RESUMEN
Copper-rich sulfides are very promising for energy conversion applications due to their environmental compatibility, cost effectiveness, and earth abundance. Based on a comparative analysis of the structural and transport properties of Cu3BiS3 with those of tetrahedrite (Cu12Sb4S13) and other Cu-rich sulfides, we highlight the role of the cationic coordination types and networks on the electrical and thermal properties. By precession-assisted 3D electron diffraction analysis, we find very high anisotropic thermal vibration of copper attributed to its 3-fold coordination, with an anisotropic atomic displacement parameter up to 0.09 Å2. Density functional theory calculations reveal that these Cu atoms are weakly bonded and give rise to low-energy Einstein-like vibrational modes that strongly scatter heat-carrying acoustic phonons, leading to ultralow thermal conductivity. Importantly, we demonstrate that the 3-fold coordination of copper in Cu3BiS3 and in other copper-rich sulfides constituted of interconnected CuS3 networks causes a hole blockade. This phenomenon hinders the possibility of optimizing the carrier concentration and electronic properties through mixed valency Cu+/Cu2+, differently from tetrahedrite and most other copper-rich chalcogenides, where the main interconnected Cu-S network is built of CuS4 tetrahedra. The comparison with various copper-rich sulfides demonstrates that seeking for frameworks characterized by the coexistence of tetrahedral and 3-fold coordinated copper is very attractive for the discovery of efficient thermoelectric copper-rich sulfides. Considering that lattice vibrations and carrier concentration are key factors for engineering transport phenomena (electronic, phonon, ionic, etc.) in copper-rich chalcogenides for various types of applications, our findings improve the guidelines for the design of materials enabling sustainable energy solutions with wide-ranging applications.
RESUMEN
A simple and effective preparation of solution-processed chalcogenide thermoelectric materials is described. First, PbTe, PbSe, and SnSe were prepared by gram-scale colloidal synthesis relying on the reaction between metal acetates and diphenyl dichalcogenides in hexadecylamine solvent. The resultant phase-pure chalcogenides consist of highly crystalline and defect-free particles with distinct cubic-, tetrapod-, and rod-like morphologies. The powdered PbTe, PbSe, and SnSe products were subjected to densification by spark plasma sintering (SPS), affording dense pellets of the respective chalcogenides. Scanning electron microscopy shows that the SPS-derived pellets exhibit fine nano-/micro-structures dictated by the original morphology of the key constituting particles, while the powder X-ray diffraction and electron microscopy analyses confirm that the SPS-derived pellets are phase-pure materials, preserving the structure of the colloidal synthesis products. The resultant solution-processed PbTe, PbSe, and SnSe exhibit low thermal conductivity, which might be due to the enhanced phonon scattering developed over fine microstructures. For undoped n-type PbTe and p-type SnSe samples, an expected moderate thermoelectric performance is achieved. In contrast, an outstanding figure-of-merit of 0.73 at 673 K was achieved for undoped n-type PbSe outperforming, the majority of the optimized PbSe-based thermoelectric materials. Overall, our findings facilitate the design of efficient solution-processed chalcogenide thermoelectrics.
RESUMEN
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 â¼100% 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 â¼4.2 W m-1 K-1 at 873 K. Combined with enhanced power factor, a peak ZT value of â¼0.4 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.
RESUMEN
Distortion of the density of states induced by specific impurities, a mechanism known as resonant level (RL), is an efficient strategy to enhance the thermoelectric performances of metals and semiconductors. So far, experimental signatures identifying the resonant nature of an impurity have relied on the so-called Ioffe-Pisarenko plot that enables visualizing the induced thermopower enhancement at specific carrier concentrations. However, this method cannot solely discern RL from other possible band-structure-related sources of thermopower enhancement such as band-shape modifications or band convergence. An independent method of resolving this problem is proposed here. A detailed theoretical and experimental analysis of the low-temperature electrical resistivity ρ0 and carrier mobility µ0 of the resonant-level system SnTe doped with In is presented as a function of the impurity concentration x. By comparing to non-resonant cases of SnTe doped with I, Mn, and Ga, we demonstrate that the construction of residual resistivity ρ0(x) and residual mobility µ0(x) plots allows to distinguish between resonant and non-resonant impurities, even when some of them induce similar thermopower enhancements. This methodology is further confirmed by analyses performed for Na- and Tl-doped PbTe, illustrating how the combination of transport measurements at low temperatures can be used to determine the resonant nature of an impurity.
RESUMEN
From the theory of two-phase composites it is concluded that in the concentration dependence of the Seebeck coefficient S a kink can occur precisely at S=0 absolute if the two phases have different kinds of carriers, electrons and holes, and if the phase grains are spherical without preferred orientations and arranged in a symmetrical fashion. This feature, indeed found to be realized in amorphous Cr1-xSix thin films deposited by ion beam sputtering from Cr-Si alloy targets, can be applied to make reference standards for S=0 at room temperature and even at higher temperatures. Additionally, it may be used to design a thermopower switch between S=0 and S≠0. It is also concluded that the structure realized in any alloy during solidification does not only depend on the diffusion mobility of the atoms and on the existence of a (relative) minimum in the Gibbs' free energy. It depends also on the fact whether this structure is compatible with the demand that (spatial) continuity of the entropy and energy flux densities and their gradients is saved during the solidification process.
RESUMEN
Rutile is the most common and stable polymorph form of titanium oxide TiO2 at all temperatures. The doping of rutile TiO2 with a small amount of niobium is reknown for being responsible for a large increase of the electrical conductivity by several orders of magnitude, broadening its technological interest towards new emerging fields such as the thermoelectric conversion of waste heat. The electronic conduction has been found to be of a polaronic nature with strongly localized charges around the Ti3+ centers while, on the other side, the relatively high value of the thermal conductivity implies the existence of lattice heat carriers, i.e. phonons, with large mean free paths which makes the nanostructuration relevant for optimizing the thermoelectric efficiency. Here, the use of a high-pressure and high-temperature sintering technique has allowed to vary the grain size in rutile TiO2 pellets from 300 to 170 nm, leading to a significant reduction of the lattice thermal conductivity. The thermoelectric properties (electrical conductivity, Seebeck coefficient and thermal conductivity) of Nb-doped rutile nanostructured ceramics, namely NbxTi1-xO2 with x varying from 1 to 5%, are reported from room temperature to â¼900 K. With the incorporation of Nb, an optimum in the thermoelectric properties together with an anomaly on the tetragonal lattice constant c are observed for a concentration of â¼2.85%, which might be the fingerprint of the formation of short Nb dimers.
RESUMEN
Because the binary chalcogenide SnTe is an interesting Pb-free alternative to the state-of-the-art thermoelectric material PbTe, significant efforts were devoted to the optimization of its thermoelectric properties over the last few years. Here, we show that saturation-annealing treatments performed at 823, 873 or 973 K under Sn-rich conditions provide a successful strategy to prepare polycrystalline samples with a controlled concentration of Sn vacancies. Both scanning transmission electron microscopy and Mössbauer spectroscopy demonstrate the absence of Sn-rich areas at the grain boundaries in the saturation-annealed samples. Transport property measurements, performed over a wide range of temperatures (5-800 K), show that this technique enables achieving thermoelectric performances at 800 K similar to those obtained using Sn self-compensation. The three saturation annealing temperatures result in comparable transport properties across the entire temperature range due to similar hole concentrations ranging between 1.0 and 1.5 × 1020 cm-3 at 300 K. As equally observed in samples prepared by other synthetic routes, the temperature dependence of the Hall mobility evidences that charge transport is strongly affected by point-defect scattering caused by the random distribution of Sn vacancies.
RESUMEN
Mo-based cluster compounds are a large class of materials with complex crystal structures that give rise to very low lattice thermal conductivity. Here, we report on the crystal structure and transport property measurements (5-800 K) of the novel Tl-filled compound Ag3Tl2Mo15Se19. This compound adopts a crystal structure described in the rhombohedral R3 c space group [ a = 9.9601(1) Å, c = 57.3025(8) Å, and Z = 6] built by the covalent arrangement of octahedral Mo6 and bioctahedral Mo9 clusters in a 1:1 ratio, with the Ag and Tl atoms filling the large cavities between them. Transport property measurements performed on polycrystalline samples indicate that this compound behaves as a heavily doped semiconductor with mixed electrical conduction. Electronic band structure calculations combined with a semiclassical approach using the Boltzmann transport equation are in good agreement with these measurements. This compound exhibits a lattice thermal conductivity as low as 0.4 W m-1 K-1 because of highly disordered Ag and Tl atoms. Because of the low thermopower values induced by the mixed electrical conduction, the dimensionless thermoelectric figure of merit ZT remains moderate with a peak value of 0.18 at 750 K.
RESUMEN
Tetrahedrites, a class of copper- and sulfur-rich minerals, exhibit inherently very low lattice thermal conductivity and adjustable electronic properties that make them interesting candidates for thermoelectric applications. Here, we investigate the influence of isovalent As substitution on the Sb site on the structural and transport properties (5-700 K) of the two solid solutions Cu12Sb4-xAsxS13 and Cu10Co2Sb4-yAsyS13 (0 ≤ x, y ≤ 4). Electronic band structure calculations predict that As has only a weak influence on the valence bands and hence, on the p-type metallic character of Cu12Sb4S13. In agreement with these predictions, all the samples of the series Cu12Sb4-xAsxS13 exhibit p-type metallic behavior with relatively low electrical resistivity and moderate thermopower values that only slightly evolve with the As content. In contrast, the substitution of Co for Cu in As-rich samples seems less favorable as suggested by a decrease in the Co concentration with increasing the As content. This trend leads to a concomitant increase in the electrical resistivity and thermopower leaving the ZT values practically unchanged with respect to purely Cu-based samples. As a result, peak ZT values ranging between 0.60 and 0.75 are achieved at 700 K for both series. The lack of significant variations in the ZT values confirms the robustness of the thermoelectric performances of tetrahedrites with respect to variations in the Sb-to-As ratio.
RESUMEN
We report on the inelastic response of the homologous compounds (PbSe)5(Bi2Se3)3m for m = 1, 2 and 3 followed in a broad temperature range (50-500 K) using high-resolution powder inelastic neutron scattering experiments. These results are complemented by low-temperature measurements of the specific heat (2-300 K). The evolution of the anisotropic crystal structure of these compounds with varying m, built from alternate Pb-Se and mBi-Se layers, only weakly influences the generalized phonon density of states. In all the three compounds, intense inelastic signals, likely mainly associated with the dynamics of the Pb atoms, are observed in the 4.5-6 meV low-energy range. The response of these low-energy modes to temperature variations indicates a conventional quasi-harmonic behavior over the whole temperature range investigated. The modes located above 8 meV show a minor temperature effect regardless of the value of m. The low-energy excess of vibrational modes manifests itself in the low-temperature specific heat as a pronounced peak in the Cp(T)/T3 data near 10 K. The lack of significant anharmonicity beyond that associated with the thermal expansion of the lattice suggests that the inherent disorder in the monoclinic unit cell and scattering at interlayer interfaces are the most important ingredients that limit the heat transport in this series of compounds.
RESUMEN
Distortion of the density of states by an impurity-induced resonant level has been shown to provide an effective strategy to improve the thermoelectric performance of semiconductors such as Bi2Te3, PbTe or SnTe. Here, combining first-principles calculations and transport property measurements, we demonstrate that Sn is a resonant impurity that distorts the valence band edge in p-type ß-As2Te3. This remarkable effect is characterized as a prominent, sharp peak in the electronic density of states near the Fermi level. To illustrate the particular influence of Sn on the thermopower of ß-As2Te3, the theoretical Ioffe-Pisarenko curve, computed within the Boltzmann transport theory, is compared with the experimental results obtained on three series of polycrystalline samples with substitution of Ga and Bi for As and I for Te. While Ga and I behave as conventional, rigid-band-like dopants and follow theoretical predictions, Sn results in significant deviations from the theoretical curve with a clear enhancement of the thermopower. Both electronic band structure calculations and transport property measurements provide conclusive evidence that this enhancement and hence, the good thermoelectric performances achieved at mid temperatures in ß-As2-xSnxTe3 can be attributed to a resonant level induced by Sn atoms. The possibility to induce resonant states in the electronic band structure of ß-As2Te3 opens new avenues to further optimize its thermoelectric performance.
RESUMEN
The crystal structure and transport properties (2-723 K) of the homologous compound Pb5Bi6Se14 with partial substitution of Te for Se are studied by means of powder X-ray diffraction, scanning electron microscopy, electrical resistivity, thermopower, thermal conductivity and Hall effect measurements. Polycrystalline samples of Pb5Bi6Se14-xTex (0 ≤ x ≤ 1.0) were prepared by a two-step synthesis method based on the pseudo-binary PbSe-Bi2Se3 phase diagram combined with Te substitution in the PbSe precursor. The successful insertion of Te into the crystal structure of Pb5Bi6Se14 was confirmed by powder X-ray diffraction and scanning electron microscopy. Transport property measurements indicate an increase in the heavily doped character of the transport with increasing the Te concentration. The extremely low lattice thermal conductivity values (0.3-0.4 W m-1 K-1 at 723 K) that approach the glassy limit at high temperatures are nearly independent of the chemical composition suggesting no influence on point-defect scattering mechanisms in the substituted compounds. Despite the inherent complexity of this system, the evolution of the electronic properties with x is well described by a simple single-parabolic band model. Because the increase in the power factor with increasing x is compensated by the concomitant increase in the electronic thermal conductivity, this substitution does not yield enhanced ZT values with respect to the pristine compound with a similar peak ZT value of 0.5 achieved at 723 K. Nevertheless, the simple synthetic method used in this study to insert a doping element opens new avenues for controlling the transport properties of the homologous series (PbSe)5(Bi2Se3)3m (m = 1, 2 and 3).
RESUMEN
We report on a detailed investigation of the crystal structure and transport properties in a broad temperature range (2-723 K) of the homologous compounds (PbSe)5(Bi2Se3)3m for m = 2, 3. Single-crystal X-ray diffraction data indicate that the m = 2, 3 compounds crystallize in the monoclinic space groups C2/m (No. 12) and P21/m (No. 11), respectively. In agreement with diffraction data, high-resolution transmission electron microscopy analyses carried out on single crystals show that the three-dimensional crystal structures are built from alternating Pb-Se and m Bi-Se layers stacked along the a axis in both compounds. Scanning electron microcopy and electron-probe microanalyses reveal deviations from the nominal stoichiometry, suggesting a domain of existence in the pseudo binary phase diagram at 873 K. The complex atomic-scale structures of these compounds lead to very low lattice thermal conductivities κL that approach the glassy limit at high temperatures. A comparison of the κL values across this series unveiled an unexpected increase with increasing m from m = 1 to m = 3, in contrast to the expectation that increasing the structural complexity should tend to lower the thermal transport. This result points to a decisive role played by the Pb-Se/Bi-Se interfaces in limiting κL in this series. Both compounds behave as heavily doped n-type semiconductors with relatively low electrical resistivity and thermopower values. As a result, moderate peak ZT values of 0.25 and 0.20 at 700 K were achieved in the m = 2, 3 compounds, respectively. The inherent poor ability of these structures to conduct heat suggests that these homologous compounds may show interesting thermoelectric properties when properly optimized by extrinsic dopants.
RESUMEN
Recrystallization of amorphous compounds can lead to the stabilization of metastable crystalline phases, which offers an interesting way to unveil novel binary or ternary compounds and control the transport properties of the obtained glass ceramics. Here, we report on a systematic study of the Cu-As-Te glassy system and show that under specific synthesis conditions using the spark-plasma-sintering technique, the α-As2Te3 and ß-As2Te3 binary phases and the previously unreported AsTe3 phase can be selectively crystallized within an amorphous matrix. The microstructures and transport properties of three different glass ceramics, each of them containing one of these phases with roughly the same crystalline fraction (â¼30% in volume), were investigated in detail by means of X-ray diffraction, scanning electron microscopy, neutron thermodiffraction, Raman scattering (experimental and lattice-dynamics calculations), and transport-property measurements. The physical properties of the glass ceramics are compared with those of both the parent glasses and the pure crystalline phases that could be successfully synthesized. SEM images coupled with Raman spectroscopy evidence a "coast-to-island" or dendriticlike microstructure with microsized crystallites. The presence of the crystallized phase results in a significant decrease in the electrical resistivity while maintaining the thermal conductivity to low values. This study demonstrates that new compounds with interesting transport properties can be obtained by recrystallization, which in turn provides a tuning parameter for the transport properties of the parent glasses.
RESUMEN
Mo-based cluster compounds are promising candidates for thermoelectric applications at high temperatures due to their very low lattice thermal conductivity values. Here, we report on a detailed investigation of the crystal structure and transport properties measured in a wide range of temperatures (2-800 K) of polycrystalline Ag3RbMo9Se11. Single-crystal X-ray diffraction shows that this compound crystallizes in the hexagonal space group P63/m. The crystal structure is formed by stacked Mo9Se11 units leaving channels that are randomly filled by Rb+ cations, while Ag+ cations are located between the Mo9Se11 units. The high disorder in the unit cell induced by these atoms and their large anisotropic thermal displacement parameters are two key characteristics that lead to very low lattice thermal conductivity as low as 0.6 W m-1 K-1 at 800 K. The combination of semiconducting-like electrical properties and low ability to transport heat leads to a maximum dimensionless thermoelectric figure of merit ZT of 0.4 at 800 K.
RESUMEN
We report on the influence of Se substitution on the electronic band structure and thermoelectric properties (5-523 K) of the solid solution α-As2Te3-xSex (0 ≤ x ≤ 1.5). All of the polycrystalline compounds α-As2Te3-xSex crystallize isostructurally in the monoclinic space group C2/m (No. 12, Z = 4). Regardless of the Se content, chemical analyses performed by scanning electron microscopy and electron probe microanalysis indicate a good chemical homogeneity, with only minute amounts of secondary phases for some compositions. In agreement with electronic band structure calculations, neutron powder diffraction suggests that Se does not randomly substitute for Te but exhibits a site preference. These theoretical calculations further predict a monotonic increase in the band gap energy with the Se content, which is confirmed experimentally by absorption spectroscopy measurements. Increasing x up to x = 1.5 leaves unchanged both the p-type character and semiconducting nature of α-As2Te3. The electrical resistivity and thermopower gradually increase with x as a result of the progressive increase in the band gap energy. Despite the fact that α-As2Te3 exhibits very low lattice thermal conductivity κL, the substitution of Se for Te further lowers κL to 0.35 W m-1 K-1 at 300 K. The compositional dependence of the lattice thermal conductivity closely follows classical models of phonon alloy scattering, indicating that this decrease is due to enhanced point-defect scattering.
RESUMEN
SnTe has been the focus of numerous experimental and theoretical studies over the last years owing to its high thermoelectric performances near 800 K when appropriately doped. Here, we demonstrate that melt-spinning, an ultrafast-quenching synthesis technique, followed by spark plasma sintering results in enhanced ZT values in polycrystalline SnTe. To illustrate the impact of this technique, the results are contrasted with those obtained on two polycrystalline samples prepared by direct quenching of molten SnTe and without quenching. SnTe melt-spun ribbons are characterized by a peculiar columnar microstructure that contributes to lower the lattice thermal conductivity below 700 K in pressed samples. More importantly, this technique results in a significant decrease in the hole concentration, giving rise to enhanced thermopower values above 500 K. The variation in the hole concentration is likely due to a slight loss of elemental Te during the melt-spinning process. Thanks to the decreased hole concentration, the thermoelectric performances are significantly enhanced with a peak ZT value of 0.6 at 800 K, which represents a 40% increase over the values measured for samples prepared with and without quenching. These findings indicate that melt-spinning provides a novel strategy to improve the thermoelectric properties of SnTe that could be worthwhile extending to substituted compounds.
RESUMEN
Mo-based cluster compounds are promising materials for high-temperature thermoelectric applications due to their intrinsic, extremely low thermal conductivity values. In this study, polycrystalline cluster compounds Cs2CuxMo12Se14 were prepared for a wide range of Cu contents (0 ≤ x ≤ 2). All samples crystallize isostructurally in the trigonal space group R3Ì . The position of the Cu atoms in the unit cell was determined by X-ray diffraction on a single-crystalline specimen indicating that these atoms fill the empty space between the Mo-Se clusters. Density functional theory calculations predict a metallic ground state for all compositions, in good agreement with the experimental findings. Magnetization measurements indicate a rapid suppression of the superconducting state that develops in the x = 0.0 sample upon Cu insertion. Transport properties measurements, performed in a wide temperature range (2-630 K) on the two end-member compounds x = 0 and x = 2, revealed a multiband electrical conduction as shown by sign reversal of the thermopower as a function of temperature.
RESUMEN
The ratio of the Zeeman splitting to the cyclotron energy (M=ΔE_{Z}/âω_{c}) for holelike carriers in bismuth has been quantified with great precision by many experiments performed during the past five decades. It exceeds 2 when the magnetic field is along the trigonal axis and vanishes in the perpendicular configuration. Theoretically, however, M is expected to be isotropic and equal to unity in a two-band Dirac model. We argue that a solution to this half-a-century-old puzzle can be found by extending the k·p theory to multiple bands. Our model not only gives a quantitative account of the magnitude and anisotropy of M for holelike carriers in bismuth, but also explains its contrasting evolution with antimony doping and pressure, both probed by new experiments reported here. The present results have important implications for the magnitude and anisotropy of M in other systems with strong spin-orbit coupling.
RESUMEN
Metastable ß-As2Te3 (R3Ì m, a = 4.047 Å and c = 29.492 Å at 300 K) is isostructural to layered Bi2Te3 and is known for similarly displaying good thermoelectric properties around 400 K. Crystallizing glassy-As2Te3 leads to multiphase samples, while ß-As2Te3 could indeed be synthesized with good phase purity (97%) by melt quenching. As expected, ß-As2Te3 reconstructively transforms into stable α-As2Te3 (C2/m, a = 14.337 Å, b = 4.015 Å, c = 9.887 Å, and ß = 95.06°) at 480 K. This ß â α transformation can be seen as the displacement of part of the As atoms from their As2Te3 layers into the van der Waals bonding interspace. Upon cooling, ß-As2Te3 displacively transforms in two steps below T(S1) = 205-210 K and T(S2) = 193-197 K into a new ß'-As2Te3 allotrope. These reversible and first-order phase transitions give rise to anomalies in the resistance and in the calorimetry measurements. The new monoclinic ß'-As2Te3 crystal structure (P2(1)/m, a = 6.982 Å, b = 16.187 Å, c = 10.232 Å, ß = 103.46° at 20 K) was solved from Rietveld refinements of X-ray and neutron powder patterns collected at low temperatures. These analyses showed that the distortion undergone by ß-As2Te3 is accompanied by a 4-fold modulation along its b axis. In agreement with our experimental results, electronic structure calculations indicate that all three structures are semiconducting with the α-phase being the most stable one and the ß'-phase being more stable than the ß-phase. These calculations also confirm the occurrence of a van der Waals interspace between covalently bonded As2Te3 layers in all three structures.