Materials exhibiting unique electronic properties arising from a characteristic crystal structure have physical properties that are sensitive to structural dimensionality. This study involves the destabilization of Sn 5s lone-pair states of SnO films by decreasing their structural dimensionality in the out-of-plane direction. The inherent dispersive band structure of the SnO films remained unchanged between 80 and 11 nm. Below 11 nm, their dispersive band structure disappeared, the O/Sn ratio increased, and the carrier type changed from the p type to the n type, whereas the Sn valency remained constant at +2. These unconventional changes arose from the electronic separation corresponding to the Debye length, which is proportional to permittivity, and were attributed to weakened interactions between Sn 5s lone-pair electrons. Therefore, designing low-permittivity materials is beneficial for reducing the crystallite size required for stabilizing lone-pair states. These results are essential for designing emergent p-type oxides and improving their semiconducting properties and performance in transparent or high-power electronics.

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http://dx.doi.org/10.1021/acs.jpclett.3c00821DOI Listing

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