Ba15Zr14Te42: a new complex ternary telluride structure with low thermal conductivity.

Heavier metal-based tellurides with complex structures are of great interest for thermoelectric (TE) applications. Herein, we report the synthesis of a new telluride Ba15Zr14Te42 using high-temperature reactions of elements. Our single-crystal X-ray diffraction study reveals that it crystallizes in the space group R3̄c of the trigonal crystal system and is isostructural to its Se analogue Ba15Zr14Se42 complex. The unit cell of the structure accommodates 426 atoms with cell dimensions of a = b = 13.2666(10) Å, c = 96.195(9) Å, and V = 14 662(3) Å3. This structure consists of 18 unique crystallographic atoms (3 × Ba, 8 × Zr, and 7 × Te). The bonding of Zr and Te atoms creates chains of ∞1[Zr14Te42]30-, which are separated by the Ba2+ cations. Although all the Zr atoms have a coordination number of 6, they form two types of coordination polyhedra by bonding with six Te atoms: slightly distorted octahedral and trigonal prisms of ZrTe6. We have synthesized polycrystalline Ba15Zr14Q42 (Q = Se/Te) samples, which were characterized by optical absorption studies to reveal direct bandgaps of <0.5 eV for the Te analogue and 1.3(1) eV for the Se analogue. The lattice thermal conductivity (klat) values of the samples are ultralow: ∼0.46 W mK-1 and ∼0.30 W mK-1 at 773 K for the Te and Se analogues, respectively. Temperature-dependent resistivity and thermopower studies were carried out for the Ba15Zr14Te42, which showed the p-type degenerate semiconducting nature of the sample at high temperatures. The theoretical DFT studies predict a bandgap of 0.14 eV for the Ba15Zr14Te42 phase.

Polarized Raman, infrared and dielectric spectra of lead-free K0.5Na0.5NbO3piezoelectric system: insights fromab-initiotheoretical and experimental studies.

The K0.5Na0.5NbO3(KNN) system has emerged as one of the most promising lead-free piezoelectric over the years. In this work, we perform a comprehensive investigation of electronic structure, lattice dynamics and dielectric properties of room temperature phase of KNN by combiningab-initioDFT based theoretical analysis and experimental characterization. We assign the symmetry labels to KNN vibrational modes and obtainab-initiopolarized Raman spectra, Infrared reflectivity, Born-effective charge tensors, oscillator strengths etc. The KNN ceramic samples are prepared using conventional solid-state method and Raman and UV-Vis diffuse reflectance spectra are obtained. The computed Raman spectrum is found to agree well with the experimental spectrum. In particular, the results suggest that the mode in range ∼840-870 cm-1reported in the experimental studies is longitudinal optical withA1symmetry. The Raman mode intensities are calculated for different light polarization set-ups that suggests the observation of different symmetry modes in different polarization set-ups. The electronic structure of KNN is investigated and optical absorption spectrum is obtained. Further, the performances of DFT semi-local, meta-GGA and hybrid exchange-correlations functionals, in the estimation of KNN band gaps are investigated. The KNN bandgap computed using GGA-1/2 and HSE06 hybrid functional schemes are found to be in excellent agreement with the experimental value. The COHP, electron localization function and Bader charge analysis is also performed to deduce the nature of chemical bonding in the KNN. Overall, our study provides several bench-mark important results on KNN that have not been reported so far.

Influence of temperature on bandgap shifts, optical properties and photovoltaic parameters of GaAs/AlAs and GaAs/AlSbp-nheterojunctions: insights fromab-initioDFT + NEGF studies.

The III-V group semiconductors are highly promising absorbers for heterojunctions based solar cell devices due to their high conversion efficiency. In this work, we explore the solar cell properties and the role of electron-phonon coupling (EPC) on the solar cell parameters of GaAs/AlSb and GaAs/AlAsp-nheterojunctions using non-equilibrium Green function method (NEGF) in combination ofab-initiodensity functional theory (DFT). In addition, the band offsets at the heterointerfaces, optical absorption and bandgap shifts (BGSs) due to temperature are estimated using DFT + NEGF approach. The interface band gaps in heterostructures are found to be lower than bulk band gaps leading to a shift in optical absorption coefficient towards lower energy side that results in stronger photocurrent. The temperature dependent electronic BGS is significantly influenced by the phonon density and phonon energy via EPC. The phonon influenced BGS is found to change the optical absorption, photocurrent density and open-circuit voltage. In case of GaAs/AlSb junction, the interface phonons are found to have significantly higher energies as compared to the bulk phonons and thereby may have important implications for photovoltaic (PV) properties. Overall, the present study reveals the influence of EPC on the optical absorption and PV properties of GaAs/AlSb and GaAs/AlSbp-nheterojunctions. Furthermore, the study shows that the DFT + NEGF method can be successfully used to obtain the reasonable quantitative estimates of temperature dependent BGSs, optical absorption and PV properties ofp-nheterojunctions.

Ba14Si4Sb8Te32(Te3): hypervalent Te in a new structure type with low thermal conductivity.

Heavier pnictogen (Sb, Bi) containing chalcogenides are well known for their complex structures and semiconducting properties for numerous applications, particularly thermoelectric materials. Here, we report the syntheses of single crystals and polycrystalline phases of a new complex quaternary polytelluride, Ba14Si4Sb8Te32(Te3), via a high-temperature reaction of elements. A single-crystal X-ray diffraction study showed that it crystallizes in an unprecedented structure type with monoclinic symmetry (space group: P21/c). The crystal structure of Ba14Si4Sb8Te32(Te3) consists of one-dimensional ∞1[Si4Sb8Te32(Te3)]28- stripes, which are separated by the Ba2+ cations. Its complex structure features linear polytelluride units of Te34- having intermediate Te⋯Te interactions. A polycrystalline Ba14Si4Sb8Te32(Te3) sample shows a direct narrow bandgap of 0.8(2) eV, which indicates its semiconducting nature. The electrical resistivity of a sintered pellet of the polycrystalline sample exponentially decreases from ∼39.3 Ωcm to ∼0.57 Ωcm on heating it from 323 K to 773 K, confirming the sample's semiconducting nature. The sign of Seebeck coefficient values is positive in the 323 K to 773 K range confirming the p-type nature of the sintered sample. Interestingly, the sample attains an extremely low thermal conductivity of ∼0.32 Wm-1K-1 at 773 K, which could be attributed to the lattice anharmonicity caused by the lone pair effect of Sb3+ species in its complex pseudo-one-dimensional crystal structure. The electronic band structure of the title phase and the strength of chemical bonding of pertinent atomic pairs have been evaluated theoretically using the DFT method.

Ba4FeAgS6: a new antiferromagnetic and semiconducting quaternary sulfide.

The single crystals of a quaternary sulfide, Ba4FeAgS6, have been synthesized by reacting elements at 873 K inside a sealed fused silica tube. The title phase is the first ordered quaternary compound of the Ba-Ag-Fe-S system. The crystal structure of Ba4FeAgS6 is characterized by a single-crystal X-ray diffraction study at 298(2) K. It crystallizes in the space group C52h - P21/n of the monoclinic crystal system with unit cell dimensions of a = 8.6367(5) Å, b = 12.0291(7) Å, c = 13.2510(7) Å, and ß = 109.015(2)°. This compound is stoichiometric, and its structure contains twelve unique crystallographic sites: four Ba, one Fe, one Ag, and six S sites. All atoms of the structure occupy the general positions. The Ba4FeAgS6 structure consists of one-dimensional chains of 1∞[FeAgS6]8- that are extended in the [100] direction. The negative charges on these chains are counterbalanced by the filling of Ba2+ cations in between the 1∞[FeAgS6]8- chains. The Fe atoms are bonded to four S atoms that form a distorted tetrahedral geometry around the central Fe atom. Each Ag atom in this structure is coordinated with four S atoms in a distorted tetrahedral fashion. These FeS4 and AgS4 motifs are the main building blocks of the Ba4FeAgS6 structure. The corner-sharing of FeS4 and AgS4 tetrahedra creates one-dimensional chains of 1∞[FeAgS6]8-. This structure does not contain any homoatomic or metallic bonds and can be charge-balanced as (Ba2+)4(Fe3+)1(Ag1+)1(S2-)6. The optical absorption study performed on a polycrystalline Ba4FeAgS6 sample reveals a direct bandgap of 1.2(1) eV. The magnetic studies reveal the antiferromagnetic behavior of Ba4FeAgS6 below 50 K. The thermal conductivity and theoretical electronic structure of Ba4FeAgS6 are also studied in detail.

Efficient and improved prediction of the band offsets at semiconductor heterojunctions from meta-GGA density functionals: A benchmark study.

Accurate theoretical prediction of the band offsets at interfaces of semiconductor heterostructures can often be quite challenging. Although density functional theory has been reasonably successful to carry out such calculations, efficient, accurate semilocal functionals are desirable to reduce the computational cost. In general, the semilocal functionals based on the generalized gradient approximation (GGA) significantly underestimate the bulk bandgaps. This, in turn, results in inaccurate estimates of the band offsets at the heterointerfaces. In this paper, we investigate the performance of several advanced meta-GGA functionals in the computational prediction of band offsets at semiconductor heterojunctions. In particular, we investigate the performance of r2SCAN (two times revised strongly constrained and appropriately normed functional), rMGGAC (revised semilocal functional based on cuspless hydrogen model and Pauli kinetic energy density functional), mTASK (modified Aschebrock and Kümmel meta-GGA functional), and local modified Becke-Johnson exchange-correlation functionals. Our results strongly suggest that these meta-GGA functionals for supercell calculations perform quite well, especially, when compared to computationally more demanding GW calculations. We also present band offsets calculated using ionization potentials and electron affinities, as well as band alignment via the branch point energies. Overall, our study shows that the aforementioned meta-GGA functionals can be used within the density functional theory framework to estimate the band offsets in semiconductor heterostructures with predictive accuracy.

Electron-phonon interaction effect on the photovoltaic parameters of indirect (direct) bandgap AlSb (GaSb) p-n junction solar cell devices: a density functional theoretical study.

Semiconductors AlSb and GaSb have emerged, in recent years, as important candidates for photovoltaic applications due to their strong absorption coefficients and other photovoltaic properties. In this study, AlSb (GaSb) p-n junction-based solar cell device parameters and properties are studied using the density functional theoretical framework and the non-equilibrium Green function approach. The effect of temperature on various solar cell parameters such as open-circuit voltage, power conversion efficiency, photocurrent density, short-circuit current, etc. is investigated using a special-thermal-displacement approach along with the GGA-1/2 exchange-correlation functional. As temperature increases, the phonons are found to significantly influence the charge carrier transport in the solar cells. The computed power conversion efficiencies for AlSb are estimated as 12.31% and 10.21% at 0 K and 400 K, respectively. The obtained results strongly indicate that the electron-phonon coupling and resulting phonon-assisted photon absorption are necessary for accurate description and prediction of solar cell properties. The estimates obtained in this study may serve as first-principles parameters with possible use in continuum model-based multiscale simulations of AlSb (GaSb) p-n homo-junction solar cells.

Five coordinated Mn in Ba4Mn2Si2Te9: synthesis, crystal structure, physical properties, and electronic structure.

We report the synthesis of single-crystals of a new transition metal-containing quaternary chalcogenide, Ba4Mn2Si2Te9, synthesized by the solid-state method at 1273 K. A single-crystal X-ray diffraction study shows that it crystallizes in the orthorhombic crystal system (space group: Pbam) with cell constants of a = 13.4690(6) Å, b = 8.7223(4) Å, and c = 10.0032(4) Å. The asymmetric unit of the structure consists of eight unique crystallographic sites: one Ba, two Mn, one Si, and four Te sites. In this structure, the two Mn sites, Mn(1) and Mn(2), are disordered, each with fractional occupancy of 50%. The short distance of 2.170(3) Å between Mn(1) and Mn(2) implies that both Mn sites are not occupied simultaneously. The Mn atoms show two types of polyhedra: unique Mn(1)Te5 units along with traditional Mn(2)Te4 tetrahedra. The main motifs of the Ba4Mn2Si2Te9 structure are dimeric Si2Te6 units (with Si-Si single bond), Mn(1)Te5, and Mn(2)Te4 polyhedra. The structure can be described as pseudo-two-dimensional if only Mn(1) atoms are present and one-dimensional when only Mn(2) atoms are filled in the structure. The extended 2∞[Mn(1)Si2Te9]10- layers and 1∞[Mn(2)Si2Te8]8- chains are separated by Ba2+ cations. The direct bandgap for the polycrystalline Ba4Mn2Si2Te9 sample is 0.6(1) eV, as determined from an optical absorption study consistent with the sample's black color. The resistivity study of the polycrystalline Ba4Mn2Si2Te9 also confirms the semiconducting behavior. The thermal conductivity (κ) values are extremely low and decrease with increasing temperature up to 0.46 W m-1 K-1 at 773 K. The DFT studies suggest that the computed bandgap depends on the magnetic ordering of Mn magnetic moments, and the value varies from ∼0.3-1.0 eV. Relative inter-atomic bond strengths of pertinent atom pairs have been analyzed using the crystal orbital Hamilton populations (COHP).

Germanium Antimony Bonding in Ba4Ge2Sb2Te10 with Low Thermal Conductivity.

A new quaternary telluride, Ba4Ge2Sb2Te10, was synthesized at high temperature via the reaction of elements. A single-crystal X-ray diffraction study shows that the title compound crystallizes in its own structure type in the monoclinic P21/c space group having cell dimensions of a = 13.984(3) Å, b = 13.472(3) Å, c = 13.569(3) Å, and ß = 90.16(3)° with four formula units per unit cell (Z = 4). The pseudo-one-dimensional crystal structure of Ba4Ge2Sb2Te10 consists of infinite 1∞[Ge2Sb2Te10]8- stripes, which are separated by Ba2+ cations. Each of the Ge(1) atoms is covalently bonded to four Te atoms, whereas the Ge(2) atom is covalently bonded with one Sb(2) and three Te atoms in a distorted tetrahedral geometry. The title compound is the first example of a chalcogenide that shows Ge-Sb bonding. The Sb(1) atom is present at the center of the seesaw geometry of four Te atoms. In contrast, the Sb(2) atom forms a seesaw geometry by coordinating with one Ge(2) and three Te atoms. Condensation of these Ge and Sb centered polyhedral units lead to the formation of 1∞[Ge2Sb2Te10]8- stripes. The temperature-dependent resistivity study suggests the semimetallic/degenerate semiconducting nature of polycrystalline Ba4Ge2Sb2Te10. The positive sign of Seebeck coefficient values indicates that the predominant charge carriers are holes in Ba4Ge2Sb2Te10. An extremely low lattice thermal conductivity of ∼0.34 W/mK at 773 K was observed for polycrystalline Ba4Ge2Sb2Te10, which is presumably due to the lattice anharmonicity induced by the stereochemically active 5s2 lone pair of Sb. The electronic structure of Ba4Ge2Sb2Te10 and the bonding of atom pairs in the structure have been analyzed by means of ELF analysis and crystal orbital Hamilton population (COHP) analysis.

Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor.

The correct treatment ofdelectrons is of prime importance in order to predict the electronic properties of the prototype chalcopyrite semiconductors. The effect ofdstates is linked with the anion displacement parameteru, which in turn influences the bandgap of these systems. Semilocal exchange-correlation functionals which yield good structural properties of semiconductors and insulators often fail to predict reasonableubecause of the underestimation of the bandgaps arising from the strong interplay betweendelectrons. In the present study, we show that the meta-generalized gradient approximation (meta-GGA) obtained from the cuspless hydrogen density (MGGAC) (2019Phys. Rev.B 100 155140) performs in an improved manner in apprehending the key features of the electronic properties of chalcopyrites, and its bandgaps are comparative to that obtained using state-of-art hybrid methods. Moreover, the present assessment also shows the importance of the Pauli kinetic energy enhancement factor,α= (τ-τW)/τunifin describing thedelectrons in chalcopyrites. The present study strongly suggests that the MGGAC functional within semilocal approximations can be a better and preferred choice to study the chalcopyrites and other solid-state systems due to its superior performance and significantly low computational cost.

Theoretical investigation of lattice dynamics, infrared reflectivity, polarized Raman spectra and nature of interlayer coupling in two-dimensional layered gallium sulfide.

Gallium sulfide (GaS) is a highly promising two-dimensional layered semiconductor owing to its remarkable thickness dependent electronic and physical properties. In this article, we perform a comprehensiveab initiostudy of lattice dynamics, mode symmetry assignments, polarized Raman and infrared (IR) reflectivity spectra of GaS system. Polarized Raman spectra are obtained for different light polarization set-ups of incoming and scattered light. The frequencies of all allowed vibrational modes at the zone-centre are calculated and symmetry labels are assigned. Furthermore, the variation of frequencies & intensities of Raman/IR active modes of ultrathin GaS films (few layers) as function of film thickness is studied. In addition, we also explore the nature of weak interlayer coupling in GaS. The weak forces between the GaS layers are usually assumed to be due to interlayer van der Waals (vdW) interaction. However, this assumption has not been reasonably explained in reported experimental studies. Our study strongly suggests that weak interlayer interactions in GaS may be primarily electrostatic (Coulomb) in nature and therefore the contribution of vdW interactions to layer-layer coupling and lattice dynamics may be significantly lower than that of electrostatic interaction. The suggested nature of interlayer coupling in GaS and related III-VI semiconductors may have important implications in determination of their various physical properties.

Ba2Ln1-xMn2Te5 (Ln = Pr, Gd, and Yb; x = Ln vacancy): syntheses, crystal structures, optical, resistivity, and electronic structure.

Three new isostructural quaternary tellurides, Ba2Ln1-xMn2Te5 (Ln = Pr, Gd, and Yb), have been synthesized by the molten-flux method at 1273 K. The single-crystal X-ray diffraction studies at 298(2) K showed that Ba2Ln1-xMn2Te5 crystallize in the space group -C2/m of the monoclinic crystal system. There are six unique crystallographic sites in this structure's asymmetric unit: one Ba site, one Ln site, one Mn site, and three Te sites. The Ln site in the Ba2Ln1-xMn2Te5 structure is partially filled, which leaves about one-third of the Ln sites vacant (□) for Pr and Gd compounds. These structures do not contain any homoatomic or metallic bonding and can be charge-balanced as (Ba2+)2(Gd/Pr3+)2/3(Mn2+)2(Te2-)5. The refined composition for the Yb compound is Ba2Yb0.74(1)Mn2Te5 and can be charge-balanced with a mixed valence state of Yb2+/Yb3+. The crystal structures of Ba2Ln1-xMn2Te5 consist of complex layers of [Ln1-xMn2Te5]4- stacked along the [100] direction, with Ba2+ cations separating these layers. The Ln atoms are bound to six Te atoms that form a distorted octahedral geometry around the central Ln atom. Each Mn atom in this structure is coordinated to four Te atoms in a distorted tetrahedral fashion. These LnTe6 and MnTe4 units are the main building blocks of the Ba2Ln1-xMn2Te5 structure. The optical absorption study performed on a polycrystalline Ba2Gd2/3Mn2Te5 sample reveals a direct bandgap of 1.06(2) eV consistent with the DFT study. A semiconducting behavior was also observed for polycrystalline Ba2Gd2/3Mn2Te5 from the resistivity study. The temperature-dependent magnetic studies on a polycrystalline sample of Ba2Gd2/3Mn2Te5 did not reveal any long-range magnetic order down to 5 K. The effective magnetic moment (µeff) of 10.37µB calculated using the Curie-Weiss law is in good agreement with the theoretical value (µcal) of 10.58µB.

First principles theoretical investigations of low Young's modulus beta Ti-Nb and Ti-Nb-Zr alloys compositions for biomedical applications.

High alloyed ß-phase stabilized titanium alloys are known to provide comparable Young's modulus as that to the human bones (~30 GPa) but is marred by its high density. In the present study the low titanium alloyed compositions of binary Ti-Nb and ternary Ti-Nb-Zr alloy systems, having stable ß-phase with low Young's modulus are identified using first principles density functional framework. The theoretical results suggest that the addition of Nb in Ti and Zr in Ti-Nb increases the stability of the ß-phase. The ß-phase in binary Ti-Nb alloys is found to be fully stabilized from 22 at.% of Nb onwards. The calculated Young's moduli of binary ß-Ti-Nb alloy system are found to be lower than that of pure titanium (116 GPa). For Ti-25(at.%)Nb composition the calculated Young's modulus comes out to be ~80 GPa. In ternary Ti-Nb-Zr alloy system, the Young's modulus of Ti-25(at.%)Nb-6.25(at.%)Zr composition is calculated to be ~50 GPa. Furthermore, the directional Young's moduli of these two selected binary (Ti-25(at.%)Nb) and ternary alloy (Ti-25(at.%)Nb-6.25(at.%)Zr) compositions are found to be nearly isotropic in all crystallographic directions.

Prediction of a switchable two-dimensional electron gas at ferroelectric oxide interfaces.

The demonstration of a quasi-two-dimensional electron gas (2DEG) in LaAlO3/SrTiO3 heterostructures has stimulated intense research activity in recent years. The 2DEG has unique properties that are promising for applications in all-oxide electronic devices. For such applications it is desirable to have the ability to control 2DEG properties by external stimulus. Here, based on first-principles calculations we predict that all-oxide heterostructures incorporating ferroelectric constituents, such as KNbO3/ATiO3 (A=Sr, Ba, Pb), allow creating a 2DEG switchable between two conduction states by ferroelectric polarization reversal. The effect occurs due to the screening charge at the interface that counteracts the depolarizing electric field and depends on polarization orientation. The proposed concept of ferroelectrically controlled interface conductivity offers the possibility to design novel electronic devices.

Magnetic tunnel junctions with ferroelectric barriers: prediction of four resistance States from first principles.

Magnetic tunnel junctions (MTJs), composed of two ferromagnetic electrodes separated by a thin insulating barrier layer, are currently used in spintronic devices, such as magnetic sensors and magnetic random access memories. Recently, driven by demonstrations of ferroelectricity at the nanoscale, thin-film ferroelectric barriers were proposed to extend the functionality of MTJs. Due to the sensitivity of conductance to the magnetization alignment of the electrodes (tunneling magnetoresistance) and the polarization orientation in the ferroelectric barrier (tunneling electroresistance), these multiferroic tunnel junctions (MFTJs) may serve as four-state resistance devices. On the basis of first-principles calculations, we demonstrate four resistance states in SrRuO(3)/BaTiO(3)/SrRuO(3) MFTJs with asymmetric interfaces. We find that the resistance of such a MFTJ is significantly changed when the electric polarization of the barrier is reversed and/or when the magnetizations of the electrodes are switched from parallel to antiparallel. These results reveal the exciting prospects of MFTJs for application as multifunctional spintronic devices.