Effects of Oxygen Partial Pressure and Substrate Temperature on the Structure and Morphology of Sc and Y Co-Doped ZrO2 Solid Electrolyte Thin Films Prepared via Pulsed Laser Deposition

Scandium (Sc) and yttrium (Y) co-doped ZrO2 (ScYSZ) thin films were prepared on a SiO2-Si substrate via pulsed laser deposition (PLD) method. In order to obtain good quality thin films with the desired microstructure, various oxygen partial pressures (PO2) from 0.01 Pa to 10 Pa and substrate temperatures (Ts) from 25 °C to 800 °C were investigated. X-ray diffraction (XRD) patterns results showed that amorphous ScYSZ thin films were formed at room substrate temperature while cubic polycrystalline thin films were obtained at higher substrate temperatures (Ts = 200 °C, 400 °C, 600 °C, 800 °C). Raman spectra revealed a distinct Raman shift at around 600 cm−1 supporting a cubic phase. However, a transition from cubic to tetragonal phase can be observed with increasing oxygen partial pressure. Photoemission spectroscopy (PES) spectra suggested supporting analysis that more oxygen vacancies in the lattice can be observed for samples deposited at lower oxygen partial pressures resulting in a cubic structure with higher dopant cation binding energies as compared to the tetragonal structure observed at higher oxygen partial pressure. On the other hand, dense morphologies can be obtained at lower PO2 (0.01 Pa and 0.1 Pa) while more porous morphologies can be obtained at higher PO2 (1.0 Pa and 10 Pa).

Growth of nanoporous high-entropy oxide thin films by pulsed laser deposition

High-entropy oxides (HEO) with entropic stabilization and compositional flexibility have great potential application in batteries and catalysis. In this work, HEO thin films were synthesized by pulsed laser deposition (PLD) from a rock-salt (Co0.2Ni0.2Cu0.2Mg0.2Zn0.2)O ceramic target. The films exhibited the target’s crystal structure, were chemically homogeneous, and possessed a three-dimensional (3D) island morphology with connected randomly shaped nanopores. The effects of varying PLD laser fluence on crystal structure and morphology were explored systematically. Increasing fluence facilitates film crystallization at low substrate temperature (300 °C) and increases film thickness (60–140 nm). The lateral size of columnar grains, islands (19 nm to 35 nm in average size), and nanopores (9.3 nm to 20 nm in average size) increased with increasing fluence (3.4 to 7.0 J/cm2), explained by increased kinetic energy of adatoms and competition between deposition and diffusion. Additionally, increasing fluence reduces the number of undesirable droplets observed on the film surface. The nanoporous HEO films can potentially serve as electrochemical reaction interfaces with tunable surface area and excellent phase stability. Graphical abstract