Reza Zamani

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.

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.

Core–Shell Nanoparticles As Building Blocks for the Bottom-Up Production of Functional Nanocomposites: PbTe–PbS Thermoelectric Properties

The bottom-up assembly of nanocrystals provides access to a three-dimensional composition control at the nanoscale not attainable by any other technology. In particular, colloidal nanoheterostructures, with intrinsic multiphase organization, are especially appealing building blocks for the bottom-up production of nanocomposites. In the present work, we use PbTe-PbS as the model material system and thermoelectricity as the paradigmatic application to investigate the potential of the bottom-up assembly of core-shell nanoparticles to produce functional nanocomposites. With this goal in mind, a rapid, high-yield and scalable colloidal synthetic route to prepare grams of PbTe@PbS core-shell nanoparticles with unprecedented narrow size distributions and exceptional composition control is detailed. PbTe@PbS nanoparticles were used as building blocks for the bottom-up production of PbTe-PbS nanocomposites with tuned composition. In such PbTe-PbS nanocomposites, synergistic nanocrystal doping effects result in up to 10-fold higher electrical conductivities than in pure PbTe and PbS nanomaterials. At the same time, the acoustic impedance mismatch between PbTe and PbS phases and a partial phase alloying provide PbTe-PbS nanocomposites with strongly reduced thermal conductivities. As a result, record thermoelectric figures of merit (ZT) of ∼1.1 were obtained from undoped PbTe and PbS phases at 710 K. These high ZT values prove the potential of the proposed processes to produce efficient functional nanomaterials with programmable properties.

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.

Colloidal synthesis and thermoelectric properties of Cu2SnSe3 nanocrystals

Copper-based selenides are attracting increasing interest due to their outstanding optoelectronic and thermoelectric properties. Herein a novel colloidal synthetic route to prepare Cu2SnSe3 nanocrystals with controlled size, shape and composition is presented. The high yield of the developed procedure allowed its up-scaling to the production of grams of colloidal Cu2SnSe3 nanocrystals. These nanocrystals were used as building blocks for the production of Cu2SnSe3 bulk nanostructured materials by spark plasma sintering. The thermoelectric properties of the prepared nanocrystalline Cu2SnSe3 pellets were characterized in the temperature range from 300 to 720 K. The obtained results show the bottom-up production of nanocrystalline materials from solution-processed nanocrystals to be a potentially advantageous alternative to conventional methods of production of efficient thermoelectric materials.

p-GaN/n-ZnO Heterojunction Nanowires: Optoelectronic Properties and the Role of Interface Polarity

In this work, simulations of the electronic band structure of a p-GaN/n-ZnO heterointerface are presented. In contrast to homojunctions, an additional energy barrier due to the type-II band alignment hinders the flow of majority charge carriers in this heterojunction. Spontaneous polarization and piezoelectricity are shown to additionally affect the band structure and the location of the recombination region. Proposed as potential UV-LEDs and laser diodes, p-GaN/n-ZnO heterojunction nanowires were fabricated by plasma-assisted molecular beam epitaxy (PAMBE). Atomic resolution annular bright field scanning transmission electron microscopy (STEM) studies reveal an abrupt and defect-free heterointerface with a polarity inversion from N-polar GaN to Zn-polar ZnO. Photoluminescence measurements show strong excitonic UV emission originating from the ZnO-side of the interface as well as stimulated emission in the case of optical pumping above a threshold of 55 kW/cm(2).

Self-Assembled GaN Nanowires on Diamond

We demonstrate the nucleation of self-assembled, epitaxial GaN nanowires (NWs) on (111) single-crystalline diamond without using a catalyst or buffer layer. The NWs show an excellent crystalline quality of the wurtzite crystal structure with m-plane faceting, a low defect density, and axial growth along the c-axis with N-face polarity, as shown by aberration corrected annular bright-field scanning transmission electron microscopy. X-ray diffraction confirms single domain growth with an in-plane epitaxial relationship of (10 ̅10)(GaN) [parallel] (01 ̅1)(Diamond) as well as some biaxial tensile strain induced by thermal expansion mismatch. In photoluminescence, a strong and sharp excitonic emission reveals excellent optical properties superior to state-of-the-art GaN NWs on silicon substrates. In combination with the high-quality diamond/NW interface, confirmed by high-resolution transmission electron microscopy measurements, these results underline the potential of p-type diamond/n-type nitride heterojunctions for efficient UV optoelectronic devices.

Tailored graphene materials by chemical reduction of graphene oxides of different atomic structure

Graphene materials with different characteristics in terms of sheet size and defects (structural and/or functional groups) were obtained by the reduction with hydrazine of two graphene oxides with similar oxygen content, but with functional groups of different type and location. The oxides were prepared from two synthetic graphites with distinct crystalline structure. Our research has obtained experimental evidence of a greater reactivity of the oxygen functional groups located in the interior of the aromatic domains on the basal planes (mainly epoxy) and a lower reactivity of oxygen functional groups located at the edges (mainly carboxyl and OH). Furthermore, these edge-located groups were found to be responsible for hydrogen bonding lateral interactions between sheets (these occur through the residual OH groups), which cause a substantial increase in the size of the reduced graphene oxide with respect to that of the parent graphene oxide. These results offer a way to tailor the characteristics of graphene materials for diverse applications.

Polarity-driven polytypic branching in cu-based quaternary chalcogenide nanostructures.

An appropriate way of realizing property nanoengineering in complex quaternary chalcogenide nanocrystals is presented for Cu2CdxSnSey(CCTSe) polypods. The pivotal role of the polarity in determining morphology, growth, and the polytypic branching mechanism is demonstrated. Polarity is considered to be responsible for the formation of an initial seed that takes the form of a tetrahedron with four cation-polar facets. Size and shape confinement of the intermediate pentatetrahedral seed is also attributed to polarity, as their external facets are anion-polar. The final polypod extensions also branch out as a result of a cation-polarity-driven mechanism. Aberration-corrected scanning transmission electron microscopy is used to identify stannite cation ordering, while ab initio studies are used to show the influence of cation ordering/distortion, stoichiometry, and polytypic structural change on the electronic band structure.

Pt doping triggers growth of TiO2 nanorods: nanocomposite synthesis and gas-sensing properties

TiO2 nanocrystals were prepared by solvothermal treatment in oleic acid at 250 °C of amorphous TiO2 nanoparticles. The latter were prepared by sol–gel processing in dodecylamine at 100 °C of starting solutions synthesized from TiCl4. For preparing Pt/TiO2 nanocomposites, with Pt/Ti nominal atomic ratio of 0.05, the required amount of Pt precursor was added to the amorphous TiO2 nanoparticles before heating at 250 °C. Control synthesis experiments, evaluated by X-ray diffraction and X-ray photoelectron spectroscopy showed Pt(acac)2 as the best Pt precursor, and 250 °C as the optimum temperature for simultaneous TiO2 crystallization and efficient Pt nucleation. Transmission electron microscopy observations evidenced Pt nanocrystals dispersed in the surrounding TiO2 host, with a mean size of 4 nm. The TiO2 host was constituted of rod-shaped anatase nanocrystals. Comparison with pure TiO2 showed that the rod shape was favored by the presence of Pt species. As an example of application, the nanocomposites were used for preparing ethanol-sensing devices. The Pt addition remarkably improved the response with respect to pure TiO2 sensors, and electrical characterization of the sensors helped in establishing that the effect of Pt was due to spillover rather than electronic sensitization.