Synthesis, Bottom up Assembly and Thermoelectric Properties of Sb-Doped PbS Nanocrystal Building Blocks.

The precise engineering of thermoelectric materials using nanocrystals as their building blocks has proven to be an excellent strategy to increase energy conversion efficiency. Here we present a synthetic route to produce Sb-doped PbS colloidal nanoparticles. These nanoparticles are then consolidated into nanocrystalline PbS:Sb using spark plasma sintering. We demonstrate that the introduction of Sb significantly influences the size, geometry, crystal lattice and especially the carrier concentration of PbS. The increase of charge carrier concentration achieved with the introduction of Sb translates into an increase of the electrical and thermal conductivities and a decrease of the Seebeck coefficient. Overall, PbS:Sb nanomaterial were characterized by two-fold higher thermoelectric figures of merit than undoped PbS.

Cu2ZnSnS4-Ag2S Nanoscale p-n Heterostructures as Sensitizers for Photoelectrochemical Water Splitting.

A cation exchange-based route was used to produce Cu2ZnSnS4 (CZTS)-Ag2S nanoparticles with controlled composition. We report a detailed study of the formation of such CZTS-Ag2S nanoheterostructures and of their photocatalytic properties. When compared to pure CZTS, the use of nanoscale p-n heterostructures as light absorbers for photocatalytic water splitting provides superior photocurrents. We associate this experimental fact to a higher separation efficiency of the photogenerated electron-hole pairs. We believe this and other type-II nanoheterostructures will open the door to the use of CZTS, with excellent light absorption properties and made of abundant and environmental friendly elements, to the field of photocatalysis.

Size and aspect ratio control of Pd2Sn nanorods and their water denitration properties.

Monodisperse Pd2Sn nanorods with tuned size and aspect ratio were prepared by co-reduction of metal salts in the presence of trioctylphosphine, amine, and chloride ions. Asymmetric Pd2Sn nanostructures were achieved by the selective desorption of a surfactant mediated by chlorine ions. A preliminary evaluation of the geometry influence on catalytic properties evidenced Pd2Sn nanorods to have improved catalytic performance. In view of these results, Pd2Sn nanorods were also evaluated for water denitration.

Cu(2)ZnSnS(4)-Pt and Cu(2)ZnSnS(4)-Au heterostructured nanoparticles for photocatalytic water splitting and pollutant degradation.

Cu2ZnSnS4, based on abundant and environmental friendly elements and with a direct band gap of 1.5 eV, is a main candidate material for solar energy conversion through both photovoltaics and photocatalysis. We detail here the synthesis of quasi-spherical Cu2ZnSnS4 nanoparticles with unprecedented narrow size distributions. We further detail their use as seeds to produce CZTS-Au and CZTS-Pt heterostructured nanoparticles. Such heterostructured nanoparticles are shown to have excellent photocatalytic properties toward degradation of Rhodamine B and hydrogen generation by water splitting.

Antimony-based ligand exchange to promote crystallization in spray-deposited Cu2ZnSnSe4 solar cells.

A multistrategy approach to overcome the main challenges of nanoparticle-based solution-processed Cu2ZnSnSe4 thin film solar cells is presented. We developed an efficient ligand exchange strategy, using an antimony salt, to displace organic ligands from the surface of Cu2ZnSnS4 nanoparticles. An automated pulsed spray-deposition system was used to deposit the nanoparticles into homogeneous and crack-free films with controlled thickness. After annealing the film in a Se-rich atmosphere, carbon-free and crystalline Cu2ZnSnSe4 absorber layers were obtained. Not only was crystallization promoted by the complete removal of organics, but also Sb itself played a critical role. The Sb-assisted crystal growth is associated with the formation of a Sb-based compound at the grain boundaries, which locally reduces the melting point, thus promoting the film diffusion-limited crystallization.

CuTe nanocrystals: shape and size control, plasmonic properties, and use as SERS probes and photothermal agents.

We report a procedure to prepare highly monodisperse copper telluride nanocubes, nanoplates, and nanorods. The procedure is based on the reaction of a copper salt with trioctylphosphine telluride in the presence of lithium bis(trimethylsilyl)amide and oleylamine. CuTe nanocrystals display a strong near-infrared optical absorption associated with localized surface plasmon resonances. We exploit this plasmon resonance for the design of surface-enhanced Raman scattering sensors for unconventional optical probes. Furthermore, we also report here our preliminary analysis of the use of CuTe nanocrystals as cytotoxic and photothermal agents.

Metal ions to control the morphology of semiconductor nanoparticles: copper selenide nanocubes.

Morphology is a key parameter in the design of novel nanocrystals and nanomaterials with controlled functional properties. Here, we demonstrate the potential of foreign metal ions to tune the morphology of colloidal semiconductor nanoparticles. We illustrate the underlying mechanism by preparing copper selenide nanocubes in the presence of Al ions. We further characterize the plasmonic properties of the obtained nanocrystals and demonstrate their potential as a platform to produce cubic nanoparticles with different composition by cation exchange.

Cu2ZnGeSe4 nanocrystals: synthesis and thermoelectric properties.

A synthetic route for producing Cu(2)ZnGeSe(4) nanocrystals with narrow size distributions and controlled composition is presented. These nanocrystals were used to produce densely packed nanomaterials by hot-pressing. From the characterization of the thermoelectric properties of these nanomaterials, Cu(2)ZnGeSe(4) is demonstrated to show excellent thermoelectric properties. A very preliminary adjustment of the nanocrystal composition has already resulted in a figure of merit of up to 0.55 at 450 °C.

Continuous production of Cu2ZnSnS4 nanocrystals in a flow reactor.

A procedure for the continuous production of Cu(2)ZnSnS(4) (CZTS) nanoparticles with controlled composition is presented. CZTS nanoparticles were prepared through the reaction of the metals' amino complexes with elemental sulfur in a continuous-flow reactor at moderate temperatures (300-330 °C). High-resolution transmission electron microscopy and X-ray diffraction analysis showed the nanocrystals to have a crystallographic structure compatible with that of the kesterite. Chemical characterization of the materials showed the presence of the four elements in each individual nanocrystal. Composition control was achieved by adjusting the solution flow rate through the reactor and the proper choice of the nominal precursor concentration within the flowing solution. Single-particle analysis revealed a composition distribution within each sample, which was optimized at the highest synthesis temperatures used.

Morphology evolution of Cu(2-x)S nanoparticles: from spheres to dodecahedrons.

An oriented attachment and growth mechanism allows an accurate control of the size and morphology of Cu(2-x)S nanocrystals, from spheres and disks to tetradecahedrons and dodecahedrons. The synthesis conditions and the growth mechanism are detailed here.

Synthesis of quaternary chalcogenide nanocrystals: stannite Cu(2)Zn(x)Sn(y)Se(1+x+2y).

A successful synthesis of Cu(2)Zn(x)Sn(y)Se(1+x+2y) (CZTSe) nanoparticles is presented. Nearly monodisperse and highly faceted CZTSe nanoparticles were prepared through reaction of metal amino complexes with saturated solutions of selenium in trioctylphosphine at high temperature. High-resolution transmission electron microscopy and X-ray diffraction analysis showed the prepared nanocrystals to have the tetragonal Cu(2)ZnSnSe(4) crystallographic structure. Nanoscale-resolved electron energy loss spectroscopy images showed the presence of the four elements in each individual nanocrystal. Further analyses of the particles' chemical composition showed the nanocrystals to be consistently Zn- and Sn-poor.

Shape control of iron oxide nanoparticles.

We present here a detailed overview on the effect of various synthesis parameters during the synthesis of iron oxide nanoparticles with different shapes, through decomposition of a preformed iron oleate complex, at high temperature. While this procedure has been previously shown to produce monodisperse magnetite spheres, the use of specific additives is demonstrated to allow for the preparation of strongly faceted iron oxide nanocrystals, with either cubic or octahedral shapes. Additionally, using squalene or octadecene as solvents was found to induce the reduction of the iron precursors and thereby lead to the formation of nanoparticles with core/shell (in the case of nanocubes) or island-like structures (in the case of octahedrons).

Luminescent energy transfer between cadmium telluride nanoparticle and lanthanide(III) chelate in competitive bioaffinity assays of biotin and estradiol.

Fluorescence resonance energy transfer has been studied between lanthanide(III) chelates as donors and protein-coupled CdTe semiconductor nanoparticles as acceptors. Wide excitation spectra and large Stokes shift of semiconductor nanoparticles and timeresolved fluorescence detection were shown to provide a combination for successful energy transfer assay. Different intrinsically fluorescent europium(III) and terbium(III) chelates coupled to single biotin molecules were studied for optimal energy transfer with streptavidin labeled semiconductor nanoparticles. No significant differences between the studied chelates were observed. The strength of the methodology was demonstrated in a clinically relevant competitive and separation-free immunoassay of estradiol, where subnanomolar limit of detection was achieved with the coefficient of variation 2-11%. The data suggested that relatively short distance was needed to obtain adequate energy transfer. Therefore, biomolecules were coupled onto the semiconductor nanoparticles without any spacers.

Electrochemical observation of the photoinduced formation of alloyed ZnSe(S) nanocrystals.

Electrochemical studies of thiol-capped ZnSe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals and their photoluminescence quantum efficiency. The evolution of the specific features in the cyclic voltammetric curves of ZnSe NCs as a function of their photochemical treatment is studied. The interpretation of the results based on the approaches previously developed for CdTe NCs is found to be in good correlation with the proposed mechanism of the ZnSe NCs phototreatment, i.e., the formation of a sulfur-enriched surface shell. By this, cyclic voltammetry has been demonstrated to be a powerful method for probing surface states of semiconductor NCs as well as for monitoring the evolution of these states during photochemical processing.

Factors governing the quality of aqueous CdTe nanocrystals: calculations and experiment.

The aqueous synthesis of thiol-stabilized semiconductor CdTe colloidal nanocrystals has been revisited. We found optimal conditions for the synthesis of high-quality CdTe NCs through a study of the influence of the initial conditions (structure and concentration of Cd-thiol complexes) on the quality of the CdTe nanocrystals. A numerical calculation shows a clear correlation between the concentration of CdL (where L is (SCH(2)COO)(2-)) in the initial solution and the photoluminescence quantum efficiency of the CdTe nanocrystals.

Size-dependent electrochemical behavior of thiol-capped CdTe nanocrystals in aqueous solution.

Electrochemical studies of thiol-capped CdTe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals. While the size dependence of the reduction and one of the oxidation potentials can be attributed to altering the energetic band positions owing to the quantum size effect, an extraordinary behavior was found for the oxidation peak observed at less positive potentials. In contrast to a prediction based on the quantum size effect, this peak moves to more negative potentials as the nanocrystals' size decreases. Moreover, the contribution of the charge associated with this peak compared to the total charge passed during the nanocrystal oxidation correlates well with the photoluminescence (PL) efficiency of individual fractions of the CdTe nanocrystals. These experimental observations allow a peak to be assigned to the oxidation of Te-related surface traps. The intra-band-gap energy level assigned to these Te-related trap states shifts toward the top of the valence band as the nanocrystal size increases, thus allowing the higher photostability of the larger nanocrystals to be explained. At a certain nanocrystal size, the trap level can even move out of the band gap.

Electrostatic and covalent interactions in CdTe nanocrystalline assemblies.

This paper focuses on the interactions between cysteamine-stabilized CdTe nanocrystals [CdTe(CA) NCs] and thioglycolic-acid-stabilized CdTe nanocrystals [CdTe(TGA) NCs]. These interactions were examined by the absorption, continuous, and time-resolved photoluminescence (PL) spectra of the electrostatically mixed and the covalently linked NCs assemblies comprised of the oppositely surface charged CdTe(CA) and CdTe(TGA) NCs and by a comparison with those of the corresponding pristine NCs. The CdTe(CA)-CdTe(TGA) coupling is dictated by the surfactant spacer, ranging between 0.93 and 1.14 nm and by electrostatic and covalent interactions, enabling a Förster resonance energy transfer (FRET) process among the NCs. The results revealed an excellent spectral overlap between the emission of the CdTe(TGA) NCs and the absorption of the CdTe(CA) NCs as well as a PL spectral red shift on the formation of electrostatic and covalent interactions. Furthermore, the measurements showed a lifetime ranging between 1.2 and 3 ns for the electrostatically mixed and the covalently linked assemblies, shorter than those of the pristine CdTe(CA) NCs and CdTe(TGA) NCs, both of which measured as approximately 5.5 ns. When CdTe(TGA) NCs performed as the most efficient donors, FRET rates of 10(10)-10(11) s(-1) were calculated for the electrostatically mixed NCs or covalently linked NCs.