Synthetic Approaches to Colloidal Nanocrystal Heterostructures Based on Metal and Metal-Oxide Materials.

Composite inorganic nanoarchitectures, based on combinations of distinct materials, represent advanced solid-state constructs, where coexistence and synergistic interactions among nonhomologous optical, magnetic, chemical, and catalytic properties lay a basis for the engineering of enhanced or even unconventional functionalities. Such systems thus hold relevance for both theoretical and applied nanotechnology-based research in diverse areas, spanning optics, electronics, energy management, (photo)catalysis, biomedicine, and environmental remediation. Wet-chemical colloidal synthetic techniques have now been refined to the point of allowing the fabrication of solution free-standing and easily processable multicomponent nanocrystals with sophisticated modular heterostructure, built upon a programmed spatial distribution of the crystal phase, composition, and anchored surface moieties. Such last-generation breeds of nanocrystals are thus composed of nanoscale domains of different materials, assembled controllably into core/shell or heteromer-type configurations through bonding epitaxial heterojunctions. This review offers a critical overview of achievements made in the design and synthetic elaboration of colloidal nanocrystal heterostructures based on diverse associations of transition metals (with emphasis on plasmonic metals) and transition-metal oxides. Synthetic strategies, all leveraging on the basic seed-mediated approach, are described and discussed with reference to the most credited mechanisms underpinning regioselective heteroepitaxial deposition. The unique properties and advanced applications allowed by such brand-new nanomaterials are also mentioned.

An Insight into Chemistry and Structure of Colloidal 2D-WS2 Nanoflakes: Combined XPS and XRD Study.

The surface and structural characterization techniques of three atom-thick bi-dimensional 2D-WS2 colloidal nanocrystals cross the limit of bulk investigation, offering the possibility of simultaneous phase identification, structural-to-morphological evaluation, and surface chemical description. In the present study, we report a rational understanding based on X-ray photoelectron spectroscopy (XPS) and structural inspection of two kinds of dimensionally controllable 2D-WS2 colloidal nanoflakes (NFLs) generated with a surfactant assisted non-hydrolytic route. The qualitative and quantitative determination of 1T' and 2H phases based on W 4f XPS signal components, together with the presence of two kinds of sulfur ions, S22- and S2-, based on S 2p signal and related to the formation of WS2 and WOxSy in a mixed oxygen-sulfur environment, are carefully reported and discussed for both nanocrystals breeds. The XPS results are used as an input for detailed X-ray Diffraction (XRD) analysis allowing for a clear discrimination of NFLs crystal habit, and an estimation of the exact number of atomic monolayers composing the 2D-WS2 nanocrystalline samples.

Non-blinking single-photon generation with anisotropic colloidal nanocrystals: towards room-temperature, efficient, colloidal quantum sources.

Blinking and single-photon emission can be tailored in CdSe/CdS core/shell colloidal dot-in-rods. By increasing the shell thickness it is possible to obtain almost non-blinking nanocrystals, while the shell length can be used to control single-photon emission probability.

Tunneling magnetoresistance with sign inversion in junctions based on iron oxide nanocrystal superlattices.

Magnetic tunnel junctions sandwiching a superlattice thin film of iron oxide nanocrystals (NCs) have been investigated. The transport was found to be controlled by Coulomb blockade and single-electron tunneling, already at room temperature. A good correlation was identified to hold between the tunnel magnetoresistance (TMR), the expected magnetic properties of the NC arrays, the charging energies evaluated from current-voltage curves, and the temperature dependence of the junction resistance. Notably, for the first time, a switching from negative to positive TMR was observed across the Verwey transition, with a strong enhancement of TMR at low temperatures.

Dynamical formation of spatially localized arrays of aligned nanowires in plastic films with magnetic anisotropy.

We present a simple technique for magnetic-field-induced formation, assembling, and positioning of magnetic nanowires in a polymer film. Starting from a polymer/iron oxide nanoparticle casted solution that is allowed to dry along with the application of a weak magnetic field, nanocomposite films incorporating aligned nanocrystal-built nanowire arrays are obtained. The control of the dimensions of the nanowires and of their localization across the polymer matrix is achieved by varying the duration of the applied magnetic field, in combination with the evaporation dynamics. These multifunctional anisotropic free-standing nanocomposite films, which demonstrate high magnetic anisotropy, can be used in a wide field of technological applications, ranging from sensors to microfluidics and magnetic devices.

Electron diffractive imaging of oxygen atoms in nanocrystals at sub-ångström resolution.

High-resolution imaging of low-atomic-number chemical elements using electron microscopy is challenging and may require the use of high doses of electrons. Electron diffractive imaging, which creates real-space images using diffraction intensities and phase retrieval methods, could overcome such issues, although it is also subject to limitations. Here, we show that a combination of electron diffractive imaging and high-resolution transmission electron microscopy can image individual TiO(2) nanocrystals with a resolution of 70 pm while exposing the specimen to a low dose of electrons. Our approach, which does not require spherical and chromatic aberration correction, can reveal the location of light atoms (oxygen) in the crystal lattice. We find that the unit cell in nanoscale TiO(2) is subtly different to that in the corresponding bulk.

Magnetic-fluorescent colloidal nanobeads: preparation and exploitation in cell separation experiments.

Nanostructures displaying fluorescence and magnetic properties at the same time are potentially useful for achieving simultaneous bio-separation and bio-sensing (e.g., magnetic separation coupled with multiplexing optical detection of different tumour cell populations). Spherical nanobeads that display both fluorescent and magnetic features are reported; they are fabricated by grafting fluorescent oligothiophene molecules to an amphiphilic polymer that is then used to enwrap iron oxide nanoparticles, which acts as the magnetic domain. By tuning experimental conditions, control over the number of magnetic nanoparticles per bead and over the bead diameter (30-400 nm) was achieved. A cell separation efficiency of the level required for cell sorting applications is also reported.

Colloidal semiconductor/magnetic heterostructures based on iron-oxide-functionalized brookite TiO2 nanorods.

A flexible colloidal seeded-growth strategy has been developed to synthesize all-oxide semiconductor/magnetic hybrid nanocrystals (HNCs) in various topological arrangements, for which the dimensions of the constituent material domains can be controlled independently over a wide range. Our approach relies on driving preferential heterogeneous nucleation and growth of spinel cubic iron oxide (IO) domains onto brookite TiO2 nanorods (b-TiO2) with tailored geometric parameters, by means of time-programmed delivery of organometallic precursors into a suitable TiO2-loaded surfactant environment. The b-TiO2 seeds exhibit size-dependent accessibility towards IO under diffusion-controlled growth regime, which allows attainment of HNCs individually made of a single b-TiO2 section functionalized with either one or multiple nearly spherical IO domains. In spite of the dissimilarity of the respective crystal-phases, the two materials share large interfacial junctions without significant lattice strain being induced across the heterostructures. The synthetic achievements have been supported by a systematic morphological, compositional and structural characterization of the as-prepared HNCs, offering a mechanistic insight into the specific role of the seeds in the control of heterostructure formation in liquid media. In addition, the impact of the formed b-TiO2/IO heterojunctions on the magnetic properties of IO has also been assessed.

Wettability conversion of colloidal TiO2 nanocrystal thin films with UV-switchable hydrophilicity.

Under pulsed laser UV irradiation, thin-film coatings made of close-packed TiO2 nanorods individually coated with surfactants can exhibit a temporary increase in their degree of surface hydroxylation without any apparent photocatalytic removal of the capping molecules. This mechanism provides a basis for achieving light-driven conversion from a highly hydrophobic to a highly hydrophilic, metastable state, followed by extremely slow recovery of the original conditions under dark ambient environment. A deeper insight into the wetting dynamics is gained by time-dependent water contact-angle and infrared spectroscopy monitoring of the film properties under different post-UV storage conditions. Our study reveals that, for reversible switchability between extreme wettability excursions and long-term repeatability of such changes to be achieved, specific modifications in the polar and nonpolar components of the TiO2 films need to be guaranteed along with preservation of the original geometric arrangement of the nanocrystal building blocks. The application of moderate vacuum is found to be an effective method for accelerating the post-UV hydrophilic-to-hydrophobic conversion, thereby enabling fast and cyclic hydrophilization/hydrophobicization alternation without any detrimental signs of significant fatigue.

Nonhydrolytic synthesis of high-quality anisotropically shaped brookite TiO2 nanocrystals.

A surfactant-assisted nonaqueous strategy, relying on high-temperature aminolysis of titanium carboxylate complexes, has been developed to access anisotropically shaped TiO2 nanocrystals selectively trapped in the metastable brookite phase. Judicious temporal manipulation of precursor supply to the reaction mixture enables systematic tuning of the nanostructure geometric features over an exceptionally wide dimensional range (30-200 nm). Such degree of control is rationalized within the frame of a self-regulated phase-changing seed-catalyzed mechanism, in which homogeneous nucleation, on one side, and heterogeneous nucleation/growth processes, on the other side, are properly balanced while switching from the anatase to the brookite structures, respectively, in a continuous unidirectional crystal development regime. The time variation of the chemical potential for the monomer species in the solution, the size dependence of thermodynamic structural stability of the involved titania polymorphs, and the reduced activation barrier for brookite nucleation onto initially formed anatase seeds play decisive roles in the crystal-phase- and shape-tailored growth of titania nanostructures by the present approach.

One-pot synthesis and characterization of size-controlled bimagnetic FePt-iron oxide heterodimer nanocrystals.

A one-pot, two-step colloidal strategy to prepare bimagnetic hybrid nanocrystals (HNCs), comprising size-tuned fcc FePt and inverse spinel cubic iron oxide domains epitaxially arranged in a heterodimer configuration, is described. The HNCs have been synthesized in a unique surfactant environment by temperature-driven sequential reactions, involving the homogeneous nucleation of FePt seeds and the subsequent heterogeneous growth of iron oxide. This self-regulated mechanism offers high versatility in the control of the geometric features of the resulting heterostructures, circumventing the use of more elaborate seeded growth techniques. It has been found that, as a consequence of the exchange coupling between the two materials, the HNCs exhibit tunable single-phase-like magnetic behavior, distinct from that of their individual components. In addition, the potential of the heterodimers as effective contrast agents for magnetic resonance imaging techniques has been examined.

Topologically controlled growth of magnetic-metal-functionalized semiconductor oxide nanorods.

Colloidal semiconductor-magnetic hybrid nanocrystals with topologically controlled composition are fabricated by heterogeneous nucleation of spherical epsilon-Co domains onto anatase TiO2 nanorods. The latter can be selectively decorated at either their tips or at multiple locations along their longitudinal sidewalls, forming lattice-matched heterointerfaces regardless of the metal deposition sites. The possibility of switching between either heterostructure growth modes arises from the facet-dependent chemical reactivity of the oxide seeds, which is governed mainly by selective adhesion of the surfactants rather than by small differences in misfit-induced interfacial strain at the relevant junction points.

Seeded growth of asymmetric binary nanocrystals made of a semiconductor TiO2 rodlike section and a magnetic gamma-Fe2O3 spherical domain.

Asymmetric binary nanocrystals (BNCs), comprising one c-axis elongated anatase TiO2 section and one gamma-Fe2O3 spherical domain attached together, are synthesized by heterogeneous nucleation of iron oxide onto the longitudinal facets of TiO2 nanorods in a ternary surfactant mixture. The topologically controlled composition of the BNCs is ascertained by a combination of powder X-ray diffraction, Raman and Mössbauer spectroscopy, high-angle annular dark-field imaging, and high-resolution transmission electron microscopy lattice fringe mapping, while their size-dependent magnetic behavior is demonstrated by ac susceptibility measurements. The heteroepitaxial growth proceeds through a mechanism never observed before for colloidal nanoheterostructures: the two domains share a restricted and locally curved junction region, which accommodates efficiently the interfacial strain and retards the formation of misfit dislocations. It is believed that these BNCs, which combine the properties of two technologically relevant oxide materials, can pave the way to reinforced applications in several fields of nanoscience, such as in photocatalysis, in malignant cell treatments, and in nanocrystal assembly.

Synthesis, properties and perspectives of hybrid nanocrystal structures.

Current efforts and success of nanoscale science and technology are related to the fabrication of functional materials and devices in which the individual units and their spatial arrangement are engineered down to the nanometer level. One promising way of achieving this goal is by assembling colloidal inorganic nanocrystals as the novel building blocks of matter. This trend has been stimulated by significant advances in the wet-chemical syntheses of robust and easily processable nanocrystals in a wide range of sizes and shapes. The increase in the degree of structural complexity of solution-grown nanostructures appears to be one of the natural directions towards which nanoscience will increasingly orient. Recently, several groups have indeed devised innovative syntheses of nanocrystals through which they have been able to group inorganic materials with different properties in the same particle. These approaches are paving the way to the development of nanosized objects able to perform multiple technological tasks. In this critical review (165 references), we will summarize the recent advances in the synthesis of colloidal nanocrystals, with emphasis on the strategies followed for the fabrication of nano-heterostructures, as well as on their properties and the perspectives in this field.