Combinations of sub 1 μm absorber films with high-work-function back surface contact layers are expected to induce large enough internal fields to overcome adverse effects of bulk defects on thin-film photovoltaic performance, particularly in earth-abundant kesterites. However, there are numerous experimental challenges involving back surface engineering, which includes exfoliation, thinning, and contact layer optimization. In the present study, a unique combination of nanocharacterization tools, including nano-Auger, Kelvin probe force microscopy (KPFM), and cryogenic focused ion beam measurements, are employed to gauge the possibility of surface potential modification in the absorber back surface via direct deposition of high-work-function metal oxides on exfoliated surfaces. Nano-Auger measurements showed large compositional nonuniformities on the exfoliated surfaces, which can be minimized by a brief bromine-methanol etching step. Cross-sectional nano-Auger and KPFM measurements on Au/MoO3/Cu2ZnSn(S,Se)4 (CZTSSe) showed an upward band bending as large as 400 meV within the CZTSSe layer, consistent with the high work function of MoO3, despite Au incorporation into the oxide layer. Density functional theory simulations of the atomic structure for bulk amorphous MoO3 demonstrated the presence of large voids within MoO3 enabling Au in-diffusion. With a less diffusive metal electrode such as Pt or Pd, upward band bending beyond this level is expected to be achieved.