Fine tunable aqueous solution synthesis of textured flexible SnS2 thin films and nanosheets.

Films and nanosheets of layered chalcogenides are currently under intense investigation owing to their application in thin film electronic, optoelectronic, and sensor devices. Here, aqueous solution processing of the environmentally benign thiostannate, (NH4)4Sn2S6·3H2O, and its subsequent thermal decomposition to form continuous highly textured SnS2 thin films are presented. We show how to control the film thickness, the coherent scattering domain size, and the crystallinity by changes in the processing parameters (i.e. thiostannate concentration or angular velocity in the spin coating process). For device applications of the semiconducting metal sulfide film it is of interest to delaminate the film from the glass substrate to create freestanding nanosheets or transfer the film to a flexible polymer substrate. It is shown how metal sulfide films can be delaminated from the glass substrate and form large area freestanding nanosheets. Furthermore, we extend the delamination process to include transfer of the thin film from the glass substrate to a low-cost flexible polymer substrate.

In situ X-ray diffraction study of the formation, growth, and phase transition of colloidal Cu(2-x)S nanocrystals.

The formation, growth, and phase transition of colloidal monodisperse spherical copper sulfide nanocrystals synthesized in dodecanethiol have been followed by in situ synchrotron powder X-ray diffraction (PXRD). The formation of nanocrystals involves a thermal decomposition of the crystalline precursor [CuSC12H25], which upon heating forms an isotropic liquid that subsequently turns into colloidal ß-chalcocite phase Cu2S nanocrystals. The redox reaction step in the precursor solution has been studied by proton NMR. Upon heating, high digenite phase nanocrystals are formed through a solid-state rearrangement phase transition of the ß-chalcocite phase nanocrystals at temperatures above 260 °C. TEM and PXRD reveal that the nanocrystal size is independent of synthesis temperature and stabilizes after the phase transition has completed. Spherical monodisperse nanocrystals are obtained in all experiments, with the nanocrystals in the ß-chalcocite phase (7 nm) being smaller than those in high digenite phase (11 nm).

Highly enhanced thermal stability of Zn4Sb3 nanocomposites.

The effects of nano-sized TiO2 and ZnO ceramic inclusions on the high temperature stability of Zn4Sb3 have been studied using multi-temperature synchrotron powder X-ray diffraction. Samples with 9 nm TiO2 nanoinclusions exhibit remarkable stability after three heating cycles to 625 K.

Low-cost high-performance zinc antimonide thin films for thermoelectric applications.

Zinc antimonide thin films with high thermoelectric performance are produced by a simple sputtering method. The phase-pure Zn(4)Sb(3) and ZnSb thin films fulfill the key requirements for commercial TE power generation: cheap elements, cheap fabrication method, high performance and thermal stability. In addition, two completely new meta-stable crystalline phases of zinc antimonide have been discovered.

Thallium chalcohalides for X-ray and γ-ray detection.

We report that the chalcohalide compound Tl(6)SeI(4) is a promising material for efficient X-ray and γ-ray detection. This material has a higher figure of merit than the current state-of-the-art material for room-temperature operation, Cd(0.9)Zn(0.1)Te (CZT). We have synthesized high-quality single-crystalline wafers of Tl(6)SeI(4) with detector-grade resistivities and good carrier transport of both electrons and holes. We demonstrate that pulse height spectra recorded using Co-57 radiation show an energy resolution matching that of a commercial CZT detector material.

Nanostructures boost the thermoelectric performance of PbS.

In situ nanostructuring in bulk thermoelectric materials through thermo-dynamic phase segregation has established itself as an effective paradigm for optimizing the performance of thermoelectric materials. In bulk PbTe small compositional variations create coherent and semicoherent nanometer sized precipitates embedded in a PbTe matrix, where they can impede phonon propagation at little or no expense to the electronic properties. In this paper the nanostructuring paradigm is for the first time extended to a bulk PbS based system, which despite obvious advantages of price and abundancy, so far has been largely disregarded in thermoelectric research due to inferior room temperature thermoelectric properties relative to the pristine fellow chalcogenides, PbSe and PbTe. Herein we report on the synthesis, microstructural morphology and thermoelectric properties of two phase (PbS)(1-x)(PbTe)(x)x = 0-0.16 samples. We have found that the addition of only a few percent PbTe to PbS results in a highly nanostructured material, where PbTe precipitates are coherently and semicoherently embedded in a PbS matrix. The present (PbS)(1-x)(PbTe)(x) nanostructured samples show substantial decreases in lattice thermal conductivity relative to pristine PbS, while the electronic properties are left largely unaltered. This in turn leads to a marked increase in the thermoelectric figure of merit. This study underlines the efficiency of the nanostructuring approach and strongly supports its generality and applicability to other material systems. We demonstrate that these PbS-based materials, which are made primarily from abundant Pb and S, outperform optimally n-type doped pristine PbTe above 770 K.

Thermoelectric clathrates of type I.

Thermoelectric clathrates hold significant promise for high temperature applications with zT values exceeding 1.3. The inorganic clathrates have been shown to be both chemically and thermally stable at high temperatures, and high performance can be obtained from both single crystals and processed powders. The clathrates also show excellent compatibility factors in segmented module applications. For a materials chemist it is furthermore of great importance that the clathrates exhibit a very rich chemistry with the ability for substitution of many different elements. This allows delicate tuning of both the crystal structure as well as the physical properties. With all these assets, it is not surprising that clathrates have been intensely investigated in the thermoelectric community during the past decade. The present perspective provides a review of the many studies concerned with the synthesis, crystal structure and thermoelectric properties of clathrates with emphasis on the type I clathrate.

Narrow band gap and enhanced thermoelectricity in FeSb2.

FeSb(2) was recently identified as a narrow-gap semiconductor with indications of strong electron-electron correlations. In this manuscript, we report on systematic thermoelectric investigation of a number of FeSb(2) single crystals with varying carrier concentrations, together with two isoelectronically substituted FeSb(2-x)As(x) samples (x = 0.01 and 0.03) and two reference compounds FeAs(2) and RuSb(2). Typical behaviour associated with narrow bands and narrow gaps is only confirmed for the FeSb(2) and the FeSb(2-x)As(x) samples. The maximum absolute thermopower of FeSb(2) spans from 10 to 45 mV/K at around 10 K, greatly exceeding that of both FeAs(2) and RuSb(2). The relation between the carrier concentration and the maximum thermopower value is in approximate agreement with theoretical predictions of the electron-diffusion contribution which, however, requires an enhancement factor larger than 30. The isoelectronic substitution leads to a reduction of the thermal conductivity, but the charge-carrier mobility is also largely reduced due to doping-induced crystallographic defects or impurities. In combination with the high charge-carrier mobility and the enhanced thermoelectricity, FeSb(2) represents a promising candidate for thermoelectric cooling applications at cryogenic temperatures.