The effects of alkali post-deposition treatments and device properties for polycrystalline thin fi lm Cu(In,Ga)Se 2 have been investigated. It is reported that these surface treatments lead to differences in interface chemistry and device properties. The behavior of defects in the space charge region as a function of different growth parameters is investigated by correlative analytical microscopy. The latter combines electron microscopy based imaging, Kelvin probe force microscopy, and atom probe tomography. Alkali treatments lead to copper depletion and consequent sharpening of the compositional profi les, and the measured electric potential differences of exposed Cu(In 1-x ,Ga x )Se 2 surfaces. Measurable differences in resistivity and potential have also been observed, which are expected to relate to the improved open-circuit voltage, fi ll-factor, and device effi ciency. This study frames one perspective as to why post-deposition alkaline treatments lead to copper depletion, a mildly n-type semiconductor interface, and higher effi ciency for a Cu(In,Ga)Se 2 thin-fi lm photovoltaic device.