Theoretical Investigation of Delafossite-Cu2ZnSnO4 as a Promising Photovoltaic Absorber.

In the quest for efficient and cost-effective photovoltaic absorber materials beyond silicon, considerable attention has been directed toward exploring alternatives. One such material, zincblende-derived Cu2ZnSnS4 (CZTS), has shown promise due to its ideal band gap size and high absorption coefficient. However, challenges such as structural defects and secondary phase formation have hindered its development. In this study, we examine the potential of another compound, Cu2ZnSnO4 (CZTO), with a similar composition to CZTS as a promising alternative. Employing ab initio density function theory (DFT) calculations in combination with an evolutionary structure prediction algorithm, we identify that the crystalline phase of delafossite structure is the most stable among the 900 (meta)stable CZTO. Its thermodynamic stability at room temperature is also confirmed by the molecular dynamics study. Excitingly, this new phase of CZTO displays a direct band gap where the dipole-allowed transition occurs, making it a strong candidate for efficient light absorptions. Furthermore, the estimation of spectroscopic limited maximum efficiency (SLME) directly demonstrates the high potential of delafossite-CZTO as a photovoltaic absorber. Our numerical results suggest that delafossite-CZTO holds promise for future photovoltaic applications.

Exotic Magnetic Anisotropy Near Digitized Dimensional Mott Boundary.

The magnetic anisotropy of low-dimensional Mott systems exhibits unexpected magnetotransport behavior useful for spin-based quantum electronics. Yet, the anisotropy of natural materials is inherently determined by the crystal structure, highly limiting its engineering. The magnetic anisotropy modulation near a digitized dimensional Mott boundary in artificial superlattices composed of a correlated magnetic monolayer SrRuO3 and nonmagnetic SrTiO3 , is demonstrated. The magnetic anisotropy is initially engineered by modulating the interlayer coupling strength between the magnetic monolayers. Interestingly, when the interlayer coupling strength is maximized, a nearly degenerate state is realized, in which the anisotropic magnetotransport is strongly influenced by both the thermal and magnetic energy scales. The results offer a new digitized control for magnetic anisotropy in low-dimensional Mott systems, inspiring promising integration of Mottronics and spintronics.

Quantum transport evidence of isolated topological nodal-line fermions.

Anomalous transport responses, dictated by the nontrivial band topology, are the key for application of topological materials to advanced electronics and spintronics. One promising platform is topological nodal-line semimetals due to their rich topology and exotic physical properties. However, their transport signatures have often been masked by the complexity in band crossings or the coexisting topologically trivial states. Here we show that, in slightly hole-doped SrAs3, the single-loop nodal-line states are well-isolated from the trivial states and entirely determine the transport responses. The characteristic torus-shaped Fermi surface and the associated encircling Berry flux of nodal-line fermions are clearly manifested by quantum oscillations of the magnetotransport properties and the quantum interference effect resulting in the two-dimensional behaviors of weak antilocalization. These unique quantum transport signatures make the isolated nodal-line fermions in SrAs3 desirable for novel devices based on their topological charge and spin transport.

Growth of delafossite CuAlO2single crystals in a reactive crucible.

Delafossite oxide CuAlO2has received great attention as a promising p-type conducting oxide. In this work, high-quality CuAlO2single crystals with a size of several millimeters (mm) are successfully synthesized with areactivecrucible melting method. The crystals are characterized by x-ray diffraction, scanning electron microscopy with energy-dispersive spectroscopy, transport measurement, and magnetic susceptibility measurement. The CuAlO2single crystals show semiconducting behavior with hole carriers, which is consistent with other crystals grown by the conventional slow-cooling method. This growth method we reported here eliminates the process of removing the remaining flux, allowing easy access to the high-quality single crystals. This new approach to growing high-quality delafossite oxide CuAlO2with a few mm size is important for new technologies that demand p-type semiconductor-based device fabrication.

Band-selective gap opening by a C 4-symmetric order in a proximity-coupled heterostructure Sr2VO3FeAs.

Complex electronic phases in strongly correlated electron systems are manifested by broken symmetries in the low-energy electronic states. Some mysterious phases, however, exhibit intriguing energy gap opening without an apparent signature of symmetry breaking (e.g., high-TC cuprates and heavy fermion superconductors). Here, we report an unconventional gap opening in a heterostructured, iron-based superconductor Sr2VO3FeAs across a phase transition at T 0 ∼150 K. Using angle-resolved photoemission spectroscopy, we identify that a fully isotropic gap opens selectively on one of the Fermi surfaces with finite warping along the interlayer direction. This band selectivity is incompatible with conventional gap opening mechanisms associated with symmetry breaking. These findings, together with the unusual field-dependent magnetoresistance, suggest that the Kondo-type proximity coupling of itinerant Fe electrons to localized V spin plays a role in stabilizing the exotic phase, which may serve as a distinct precursor state for unconventional superconductivity.

Correlated oxide Dirac semimetal in the extreme quantum limit.

Quantum materials (QMs) with strong correlation and nontrivial topology are indispensable to next-generation information and computing technologies. Exploitation of topological band structure is an ideal starting point to realize correlated topological QMs. Here, we report that strain-induced symmetry modification in correlated oxide SrNbO3 thin films creates an emerging topological band structure. Dirac electrons in strained SrNbO3 films reveal ultrahigh mobility (µmax ≈ 100,000 cm2/Vs), exceptionally small effective mass (m* ~ 0.04me), and nonzero Berry phase. Strained SrNbO3 films reach the extreme quantum limit, exhibiting a sign of fractional occupation of Landau levels and giant mass enhancement. Our results suggest that symmetry-modified SrNbO3 is a rare example of correlated oxide Dirac semimetals, in which strong correlation of Dirac electrons leads to the realization of a novel correlated topological QM.

Strain-Induced Atomic-Scale Building Blocks for Ferromagnetism in Epitaxial LaCoO3.

The origin of strain-induced ferromagnetism, which is robust regardless of the type and degree of strain in LaCoO3 (LCO) thin films, is enigmatic despite intensive research efforts over the past decade. Here, by combining scanning transmission electron microscopy with ab initio density functional theory plus U calculations, we report that the ferromagnetism does not emerge directly from the strain itself but rather from the creation of compressed structural units within ferroelastically formed twin-wall domains. The compressed structural units are magnetically active with the rocksalt-type high-spin/low-spin order. Our study highlights that the ferroelastic nature of ferromagnetic structural units is important for understanding the intriguing ferromagnetic properties in LCO thin films.

Twin-Domain Formation in Epitaxial Triangular Lattice Delafossites.

Twin domains are often found as structural defects in symmetry mismatched epitaxial thin films. The delafossite ABO2, which has a rhombohedral structure, is a good example that often forms twin domains. Although bulk metallic delafossites are known to be the most conducting oxides, high conductivity is yet to be realized in thin film forms. Suppressed conductivity found in thin films is mainly caused by the formation of twin domains, and their boundaries can be a source of scattering centers for charge carriers. To overcome this challenge, the underlying mechanism for their formation must be understood so that such defects can be controlled and eliminated. Here, we report the origin of structural twins formed in a CuCrO2 delafossite thin film on a substrate with hexagonal or triangular symmetries. A robust heteroepitaxial relationship is found for the delafossite film with the substrate, and the surface termination turns out to be critical to determine and control the domain structure of epitaxial delafossites. Based on such discoveries, we also demonstrate twin-free epitaxial thin films grown on high-miscut substrates. This finding provides an important synthesis strategy for growing single-domain delafossite thin films and can be applied to other delafossites for the epitaxial synthesis of high-quality thin films.

Strain-driven autonomous control of cation distribution for artificial ferroelectrics.

In past few decades, there have been substantial advances in theoretical material design and experimental synthesis, which play a key role in the steep ascent of developing functional materials with unprecedented properties useful for next-generation technologies. However, the ultimate goal of synthesis science, i.e., how to locate atoms in a specific position of matter, has not been achieved. Here, we demonstrate a unique way to inject elements in a specific crystallographic position in a composite material by strain engineering. While the use of strain so far has been limited for only mechanical deformation of structures or creation of elemental defects, we show another powerful way of using strain to autonomously control the atomic position for the synthesis of new materials and structures. We believe that our synthesis methodology can be applied to wide ranges of systems, thereby providing a new route to functional materials.

Interfacial tuning of chiral magnetic interactions for large topological Hall effects in LaMnO3/SrIrO3 heterostructures.

Chiral interactions in magnetic systems can give rise to rich physics manifested, for example, as nontrivial spin textures. The foremost interaction responsible for chiral magnetism is the Dzyaloshinskii-Moriya interaction (DMI), resulting from inversion symmetry breaking in the presence of strong spin-orbit coupling. However, the atomistic origin of DMIs and their relationship to emergent electrodynamic phenomena, such as topological Hall effect (THE), remain unclear. Here, we investigate the role of interfacial DMIs in 3d-5d transition metal-oxide-based LaMnO3/SrIrO3 superlattices on THE from a chiral spin texture. By additively engineering the interfacial inversion symmetry with atomic-scale precision, we directly link the competition between interfacial collinear ferromagnetic interactions and DMIs to an enhanced THE. The ability to control the DMI and resulting THE points to a pathway for harnessing interfacial structures to maximize the density of chiral spin textures useful for developing high-density information storage and quantum magnets for quantum information science.

Interfacial stabilization for epitaxial CuCrO2 delafossites.

ABO2 delafossites are fascinating materials that exhibit a wide range of physical properties, including giant Rashba spin splitting and anomalous Hall effects, because of their characteristic layered structures composed of noble metal A and strongly correlated BO2 sublayers. However, thin film synthesis is known to be extremely challenging owing to their low symmetry rhombohedral structures, which limit the selection of substrates for thin film epitaxy. Hexagonal lattices, such as those provided by Al2O3(0001) and (111) oriented cubic perovskites, are promising candidates for epitaxy of delafossites. However, the formation of twin domains and impurity phases is hard to suppress, and the nucleation and growth mechanisms thereon have not been studied for the growth of epitaxial delafossites. In this study, we report the epitaxial stabilization of a new interfacial phase formed during pulsed-laser epitaxy of (0001)-oriented CuCrO2 epitaxial thin films on Al2O3 substrates. Through a combined study using scanning transmission electron microscopy/electron-energy loss spectroscopy and density functional theory calculations, we report that the nucleation of a thermodynamically stable, atomically thick CuCr1-xAlxO2 interfacial layer is the critical element for the epitaxy of CuCrO2 delafossites on Al2O3 substrates. This finding provides key insights into the thermodynamic mechanism for the nucleation of intermixing-induced buffer layers that can be used for the growth of other noble-metal-based delafossites, which are known to be challenging due to the difficulty in initial nucleation.

Large anomalous Hall current induced by topological nodal lines in a ferromagnetic van der Waals semimetal.

Topological semimetals host electronic structures with several band-contact points or lines and are generally expected to exhibit strong topological responses. Up to now, most work has been limited to non-magnetic materials and the interplay between topology and magnetism in this class of quantum materials has been largely unexplored. Here we utilize theoretical calculations, magnetotransport and angle-resolved photoemission spectroscopy to propose Fe3GeTe2, a van der Waals material, as a candidate ferromagnetic (FM) nodal line semimetal. We find that the spin degree of freedom is fully quenched by the large FM polarization, but the line degeneracy is protected by crystalline symmetries that connect two orbitals in adjacent layers. This orbital-driven nodal line is tunable by spin orientation due to spin-orbit coupling and produces a large Berry curvature, which leads to a large anomalous Hall current, angle and factor. These results demonstrate that FM topological semimetals hold significant potential for spin- and orbital-dependent electronic functionalities.

Frustration-driven C 4 symmetric order in a naturally-heterostructured superconductor Sr2VO3FeAs.

A subtle balance between competing interactions in iron-based superconductors (FeSCs) can be tipped by additional interfacial interactions in a heterostructure, often inducing exotic phases with unprecedented properties. Particularly when the proximity-coupled layer is magnetically active, rich phase diagrams are expected in FeSCs, but this has not been explored yet. Here, using high-accuracy 75As and 51V nuclear magnetic resonance measurements, we investigate an electronic phase that emerges in the FeAs layer below T 0 ~ 155 K of Sr2VO3FeAs, a naturally assembled heterostructure of an FeSC and a Mott-insulating vanadium oxide. We find that frustration of the otherwise dominant Fe stripe and V Neel fluctuations via interfacial coupling induces a charge/orbital order in the FeAs layers, without either static magnetism or broken C 4 symmetry, while suppressing the Neel antiferromagnetism in the SrVO3 layers. These findings demonstrate that the magnetic proximity coupling stabilizes a hidden order in FeSCs, which may also apply to other strongly correlated heterostructures.

Switching Magnetism and Superconductivity with Spin-Polarized Current in Iron-Based Superconductor.

We explore a new mechanism for switching magnetism and superconductivity in a magnetically frustrated iron-based superconductor using spin-polarized scanning tunneling microscopy (SPSTM). Our SPSTM study on single-crystal Sr_{2}VO_{3}FeAs shows that a spin-polarized tunneling current can switch the Fe-layer magnetism into a nontrivial C_{4} (2×2) order, which cannot be achieved by thermal excitation with an unpolarized current. Our tunneling spectroscopy study shows that the induced C_{4} (2×2) order has characteristics of plaquette antiferromagnetic order in the Fe layer and strongly suppresses superconductivity. Also, thermal agitation beyond the bulk Fe spin ordering temperature erases the C_{4} state. These results suggest a new possibility of switching local superconductivity by changing the symmetry of magnetic order with spin-polarized and unpolarized tunneling currents in iron-based superconductors.

Correlation of Fe-Based Superconductivity and Electron-Phonon Coupling in an FeAs/Oxide Heterostructure.

Interfacial phonons between iron-based superconductors (FeSCs) and perovskite substrates have received considerable attention due to the possibility of enhancing preexisting superconductivity. Using scanning tunneling spectroscopy, we studied the correlation between superconductivity and e-ph interaction with interfacial phonons in an iron-based superconductor Sr_{2}VO_{3}FeAs (T_{c}≈33 K) made of alternating FeSC and oxide layers. The quasiparticle interference measurement over regions with systematically different average superconducting gaps due to the e-ph coupling locally modulated by O vacancies in the VO_{2} layer, and supporting self-consistent momentum-dependent Eliashberg calculations provide a unique real-space evidence of the forward-scattering interfacial phonon contribution to the total superconducting pairing.

Broken-Symmetry Quantum Hall States in Twisted Bilayer Graphene.

Twisted bilayer graphene offers a unique bilayer two-dimensional-electron system where the layer separation is only in sub-nanometer scale. Unlike Bernal-stacked bilayer, the layer degree of freedom is disentangled from spin and valley, providing eight-fold degeneracy in the low energy states. We have investigated broken-symmetry quantum Hall (QH) states and their transitions due to the interplay of the relative strength of valley, spin and layer polarizations in twisted bilayer graphene. The energy gaps of the broken-symmetry QH states show an electron-hole asymmetric behaviour, and their dependence on the induced displacement field are opposite between even and odd filling factor states. These results strongly suggest that the QH states with broken valley and spin symmetries for individual layer become hybridized via interlayer tunnelling, and the hierarchy of the QH states is sensitive to both magnetic field and displacement field due to charge imbalance between layers.

Anomalous Magnetothermopower in a Metallic Frustrated Antiferromagnet.

We report the temperature T and magnetic field H dependence of the thermopower S of an itinerant triangular antiferromagnet PdCrO_{2} in high magnetic fields up to 32 T. In the paramagnetic phase, the zero-field thermopower is positive with a value typical of good metals with a high carrier density. In marked contrast to typical metals, however, S decreases rapidly with increasing magnetic field, approaching zero at the maximum field scale for T>70 K. We argue here that this profound change in the thermoelectric response derives from the strong interaction of the 4d correlated electrons of the Pd ions with the short-range spin correlations of the Cr^{3+} spins that persist beyond the Néel ordering temperature due to the combined effects of geometrical frustration and low dimensionality.

Direct observation of localized spin antiferromagnetic transition in PdCrO2 by angle-resolved photoemission spectroscopy.

We report the first case of the successful measurements of a localized spin antiferromagnetic transition in delafossite-type PdCrO2 by angle-resolved photoemission spectroscopy (ARPES). This demonstrates how to circumvent the shortcomings of ARPES for investigation of magnetism involved with localized spins in limited size of two-dimensional crystals or multi-layer thin films that neutron scattering can hardly study due to lack of bulk compared to surface. Also, our observations give direct evidence for the spin ordering pattern of Cr(3+) ions in PdCrO2 suggested by neutron diffraction and quantum oscillation measurements, and provide a strong constraint that has to be satisfied by a microscopic mechanism for the unconventional anomalous Hall effect recently reported in this system.

Quantum oscillations of the metallic triangular-lattice antiferromagnet PdCrO2.

We report the electronic and transport properties of the triangular antiferromagnet PdCrO(2) at high magnetic fields up to 33 T, using measurements of the de Haas-van Alphen oscillations and the Hall resistivity. The de Haas-van Alphen oscillations below the magnetic ordering temperature T(N) reveal several two-dimensional Fermi surfaces of smaller size than those found in nonmagnetic PdCoO(2), consistent with the band structure calculations. This evidences Fermi surface reconstruction due to the 120° helical ordering of the localized Cr spins, suggesting significant coupling of the itinerant electrons to the underlying spin texture. This induces the nonlinear Hall resistivity at low temperatures via the magnetic breakdown in the reconstructed Fermi surface. Furthermore, such a coupling leads to the unconventional anomalous Hall effects near T(N) due to the field-induced spin chirality at high magnetic fields.