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Abstract:

Combination of a cryogenic ion-trap machine, operated at 4.7 K, with the free-electron-laser FELIX allows the first experimental characterization of the unusually bright antisymmetric stretch (ν₃) and Ï€-bending (ν₂) fundamentals of the He–X⁺–He (X = H, D) chromophore of the in situ prepared HHe_n⁺ and DHe_n⁺Ìý(n = 3–6) complexes. The band origins obtained are fully supported by first-principles quantum-chemical computations, performed at the MP2, the CCSD(T), and occasionally the CCSDTQ levels employing extended basis sets. Both the experiments and the computations are consistent with structures for the species with n = 3 and 6 being of T-shaped C_2v and of D_4h symmetry, respectively, while the species with n = 4 are suggested to exhibit interesting dynamical phenomena related to large-amplitude motions.

Abstract:

Metal halide perovskite semiconductors have the potential to enable low-cost, flexible and efficient solar cells for a wide range of applications. Physical vapour deposition by co-evaporation of precursors is a method which results in very smooth and pin-hole-free perovskite thin films and allows excellent control over film thickness and composition. However, for a deposition method to become industrially scalable, reproducible process control and high device yields are essential. Unfortunately, to date the control and reproducibility of evaporating organic precursors such as methylammonium iodide (MAI) has proved extremely challenging. We show that the established method of controlling the evaporation-rate of MAI with quartz micro balances (QMBs) is critically sensitive to the concentration of the impurities MAH2PO3 and MAH2PO2 that are usually present in MAI after synthesis. Therefore, controlling the deposition rate of MAI with QMBs is unreliable since the concentration of such impurities typically varies from MAI batch-to-batch and even during the course of a deposition. However once reliable control of MAI deposition is achieved, we find that the presence of precursor impurities during perovskite deposition does not degrade solar cell performance. Our results indicate that as long as precursor deposition rates are well controlled, physical vapour deposition will allow high solar cell device yields even if the purity of precursors change from run to run.