arXiv subjects

Sangmoon Yoon

Publications and source records attributed to Sangmoon Yoon.

17 recordsLinked to original sources

arXiv2025

Awakening catalytically active surface of BaRuO3 thin film for alkaline hydrogen evolution

The dynamic reconstruction of surfaces during electrochemical reactions plays a crucial role in determining the performance of electrocatalysts. However, because reconstructions occur at the atomic level, direct observation and elucidation of the underlying mechanism are challenging for conventional powder type catalysts with ill defined lattices. In this study, the catalytically active surface of 3C BaRuO3 (BRO) epitaxial thin films emerges upon the dynamic introduction of surface Ru clusters, for the alkaline hydrogen evolution reaction (HER). Based on the mass activity at overpotential 100 mV, the intrinsic HER performance increases dramatically from 0.11 to 7.72 A/mg immediately after the initial HER cycle and eventually saturates at 1.05 A/mg after continuous operation. The formation of Ru clusters on the catalyst surface, driven by selective Ba leaching under alkaline HER conditions, is observed experimentally. Density functional theory calculations demonstrate that HER activity increased with enhanced H* adsorption owing to the dynamic Ru6 cluster formation. A strategy for stabilizing the 'awakened' active surface of BRO is further proposed by validating that the atomic-scale control of the film thickness can effectively maintain the highly active state. This study offers fundamental insights into the design and stabilization of the highly active Ru-based electrocatalysts for the alkaline HER.

cond-mat.mtrl-sci↗

arXiv2025

Correlative 3D Mapping of Structure, Composition, and Valence State Dynamics in Battery Cathodes via Simultaneous ADF-EDS-EELS Tomography

Understanding degradation in battery cathodes and other functional materials requires simultaneous knowledge of structural, chemical, and electronic changes in three dimensions (3D). Here, we present a simultaneous ADF-EDS-EELS tomography method that enables 3D mapping of atomic structure, composition, valence states, and transition metal inhomogeneity within a single, low-dose STEM tilt series acquisition. Applied to LiNi1/3Co1/3Mn1/3O2 (NCM111) particles at different electrochemical cycling stages, this method reveals nanoscale degradation processes with full spatial correlation. We observe that while chemical composition evolves uniformly throughout the entire primary particle, valence state changes and transition metal segregation are strongly depth-dependent and concentrated near the surface. This coexistence of bulk and surface-driven degradation dynamics reveals distinct mechanisms acting at different spatial scales. The evolution of inhomogeneity and valence states deviates from simple phase transition models, highlighting the roles of ion migration and dissolution-driven segregation. Our findings establish valence state gradients and nanoscale inhomogeneity as active contributors to cathode failure. More broadly, this correlative 3D platform opens new opportunities for studying redox-driven transformations in fields such as neuromorphic computing and heterogeneous catalysis, where composition-structure-function coupling is inherently three-dimensional.

cond-mat.mtrl-sci↗

arXiv2025

Overcoming Quantum Resistivity Scaling in Nanoscale Interconnects Using Delafossite PdCoO2

Continued scaling into the sub 7 nm regime exacerbates quantum limited resistivity in Cu interconnects. We evaluated layered PdCoO2 and explicitly benchmarked it against Cu to identify mechanisms that maintain conductivity under confinement. Using a momentum resolved relaxation time formalism derived from the conductivity tensor, we link k and energy resolved velocities, life times, and mean free paths (MFPs) to thickness dependent resistivity for films and wires. PdCoO2 exhibits quasi 2D transport with high inplane velocities and strongly anisotropic MFPs (15 nm inplane, 3 nm outofplane near EF), whereas Cu shows an isotropic 22 nm MFP. Under identical boundary conditions including a realistic 2 nm liner/diffusion barrier for Cu, PdCoO2 displays suppressed boundary scattering and a much slower resistivity increase from bulk down to sub 30 nm, preserving near bulk conductivity and remaining viable at 2 nm. Thickness trends reveal dual slope changes in PdCoO2 (35 nm and 7 nm) set by anisotropic MFPs, contrasting with the single characteristic scale of Cu (40 nm). The calculated bulk values and scaling curves track available measurements for both materials. These results establish PdCoO2 as a scalable interconnect that outperforms Cu under quantum confinement and provide a quantitative framework to screen layered conductors for next generation nanoelectronic interconnects.

cond-mat.mtrl-sci↗

arXiv2023

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 the 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 absorption. 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 another promise for future photovoltaic applications.

cond-mat.mtrl-sci↗

arXiv2023

Control of Impurity Phase Segregation in a PdCrO$_2$/CuCrO$_2$ Heterostructure

PdCrO$_2$ films are synthesized on CuCrO$_2$ buffer layers on Al$_2$O$_3$ substrates. This synthesis is accompanied by impurity phase segregation, which hampers the synthesis of high quality PdCrO$_2$ films. The potential causes of impurity phase segregation were studied by using a combination of experiments and ab initio calculations. X-ray diffraction and scanning transmission electron microscopy experiments revealed impurity phases of Cu$_x$Pd$_{1-x}$ alloy and chromium oxides, Cr$_2$O$_3$ and Cr$_3$O$_4$, in PdCrO$_2$. Calculations determined that oxygen deficiency can cause the impurity phase segregation. Therefore, preventing oxygen release from delafossites could suppress the impurity phase segregation. The amounts of Cr$_2$O$_3$ and Cr$_3$O$_4$ depend differently on temperature and oxygen partial pressure. A reasonable theory-based explanation for this experimental observation is provided.

cond-mat.mtrl-sci↗

arXiv2022

Tunable Ferromagnetism in LaCoO3 Epitaxial Thin Films

Ferromagnetic insulators play a crucial role in the development of low-dissipation quantum magnetic devices for spintronics. Epitaxial LaCoO3 thin film is a prominent ferromagnetic insulator, in which the robust ferromagnetic ordering emerges owing to epitaxial strain. Whereas it is evident that strong spin-lattice coupling induces ferromagnetism, the reported ferromagnetic properties of epitaxially strained LaCoO3 thin films were highly consistent. For example, even under largely modulated degree of strain, the reported Curie temperatures of epitaxially strained LaCoO3 thin films lie within 80-85 K, without much deviation. In this study, substantial enhancement (~18%) in the Curie temperature of epitaxial LaCoO3 thin films is demonstrated via crystallographic orientation dependence. By changing the crystallographic orientation of the films from (111) to (110), the crystal-field energy was reduced and the charge transfer between the Co and O orbitals was enhanced. These modifications led to a considerable enhancement of the ferromagnetic properties (including the Curie temperature and magnetization), despite the identical nominal degree of epitaxial strain. The findings of this study provide insights into facile tunability of ferromagnetic properties via structural symmetry control in LaCoO3.

cond-mat.mtrl-sci↗

arXiv2022

Preparation of large Cu3Sn single crystal by Czochralski method

Cu3Sn was recently predicted to host topological Dirac fermions, but related research is still in its infancy. The growth of large and high-quality Cu3Sn single crystals is, therefore, highly desired to investigate the possible topological properties. In this work, we report the single crystal growth of Cu3Sn by Czochralski (CZ) method. Crystal structure, chemical composition, and transport properties of Cu3Sn single crystals were analyzed to verify the crystal quality. Notably, compared to the mm-sized crystals from a molten Sn-flux, the cm-sized crystals obtained by the CZ method are free from contamination from flux materials, paving the way for the follow-up works.

cond-mat.mtrl-sci↗

arXiv2022

Growth of delafossite CuAlO2 single crystals in a reactive crucible

Delafossite oxide CuAlO2 has engaged great attention as a promising p-type conducting oxide. In this work, high-quality CuAlO2 single crystals with a size of several millimeters (mm) are successfully achieved with a reactive crucible melting method. The crystals are characterized by X-ray diffraction, scanning electron microscopy with energy-dispersive spectroscopy, transport measurement, and magnetic susceptibility measurement. The grown single crystals are free of contamination from a copper oxide flux. This work provides a new approach to growing high-quality delafossite oxide CuAlO2 with a few mm size.

cond-mat.mtrl-sci↗

arXiv2021

Spatial symmetry constraint of charge-ordered kagome superconductor CsV$_3$Sb$_5$

Elucidating the symmetry of intertwined orders in exotic superconductors is at the quantum frontier. Recent surface sensitive studies of the topological kagome superconductor CsV$_3$Sb$_5$ discovered a cascade 4a$_0$ superlattice below the charge density wave (CDW) ordering temperature, which can be related to the pair density modulations in the superconducting state. If the 4a$_0$ phase is a bulk and intrinsic property of the kagome lattice, this would form a striking analogy to the stripe order and pair density wave discovered in the cuprate high-temperature superconductors, and the cascade ordering found in twisted bilayer graphene. High-resolution X-ray diffraction has recently been established as an ultra-sensitive probe for bulk translational symmetry-breaking orders, even for short-range orders at the diffusive limit. Here, combining high-resolution X-ray diffraction, scanning tunneling microscopy and scanning transmission electron microscopy, we demonstrate that the 4a$_0$ superstructure emerges uniquely on the surface and hence exclude the 4a$_0$ phase as the origin of any bulk transport or spectroscopic anomaly. Crucially, we show that our detected 2$\times$2$\times$2 CDW order breaks the bulk rotational symmetry to C2, which can be the driver for the bulk nematic orders and nematic surface superlattices including the 4a$_0$ phase. Our high-resolution data impose decisive spatial symmetry constraints on emergent electronic orders in the kagome superconductor CsV$_3$Sb$_5$.

cond-mat.mtrl-sci↗

arXiv2021

Correlated Oxide Dirac Semimetal in the Extreme Quantum Limit

Quantum materials (QMs) with strong correlation and non-trivial 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. Herein, 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 ultra-high mobility (100,000 cm2/Vs), exceptionally small effective mass (0.04me), and non-zero Berry phase. More importantly, 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 a correlated topological QM, in which strong correlation of Dirac electrons leads to the realization of fractional occupation of Landau levels.

cond-mat.str-el↗

arXiv2021

Atomic structure of initial nucleation layer in hexagonal perovskite BaRuO$_3$ thin films

Hexagonal perovskites are an attractive group of materials due to their various polymorph phases and rich structure-property relationships. BaRuO3 (BRO) is a prototypical hexagonal perovskite, in which the electromagnetic properties are significantly modified depending on its atomic structure. Whereas thin-film epitaxy would vastly expand the application of hexagonal perovskites by epitaxially stabilizing various metastable polymorphs, the atomic structure of epitaxial hexagonal perovskites, especially at the initial growth stage, has rarely been investigated. In this study, we show that an intriguing nucleation behavior takes place during the initial stabilization of a hexagonal perovskite 9R BaRuO3 (BRO) thin film on a (111) SrTiO3 (STO) substrate. We use high-resolution high-angle annular dark field scanning transmission electron microscopy in combination with geometrical phase analysis to understand the local strain relaxation behavior. We find that nano-scale strained layers, composed of different RuO6 octahedral stacking, are initially formed at the interface, followed by a relaxed single crystal9R BRO thin film. Within the interface layer, hexagonal BROs are nucleated on the STO (111) substrate by both corner- and face-sharing. More interestingly, we find that the boundaries between the differently-stacked nucleation layers, i.e. heterostructural boundaries facilitates strain relaxation, in addition to the formation of conventional misfit dislocations evolving from homostructural boundaries. Our observations reveal an important underlying mechanism to understand the thin-film epitaxy and strain accommodation in hexagonal perovskites.

cond-mat.mtrl-sci↗

arXiv2021

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, the 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 a 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 epitaxial synthesis of high-quality thin films.

cond-mat.mtrl-sci↗

arXiv2021

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.

cond-mat.mtrl-sci↗

arXiv2021

Importance of anisotropic Coulomb interactions in the electronic and magnetic properties of Mn$_3$O$_4$

We report the importance of anisotropic Coulomb interactions in DFT+U calculations of the electronic and magnetic properties of Mn$_3$O$_4$. The effects of anisotropic interactions in Mn$^{2+}$ and Mn$^{3+}$ are separately examined by defining two different sets of Hubbard parameters: $U^{2+}$ and $J^{2+}$ for Mn$^{2+}$ and $U^{3+}$ and $J^{3+}$ for Mn$^{3+}$. The anisotropic interactions in Mn$^{3+}$ have a significant impact on the physical properties of Mn$_3$O$_4$ including local magnetic moments, canted angle, spontaneous magnetic moment, and superexchange coupling, but those in Mn$^{2+}$ do not make any noticeable difference. Weak ferromagnetic interchain superexchange, observed in experiments, is predicted only if a sizable anisotropic interaction is considered in Mn$^{3+}$. By analyzing the eigenoccupations of the on-site Mn density matrix, we found that the spin channel involving Mn$^{3+}$ $d_{x^2-y^2}$ orbitals, which governs the 90$^\circ$ correlation superexchange, is directly controlled by the anisotropic interactions. These findings demostrate that the exchange correction $J$ for the intraorbital Coulomb potential is of critical importance for first-principles description of reduced Mn oxides containing Mn$^{3+}$ or Mn$^{4+}$.

cond-mat.mtrl-sci↗

arXiv2020

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 \textit{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.

cond-mat.mtrl-sci↗

arXiv2020

Pulsed-laser epitaxy of metallic delafossite PdCrO$_2$ films

Alternate stacking of a highly conducting metallic layer with a magnetic triangular layer found in delafossite PdCrO2 provides an excellent platform for discovering intriguing correlated quantum phenomena. Thin film growth of the material may enable not only tuning the basic physical properties beyond what bulk materials can exhibit, but also developing novel hybrid materials by interfacing with dissimilar materials, yet this has proven to be extremely challenging. Here, we report the epitaxial growth of metallic delafossite PdCrO2 films by pulsed laser epitaxy (PLE). The fundamental role of the PLE growth conditions, epitaxial strain, and chemical and structural characteristics of the substrate is investigated by growing under various growth conditions and on various types of substrates. While strain plays a large role in improving the crystallinities, the direct growth of epitaxial PdCrO2 films without impurity phases was not successful. We attribute this difficulty to both the chemical and structural dissimilarities between the substrates and volatile nature of PdO layer, which make nucleation of the right phase difficult. This difficulty was overcome by growing CuCrO2 buffer layers before PdCrO2 were grown. Unlike PdCrO2, CuCrO2 films were rather readily grown with a relatively wide growth window. Only monolayer thick buffer layer was sufficient to grow the correct PdCrO2 phase. This result indicates that the epitaxy of Pd-based delafossites is extremely sensitive to the chemistry and structure of the interface, necessitating near perfect substrate materials. The resulting films are commensurately strained and show an antiferromagnetic transition at 40 K that persists down to as thin as 3.6 nm in thickness.

physics.app-ph↗

arXiv2019

Noncollinear magnetic sampling method for paramagnetic Mott insulator MnO

We present a new approach based on the static density functional theory (DFT) to describe paramagentic MnO, which is a representative paramagnetic Mott insulator. We appended the spin noncollinearity and the canonical ensemble to the magnetic sampling method (MSM), which is one of the supercell approaches based on 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 revealed 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 as an alternative to the $\textit{ab initio}$ framework of dynamic mean field theory based on DFT in the simulation of the high-temperature properties of Mott insulators.

cond-mat.str-el↗