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We investigated the feasibility of the co-doping effect of zinc and chromium for copper and vanadium substitution, respectively, and reported the first successful Cr incorporation within the bulk Sn-based colusite structure.

In this work, a series of Bi2Te3/X mol% MoS2 (X = 0, 25, 50, 75) bulk nanocomposites were prepared by hydrothermal reaction followed by reactive spark plasma sintering (SPS). X-ray diffraction analysis (XRD) indicates that the native nanopowders, comprising of Bi2Te3/MoS2 heterostructure, are highly reactive during the electric field-assisted sintering by SPS. The nano-sized MoS2 particles react with the Bi2Te3 plates matrix forming a mixed-anion compound, Bi2Te2S, at the interface between the nanoplates. The transport properties characterizations revealed a significant influence of the nanocomposite structure formation on the native electrical conductivity, Seebeck coefficient, and thermal conductivity of the initial Bi2Te3 matrix. As a result, enhanced ZT values have been obtained in Bi2Te3/25 mol% MoS2 over the temperature range of 300–475 K induced mainly by a significant increase in the electrical conductivity.

Alongiside the growing demand for wearable and implantable electronics, the development of flexible thermoelectric (FTE) materials holds great promise and has recently become a highly necessitated and efficient method for converting heat to electricity. Conductive polymers were widely used in previous research; however, n-type polymers suffer from instability compared to the p-type polymers, which results in a deficiency in the n-type TE leg for FTE devices. The development of the n-type FTE is still at a relatively early stage with limited applicable materials, insufficient conversion efficiency, and issues such as an undesirably high cost or toxic element consumption. In this work, as a prototype, a flexible n-type rare-earth free skutterudite (CoSb3)/poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS) binary thermoelectric film was fabricated based on ball-milled skutterudite via a facile top-down method, which is promising to be widely applicable to the hybridization of conventional bulk TE materials. The polymers bridge the separated thermoelectric particles and provide a conducting pathway for carriers, leading to an enhancement in electrical conductivity and a competitive Seebeck coefficient. The current work proposes a rational design towards FTE devices and provides a perspective for the exploration of conventional thermoelectric materials for wearable electronics.

Alongiside the growing demand for wearable and implantable electronics, the development of flexible thermoelectric (FTE) materials holds great promise and has recently become a highly necessitated and efficient method for converting heat to electricity. Conductive polymers were widely used in previous research; however

Funder: White Rock Foundation, Funder: Jardine Foundation, Funder: Cambridge Commonwealth European and International Trust, Coordination nanosheets are an emerging class of 2D, bottom-up materials having fully π-conjugated, planar, graphite-like structures with high electrical conductivities. Since their discovery, great effort has been devoted to expand the variety of coordination nanosheets; however, in most cases, their low crystallinity in thick films hampers practical device applications. In this study, mixtures of nickel and copper ions are employed to fabricate benzenehexathiolato (BHT)-based coordination nanosheet films, and serendipitously, it is found that this heterometallicity preferentially forms a structural phase with improved film crystallinity. Spectroscopic and scattering measurements provide evidence for a bilayer structure with in-plane periodic arrangement of copper and nickel ions with the NiCu2 BHT formula. Compared with homometallic films, heterometallic films exhibit more crystalline microstructures with larger and more oriented grains, achieving higher electrical conductivities reaching metallic behaviors. Low dependency of Seebeck coefficient on the mixing ratio of nickel and copper ions supports that the large variation in the conductivity data is not caused by change in the intrinsic properties of the films. The findings open new pathways to improve crystallinity and to tune functional properties of 2D coordination nanosheets.

Filled skutterudites are currently studied as promising thermoelectric materials due to their high power factor and low thermal conductivity. The latter property, in particular, can be enhanced by adding scattering centers, such as the ones deriving from low dimensionality and the presence of interfaces. This work reports on the synthesis and characterization of thin films belonging to the Smy(FexNi1−x)4Sb12-filled skutterudite system. Films were deposited under vacuum conditions by the pulsed laser deposition (PLD) method on fused silica substrates, and the deposition temperature was varied. The effect of the annealing process was studied by subjecting a set of films to a thermal treatment for 1 h at 423 K. Electrical conductivity σ and Seebeck coefficient S were acquired by the four-probe method using a ZEM-3 apparatus performing cycles in the 348–523 K temperature range, recording both heating and cooling processes. Films deposited at room temperature required three cycles up to 523 K before being stabilized, thus revealing the importance of a proper annealing process in order to obtain reliable physical data. XRD analyses confirm the previous result, as only annealed films present a highly crystalline skutterudite not accompanied by extra phases. The power factor of annealed films is shown to be lower than in the corresponding bulk samples due to the lower Seebeck coefficients occurring in films. Room temperature thermal conductivity, on the contrary, shows values comparable to the ones of doubly doped bulk samples, thus highlighting the positive effect of interfaces on the introduction of scattering centers, and therefore on the reduction of thermal conductivity.

In the present study, we have focused on the elaboration of control of Te-doped CoSb3 thin films by RF magnetron sputtering which is an attractive technique for industrial development of thermoelectric (TE) thin films. We have successfully synthesized sputtering targets with a reliable approach in order to obtain high-quality films with controlled stoichiometry. TE properties were then probed and revealed a reliable n-type behavior characterized by poor electrical transport properties. Tellurium substitution was realized by co-sputtering deposition and allowed obtaining a significant enhancement of the power factor with promising values of PF ≈ 0.21 mW m−1 K−2 near room temperature. It is related to the Te doping effect which leads to an increase of the Seebeck coefficient and the electrical conductivity simultaneously. However, despite this large improvement, the properties remained far from the bulk material and further developments are necessary to improve the carrier mobility reduced by the thin film formatting.

International audience; We report here a rich variation of the thermoelectric properties of a series of Cu-Sn based thiospinels of composition CuM1+xSn1-xS4 upon partial substitution at the Sn-site with a variety of transition elements (M = Ti, V, Cr, Co). The optimized synthesis and processing conditions we used enabled us to realize highly densified and homogeneous compounds. The V-series was found to exhibit the lowest performing thermoelectric properties, whereas Co and Ti substituted compounds showed moderate thermoelectric properties with a maximum figure of merit (zT(max)) of similar to 0.02 and similar to 0.07 at 673 K, respectively. In contrast, the Cr substituted compounds exhibited better thermoelectric performance with zT similar to 0.2 at 673 K for the composition CuCr1.2Sn0.8S4. Both p- and n-type compounds were obtained; specifically, the Co and Ti series were found to be n-type, and the Cr series was found to be p-type. Besides the suppressed thermal transport, the attractive thermoelectric properties with the Cr-series can be attributed to the simultaneous increase of the Seebeck coefficient and electrical conductivity with increasing temperature, thus resulting in an improved power factor. Experimental and DFT theoretical calculations also predict a considerable interaction between the carriers and magnetic moments, contributing to a higher effective mass, thus leading to higher thermopower and power factor for the Cr-series. Computed electronic density of states and band structures, in agreement with the experimental findings, envisaged n-type half-metallic character for the CuTi1+xSn1-xS4 paramagnetic compounds, n-type conducting behavior for the CuCo1+xSn1-xS4 compounds, p-type weak half-metallic character for the CuV1+xSn1-xS4 compounds, and p-type semiconducting behavior for the CuCr1+xSn1-xS4 ferromagnetic compounds. Computation of the electronic transport coefficients using the Boltzmann transport equation also suggests a better thermoelectric property, especially the thermopower, for the Cr-series when compared to its Ti/V/Co counterparts.

We report thermal conductivity (κ) above 300 K for perovskite ferroelectrics BaTiO3 (T c ≈ 402 K) and PbTiO3 (763 K), as well as antiferroelectrics PbZrO3 (503 K) and PbHfO3 (476 and 433 K). BaTiO3 and PbTiO3 show similar κ in the paraelectric phase. In contrast, smaller and glasslike κ is found above T c for PbZrO3 and PbHfO3, signifying the presence of large anharmonic distortions in the paraelectric phase. Low-temperature heat capacity on PbZrO3 shows a lack of glasslike thermal behavior in the antiferroelectric phase.

Filled skutterudites are currently studied as promising thermoelectric materials due to their high power factor and low thermal conductivity. The latter property, in particular, can be enhanced by adding scattering centers, such as the ones deriving from low dimensionality and the presence of interfaces. This work reports on the synthesis and characterization of thin films belonging to the Smy(FexNi1−x)4Sb12-filled skutterudite system. Films were deposited under vacuum conditions by the pulsed laser deposition (PLD) method on fused silica substrates, and the deposition temperature was varied. The effect of the annealing process was studied by subjecting a set of films to a thermal treatment for 1 h at 423 K. Electrical conductivity σ and Seebeck coefficient S were acquired by the four-probe method using a ZEM-3 apparatus performing cycles in the 348–523 K temperature range, recording both heating and cooling processes. Films deposited at room temperature required three cycles up to 523 K before being stabilized, thus revealing the importance of a proper annealing process in order to obtain reliable physical data. XRD analyses confirm the previous result, as only annealed films present a highly crystalline skutterudite not accompanied by extra phases. The power factor of annealed films is shown to be lower than in the corresponding bulk samples due to the lower Seebeck coefficients occurring in films. Room temperature thermal conductivity, on the contrary, shows values comparable to the ones of doubly doped bulk samples, thus highlighting the positive effect of interfaces on the introduction of scattering centers, and therefore on the reduction of thermal conductivity.

A novel heterogeneous catalytic nanomaterial based on a molybdenum cluster-based halide (MC) and a single-layered copper hydroxynitrate (CHN) was first prepared by colloidal processing under ambient conditions. The results of the elemental composition and crystalline pattern indicated that CHN was comprehensively synthesized with the support of the MC compound. The absorbing characteristic in the ultraviolet and near-infrared regions was promoted by both of the ingredients. The proper chemical interaction between the materials is a crucial reason to modify the structure of the MCs and only a small decrease in the magnetic susceptibility of CHN. The heterogeneous catalytic activity of the obtained MC@CHN material was found to have a high efficiency and excellent reuse when it is activated by hydrogen peroxide (H2O2) for the degrading reaction of the organic pollutant at room temperature. A reasonable catalytic mechanism was proposed to explain the distinct role of the copper compound, Mo6 compound, and H2O2 in the production of the radical hydroxyl ion. This novel nanomaterial will be an environmentally promising candidate for dye removal., Graphical abstract

International audience; GeTe, which undergoes phase transition between low symmetric rhombohedral to high symmetric cubic phase between 550-700 K (depending on the dopant and composition) and its alloys have widely been considered as promising candidates for mid-temperature range thermoelectrics. A variety of dopants have been tried in the past to improve further the thermoelectric performance of GeTe. In this work, an extensive experimental-and theoretical-based screening of transition (Y, Zr, Hf, V, Nb, Mo, and Ru) and rare-earth elements (La, Pr) that were not used in the past, are studied to explore if they can be of any potential use as dopants in thermoelectric GeTe. Out of these studied dopants, Ru, Nb, Pr, V, and Mo were found to be detrimental, Y and Hf to be reasonable, and Zr and La to be more promising. The transition or rare-earth dopant dependent variation in transport properties and thermoelectric performance of GeTe is corroborated with a concoction of factors ranging from modifications of the band gap, energy difference between the two valance band maxima, magnetic character, nature of the dopant or impurity state and their position with regard to the Fermi level, secondary cubic GeTe phase, etc. Contrary to the classical approaches where intrinsic Ge vacancies (that are inherently formed due to the thermodynamic nature of GeTe) are suppressed to improve their thermoelectric performance, an opposite approach is adopted in this work. Here by intentionally creating more electrically dormant Ge vacancies and modulating/balancing it with Zr-doping, an improved figure of merit, zT ~1.3 at 673 K is obtained for Ge-deficient Ge0.98Zr0.005Te compound, thanks to the suppression of the lattice contribution to the thermal conductivity arising due to the large density of planar defects in these vacancy-induced compounds. These optimized Ge-deficient Zr-doped materials when codoped with Sb, results in effective convergence of electronic band valleys by tuning the crystal field effect and reduced thermal transport, thus yielding a high zT ~1.8 at 723 K. This work not only screens a directory of dopant elements to enrich the current state of the knowledge on GeTe-based compounds, but also indicates that the strategy of creation and synchronization of Ge-vacancies with a certain dopant is an alternative and effective route for enhancing zT.

In the present study, we have focused on the elaboration of control of Te-doped CoSb

The influence of structural disorder on the thermal transport in the colusite $\mathrm{C}{\mathrm{u}}_{26}{\mathrm{V}}_{2}\mathrm{S}{\mathrm{n}}_{6}{\mathrm{S}}_{32}$ has been investigated by means of low-temperature thermal conductivity and specific heat measurements (2--300 K), $^{119}\mathrm{Sn}$ M\"ossbauer spectroscopy and temperature-dependent powder inelastic neutron scattering (INS). Variations in the high-temperature synthesis conditions act as a key parameter for tuning the degree of disorder in colusite compounds. Intriguingly, we find that all synthesized samples are disordered, the degree of which varies with the synthesis conditions used. M\"ossbauer data clearly evidence that Sn atoms do not solely occupy the $6c$ site of the crystal lattice but are present on possibly both the Cu and V sites, leading to a random distribution of these three cations within the unit cell. Increasing the disorder in these materials tends to lead to a smearing out of the main features in the phonon density of states measured by INS. Although the evolution of the inelastic signal upon warming is well described by a quasiharmonic approximation, elastic properties calculations indicate large average Gr\"uneisen parameters, consistent with those determined experimentally from thermodynamic data. Increasing the level of disorder results in a decreased average Gr\"uneisen parameter suggesting that the lowered lattice thermal conductivity is not driven by enhanced anharmonicity. These results provide experimental evidence to support that the remarkable changeover in the lattice thermal conductivity from crystalline to glasslike is solely driven by enhanced disorder accompanied by local lattice distortions.

International audience; A complete thiospinel solid solution CuCoxTi2-xS4 (0 ≤ x

Équipe 103 : Composés intermétalliques et matériaux hybrides; International audience; This paper describes Cu4Sn7S16 material as a potential thermoelectric comprising low cost and non-toxic elements, whose complex crystal structure permits intrinsic low thermal conductivity. We begin by identifying two different synthesis approaches to obtain pure and fully dense samples, using conventional sealed tube and mechanical alloying methods combined with Spark Plasma Sintering. We then confirm the complex rhombohedral structure (R-3m, a similar to 7.37 angstrom, c similar to 36.02 angstrom) using both Rietveld refinement of powder X-ray diffraction patterns and High Resolution Transmission Electron Microscopy (HRTEM) analyses. Finally, we characterize the electrical and thermal properties at high temperatures on highly dense samples. The electrical behavior is also shown for the first time to change from semiconducting to metallic behavior according to sample preparation, suggesting that the material is highly sensitive to cationic site occupancy and Cu:Sn:S ratio. The complex crystallographic structure of Cu4Sn7S16 causes low thermal conductivity, which is found below 1.1 W/mK above room temperature. The focus of this paper is to drawn attention to the way in which complex structures specifically designed to induce intrinsic low thermal conductivity can be potentially attractive thermoelectrics, even in materials that are intrinsically poor conductors.