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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Origin of the magnetic and orbital ordering in α-Sr 2 CrO 4

Motivated by recent experimental progress in transition metal oxides with the K 2 NiF 4 structure, in this study we investigate the magnetic and orbital ordering in α-Sr 2 CrO 4 . Using first principles calculations, first we derive a three-orbital Hubbard model, which reproduces the ab initio band structure near the Fermi level. The unique reverse splitting of t 2g orbitals in α-Sr 2 CrO 4 , with the 3d 2 electronic configuration for the Cr 4+ oxidation state, opens up the possibility of orbital ordering in this material. Using real-space Hartree-Fock for multi-orbital systems, we constructed the ground state phase diagram for the two dimensional compound α-Sr 2 CrO 4 . We found stable ferromagnetic, antiferromagnetic, antiferro-orbital, and staggered orbital stripe ordering in robust regions of the phase diagram. Furthermore, using the density matrix renormalization group method for two-leg ladders with the realistic hopping parameters of α-Sr 2 CrO 4 , we explore magnetic and orbital ordering for experimentally relevant interaction parameters. Again, we find a clear signature of antiferromagnetic spin ordering along with antiferro-orbital ordering at moderate to large Hubbard interaction strength. We also explore the orbital-resolved density of states with Lanczos, predicting insulating behavior for the compound α-Sr 2 CrO 4 , in agreement with experiments. Finally, an intuitive understanding of the results is provided based on a hierarchy between orbitals, with d xy driving the spin order, while electronic repulsion and the effective one dimensionality of the movement within the d xz and d yz orbitals driving the orbital order.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chern numbers of topological phonon band crossing determined with inelastic neutron scattering

Topological invariants in the band structure, such as Chern numbers, are important for the understanding and classification of the topological properties of matter and dictate the occurrence of exotic behaviors, yet their direct spectroscopic determination has been largely limited to electronic bands. Here, we use inelastic neutron scattering in conjunction with ab initio calculations to identify a variety of topological phonon band crossings in MnSi and CoSi single crystals. We find a distinct relation between the Chern numbers of a band-crossing node and the scattering intensity modulation in momentum space around the node. Given sufficiently high resolution, our method can be used to determine arbitrarily large Chern numbers of topological phonon band-crossing nodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Topological antiferromagnetic semimetal for spintronics: A case study of a layered square-net system EuZnSb 2

Here, we use the first-principles and effective Hamiltonian methods to study the electronic structure and magnetic properties of a recently synthesized layered antiferromagnetic square-net topological semimetal EuZnSb2 [Phys. Rev. Res. 2, 033462 (2020)]. The main message of the paper is that effects of small changes in the band structure produced by the magnetic ordering and changes in the orientation of the Néel vector are amplified in such transport properties as the spin Hall conductivity. We predict that the effects of the broken symmetry introduced by the ordering of the Néel vector, being very weak in the bulk, are pronounced in the surface electronic dispersion, suggesting that surface probes may be more suited to measure them. The coexistence of the magnetism with many other competing phases make this material interesting and possibly useful for quantum spintronics applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Beyond triplet: Unconventional superconductivity in a spin-3/2 topological semimetal

In all known fermionic super fluids, Cooper pairs are composed of spin-1/2 quasi-particles that pair to form either spin-singlet or spin-triplet bound states. The "spin" of a Bloch electron, however, is xed by the symmetries of the crystal and the atomic orbitals from which it is derived, and in some cases can behave as if it were a spin-3/2 particle. The superconducting state of such a system allows pairing beyond spin-triplet, with higher spin quasi-particles combining to form quintet or even septet pairs. Here, we report evidence of unconventional superconductivity emerging from a spin-3/2 quasiparticle electronic structure in the half-Heusler semimetal YPtBi, a low-carrier density noncentrosymmetric cubic material with a high symmetry that preserves the p-like j = 3/2 manifold in the Bi-based Γ 8 band in the presence of strong spin-orbit coupling. With a striking linear temperature dependence of the London penetration depth, the existence of line nodes in the superconducting order parameter Δ is directly explained by a mixed-parity Cooper pairing model with high total angular momentum, consistent with a high-spin fermionic super fluid state. We propose a k ∙ p model of the j = 3/2 fermions to explain how a dominant J=3 septet pairing state is the simplest solution that naturally produces nodes in the mixed even-odd parity gap. Together with the underlying topologically non-trivial band structure, the unconventional pairing in this system represents a truly novel form of super fluidity that has strong potential for leading the development of a new generation of topological superconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Vortex matter in low-dimensional systems with proximity-induced superconductivity

We theoretically study the vortex matter structure in low-dimensional systems with superconducting order induced by proximity to a bulk superconductor. We analyze the effects of microscopic coupling mechanisms between the two systems and the effects of possible mismatch in the band structures of these materials on the energy spectrum of vortex-core electrons. The unusual structure of vortex cores is discussed in the context of recent tunneling microscopy/spectroscopy experiments.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Weak Dispersion of Exciton Landé Factor with Band Gap Energy in Lead Halide Perovskites: Approximate Compensation of the Electron and Hole Dependences

The optical properties of lead halide perovskite semiconductors in vicinity of the bandgap are controlled by excitons, so that investigation of their fundamental properties is of critical importance. The exciton Landé or g-factor g X is the key parameter, determining the exciton Zeeman spin splitting in magnetic fields. The exciton, electron, and hole carrier g-factors provide information on the band structure, including its anisotropy, and the parameters contributing to the electron and hole effective masses. Here, g X is measured by reflectivity in magnetic fields up to 60 T for lead halide perovskite crystals. The materials band gap energies at a liquid helium temperature vary widely across the visible spectral range from 1.520 up to 3.213 eV in hybrid organic–inorganic and fully inorganic perovskites with different cations and halogens: FA 0.9 Cs 0.1 PbI 2.8 Br 0.2 , MAPbI 3 , FAPbBr 3 , CsPbBr 3 , and MAPb(Br 0.05 Cl 0.95 ) 3 . The exciton g-factors are found to be nearly constant, ranging from +2.3 to +2.7. Thus, the strong dependences of the electron and hole g-factors on the bandgap roughly compensate each other when combining to the exciton g-factor. The same is true for the anisotropies of the carrier g-factors, resulting in a nearly isotropic exciton g-factor. The experimental data are compared favorably with model calculation results.

36 MATERIALS SCIENCE↗
NASA NTRS1995

Non-parabolic hydrodynamic formulations for the simulation of inhomogeneous semiconductor devices

Hydrodynamic models are becoming prevalent design tools for small scale devices and other devices in which high energy effects can dominate transport. Most current hydrodynamic models use a parabolic band approximation to obtain fairly simple conservation equations. Interest in accounting for band structure effects in hydrodynamic device simulation has begun to grow since parabolic models can not fully describe the transport in state of the art devices due to the distribution populating non-parabolic states within the band. This paper presents two different non-parabolic formulations of the hydrodynamic model suitable for the simulation of inhomogeneous semiconductor devices. The first formulation uses the Kane dispersion relationship (hk)(exp 2)/2m = W(1 + alpha(W)). The second formulation makes use of a power law ((hk)(exp 2)/2m = xW(sup y)) for the dispersion relation. Hydrodynamic models which use the first formulation rely on the binomial expansion to obtain moment equations with closed form coefficients. This limits the energy range over which the model is valid. The power law formulation readily produces closed form coefficients similar to those obtained using the parabolic band approximation. However, the fitting parameters (x,y) are only valid over a limited energy range. The physical significance of the band non-parabolicity is discussed as well as the advantages/disadvantages and approximations of the two non-parabolic models. A companion paper describes device simulations based on the three dispersion relationships: parabolic, Kane dispersion, and power low dispersion.

Smith, Arlynn W.↗
DOE OSTI2021

Electrically Pumped Epitaxially Regrown GaSb-Based Type-I Quantum-Well Surface-Emitting Lasers with Buried High-Index-Contrast Photonic Crystal Layer

Epitaxially regrown electrically pumped photonic crystal surface-emitting lasers (PCSELs) emitting near 2 and 2.6 μm are designed, fabricated, and characterized. A high-index-contrast photonic crystal layer is incorporated into the GaSb-based laser heterostructure by air-hole-retaining epitaxial regrowth. A square lattice of triangular holes is etched in the top waveguide core layer of the incomplete laser heterostructure. The nanopatterned surface is subsequently cleaned and regrown with AlGaAsSb p-cladding material. Transmission electron microscopy studies demonstrate uniform regrowth over the nanopatterned GaSb surface. The selected regrowth regimes yield a buried 2D array of elongated air-holes. The diode PCSELs based on moderately etched nanopatterns demonstrate band-edge lasing near 2 μm up to room temperatures. The cascade diode PCSELs operate near 2.6 μm with minimum threshold current densities of about 500 A cm -2 achieved at 180 K. The devices generate mW level output in narrow divergence beam emitted from the window in substrate contact. The angle-resolved electroluminescence measurements reveal a four-sub-band band structure with an apparent photonic bandgap corresponding to the buried high-index-contrast square photonic crystal layer. Finally, the PCSELs made of heterostructures supporting two modes in the vertical direction demonstrate two sets of sub-bands showing anti-crossing-like interaction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Ab Initio Theoretical Prediction of Structural, Electronic, and Magnetic Properties in the 3d (Mn)-Doped Zinc-Blende MgSe: A DFT-mBJ Approach

In this paper, we have investigated the structural, electronic, and magnetic properties of magnesium selenium (MgSe) doped with transition metal manganese (Mn) impurity in the cubic diluted magnetic semiconductor (DMS) zinc blende structure. The compounds which we are interested are as Mg{sub 1−x}Mn{sub x}Se where x change between 0 and 1 by step 0.25. All properties are studied, using first-principles calculation of density functional theory under the framework of the full-potential linearized augmented plane waver (FP-LAPW). In our study, we employed the Wu-Cohen generalized approximation (WC-GGA) to optimize the crystal structure, whereas Tran-Blaha modified Becke-Johnson potential (TB-mBJ) as a new functional was applied to compute the electronic and magnetic properties in order to get some better degree of precision. The electronic band structures and density of state plots reveal ferromagnetic semiconducting behavior in these compounds, and the exchange constants N{sub 0}α and N{sub 0}β are calculated to validate the effects resulting from exchange splitting process. Moreover, for each concentration x, the value of total magnetic moment has been estimated to equal to 5 μ{sub B}. The important magnetic moments values obtained in these compounds indicate the potential for their use in spintronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Discovery of a high-pressure phase of rutile-like CoO 2 and its potential as a cathode material

Due to the structural failure of layered CoO 2 , there has been considerable effort to improve the reversible capacity of commercial LiCoO 2 cathode materials. Using a global structural search, we have discovered a rutile-like CoO 2 phase as the ground state at 50 GPa. The material is thermally, mechanically and dynamically stable, even after removing the pressure. We show that, when lithiated, this LiCoO 2 material can serve as an improved cathode material for Li-ion batteries. Its many advantages include good structural stability against transition metal migration and oxygen loss, one-dimensional channels for Li ion diffusion with variable energy barriers (0.36–0.86 eV), enhanced ionic mobility, and good intrinsic electronic conductivity brought about by its metallic band structure. Furthermore, with a voltage platform of 3.2–3.8 V, it provides better stability against conventional carbonate solvents than conventional layered cathode materials (>4.0 V). All these features demonstrate that the non-layered CoO 2 phase synthesized at high pressure would be a promising cathode material, providing a performance beyond that of the currently used layered phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Enhanced carrier mobility and direct tunneling probability of biaxially strained Ge{sub 1−x}Sn{sub x} alloys for field-effect transistors applications

The carrier transport and tunneling capabilities of biaxially strained Ge{sub 1−x}Sn{sub x} alloys with (001), (110), and (111) orientations were comprehensively investigated and compared. The electron band structures of biaxially strained Ge{sub 1−x}Sn{sub x} alloys were calculated by the nonlocal empirical pseudopotential method and the modified virtual crystal approximation was adopted in the calculation. The electron and hole effective masses at the band edges were extracted using a parabolic line fit. It is shown that the applied biaxial strain and the high Sn composition are both helpful for the reduction of carrier effective masses, which leads to the enhanced carrier mobility and the boosted direct band-to-band-tunneling probability. Furthermore, the strain induced valance band splitting reduces the hole interband scattering, and the splitting also results in the significantly enhanced direct tunneling rate along the out-of-plane direction compared with that along the in-plane direction. The biaxially strained (111) Ge{sub 1−x}Sn{sub x} alloys exhibit the smallest band gaps compared with (001) and (110) orientations, leading to the highest in-plane and out-of-plane direct tunneling probabilities. The small effective masses on (110) and (111) planes in some strained conditions also contribute to the enhanced carrier mobility and tunneling probability. Therefore, the biaxially strained (110) and (111) Ge{sub 1−x}Sn{sub x} alloys have the potential to outperform the corresponding (001) Ge{sub 1−x}Sn{sub x} devices. It is important to optimize the applied biaxial strain, the Sn composition, and the substrate orientation for the design of high performance Ge{sub 1−x}Sn{sub x} field-effect transistors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Comparison of interband related optical transitions and excitons in ZnGeN 2 and GaN

The optical dielectric function of ZnGeN 2 is calculated from the interband transitions using the energy bands calculated in the quasiparticle self-consistent (QS)GW^ method using two different levels of approximation: the independent particle approximation (IPA) and the Bethe-Salpeter Equation (BSE) approach. The first allows us to relate peaks in ε 2 to specific bands and k-points but does not include electron-hole interaction effects. The second includes electron-hole interaction or excitonic effects. The corresponding changes in the shape of ε 2 (ω) are found to be similar to those in GaN. The screened Coulomb interaction W^ is here calculated including electron-hole interactions in the polarization function and gives a band structure already going beyond the random phase approximation. The static dielectric constants including only electronic screening, commonly referred to as ε∞ , were calculated separately by extrapolating the wave vector dependent macroscopic dielectric function in the long-wavelength limit. Below the quasiparticle gap, we find three bound excitons optically active for different polarization. The convergence of these bound excitons with respect to the density of the k-mesh used in the BSE is studied and found to require a fine mesh. It is also found that these bound excitons originate from only the lowest conduction band and the top three valence bands. To incorporate the lattice screening, we include a scaling factor (ε∞/ε 0 ) 2 , which allows us to obtain exciton binding energies of the correct order of magnitude similar to those in GaN. Here, the excitons are related to each of the three fold split valence bands and the splittings of the latter are also studied as function of strain. Finally, a relation between the anisotropic effective masses and the valence band splitting is pointed out and explained.

36 MATERIALS SCIENCE↗
DOE OSTI2017

First-principles calculation on electronic structure and optical property of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} phosphor

The crystal structure, electronic structure and optical properties of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} with varying Eu doping concentrations are computed by the density functional theory (DFT) and compared with experimental results. The results show that the lattice parameters of primitive cells of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x} become smaller and Eu–N bond length shortens as Eu concentration increases. The band structure of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x} exhibits a direct optical band gap and it's propitious to luminescence. The energy differences from the lowest Eu 5d state to the lowest Eu 4f state decrease with increasing Eu concentrations. The analysis of simulative absorption spectra indicates that the electron transition from Eu 4f states to 5d states of both Eu and Ba atoms contributes to the absorption of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x}. Under the coupling effect between Eu and Ba, Ba in BaSi{sub 2}O{sub 2}N{sub 2} exhibits longer wavelength absorption and increases absorption efficiency. The emission wavelength is deduced by measuring energy differences from the lowest Eu 5d state to the lowest Eu 4f state, and the result is in good agreement with experimental value within experimental Eu{sup 2+} doping range. - Graphical abstract: The structure and optical property of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} are computed by DFT and its absorption mechanism is analysed. Results show that absorption peak α is from the host lattice absorption. The absorption peaks β, γ and δ are from Eu 4f to Eu 5d and Ba 6s 5d states. The absorption is attributed to the coupling effect of Eu and Ba atom. - Highlights: • The crystal, electronic structure and optical properties of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} are computed by DFT. • The lattice parameters of primitive cells reduces and Eu–N bond length shortens as Eu{sup 2+} increases. • The energy gap from Eu 5d state to Eu 4f state decrease with increasing Eu concentrations. • Both Eu and Ba atoms contributes to the absorption of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x}. • The deduced emission wavelength is in good agreement with experimental value.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Electronic-Structure Origin of Cation Disorder in Transition-Metal Oxides

Cation disorder is an important design criterion for technologically relevant transition-metal (TM) oxides, such as radiation-tolerant ceramics and Li-ion battery electrodes. In this Letter, we use a combination of first-principles calculations, normal mode analysis, and band-structure arguments to pinpoint a specific electronic-structure effect that influences the stability of disordered phases. We find that the electronic configuration of a TM ion determines to what extent the structural energy is affected by site distortions. In conclusion, this mechanism explains the stability of disordered phases with large ionic radius differences and provides a concrete guideline for the discovery of novel disordered compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Investigation of surface defect states in CeO{sub 2-y} nanocrystals by Scanning−tunneling microscopy/spectroscopy and ellipsometry

Synthesis process strongly influences the nanocrystalline CeO{sub 2-y} defective structure. The presence of surface defects, in the form of oxygen vacancies in different charge states (F centers), can change the electronic properties of ceria nanocrystals. Nanocrystalline CeO{sub 2-y} samples were synthesized using three different methods (precipitation, self-propagating room temperature, and hydrothermal synthesis). Raman spectroscopy was used to identify the presence of oxygen vacancies which presumably were formed at the nanoparticle surface. The defect concentration depended on the crystallite size of differently prepared CeO{sub 2-y} samples. Scanning tunneling microscopy/spectroscopy and ellipsometry were employed to investigate the electronic band structure of defective CeO{sub 2-y} nanocrystals. Scanning tunneling spectroscopy measurements demonstrated that inside the band gap of CeO{sub 2-y} nanocrystals, besides the filled 4 f states, appeared additional states which were related to occupied and empty F center defect states. From the ellipsometric measurements, using the critical points model, the energy positions of different F centers states and the values of the reduced band gap energies were determined. The analysis of obtained data pointed out that depending on the synthesis method, different types of F centers (F{sup +} and F{sup 0}) can be formed in the CeO{sub 2-y} nanocrystals. The formation of different F center defect states inside the ceria gap have a strong impact on the electrical, optical, and magnetic properties of ceria nanocrystals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2012

Structure, growth and properties of a novel polar material, KSr{sub 4}B{sub 3}O{sub 9}

A novel polar material, KSr{sub 4}B{sub 3}O{sub 9}, has been obtained by the high temperature solution method for the first time. It crystallizes in the polar space group Ama2. The material exhibits a three-dimensional structure consisting of interconnecting KO{sub 10} groups, SrO{sub x} (x=8, 9) units and isolated BO{sub 3} triangles. DSC/TG curve shows that KSr{sub 4}B{sub 3}O{sub 9} melts incongruently. The calculated band structures and the density of states of KSr{sub 4}B{sub 3}O{sub 9} suggest that its direct gap is 3.897 eV. The absorption spectrum indicates the absorption edge of KSr{sub 4}B{sub 3}O{sub 9} is about 302 nm. It produces SHG intensity about as large as that of KH{sub 2}PO{sub 4} (KDP) and is phase matchable. - Graphical abstract: Viewed along the c-axis, B(2)O{sub 3} triangles and B(3)O{sub 3} triangles are parallel with the (0 1 0) face and opposite to each other. However, all the B(1)O{sub 3} triangles have the same direction along the c-axis. So the main SHG efficiency of the compound comes from B(1)O{sub 3} triangles according to the anion group theory. Highlights: Black-Right-Pointing-Pointer A polar material, KSr{sub 4}B{sub 3}O{sub 9}, has been obtained by high temperature solution method. Black-Right-Pointing-Pointer The material consists of KO{sub 10} units, SrO{sub x}(x=8, 9) units and isolated BO{sub 3} units. Black-Right-Pointing-Pointer KSr{sub 4}B{sub 3}O{sub 9} produces SHG intensity as large as that of KDP and is phase matchable. Black-Right-Pointing-Pointer The absorption edge of KSr{sub 4}B{sub 3}O{sub 9} is about 302 nm.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Metal ion displacements in noncentrosymmetric chalcogenides La{sub 3}Ga{sub 1.67}S{sub 7}, La{sub 3}Ag{sub 0.6}GaCh{sub 7} (Ch=S, Se), and La{sub 3}MGaSe{sub 7} (M=Zn, Cd)

The quaternary Ga-containing chalcogenides La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}, La{sub 3}ZnGaSe{sub 7}, and La{sub 3}CdGaSe{sub 7}, as well as the related ternary chalcogenide La{sub 3}Ga{sub 1.67}S{sub 7}, were prepared by reactions of the elements at 950 °C. They adopt noncentrosymmetric hexagonal structures (space group P6{sub 3}, Z=2) with cell parameters (a=10.2 Å, c=6.1 Å for the sulfides; a=10.6 Å, c=6.4 Å for the selenides) that are largely controlled by the geometrical requirements of one-dimensional stacks of Ga-centered tetrahedra separated by the La atoms. Among these compounds, which share the common formulation La{sub 3}M{sub 1–x}GaCh{sub 7} (M=Ga, Ag, Zn, Cd; Ch=S, Se), the M atoms occupy sites within a stacking of trigonal antiprisms formed by Ch atoms. The location of the M site varies between extremes with trigonal antiprismatic (CN6) and trigonal planar (CN3) geometry. Partial occupation of these sites and intermediate ones accounts for the considerable versatility of these structures and the occurrence of large metal displacement parameters. The site occupations can be understood in a simple way as being driven by the need to satisfy appropriate bond valence sums for both the M and Ch atoms. Band structure calculations rationalize the substoichiometry observed in the Ag-containing compounds (La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}) as a response to overbonding. X-ray photoelectron spectroscopy supports the presence of monovalent Ag atoms in these compounds, which are not charge-balanced. - Graphical abstract: Partial occupation of metal atoms in multiple sites accounts for versatility in Ga-containing chalcogenides La{sub 3}M{sub 1–x}GaCh{sub 7} with noncentrosymmetric hexagonal structures. - Highlights: • La{sub 3}M{sub 1–x}GaCh{sub 7} (M =Ga, Ag, Zn, Cd; Ch =S, Se) adopt related hexagonal structures. • Large displacements of M atoms originate from partial occupation of multiple sites. • Bond valence sum arguments give a simple explanation for site preference. • XPS studies confirm presence of monovalent Ag in La{sub 3}Ag{sub 0.6}GaCh{sub 7}. • Substoichiometry in La{sub 3}Ag{sub 0.6}GaCh{sub 7} avoids occupation of Ag–Ch antibonding levels.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mixed-Valent Copper Chalcogenides: Tuning Structures and Electronic Properties Using Multiple Anions

A series of mixed-anion copper chalcogenides have been prepared using solid-state methods including ACu 4.2 TeS 2 (A = K, Rb, Cs), which adopt the KCu 4 S 3 structure type. The mixedanion motif has an expanded sublattice, relative to KCu 4 S 3 , that can accommodate additional Cu atoms at its interstitial sites that are unoccupied in the parent structure. The variable temperature transport shows that the materials are p-type metals with carrier densities on the order of 10 21 cm -3 and room-temperature electrical conductivity as high as 4000 S cm -1 . Band structures calculated using density functional theory corroborate the experimental data and indicate that the interstitial Cu atoms lower the carrier concentration and increase the Fermi level of the materials. The layered structure has Te and S atoms occupying unique sites within the ACu 4.2 TeS 2 structure, where relatively hard S 2- anions prefer Wyckoff positions where they can form energetically favorable acid-base interactions with hard alkali cations. The phenomenon is observed in the related K 3 Cu 8 Te 2 S 4 system, which also has a fully ordered layered structure. Here, we believe that the report provides new chemical guidelines for targeting ordered multianion structures, as well as a unique method for tuning the electronic properties of metallic chalcogenides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗