Composite phases have been shown to improve both the thermoelectric efficiency and mechanical properties of materials. Here, we demonstrate an improved thermoelectric figure of merit, power factor, and mechanical properties for the high-temperature p-type Zintl phase Yb 14 MgSb 11 . Composites with 0, 1, 2, 3, 4, 6, and 8 vol % 6−10 μm reduced Fe powder were prepared via a fast, scalable, mechanical milling and spark plasma sintering procedure. Powder X-ray diffraction, scanning electron microscopy, and transmission electron microscopy show that Fe is not incorporated into the Yb 14 MgSb 11 structure. First-order reversal curves and scanning electron microscopy images show that the Fe inclusions are larger and closer together with increasing Fe content. Thermogravimetric and differential scanning calorimetry show that the composites are stable up to 1273 K. The elastic constants of the 8 vol % Fe composite were measured by resonant ultrasound spectroscopy and show that Yb 14 MgSb 11 becomes stiffer with increasing Fe volume % and SEM after indentations show crack arresting occurs at the Fe interface. Thermoelectric properties on dense pellets are measured from 300 K − 1273 K. The thermoelectric power factor (PF = S 2 /ρ) increases with increasing Fe content, with the 8 vol % Fe resulting in 40% higher PF than pristine Yb 14 MgSb 11 . The increase in PF is attributed to a systematic reduction in electrical resistivity. Peak thermoelectric figure of merit [zT = (S 2 T)/(κρ)] is observed at 3 vol % Fe, an 11% improvement in zT compared to Yb 14 MgSb 11 . Yb 14 MgSb 11 composites with Fe are compatible with Ce 0.9 Fe 3.5 Co 0.5 Sb 12 for thermoelectric generator couple segmentation. KEYWORDS: composite, thermoelectric, transport properties, Zintl phase, SPS synthesis, first-order reversal curves PFS 2 =ρ by band structure engineering, such as band convergence, tuning the electronic states with resonance levels, or simple substitutional alloying. There has also been significant research

Colloidal germanium (Ge) nanocrystals (NCs) are of great interest with possible applications for photovoltaics and near-IR detectors. In many examples of colloidal reactions, Ge­(II) precursors are employed, and NCs of diameter ∼3–10 nm have been prepared. Herein, we employed a two-step microwave-assisted reduction of GeI4 in oleylamine (OAm) to prepare monodispersed Ge NCs with a size of 18.9 ± 1.84 nm. More importantly, the as-synthesized Ge NCs showed high crystallinity with single-crystal nature as indicated by powder X-ray diffraction, selected area electron diffraction, and high-resolution transmission electron microscopy. The Tauc plot derived from photothermal deflection spectroscopy measurement on Ge NCs thin films shows a decreased bandgap of the Ge NCs obtained from GeI4 compared with that of the Ge NCs from GeI2 with a similar particle size, indicating a higher crystallinity of the samples prepared with the two-step reaction from GeI4. The calculated Urbach energy indicates less disorder in the larger NCs. This disorder might correlate with the fraction of surface states associated with decreased particle size or with the increased molar ratio of ligands to germanium. Solutions involved in this two-step reaction were investigated with 1H NMR spectroscopy and high-resolution mass spectrometry (MS). One possible reaction pathway is proposed to unveil the details of the reaction involving GeI4 and OAm. Overall, this two-step synthesis produces high-quality Ge NCs and provides new insight on nanoparticle synthesis of covalently bonding semiconductors.

Crystallization of amorphous materials by thermal annealing has been investigated for numerous applications in the fields of nanotechnology, such as thin-film transistors and thermoelectric devices. The phase transition and shape evolution of amorphous germanium (Ge) and Ag@Ge core–shell nanoparticles with average diameters of 10 and 12 nm, respectively, were investigated by high-energy electron beam irradiation and in situ heating within a transmission electron microscope. The transition of a single Ge amorphous nanoparticle to the crystalline diamond cubic structure at the atomic scale was clearly demonstrated. Depending on the heating temperature, a hollow Ge structure can be maintained or transformed into a solid Ge nanocrystal through a diffusive process during the amorphous to crystalline phase transition. Selected area diffraction patterns were obtained to confirm the crystallization process. In addition, the thermal stability of Ag@Ge core–shell nanoparticles with an average core of 7.4 and a 2.1 nm Ge shell was studied by applying the same beam conditions and temperatures. The results show that at a moderate temperature (e.g., 385 °C), the amorphous Ge shell can completely crystallize while maintaining the well-defined core–shell structure, while at a high temperature (e.g., 545 °C), the high thermal energy enables a freely diffusive process of both Ag and Ge atoms on the carbon support film and leads to transformation into a phase segregated Ag–Ge Janus nanoparticle with a clear interface between the Ag and Ge domains. This study provides a protocol as well as insight into the thermal stability and strain relief mechanism of complex nanostructures at the single nanoparticle level with atomic resolution.

ZnS:Cu,Tm nanocrystal with 15nm cubic structures have been synthesized by hydrothermal approach at 200°C. The photoluminescence (PL) properties and the effect of hydrothermal treatment time on the structure, morphology and PL spectra of ZnS:Cu,Tm samples have been studied. The as-obtained samples have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and FT-IR spectra.The result indicated that the PL emission spectrum of codoped with Cu and Tm sample compares with undoped ZnS and doped with Cu alone samples has a significant changes, while the PL emission peak has red shift and PL emission intensity increased. The samples size and crystallization are increase with extending of the treatment time. However, when the hydrothermal treatment time is too long(>12h), the PL emission intensity of sample instead of decreased. Demonstrated changes in surface state of nanomaterials have a greater impact on its luminescence properties.

We report a systematic study on the synthesis of highly monodisperse hollow germanium (Ge) nanoparticles (NPs) via galvanic replacement reactions between GeI2 and Ag NPs. By fine-tuning the synthetic parameters such as temperature, precursor molar ratio, ligand concentration, and so forth, the morphology and surface structure of the Ge NPs can be precisely controlled. We also report a method to synthesize solid Ge NPs and Ag@Ge core–shell metal–semiconductor NPs with a controllable uniform shell thickness. An inward diffusion mechanism for galvanic replacement is proposed and supported by imaging the different stages of the reaction and analysis of the products. This mechanism allows the reaction to be self-terminated and achieves nanometer-sized accuracy. The galvanic reaction may be applied to other semiconductors and could serve as a powerful alternative to the classical nucleation-growth mechanism and subsequently advance the scale-up and further energy storage applications.

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