Controlling nanomaterial growth via the "specific microwave effect" can be achieved by selective heating of the chalcogenide precursor. The high polarizability of the precursor allows instantaneous activation and subsequent nucleation leading to the synthesis of CdSe and CdTe in nonmicrowave absorbing alkane solvents. Regardless of the desired size, narrow dispersity nanocrystals can be isolated in less than 3 min with high quantum efficiencies and elliptical morphologies. The reaction does not require a high temperature injection step, and the alkane solvent can be easily removed. In addition, batch-to-batch variance in size is 4.2 +/- 0.14 nm for 10 repeat experimental runs. The use of a stopped-flow reactor allows near continuous automation of the process leading to potential industrial benefits.

A century ago Ostwald described the "Rule of Stages" after deducing that crystal formation must occur through a series of intermediate crystallographic phases prior to formation of the final thermodynamically stable structure. Direct evidence of the Rule of Stages is lacking, and the theory has not been implemented to allow isolation of a selected structural phase. Here we report the role of Ostwald's Rule of Stages in the growth of CdSe quantum dots (QDs) from molecular precursors in the presence of hexadecylamine. It is observed that, by controlling the rate of growth through the reaction stoichiometry and therefore the probability of ion-packing errors in the growing QD, the initially formed zinc blende (ZB) critical nuclei representing the kinetic phase can be maintained at sizes >14 nm in diameter without phase transformation to the thermodynamic wurtzite (WZ) structure. An intermediate pseudo-ZB structure is observed to appear at intermediate reaction conditions, as predicted by Ostwald. The ZB and pseudo-ZB structures convert to the WZ lattice above a critical melting temperature. This study validates Ostwald's Rule of Stages and provides a phase diagram for growth of CdSe QDs exhibiting a specific crystallographic motif.

Nanocrystal quantum dots are generally coated with an organic ligand layer. These layers are a necessary consequence of their chemical synthesis, and in addition they play a key role in controlling the optical and electronic properties of the system. Here we describe a method for quantitative measurement of the ligand layer in 3 nm diameter lead sulfide–oleic acid quantum dots. Complementary small-angle X-ray and neutron scattering (SAXS and SANS) studies give a complete and quantitative picture of the nanoparticle structure. We find greater-than-monolayer coverage of oleic acid and a significant proportion of ligand remaining in solution, and we demonstrate reversible thermal cycling of the oleic acid coverage. We outline the effectiveness of simple purification procedures with applications in preparing dots for efficient ligand exchange. Our method is transferrable to a wide range of colloidal nanocrystals and ligand chemistries, providing the quantitative means to enable the rational design of ligand-exchange procedures.

Iridescence is an optical phenomenon whereby colour changes with the illumination and viewing angle. It can be produced by thin film interference or diffraction. Iridescent optical structures are fairly common in nature, but relatively little is known about their production or evolution. Here we describe the structures responsible for producing blue-green iridescent colour in Heliconius butterflies. Overall the wing scale structures of iridescent and non-iridescent Heliconius species are very similar, both having longitudinal ridges joined by cross-ribs. However, iridescent scales have ridges composed of layered lamellae, which act as multilayer reflectors. Differences in brightness between species can be explained by the extent of overlap of the lamellae and their curvature as well as the density of ridges on the scale. Heliconius are well known for their Müllerian mimicry. We find that iridescent structural colour is not closely matched between co-mimetic species. Differences appear less pronounced in models of Heliconius vision than models of avian vision, suggesting that they are not driven by selection to avoid heterospecific courtship by co-mimics. Ridge profiles appear to evolve relatively slowly, being similar between closely related taxa, while ridge density evolves faster and is similar between distantly related co-mimics.

Despite a long history of success in formation of transition-metal-doped quantum dots (QDs), the origin of magnetism in diluted magnetic semiconductors (DMSs) is yet a controversial issue. Cr(II)-doped II-VI DMSs are half-metallic, resulting in high-temperature ferromagnetism. The magnetic properties reflect a strong p-d exchange interaction between the spin-up Cr(II) t(2g) level and the Se 4p. In this study, ultrasmall (~3.1 nm) Cr(II)-doped CdSe DMSQDs are shown to exhibit room-temperature ferromagnetism, as expected from theoretical arguments. Surprisingly, a low-temperature phase transition is observed at 20 K that is believed to reflect the onset of long-range ordering of the single-domain DMSQD.