The past two decades have witnessed the rapid growth of thermoelectric (TE) research. Novel concepts and paradigms are described here that have emerged, targeting superior TE materials and higher TE performance. These superior aspects include band convergence, "phonon-glass electron-crystal", multiscale phonon scattering, resonant states, anharmonicity, etc. Based on these concepts, some new TE materials with distinct features have been identified, including solids with high band degeneracy, with cages in which atoms rattle, with nanostructures at various length scales, etc. In addition, the performance of classical materials has been improved remarkably. However, the figure of merit zT of most TE materials is still lower than 2.0, generally around 1.0, due to interrelated TE properties. In order to realize an "overall zT > 2.0," it is imperative that the interrelated properties are decoupled more thoroughly, or new degrees of freedom are added to the overall optimization problem. The electrical and thermal transport must be synergistically optimized. Here, a detailed discussion about the commonly adopted strategies to optimize individual TE properties is presented. Then, four main compromises between the TE properties are elaborated from the point of view of the underlying mechanisms and decoupling strategies. Finally, some representative systems of synergistic optimization are also presented, which can serve as references for other TE materials. In conclusion, some of the newest ideas for the future are discussed.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/adma.201702816

Compromise and Synergy in High-Efficiency Thermoelectric Materials.

▪ Abstract Recently there has been a resurgence of research efforts related to the investigation of new and novel materials for small-scale thermoelectric refrigeration and power generation applications. These materials need to couple and optimize a variety of properties in order to exhibit the necessary figure of merit, i.e. the numerical expression that is commonly used to compare one potential thermoelectric material with another. The figure of merit is related to the coefficient of performance or efficiency of a particular device made from a material. The best thermoelectric material should possess thermal properties similar to that of a glass and electrical properties similar to that of a perfect single-crystal material, i.e. a poor thermal conductor and a good electrical conductor. Skutterudites are materials that appear to have the potential to fulfill such criteria. These materials exhibit many types of interesting properties. For example, skutterudites are members of a family of compounds we call...

SKUTTERUDITES : A phonon-glass-electron crystal approach to advanced thermoelectric energy conversion applications

Kesterite-based solar cells are attracting considerable attention in recent years, owing to the reduced toxicity and greater abundance of their constituent elements. In this brief review, we discuss the current status of this important technology by focusing on three key aspects of the device: (i) the interface between the kesterite absorber and the Mo back contact, (ii) the kesterite absorber bulk defects and grain boundaries and (iii) the interface between the kesterite absorber and the buffer layer. By identifying key issues to be addressed, we provide suggestions for their potential improvement and future research. Copyright © 2016 John Wiley & Sons, Ltd.

The current status and future prospects of kesterite solar cells: a brief review

Publisher Summary This chapter describes the relevant physical, chemical, and materials issues pertaining to skutterudites and includes the latest exciting developments. As the search for novel, promising thermoelectrics intensifies; skutterudites have emerged as prospective candidates for achieving figures of merit well in excess of unity. The name “skutterudite” is derived from a small mining town in Norway called “Skutterud,” where a CoAs3-based mineral had been mined extensively. The compounds identical in structure to CoAs3—the structures first identified by Oftedal in 1928—have since been known as skutterudites. Skutterudite structure offers interesting possibilities to alter both the electronic and lattice properties. The chapter discusses the structural aspects and bonding of binary skutterudites and filled skutterudites. The inability to prepare pure binary skutterudites with transition metals other than those of the Co group does not mean that cobalt cannot be partially replaced by its immediate neighbors in the periodic table—iron and nickel. The lattice thermal conductivity is one of the key parameters determining the thermoelectric figure of merit. It is, thus, essential to understand the lattice dynamics in skutterudites and to have a good grasp of the phonon density of states. Skutterudites are compounds with the highest pnicogen concentration forming stable compounds with Co, Rh, and Ir at ambient conditions. The fundamental point about the binary skutterudites is that they are diamagnetic solids.

Chapter 5 Skutterudites: Prospective novel thermoelectrics

Photovoltaic thin film solar cells based on kesterite Cu2ZnSn(Sx,Se1–x)4 compounds (CZTSSe) have reached >12% sunlight-to-electricity conversion efficiency. This is still far from the >20% record devices known in Cu(In1–y,Gay)Se2 and CdTe parent technologies. A selection of >9% CZTSSe devices reported in the literature is examined to review the progress achieved over the past few years. These devices suffer from a low open-circuit voltage (Voc) never better than 60% of the Voc max, which is expected from the Shockley-Queisser radiative limit (S-Q limit). The possible role of anionic (S/Se) distribution and of cationic (Cu/Zn) disorder on the Voc deficit and on the ultimate photovoltaic performance of kesterite devices, are clarified here. While the S/Se anionic distribution is expected to be homogeneous for any ratio x, some grain-to-grain and other non-uniformity over larger area can be found, as quantified on our CZTSSe films. Nevertheless, these anionic distributions can be considered to have a negligible impact on the Voc deficit. On the Cu/Zn order side, even though significant bandgap changes (>10%) can be observed, a similar conclusion is brought from experimental devices and from calculations, still within the radiative S-Q limit. The implications and future ways for improvement are discussed.

Is the Cu/Zn disorder the main culprit for the voltage deficit in kesterite solar cells?

Cu${}_{2}$ZnSnS${}_{4}$ single crystals prepared by the chemical vapor transport technique were investigated by x-ray diffraction, chemical microprobe analysis, and Raman and photoluminescence spectroscopies. Single-crystal x-ray measurements show that Cu${}_{2}$ZnSnS${}_{4}$ crystallizes in the kesterite structure with the space group $I\overline{4}$ and unit cell parameters a = 5.4174(2) and c = 10.7903(7) $\AA{}$ at 150 K. Photoluminescence measurements show one broad asymmetric band peaked at 1.29 eV at low temperature. Temperature and excitation intensity dependencies of the luminescence band indicate that the transition is due to a free-to-bound recombination with an activation energy of 140 meV. We attribute this activation energy to the intrinsic acceptor-type Cu${}_{\mathrm{Zn}}$ antisite defect in close agreement with results from density-functional theory. It is shown that by a detailed analysis of the temperature dependence of the free-to-bound luminescence transition the majority carrier density can be deduced, which in our case is estimated at $\mathrm{p}\ensuremath{\approx}{10}^{16}$ cm${}^{\ensuremath{-}3}$.

Free-to-bound recombination in near stoichiometric Cu 2 ZnSnS 4 single crystals

Transport properties of lightly doped CoSb 3 single crystals

We report upper critical field Bc2(T) data for LaO0.9F0.1FeAs1- δ in a wide temperature and field range up to 60 T. The large slope of Bc2≈- 5.4 to -6.6 T K-1 near an improved Tc≈28.5 K of the in-plane Bc2(T) contrasts with a flattening starting near 23 K above 30 T we regard as the onset of Pauli-limited behaviour (PLB) with Bc2(0)≈63–68 T. We interpret a similar hitherto unexplained flattening of the Bc2(T) curves reported for at least three other disordered closely related systems, Co-doped BaFe2As2, (Ba,K) Fe2As2 and NdO0.7F0.3FeAs (all single crystals), for applied fields H∥(a,b), also as a manifestation of PLB. Their Maki parameters have been estimated by analysing their Bc2(T) data within the Werthamer–Helfand–Hohenberg approach. The pronounced PLB of (Ba, K)Fe2As2 single crystals obtained from an Sn flux is attributed also to a significant As deficiency detected by wavelength dispersive x-ray spectroscopy as reported by Ni et al (2008 Phys. Rev. B 78 014507). Consequences of our results are discussed in terms of disorder effects within conventional superconductivity (CSC) and unconventional superconductivity (USC). USC scenarios with nodes on individual Fermi surface sheets (FSS), e.g. p- and d-wave SC, can be discarded for our samples. The increase of dBc2/dT|Tc by sizeable disorder provides evidence for an important intraband (intra-FSS) contribution to the orbital upper critical field. We suggest that it can be ascribed either to an impurity-driven transition from s± USC to CSC of an extended s++-wave state or to a stabilized s±-state provided As-vacancies cause predominantly strong intraband scattering in the unitary limit. We compare our results with Bc2 data from the literature, which often show no PLB for fields below 60–70 T probed so far. A novel disorder-related scenario of a complex interplay of SC with two different competing magnetic instabilities is suggested.

/pdf/orbital-and-spin-effects-for-the-upper-critical-field-in-as-4ftq7gbe29.pdf

Orbital and spin effects for the upper critical field in As-deficient disordered Fe pnictide superconductors

We report B_c2 data for LaO_{0.9}F_{0.1}FeAs_{1-delta} in a wide T and field range up to 60 Tesla. The large slope of B_c2 approx ~ -6 Tesla/K near an improved T_c = 28.5 K of the in-plane B_c2(T) contrasts with a flattening starting at 23 K above 30 Tesla we regard as the onset of Pauli-limited behavior (PLB) with B_c2(0) about 65 Tesla. We interpret a similar hitherto unexplained flattening of the B_c2(T) curves reported for at least three other disordered closely related systems as also as a manifestation of PLB. Their Maki parameters have been estimated analyzing their B_c2(T) data within the WHH approach. The pronounced PLB of (Ba,K)Fe_2As_2 single crystals from a tin-flux is attributed also to a significant As deficiency. Consequences of our results are discussed in terms of disorder effects within conventional (CSC) and unconventional superconductivity (USC). USC scenarios with nodes on individual Fermi surface sheets (FSS), can be discarded for our samples. The increase of dB_c2/dT|_{T_c} by sizeable disorder provides evidence for an important intraband (intra-FSS) contribution to the orbital upper critical field. We suggest that it can be ascribed either to an impurity driven transition from s_{+-} USC to CSC of an extended s_{++}-wave state or to a stabilized s_{+-}-state provided As-vacancies cause predominantly strong intraband scattering in the unitary limit. We compare our results with B_c2 data from the literature with no PLB for fields below 60 to 70 Tesla probed so far. A novel disorder related scenario of a complex interplay of SC with two different competing magnetic instabilities is suggested.

E. Arushanov

Papers

Free-to-bound recombination in near stoichiometric Cu 2 ZnSnS 4 single crystals

Transport properties of lightly doped CoSb 3 single crystals

Orbital and spin effects for the upper critical field in As-deficient disordered Fe pnictide superconductors

Orbital and spin effects for the upper critical field in As deficient disordered Fe pnictide superconductors

Crystal growth and characterization of II3V2 compounds