Discovery of Self-Assembled 2D Ru/Si Superlattices Boosting Hydrogen Evolution.

2D heterostructuring is a versatile methodology for designing nanoarchitecture catalytic systems that allow for reconstruction and modulation of interfaces and electronic structures. However, catalysts with such structures are extremely scarce due to limited synthetic strategies. Here, a highly ordered 2D Ru/Si/Ru/Si… nano-heterostructures (RSHS) is reported by acid etching of the LaRuSi electride. RSHS shows a superior electrocatalytic activity for hydrogen evolution with an overpotential of 14 mV at 10 mA cm-2 in alkaline media. Both experimental analysis and first-principles calculations demonstrate that the electronic states of Ru can be tuned by strong interactions of the interfacial Ru-Si, leading to an optimized hydrogen adsorption energy. Moreover, due to the synergistic effect of Ru and Si, the energy barrier of water dissociation is significantly reduced. The well-organized superlattice structure will provide a paradigm for construction of efficient catalysts with tunable electronic states and dual active sites.

Design, Synthesis, and Optoelectronic Properties of the High-Purity Phase in Layered AETMN2 (AE = Sr, Ba; TM = Ti, Zr, Hf) Semiconductors.

We report the synthesis and optoelectronic properties of high phase-purity (>94 mol %) bulk polycrystals of KCoO2-type layered nitrides AETMN2 (AE = Sr, Ba; and TM = Ti, Zr, Hf), which are expected to exhibit unique electron transport properties originating from their natural two-dimensional (2D) electronic structure, but high-purity intrinsic samples have yet been reported. The bulks were synthesized using a solid-state reaction between AENH and TMN precursors with NaN3 to achieve high N chemical potential during the reaction. The AETMN2 bulks are n-type semiconductors with optical band gaps of 1.63 eV for SrTiN2, 1.97 eV for BaZrN2, and 2.17 eV for BaHfN2. SrTiN2 and BaZrN2 bulks show degenerated electron conduction due to the natural high-density electron doping and paramagnetic behavior in all of the temperature ranges examined, while such unintentional carrier generation is largely suppressed in BaHfN2, which exhibits nondegenerated electron conduction. The BaHfN2 sample also exhibits weak ferromagnetic behavior at temperatures lower than 35 K. Density functional theory calculations suggest that the high-density electron carriers in SrTiN2 come from oxygen impurity substitution at the N site (ON) acting as a shallow donor even if the high-N chemical potential synthesis conditions are employed. On the other hand, the formation energy of ON becomes larger in BaHfN2 because of the stronger TM-N chemical bonds. Present results demonstrate that the easiness of impurity incorporation is designed by density functional calculations to produce a more intrinsic semiconductor in wider chemical conditions, opening a way to cultivating novel functional materials that are sensitive to atmospheric impurities and defects.

Large phonon drag thermopower boosted by massive electrons and phonon leaking in LaAlO3/LaNiO3/LaAlO3 heterostructure.

An unusually large thermopower (S) enhancement is induced by heterostructuring thin films of the strongly correlated electron oxide LaNiO3. The phonon-drag effect, which is not observed in bulk LaNiO3, enhances S for thin films compressively strained by LaAlO3 substrates. By a reduction in the layer thickness down to three unit cells and subsequent LaAlO3 surface termination, a 10 times S enhancement over the bulk value is observed due to large phonon drag S (Sg), and the Sg contribution to the total S occurs over a much wider temperature range up to 220 K. The Sg enhancement originates from the coupling of lattice vibration to the d electrons with large effective mass in the compressively strained ultrathin LaNiO3, and the electron-phonon interaction is largely enhanced by the phonon leakage from the LaAlO3 substrate and the capping layer. The transition-metal oxide heterostructures emerge as a new playground to manipulate electronic and phononic properties in the quest for high-performance thermoelectrics.

Ion Substitution Effect on Defect Formation in Two-Dimensional Transition Metal Nitride Semiconductors, AETiN2 (AE = Ca, Sr, and Ba).

A layered semiconductor, SrTiN2, has an interesting crystal structure as a two-dimensional (2D) electron system embedded in a three-dimensional bulk periodic structure because it has alternate stacking of a SrN blocking layer and a TiN conduction layer, in which the Ti 3dxy orbital forms the conduction band minimum (CBM) similar to the SrTiO3-based thin-film heterostructure. However, SrTiN2 has been reported to exhibit nearly degenerate conduction, but we reported that it would be due to the easy formation of nitrogen vacancies and oxygen impurities from air. In this paper, we extend the materials to family compounds, alkaline earth (AE) ion-substituted, AETiN2 (AE = Ca, Sr, and Ba), and investigated how we can suppress the defect formation by (hybrid) density functional theory calculations. All AETiN2 compounds possess thermodynamic stability in the wide nitrogen (N) chemical potential window. Especially, CaTiN2 is the most stable even against N-poor conditions. Unintentional carrier generation occurs due to the nitrogen vacancies (VN), oxygen substitution (ON), and hydrogen anion substitution (HN) at the nitrogen sites. The VN and HN impurities can be suppressed under N-moderate and N-rich conditions. The ON defect is easily formed in SrTiN2 and also in BaTiN2 under N-rich conditions, but its formation can be suppressed in CaTiN2. Present results suggest that high-purity CaTiN2 can be obtained under wider N chemical conditions, which would lead to the realization of the novel functional properties originating from Ti 3dxy 2D bands embedded in the bulk crystal structure.

Transparent amorphous oxide semiconductors for organic electronics: Application to inverted OLEDs.

Efficient electron transfer between a cathode and an active organic layer is one key to realizing high-performance organic devices, which require electron injection/transport materials with very low work functions. We developed two wide-bandgap amorphous (a-) oxide semiconductors, a-calcium aluminate electride (a-C12A7:e) and a-zinc silicate (a-ZSO). A-ZSO exhibits a low work function of 3.5 eV and high electron mobility of 1 cm2/(V · s); furthermore, it also forms an ohmic contact with not only conventional cathode materials but also anode materials. A-C12A7:e has an exceptionally low work function of 3.0 eV and is used to enhance the electron injection property from a-ZSO to an emission layer. The inverted electron-only and organic light-emitting diode (OLED) devices fabricated with these two materials exhibit excellent performance compared with the normal type with LiF/Al. This approach provides a solution to the problem of fabricating oxide thin-film transistor-driven OLEDs with both large size and high stability.

On the Origin of the Negative Thermal Expansion Behavior of YCu.

Among the intermetallics and alloys, YCu is an unusual material because it displays negative thermal expansion without spin ordering. The mechanism behind this behavior that is caused by the structural phase transition of YCu has yet to be fully understood. To gain insight into this mechanism, we experimentally examined the crystal structure of the low-temperature phase of YCu and discuss the origin of the phase transition with the aid of thermodynamics calculations. The result shows that the high-temperature (cubic CsCl-type) to low-temperature (orthorhombic FeB-type) structural phase transition is driven by the rearrangement of three covalent bonds, namely, Y-Cu, Y-Y, and Cu-Cu, which compete for the bonding energy and phonon entropy. At low temperatures, the mixing of Y and Cu does not take place easily because of the weak attractive force between these atoms expected from the small negative mixing enthalpy. This causes all three interactions to take part in the bonding, and Y and Cu are segregated to form an FeB-type structure, which is stabilized by internal energy. At higher temperatures, Cu ions are bound loosely with Y ions due to the large Y-Cu distance (3.01 Å), which results in large vibration entropy and stabilizes a CsCl-type crystal structure. In addition, the CsCl-type structure is reinforced by the Y-Y interaction between next-nearest neighbors, resulting in a smaller unit cell volume. The crystal structure has the simple cubic framework of Y containing Cu ions bound loosely at the cavity sites. The calculated frequency of the Y-like phonon modes is much higher than that of the Cu-like modes, indicating the presence of Y-Y covalent interactions in the CsCl-type phase.

Electric field-induced superconducting transition of insulating FeSe thin film at 35 K.

It is thought that strong electron correlation in an insulating parent phase would enhance a critical temperature (Tc) of superconductivity in a doped phase via enhancement of the binding energy of a Cooper pair as known in high-Tc cuprates. To induce a superconductor transition in an insulating phase, injection of a high density of carriers is needed (e.g., by impurity doping). An electric double-layer transistor (EDLT) with an ionic liquid gate insulator enables such a field-induced transition to be investigated and is expected to result in a high Tc because it is free from deterioration in structure and carrier transport that are in general caused by conventional carrier doping (e.g., chemical substitution). Here, for insulating epitaxial thin films (∼10 nm thick) of FeSe, we report a high Tc of 35 K, which is 4× higher than that of bulk FeSe, using an EDLT under application of a gate bias of +5.5 V. Hall effect measurements under the gate bias suggest that highly accumulated electron carrier in the channel, whose area density is estimated to be 1.4 × 10(15) cm(-2) (the average volume density of 1.7 × 10(21) cm(-3)), is the origin of the high-Tc superconductivity. This result demonstrates that EDLTs are useful tools to explore the ultimate Tc for insulating parent materials.

Bandgap Optimization of Perovskite Semiconductors for Photovoltaic Applications.

The bandgap is the most important physical property that determines the potential of semiconductors for photovoltaic (PV) applications. This Minireview discusses the parameters affecting the bandgap of perovskite semiconductors that are being widely studied for PV applications, and the recent progress in the optimization of the bandgaps of these materials. Perspectives are also provided for guiding future research in this area.

CsFe4-δSe4: A Compound Closely Related to Alkali-Intercalated FeSe Superconductors.

We report the synthesis and characterizations of a new FeSe-based compound CsFe4-δSe4, which is closely related to alkali intercalated FeSe superconductors while exhibits distinct features. It does not undergo phase separation and antiferromagnetic transition. Powder neutron diffractions, electron microscopy and high-angle annular-dark-field images confirm that CsFe4-δSe4 possesses an ordered Cs arrangement as √2 × âˆš2 superstructure, evidencing a B-centered orthorhombic lattice with a space group of Bmmm. The temperature-dependent powder neutron diffractions indicate no structural and magnetic transition from 320 to 5 K. In contrast to the symmetry-breaking in FeSe, this phase naturally possesses the orthorhombic symmetry even at room temperature. DFT calculations and transport measurements reveal a novel Fermi surface geometry with two electron-like sheets centered on Γ point and intermediate density of states at the Fermi level comparing with the value of FeSe and the superconducting A xFe2Se2.

Multiple states and roles of hydrogen in p-type SnS semiconductors.

Hydrogen (H) plays critical roles in the electrical properties of semiconductor materials and devices. In this work, we report multiple states and roles of H in SnS by H plasma treatment and density functional theory (DFT) calculations. The as-deposited SnS films include impurity H at 2.3 × 1019 cm-3, four orders of magnitude larger than the hole density. The DFT calculations reveal that H exists in multiple states at the equilibrium mainly at the interstitial and the Sn-substitutional sites, which have formation enthalpies lower than those for the intrinsic defects. These H states work as donors and acceptors, respectively, and strongly pin the Fermi level in the p-type region. The native p-type conduction in the actual SnS semiconductors is caused mainly by the H-on-Sn (HSn) acceptors, rather than the previously reported Sn vacancies (VSn) for pure SnS. It is also confirmed that even stronger H doping with larger H chemical potentials cannot convert SnS to an n-type conductor because it reduces SnS to Sn metal.

An Exceptionally Narrow Band-Gap (∼4 eV) Silicate Predicted in the Cubic Perovskite Structure: BaSiO3.

The electronic structures of 35 A2+B4+O3 ternary cubic perovskite oxides, including their hypothetical chemical compositions, were calculated by a hybrid functional method with the expectation that peculiar electronic structures and unique carrier transport properties suitable for semiconductor applications would be hidden in high-symmetry cubic perovskite oxides. We found unique electronic structures of Si-based oxides (A = Mg, Ca, Sr, and Ba, and B = Si). In particular, the unreported cubic BaSiO3 has a very narrow band gap (4.1 eV) compared with conventional nontransition-metal silicates (e.g., ∼9 eV for SiO2 and the calculated value of 7.3 eV for orthorhombic BaSiO3) and a small electron effective mass (0.3m0, where m0 is the free electron rest mass). The narrow band gap is ascribed to the nonbonding state of Si 3s and the weakened Madelung potential. The existence of the predicted cubic perovskite structure of BaSiO3 was experimentally verified by applying a high pressure of 141 GPa. The present finding indicates that it could be possible to develop a new transparent oxide semiconductor of earth abundant silicates if the symmetry of its crystal structure is appropriately chosen. Cubic BaSiO3 is a candidate for high-performance oxide semiconductors if this phase can be stabilized at room temperature and ambient pressure.

Electric double-layer transistor using layered iron selenide Mott insulator TlFe1.6Se2.

A(1-x)Fe(2-y)Se2 (A = K, Cs, Rb, Tl) are recently discovered iron-based superconductors with critical temperatures (Tc) ranging up to 32 K. Their parent phases have unique properties compared with other iron-based superconductors; e.g., their crystal structures include ordered Fe vacancies, their normal states are antiferromagnetic (AFM) insulating phases, and they have extremely high Néel transition temperatures. However, control of carrier doping into the parent AFM insulators has been difficult due to their intrinsic phase separation. Here, we fabricated an Fe-vacancy-ordered TlFe1.6Se2 insulating epitaxial film with an atomically flat surface and examined its electrostatic carrier doping using an electric double-layer transistor (EDLT) structure with an ionic liquid gate. The positive gate voltage gave a conductance modulation of three orders of magnitude at 25 K, and further induced and manipulated a phase transition; i.e., delocalized carrier generation by electrostatic doping is the origin of the phase transition. This is the first demonstration, to the authors' knowledge, of an EDLT using a Mott insulator iron selenide channel and opens a way to explore high Tc superconductivity in iron-based layered materials, where carrier doping by conventional chemical means is difficult.

The Unique Electronic Structure of Mg2 Si: Shaping the Conduction Bands of Semiconductors with Multicenter Bonding.

The electronic structures of the antifluorite-type compound Mg2 Si is described in which a sublattice of short cation-cation contacts creates a very low conduction band minimum. Since Mg2 Si shows n-type conductivity without intentional carrier doping, the present result indicates that the cage defined by the cations plays critical roles in carrier transport similar to those of inorganic electrides, such as 12 CaO⋅7 Al2 O3 :e- and Ca2 N. A distinct difference in the location of conduction band minimum between Mg2 Si and the isostructural phase Na2 S is explained in terms of factors such as the differing interaction strengths of the Si/S 3s orbitals with the cation levels, with the more core-like character of the S 3s leading to a relatively low conduction band energy at the Γ point. Based on these results and previous research on electrides, approaches can be devised to control the energy levels of cation sublattices in semiconductors.

Analysis of various types of single-polypeptide-chain (sc) heterodimeric A2AR/D2R complexes and their allosteric receptor-receptor interactions.

Adenosine A2A receptor (A2AR) heteromerizes with dopamine D2 receptor (D2R). However, these class A G protein-coupled receptor (GPCR) dimers are not fully formed, but depend on the equilibrium between monomer and dimer. In order to stimulate the heteromerization, we have previously shown a successful design for a fusion receptor, single-polypeptide-chain (sc) heterodimeric A2AR/D2R complex. Here, using whole cell binding assay, six more different scA2AR/D2R constructs were examined. Not only in scA2AR/D2R 'liberated' with longer spacers between the two receptors, which confer the same configuration as the prototype, the A2AR-odr4TM-D2LR, but differ in size (Forms 1-3), but also in scA2AR/D2LR (Form 6) fused with a transmembrane (TM) of another type II TM protein, instead of odr4TM, neither of their fixed stoichiometry (the apparent ratios of A2AR to D2R binding sites) was 1, suggesting their compact folding. This suggests that type II TM, either odr4 or another, facilitates the equilibrial process of the dimer formation between A2AR and D2LR, resulting in the higher-order oligomer formation from monomer of scA2AR/D2LR itself. Also, in the reverse type scA2AR/D2LR, i.e., the D2LR-odr4TM-A2AR, counter agonist-independent binding cooperativity (cooperative folding) was found to occur (Forms 4 and 5). In this way, the scA2AR/D2LR system has unveiled the cellular phenomenon as a snapshot of the molecular behavior in A2AR/D2LR dimer. Thus, these results indicate that the various designed types of functional A2AR/D2R exist even in living cells and that this fusion expression system would be useful to analyze as a model of the interaction between class A GPCRs.

Two distinct effector memory cell populations of WT1 (Wilms' tumor gene 1)-specific cytotoxic T lymphocytes in acute myeloid leukemia patients.

Wilms' tumor gene 1 (WT1) protein is a promising tumor-associated antigen for cancer immunotherapy. We have been performing WT1 peptide vaccination with good clinical responses in over 750 patients with leukemia or solid cancers. In this study, we generated single-cell gene-expression profiles of the effector memory (EM) subset of WT1-specific cytotoxic T lymphocytes (CTLs) in peripheral blood of nine acute myeloid leukemia patients treated with WT1 peptide vaccine, in order to discriminate responders (WT1 mRNA levels in peripheral blood decreased to undetectable levels, decreased but stayed at abnormal levels, were stable at undetectable levels, or remained unchanged from the initial abnormal levels more than 6 months after WT1 vaccination) from non-responders (leukemic blast cells and/or WT1 mRNA levels increased relative to the initial state within 6 months of WT1 vaccination) prior to WT1 vaccination. Cluster and principal component analyses performed using 83 genes did not discriminate between responders and non-responders prior to WT1 vaccination. However, these analyses revealed that EM subset of WT1-specific CTLs could be divided into two groups: the "activated" and "quiescent" states; in responders, EM subset of the CTLs shifted to the "quiescent" state, whereas in non-responders, those shifted to the "activated" state following WT1 vaccination. These results demonstrate for the first time the existence of two distinct EM states, each of which was characteristic of responders or non-responders, of WT1-specific CTLs in AML patients, and raises the possibility of using advanced gene-expression profile analysis to clearly discriminate between responders and non-responders prior to WT1 vaccination.

Intrinsic defects in a photovoltaic perovskite variant Cs2SnI6.

Cs2SnI6, a rarely studied perovskite variant material, is recently gaining a lot of interest in the field of photovoltaics owing to its nontoxicity, air-stability and promising photovoltaic properties. In this work, we report intrinsic defects in Cs2SnI6 using first-principles density functional theory calculations. It is revealed that iodine vacancy and tin interstitial are the dominant defects that are responsible for the intrinsic n-type conduction in Cs2SnI6. Tin vacancy has a very high formation energy (>3.6 eV) due to the strong covalency in the Sn-I bonds and is hardly generated for p-type doping. All the dominant defects in Cs2SnI6 have deep transition levels in the band gap. It is suggested that the formation of deep defects can be suppressed significantly by employing an I-rich synthesis condition, which is inevitable for photovoltaic and other semiconductor applications.

Narrow bandgap in ß-BaZn2As2 and its chemical origins.

ß-BaZn2As2 is known to be a p-type semiconductor with the layered crystal structure similar to that of LaZnAsO, leading to the expectation that ß-BaZn2As2 and LaZnAsO have similar bandgaps; however, the bandgap of ß-BaZn2As2 (previously reported value ~0.2 eV) is 1 order of magnitude smaller than that of LaZnAsO (1.5 eV). In this paper, the reliable bandgap value of ß-BaZn2As2 is determined to be 0.23 eV from the intrinsic region of the temperature dependence of electrical conductivity. The origins of this narrow bandgap are discussed based on the chemical bonding nature probed by 6 keV hard X-ray photoemission spectroscopy, hybrid density functional calculations, and the ligand theory. One origin is the direct As-As hybridization between adjacent [ZnAs] layers, which leads to a secondary splitting of As 4p levels and raises the valence band maximum. The other is that the nonbonding Ba 5d(x(2)-y(2)) orbitals form an unexpectedly deep conduction band minimum (CBM) in ß-BaZn2As2 although the CBM of LaZnAsO is formed mainly of Zn 4s. These two origins provide a quantitative explanation for the bandgap difference between ß-BaZn2As2 and LaZnAsO.

In Silico Analyses of Vertebrate G-Protein-Coupled Receptor Fusions United With or Without an Additional Transmembrane Sequence Indicate Classification into Three Groups of Linkers.

Natural G-protein-coupled receptors (GPCRs) rarely have an additional transmembrane (TM) helix, such as an artificial TM-linker that can unite two class A GPCRs in tandem as a single-polypeptide chain (sc). Here, we report that three groups of TM-linkers exist in the intervening regions of natural GPCR fusions from vertebrates: (1) the original consensus (i.e., consensus 1) and consensus 2~4 (related to GPCR itself or its receptor-interacting proteins); (2) the consensus but GPCR-unrelated ones, 1~7; and (3) the inability to apply 1/2 that show no similarity to any other proteins. In silico analyses indicated that all natural GPCR fusions from Amphibia lack a TM-linker, and reptiles have no GPCR fusions; moreover, in either the GPCR-GPCR fusion or fusion protein of (GPCR monomer) and non-GPCR proteins from vertebrates, excluding tetrapods, i.e., so-called fishes, TM-linkers differ from previously reported mammalian and are avian sequences and are classified as Groups 2 and 3. Thus, previously reported TM-linkers were arranged: Consensus 1 is [T(I/A/P)(A/S)-(L/N)(I/W/L)(I/A/V)GL(L/G)(A/T)(S/L/G)(I/L)] first identified in invertebrate sea anemone Exaiptasia diaphana (LOC110241027) and (330-SPSFLCI-L-SLL-340) identified in a tropical bird Opisthocomus hoazin protein LOC104327099 (XP_009930279.1); GPCR-related consensus 2~4 are, respectively, (371-prlilyavfc fgtatg-386) in the desert woodrat Neotoma lepida A6R68_19462 (OBS78147.1), (363-lsipfcll yiaallgnfi llfvi-385) in Gavia stellate (red-throated loon) LOC104264164 (XP_009819412.1), and (479-ti vvvymivcvi glvgnflvmy viir-504) in a snailfish GPCR (TNN80062.1); In Mammals Neotoma lepida, Aves Erythrura gouldiae, and fishes protein (respectively, OBS83645.1, RLW13346.1 and KPP79779.1), the TM-linkers are Group 2. Here, we categorized, for the first time, natural TM-linkers as rare evolutionary events among all vertebrates.

Antisite-Defects Control of Magnetic Properties in MnSb2Te4.

The intrinsic magnetic topological materials Mn(Sb/Bi)2n+2Te3n+4 have attracted extensive attention due to their topological quantum properties. Although, the Mn-Sb/Bi antisite defects have been frequently reported to exert significant influences on both magnetism and band topology, their formation mechanism and the methods to manipulate their distribution and concentration remain elusive. Here, we present MnSb2Te4 as a typical example and demonstrate that Mn-Sb antisite defects and magnetism can be tuned by controlling the crystal growth conditions. The cooling rate is identified as the primary key parameter. Magnetization and chemical analysis demonstrate that a slower cooling rate would lead to a higher Mn concentration, a higher magnetic transition temperature, and a higher saturation moment. Further analysis indicates that the Mn content at the original Mn site (MnMn, 3a site) varies more significantly with the cooling rate than the Mn content at the Sb site (MnSb, 6c site). Based on experimental observations, magnetic phase diagrams regarding MnMn and MnSb concentrations are constructed. With the assistance of first-principles calculations, it is demonstrated that the Mn-Sb mixing states primarily result from the mixing entropy and the growth kinetics. The present findings offer valuable insights into defects engineering for preparation of two-dimensional quantum materials.

Inverse-Perovskite Ba3 BO (B = Si and Ge) as a High Performance Environmentally Benign Thermoelectric Material with Low Lattice Thermal Conductivity.

High energy-conversion efficiency (ZT) of thermoelectric materials has been achieved in heavy metal chalcogenides, but the use of toxic Pb or Te is an obstacle for wide applications of thermoelectricity. Here, high ZT is demonstrated in toxic-element free Ba3 BO (B = Si and Ge) with inverse-perovskite structure. The negatively charged B ion contributes to hole transport with long carrier life time, and their highly dispersive bands with multiple valley degeneracy realize both high p-type electronic conductivity and high Seebeck coefficient, resulting in high power factor (PF). In addition, extremely low lattice thermal conductivities (κlat ) 1.0-0.4 W m-1  K-1 at T = 300-600 K are observed in Ba3 BO. Highly distorted O-Ba6 octahedral framework with weak ionic bonds between Ba with large mass and O provides low phonon velocities and strong phonon scattering in Ba3 BO. As a consequence of high PF and low κlat , Ba3 SiO (Ba3 GeO) exhibits rather high ZT = 0.16-0.84 (0.35-0.65) at T = 300-623 K (300-523 K). Finally, based on first-principles carrier and phonon transport calculations, maximum ZT is predicted to be 2.14 for Ba3 SiO and 1.21 for Ba3 GeO at T = 600 K by optimizing hole concentration. Present results propose that inverse-perovskites would be a new platform of environmentally-benign high-ZT thermoelectric materials.