO(0001) thin films grown via ultra-high vacuum direct current magnetron sputtering of TaC target in 20 mTorr (2.7 Pa) pure Ar atmospheres.

Growth Kinetics of Two-Dimensional Hexagonal Boron Nitride Layers on Pd(111).

Using variable-temperature scanning tunneling microscopy (300-673 K) during chemical vapor deposition of two-dimensional hexagonal boron nitride (hBN) on Pd(111) from borazine precursor at pressures up to 10 mbar, we identify the mechanisms leading to carpetlike uphill or downhill growth across the Pd steps. Deposition at a higher rate and lower temperature promotes uphill growth via preferential attachment at the ascending and descending step-edges, whereas a lower deposition rate and higher temperature lead to downhill growth via nucleation and growth of islands on Pd terraces. We attribute this unusual growth behavior to differences in temperature-dependent rates of hBN deposition at the steps versus on the Pd terraces.

Variable-Temperature Scanning Tunneling Microscopy Studies of Graphene Growth Using Benzene on Pd(111).

Using a combination of ultrahigh-vacuum variable-temperature scanning tunneling microscopy, Raman spectroscopy, and scanning electron microscopy, we investigated the growth of graphene using benzene on Pd(111) at temperatures up to 1100 K. Benzene adsorbs readily on Pd(111) at room temperature and forms an ordered superstructure upon annealing at 473 K. Exposure to benzene at 673 K enhances Pd step motion and yields primarily amorphous carbon upon cooling to room temperature.

Kinetics of Au-Ga Droplet Mediated Decomposition of GaAs Nanowires.

Particle-assisted III-V semiconductor nanowire growth and applications thereof have been studied extensively. However, the stability of nanowires in contact with the particle and the particle chemical composition as a function of temperature remain largely unknown. In this work, we use in situ transmission electron microscopy to investigate the interface between a Au-Ga particle and the top facet of an ⟨1̅1̅1̅⟩-oriented GaAs nanowire grown via the vapor-liquid-solid process.

Ultrahigh vacuum dc magnetron sputter-deposition of epitaxial Pd(111)/AlO(0001) thin films.

Pd(111) thin films, ∼245 nm thick, are deposited on AlO(0001) substrates at ≈0.5, where is the Pd melting point, by ultrahigh vacuum dc magnetron sputtering of Pd target in pure Ar discharges. Auger electron spectra and low-energy electron diffraction patterns acquired from the as-deposited samples reveal that the surfaces are compositionally pure 111-oriented Pd.

One-Step Synthesis of Tunable-Size Gold Nanoplates on Graphene Multilayers.

Au nanoplates (quasi-two-dimensional single crystals) are most commonly synthesized using a mixture of Au precursors via approaches involving multiple processing steps and the use of seed crystals. Here, we report the synthesis of truncated-hexagonal {111}-oriented micrometer-scale Au nanoplates on graphene multilayers using only potassium tetrabromoaurate (KAuBr) as the precursor. We demonstrate that the nanoplate sizes can be controllably varied from tens of nanometers up to a few micrometers by introducing desired concentrations of chloroauric acid (HAuCl) to KAuBr and their thicknesses from ∼13 to ∼46 nm with the synthesis time.

Control of Growth Front Evolution by Bi Additives during ZnAu Electrodeposition.

The performance of many electrochemical energy storage systems can be compromised by the formation of metal dendrites during charging. Additives in the electrolyte represent a useful strategy to mitigate dendrite formation, but understanding the mechanisms involved requires knowledge of the nanoscale effects of additives during electrochemical deposition. Here we quantify the effects of an inorganic additive on the morphology of an evolving electrochemical growth front, using liquid cell electron microscopy to provide the necessary spatial and temporal resolution.

Electrochemical electron beam lithography: Write, read, and erase metallic nanocrystals on demand.

We develop a solution-based nanoscale patterning technique for site-specific deposition and dissolution of metallic nanocrystals. Nanocrystals are grown at desired locations by electron beam-induced reduction of metal ions in solution, with the ions supplied by dissolution of a nearby electrode via an applied potential. The nanocrystals can be "erased" by choice of beam conditions and regrown repeatably.

The Role of Surface Passivation in Controlling Ge Nanowire Faceting.

In situ transmission electron microscopy observations of nanowire morphologies indicate that during Au-catalyzed Ge nanowire growth, Ge facets can rapidly form along the nanowire sidewalls when the source gas (here, digermane) flux is decreased or the temperature is increased. This sidewall faceting is accompanied by continuous catalyst loss as Au diffuses from the droplet to the wire surface. We suggest that high digermane flux and low temperatures promote effective surface passivation of Ge nanowires with H or other digermane fragments inhibiting diffusion and attachment of Au and Ge on the sidewalls.

Control of Electron Beam-Induced Au Nanocrystal Growth Kinetics through Solution Chemistry.

Measurements of solution-phase crystal growth provide mechanistic information that is helpful in designing and synthesizing nanostructures. Here, we examine the model system of individual Au nanocrystal formation within a defined liquid geometry during electron beam irradiation of gold chloride solution, where radiolytically formed hydrated electrons reduce Au ions to solid Au. By selecting conditions that favor the growth of well-faceted Au nanoprisms, we measure growth rates of individual crystals.

Shape-directional growth of Pt and Pd nanoparticles.

The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth.

Jumping-catalyst dynamics in nanowire growth.

Nanowire growth is generally considered a steady-state process, but oscillatory phenomena are known to often play a fundamental role. Here we identify a natural sequence of distinct growth modes, in two of which the catalyst droplet jumps periodically on and off a crystal facet. The oscillatory modes result from a mismatch between catalyst size and wire diameter; they enable growth of straight smooth-sided wires even when the droplet is too small to span the wire tip.

Au transport in catalyst coarsening and Si nanowire formation.

The motion of Au between AuSi liquid eutectic droplets, both before and during vapor-liquid-solid growth, is important in controlling tapering and diameter uniformity in Si nanowires. We measure the kinetics of coarsening of AuSi droplets on Si(001) and Si(111), quantifying the size evolution of droplets during annealing in ultrahigh vacuum using in situ transmission electron microscopy. For individual droplets, we show that coarsening kinetics are modified when disilane or oxygen is added: coarsening rates increase in the presence of disilane but decrease in oxygen.

The influence of laser-induced nanosecond rise-time stress waves on the microstructure and surface chemical activity of single crystal Cu nanopillars.

An apparatus and test procedure for fabrication and loading of single crystal metal nanopillars under extremely high pressures (>1 GPa) and strain rates (>10 s), using laser-generated stress waves, are presented. Single-crystalline Cu pillars (∼1.20 m in tall and ∼0.

Strategies to control morphology in hybrid group III-V/group IV heterostructure nanowires.

By combining in situ and ex situ transmission electron microscopy measurements, we examine the factors that control the morphology of "hybrid" nanowires that include group III-V and group IV materials. We focus on one materials pair, GaP/Si, for which we use a wide range of growth parameters. We show through video imaging that nanowire morphology depends on growth conditions, but that a general pattern emerges where either single kinks or inclined defects form some distance after the heterointerface.

Near room-temperature synthesis of transfer-free graphene films.

Large-area graphene films are best synthesized via chemical vapour and/or solid deposition methods at elevated temperatures (~1,000 °C) on polycrystalline metal surfaces and later transferred onto other substrates for device applications. Here we report a new method for the synthesis of graphene films directly on SiO(2)/Si substrates, even plastics and glass at close to room temperature (25-160 °C). In contrast to other approaches, where graphene is deposited on top of a metal substrate, our method invokes diffusion of carbon through a diffusion couple made up of carbon-nickel/substrate to form graphene underneath the nickel film at the nickel-substrate interface.

Geometrical frustration in nanowire growth.

Idealized nanowire geometries assume stable sidewalls at right angles to the growth front. Here we report growth simulations that include a mix of nonorthogonal facet orientations, as for Au-catalyzed Si. We compare these with in situ microscopy observations, finding striking correspondences.

Periodically changing morphology of the growth interface in Si, Ge, and GaP nanowires.

Nanowire growth in the standard <111> direction is assumed to occur at a planar catalyst-nanowire interface, but recent reports contradict this picture. Here we show that a nonplanar growth interface is, in fact, a general phenomenon. Both III-V and group IV nanowires show a distinct region at the trijunction with a different orientation whose size oscillates during growth, synchronized with step flow.

Moiré superstructures of graphene on faceted nickel islands.

Using scanning tunneling microscopy and spectroscopy, in combination with density functional theory calculations, we investigated the morphology and electronic structure of monolayer graphene grown on the (111) and (110) facets of three-dimensional nickel islands on highly oriented pyrolytic graphite substrate. We observed graphene domains exhibiting hexagonal and striped moiré patterns with periodicities of 22 and 12 Å, respectively, on (111) and (110) facets of the Ni islands. Graphene domains are also observed to grow, as single crystals, across adjacent facets and over facet boundaries.

Synthesis and surface activity of single-crystalline Co3O4 (111) holey nanosheets.

Single crystalline, thermally stable, Co(3)O(4) (111) holey nano-sheets were prepared by an efficient, template-free, wet chemical synthetic approach. The high energy (111) surfaces formed can be used as highly active heterogeneous catalysts for methanol decomposition.

Three-dimensional morphology control during wet chemical synthesis of porous chromium oxide spheres.

Controlling the morphological evolution in nanostructures is essential for improving their functionality, for example, in catalysis. Here, we demonstrate, using chromium oxide as a model system, that morphologies of functional binary oxide particles can be tailored by an efficient template-free synthetic approach. We construct a morphological "phase diagram" for chromium oxide spheres that shows the evolution of size and surface roughness as a function of the precursor and urea concentrations.