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.
The conversion of thermal energy to electricity and vice versa by means of solid state thermoelectric devices is extremely appealing. However, its cost-effectiveness is seriously hampered by the relatively high production cost and low efficiency of current thermoelectric materials and devices. To overcome present challenges and enable a successful deployment of thermoelectric systems in their wide application range, materials with significantly improved performance need to be developed. Nanostructuration can help in several ways to reach the very particular group of properties required to achieve high thermoelectric performances. Nanodomains inserted within a crystalline matrix can provide large charge carrier concentrations without strongly influencing their mobility, thus allowing to reach very high electrical conductivities. Nanostructured materials contain numerous grain boundaries that efficiently scatter mid- and long-wavelength phonons thus reducing the thermal conductivity. Furthermore, nanocrystalline domains can enhance the Seebeck coefficient by modifying the density of states and/or providing type- and energy-dependent charge carrier scattering. All these advantages can only be reached when engineering a complex type of material, nanocomposites, with exquisite control over structural and chemical parameters at multiple length scales. Since current conventional nanomaterial production technologies lack such level of control, alternative strategies need to be developed and adjusted to the specifics of the field. A particularly suitable approach to produce nanocomposites with unique level of control over their structural and compositional parameters is their bottom-up engineering from solution-processed nanoparticles. In this work, we review the state-of-the-art of this technology applied to the thermoelectric field, including the synthesis of nanoparticles of suitable materials with precisely engineered composition and surface chemistry, their combination and consolidation into nanostructured materials, the strategies to electronically dope such materials and the attempts to fabricate thermoelectric devices using nanoparticle-based nanopowders and inks.
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.
In the present work, we demonstrate crystallographically textured n-type BiTeSe nanomaterials with exceptional thermoelectric figures of merit produced by consolidating disk-shaped BiTeSe colloidal nanocrystals (NCs). Crystallographic texture was achieved by hot pressing the asymmetric NCs in the presence of an excess of tellurium. During the hot press, tellurium acted both as lubricant to facilitate the rotation of NCs lying close to normal to the pressure axis and as solvent to dissolve the NCs approximately aligned with the pressing direction, which afterward recrystallize with a preferential orientation. NC-based BiTeSe nanomaterials showed very high electrical conductivities associated with large charge carrier concentrations, n. We hypothesize that such large n resulted from the presence of an excess of tellurium during processing, which introduced a high density of donor Te antisites. Additionally, the presence in between grains of traces of elemental Te, a narrow band gap semiconductor with a work function well below BiTeSe , might further contribute to increase n through spillover of electrons, while at the same time blocking phonon propagation and hole transport through the nanomaterial. NC-based BiTeSe nanomaterials were characterized by very low thermal conductivities in the pressing direction, which resulted in ZT values up to 1.31 at 438 K in this direction. This corresponds to a ca. 40% ZT enhancement from commercial ingots. Additionally, high ZT values were extended over wider temperature ranges due to reduced bipolar contribution to the Seebeck coefficient and the thermal conductivity. Average ZT values up to 1.15 over a wide temperature range, 320 to 500 K, were measured, which corresponds to a ca. 50% increase over commercial materials in the same temperature range. Contrary to most previous works, highest ZT values were obtained in the pressing direction, corresponding to the c crystallographic axis, due to the predominance of the thermal conductivity reduction over the electrical conductivity difference when comparing the two crystal directions.
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