Two-dimensional bismuth-rich nanosheets through the evaporative thinning of Se-doped Bi2Te3

• A Bi-rich tetradymite material is confined to two dimensions for the first time.
• A facile evaporative thinning method is successfully extended to a ternary system.
• We report a large composition shift from Se-doped Bi2Te3 to final Bi-rich nanosheet.
• An in-depth preferential vapor pressure mechanism explains these composition shifts.

High bulk conductance obscures the behavior of surface states in the prototypical topological insulators Bi2Te3 and Bi2Se3. However, ternary phases of Bi2Te3−ySey with balanced donor and acceptor levels may lead to large bulk resistivity, allowing for the observation of the surface states. Additionally, the contribution of the bulk conductance may be further suppressed by nanostructuring, increasing the surface-to-volume ratio. Herein we report the synthesis of a ternary tetradymite newly confined to two dimensions. Ultra-thin large-area stable nanosheets were fabricated via evaporative thinning of a Bi2Te2.9Se0.1 original phase. Owing to vapor pressure differences, a compositional shift to a final Bi-rich phase is observed. The Se/Te ratio of the nanosheet increases tenfold, due to the higher stability of the Bi–Se bonds. Hexagonal crystal symmetry is maintained despite dramatic changes in thickness and stoichiometry. Given that small variations in stoichiometry of this ternary system can incur large changes in carrier concentration and switch majority carrier type, the large compositional shifts found in this case imply that compositional analysis of similar CVD and PVD grown materials is critical to correctly interpret topological insulator performance. Further, the characterization techniques deployed, including STEM-EDS and ToF-SIMS, serve as a case study in determining such compositional shifts in two-dimensional form.