Metal-oxide semiconductors (MOS) are widely utilized for catalytic and photocatalytic applications in which the dynamics of charged carriers (e.g., electrons, holes) play important roles. Under operation conditions, photoinduced surface oxygen vacancies (PI-SOV) can greatly impact the dynamics of charge carriers. However, current knowledge regarding the effect of PI-SOV on the dynamics of hole migration in MOS films, such as titanium dioxide, is solely based upon volume-averaged measurements and/or vacuum conditions. This limits the basic understanding of hole-vacancy interactions, as they are not capable of revealing time-resolved variations during operation. Here, we measured the effect of PI-SOV on the dynamics of hole migration using time-resolved atomic force microscopy. Our findings demonstrate that the time constant associated with hole migration is strongly affected by PI-SOV, in a reversible manner. These results will nucleate an insightful understanding of the physics of hole dynamics and thus enable emerging technologies, facilitated by engineering hole-vacancy interactions.

Two-dimensional (2D) silica (SiO) and aluminosilicate (AlSiO) bilayers grown on Pd(111) were fabricated and systematically studied using ultrahigh vacuum surface analysis in combination with theoretical methods, including Auger electron spectroscopy, X-ray photoelectron spectroscopy, low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory. Based on LEED results, both SiO and AlSiO bilayers start ordering above 850 K in 2 × 10 Torr oxygen. Both bilayers show hexagonal LEED patterns with a periodicity approximately twice that of the Pd(111) surface. Importantly, the SiO bilayer forms an incommensurate crystalline structure whereas the AlSiO bilayer crystallizes in a commensurate structure. The incommensurate crystalline SiO structure on Pd(111) resulted in a moiré pattern observed with LEED and STM. Theoretical results show that straining the pure SiO bilayer to match Pd(111) would cost 0.492 eV per unit cell; this strain energy is reduced to just 0.126 eV per unit cell by replacing 25% of the Si with Al which softens the material and expands the unstrained lattice. Furthermore, the missing electron created by substituting Al for Si is supplied by Pd creating a chemical bond to the AlSiO bilayer, whereas van der Waals interactions predominate for the SiO bilayer. The results reveal how the interplay between strain, doping, and charge transfer determine the structure of metal-supported 2D silicate bilayers and how these variables may potentially be exploited to manipulate 2D materials structures.