Nucleation of nanoparticles using the exsolution phenomenon is a promising pathway to design durable and active materials for catalysis and renewable energy. Here, we focus on the impact of surface orientation of the host lattice on the nucleation dynamics to resolve questions with regards to “preferential nucleation sites”. For this, we carried out a systematic model study on three differently oriented perovskite thin films. Remarkably, in contrast to the previous bulk powder-based study suggesting that the (110)-surface is a preferred plane for exsolution, we identify that other planes such as (001)- and (111)-facets also reveal vigorous exsolution. Moreover, particle size and surface coverage vary significantly depending on the surface orientation. Exsolution of (111)-oriented film produces the largest number of particles, the smallest particle size, the deepest embedment, and the smallest and most uniform interparticle distance among the oriented films. Based on classic nucleation theory, we elucidate that the differences in interfacial energies as a function of substrate orientation play a crucial role in controlling the distinct morphology and nucleation behavior of exsolved nanoparticles. Our finding suggests new design principles for tunable solid-state catalyst or nanoscale metal decoration.
Heterogeneous interfaces exhibit the unique phenomena by the redistribution of charged species to equilibrate the chemical potentials. Despite recent studies on the electronic charge accumulation across chemically inert interfaces, the systematic research to investigate massive reconfiguration of charged ions has been limited in heterostructures with chemically reacting interfaces so far. Here, we demonstrate that a chemical potential mismatch controls oxygen ionic transport across TiO 2 /VO 2 interfaces, and that this directional transport unprecedentedly stabilizes high-quality rutile TiO 2 epitaxial films at the lowest temperature (≤ 150°C) ever reported, at which rutile phase is difficult to be crystallized. Comprehensive characterizations reveal that this unconventional low-temperature epitaxy of rutile TiO 2 phase is achieved by lowering the activation barrier by increasing the "effective" oxygen pressure through a facile ionic pathway from VO 2-δ sacrificial templates. This discovery shows a robust control of defect-induced properties at oxide interfaces by the mismatch of thermodynamic driving force, and also suggests a strategy to overcome a kinetic barrier to phase stabilization at exceptionally low temperature.
The scattering of charge carriers by line defects, i.e., threading dislocations (TDs), severely limits electron mobility in epitaxial semiconductor films grown on dissimilar substrates. The density of TDs needs to be decreased to further enhance electron mobility in lattice-mismatched epitaxial films and heterostructures for application in highperformance electronic devices. Here, we report a strategy for the post-treatment of epitaxial La-doped BaSnO 3 (LBSO) films by delicately controlling the oxygen partial pressure p(O 2 ), which achieved a significant increase in the room temperature (RT) electron mobility (μ e ) to μ e = 122 cm 2 V −1 s −1 at a carrier concentration of 1.1 × 10 20 cm. This mobility enhancement is mostly attributed to an oxygen vacancy-assisted recovery process that reduces the density of TDs by accelerating the movement of dislocations in ionic crystals under a p(O 2 )-controlled treatment despite an increase in the density of charged point defects. Our finding suggests that accurate control of the interactions between point defects and line defects can reduce dominant carrier scattering by charged dislocations in epitaxial oxide semiconductors that have dissimilar substrates. This method provides alternative approaches to achieving perovskite oxide heterostructures that have high RT μ e values.
In situ exsolution of metal nanoparticles (NPs) is emerging as an alternative technique to deliver thermally stable and evenly dispersed metal NPs, which exhibit excellent adhesion with conducting perovskite oxide supports. Here we provide the first demonstration that Ni metal NPs with high areal density (∼175 μm–2) and fine size (∼38.65 nm) are exsolved from an A-site-deficient perovskite stannate support (La0.2Ba0.7Sn0.9Ni0.1O3−δ (LBSNO)). The NPs are strongly anchored and impart coking resistance, and the Ni-exsolved stannates show exceptionally high electrical conductivity (∼700 S·cm–1). The excellent conductivity is attributed to conduction between delocalized Sn 5s orbitals along with structural improvement toward ABO3 stoichiometry in the stannate support. We also reveal that experimental conditions with strong interaction must be optimized to obtain Ni exsolution without degrading the perovskite stannate framework. Our finding suggests a unique process to induce the formation of metal NPs embedded in stannate with excellent electrical properties.
We report the enhancement of room-temperature electron mobility in La-doped BaSnO3 (LBSO) thin films with thermal strain induced by high temperature nitrogen (N2) annealing. Simple annealing under an N2 environment consistently doubled the electron mobility of the LBSO films on the SrTiO3 (STO) substrates to as high as 78 cm2 V−1 s−1 at a carrier concentration of 4.0 × 1020 cm−3. This enhancement is mainly attributed to annihilation of extended defects as a consequence of compressive strain induced by the difference in the thermal expansion coefficients of LBSO and STO. Our study suggests that thermal strain can be exploited to reduce extended defects and to facilitate electron transport in transparent oxide semiconductors.
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