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The presence of 6s2 (5s2) lone-pair electrons on the B-site Pb (Sn) in all-inorganic and hybrid halide ABX3 perovskites distinguishes these materials from the familiar tetrahedral semiconductors traditionally employed in optoelectronics and is key to many of their appealing properties. These electrons are stereochemically active, albeit often in a hidden fashion, resulting in unusual and highly anharmonic lattice dynamics that are linked to many of the special optoelectronic properties displayed by this material class. This article describes the connections between this atypical electronic configuration and the electronic structure and lattice dynamics of these compounds. We illustrate how the lone pair leads to favorable bandwidths and band alignments, mobile holes, large ionic dielectric response, large positive thermal expansion, and even possibly defect-tolerant electronic transport. Taken together, the evidence suggests that other high-performing semiconductors may be found among compounds with lone-pair-bearing cations in high symmetry environments and a high degree of connectivity between atoms.
Metal chalcogenides have attracted great attention because of their broad applications. It has been well acknowledged that microstructure can alter the intrinsic properties and performance of metal chalcogenides. The structure–property–performance relationships can be investigated at atomic scale with scanning transmission and transmission electron microscopy (STEM and TEM). Nevertheless, careful specimen preparation is paramount for accurate analyses and interpretations. In this work, we compare the effects of a variety of well-established TEM specimen preparation methods on the observed microstructure of an ingot stoichiometric lead telluride (PbTe). Most importantly, from aberration corrected STEM and first principles calculations, we discovered that argon (Ar) ion milling can lead to surface irradiation damage in the form of Pb vacancy clusters and self-interstitial atom (SIA) clusters. The SIA clusters appear as orthogonal nanoscale features when characterized along the <001> crystal orientation of the rock salt structured PbTe. This obfuscates the interpretation of the intrinsic microstructure of metal chalcogenides, especially lead chalcogenides. We demonstrate that with sufficiently low energy (300 eV) Ar ion cleaning or appropriate high-temperature annealing, the surface damage layer can be properly cleaned and the orthogonal nanoscale features are significantly reduced. This reveals the materials’ intrinsic structure and can be used as the standard protocol for future TEM specimen preparation of lead-based chalcogenide materials.
With more than two-thirds of utilized energy being lost as waste heat, there is compelling motivation for high-performance thermoelectric materials that can directly convert heat to electrical energy. However, over the decades, practical realization of thermoelectric materials has been limited by the hitherto low figure of merit, ZT, which governs the Carnot efficiency. This article describes our long-standing efforts to advance ZT to record levels starting from exploratory synthesis and evolving into the nanostructuring and panoscopic paradigm, which has helped to usher in a new era of investigation for thermoelectrics. The term panoscopic is meant as an attempt to integrate all length scales and multiple physical concepts into a single material. As in any other energy-conversion technology involving materials, thermoelectrics research is a challenging exercise in taming “contra-indicated” properties. Critical properties such as high electrical conductivity, thermoelectric power, low thermal conductivity, and mechanical strength do not tend to favor coexistence in a single material. How these can be achieved in certain systems leading to record values of ZT is also described. Endotaxial nanostructures and mesoscale engineering in thermoelectrics enable effective phonon scattering with negligible electron scattering. By combining all relevant length scales hierarchically, we can achieve large enhancements in thermoelectric performance. The field, however, continues to produce surprises.
We investigated the valence band structure of PbSe by a combined study of the optical and transport properties of p-type Pb1-xNaxSe, with Na concentrations ranging from 0 – 4%, yielding carrier densities in a wide range of 1018 – 1020 cm−3. Room temperature infrared reflectivity studies showed that the susceptibility (or conductivity) effective mass m* increases from ∼ 0.06mo to ∼ 0.5mo on increasing Na content from 0.08% to 3%. The Seebeck coefficient scales with doping in the whole temperature range, yielding lower values for higher Na contents, while the Hall coefficient increases on heating from room temperature showing a peak close to 650 K. The room temperature Pisarenko plot is well described by the simple parabolic band model up to ∼ 1·1020 cm−3. In order to describe the behaviour in the whole concentration range, the application of the two band model, i.e. light hole and heavy hole, was used giving density of states effective masses 0.28mo and 2.5mo for the two bands respectively.
The application of micro-fourier transform infrared (FTIR) mapping analysis to thermoelectric materials towards identification of doping inhomogeneities is described. Micro-FTIR, in conjunction with fitting, is used as analytical tool for probing carrier content gradients. The plasmon frequency ωP2 was studied as potential effective probe for carrier inhomogeneity and consequently doping differentiation based on its dependence of the carrier concentration. The method was applied to PbTe-, PbSe- and Mg2Si- based thermoelectric materials.
PbTe-PbS materials are promising for thermoelectric power generation applications. For the composition of (Pb0.95Sn0.05Te)0.92(PbS)0.08 nanostructuring from nucleation and growth and spinodal decomposition has been reported along with thermal conductivity of approximately 1.1 W/m·K at 650 K . Based on temperature-dependent measurements of electrical conductivity, thermopower, and thermal conductivity, the thermoelectric figure of merit, ZT, are ~1.5 at 650 K for cast ingots.
To develop larger quantities of material for device fabrication, advancement in the synthesis, processing and production of (Pb0.95Sn0.05Te)0.92(PbS)0.08 is necessary. Powder processing of samples is a well-known technique for increasing sample strength, and uniformity. In this presentation, we show sample fabrication and processing details of pulsed electric current sintering (PECS) processed (Pb0.95Sn0.05Te)0.92(PbS)0.08 materials and their thermoelectric properties along with the latest advancements in the preparation of these materials.
We address the issue of decreasing band-gap with increasing atomic number, inherent in semiconducting materials, by introducing a concept we call dimensional reduction. The concept leads to semiconductor compounds containing high atomic number elements and simultaneously exhibiting a large band gap and high mass density suggesting that dimensional reduction can be successfully employed in developing new γ-ray detecting materials. As an example we discuss the compound Cs2Hg6S7 that exhibits a band-gap of 1.65eV and mobility-lifetime products comparable to those of optimized Cd0.9Zn0.1Te.
In this work we report on the infrared properties of the thermoelectric (1-x)PbTe-xPbSnS2 system with x=0.03, 0.06, 0.11 and 0.33. The results obtained by the analysis of the reflectivity spectra are discussed together with the structural and morphological characteristics obtained by XRD and SEM-EDS measurements. The system was found macroscopically homogeneous for x=0.03 and x=0.06 and phase separated for x=0.11 and x=0.33. The analyzed ~150cm-1 PbS impurity mode demonstrated a composition close to the PbTe0.98S0.02 for the major phase. The incorporation of PbSnS2 causes a reduction in plasma frequency (decrease in carrier frequency concentration) and an increase in carrier mobility.
We have shown that (Pb1-mSnmTe)1-x(PbS)x where m = 0.05 and x = 0.08 exhibits a ZT of ˜1.4 at 700 K. This system incorporates two thermoelectric systems: PbSxTe1-x and Pb1-xSnxTe. Here we report the thermoelectric properties of PbSxTe1-x (x = 0.08 and 0.30). The material PbS0.08Te0.92 exhibits nucleation and growth of PbS precipitates, while PbS0.30Te0.70 exhibits PbS precipitation through spinodal decomposition phase separation. We report the thermoelectric properties of this system as a result of the differing precipitation phenomena.
We previously reported the synthesis of nanostructured composite PbTe with excess Pb and Sb metal inclusions. The electrical conductivity shows an unusual temperature dependence that depends on the inclusion Pb/Sb ratio, resulting in marked enhancements in power factor and ZT at 700 K. Additional investigation of the transport and structure of these materials is reported here. Measurements of the scattering parameter reveals there is little change in electron scattering with respect to pure PbTe. High resolution electron microscopy was used to determine additional information about the nature of the precipitate phases present in the samples. High temperature transmission electron microscopy reveals that the precipitates begin to dissolve at high temperatures and completely disappear at T > 619K. A qualitative explanation of the unusual transport behavior of these materials is presented.
Solid solutions of β-K2Bi8-xSbxSe13 are an interesting series of materials for thermoelectric investigations due to their very low thermal conductivity and highly anisotropic electrical properties. In this work, we aimed to synthesize solid solutions of β-K2Bi8-xSbxSe13 type materials using powder techniques. The synthesis was based on mechanical alloying as well as sintering procedures. The products were studied in terms of structural features, composition and purity with powder x-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Preliminary results on thermoelectric properties as well as IR reflectivity measurements are presented.
We performed comparative investigations of the Ag1-xPb18MTe20 (M = Bi, Sb) (x = 0, 0.14, 0.3) system to better understand the roles of Sb and Bi on the thermoelectric properties. In both systems, the electrical conductivity nearly keeps the same values, while the Seebeck coefficient decreases dramatically in going from Sb to Bi. Compared to the lattice thermal conductivity of PbTe, that of AgPb18BiTe20 is substantially reduced. The lattice thermal conductivity of the Bi analog, however, is higher than that of AgPb18SbTe20 and this is attributed largely to the decrease in the degree of mass fluctuation between the nanostructures and the matrix (for the Bi analog). As a result the dimensionless figure of merit ZT of Ag1-xPb18MTe20 (M = Bi) is found to be smaller than that of Ag1-xPb18MTe20 (M = Sb).