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.

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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.

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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

For the first time, the latent heat of fusion $\ensuremath{\Delta}{H}_{m}$ for Sn particles formed by evaporation on inert substrate with radii ranging from 5 to 50 nm has been measured directly using a novel scanning nanocalorimeter. A particle-size-dependent reduction of $\ensuremath{\Delta}{H}_{m}$ has been observed. An ``excluded volume'' is introduced to describe the latent heat of fusion from the enhanced surface melting of small particles. Melting point depression has also been found by our nanocalorimetric technique.

http://allen.matse.illinois.edu/pdf/allen_prl_070196.pdf

Size-Dependent Melting Properties of Small Tin Particles: Nanocalorimetric Measurements.

The melting behavior of 0.1\char21{}10-nm-thick discontinuous indium films formed by evaporation on amorphous silicon nitride is investigated by an ultrasensitive thin-film scanning calorimetry technique. The films consist of ensembles of nanostructures for which the size dependence of the melting temperature and latent heat of fusion are determined. The relationship between the nanostructure radius and the corresponding melting point and latent heat is deduced solely from experimental results (i.e., with no assumed model) by comparing the calorimetric measurements to the particle size distributions obtained by transmission electron microscopy. It is shown that the melting point of the investigated indium nanostructures decreases as much as 110 K for particles with a radius of 2 nm. The experimental results are discussed in terms of existing melting point depression models. Excellent agreement with the homogeneous melting model is observed.

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Size-dependent melting point depression of nanostructures: Nanocalorimetric measurements

http://allen.matse.illinois.edu/pdf/allen_tca_032304.pdf

Thin-film differential scanning nanocalorimetry: heat capacity analysis

We introduce a scanning calorimeter for use with a single solid or liquid sample with a volume down to a few nanoliters. Its use is demonstrated with the melting of 52 nL of indium, using heating rates from 100 to 1000 K/s. The heat of fusion was measured to within 5% of the bulk value, and the sensitivity of the measurement was ±7 μW. The heat of vaporization of water was measured in the scanning mode to be within ±23% of the bulk value by actively vaporizing water droplets from 2 to 100 nL in volume. Results within 25% were obtained for the heat of vaporization by using the calorimeter in a heat-conductive mode and measuring the passive evaporation of water. Temperature measurements over a period of 10 h had a standard deviation of 3 mK.

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Scanning calorimeter for nanoliter-scale liquid samples

This paper reports a new photoluminescence (PL) band in indirect $\mathrm{Ga}{\mathrm{As}}_{1\ensuremath{-}x}{\mathrm{P}}_{x}$ that lies between donor-bound and free exciton PL peaks. It has relatively strong $X$-point phonon sidebands and an asymmetric shape with an abrupt high-energy cutoff. The lifetime varies rapidly over the PL linewidth. Properties of excitons in fluctuating random-alloy potentials are discussed. It is suggested that this line is due to excitons trapped by such potentials.

S. L. Lai

Papers

Size-Dependent Melting Properties of Small Tin Particles: Nanocalorimetric Measurements.

Size-dependent melting point depression of nanostructures: Nanocalorimetric measurements

Thin-film differential scanning nanocalorimetry: heat capacity analysis

Scanning calorimeter for nanoliter-scale liquid samples

Evidence for Exciton Localization by Alloy Fluctuations in Indirect-Gap Ga As 1 − x P x