Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy

Using advanced near-UV photoemission spectroscopy (PES) in constant final state mode (CFSYS) with a very high dynamic range, we investigate the triple-cation lead halide perovskite Cs_0.05(MA_0.17FA_0.83)_0.95Pb(I_0.83Br_0.17)₃ and gain detailed insights into the density of occupied states (DOS) in the valence band and band gap. A valence band model is established which includes the parabolic valence band edge and an exponentially decaying band tail in a single equation. This allows us to precisely determine two valence band maxima (VBM) at different k-vectors in the angle-integrated spectra, where the highest one, resulting from the VBM at the R-point in the Brillouin zone, is found between −1.50 to −1.37 eV relative to the Fermi energy E_F. We investigate quantitatively the formation of defect states in the band gap up to E_F upon decomposition of the perovskites during sample transfer, storage, and measurements: during near-UV-based PES, the density of defect states saturates at a value that is around 4 orders of magnitude below the density of states at the valence band edge. However, even short air exposure, or 3 h of X-ray illumination, increased their density by almost a factor of six and ∼40, respectively. Upon prolonged storage in vacuum, the formation of a distinct defect peak is observed. Thus, near-UV CFSYS with modeling as shown here is demonstrated as a powerful tool to characterize the valence band and quantify defect states in lead halide perovskites.