Direct Observation of Atomic Step-Assisted Stabilization of Polar Surfaces.

Polar surfaces are intrinsically unstable and thus highly reactive due to the uncompensated surface charges. The charge compensation is accompanied by various surface reconstructions, establishing novel functionality for their applications. The present in situ atomic-scale electron microscopy study directly shows that the atomic step and step-assisted reconstruction play central roles in the charge compensation of polar oxide surfaces. The flat (LaO)+ -terminated LaAlO3 (001) polar surface, when annealed at high temperature in vacuum, transits to the (015) vicinal surface via the dynamic motion and interaction of atomic steps. While the (015) vicinal surface possesses zero polarization along the surface normal, a thermodynamic ground state is achieved when the in-plane polarization is fully compensated via the reconstruction of step-edge atoms; the step-edge La atoms are displaced from their ordinary atomic sites toward the adjacent Al step-edge sites, resulting in the formation of negatively charged La vacancies at the corresponding step edges. As confirmed by first-principles calculations, the observed step reconstruction of (015) vicinal surface can completely cancel both out-of-plane and in-plane electric fields. This hitherto unknown mechanism reveals the central role of step reconstruction in stabilizing a polar surface, providing valuable insights for understanding the novel charge compensation mechanism accompanied by the step reconstruction.

Vacancy driven surface disorder catalyzes anisotropic evaporation of ZnO (0001) polar surface.

The evaporation and crystal growth rates of ZnO are highly anisotropic and are fastest on the Zn-terminated ZnO (0001) polar surface. Herein, we study this behavior by direct atomic-scale observations and simulations of the dynamic processes of the ZnO (0001) polar surface during evaporation. The evaporation of the (0001) polar surface is accelerated dramatically at around 300 °C with the spontaneous formation of a few nanometer-thick quasi-liquid layer. This structurally disordered and chemically Zn-deficient quasi-liquid is derived from the formation and inward diffusion of Zn vacancies that stabilize the (0001) polar surface. The quasi-liquid controls the dissociative evaporation of ZnO with establishing steady state reactions with Zn and O2 vapors and the underlying ZnO crystal; while the quasi-liquid catalyzes the disordering of ZnO lattice by injecting Zn vacancies, it facilitates the desorption of O2 molecules. This study reveals that the polarity-driven surface disorder is the key structural feature driving the fast anisotropic evaporation and crystal growth of ZnO nanostructures along the [0001] direction.

Highly efficient blue InGaN nanoscale light-emitting diodes.

Indium gallium nitride (InGaN)-based micro-LEDs (µLEDs) are suitable for meeting ever-increasing demands for high-performance displays owing to their high efficiency, brightness and stability1-5. However, µLEDs have a large problem in that the external quantum efficiency (EQE) decreases with the size reduction6-9. Here we demonstrate a blue InGaN/GaN multiple quantum well (MQW) nanorod-LED (nLED) with high EQE. To overcome the size-dependent EQE reduction problem8,9, we studied the interaction between the GaN surface and the sidewall passivation layer through various analyses. Minimizing the point defects created during the passivation process is crucial to manufacturing high-performance nLEDs. Notably, the sol-gel method is advantageous for the passivation because SiO2 nanoparticles are adsorbed on the GaN surface, thereby minimizing its atomic interactions. The fabricated nLEDs showed an EQE of 20.2 ± 0.6%, the highest EQE value ever reported for the LED in the nanoscale. This work opens the way for manufacturing self-emissive nLED displays that can become an enabling technology for next-generation displays.

Infrared Transparent and Electromagnetic Shielding Correlated Metals via Lattice-Orbital-Charge Coupling.

Despite being a requisite for modern transparent electronics, few metals have a sufficiently high infrared transmittance due to the free electron response. Here, upon alloying the correlated metal SrVO3 with BaVO3, the medium wavelength infrared transmittance at a wavelength of 4 µm is found to be 50% higher than those for Sn-doped In2O3 (ITO) and La-doped BaSnO3 (BLSO). The room temperature resistivity of the alloy of ∼100 µΩ cm is 1 order of magnitude lower than those of ITO and BLSO, guaranteeing a profound electromagnetic shielding effectiveness of 22-31 dB at 10 GHz in the X-band. Systematic investigations reveal symmetry breaking of VO6 oxygen octahedra in SrVO3 due to the substitution of Sr2+ with larger Ba2+ ions, localization of electrons in the lower energy V-dyz and dzx orbitals, and stronger correlation effects. The lattice-orbital-charge-coupled engineering of the electronic band structure in correlated metals offers a new design strategy to create super-broad-band transparent conductors with an enhanced shielding capability.

Molecular Tunability of Magnetic Exchange Bias and Asymmetrical Magnetotransport in Metalloporphyrin/Co Hybrid Bilayers.

Individual molecular spins are promising quantum states for emerging computation technologies. The "on surface" configuration of molecules in proximity to a magnetic film allows control over the orientations of molecular spins and coupling between them. The stacking of planar molecular spins could favor antiferromagnetic interlayer couplings and lead to pinning of the magnetic underlayer via the exchange bias, which is extensively utilized in ultrafast and high-density spintronics. However, fundamental understanding of the molecular exchange bias and its operating features on a device has not been unveiled. Here, we showed tunable molecular exchange bias and its asymmetrical magnetotransport characteristics on a device by using the metalloporphyrin/cobalt hybrid films. A series of the distinctive molecular layers showcased a wide range of the interfacial exchange coupling and bias. The transport behaviors of the hybrid bilayer films revealed the molecular exchange bias effect on a fabricated device, representing asymmetric characteristics on anisotropic and angle-dependent magnetoresistances. Theoretical simulations demonstrated close correlations among the interfacial distance, magnetic interaction, and exchange bias. This study of the hybrid interfacial coupling and its impact on magnetic and magnetotransport behaviors will extend functionalities of molecular spinterfaces for emerging information technologies.

Atomistic study of the alloying behavior of crystalline SnSe1-xSx.

Recently, layered chalcogenide alloys (LCAs) have been extensively investigated for use in various practical applications by selectively controlling the amount of foreign components. However, the alloying behavior of layered chalcogenides has been rarely explored at the atomistic level. Here, we study the microstructural evolution of SnSe1-xSx alloys on the atomic scale by combining scanning tunneling microscopy (STM) measurements with first-principles density functional theory (DFT) calculations. STM topographic images suggest that S atoms substituted in SnSe1-xSx are not randomly distributed, but tend to form local SnS clusters. The degree of S atom alloying was quantitatively estimated to be about 60% from STM images, indicating that homo-atoms (S-S) are a preferred arrangement over hetero-atoms (S-Se). Our DFT calculations further confirmed that the mixing energy of random SnSe1-xSx alloys showed positive behavior over the whole S composition range considered. This result suggests that SnSe1-xSx has a tendency toward local phase segregation into SnSe and SnS rather than random alloys. We expect our atomistic study on the alloying behavior to provide important insight for fabricating optimal SnSe1-xSx alloys with high thermoelectric properties.