AP-XPS beamline, a platform for operando science at Pohang Accelerator Laboratory.

Beamline 8A (BL 8A) is an undulator-based soft X-ray beamline at Pohang Accelerator Laboratory. This beamline is aimed at high-resolution ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), soft X-ray absorption spectroscopy (soft-XAS) and scanning photoemission microscopy (SPEM) experiments. BL 8A has two branches, 8A1 SPEM and 8A2 AP-XPS, that share a plane undulator, the first mirror (M1) and the monochromator. The photon beam is switched between the two branches by changing the refocusing mirrors after the monochromator. The acceptance angle of M1 is kept glancing at 1.2°, and Pt is coated onto the mirrors to achieve high reflectance, which ensures a wide photon energy range (100-2000 eV) with high resolution at a photon flux of ∼1013 photons s-1. In this article, the main properties and performance of the beamline are reported, together with selected experiments performed on the new beamline and experimental system.

Gas-Permeable Iron-Doped Ceria Shell on Rh Nanoparticles with High Activity and Durability.

Strong metal-support interaction (SMSI) is a promising strategy to control the structure of the supported metal catalyst. Especially, encapsulating metal nanoparticles through SMSI can enhance resistance against sintering but typically blocks the access of reactants onto the metal surface. Here, we report gas-permeable shells formed on Rh nanoparticles with enhanced activity and durability for the surface reaction. First, Fe species were doped into ceria, enhancing the transfer of surface oxygen species. When Rh was deposited onto the Fe-doped ceria (FC) and reduced, a shell was formed on Rh nanoparticles. Diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) results show that the shell is formed upon reduction and removed upon oxidation reversibly. CO adsorption on the Rh surface through the shell was confirmed by cryo-DRIFTS. The reverse water gas shift (RWGS) reaction (CO2 + H2 → CO + H2O) occurred on the encapsulated Rh nanoparticles effectively with selective CO formation, whereas bare Rh nanoparticles deposited on ceria produced methane as well. The CO adsorption became much weaker on the encapsulated Rh nanoparticles, and H2-spillover occurred more on the FC, resulting in high activity for RWGS. The exposed Rh nanoparticles deposited on ceria presented degradation at 400 °C after 150 h of RWGS, whereas the encapsulated Rh nanoparticles showed no degradation with superior durability. Enhancing surface oxygen transfer can be an efficient way to form gas-permeable overlayers on metal nanoparticles with high activity and durability.

Covalent-bonding-induced strong phonon scattering in the atomically thin WSe2 layer.

In nano-device applications using two-dimensional (2D) van der Waals materials, a heat dissipation through nano-scale interfaces can be a critical issue for optimizing device performances. By using a time-domain thermoreflectance measurement technique, we examine a cross-plane thermal transport through mono-layered (n = 1) and bi-layered (n = 2) WSe2 flakes which are sandwiched by top metal layers of Al, Au, and Ti and the bottom Al2O3 substrate. In these nanoscale structures with hetero- and homo-junctions, we observe that the thermal boundary resistance (TBR) is significantly enhanced as the number of WSe2 layers increases. In particular, as the metal is changed from Al, to Au, and to Ti, we find an interesting trend of TBR depending on the WSe2 thickness; when referenced to TBR for a system without WSe2, TBR for n = 1 decreases, but that for n = 2 increases. This result clearly demonstrates that the stronger bonding for Ti leads to a better thermal conduction between the metal and the WSe2 layer, but in return gives rise to a large mismatch in the phonon density of states between the first and second WSe2 layers so that the WSe2-WSe2 interface becomes a major thermal resistance for n = 2. By using photoemission spectroscopy and optical second harmonic generation technique, we confirm that the metallization induces a change in the valence state of W-ions, and also recovers a non-centrosymmetry for the bi-layered WSe2.

Understanding how excess lead iodide precursor improves halide perovskite solar cell performance.

The presence of excess lead iodide in halide perovskites has been key for surpassing 20% photon-to-power conversion efficiency. To achieve even higher power conversion efficiencies, it is important to understand the role of remnant lead iodide in these perovskites. To that end, we explored the mechanism facilitating this effect by identifying the impact of excess lead iodide within the perovskite film on charge diffusion length, using electron-beam-induced current measurements, and on film formation properties, from grazing-incidence wide-angle X-ray scattering and high-resolution transmission electron microscopy. Based on our results, we propose that excess lead iodide in the perovskite precursors can reduce the halide vacancy concentration and lead to formation of azimuthal angle-oriented cubic α-perovskite crystals in-between 0° and 90°. We further identify a higher perovskite carrier concentration inside the nanostructured titanium dioxide layer than in the capping layer. These effects are consistent with enhanced lead iodide-rich perovskite solar cell performance and illustrate the role of lead iodide.