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Reliable chemical state analysis of Sn semiconductors by XPS is hindered bythe marginal observed shift in the Sn 3d region. For hybrid Sn-basedperovskites especially, errors associated with charge referencing can easilyexceed chemistry-related shifts. Studies based on the modified Auger parameter${\alpha}'$ provide a suitable alternative and have been used previously toresolve different chemical states in Sn alloys and oxides. However, themeaningful interpretation of Auger parameter variations on Sn-based perovskitesemiconductors requires fundamental studies. In this work, we perform acomprehensive Auger parameter study through systematic compositional variationsof Sn halide perovskites. We find that in addition to the oxidation state,${\alpha}'$ is highly sensitivity to the composition of the halide-site,inducing shifts of up to ${\Delta}{\alpha}' = 2 eV$ between ASnI$_3$ andASnBr$_3$ type perovskites. The reported dependencies of ${\alpha}'$ on the Snoxidation state, coordination and local chemistry provide a framework thatenables reliable tracking of degradation as well as X-site interaction forSn-based perovskites and related compounds. The higher robustness andsensitivity of such studies not only enables more in-depth surface analysis ofSn-based perovskites than previously performed, but also increasesreproducibility across laboratories.

Resolving oxidation states and Sn-halide interactions of perovskites through Auger parameter analysis in XPS