Post-deposition CdCl$_2$ treatment of polycrystalline CdTe is known to increase photovoltaic efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this study, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries. In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl$_2$ treatment and ambient oxygen exposure. Qualitatively, grain boundaries displayed lower work function and downward band bending relative to grain interiors, but only after air exposure of CdCl$_2$-treated CdTe. Analysis of numerous space charge regions at grain boundaries (GBs) showed an average depletion width of 290 nm and an average band bending magnitude of 70 meV, corresponding to a GB trap density of 10$^{11}$ cm$^{-2}$ and a net carrier density of 10$^{15}$ cm$^{-3}$. These results suggest that both CdCl$_2$ treatment and oxygen exposure may be independently tuned to enhance CdTe photovoltaic performance by engineering the interface and bulk electronic structure.
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