Gold is known as a shiny, yellow noble metal that does not tarnish, has a face centred cubic structure, is non-magnetic and melts at 1336 K. However, a small sample of the same gold is quite different, providing it is tiny enough: 10 nm particles absorb green light and thus appear red. The meltingtemperature decreases dramatically as the size goes down. Moreover, gold ceases to be noble, and 2–3 nm nanoparticles are excellent catalysts which also exhibit considerable magnetism. At this size they are still metallic, but smaller ones turn into insulators. Their equilibrium structure changes to icosahedral symmetry, or they are even hollow or planar, depending on size. The present tutorial review intends to explain the origin of this special behaviour of nanomaterials.

Size matters: why nanomaterials are different

The regulation of engineered nanoparticles requires a widely agreed definition of such particles. Nanoparticles are routinely defined as particles with sizes between about 1 and 100 nm that show properties that are not found in bulk samples of the same material. Here we argue that evidence for novel size-dependent properties alone, rather than particle size, should be the primary criterion in any definition of nanoparticles when making decisions about their regulation for environmental, health and safety reasons. We review the size-dependent properties of a variety of inorganic nanoparticles and find that particles larger than about 30 nm do not in general show properties that would require regulatory scrutiny beyond that required for their bulk counterparts.

/pdf/towards-a-definition-of-inorganic-nanoparticles-from-an-4qpaj5a6q5.pdf

Towards a definition of inorganic nanoparticles from an environmental, health and safety perspective

The structural properties of free nanoclusters are reviewed. Special attention is paid to the interplay of energetic, thermodynamic, and kinetic factors in the explanation of cluster structures that are actually observed in experiments. The review starts with a brief summary of the experimental methods for the production of free nanoclusters and then considers theoretical and simulation issues, always discussed in close connection with the experimental results. The energetic properties are treated first, along with methods for modeling elementary constituent interactions and for global optimization on the cluster potential-energy surface. After that, a section on cluster thermodynamics follows. The discussion includes the analysis of solid-solid structural transitions and of melting, with its size dependence. The last section is devoted to the growth kinetics of free nanoclusters and treats the growth of isolated clusters and their coalescence. Several specific systems are analyzed.

/pdf/structural-properties-of-nanoclusters-energetic-56vj4t3ucw.pdf

Structural properties of nanoclusters: Energetic, thermodynamic, and kinetic effects

In this article, the effects of size and confinement at the nanometre size scale on both the melting temperature, Tm, and the glass transition temperature, Tg, are reviewed. Although there is an accepted thermodynamic model (the Gibbs–Thomson equation) for explaining the shift in the first-order transition, Tm, for confined materials, the depression of the melting point is still not fully understood and clearly requires further investigation. However, the main thrust of the work is a review of the field of confinement and size effects on the glass transition temperature. We present in detail the dynamic, thermodynamic and pseudo-thermodynamic measurements reported for the glass transition in confined geometries for both small molecules confined in nanopores and for ultrathin polymer films. We survey the observations that show that the glass transition temperature decreases, increases, remains the same or even disappears depending upon details of the experimental (or molecular simulation) conditions. Indeed, different behaviours have been observed for the same material depending on the experimental methods used. It seems that the existing theories of Tg are unable to explain the range of behaviours seen at the nanometre size scale, in part because the glass transition phenomenon itself is not fully understood. Importantly, here we conclude that the vast majority of the experiments have been carried out carefully and the results are reproducible. What is currently lacking appears to be an overall view, which accounts for the range of observations. The field seems to be experimentally and empirically driven rather than responding to major theoretical developments.

https://iopscience.iop.org/article/10.1088/0953-8984/17/15/R01/pdf

Effects of confinement on material behaviour at the nanometre size scale

Size dependence of nanostructures: Impact of bond order deficiency

Electronic Raman scattering and the metal-insulator transition in doped silicon

Inelastic light scattering from photoproduced carriers is observed in stressed high-purity silicon at low temperatures. The two electronic Raman structures observed correspond to transitions between stress-split valence bands at the zone center. These transitions can be stress-tuned to the $\ensuremath{\Gamma}$-point phonon energy, thereby exhibiting Fano-type interference between competing scattering amplitudes.

Electronic Raman Scattering and Antiresonance Behavior in Highly Stressed Photoexcited Silicon.

The authors introduce a high-sensitivity ({approximately}1 J/m{sup 2}) scanning microcalorimeter that can be used to perform direct calorimetric measurements on thin film samples at ultrafast heating rate ({approximately} 10{sup 4} C/s). This novel microcalorimeter is fabricated by utilizing SiN thin-film membrane technology, resulting in dramatically reduced thermal mass of the system. Calorimetric measurements are accomplished by applying a dc-current pulse to the thin-film metal (Ni) heater which also serves as a thermometer, and monitoring the real-time voltage and current of the heater. The temperature of the system and the energy delivered to the system are then determined. This calorimetric technique has been demonstrated by measuring the melting process of thin Sn films with thickness ranging from 13 to 1,000 {angstrom}, and shows potential for calorimetric probing of irreversible reactions at interfaces and surfaces, as well as transformations in nanostructured materials,

An Ultrafast Thin-Film Microcalorimeter with Monola Yer Sensitivity (J/m2)

The evolution of microstructure during Au-mediated solid phase epitaxial growth of a SiGe alloy film on Si(001) (c-Si) was investigated by in situ resistance measurements, X-ray diffraction, conventional and high-resolution transmission electron microscopy, and chemical microanalyis. Annealing a-Ge/Au bilayers on c-Si to temperatures below 120°C caused changes primarily in the microstructure of the Au film. Increases in temperature to ≃150°C resulted in the diffusion of Ge through the grain boundaries of Au. The Au, displaced by crystalline Ge at the grain boundaries, diffused along columnar voids of amorphous Ge (a-Ge) leading to the formation of Au-rich crystallites in the top layer. Results indicate that the Ge that had reached the Au/c-Si interface grew epitaxially on c-Si at temperatures below 150°C. As the temperature was further increased, some Si from the substrate dissolved into Au and got incorporated in the growing epilayer. At 310°C, the initial Au film was displaced completely by a laterally continuous Si ξ Gei. ξ (ξ ∼ 0.2) epilayer whose thickness was limited by that of the initial Au film. Twins, and residual amounts of Au near the SiGe/c-Si interface, were the predominant defects observed in the SiGe epilayer.

S. L. Lai

Papers

Electronic Raman scattering and the metal-insulator transition in doped silicon

Electronic Raman Scattering and Antiresonance Behavior in Highly Stressed Photoexcited Silicon.

An Ultrafast Thin-Film Microcalorimeter with Monola Yer Sensitivity (J/m2)

Evolution of Microstructure During Low-Temperature Solid Phase Epitaxial Growth of SiξGe1-ξ on Si(001)