Interest in nanowires continues to grow, fuelled in part by applications in nanotechnology. The ability to engineer nanowire properties makes them especially promising in nanoelectronics. Most silicon nanowires are grown using the vapour-liquid-solid (VLS) mechanism, in which the nanowire grows from a gold/silicon catalyst droplet during silicon chemical vapour deposition. Despite over 40 years of study, many aspects of VLS growth are not well understood. For example, in the conventional picture the catalyst droplet does not change during growth, and the nanowire sidewalls consist of clean silicon facets. Here we demonstrate that these assumptions are false for silicon nanowires grown on Si(111) under conditions where all of the experimental parameters (surface structure, gas cleanliness, and background contaminants) are carefully controlled. We show that gold diffusion during growth determines the length, shape, and sidewall properties of the nanowires. Gold from the catalyst droplets wets the nanowire sidewalls, eventually consuming the droplets and terminating VLS growth. Gold diffusion from the smaller droplets to the larger ones (Ostwald ripening) leads to nanowire diameters that change during growth. These results show that the silicon nanowire growth is fundamentally limited by gold diffusion: smooth, arbitrarily long nanowires cannot be grown without eliminating gold migration.

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.

We have formed compositionally abrupt interfaces in silicon-germanium (Si-Ge) and Si-SiGe heterostructure nanowires by using solid aluminum-gold alloy catalyst particles rather than the conventional liquid semiconductor-metal eutectic droplets. We demonstrated single interfaces that are defect-free and close to atomically abrupt, as well as quantum dots (i.e., Ge layers tens of atomic planes thick) embedded within Si wires. Real-time imaging of growth kinetics reveals that a low solubility of Si and Ge in the solid particle accounts for the interfacial abruptness. Solid catalysts that can form functional group IV nanowire-based structures may yield an extended range of electronic applications.

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. 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.

We examine individual Si nanowires grown by the vapor-liquid-solid mechanism, using real-time in situ ultra high vacuum transmission electron microscopy. By directly observing Au-catalyzed growth of Si wires from disilane, we show that the growth rate is independent of wire diameter, contrary to the expected behavior. Our measurements show that the unique rate-limiting step here is the irreversible, kinetically limited, dissociative adsorption of disilane directly on the catalyst surface. We also identify a novel dependence of growth rate on wire taper.

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 Å 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.Graphene 1,2 sa two-dimensional crystalline sheet of carbon atoms arranged in a honeycomb latticesgenerated enormous interest in the research community owing to its ultrathin geometry and properties such as high carrier mobility, 3 excellent thermal conductivity, 4 and high mechanical strength. 5 One of the attractive features of free-standing graphene, a semimetal, is its semiconducting behavior 6,7 at length scales below 500 Å with a size-dependent band gap. [8][9][10] Previous reports [11][12][13] have shown that a band gap can also be opened in graphene grown on insulating SiC(0001) and BN(0001) via interactions with the substrate. Here, we report the formation of semiconducting graphene layers with a band gap of 0.3 ( 0.1 eV on Pd(111), a metallic substrate. Using in situ scanning tunneling microscopy (STM) and spectroscopy (STS), we determine the electronic structure of graphene islands grown in situ via chemical vapor deposition on Pd(111). In contrast to recent reports on nanoribbons, where the band gap originates from size/ edge effects, 8-10 the band gap in epitaxial graphene on palladium is caused by a strong interaction with the Pd substrate and the ensuing breaking of translational symmetry between the two hexagonal close-packed sublattices of graphene. Our experiments illustrate the control over the electronic properties of graphene through interactions with substrates in well-defined epitaxial configurations. This approach opens up the possibility of preparing metal-semiconducting graphene structures and metal-doped graphenebased devices with potentially new applications.Using STM, we followed the formation and growth of graphene on Pd(111) during ethylene deposition over a range of pressures, substrate temperatures, and times. Panels A and B of Figure 1 are representative STM images of graphene islands acquired from a Pd(111) surface in situ during ethylene deposition at 968 K. In our experiments, island sizes vary between 200 and 2000 Å and are commonly observed at or near the Pd step edges as in Figure 1A, or spanning across multiple terraces as in Figure 1B. During ethylene deposition, we observe graphene islands on the...

We present an extensive investigation of the epitaxial growth of Au-assisted axial heterostructure nanowires composed of group IV and III-V materials and derive a model to explain the overall morphology of such wires. By analogy with 2D epitaxial growth, this model relates the wire morphology (i.e., whether it is kinked or straight) to the relationship of the interface energies between the two materials and the particle. This model suggests that, for any pair of materials, it should be easier to form a straight wire with one interface direction than the other, and we demonstrate this for the material combinations presented here. However, such factors as kinetics and the use of surfactants may permit the growth of straight double heterostructure nanowires. Finally, we demonstrate that branched nanowire heterostructures, also known as nanotrees, can be successfully explained by the same model.

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.