Growth of Highly Oriented (VNbMoTaW)S2 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)S2, layers with controllable thicknesses on free-standing graphene membranes and on bare and hBN-covered Al2O3(0001) substrates via ultra-high-vacuum reactive dc magnetron sputtering of the VNbMoTaW target in Kr and H2S gas mixtures. Using a combination of density functional theory calculations, Raman spectroscopy, X-ray diffraction, scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy, we determine that the as-deposited layers are single-phase, 2H-structured, and 0001-oriented (V0.10Nb0.16Mo0.19Ta0.28W0.27)S2.44. Our synthesis route is general and applicable for heteroepitaxial growth of a wide variety of TMDC alloys and potentially other multielement alloy vdW compounds with the desired compositions.

Borazine Promoted Growth of Highly Oriented Thin Films.

We report on a phenomenon, where thin films sputter-deposited on single-crystalline Al2O3(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 Al2O3(0001) under the same conditions. We observed this phenomenon in face-centered cubic Pd, body-centered cubic Mo, and trigonal Ta2C thin films grown on Al2O3(0001). Interestingly, intermittent exposure to borazine during the growth of Ta2C thin films on Ta2C yields better crystallinity than direct deposition of monolithic Ta2C. We attribute these rather unusual results to a combination of both enhanced adatom mobilities on, and epitaxial registry with, surfaces exposed to borazine during the deposition. We expect that our approach can potentially help improve the crystalline quality of thin films deposited on a variety of substrates.

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/N2 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 (V0.21Nb0.18Ta0.19Mo0.21W0.21)N1.05 with lattice parameter a = 0.4249 nm. The alloy nitride film exhibits dense columnar microstructure near the substrate-film interface with coherent 001 grain growth limited to a few tens of nanometers, followed by an outgrowth of quasi one-dimensional nanorods with 3-fold symmetric facets. We attribute the self-organized growth of rather unusual 111-textured nanorods on isostructural MgO(001) to kinetic limitations of the sputter-deposition process exacerbated by the sluggish diffusion of the multicomponent adspecies and the preferential growth of {111} crystals.

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

Using in situ 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 10-6 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. Our results illustrate how growth mechanisms can be activated by a pair of parameters (substrate temperature and partial pressure of borazine) and provide new insights into the mechanisms underlying carpetlike growth of hBN and other layered materials.

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

Using a combination of in situ ultrahigh-vacuum variable-temperature scanning tunneling microscopy, ex situ 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. Monolayer graphene domains, 10-30 nm in size, appear during annealing this sample at 873 K. Dosing benzene at 1100 K results in graphene domains with varying degrees of crystallinity, while post-deposition annealing at 1100 K for 1200 s yields monolayer graphene domains larger than 150 × 150 nm2. Our results, which indicate that graphene growth on Pd(111) using benzene requires deposition/annealing temperatures higher than 673 K, are in striking contrast with the reported growth of graphene using benzene at temperatures as low as 373 K on relatively inert Cu surfaces.

Ultra-high vacuum dc magnetron sputter-deposition of 0001-textured trigonal α-Ta2C/Al2O3(0001) thin films.

We report on the effects of substrate temperature (1073 K ≤ T s ≤ 1373 K) and deposition time t (= 3 ~ 30 min.) on the crystallinity of Ta2C/Al2O3(0001) thin films grown via ultra-high vacuum direct current magnetron sputtering of TaC target in 20 mTorr (2.7 Pa) pure Ar atmospheres. Using X-ray diffraction and transmission electron microscopy, we determine that the layers are 0001-oriented, trigonal-structured α-Ta2C at all T s. With increasing T s, we obtain smoother and thinner layers with enhanced out-of-plane coherency and decreasing unit cell volume. Interestingly, the Ta2C 0001 texture improves with increasing T s up to 1273 K above which the layers are relatively more polycrystalline. At T s = 1373 K, during early stages of deposition, the Ta2C layers grow heteroepitaxially on Al2O3(0001) with ( 0001 ) Ta 2 C ‖ ( 0001 ) Al 2 O 3 and [ 10 1 ¯ 0 ] Ta 2 C ‖ [ 11 2 ¯ 0 ] Al 2 O 3 . With increasing t, we observe the formation of anti-phase domains and misoriented grains resulting in polycrystalline layers. We attribute the observed enhancement in 0001 texture to increased surface adatom mobilities and the development of polycrystallinity to reduced incorporation of C in the lattice with increasing T s. We expect that our results help develop methods for the synthesis of high-quality Ta2C thin films.

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. We observed a thermally activated bilayer-by-bilayer removal of the GaAs facet in contact with the liquid particle during annealing between 300 and 420 °C in vacuum. Interestingly, the GaAs-removal rates initially depend on the thermal history of the sample and are time-invariant at later times. In situ X-ray energy dispersive spectroscopy was also used to determine that the Ga content in the particle at any given temperature remains constant over extended periods of time and increases with increasing temperature from 300 to 400 °C. We attribute the observed phenomena to droplet-assisted decomposition of GaAs at a rate that is controlled by the amount of Ga in the droplet. We suggest that the observed transients in removal rates are a direct consequence of time-dependent changes in the Ga content. Our results provide new insights into the role of droplet composition on the thermal stability of GaAs nanowires and complement the existing knowledge on the factors influencing nanowire growth. Moreover, understanding the nanowire stability and decomposition is important for improving processing protocols for the successful fabrication and sustained operation of nanowire-based devices.

Ultrahigh vacuum dc magnetron sputter-deposition of epitaxial Pd(111)/Al2O3(0001) thin films.

Pd(111) thin films, ∼245 nm thick, are deposited on Al2O3(0001) substrates at ≈0.5Tm, where Tm 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 in situ from the as-deposited samples reveal that the surfaces are compositionally pure 111-oriented Pd. Double-axis x-ray diffraction (XRD) ω-2θ scans show only the set of Pd 111 peaks from the film. In triple-axis high-resolution XRD, the full width at half maximum intensity Γω of the Pd 111 ω-rocking curve is 630 arc sec. XRD 111 pole figure obtained from the sample revealed six peaks 60°-apart at a tilt angles corresponding to Pd 111 reflections. XRD ϕ scans show six 60°-rotated 111 peaks of Pd at the same ϕ angles for 11[Formula: see text]3 of Al2O3 based on which the epitaxial crystallographic relationships between the film and the substrate are determined as [Formula: see text]ǁ[Formula: see text] with two in-plane orientations of [Formula: see text]ǁ[Formula: see text] and [Formula: see text]ǁ[Formula: see text]. Using triple axis symmetric and asymmetric reciprocal space maps, interplanar spacings of out-of-plane (111) and in-plane (11[Formula: see text]) are found to be 0.2242 ± 0.0003 and 0.1591 ± 0.0003 nm, respectively. These values are 0.18% lower than 0.2246 nm for (111) and the same, within the measurement uncertainties, as 0.1588 nm for (11[Formula: see text]) calculated from the bulk Pd lattice parameter, suggesting a small out-of-plane compressive strain and an in-plane tensile strain related to the thermal strain upon cooling the sample from the deposition temperature to room temperature. High-resolution cross-sectional transmission electron microscopy coupled with energy dispersive x-ray spectra obtained from the Pd(111)/Al2O3(0001) samples indicate that the Pd-Al2O3 interfaces are essentially atomically abrupt and dislocation-free. These results demonstrate the growth of epitaxial Pd thin films with (111) out-of-plane orientation with low mosaicity on Al2O3(0001).

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 (KAuBr4) 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 (HAuCl4) to KAuBr4 and their thicknesses from ∼13 to ∼46 nm with the synthesis time. Through a series of experiments carried out as a function of synthesis time and precursor composition [mixtures of HAuCl4 and KAuBr4, KBr, or ionic liquid 1-butyl-3-methylimidazolium bromide ([Bmim]Br)], we identify the optimal HAuCl4 and KAuBr4 concentrations and synthesis times that yield the largest and the thinnest size nanoplates. We show that the nanoplates are kinetically limited morphologies resulting from preferential growth of {111} facets facilitated by bromide ions in KAuBr4 solutions; we suggest that the presence of chloride ions enhances the rate of Au deposition and the relative concentration of chloride and bromide ions determines the shape anisotropy of resulting crystals. Our results provide new insights into the kinetics of nanoplate formation and show that a single precursor containing both Au and Br is sufficient to crystallize nanoplates on graphitic layers, which serve as reducing agent while enabling the nucleation and growth of Au nanoplates. We suggest that a similar approach may be used for the synthesis of nanoplates of other metals on weakly interacting van der Waals layers for, potentially, a variety of new applications.

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. We examine deposition of ZnAu on Au in the presence of Bi additive, and show that low concentrations of Bi delay but do not prevent the formation of growth front instabilities. We describe a model in which Bi segregates at the growth front and promotes the surface diffusion and relaxation of Zn, allowing better coverage of the initial Au electrode surface. A more precise knowledge of the mechanism of inorganic additive effects may help in designing electrolyte chemistry for battery and other applications where morphology control is essential.

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. We demonstrate these processes via in situ transmission electron microscopy using Au as the model material and extend to other metals. We anticipate that this approach can be used to deposit multicomponent alloys and core-shell nanostructures with nanoscale spatial and compositional resolutions for a variety of possible applications.

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. The volume of each crystal increases linearly with irradiation time at a rate unaffected by its shape or proximity to neighboring crystals, implying a growth process that is controlled by the arrival of atoms from solution. Furthermore, growth requires a threshold dose rate, suggesting competition between reduction and oxidation processes in the solution. Above this threshold, the growth rate follows a power law with dose rate. To explain the observed dose rate dependence, we demonstrate that a reaction-diffusion model is required that explicitly accounts for the species H(+) and Cl(-). The model highlights the necessity of considering all species present when interpreting kinetic data obtained from beam-induced processes, and suggest conditions under which growth rates can be controlled with higher precision.

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. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that employs AgNO3 to produce {111} faceted Pt nanocrystals. The insight gained about the role of auxiliary species is then utilized to predict the shape of Pd nanocrystals and to corroborate other shape-directing syntheses reported in literature. The fundamental understanding obtained herein by combining modeling with experimentation is a step toward computationally guided syntheses and, in principle, applicable to predictive design of the growth of crystalline solids at all length scales (nano to bulk).

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. We show that pure Si nanowires can be made to exhibit the same kinks and defects by changing their droplet volume. From this we derive a model where droplet geometry drives growth morphology and discuss optimization strategies. We finally discuss morphology control for material pairs where the second material kinks immediately at the heterointerface and show that an interlayer between segments can enable the growth of unkinked hybrid nanowires.

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. The resulting graphene layers exhibit tunable structural and optoelectronic properties by nickel grain boundary engineering and show micrometre-sized grains on SiO(2) surfaces and nanometre-sized grains on plastic and glass surfaces. The ability to synthesize graphene directly on non-conducting substrates at low temperatures opens up new possibilities for the fabrication of multiple nanoelectronic devices.

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. Scanning tunneling spectroscopy data indicate that the graphene layers are metallic on both Ni(111) and Ni(110), in agreement with the calculations. We attribute this behavior to a strong hybridization between the d-bands on Ni and the π-bands of carbon. Our findings point to the possibility of preparing large-area epitaxial graphene layers even on polycrystalline Ni substrates.

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.

Growth of semiconducting graphene on palladium.

We report in situ scanning tunneling microscopy studies of graphene growth on Pd(111) during ethylene deposition at temperatures between 723 and 1023 K. We observe the formation of monolayer graphene islands, 200-2000 A in size, bounded by Pd surface steps. Surprisingly, the topographic image contrast from graphene islands reverses with tunneling bias, suggesting a semiconducting behavior. Scanning tunneling spectroscopy measurements confirm that the graphene islands are semiconducting, with a band gap of 0.3 +/- 0.1 eV. On the basis of density functional theory calculations, we suggest that the opening of a band gap is due to the strong interaction between graphene and the Pd substrate. Our findings point to the possibility of preparing semiconducting graphene layers for future carbon-based nanoelectronic devices via direct deposition onto strongly interacting substrates.

Kinetic control of self-catalyzed indium phosphide nanowires, nanocones, and nanopillars.

The morphological phase diagram is reported for InP nanostructures grown on InP (111)B as a function of temperature and V/III ratio. Indium droplets were used as the catalyst and were generated in situ in the metalorganic vapor-phase epitaxy reactor. Three distinct nanostructures were observed: wires, cones, and pillars. It is proposed that the shape depends on the relative rates of indium phosphide deposition via the vapor-liquid-solid (VLS) and vapor-phase epitaxy (VPE) processes. The rate of VLS is relatively insensitive to temperature and results in vertical wire growth starting at 350 degrees C. By contrast, the rate of VPE accelerates with temperature and drives the lateral growth of cones at 385 degrees C and then pillars at 400 degrees C.

Self-catalyzed epitaxial growth of vertical indium phosphide nanowires on silicon.

Vertical indium phosphide nanowires have been grown epitaxially on silicon (111) by metalorganic vapor-phase epitaxy. Liquid indium droplets were formed in situ and used to catalyze deposition. For growth at 350 degrees C, about 70% of the wires were vertical, while the remaining ones were distributed in the 3 other <111> directions. The vertical fraction, growth rate, and tapering of the wires increased with temperature and V/III ratio. At 370 degrees C and V/III equal to 200, 100% of the wires were vertical with a density of approximately 1.0 x 10(9) cm(-2) and average dimensions of 3.9 mum in length, 45 nm in base width, and 15 nm in tip width. X-ray diffraction and transmission electron microscopy revealed that the wires were single-crystal zinc blende, although they contained a high density of rotational twins perpendicular to the <111> growth direction. The room temperature photoluminescence spectrum exhibited one peak centered at 912 +/- 10 nm with a FWHM of approximately 60 nm.