In Situ Evolution of Secondary Metallic Phases in Off-Stoichiometric ZrNiSn for Enhanced Thermoelectric Performance.

The full-Heusler (FH) inclusions in the half-Heusler (HH) matrix is a well-studied approach to reduce the lattice thermal conductivity of ZrNiSn HH alloy. However, excess Ni in ZrNiSn may lead to the in situ formation of FH and/or HH alloys with interstitial Ni defects. The excess Ni develops intermediate electronic states in the band gap of ZrNiSn and also generates defects to scatter phonons, thus providing additional control to tailor electronic and phonon transport properties synergistically. In this work, we present the implication of isoelectronic Ge-doping and excess Ni on the thermoelectric transport of ZrNiSn. The synthesized ZrNi1.04Sn1-xGex (x = 0-0.04) samples were prepared by arc-melting and spark plasma sintering, and were extensively probed for microstructural analysis. The in situ evolution of minor secondary phases, i.e., FH, Ni-Sn, and Sn-Zr, primarily observed post sintering resulted in simultaneous optimization of the electrical power factor and lattice thermal conductivity. A ZT of ∼1.06 at ∼873 K was attained, which is among the highest for Hf-free ZrNiSn-based HH alloys. Additionally, ab initio calculations based on density functional theory (DFT) were performed to provide comparative insights into experimentally measured properties and understand underlying physics. Further, mechanical properties were experimentally extracted to determine the usability of synthesized alloys for device fabrication.

Wide spectral photoresponse of template assisted out of plane grown ZnO/NiO composite nanowire photodetector.

Zinc oxide (ZnO) one-dimensional nanostructures are extensively used in ultra-violet (UV) detection. To improve the optical sensing capability of ZnO, various nickel oxide (NiO) based p-n junctions have been employed. ZnO/NiO heterojunction based sensing has been limited to UV detection and not been extended to the visible region. In the present work, p-NiO/n-ZnO composite nanowire (NW) heterojunction based UV-visible photodetector is fabricated. A porous anodic aluminum oxide template based electrochemical deposition method is adopted for well separated and vertically aligned growth of composite NWs. The photoresponse is studied in an out of plane contact configuration. The fabricated photodetector shows fast response under UV-visible light with a rise and decay time of tens of ms. The wide spectral photoresponse is analyzed in terms of conduction from defect states of ZnO and interfacial defects during p-n junction formation. Light interaction with heterojunction along the length of the composite NW results in enhanced visible photoresponse of the detector and is further supported by simulation.

Compositional Tailoring for Realizing High Thermoelectric Performance in Hafnium-Free n-Type ZrNiSn Half-Heusler Alloys.

Compositional tailoring enables fine-tuning of thermoelectric (TE) transport parameters by synergistic modulation of electronic and vibrational properties. In the present work, the aspects of compositionally tailored defects have been explored in ZrNiSn-based half-Heusler (HH) TE materials to achieve high TE performance and cost effectiveness in n-type Hf-free HH alloys. In off-stoichiometric Ni-rich ZrNi1+xSn alloys in a low Ni doping limit (x < 0.1), excess Ni induces defects (Ni/vacancy antisite + interstitials), which tend to cause band structure modification. In addition, the structural similarity of HH and full-Heusler (FH) compounds and formation energetics lead to an intrinsic phase segregation of FH nanoscale precipitates that are coherently dispersed within the ZrNiSn HH matrix as nanoclusters. A consonance was achieved experimentally between these two competing mechanisms for optimal HH composition having both FH precipitates and Ni/vacancy antisite defects in the HH matrix by elevating the sintering temperature up to the solubility limit range of the ZrNiSn system. Defect-mediated optimization of electrical and thermal transport via carrier concentration tuning, energy filtering, and possibly all scale-hierarchical architecture resulted in a maximum ZT ≈ 1.1 at 873 K for the optimized ZrNi1.03Sn composition. Our findings highlight the realistic prospect of enhancing TE performance via compositional engineering approach for wide applications of TE.

Enhancement in thermoelectric performance of SiGe nanoalloys dispersed with SiC nanoparticles.

SiGe is one of the most widely used thermoelectric materials for radioisotope thermoelectric generator applications for harnessing waste-heat at high temperatures. In the present study, we report a simple experimental strategy for enhancing the thermoelectric and mechanical properties of n-type SiGe nanoalloys by dispersing SiC nanoparticles in a SiGe nanoalloy matrix. This strategy yielded a high value of figure-of-merit (ZT) of ∼1.7 at 900 °C in the SiGe/SiC nanocomposite, which is nearly twice that reported for its pristine bulk counterpart and ∼15% higher than that of pristine SiGe nanoalloys. This significant enhancement in the ZT primarily originates from a reduction in the lattice thermal conductivity, owing to a high density of nano-scale interfaces, lattice-scale modulations and mass fluctuations, which lead to extensive scattering of heat-carrying phonons. The dispersion of SiC nanoparticles also significantly enhances the mechanical properties of the resulting SiGe/SiC nanocomposite, including fracture toughness and hardness. The enhancement in the thermoelectric and mechanical properties of the SiGe/SiC nanocomposites has been correlated with their microstructural features, elucidated employing X-ray diffraction, and scanning and transmission electron microscopy.

The role of nanoscale defect features in enhancing the thermoelectric performance of p-type nanostructured SiGe alloys.

Despite SiGe being one of the most widely studied thermoelectric materials owing to its application in radioisotope thermoelectric generators (RTG), the thermoelectric figure-of merit (ZT) of p-type SiGe is still quite low, resulting in poor device efficiencies. In the present study, we report a substantial enhancement in ZT∼ 1.2 at 900 °C for p-type nanostructured Si80Ge20 alloys by creating several types of defect features within the Si80Ge20 nanostructured matrix in a spectrum of nano to meso-scale dimensions during its nanostructuring, by employing mechanical alloying followed by spark plasma sintering. This enhancement in ZT, which is ∼25% over the existing state-of-the-art value for a p-type nanostructured Si80Ge20 alloy, is primarily due to its ultralow thermal conductivity of ∼2.04 W m(-1) K(-1) at 900 °C, resulting from the scattering of low-to-high wavelength heat-carrying phonons by different types of defect features in a range of nano to meso-scale dimensions in the Si80Ge20 nanostructured matrix. These include point defects, dislocations, isolated amorphous regions, nano-scale grain boundaries and more importantly, the nano to meso-scale residual porosity distributed throughout the Si80Ge20 matrix. These nanoscale multi-dimensional defect features have been characterized by employing scanning and transmission electron microscopy and correlated with the electrical and thermal transport properties, based on which the enhancement of ZT has been discussed.