Na Deposition on MnO(100)

• Na deposition on MnO(100) follows a Stranski–Krastanov growth mode.
• Na in the first monolayer binds as an irreversibly-adsorbed, oxidic surface species.
• For Na coverages above 1 ML, metallic Na islands are formed.
• CO2 TPD can distinguish between metallic Na islands and oxidic Na in the first ML.
• Oxidic Na goes subsurface at high temperatures driving a (2 × 2) reconstruction.

Na deposition on the MnO(100) surface was investigated by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). Na TPD and XPS results indicate that adsorbed Na interacts strongly with the MnO substrate to form an irreversibly-adsorbed, oxidic Na compound on the surface for coverages up to 1 monolayer (ML). This strongly-bound Na diffuses into the MnO subsurface and bulk at elevated temperatures above 500 K. For Na coverages above 1 ML, metallic Na is present and desorbs from the surface below 500 K. The deposition of Na on MnO(100) follows a Stranski–Krastanov (SK) growth mode, with the formation of metallic Na islands following completion of the first Na monolayer. After Na deposition, the surface exhibits a diffuse (1 × 1) LEED pattern, suggesting the formation of disordered Na overlayers. After heating to 1000 K, the surface presents a (2 × 2) LEED pattern indicating that a surface reconstruction is induced by the diffusion of Na into the near surface region. CO2 can be used as a probe molecule in TPD to distinguish between metallic Na islands and oxidic Na in the first ML, and to indicate when Na that is still observable by XPS goes subsurface.

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