Multiband Electronic Structure Research Articles

S-d Coupling-Induced Dynamic Off-Centering of Cu Drives High Thermoelectric Performance in TlCuS.

Seeking new and efficient thermoelectric materials requires a detailed comprehension of chemical bonding and structure in solids at microscopic levels, which dictates their intriguing physical and chemical properties. Herein, we investigate the influence of local structural distortion on the thermoelectric properties of TlCuS, a layered metal sulfide featuring edge-shared Cu-S tetrahedra within Cu2S2 layers. While powder X-ray diffraction suggests average crystallographic symmetry with no distortion in CuS4 tetrahedra, the synchrotron X-ray pair distribution function experiment exposes concealed local symmetry breaking, with dynamic off-centering distortions of the CuS4 tetrahedra. The Cu off-centering is driven by the on-site coupling of filled 3d and unoccupied 4s orbitals (s-d) of Cu through a second-order Jahn-Teller mechanism. Bond softening by the p-d* (S-3p and Cu-3d) antibonding interaction coupled with dynamic off-centering distortions causes significant anharmonicity in the lattice, which acts as a phonon-blocking mechanism conducive to ultralow lattice thermal conductivity (κlat) (∼0.35-0.23 W m-1 K-1 in the ∼296-573 K temperature range) in TlCuS. The synergy between low κlat and multiband electronic structure leads to thermoelectric figure-of-merits (zT) of ∼1 and ∼1.3 at 573 K for pristine TlCuS and TlCu0.98S, respectively, underscoring the potential of metal sulfides as promising high-performance thermoelectrics.

Multiband Quantum Materials

Quantum materials are defined by the emergence of new properties resulting from collective quantum effects and by holding promise for their quantum applications. Novel superconductors, from high-Tc cuprates and iron-based superconductors to twisted monolayers, exhibit a higher level of emergent complexity, with a multiband electronic structure playing a pivotal role in their comprehension and potential applications. Here, we provide a brief overview of key multiband effects in these superconductors and topological semimetals, offering guidelines for the theory-assisted development of new quantum materials and devices.

Unusual crossover from Bardeen-Cooper-Schrieffer to Bose-Einstein-condensate superconductivity in iron chalcogenides

The BCS-BEC (Bardeen-Cooper-Schrieffer–Bose-Einstein-condensate) crossover from strongly overlapping Cooper pairs to non-overlapping composite bosons in the strong coupling limit has been a long-standing issue of interacting many-body fermion systems. Recently, FeSe semimetal with hole and electron bands emerged as a high-transition-temperature (high-Tc) superconductor located in the BCS-BEC crossover regime, owing to its very small Fermi energies. In FeSe, however, an ordinary BCS-like heat-capacity jump is observed at Tc, posing a fundamental question on the characteristics of the BCS-BEC crossover. Here we report on high-resolution heat capacity, magnetic torque, and scanning tunneling spectroscopy measurements in FeSe1−xSx. Upon entering the tetragonal phase at x > 0.17, where nematic order is suppressed, Tc discontinuously decreases. In this phase, highly non-mean-field behaviours consistent with BEC-like pairing are found in the thermodynamic quantities with giant superconducting fluctuations extending far above Tc, implying the change of pairing nature. Moreover, the pseudogap formation, which is expected in BCS-BEC crossover of single-band superconductors, is not observed in the tunneling spectra. These results illuminate highly unusual features of the superconducting states in the crossover regime with multiband electronic structure and competing electronic instabilities.

Review of Single Crystal Synthesis of 11 Iron-Based Superconductors.

The 11 system in the iron-based superconducting family has become one of the most extensively studied materials in the research of high-temperature superconductivity, due to their simple structure and rich physical properties. Many exotic properties, such as multiband electronic structure, electronic nematicity, topology and antiferromagnetic order, provide strong support for the theory of high-temperature superconductivity, and have been at the forefront of condensed matter physics in the past decade. One noteworthy aspect is that a high upper critical magnetic field, large critical current density and lower toxicity give the 11 system good application prospects. However, the research on 11 iron-based superconductors faces numerous obstacles, mainly stemming from the challenges associated with producing high-quality single crystals. Since the discovery of FeSe superconductivity in 2008, researchers have made significant progress in crystal growth, overcoming the hurdles that initially impeded their studies. Consequently, they have successfully established the complete phase diagrams of 11 iron-based superconductors, including FeSe1-xTex, FeSe1-xSx and FeTe1-xSx. In this paper, we aim to provide a comprehensive summary of the preparation methods employed for 11 iron-based single crystals over the past decade. Specifically, we will focus on hydrothermal, chemical vapor transport (CVT), self-flux and annealing methods. Additionally, we will discuss the quality, size, and superconductivity properties exhibited by single crystals obtained through different preparation methods. By exploring these aspects, we can gain a better understanding of the advantages and limitations associated with each technique. High-quality single crystals serve as invaluable tools for advancing both the theoretical understanding and practical utilization of high-temperature superconductivity.

Evidence for Anisotropic Superconductivity Beyond Pauli Limit in Infinite-Layer Lanthanum Nickelates.

After being expected to be a promising analog to cuprates for decades, superconductivity has recently been discovered in infinite-layer nickelates, providing new opportunities to explore mechanisms of high-temperature superconductivity. However, in sharp contrast to the single-band and anisotropic superconductivity in cuprates, nickelates exhibit a multi-band electronic structure and an unexpected isotropic superconductivity as reported recently, which challenges the cuprate-like picture in nickelates. Here, it is shown that strong anisotropic magnetotransport behaviors exist in La-based nickelate films with enhanced crystallinity and superconductivity ( = 18.8 K, = 16.5 K). The upper critical fields are anisotropic and violate the estimated Bardeen-Cooper-Schrieffer (BCS) Pauli limit ( ) for in-plane magnetic fields. Moreover, the anisotropic superconductivity is further manifested by the cusp-like peak of the angle-dependent Tc and the vortex motion anisotropy under external magnetic fields.

Nonequilibrium Green’s function approach to multi-band Cooper-pair transport: linear magnetoresistance effect due to nonunitary superconductivity

Many-body transport has emerged as an efficient tool for understanding interaction effects in quantum materials with a multi-band electronic structure. This paper proposes a formula for the two-particle transmission coefficient for Cooper-pair transport between multi-band normal and superconducting materials. The approach employs a tight-binding nonequilibrium Green’s function technique, allowing a direct calculation of the two-particle current, without invoking the paradigm of Andreev reflection. As an application of the theory, we demonstrate a low-field linear magnetoresistance effect for superconductors with an induced nonunitary order parameter. These results uncover an unexplored route for detecting unconventional nonunitary superconductivity in quantum materials of current theoretical and experimental interest.

Unconventional localization of electrons inside of a nematic electronic phase

The magnetotransport behavior inside the nematic phase of bulk FeSe reveals unusual multiband effects that cannot be reconciled with a simple two-band approximation proposed by surface-sensitive spectroscopic probes. In order to understand the role played by the multiband electronic structure and the degree of two-dimensionality, we have investigated the electronic properties of exfoliated flakes of FeSe by reducing their thickness. Based on magnetotransport and Hall resistivity measurements, we assess the mobility spectrum that suggests an unusual asymmetry between the mobilities of the electrons and holes, with the electron carriers becoming localized inside the nematic phase. Quantum oscillations in magnetic fields up to 38 T indicate the presence of a hole-like quasiparticle with a lighter effective mass and a quantum scattering time three times shorter, as compared with bulk FeSe. The observed localization of negative charge carriers by reducing dimensionality can be driven by orbitally dependent correlation effects, enhanced interband spin fluctuations, or a Lifshitz-like transition, which affect mainly the electron bands. The electronic localization leads to a fragile two-dimensional superconductivity in thin flakes of FeSe, in contrast to the two-dimensional high-[Formula: see text] induced with electron doping via dosing or using a suitable interface.

Laser-induced charge and spin photocurrents at the BiAg2 surface: A first-principles benchmark

Here, we report first principles calculations and analysis of laser-induced photocurrents at the surface of a prototype Rashba system. By referring to Keldysh non-equilibrium formalism combined with the Wannier interpolation scheme we perform first-principles electronic structure calculations of a prototype BiAg$_2$ surface alloy, which is a well-known material realization of the Rashba model. In addition to non-magnetic ground state situation we also study the case of in-plane magnetized BiAg$_2$. We calculate the laser-induced charge photocurrents for the ferromagnetic case and the laser-induced spin photocurrents for both the non-magnetic and the ferromagnetic cases. Our results confirm the emergence of very large in-plane photocurrents as predicted by the Rashba model. The resulting photocurrents satisfy all the symmetry restrictions with respect to the light helicity and the magnetization direction. We provide microscopic insights into the symmetry and magnitude of the computed currents based on the ab-initio multi-band electronic structure of the system, and scrutinize the importance of resonant two-band and three-band transitions for driven currents, thereby establishing a benchmark picture of photocurrents at Rashba-like surfaces and interfaces. Our work contributes to the study of the role of the interfacial Rashba spin-orbit interaction as a mechanism for the generation of in-plane photocurrents, which are of great interest in the field of ultrafast and terahertz spintronics.

Direct observation of multiband charge density waves in NbTe2

The electronic structure of periodic lattice distortion (PLD) in ${\mathrm{NbTe}}_{2}$ was examined using low-temperature scanning tunneling spectroscopy and microscopy. The striped PLDs with $3\ifmmode\times\else\texttimes\fi{}1$ and $1\ifmmode\times\else\texttimes\fi{}\frac{9}{2}$ superstructures were characterized in real and reciprocal space. The simultaneous formation of momentum-specific suppressions in the spectral weight and phase shifts of the wavefront related to the superstructures were observed at multiple energies. These unusual energy dependencies are well agreed with the charge density waves (CDWs) formed in the multiband electronic structure of ${\mathrm{NbTe}}_{2}$. Fermi-surface nesting and reconstruction of the reciprocal lattice were suggested in developing the multiband CDWs in ${\mathrm{NbTe}}_{2}$.

Multiband effects in thermoelectric and electrical transport properties of kagome superconductors AV3Sb5 (A = K, Rb, Cs)

We studied the effects of multiband electronic structure on the thermoelectric and electrical transport properties in the normal state of kagome superconductors AV3Sb5 (A = K, Rb, Cs). In all three members, the multiband nature is manifested by sign changes in the temperature dependence of the Seebeck and Hall resistivity, together with sublinear response of the isothermal Nernst and Hall effects to external magnetic fields in the charge ordered state. Moreover, ambipolar transport effects appear ubiquitously in all three systems, giving rise to sizable Nernst signal. Finally, possible origins of the sign reversal in the temperature dependence of the Hall effect are discussed.

Suppression of fluctuations in a two-band superconductor with a quasi-one-dimensional band

Chain-like structured superconductive materials (such as A_2Cr_3As_3, with A = K, Rb, Cs) exhibit the multiband electronic structure of single-particle states, where coexisting quasi-one-dimensional (Q1D) and conventional higher-dimensional energy bands take part in the creation of the aggregate superconducting condensate. When the chemical potential approaches the edge of a Q1D band in a single-band superconductor, the corresponding mean-field critical temperature increases significantly but the superconductivity is quenched by fluctuations. However, recent investigation has revealed that when a Q1D band is coupled to a higher dimensional one by the interband Cooper-pair transfer, the thermal superconductive fluctuations can be suppressed so that the resulting critical temperature can be close to its mean-field value. In the present work, we calculate the mean-field T_c0 and fluctuation-shifted T_c critical temperatures for a two-band superconductor where a Q1D band coexists with a higher-dimensional band, and investigate how the thermal fluctuations are sensitive to the system parameters. We find that T_c is close to T_c0 in a wide range of microscopic parameters, and even the dimensionality of the higher-dimensional band does not play an essential role. Thus, the screening mechanism for suppressing fluctuations via the pair-exchange coupling between the bands is indeed relevant for a large class of Q1D multiband superconducting materials, encouraging further experiments aimed at reaching larger critical temperatures in such multiband superconductors.

Pressure-Induced Superconductivity in Flat-Band Kagome Compounds Pd3P2(S1 – x Se x )8

We performed high-pressure transport studies on the flat-band Kagome compounds, Pd3P2(S1 – x Se x )8 (x = 0, 0.25), with a diamond anvil cell. For both compounds, the resistivity exhibits an insulating behavior with pressure up to 17 GPa. With pressure above 20 GPa, a metallic behavior is observed at high temperatures in Pd3P2S8, and superconductivity emerges at low temperatures. The onset temperature of superconducting transition T C rises monotonically from 2 K to 4.8 K and does not saturate with pressure up to 43 GPa. For the Se-doped compound Pd3P2(S0.75Se0.25)8, the T C is about 1.5 K higher than that of the undoped one over the whole pressure range, and reaches 6.4 K at 43 GPa. The upper critical field with field applied along the c axis at typical pressures is about 50% of the Pauli limit, suggesting a 3D superconductivity. The Hall coefficient in the metallic phase is low and exhibits a peaked behavior at about 30 K, which suggests either a multi-band electronic structure or an electron correlation effect in the system.

High-harmonic generation in Weyl semimetal \u03b2-WP2 crystals

As a quantum material, Weyl semimetal has a series of electronic-band-structure features, including Weyl points with left and right chirality and corresponding Berry curvature, which have been observed in experiments. These band-structure features also lead to some unique nonlinear properties, especially high-order harmonic generation (HHG) due to the dynamic process of electrons under strong laser excitation, which has remained unexplored previously. Herein, we obtain effective HHG in type-II Weyl semimetal β-WP2 crystals, where both odd and even orders are observed, with spectra extending into the vacuum ultraviolet region (190 nm, 10th order), even under fairly low femtosecond laser intensity. In-depth studies have interpreted that odd-order harmonics come from the Bloch electron oscillation, while even orders are attributed to Bloch oscillations under the “spike-like” Berry curvature at Weyl points. With crystallographic orientation-dependent HHG spectra, we further quantitatively retrieved the electronic band structure and Berry curvature of β-WP2. These findings may open the door for exploiting metallic/semimetallic states as solid platforms for deep ultraviolet radiation and offer an all-optical and pragmatic solution to characterize the complicated multiband electronic structure and Berry curvature of quantum topological materials.

Ultralow Thermal Conductivity, Multiband Electronic Structure and High Thermoelectric Figure of Merit in TlCuSe

The entanglement of lattice thermal conductivity, electrical conductivity, and Seebeck coefficient complicates the process of optimizing thermoelectric performance in most thermoelectric materials. Semiconductors with ultralow lattice thermal conductivities and high power factors at the same time are scarce but fundamentally interesting and practically important for energy conversion. Herein, an intrinsic p-type semiconductor TlCuSe that has an intrinsically ultralow thermal conductivity (0.25 W m-1 K-1 ), a high power factor (11.6µW cm-1 K-2 ), and a high figure of merit, ZT (1.9) at 643 K is described. The weak chemical bonds, originating from the filled antibonding orbitals p-d* within the edge-sharing CuSe4 tetrahedra and long TlSe bonds in the PbClF-type structure, in conjunction with the large atomic mass of Tl lead to an ultralow sound velocity. Strong anharmonicity, coming from Tl+ lone-pair electrons, boosts phonon-phonon scattering rates and further suppresses lattice thermal conductivity. The multiband character of the valence band structure contributing to power factor enhancement benefits from the lone-pair electrons of Tl+ as well, which modify the orbital character of the valence bands, and pushes the valence band maximum off the Γ-point, increasing the band degeneracy. The results provide new insight on the rational design of thermoelectric materials.

Discovery of multivalley Fermi surface responsible for the high thermoelectric performance in Yb14MnSb11 and Yb14MgSb11.

The Zintl phases, Yb14 MSb11 (M = Mn, Mg, Al, Zn), are now some of the highest thermoelectric efficiency p-type materials with stability above 873 K. Yb14MnSb11 gained prominence as the first p-type thermoelectric material to double the efficiency of SiGe alloy, the heritage material in radioisotope thermoelectric generators used to power NASA's deep space exploration. This study investigates the solid solution of Yb14Mg1-x Al x Sb11 (0 ≤ x ≤ 1), which enables a full mapping of the metal-to-semiconductor transition. Using a combined theoretical and experimental approach, we show that a second, high valley degeneracy (N v = 8) band is responsible for the groundbreaking performance of Yb14 MSb11 This multiband understanding of the properties provides insight into other thermoelectric systems (La3-x Te4, SnTe, Ag9AlSe6, and Eu9CdSb9), and the model predicts that an increase in carrier concentration can lead to zT > 1.5 in Yb14 MSb11 systems.

Doping evolution of the Mott–Hubbard landscape in infinite-layer nickelates

The recent observation of superconductivity in [Formula: see text] has raised fundamental questions about the hierarchy of the underlying electronic structure. Calculations suggest that this system falls in the Mott-Hubbard regime, rather than the charge-transfer configuration of other nickel oxides and the superconducting cuprates. Here, we use state-of-the-art, locally resolved electron energy-loss spectroscopy to directly probe the Mott-Hubbard character of [Formula: see text] Upon doping, we observe emergent hybridization reminiscent of the Zhang-Rice singlet via the oxygen-projected states, modification of the Nd 5d states, and the systematic evolution of Ni 3d hybridization and filling. These experimental data provide direct evidence for the multiband electronic structure of the superconducting infinite-layer nickelates, particularly via the effects of hole doping on not only the oxygen but also nickel and rare-earth bands.

The transport properties of iron-based superconductors

There are a variety of order states in iron-based pnictides, such as electronic nematic phase, spin density wave, and so on, which leads to plenty of novel physical phenomena. The measurements of transport properties can provide extremely useful information for understanding of the low-energy excitations of iron-based superconductors. Due to the multi-band electronic structure in iron-based pnictides, the temperature dependence of resistivity and Hall coefficient varies with different systems, however, there are no evidence for the pseudo-gap opening in the normal state which is a common feature in underdoped high-<inline-formula><tex-math id="M2">\begin{document}$T_{\rm{c}}$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1-20201836_M2.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1-20201836_M2.png"/></alternatives></inline-formula> cuprates. In the hole-doped iron-based superconductors, the Hall coefficient changes its sign in low temperatures, and meanwhile the resistivity shows a broad hump in the same temperature range. Such a behavior is proposed as a crossover from incoherent to coherent transport. The Seebeck coefficients of iron-based superconductors also show remarkable differences from the cuprates. In iron-based superconductors, the absolute value of Seebeck coefficients in the normal state becomes the largest at the optimally doping point with highest <inline-formula><tex-math id="M3">\begin{document}$T_{\rm{c}}$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1-20201836_M3.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1-20201836_M3.png"/></alternatives></inline-formula>, which is probably related to the strong inter-band scattering. The Nernst effect in the normal state of iron-based superconductors indicates that superconducting phase fluctuations is not obvious above <inline-formula><tex-math id="M4">\begin{document}$T_{\rm{c}}$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1-20201836_M4.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1-20201836_M4.png"/></alternatives></inline-formula>, which is also significantly different from the cuprates. These unusual thermoelectric properties observed in iron-based superconductors have not been observed in the nickel-based pnictide superconductors with the analogous structure, i.e., LaNiAsO, and the nickel-based superconductors behave more like a usual metal. All these results above illustrate that these unusual transport properties of iron-based superconductors are inherently associated with their high temperature superconductivity, and these factors should be taken into account in the theory on its superconducting mechanism.

Exotic Superconducting States in FeSe-based Materials

High-temperature superconductivity and a wide variety of exotic superconducting states discovered in FeSe-based materials have been at the frontier of research on condensed matter physics over the past decade. Unique properties originating from the multiband electronic structure, strongly orbital-dependent phenomena, extremely small Fermi energy, electronic nematicity, and topological aspects give rise to many distinct and fascinating superconducting states. Here, we provide an overview of our current understanding of the superconductivity of {\it bulk} FeSe-based materials, focusing on FeSe and the isovalent substituted FeSe$_{1-x}$S$_{x}$ and FeSe$_{1-x}$Te$_{x}$. We discuss the highly nontrivial superconducting properties in FeSe, including extremely anisotropic pairing states, crossover phenomena from Bardeen--Cooper--Schrieffer (BCS) to Bose--Einstein condensation (BEC) states, a novel field-induced superconducting phase, and broken time-reversal symmetry. We also discuss the evolution of the superconducting gap function with sulfur and tellurium doping, paying particular attention to the impact of quantum critical nematic fluctuations and the topological superconductivity. FeSe-based materials provide an excellent playground to study various exotic superconducting states.

All-oxide ferromagnetic resonance and spin pumping with SrIrO3

$\mathrm{SrIr}{\mathrm{O}}_{3}$ is a semimetallic complex oxide of interest for spintronic applications due to the large spin-orbit coupling arising from iridium. It has unusual charge transport properties derived from a complex multiband electronic structure, with electron and hole pockets both contributing to conductivity. We report ferromagnetic resonance of $\mathrm{L}{\mathrm{a}}_{0.7}\mathrm{S}{\mathrm{r}}_{0.3}\mathrm{Mn}{\mathrm{O}}_{3}$ and $\mathrm{SrIr}{\mathrm{O}}_{3}$ epitaxial bilayer films on ${(\mathrm{LaAl}{\mathrm{O}}_{3})}_{0.3}{(\mathrm{S}{\mathrm{r}}_{2}\mathrm{AlTa}{\mathrm{O}}_{6})}_{0.7}$ substrates. Anomalous trends in the out-of-plane magnetic anisotropy and Land\'e $g$ factor suggest that orbital magnetism is modified by proximity of $\mathrm{SrIr}{\mathrm{O}}_{3}$ at low temperatures, likely contributing to large (\ensuremath{\sim}fivefold) enhancements in Gilbert damping. However, enhanced Gilbert damping due to spin pumping is also apparent in the temperature range 250--300 K. The effective spin-mixing conductance is evaluated to be ${G}_{\ensuremath{\uparrow}\ensuremath{\downarrow}}^{\mathrm{eff}}\ensuremath{\sim}0.5\ifmmode\times\else\texttimes\fi{}{10}^{14}\phantom{\rule{0.16em}{0ex}}{\mathrm{\ensuremath{\Omega}}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{m}}^{\ensuremath{-}2}$, and the spin scattering length scale of $\mathrm{SrIr}{\mathrm{O}}_{3}$ is of the order of \ensuremath{\sim}1 nm. Our work demonstrates the delicate interplay of pure spin current with interfacially mediated spin-orbit effects in a complex oxide heterostructure, exploiting temperature as a control parameter, and should be of interest for both spin pumping and understanding the electronic structure of thin film iridates.

Microstructural control of the transport properties of β-FeSe films grown by sputtering

We have investigated the correlation between structural and transport properties in sputtered β-FeSe films grown onto SrTiO3 (100). The growth parameters, such as substrate temperature and thickness, have been varied in order to explore different regimes. In the limit of textured thick films, we found promising features like an enhanced Tc∼12 K, a relatively high Hc2, and a low anisotropy. By performing magnetoresistance and Hall coefficient measurements, we investigate the influence of the disorder associated with the textured morphology on some features attributed to subtle details of the multiband electronic structure of β-FeSe. Regarding the superconductor-insulator transition induced by reducing the thickness, we found a nontrivial evolution of the structural properties and morphology associated with a strained initial growth and the coalescence of grains. Finally, we discuss the origin of the insulating behavior in high-quality stressed epitaxial thin films. We found that a lattice distortion, described by Poisson’s coefficient associated with the lattice parameters a and c, may play a key role.