Templated Assembly of Nanoparticles into Continuous Arrays.

The templated assembly of nanoparticles has been limited so far to yield only discontinuous nanoparticle clusters confined within lithographically patterned cavities. Here, we explored the templated assembly of nanoparticles into continuous 2D structures, using lithographically patterned templates with topographical features sized as the assembled nanoparticles. We found that these features act as nucleation centers, whose exact arrangement determines four possible assembly regimes (i) rotated, (ii) disordered, (iii) closely packed, and (iv) unpacked. These regimes produce structures strikingly different from their geometry, orientation, long-range and short-range orders, and packing density. Interestingly, for templates with relatively distant nucleation centers, these four regimes are replaced with three new ones, which produce large monocrystalline domains that are either (i) uniformly rotated, (ii) uniformly aligned, or (iii) nonuniformly rotated relative to the nucleation lattice. We rationalized our experimental data using a mathematical model, which examines all the alignment possibilities between the nucleation centers and the ideal hexagonal assembly. Our finding provides a new approach for the à la carte obtainment of various nanoscale structures unachievable by natural self-assembly and opens a route for the fabrication of numerous functional nanodevices and nanosystems that could not be realized so far by the standard bottom-up approach.

Electrical and Optical Properties of γ-SnSe: A New Ultra-narrow Band Gap Material.

We describe the unusual properties of γ-SnSe, a new orthorhombic binary phase in the tin monoselenide system. This phase exhibits an ultranarrow band gap under standard pressure and temperature conditions, leading to high conductivity under ambient conditions. Density functional calculations identified the similarity and difference between the new γ-SnSe phase and the conventional α-SnSe based on the electron localization function. Very good agreement was obtained for the band gap width between the band structure calculations and the experiment, and insight provided for the mechanism of reduction in the band gap. The unique properties of this material may render it useful for applications such as thermal imaging devices and solar cells.

Carbon nanowires under compression and their vibrational anomalies.

Anomalous pressure dependence of Raman frequencies of carbon nanowires encapsulated in carbon nanotubes has been recently reported. Two hypotheses have been proposed to explain this phenomenon in linear carbon chains: softening of a carbon bond with pressure or charge transfer to the chain. However, carbon chains bend easily under stress, although stable structures under these conditions have yet to be discovered. In this study, we model linear and bent carbon nanowires under compression, including both stable and metastable structures. The structures, electronic properties, and vibrational frequencies are obtained through first-principles calculations within density functional theory. We find that polyyne, the dimerized linear ground-state structure of carbon chains at zero strain, is not stable under compression for an infinite carbon chain. Instead, the chain transforms into two possible configurations, a previously unknown three-dimensional helical shape or a two-dimensional sinusoidal shape. These structures can be modeled using an analytical atomistic force-constant model or with a continuum approach. In the continuum approach, an eigenvalue wave equation describes the energy and geometry of the chain. Moreover, this equation produces excited (metastable) structural states and can be applied to other one-dimensional systems. The wave equation formulation indicates that the much-pursued concept of Young's modulus in one-dimensional chains is ill-defined. Finally, the Raman anomaly under compression is not observed within the atomistic force-constant model contrary to assumptions in the literature. Instead, this anomaly can be understood using a model in which charge transfer between the nanotube and the nanowire occurs upon contact.

Stability of cubic tin sulphide nanocrystals: role of ammonium chloride surfactant headgroups.

New semiconducting metastable cubic phases have been recently discovered in the tin monosulfide and monoselenide systems. Surface energy calculations and experimental studies indicate that this cubic π-phase is stabilized by specific ligand adsorption on the surface. In this work, it is shown experimentally that the synthesis carried out using mixtures of oleylamine and oleylammonium chloride (OACl) surfactants results in the cubic phase, transforming the growth from orthorhombic to cubic nanoparticles with increasing OACl concentration up to a limiting point. Complementary ab initio calculations find that adsorbed ligands lower the surface energies for both the cubic phase and the orthorhombic phase, relative to the pristine surfaces. The decrease in the surface energy increases with ligand coverage. Stronger binding energies to the cubic phase suggest a higher coverage, and therefore preferential stabilization of this phase. Upon further increasing the coverage, the surface energy becomes negative, effectively destabilizing the particles in agreement with experimental observations. Bonding analysis shows that Cl bonds to Sn and replaces missing Sn-S bonds at the surface of the cubic structure. In the competing orthorhombic layered phase, Cl also bonds to a Sn atom but at the expense of one of the Sn-S bonds of this Sn atom. This observation can explain the trends of the surface energies. This combined experimental and computational analysis sheds light on the stabilization processes of these nano-materials and indicates the path to improve synthetic routes.

π-Phase Tin and Germanium Monochalcogenide Semiconductors: An Emerging Materials System.

Cubic π-phase monochalcogenides (MX, M = Sn, Ge; X = S, Se) are an emerging new class of materials that has recently been discovered. Here, their thermodynamic stability, progress in synthetic routes, properties, and prospective applications are reviewed. The thermodynamic stability is demonstrated through density functional theory total energy and phonon spectra calculations, which show that the π-phase polytype is stable across the monochalcogenide family. To date, only π-phase tin monochalcogenides have been observed experimentally while π-phase Ge-monochalcogenides are predicted to be stable but are yet to be experimentally realized. Various synthetic preparation protocols of π-SnS and π-SnSe are described, focusing on surfactant-assisted nanoparticle synthesis and chemical deposition of thin films from aqueous-bath compositions. These techniques provide materials with different surface energies, which are likely to play a major role in stabilizing the π-phase in nanoscale materials. The properties of this newly discovered family of semiconducting materials are discussed in comparison with their conventional orthorhombic polymorphs. These could benefit a number of photovoltaic and optoelectronic applications since, apart from being cubic, they also possess characteristic advantages, such as moderately low toxicity and natural abundance.