Doping bismuth selenide (Bi2Se3) with elements such as copper and strontium (Sr) can induce superconductivity, making the doped materials interesting candidates to explore potential topological superconducting behaviors. It was thought that the superconductivity of doped Bi2Se3 was induced by dopant atoms intercalated in van der Waals gaps. However, several experiments have shown that the intercalation of dopant atoms may not necessarily make doped Bi2Se3 superconducting. Thus, the structural origin of superconductivity in doped Bi2Se3 remains an open question.Herein, we combined material synthesis and characterization, high-resolution transmission electron microscopy, and first-principles calculations to study the doping structure of Sr-doped Bi2Se3. We found that the emergence of superconductivity is strongly related with n-type dopant atoms. Atomic-level energy-dispersive X-ray mapping revealed various n-type Sr dopants that occupy intercalated and interstitial positions. First-principles calculations showed that the formation energy of a specific interstitial Sr doping position depends strongly on Sr doping level. This site changes from a metastable position at low Sr doping level to a stable position at high Sr doping level. The calculation results explain why quenching is necessary to obtain superconducting samples when the Sr doping level is low and also why slow furnace cooling can yield superconducting samples when the Sr doping level is high. Our findings suggest that Sr atoms doped at interstitial locations, instead of those intercalated in van der Waals gaps, are most likely to be responsible for the emergence of superconductivity in Sr-doped Bi2Se3.3

We grew Sr-doped Bi2Se3 thin films using molecular beam epitaxy, and their high quality was verified using transmission electron microscopy. The thin films exhibited weak antilocalisation behaviours in magneto-resistance measurements, a typical transport signature of topological insulators, but were not superconducting. In addition, the carrier densities of the non-superconducting thin-film samples were similar to those of their superconducting bulk counterparts. Atom-by-atom energy-dispersive X-ray mapping also revealed similar Sr doping structures in the bulk and thin-film samples. Because no qualitative distinction between non-superconducting thin-film and superconducting bulk samples had been found, we turned to a quantitative statistical analysis, which uncovered a key structural difference between the bulk and thin-film samples. The separation between Bi layers in the same quintuple layer was compressed whereas that between the closest Bi layers in two neighbouring quintuple layers was expanded in the thin-film samples compared with the separations in pristine bulk Bi2Se3. In marked contrast, the corresponding changes in the bulk doped samples showed opposite trends. These differences may provide insight into the absence of superconductivity in doped topological insulator thin films.