Machine Learning Prediction Models for Solid Electrolytes Based on Lattice Dynamics Properties.

Recently, machine-learning approaches have accelerated computational materials design and the search for advanced solid electrolytes. However, the predictors are currently limited to static structural parameters, which may not fully account for the dynamic nature of ionic transport. In this study, we meticulously curated features considering dynamic properties and developed machine-learning models to predict the ionic conductivity, σ, of solid electrolytes. We compiled 14 phonon-related descriptors from first-principles phonon calculations along with 16 descriptors related to the structure and electronic properties. Our logistic regression classifiers exhibit an accuracy of 93%, while the random forest regression model yields a root-mean-square error for log(σ) of 1.179 S/cm and R2 of 0.710. Notably, phonon-related features are essential for estimating the ionic conductivities in both models. Furthermore, we applied our prediction model to screen 264 Li-containing materials and identified 11 promising candidates as potential superionic conductors.

An Ab Initio Study of the Origin of Structural Stability in P2-NaMnO2 with Li Doping at High Voltage.

P2-type sodium cathode materials generally exhibit a P2-O2 phase transition upon deintercalation at high voltage, which is detrimental to their cycling performance. Herein, using first-principles calculations, we investigate the structural stability and phase transition of P2-Na0MnO2 upon substitution of Li for Mn as a model of a high-voltage phase. The phonon of P2-Na0MnO2 shows an imaginary phonon frequency, indicating instability, which is consistent with the experimental P2-O2 transformation. On the contrary, the phonon of P2-Na0Li0.25Mn0.75O2 shows dynamic stability. We demonstrate that the substitution of the Li ion induces the redistribution of charge from the out-of-plane to in-plane orbitals along with a reduced charge of oxygen. Furthermore, we consider the various Li doping compositions and suggest that the density of the next-nearest-neighbor Li-ion pairs also plays an important role in stabilizing the P2 phase. On the basis of our findings, we propose a minimum of ∼20% Li doping to stabilize P2-NaLixMn1-xO2 at high voltage.

First-principles study on small polaron and Li diffusion in layered LiCoO2.

Li-ion conductivity is one of the essential properties that influences the performance of cathode materials for Li-ion batteries. Here, using density functional theory, we investigate the polaron stability and its effect on the Li-ion diffusion in layered LiCoO2 with various magnetic orderings. We show that the local magnetism promotes the localized Co4+ polaron with the Li-diffusion barrier of ∼0.34 eV. While the Li-ion diffuses, the polaron migrates in the opposite direction to the Li movement. In the non-magnetic structure, on the other hand, the polaron does not form, and the Li diffusion barrier is lowered to 0.21 eV. Although the presence of the polaron raises the diffusion barrier, the magnetically ordered structures are energetically more stable during the migration than the non-magnetic case. Thus, our work advocates the hole polaron migration scenario for Li-ion diffusion. We further demonstrate that the strong electron correlation of Co ions plays an essential role in stabilizing the Co4+ polaron.

Large-gap insulating dimer ground state in monolayer IrTe2.

Monolayers of two-dimensional van der Waals materials exhibit novel electronic phases distinct from their bulk due to the symmetry breaking and reduced screening in the absence of the interlayer coupling. In this work, we combine angle-resolved photoemission spectroscopy and scanning tunneling microscopy/spectroscopy to demonstrate the emergence of a unique insulating 2 × 1 dimer ground state in monolayer 1T-IrTe2 that has a large band gap in contrast to the metallic bilayer-to-bulk forms of this material. First-principles calculations reveal that phonon and charge instabilities as well as local bond formation collectively enhance and stabilize a charge-ordered ground state. Our findings provide important insights into the subtle balance of interactions having similar energy scales that occurs in the absence of strong interlayer coupling, which offers new opportunities to engineer the properties of 2D monolayers.

Direct Observation of Orbital Driven Strong Interlayer Coupling in Puckered Two-Dimensional PdSe2.

Interlayer coupling between individual unit layers is known to be critical in manipulating the layer-dependent properties of two-dimensional (2D) materials. While recent studies have revealed that several 2D materials with significant degrees of interlayer interaction (such as black phosphorus) show strongly layer-dependent properties, the origin based on the electronic structure is drawing intensive attention along with 2D materials exploration. Here, the direct observation of a highly dispersive single electronic band along the interlayer direction in puckered 2D PdSe2 as an experimental hallmark of strong interlayer couplings is reported. Remarkably large band dispersion along the kz -direction near Fermi level, which is even wider than the in-plane one, is observed by the angle-resolved photoemission spectroscopy measurement. Employing X-ray absorption spectroscopy and density functional theory calculations, it is revealed that the strong interlayer coupling in 2D PdSe2 originates from the unique directional bonding of Pd d orbitals associated with unexpected Pd 4d9 configuration, which consequently plays a decisive role for the strong layer-dependency of the band gap.

Machine-Learning-Guided Prediction Models of Critical Temperature of Cuprates.

Cuprates have been at the center of long debate regarding their superconducting mechanism; therefore, predicting the critical temperatures of cuprates remains elusive. Herein, using machine learning and first-principles calculations, we predict the maximum superconducting transition temperature (Tc,max) of hole-doped cuprates and suggest the functional form for Tc,max with the root-mean-square-error of 3.705 K and R2 of 0.969. We have found that the Bader charge of apical oxygen, the bond strength between apical atoms, and the number of superconducting layers are essential to estimate Tc,max. Furthermore, we predict the Tc,max of hypothetical cuprates generated by replacing apical cations with other elements. Among the hypothetical structures, the cuprates with Ga show the highest predicted Tc,max values, which are 71, 117, and 131 K for one, two, and three CuO2 layers, respectively. These findings suggest that machine learning could guide the design of new high-Tc superconductors in the future.

Superconductivity emerging from a stripe charge order in IrTe2 nanoflakes.

Superconductivity in the vicinity of a competing electronic order often manifests itself with a superconducting dome, centered at a presumed quantum critical point in the phase diagram. This common feature, found in many unconventional superconductors, has supported a prevalent scenario in which fluctuations or partial melting of a parent order are essential for inducing or enhancing superconductivity. Here we present a contrary example, found in IrTe2 nanoflakes of which the superconducting dome is identified well inside the parent stripe charge ordering phase in the thickness-dependent phase diagram. The coexisting stripe charge order in IrTe2 nanoflakes significantly increases the out-of-plane coherence length and the coupling strength of superconductivity, in contrast to the doped bulk IrTe2. These findings clarify that the inherent instabilities of the parent stripe phase are sufficient to induce superconductivity in IrTe2 without its complete or partial melting. Our study highlights the thickness control as an effective means to unveil intrinsic phase diagrams of correlated van der Waals materials.

Quenchable amorphous glass-like material from VF3.

The quite simple but relatively stable VF3-type compounds are known to be of major interest due to their building blocks - octahedra that are extremely important in perovskites as well. Here, we show that the VF6 octahedron in VF3 varies over a fairly wide pressure range (0-50 GPa), maintaining undisturbed rhombohedral crystal symmetry. Half of this pressure, VF6 rotates easily while the other undergoes strong uniaxial deformation in a "super-dense" condition. The congested sphere packing ultimately does not endure and drives the material to amorphize. We observed that the amorphous state could be quenched and acquire a transparent glass-like appearance when unloaded to ambient conditions. Dramatic, pressure-induced changes are clarified by phonon dispersion curves with the imaginary phonon mode, the so-called phonon soft mode, which indicates the structural instability. The distortion of the VF6 octahedra is attributed to the distinctive amorphization that could be further searched for throughout the whole almost identical VF3-type series providing metal trifluorides of various amorphous species.

Unusual Pressure-Induced Quantum Phase Transition from Superconducting to Charge-Density Wave State in Rare-Earth-Based Heusler LuPd_{2}In Compound.

We investigate the pressure effects on the electronic structures and phonon properties of rare-earth-based cubic-Heusler compound LuPd_{2}In, on the basis of ab initio density functional theory. We find the occurrence of intriguing phase transition from the superconducting (SC) to charge-density wave (CDW) state under pressure (P), which is quite unusual in that the pressure is detrimental to the CDW state in usual systems. The SC transition temperature T_{C} of LuPd_{2}In increases first with increasing pressure, up to P_{C}≈28 GPa, above which a quantum phase transition into the CDW state takes place. This extraordinary transition originates from the occurrence of phonon softening instability at a special q=M in the Brillouin zone. We thus propose that LuPd_{2}In is a quite unique material, in which the CDW quantum critical point is realized under the SC dome by applying the pressure.

Pressure-induced phase transitions and superconductivity in magnesium carbides.

Crystal structure prediction and in silico physical property observations guide experimental synthesis in high-pressure research. Here, we used magnesium carbides as a representative example of computational high-pressure studies. We predicted various compositions of Mg-C compounds up to 150 GPa and successfully reproduced previous experimental results. Interestingly, our proposed MgC2 at high pressure >7 GPa consists of extended carbon bonds, one-dimensional graphene layers, and Mg atomic layers, which provides a good platform to study superconductivity of metal intercalated graphene nano-ribbons. We found that this new phase of MgC2 could be recovered to ambient pressure and exhibited a strong electron-phonon coupling (EPC) strength of 0.6 whose corresponding superconductivity transition temperature reached 15 K. The EPC originated from the cooperation of the out-of-plane and the in-plane phonon modes. The geometry confinement and the hybridization between the Mg s and C pz orbitals significantly affect the coupling of phonon modes and electrons. These results show the importance of the high-pressure route to the synthesis of novel functional materials, which can promote the search for new phases of carbon-based superconductors.

Apical Charge Flux-Modulated In-Plane Transport Properties of Cuprate Superconductors.

For copper-based superconductors, the maximum superconducting transition temperature T_{c,max} of different families measured from experiment can vary from 38 K in La_{2}CuO_{4} to 135 K in HgBa_{2}Ca_{2}Cu_{3}O_{8} at the optimal hole doping concentration. We demonstrate herein, using ab initio computations, a new trend suggesting that the cuprates with stronger out-of-CuO_{2}-plane chemical bonding between the apical anion (O, Cl) and apical cation (e.g., La, Hg, Bi, Tl) are generally correlated with higher T_{c,max} in experiments. We then show the underlying fundamental phenomena of coupled apical charge flux and lattice dynamics when the apical oxygen oscillates vertically. This triggers the charge flux among the apical cation, apical anion, and the in-plane CuO_{4} unit. The effect not only dynamically modulates the site energy of the hole at a given Cu site to control the in-plane charge transfer energy, but also can modulate the in-plane hole hopping integral simultaneously in a dynamic way by the cooperative apical charge fluxes.

Emergence of Kondo Resonance in Graphene Intercalated with Cerium.

The interaction between a magnetic impurity, such as cerium (Ce) atom, and surrounding electrons has been one of the core problems in understanding many-body interaction in solid and its relation to magnetism. Kondo effect, the formation of a new resonant ground state with quenched magnetic moment, provides a general framework to describe many-body interaction in the presence of magnetic impurity. In this Letter, a combined study of angle-resolved photoemission (ARPES) and dynamic mean-field theory (DMFT) on Ce-intercalated graphene shows that Ce-induced localized states near Fermi energy, EF, hybridized with the graphene π-band, exhibit gradual increase in spectral weight upon decreasing temperature. The observed temperature dependence follows the expectations from the Kondo picture in the weak coupling limit. Our results provide a novel insight how Kondo physics emerges in the sea of two-dimensional Dirac electrons.

Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials.

Layered sodium transition metal oxides of NaTMO2 (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO2. Here, a novel spontaneous TM layer rippling in the sodium ion battery cathode materials is reported, revealed by in situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy, and density functional theory simulation, where the softening and distortion of FeO6 octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.

Observation of variable hybridized-band gaps in Eu-intercalated graphene.

We report europium (Eu)-induced changes in the π-band of graphene (G) formed on the 6H-SiC(0001) surface by a combined study of photoemission measurements and density functional theory (DFT) calculations. Our photoemission data reveal that Eu intercalates upon annealing at 120 °C into the region between the graphene and the buffer layer (BL) to form a G/Eu/BL system, where a band gap of 0.29 eV opens at room temperature. This band gap is found to increase further to 0.48 eV upon cooling down to 60 K. Our DFT calculations suggest that the increased band gap originates from the enhanced hybridization of the graphene π-band with the Eu 4f band due to the increased magnetic ordering upon cooling. These Eu atoms continue to intercalate further down below the BL to produce bilayer graphene (G/BL/Eu) upon annealing at 300 °C. The π-band stemming from the BL then exhibits another band gap of 0.37 eV, which appears to be due to the strong hybridization between the π-band of the BL and the Eu 4f band. The Eu-intercalated graphene thus illustrates an example of versatile band gaps formed under different thermal treatments, which may play a critical role for future applications in graphene-based electronics.

Nanoscale Superconducting Honeycomb Charge Order in IrTe2.

Entanglement of charge orderings and other electronic orders such as superconductivity is in the core of challenging physics issues of complex materials including high temperature superconductivity. Here, we report on the observation of a unique nanometer scale honeycomb charge ordering of the cleaved IrTe2 surface, which hosts a superconducting state. IrTe2 was recently established to exhibit an intriguing cascade of stripe charge orders. The stripe phases coexist with a hexagonal phase, which is formed locally and falls into a superconducting state below 3 K. The atomic and electronic structures of the honeycomb and hexagon pattern of this phase are consistent with the charge order nature, but the superconductivity does not survive on neighboring stripe charge order domains. The present work provides an intriguing physics issue and a new direction of functionalization for two-dimensional materials.

Magnetic effects in sulfur-decorated graphene.

The interaction between two different materials can present novel phenomena that are quite different from the physical properties observed when each material stands alone. Strong electronic correlations, such as magnetism and superconductivity, can be produced as the result of enhanced Coulomb interactions between electrons. Two-dimensional materials are powerful candidates to search for the novel phenomena because of the easiness of arranging them and modifying their properties accordingly. In this work, we report magnetic effects in graphene, a prototypical non-magnetic two-dimensional semi-metal, in the proximity with sulfur, a diamagnetic insulator. In contrast to the well-defined metallic behaviour of clean graphene, an energy gap develops at the Fermi energy for the graphene/sulfur compound with decreasing temperature. This is accompanied by a steep increase of the resistance, a sign change of the slope in the magneto-resistance between high and low fields, and magnetic hysteresis. A possible origin of the observed electronic and magnetic responses is discussed in terms of the onset of low-temperature magnetic ordering. These results provide intriguing insights on the search for novel quantum phases in graphene-based compounds.

The mechanism of charge density wave in Pt-based layered superconductors: SrPt2As2 and LaPt2Si2.

The intriguing coexistence of the charge density wave (CDW) and superconductivity in SrPt2As2 and LaPt2Si2 has been investigated based on the ab initio density functional theory band structure and phonon calculations. We have found that the CDW instabilities for both cases arise from the q-dependent electron-phonon coupling with quasi-nesting feature of the Fermi surface. The band structure obtained by the band-unfolding technique reveals the sizable q-dependent electron-phonon coupling responsible for the CDW instability. The local split distortions of Pt atoms in the [As-Pt-As] layers play an essential role in driving the five-fold supercell CDW instability as well as the phonon softening instability in SrPt2As2. By contrast, the CDW and phonon softening instabilities in LaPt2Si2 occur without split distortions of Pt atoms. The phonon calculations suggest that the CDW and the superconductivity coexist in [X-Pt-X] layers (X = As or Si) for both cases.

Origin of first-order-type electronic and structural transitions in IrTe2.

We have explored the origin of unusual first-order-type electronic and structural transitions in IrTe2, based on the first-principles total energy density functional theory analysis. We have clarified that the structural transition occurs through the interplay among the charge density wavelike lattice modulation with q1/5=(1/5,0,1/5), in-plane dimer ordering, and the uniform lattice deformation. The Ir-Ir dimer formation via a molecular-orbital version of the Jahn-Teller distortion in the Ir-Ir zigzag stripe is found to play the most important role in producing the charge disproportionation state. Angle-resolved photoemission spectroscopy reveals the characteristic features of structural transition, which are in good agreement with the density functional theory bands obtained by the band-unfolding technique.

Aptamer-based single-molecule imaging of insulin receptors in living cells.

We present a single-molecule imaging platform that quantitatively explores the spatiotemporal dynamics of individual insulin receptors in living cells. Modified DNA aptamers that specifically recognize insulin receptors (IRs) with a high affinity were selected through the SELEX process. Using quantum dot-labeled aptamers, we successfully imaged and analyzed the diffusive motions of individual IRs in the plasma membranes of a variety of cell lines (HIR, HEK293, HepG2). We further explored the cholesterol-dependent movement of IRs to address whether cholesterol depletion interferes with IRs and found that cholesterol depletion of the plasma membrane by methyl-ß-cyclodextrin reduces the mobility of IRs. The aptamer-based single-molecule imaging of IRs will provide better understanding of insulin signal transduction through the dynamics study of IRs in the plasma membrane.