arXiv subjects

Woo Seok Choi

Publications and source records attributed to Woo Seok Choi.

69 records · Page 4Linked to original sources

arXiv2013

Orienting oxygen vacancies for fast catalytic reaction

Catalysis is indispensable to chemical processes and relevant to many aspects of modern life. Owing to the intriguing electronic structures and good ionic properties, multivalent transition metal oxides have attracted attention as key catalysts for various energy and environmental applications. Here, we demonstrate that brownmillerite strontium cobaltite (SrCoO2.5) can be a good cathode material for sold oxide fuel cells and rechargeable batteries due to the open oxygen frameworks. When the orientation of oxygen vacancy channels (OVCs) is properly controlled, one can drastically increase the surface oxygen exchange rate approximately up to two orders of magnitude. The improved oxygen reduction kinetics is attributed to a substantial decrease in the thermal activation energy. Importantly, the strong enhancement of crystallographic orientation-dependent oxygen reduction reaction required the creation of neither structural disorders nor chemical doping. Thus, our epitaxial approach can pave a novel pathway to providing precise interpretation of oxygen reduction reactions and to developing oxide-based energy materials.

cond-mat.mtrl-sci↗

arXiv2013

Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge

Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation's oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoOx) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO3-δ or the brownmillerite SrCoO2.5. Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200~300 °C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low temperature redox activity in SrCoO3-δ is attributed to a small Gibbs free energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low temperature cathode materials.

cond-mat.mtrl-sci↗

arXiv2013

Reversal of the lattice structure in SrCoOx epitaxial thin films studied by real-time optical spectroscopy and first-principles calculations

Using real-time spectroscopic ellipsometry, we directly observed a reversible lattice and electronic structure evolution in SrCoOx (x = 2.5 - 3) epitaxial thin films. Drastically different electronic ground states, which are extremely susceptible to the oxygen content x, are found in the two topotactic phases, i.e. the brownmillerite SrCoO2.5 and the perovskite SrCoO3. First principles calculations confirmed substantial differences in the electronic structure, including a metal-insulator transition, which originates from the modification in the Co valence states and crystallographic structures. More interestingly, the two phases can be reversibly controlled by changing the ambient pressure at greatly reduced temperatures. Our finding provides an important pathway to understanding the novel oxygen-content-dependent phase transition uniquely found in multivalent transition metal oxides.

cond-mat.str-el↗

arXiv2013

Topotactic phase transformation of the brownmillerite SrCoO2.5 to the perovskite SrCoO3-δ

Oxygen stoichiometry is one of the most important elements in determining the physical properties of transition metal oxides (TMOs). A small fractional change in the oxygen content, resulting in the variation of valence state of the transition metal, can drastically modify the materials functionalities. In particular, TMOs with mixed valences have attracted attention for many energy applications. Previous studies also showed that the ability to control the number of d-band electron populations and detailed spin configurations is critical for improved catalytic performance of TMOs. In this context, SrCoO$_{x}$ (2.5 < x < 3.0) is an ideal class of materials due to the existence of two structurally distinct topotatic phases, i.e. the brownmillerite SrCoO$_{2.5}$(BM-SCO) and the perovskite SrCoO$_{3}$. Especially, BM-SCO has atomically-ordered one-dimensional vacancy channels, which can accommodate additional oxygen. Moreover, SrCoO$_{x}$ exhibits a wide spectrum of physical properties depending on the oxygen stoichiometry. Since SrCoOx has only a single knob to control the Co valence state without cation doping, it is an attractive material for studying the valence state dependent physical properties. However, so far, the growth of high quality single crystalline materials has not been much studied due to difficulty in controlling the right oxidation state. In this work, we report on the epitaxial growth of BM-SCO single crystalline films on SrTiO3 by pulsed laser epitaxy. In order to examine the topotactic phase transformation to the perovskite SrCoO$_{3-δ}$, some of samples were subsequently in-situ annealed at various oxygen pressure P(O$_{2}$). We found that post-annealing in high P(O$_{2}$) (> several hundreds of Torr) could fill some of oxygen vacancies accompanying systematic evolution in electronic, magnetic, and thermoelectric properties.

cond-mat.mtrl-sci↗

arXiv2012

Atomic layer engineering of perovskite oxides for chemically sharp heterointerfaces

Advances in synthesis techniques and materials understanding have given rise to oxide heterostructures with intriguing physical phenomena that cannot be found in their constituents. In these structures, precise control of interface quality, including oxygen stoichiometry, is critical for unambiguous tailoring of the interfacial properties, with deposition of the first monolayer being the most important step in shaping a well-defined functional interface. Here, we studied interface formation and strain evolution during the initial growth of LaAlO3 on SrTiO3 by pulsed laser deposition, in search of a means for controlling the atomic-sharpness of the interfaces. Our experimental results show that growth of LaAlO3 at a high oxygen pressure dramatically enhances interface abruptness. As a consequence, the critical thickness for strain relaxation was increased, facilitating coherent epitaxy of perovskite oxides. This provides a clear understanding of the role of oxygen pressure during the interface formation, and enables the synthesis of oxide heterostructures with chemically-sharper interfaces.

cond-mat.mtrl-sci↗

arXiv2012

Fractionally delta-doped oxide superlattices for higher carrier mobilities

A 2D electron gas system in an oxide heterostructure serves as an important playground for novel phenomena. Here, we show that, by using fractional delta-doping to control the interface's composition in LaxSr1-xTiO3/SrTiO3 artificial oxide superlattices, the filling-controlled 2D insulator-metal transition can be realized. The atomic-scale control of d-electron band filling, which in turn contributes to the tuning of effective mass and density of the charge carriers, is found to be a fascinating route to substantially enhanced carrier mobilities.

cond-mat.str-el↗

arXiv2012

Strain-Induced Spin States in Atomically Ordered Cobaltites

Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO3, a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO3 epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior resulting in stripe-like, lattice modulated patterns, which did not involve uncontrolled misfit dislocations or other defects. The modulation entails the formation of ferromagnetically ordered sheets comprising intermediate or high spin Co3+, thus offering an unambiguous description for the exotic magnetism found in epitaxially strained LaCoO3 films. This observation provides a novel route to tailoring the electronic and magnetic properties of functional oxide heterostructures.

cond-mat.mtrl-sci↗

arXiv2012

Strongly coupled phase transition in ferroelectric/correlated electron oxide heterostructures

We fabricated ultrathin ferroelectric/correlated electron oxide heterostructures composed of the ferroelectric Pb(Zr0.2Ti0.8)O3 and the correlated electron oxide (CEO) La0.8Sr0.2MnO3 on SrTiO3 substrates by pulsed laser epitaxy. The hole accumulation in the ultrathin CEO layer was substantially modified by heterostructuring with the ferroelectric layer, resulting in an insulator-metal transition. In particular, our thickness dependent study showed that drastic changes in transport and magnetic properties were strongly coupled to the modulation of charge carriers by ferroelectric field effect, which was confined to the vicinity of the interface. Thus, our results provide crucial evidence that strong ferroelectric field effect control can be achieved in ultrathin (10 nm) heterostructures, yielding at least a 100,000-fold change in resistivity.

cond-mat.mtrl-sci↗

arXiv2012

Wide band gap tunability in complex transition metal oxides by site-specific substitution

Fabricating complex transition metal oxides with a tuneable band gap without compromising their intriguing physical properties is a longstanding challenge. Here we examine the layered ferroelectric bismuth titanate and demonstrate that, by site-specific substitution with the Mott insulator lanthanum cobaltite, its band gap can be narrowed as much as one electron volt, while remaining strongly ferroelectric. We find that when a specific site in the host material is preferentially substituted, a split-off state responsible for the band gap reduction is created just below the conduction band of bismuth titanate. This provides a route for controlling the band gap in complex oxides for use in emerging oxide opto-electronic and energy applications.

cond-mat.mtrl-sci↗

arXiv2012

Band gap tuning in ferroelectric Bi4Ti3O12 by alloying LaTMO3 (TM = Ti, V, Cr, Mn, Co, Ni, and Al)

We fabricated ferroelectric Bi4Ti3O12 (BiT) single crystalline thin films site-specifically substituted with LaTMO3 (TM = Al, Ti, V, Cr, Mn, Co, and Ni) on SrTiO3 substrates by pulsed laser epitaxy. When transition metals are incorporated into a certain site of the BiT, some of BiT-LaTMO3 showed a substantially decreased band gap, coming from the additional optical transition between oxygen 2p and TM 3d states. Specifically, all alloys with Mott insulators revealed a possibility of band gap reduction. Among them, BiT-LaCoO3 showed the largest band gap reduction by ~1 eV, positioning itself as a promising material for highly efficient opto-electronic devices.

cond-mat.mtrl-sci↗

arXiv2011

Charge states and magnetic ordering in LaMnO3/SrTiO3 superlattices

We investigated the magnetic and optical properties of [(LaMnO3)n/(SrTiO3)8]20 (n = 1, 2, and 8) superlattices grown by pulsed laser deposition. We found a weak ferromagnetic and semiconducting state developed in all superlattices. An analysis of the optical conductivity showed that the LaMnO3 layers in the superlattices were slightly doped. The amount of doping was almost identical regardless of the LaMnO3 layer thickness up to eight unit cells, suggesting that the effect is not limited to the interface. On the other hand, the magnetic ordering became less stable as the LaMnO3 layer thickness decreased, probably due to a dimensional effect.

cond-mat.str-el↗

arXiv2010

Electronic structure and anomalous band-edge absorption feature in multiferroic MnWO4: An optical spectroscopic study

We investigated the electronic structure and lattice dynamics of multiferroic MnWO4 by optical spectroscopy. With variation of polarization, temperature, and magnetic field, we obtained optical responses over a wide range of photon energies. The electronic structure of MnWO4 near to the Fermi level was examined, with inter-band transitions identified in optical conductivity spectra above a band-gap of 2.5 eV. As for the lattice dynamics, we identified all the infrared transverse optical phonon modes available according to the group-theory analysis. Although we did not observe much change in global electronic structure across the phase transition temperatures, an optical absorption at around 2.2 eV showed an evident change depending upon the spin configuration and magnetic field. The behavior of this band-edge absorption indicates that spin-orbit coupling plays an important role in multiferroic MnWO4.

cond-mat.str-el↗

arXiv2010

Dimensional crossover of polaron dynamics in Nb:SrTiO3/SrTiO3 superlattices: Possible mechanism of thermopower enhancement

Using optical spectroscopy, we investigated the electrodynamic properties of Nb:SrTiO3/SrTiO3 superlattices. In these superlattices, a large enhancement of the Seebeck coefficient (S) has been reported with decreasing Nb:SrTiO3 layer thickness [refer to H. Ohta et al., Nature Mater. 6, 129 (2007)]. By analyzing the optical spectra, we found that the polaron plays an important role in determining the electrodynamic properties of the superlattices. With decreasing Nb:SrTiO3 layer thickness from eleven to one unit cell, we observed a threefold enhancement of the polaron effective mass and relaxation time. Such increases were attributed to a dimensional crossover of polaron from 3D to quasi-2D. Moreover, the modified nature of the polaron at low dimensions enhanced the thermoelectric properties of the oxide superlattice, by simultaneously increasing S and preventing the decrease of carrier mobility. Our results indicate that strong electron-phonon coupling can provide an alternative pathway in searching efficient thermoelectric materials.

cond-mat.str-el↗

arXiv2008

Optical spectroscopic investigation on the coupling of electronic and magnetic structure in multiferroic hexagonal RMnO3 (R = Gd, Tb, Dy, and Ho) thin films

We investigated the effects of temperature and magnetic field on the electronic structure of hexagonal RMnO3 (R = Gd, Tb, Dy, and Ho) thin films using optical spectroscopy. As the magnetic ordering of the system was disturbed, a systematic change in the electronic structure was commonly identified in this series. The optical absorption peak near 1.7 eV showed an unexpectedly large shift of more than 150 meV from 300 K to 15 K, accompanied by an anomaly of the shift at the Neel temperature. The magnetic field dependent measurement clearly revealed a sizable shift of the corresponding peak when a high magnetic field was applied. Our findings indicated strong coupling between the magnetic ordering and the electronic structure in the multiferroic hexagonal RMnO3 compounds.

cond-mat.str-el↗

arXiv2007

Ferroelectricity in artificial bicolor oxide superlattices

We report on the growth and properties of high quality bicolor oxide superlattices, composed of two perovskites out of BaTiO3, CaTiO3, and SrTiO3. The artificially grown superlattices are structurally unique and have a macroscopically homogeneous phase, which is not feasible to recreate in bulk form. By artificial structuring, it is found that the polarization of such superlattices can be highly increased as compared to pseudo-binary ceramics with the same overall composition. Such strong enhancement in superlattice is attributed to newly-developed ionic motions of A-site cations at the hetero-interfaces due to the interfacial coupling of electrostatic and elastic interactions, which cannot be found in single phase materials.

cond-mat.mtrl-sci↗