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The formation of well-controlled interfaces between materials of different structure and bonding is a key requirement when developing new devices and functionalities. Of particular importance are epitaxial or low defect density interfaces between two-dimensional materials and three-dimensional semiconductors or metals, where an interfacial structure influences electrical conductivity in field effect and optoelectronic devices, charge transfer for spintronics and catalysis, and proximity-induced superconductivity. Epitaxy and hence well-defined interfacial structure has been demonstrated for several metals on van der Waals-bonded substrates. Semiconductor epitaxy on such substrates has been harder to control, for example during chemical vapor deposition of Si and Ge on graphene. Here, we demonstrate a catalytically mediated heteroepitaxy approach to achieve epitaxial growth of three-dimensional semiconductors such as Ge and Si on van der Waals-bonded materials such as graphene and hexagonal boron nitride. Epitaxy is “transferred” from the substrate to semiconductor nanocrystals via solid metal nanocrystals that readily align on the substrate and catalyze the formation of aligned nuclei of the semiconductor. In situ transmission electron microscopy allows us to elucidate the reaction pathway for this process and to show that solid metal nanocrystals can catalyze semiconductor growth at a significantly lower temperature than direct chemical vapor deposition or deposition mediated by liquid catalyst droplets. We discuss Ge and Si growth as a model system to explore the details of such hetero-interfacing and its applicability to a broader range of materials.

International audience; In situ transmission electron microscopy reveals that an atomically thin crystalline phase at the surface of liquid Au–Si is stable over an unexpectedly wide range of conditions. By measuring the surface structure as a function of liquid temperature and composition, a simple thermodynamic model is developed to explain the stability of the ordered phase. The presence of surface ordering plays a key role in the pathway by which the Au–Si eutectic solidifies and also dramatically affects the catalytic properties of the liquid, explaining the anomalously slow growth kinetics of Si nanowires at low temperature. A strategy to control the presence of the surface phase is discussed, using it as a tool in designing strategies for nanostructure growth.

We show that templating a Si surface with a focused beam of Si2+ or Si+ ions can create suitable nucleation sites for the subsequent growth of self-assembled Ge quantum dots by chemical vapor deposition. To determine the mechanism of patterning we use atomic force microscopy to show that, similar to Ga+ patterning, the formation of a surface pit is required to enable control over Ge quantum dot locations. We find that relatively high implantation doses are required to achieve patterning, and these doses lead to amorphization of the substrate. We assess the degree to which the substrate crystallinity can be recovered by subsequent processing. Using in situ transmission electron microscopy heating experiments we find that recrystallization is possible at the growth temperature of the Ge quantum dots, but defects remain that follow the pattern of the initial implantation. We discuss the formation mechanism of the defects and the benefits of using Si ions for patterning both defects and quantum dots on Si substrates.

We report layer-by-layer (LBL) assembly of graphene/carbon-coated mesoporous SnO 2 spheres (Gr/C-SnO 2 spheres), without binder and conducting additives, as anode materials with excellent Li-ion insertion–extraction properties. Our results indicate that these novel LBL assembled electrodes have high reversible Li storage capacity, improved cycling, and especially good rate performance, even at high specific currents. The superior electrochemical performance offered by these LBL assembled Gr/C-SnO 2 spheres is attributed to the enhanced electronic conductivity and effective diffusion of Li ions in the interconnected network of nanoparticles forming the mesoporous SnO 2 spheres.

We visualize atomic level dynamics during Si nanowire growth using aberration corrected environmental transmission electron microscopy, and compare with lower pressure results from ultra-high vacuum microscopy. We discuss the importance of higher pressure observations for understanding growth mechanisms and describe protocols to minimize effects of the higher pressure background gas.

We measured the nucleation and growth kinetics of solid silicon (Si) from liquid gold-silicon (AuSi) catalyst particles as the Si supersaturation increased, which is the first step of the vapor-liquid-solid growth of nanowires. Quantitative measurements agree well with a kinetic model, providing a unified picture of the growth process. Nucleation is heterogeneous, occurring consistently at the edge of the AuSi droplet, yet it is intrinsic and highly reproducible. We studied the critical supersaturation required for nucleation and found no observable size effects, even for systems down to 12 nanometers in diameter. For applications in nanoscale technology, the reproducibility is essential, heterogeneity promises greater control of nucleation, and the absence of strong size effects simplifies process design.

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

Nanowire growth by the vapour-liquid-solid (VLS) process enables a high level of control over nanowire composition, diameter, growth direction, branching and kinking, periodic twinning, and crystal structure. The tremendous impact of VLS-grown nanowires is due to this structural versatility, generating applications ranging from solid-state lighting and single-photon sources to thermoelectric devices. Here, we show that the morphology of these nanostructures can be further tailored by using the liquid droplets that catalyse nanowire growth as a 'mixing bowl', in which growth materials are sequentially supplied to nucleate new phases. Growing within the liquid, these phases adopt the shape of faceted nanocrystals that are then incorporated into the nanowires by further growth. We demonstrate this concept by epitaxially incorporating metal-silicide nanocrystals into Si nanowires with defect-free interfaces, and discuss how this process can be generalized to create complex nanowire-based heterostructures.

We have usedin situelectron microscopy to observe the nucleation of Ge islands on lithographically patterned Si(001) mesas. Images were obtained at video rate during chemical vapor deposition of Ge, using a reflection electron microscopy geometry that allows nucleation to be observed over large areas. By comparing the kinetics of nucleation and coarsening on substrates modified by different annealing conditions, we find that the final island arrangement depends on the nature of the mesa sidewalls, and we suggest that this may be due to changes in diffusion of Ge across the nonplanar surface.

The formation of abrupt Si/Ge heterointerfaces in nanowires presents useful possibilities for bandgap engineering. We grow Si nanowires containing thick Ge layers and sub-1 nm thick Ge “quantum wells” and measure the interfacial strain fields using geometric phase analysis. Narrow Ge layers show radial compressive strains of several percent, while stress at the Si/Ge interface causes lattice rotation. High strains can be achieved in these heterostructures, but we show that they are unstable to interdiffusion.

Real-time observations were made of the shape change from pyramids to domes during the growth of germanium-silicon islands on silicon (001). Small islands are pyramidal in shape, whereas larger islands are dome-shaped. During growth, the transition from pyramids to domes occurs through a series of asymmetric transition states with increasing numbers of highly inclined facets. Postgrowth annealing of pyramids results in a similar shape change process. The transition shapes are temperature dependent and transform reversibly to the final dome shape during cooling. These results are consistent with an anomalous coarsening model for island growth.

We use focused beams of Ga(+), Au(+) and Si(++) ions to induce local microstructural changes in single crystal silicon. The ions were delivered as single spot pulses into thin Si membranes that could subsequently be imaged and annealed in situ in a transmission electron microscope. For each ion, the focused ion beam implantation created an array of amorphous regions in the crystalline membrane. Annealing causes solid phase epitaxial regrowth to take place, but we show that the resulting microstructure depends on the ion species. For Ga(+) and Au(+), precipitates remain after recrystallization, while for Si(++), dislocation loops form around the periphery of each implanted spot. We attribute these loops to defects formed during solid phase epitaxial regrowth, with controlled placement of the loops possible.

Nanowire growth in the standard111direction 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. We develop an explicit model for this structure that agrees well with experiment and shows that the oscillations provide a direct visualization of catalyst supersaturation. We discuss the implications for wire growth and structure.

Sharp Nanowires The potential for using nanowires in devices can be limited by the ability to synthesize them from two or more materials while maintaining compositional purity at the interfaces. Instead of using liquid droplets at the eutectic point when the melting point is at a minimum, Wen et al. (p. 1247 ) show that generating the wires at solid alloy catalysts allows fabrication of silicon germanium wires with atomically sharp interfaces. The system works well because an AlAu alloy composition was chosen in which Si and Ge have a low solubility but which have a high enough eutectic temperature so that nanowire growth is not limited by the reactivity of the Si and Ge precursors.

Nanowires are conventionally assumed to grow via the vapor-liquid-solid process, in which material from the vapor is incorporated into the growing nanowire via a liquid catalyst, commonly a low–melting point eutectic alloy. However, nanowires have been observed to grow below the eutectic temperature, and the state of the catalyst remains controversial. Using in situ microscopy, we showed that, for the classic Ge/Au system, nanowire growth can occur below the eutectic temperature with either liquid or solid catalysts at the same temperature. We found, unexpectedly, that the catalyst state depends on the growth pressure and thermal history. We suggest that these phenomena may be due to kinetic enrichment of the eutectic alloy composition and expect these results to be relevant for other nanowire systems.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7–August 11, 2011.

The recent demonstration of single-crystal organic optoelectronic devices has received widespread attention1,2,3,4. But practical applications of such devices require the use of inexpensive organic films deposited on a wide variety of substrates. Unfortunately, the physical properties of these organic thin films do not compare favourably to those of single-crystal materials. Moreover, the basic physical principles governing organic thin-film growth and crystallization are not well understood. Here we report an in situ study of the evolution of pentacene thin films, utilizing the real-time imaging capabilities of photoelectron emission microscopy. By a combination of careful substrate preparation and surface energy control, we succeed in growing thin films with single-crystal grain sizes approaching 0.1 millimetre (a factor of 20–100 larger than previously achieved), which are large enough to fully contain a complete device. We find that organic thin-film growth closely mimics epitaxial growth of inorganic materials, and we expect that strategies and concepts developed for these inorganic systems will provide guidance for the further development and optimization of molecular thin-film devices.

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Extended abstract of a paper presented at Microscopy and Microanalysis 2009 in Richmond, Virginia, USA, July 26 – July 30, 2009

Extended abstract of a paper presented at Microscopy and Microanalysis 2008 in Albuquerque, New Mexico, USA, August 3 – August 7, 2008

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2006

Germanium nucleation on a silicon surface typically proceeds via spontaneous formation of nanoscopic islands, or quantum dots (QDs), at random locations. However, potential applications of epitaxial QDs, such as quantum cellular automata, require precise control of Ge island positions on Si in clusters with the individual islands' separation of tens of nanometers or less. Controlled Ge island placement with an inter-island separation down to 100 nm can be reliably obtained by depositing Ge onto a Si(001) surface modified with a low dose focused ion beam (FIB) pattern to create preferred nucleation sites for individual islands. Here we investigate QD self-assembly of multiple islands on single topographical features intended to obtain clusters of QDs with smaller separations. We observe formation of 50 nm clusters on a single location defined by the FIB patterning of a larger and shallower feature, where cluster formation is promoted by reduced surface diffusion. We also discuss cluster formation on single sites defined by residual trenches on a footprint of a larger island that has been desorbed. We propose that controlled placement of islands during the first deposition may result in greater control over subsequent cluster size and placement fidelity due to improved uniformity of target features.

not Available.

The introduction of a surfactant changes the growth in the Si(111)/Ge system from islanding to a continuous film. A Sb monolayer floats at the growth front without detectable incorporation in the growing film. The surfactant strongly influences the growth kinetics and prevents intermixing or indiffusion of Ge or Si. Up to 8 ML thickness the Ge film is completely strained and pseudomorphic; for thicker films the strain due to the 4.2% misfit is relieved by the generation of defects, which are finally all confined in a dislocation network at the interface. Low-defect, fully relaxed epitaxial Ge films of arbitrary thickness can be grown. Similarly, low-defect relaxed Si can be grown on Ge(111). Medium-energy ion scattering, high-resolution transmission electron microscopy, x-ray-photoelectron spectroscopy, and Raman scattering show that the crystal quality of these Ge films is excellent.

The rate of heteroepitaxial strain relaxation via misfit dislocation introduction is strongly limited by the kinetics of dislocation nucleation, propagation and interaction. Here we describe real-time observations of the interaction between moving threading dislocations and pre-existing interfacial misfit dislocations using in-situ transmission electron microscopy. This was accomplished both during in-situ observations of the heteroepitaxial growth process using a modified ultrahigh vacuum TEM (UHV-TEM) equipped with chemical vapor deposition capabilities, as well as during in-situ anneals of metastable structures grown by molecular beam epitaxy.In Figure 1, we present our UHV-TEM observations of the epilayer thicknesses and compositions at which dislocation interactions result in blocking of the propagating threading segment, and compare these with the theoretical predictions of Freund and those of Schwarz and Tersoff. Our results show that dislocation blocking can significantly affect the overall rate of strain relaxation in these structures. This is important, as blocked threading segments introduce undesired band gap states into electronic devices and can act as easy diffusion paths for impurities and dopants.

A direct dependence between the inadvertent formation of SiO2 on gold films deposited on silicon ⟨111⟩ substrates, and the nucleation and yield of epitaxial, gold catalyzed, silicon nanowires grown on such substrates is reported. The unintended SiO2 layer formed due to the diffusion of silicon from the underlying substrate through the gold film is observed to be 0.5nm with medium energy ion scattering after brief exposures of 10–15min in air. Silicon nanowires grown at 500°C on such samples show reduced nucleation and growth. A remarkable improvement in nanowire nucleation density and epitaxy is observed on removing the SiO2 overlayer prior nanowire growth.