Realization of Band Convergence in p-Type TiCoSb Half-Heusler Alloys Significantly Enhances the Thermoelectric Performance.

Band engineering is a promising approach that proved successful in enhancing the thermoelectric performance of several families of thermoelectric materials. Here, we show how this mechanism can be induced in the p-type TiCoSbhalf-Heusler (HH) compound to effectively improve the Seebeck coefficient. Both the Pisarenko plot and electronic band structure calculations demonstrate that this enhancement is due to increased density-of-states effective mass resulting from the convergence of two valence band maxima. Our calculations evidence that the valence band maximum of TiCoSb lying at the Γ point exhibits a small energy difference of 51 meV with respect to the valence band edge at the L point. Experimentally, this energy offset can be tuned by both Fe and Sn substitutions on the Co and Sb site, respectively. A Sn doping level as low as x = 0.03 is sufficient to drive more than ∼100% increase in the power factor at room temperature. Further, defects at various length scales, that include point defects, edge dislocations, and nanosized grains evidenced by electron microscopy (field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM)), result in enhanced phonon scattering which substantially reduces the lattice thermal conductivity to ∼4.2 W m-1 K-1 at 873 K. Combined with enhanced power factor, a peak ZT value of ∼0.4 was achieved at 873 K in TiCo0.85Fe0.15Sb0.97Sn0.03. In addition, the microhardness and fracture toughness were found to be enhanced for all of the synthesized samples, falling in the range of 8.3-8.6 GPa and 1.8-2 MPa·m-1/2, respectively. Our results highlight how the combination of band convergence and microstructure engineering in the HH alloy TiCoSb is effective for tuning its thermoelectric performance.

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.

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.

Surface-Engineered Nanostructure-Based Efficient Nonpolar GaN Ultraviolet Photodetectors.

Surface-engineered nanostructured nonpolar (112̅0) gallium nitride (GaN)-based high-performance ultraviolet (UV) photodetectors (PDs) have been fabricated. The surface morphology of a nonpolar GaN film was modified from pyramidal shape to flat and trigonal nanorods displaying facets along different crystallographic planes. We report the ease of enhancing the photocurrent (5.5-fold) and responsivity (6-fold) of the PDs using a simple and convenient wet chemical-etching-induced surface engineering. The fabricated metal-semiconductor-metal structure-based surface-engineered UV PD exhibited a significant increment in detectivity, that is, from 0.43 to 2.83 (×108) Jones, and showed a very low noise-equivalent power (∼10-10 W Hz-1/2). The reliability of the nanostructured PD was ensured via fast switching with a response and decay time of 332 and 995 ms, which were more than five times faster with respect to the unetched pyramidal structure-based UV PD. The improvement in device performance was attributed to increased light absorption, efficient transport of photogenerated carriers, and enhancement in conduction cross section via elimination of recombination/trap centers related to defect states. Thus, the proposed method could be a promising approach to enhance the performance of GaN-based PD technology.

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.

An interaction potential to study the thermal structure evolution of a thermoelectric material: ß-Cu2 Se.

An interaction potential model has been developed, for the first time, for ß-Cu2 Se using the ab initio derived data. The structure and elastic constants of ß-Cu2 Se using the derived force-field are within a few percent of DFT derived structure and elastic constants and reported experimental structure. The derived force-field also shows remarkable ability to reproduce temperature dependent behavior of the specific heat and thermal expansion coefficient. The thermal structure evolution of the ß-Cu2 Se is studied by performing the molecular dynamic simulations using the derived force-field. The simulation results demonstrate that the Cu ions moves around the equilibrium lattice position within the temperature range of 500-800 K. However, at a temperature > 800 K, the Cu ions starts diffusing within the material, while the Se ions remains in their lattice position. The evaluated thermodynamic properties such as free energy and excess entropy, show that the increased Cu-Se interaction with the temperature makes the system more thermodynamically stable. © 2017 Wiley Periodicals, Inc.

Wet chemical etching induced stress relaxed nanostructures on polar & non-polar epitaxial GaN films.

We report formation of aligned nanostructures on epitaxially grown polar and nonpolar GaN films via wet chemical (hot H3PO4 and KOH) etching. The morphological evolution exhibited stress relaxed faceted nanopyramids, flat/trigonal nanorods and porous structures with high hydrophilicity and reduced wettability. The nanostructured films divulged significant suppression of defects and displayed an enhanced intensity ratio of the near band edge emission to the defect band. Extensive photoemission analysis revealed variation in oxidation state along with elimination of OH- and adsorbed H2O molecules from the chemically modified surfaces. Fermi level pinning, and alteration in the surface polarity with substantial changes in the electron affinities were also perceived. The temperature dependent current-voltage analysis of the nanostructured surfaces displayed enhancement in current conduction. The in-depth analysis demonstrates that the chemically etched samples could potentially be utilized as templates in the design/growth of III-nitride based high performance devices.

Luminescence and advanced mass spectroscopic characterization of sodium zinc orthophosphate phosphor for low-cost light-emitting diodes.

A new rare-earth-free NaZnPO4:Mn(2+) (NZP:Mn) phosphor powder has been developed by our group and investigated meticulously for the first time using secondary ion mass spectroscopy and chemical imaging techniques. The studies confirmed the effective incorporation of Mn(2+) into the host lattice, resulting in an enhancement of photoluminescence intensity. Phase purity has been verified and structure parameters have been determined successfully by Rietveld refinement studies. The NZP:Mn phosphor powder exhibits strong absorption bands in the ultraviolet and visible (300-470 nm) regions with a significant broad yellow-green (~543 nm) emission due to the characteristic spin forbidden d-d transition ((4)T1→(6)A1) of Mn(2+) ions, indicating weak crystal field strength at the zinc-replaced manganese site. The decay constants are a few milliseconds, which is a pre-requisite for applications in many display devices. The results obtained suggest that this new phosphor powder will find many interesting applications in semiconductor physics, as cost-effective light-emitting diodes (LEDs), as solar cells and in photo-physics.

Emerging cool white light emission from Dy(3+) doped single phase alkaline earth niobate phosphors for indoor lighting applications.

Single-phase cool white-light emitting BaNb2O6:Dy(3+) phosphors have been synthesized via a conventional solid-state reaction method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) observations and spectrofluorophotometric measurements. XRD and Rietveld structural refinement studies confirm that all the samples exhibit pure orthorhombic structure [space group -C2221(20)]. SEM observations reveal the dense particle packaging with irregular morphology in a micron range. The as-prepared phosphors exhibit blue (482 nm) and yellow (574 nm) emissions under 349, 364, 386 and 399 nm excitations corresponding to (4)F9/2→(6)HJ (J = 15/2, 13/2) transitions of Dy(3+) ions. The energy transfer mechanism between Dy(3+) ions has been studied in detail and the luminescence decay lifetime for the (4)F9/2 level was found to be around 146.07 µs for the optimized phosphor composition. The calculated Commission Internationale de L'Eclairage (CIE) chromaticity coordinates for the optimized phosphor are (x = 0.322, y = 0.339), which are close to the National Television Standard Committee (NTSC) (x = 0.310, y = 0.316) coordinates. The values of CIE chromaticity coordinates and correlated color temperature (CCT) of 5907 K endorse cool white-light emission from the phosphor. The study reveals that BaNb2O6:Dy(3+) phosphor could be a potential candidate for near ultra-violet (NUV) excited white-LED applications.

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.

Bulk superconductivity in bismuth oxysulfide Bi4O4S3.

A very recent report on the observation of superconductivity in Bi(4)O(4)S(3) [Mizuguchi, Y.; http://arxiv.org/abs/1207.3145] could potentially reignite the search for superconductivity in a broad range of layered sulfides. We report here the synthesis of Bi(4)O(4)S(3) at 500 °C by a vacuum encapsulation technique and its basic characterizations. The as-synthesized Bi(4)O(4)S(3) was contaminated with small amounts of Bi(2)S(3) and Bi impurities. The majority phase was found to be tetragonal (space group I4/mmm) with lattice parameters a = 3.9697(2) Å and c = 41.3520(1) Å. Both AC and DC magnetization measurements confirmed that Bi(4)O(4)S(3) is a bulk superconductor with a superconducting transition temperature (T(c)) of 4.4 K. Isothermal magnetization (M-H) measurements indicated closed loops with clear signatures of flux pinning and irreversible behavior. The lower critical field (H(c1)) at 2 K for the new superconductor was found to be ~15 Oe. Magnetotransport measurements showed a broadening of the resistivity (ρ) and a decrease in T(c) (ρ = 0) with increasing magnetic field. The extrapolated upper critical field H(c2)(0) was ~31 kOe with a corresponding Ginzburg-Landau coherence length of ~100 Å . In the normal state, the ρ ~ T(2) dependence was not indicated. Hall resistivity data showed a nonlinear magnetic field dependence. Our magnetization and electrical transport measurements substantiate the appearance of bulk superconductivity in as-synthesized Bi(4)O(4)S(3). On the other hand, Bi heat-treated at the same temperature is not superconducting, thus excluding the possibility of impurity-driven superconductivity in the newly discovered superconductor Bi(4)O(4)S(3).