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The direct observation of the complete electronic band structure of a family of PbS CQD solids via photoelectron spectroscopy is reported. We investigate how materials processing strategies, such as the latest passivation methods that produce record-performance photovoltaics, achieve their performance advances. Halide passivated films show a drastic reduction in states in the midgap, contributing to a marked improvement in the device performance. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.