Colloidal semiconductor nanocrystals have been exploited in several applications in which they serve as fluorophores, because of the tunability of the wavelength of the emitted light. [1][2][3] The possibility of exactly controlling the size of nanocrystals is of great importance in the development of these materials, as this will lead to nano-objects with well-defined and reproducible properties. Whereas this goal seems to be hard to achieve with large nanocrystals, it might be viable for clusters consisting of a few tens or hundreds of atoms, as in this size regime a handful of structures can have an exceptionally high stability and therefore would form preferentially over any other combination of atoms. This concept is already well-known for several metal clusters, as for some of them several "magic" structures exist that are formed by closed shells of atoms. [4][5][6][7] Cluster molecules that can be considered as the smallest building units of semiconductors have been investigated in the past.As an example several tetrahedral cluster molecules based on the general formula [z-(where E = S or Se; M = Zn or Cd; and R = alkyl or aryl) or similar were reported some years ago. [8,9] The series was formed only by clusters containing a well-defined number of atoms, and therefore, characterized by particularly stable structures; thus, these structures can also be termed "magic-size clusters" (MSCs). Different families of almost monodisperse CdS clusters of sizes down to 1.3 nm were reported by Vossmeyer et al., [10] whereas CdSe MSCs were observed later in the solution growth of colloidal nanocrystals [11] and the various cluster sizes found were explained as arising from the aggregation of smaller clusters. Soloviev et al. synthesized and crystallized a homologous series of CdSe cluster molecules [12,13] (very similar in structure to those reported earlier [8,9] ) that were capped by selenophenol ligands. Also in many high-temperature organometallic syntheses of colloidal CdSe nanocrystals, either the transient formation of ultrasmall, highly stable CdSe clusters was noticed, [14,15] or these clusters could be isolated using size-selective precipitation. [16,17] Recently, one type of CdSe MSC has been synthesized in a water-in-oil reverse-micelle system.[18]Here, we report a method for controlling the sequential growth in solution of CdSe MSCs of progressively larger sizes. Each of these types of clusters is characterized by a sharp optical-absorption feature at a well-defined energy. During the synthesis, the relative populations of the different families of MSCs varied, as smaller MSCs evolved into larger MSCs. We can model the time evolution of the concentration of the various magic sizes using a modification of a continuous-growth model, by taking into account the much higher stability of the various MSCs over nanocrystals of any intermediate size.For the synthesis of the CdSe MSCs reported here a mixture of dodecylamine and nonanoic acid was used to decompose cadmium oxide at 200°C under an inert atmosphere. Th...

We describe an approach to synthesize colloidal nanocrystal heterodimers composed of CoPt(3) and Au. The growth is based on the nucleation of gold domains on preformed CoPt(3) nanocrystals. It is a highly versatile methodology which allows us to tune independently the size of the two domains in each dimer by varying several reaction parameters. The statistical analysis of the distribution of the domain sizes in the dimers and the compositional mapping achieved by dark field imaging and energy dispersive spectroscopy confirm that the two domains in each dimer are indeed made of CoPt(3) and Au, respectively. Structural characterization by high-resolution transmission electron microscopy shows that the two domains, both having cubic fcc Bravais lattice, can share a common {111}, {100}, or {110} facet, depending on the size of the initial CoPt(3) seeds. The magnetization measurements evidence a ferromagnetic CoPt(3) phase with a relatively low anisotropy as a consequence of their disordered crystalline structure, regardless of the presence of a Au tip. We believe that this prototype of nanocrystal dimer, which can be manipulated under air, can find several applications in nanoscience, as the Au section can be exploited as the preferential anchor point for various molecules, while the CoPt(3) domain can be used for magnetic detection.

A strategy to access several types of Au-tipped dumbbell-like nanocrystal heterostructures is presented, which involves the selective oxidation of either PbSe or CdTe sacrificial domains, initially grown on CdSe and CdS nanorods, with a Au(III) : surfactant complex. The formation of gold patches is supported by TEM, XRD and elemental analysis. This approach has allowed us to grow Au domains onto specific locations of anisotropically shaped nanocrystals for which direct metal deposition is unfeasible, as for the case of CdS nanorods. We believe that this strategy may be of general utility to create other types of complex colloidal nanoheterostructures, provided that a suitable sacrificial material can be grown on top of the starting nanocrystal seeds.

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