To save content items to your account,
please confirm that you agree to abide by our usage policies.
If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account.
Find out more about saving content to .
To save content items to your Kindle, first ensure firstname.lastname@example.org
is added to your Approved Personal Document E-mail List under your Personal Document Settings
on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part
of your Kindle email address below.
Find out more about saving to your Kindle.
Note you can select to save to either the @free.kindle.com or @kindle.com variations.
‘@free.kindle.com’ emails are free but can only be saved to your device when it is connected to wi-fi.
‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.
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.