Colloidal inorganic nanocrystals (NCs) constitute an important class of advanced nanomaterials owing to the flexibility with which their dimensionality-dependent physical–chemical properties can be controlled by engineering their compositional, structural, and geometric features in the synthesis stage and the versatility with which they can be exploited in disparate technological fields, spanning from optoelectronics, energy conversion/production to catalysis, and biomedicine. In recent years, building upon knowledge acquired on the thermodynamic and kinetic processes that underlie NC evolution in liquid media, synthetic nanochemistry research has made tremendous advances, opening new possibilities for designing, creating, and mastering increasingly complex NC-based assemblies, in which sections of different materials are grouped together into free-standing, easily processable multifunctional nanocomposite systems. This chapter will provide an overview of this fast-growing research field by illustrating progress achieved in the wet-chemical development of last-generation breeds of so-called hybrid or heterostructured nanocrystals (HNCs) in asymmetric non-core/shell geometries, in which distinct material modules are interconnected in heterodimer, heterooligomer, and anisotropic multidomain architectures via heteroepitaxial bonding interfaces of limited extension. The focus will be on HNCs that incorporate at least one magnetic material component combined with semiconductors and/or plasmonic metals, which hold potential for generating enhanced, unconventional magnetic behavior, on one side, and diversified or even new properties and capabilities, on the other side. Various synthetic strategies, all based on the manipulation of seeded-growth techniques, will be described and rationally interpreted within the framework of the currently understood mechanisms of colloidal heteroepitaxy.

Inorganic nanomaterials represent unique solid-state platforms on which unusual optoelectronic, magnetic chemical, and catalytic properties can be manipulated, tuned, and even allowed to coexist and exchange-couple, holding considerable potential for both fundamental studies and practical applications in optoelectronics, energy technologies, catalysis, and biomedicine. Among the available synthetic approaches, colloidal techniques stand out as powerful routes to nanocrystals with programmable composition, crystal structure, geometry, and surface functionalities. Knowledge of thermodynamic and kinetic growth conditions and processes underlying monophasic nanocrystal evolution in liquid media has triggered significant advances in these fabrication tools, paving the way to increasingly sophisticate multifunctional hybrid nanoarchitectures, in which sections of different materials are assembled together as free-standing, easily processable all-inorganic nanoheterostructures. In this chapter we will illustrate recent progress made in the wet-chemical development and characterization of last-generation breeds of colloidal heterostructured nanocrystals (HNCs), in which distinct material modules are interconnected via direct bonding (heteroepitaxial) interfaces in elaborate onion-like or oligomer-type topologies. Emphasis will be put on HNCs that entail at least one magnetic material component, combined with semiconductors and/or plasmonic metals as a means of generating enhanced, unconventional magnetic behavior as well as diversified properties and capabilities. Diverse synthetic strategies, all based on manipulation of seeded-growth techniques, will be described and interpreted within the framework of the relevant heteroepitaxial deposition mechanisms that enable topological selection of HNCs with selected spatial configurations.

Thin-film processing of colloidal semiconductor nanocrystals (NCs) is a prerequisite for their use in (opto-)electronic devices. The commonly used spin-coating is highly materials consuming as the overwhelming amount of deposited matter is ejected from the substrate during the spinning process. Also, the well-known dip-coating and drop-casting procedures present disadvantages in terms of the surface roughness and control of the film thickness. We show that the doctor blade technique is an efficient method for preparing nanocrystal films of controlled thickness and low surface roughness. In particular, by optimizing the deposition conditions, smooth and pinhole-free films of 11 nm CuInSe2 NCs have been obtained exhibiting a surface roughness of 13 nm root mean square (rms) for a 350 nm thick film, and less than 4 nm rms for a 75 nm thick film.

We report the evidence of a polarized single photon flux from a colloidal nanoparticle. We analyze, by time and polarization resolved spectroscopy measurements, the polarization behavior of a single CdSe/CdS core/shell dot in rod, achieving a polarization ratio at room temperature of ∼75% and a lifetime of the excited state of ∼11 ns.

In this work we report on our recent studies on Silicon-Nitride PhC single-defect nanocavity membranes embedding colloidal nanocrystals. A novel structure consisting of a layer of nanocrystals sandwiched between two layers of Silicon-Nitride has been used. Photoluminescence measurements prove the efficient coupling among the nanoemitters and the optical modes localized in the Si3N4 photonic crystal nanocavities, showing enhancement of the spontaneous emission in resonant conditions. This technology enables the realization of NC-based ultra-small lasers and non-classical light sources operating at visible wavelengths on silicon substrates.

The oscillator strength in CdSe/CdS colloidal dot-in-rods is evaluated and assessed to be of ~1.5. On the basis of this finding, the possibility to reach the strong coupling regime with photonic crystals nanocavities is discussed. In spite that carefully choosing the cavity parameters the strong coupling regime could be analytically achieved at room temperature, theoretical considerations show that the typical Rabi doublet cannot be resolved. The work draws also a viable strategy toward the observation of the strong coupling at cryogenic temperatures.

Highly oriented hybrid thin films composed of rod-shaped CdSe nanocrystals and poly(3-hexylthiophene) are prepared by mechanical rubbing. The orientation distribution of both CdSe nanorods and crystalline P3HT domains is determined by a combination of transmission electron microscopy (electron diffraction, low dose high-resolution TEM, and tomography), grazing incidence X-ray diffraction measurements, and UV-vis spectroscopy. After rubbing, P3HT crystalline domains show a preferential face-on orientation ((010) contact plane) and the chains align parallel to the rubbing direction. CdSe nanorods also align parallel to the rubbing direction, but the level of alignment is a function of their concentration in the polymer matrix: the lower their concentration, the higher the level of in-plane orientation of both the nanorods and the polymer chains. GIXD and electron diffraction suggest that CdSe nanorods adopt a preferential contact plane on the substrate after rubbing. The high in-plane alignment of the nanorods is mainly due to the orientation of the surrounding P3HT matrix. In particular, low dose HR-TEM shows that the local orientation of individual NRs matches the orientation of the surrounding pi-stacked P3HT chains. For a high NR concentration, bundling of NRs into larger aggregates prevents their efficient alignment by rubbing.

Highly oriented and nanostructured hybrid thin films made of regioregular poly(3-hexylthiophene) and colloidal CdSe nanocrystals are prepared by a zone melting method using epitaxial growth on 1,3,5-trichlorobenzene oriented crystals. The structure of the films has been analyzed by X-ray diffraction using synchrotron radiation, electron diffraction and 3D electron tomography to afford a multi-scale structural and morphological description of the highly structured hybrid films. A quantitative analysis of the reconstructed volumes based on electron tomography is used to establish a 3D map of the distribution of the CdSe nanocrystals in the bulk of the films. In particular, the influence of the P3HT-CdSe ratio on the 3D structure of the hybrid layers has been analyzed. In all cases, a bi-layer structure was observed. It is made of a first layer of pure oriented semi-crystalline P3HT grown epitaxially on the TCB substrate and a second P3HT layer containing CdSe nanocrystals uniformly distributed in the amorphous interlamellar zones of the polymer. The thickness of the P3HT layer containing CdSe nanoparticles increases gradually with increasing content of NCs in the films. A growth model is proposed to explain this original transversal organization of CdSe NCs in the oriented matrix of P3HT.

We propose colloidal CdSe/CdS dots in rods as nonclassical sources for quantum information technology. Such nanoemitters show specific properties such as strongly polarized emission of on-demand single photons at room temperature, dipolelike behavior and mono-exponential recombination rates, making us envision their suitability as sources of single photons with well defined quantum states in quantum cryptography based devices.

Authors aimed to provide a magnetic responsiveness to bone-mimicking nano-hydroxyapatite (n-HA). For this purpose, dextran-grafted iron oxide nanoarchitectures (DM) were synthesized by a green friendly and scalable alkaline co-precipitation method at room temperature and used to functionalize n-HA crystals. Different amounts of DM hybrid structures were added into the nanocomposites (DM/n-HA 1:1, 2:1 and 3:1weight ratio) which were investigated through extensive physicochemical (XRD, ICP, TGA and Zetapotential), microstructural (TEM and DLS), magnetic (VSM) and biological analyses (MTT proliferation assay). X-ray diffraction patterns have confirmed the n-HA formation in the presence of DM as a co-reagent. Furthermore, the addition of DM during the synthesis does not affect the primary crystallite domains of DM/n-HA nanocomposites. DM/n-HAs have shown a rising of the magnetic moment values by increasing DM content up to 2:1 ratio. However, the magnetic moment value recorded in the DM/n-HA 3:1 do not further increases showing a saturation behavior. The cytocompatibility of the DM/n-HA was evaluated with respect to the MG63 osteoblast-like cell line. Proliferation assays revealed that viability, carried out in the absence of external magnetic field, was not affected by the amount of DM employed. Interestingly, assays also suggested that the DM/n-HA nanocomposites exhibit a possible shielding effect with respect to the antiproliferative activity induced by the DM particles alone.