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.

Effects of paramagnetic fluctuations on the thermochemistry of MnO(100) surfaces in the oxygen evolution reaction.

We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method plus U" (NCMSM+U). Various physical properties, such as the electronic structure, free energy, and charge occupation, of the MnO(100) surface in the PM state with several OER intermediates, were reckoned and compared to those in the antiferromagnetic (AFM) state. We found that PM fluctuation enhances charge transfer from a surface Mn ion to each of the intermediates and strengthens the chemical bond between them, while not altering the overall features, such as the rate determining step and resting state, in reaction pathways. The enhanced charge transfer can be attributed to the delocalized nature of valence bands observed in the PM surface. In addition, it was observed that chemical-bond enhancement depends on the intermediates, resulting in significant deviations in reaction energy barriers. Our study suggests that PM fluctuations play a significant role in the thermochemistry of chemical reactions occurring on correlated oxide surfaces.

A "non-dynamical" way of describing room-temperature paramagnetic manganese oxide.

We present a new approach based on static density functional theory (DFT) to describe paramagnetic manganese oxides, representative paramagnetic Mott insulators. We appended spin noncollinearity and a canonical ensemble to the magnetic sampling method (MSM), which is one of the supercell approaches based on the disordered local moment model. The combination of the noncollinear MSM (NCMSM) with DFT+U represents a highly favorable computational method called NCMSM+U to accurately determine the paramagnetic properties of MnO with moderate numerical cost. The effects of electron correlations and spin noncollinearity on the properties of MnO were also investigated. We found that the spin noncollinearity plays an important role in determining the detailed electronic profile and precise energetics of paramagnetic MnO. Our results illustrate that the NCMSM+U approach may be used for insulating materials as an alternative to the ab initio framework of dynamic mean field theory based on DFT in the simulation of the room-temperature paramagnetic properties.

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.

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.

Atomic Reconstruction and Oxygen Evolution Reaction of Mn3O4 Nanoparticles.

Understanding the chemical states of individual surface atoms and their arrangements is essential for addressing several current issues such as catalysis, energy stroage/conversion, and environmental protection. Here, we exploit a profile imaging technique to understand the correlation between surface atomic structures and the oxygen evolution reaction (OER) in Mn3O4 nanoparticles. We image surface structures of Mn3O4 nanoparticles and observe surface reconstructions in the (110) and (101) planes. Mn3+ ions at the surface, which are commonly considered as the active sites in OER, disappear from the reconstructed planes, whereas Mn3+ ions are still exposed at the edges of nanoparticles. Our observations suggest that surface reconstructions can deactivate low-index surfaces of Mn oxides in OER. These structural and chemical observations are further validated by density functional theory calculations. This work shows why atomic-scale characterization of surface structures is crucial for a molecular-level understanding of a chemical reaction in oxide nanoparticles.

Discovery of conjoined charge density waves in the kagome superconductor CsV3Sb5.

The electronic instabilities in CsV3Sb5 are believed to originate from the V 3d-electrons on the kagome plane, however the role of Sb 5p-electrons for 3-dimensional orders is largely unexplored. Here, using resonant tender X-ray scattering and high-pressure X-ray scattering, we report a rare realization of conjoined charge density waves (CDWs) in CsV3Sb5, where a 2 × 2 × 1 CDW in the kagome sublattice and a Sb 5p-electron assisted 2 × 2 × 2 CDW coexist. At ambient pressure, we discover a resonant enhancement on Sb L1-edge (2s→5p) at the 2 × 2 × 2 CDW wavevectors. The resonance, however, is absent at the 2 × 2 × 1 CDW wavevectors. Applying hydrostatic pressure, CDW transition temperatures are separated, where the 2 × 2 × 2 CDW emerges 4 K above the 2 × 2 × 1 CDW at 1 GPa. These observations demonstrate that symmetry-breaking phases in CsV3Sb5 go beyond the minimal framework of kagome electronic bands near van Hove filling.

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.

Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

A quasi-two-dimensional electron gas (2DEG) evolved at the LaAlO3 (LAO)/SrTiO3 (STO) interface has attracted significant attention, because the insertion of perovskite titanates can tune the 2DEG conductivity. However, this depends on the Ti-O-Ti bonding angle and structural symmetry. In this study, we controlled the octahedral tilt of the LAO/CaTiO3 (CTO) interface by heterostructuring it with CTO grown on STO substrates of various thicknesses. The 2DEG was maintained when the thickness of CTO was below the critical thickness of 5 unit cells (uc); however, it was suppressed when the CTO thickness was above the critical thickness. High-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) combined with integrated differential phase contrast (iDPC) STEM imaging was used to visualize the TiO6 octahedral tilt propagation and symmetry of the 5 uc and 24 uc CTO films. The symmetry of the 5 uc CTO film resembled that of the STO substrate, whereas the octahedral tilt propagated in the 24 uc CTO film due to the structural relaxation. These results show that the interface engineering of the octahedral tilt can enable or suppress the formation of the 2DEG in perovskite oxides.

Correction: Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

Correction for 'Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces' by Woonbae Sohn et al., Nanoscale, 2021, 13, 708-715, DOI: 10.1039/D0NR07545K.

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.

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.

Effects of the Heterointerface on the Growth Characteristics of a Brownmillerite SrFeO2.5 Thin Film Grown on SrRuO3 and SrTiO3 Perovskites.

Manipulation of the heterointerfacial structure and/or chemistry of transition metal oxides is of great interest for the development of novel properties. However, few studies have focused on heterointerfacial effects on the growth characteristics of oxide thin films, although such interfacial engineering is crucial to determine the growth dynamics and physical properties of oxide heterostructures. Herein, we show that heterointerfacial effects play key roles in determining the growth process of oxide thin films by overcoming the simple epitaxial strain energy. Brownmillerite (SrFeO2.5; BM-SFO) thin films are epitaxially grown along the b-axis on both SrTiO3(001) and SrRuO3/SrTiO3(001) substrates, whereas growth along the a-axis is expected from conventional epitaxial strain effects originating from lattice mismatch with the substrates. Scanning transmission electron microscopy measurements and first principles calculations reveal that these peculiar growth characteristics of BM-SFO thin films originate from the heterointerfacial effects governed by their distinct interfacial structures. These include octahedral connectivity between dissimilar oxides containing different chemical species and a peculiar transition layer for BM-SFO/SrRuO3/SrTiO3(001) and BM-SFO/SrTiO3(001) heterostructures, respectively. These effects enable subtle control of the growth process of oxide thin films and could facilitate the fabrication of novel functional devices.

Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni-Mn3O4 nanoparticles during water oxidation catalysis.

High-valent metal-oxo moieties have been implicated as key intermediates preceding various oxidation processes. The critical O-O bond formation step in the Kok cycle that is presumed to generate molecular oxygen occurs through the high-valent Mn-oxo species of the water oxidation complex, i.e., the Mn4Ca cluster in photosystem II. Here, we report the spectroscopic characterization of new intermediates during the water oxidation reaction of manganese-based heterogeneous catalysts and assign them as low-spin Mn(IV)-oxo species. Recently, the effects of the spin state in transition metal catalysts on catalytic reactivity have been intensely studied; however, no detailed characterization of a low-spin Mn(IV)-oxo intermediate species currently exists. We demonstrate that a low-spin configuration of Mn(IV), S = 1/2, is stably present in a heterogeneous electrocatalyst of Ni-doped monodisperse 10-nm Mn3O4 nanoparticles via oxo-ligand field engineering. An unprecedented signal (g = 1.83) is found to evolve in the electron paramagnetic resonance spectrum during the stepwise transition from the Jahn-Teller-distorted Mn(III). In-situ Raman analysis directly provides the evidence for Mn(IV)-oxo species as the active intermediate species. Computational analysis confirmed that the substituted nickel species induces the formation of a z-axis-compressed octahedral C4v crystal field that stabilizes the low-spin Mn(IV)-oxo intermediates.

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.

The Role of Zr Doping in Stabilizing Li[Ni0.6 Co0.2 Mn0.2 ]O2 as a Cathode Material for Lithium-Ion Batteries.

Ni-rich layered LiNi1-x-y Cox Mny O2 systems are the most promising cathode materials for high energy density Li-ion batteries (LIBs). However, Ni-rich cathode materials inevitably suffer from rapid capacity fading and poor rate capability owing to structural instability and unstable surface side reactions. Zr doping has proven to be an effective method to enhance the cycle and rate performances by stabilizing the structure and increasing the Li+ diffusion rate. Herein, effects of Zr-doping on the structural stability and Li+ diffusion kinetics are thoroughly investigated in LiNi0.6 Co0.2 Mn0.2 O2 (LNCM) cathode material using atomic-resolution scanning transmission electron microscopy imaging, XRD Rietveld refinement, and density functional theory calculations. Zr doping mitigates the degree of cation mixing, decreases the structural transformation, and facilitates Li+ diffusion resulting in improved cyclic performance and rate capability. Based on the obtained results, an atomistic model is proposed to explain the effects of Zr doping on the structural stability and Li+ diffusion kinetics in LNCM cathode materials.

Latent Order in High-Angle Grain Boundary of GaN.

We report the existence of latent order during core relaxation in the high-angle grain boundaries (GBs) of GaN films using atomic-resolution scanning transmission electron microscopy and ab initio density functional theory calculations. Core structures in the high-angle GBs are characterized by two pairs of Ga-N bonds located next to each other. The core type correlates strongly with the bond angle differences. We identify an order of core relaxation hidden in the high-angle GBs by further classifying the 5/7 atom cores into a stable 5/7 core (5/7(S)) and a metastable 5/7 core (5/7(M)). This core-type classification indicates that metastable cores can exist at real high-angle GBs under certain circumstances. Interestingly, 5/7(M) exhibits distinct defect states compared to 5/7(S), despite their similar atomic configurations. We investigate the reconstruction of defect states observed in 5/7(M) by analyzing the real-space wave functions. An inversion occurred between two localized states during the transition from 5/7(S) to 5/7(M). We suggest an inversion mechanism to explain the formation of new defect states in 5/7(M).

Solid-Phase Epitaxial Growth of an Alumina Layer Having a Stacking-Mismatched Domain Structure of the Intermediate γ-Phase.

Solid-phase epitaxy (SPE), a solid-state phase transition of materials from an amorphous to a crystalline phase, is a convenient crystal growing technique. In particular, SPE can be used to grow α-Al2O3 epitaxially with a novel structure that provides an effective substrate for improved performance of light-emitting diodes (LEDs). However, the inevitable two-step phase transformation through the γ-Al2O3 phase hinders the expected improved crystallinity of α-Al2O3, and thereby further enhancement of LED performance. Herein, we provide a fundamental understanding of the SPE growth mechanism from amorphous to metastable γ-Al2O3 using transmission electron microscopy (TEM) and density functional theory (DFT) calculations. The nanobeam precession electron diffraction technique enabled clear visualization of the double-positioning domain distribution in the SPE γ-Al2O3 film and emphasized the need for careful selection of the viewing directions for any investigation of double-positioning domains. Void and stacking fault defects further investigated by high-resolution scanning TEM (STEM) analyses revealed how double-positioning domains and other SPE growth behaviors directly influence the crystallinity of SPE films. Additionally, DFT calculations revealed the origins of SPE growth behavior. The double-positioning γ-Al2O3 domains randomly nucleate from the α-Al2O3 substrate regardless of the α-Al2O3 termination layer, but the large energy requirement for reversal of the γ-Al2O3 stacking sequence prevents it from switching the domain type during the crystal growth. We expect that this study will be useful to improve the crystallinity of SPE γ- and α-Al2O3 films.

High-resolution observation of nucleation and growth behavior of nanomaterials using a graphene template.

By using graphene as an electron beam-transparent substrate for both nanomaterial growth and transmission electron microscopy (TEM) measurements, we investigate initial growth behavior of nanomaterials. The direct growth and imaging method using graphene facilitate atomic-resolution imaging of nanomaterials at the very early stage of growth. This enables the observation of the transition in crystal structure of ZnO nuclei and the formation of various defects during nanomaterial growth.