The highly developed crystallization process with respect to perovskite thin films is favorable for efficient solar cells. Here, an innovative intermolecular self-assembly approach was employed to retard the crystallization of PbI2 in dimethylformamide (DMF) by additional solvent of dimethyl sulfoxide (DMSO), which was proved to be capable of coordinating with PbI2 by coordinate covalent bond. The obtained PbI2(DMSO)x (0 ≤ x ≤ 1.86) complexes tend to be closely packed by means of intermolecular self-assembly. Afterward, an intramolecular exchange of DMSO with CH3NH3I (MAI) enabled the complexes to deform their shape and finally to reorganize to be an ultraflat and dense thin film of CH3NH3PbI3. The controllable grain morphology of perovskite thin film allows obtaining a power conversion efficiency (PCE) above 17% and a stabilized power output above 16% within 240 s by controlling DMSO species in the complex-precursor system (CPS). The present study gives a reproductive and facile strategy toward high quality of perovskite thin films and efficient solar cells.

Perovskite solar cells (PSCs) have recently demonstrated high efficiencies of over 22%, but the thermal stability is still a major challenge for commercialization. In this work, the thermal degradation process of the inverted structured PSCs induced by the silver electrode is thoroughly investigated. Elemental depth profiles indicate that iodide and methylammonium ions diffuse through the electron‐trasnporting layer and accumulate at the Ag inner surface. The driving force of forming AgI then facilitates the ions extraction. Variations on the morphology and current mapping of the MAPbI3 thin films upon thermal treatment reveal that the loss of ions occurs at the grain boundaries and leads to the reconstruction of grain domains. Consequently, the deteriorated MAPbI3 thin film, the poor electron extraction, and the generation of AgI barrier result in the degradation of efficiencies. These direct evidences provide in‐depth understanding of the effect of thermal stress on the devices, offering both experimental support and theoretical guidance for the improvement on the thermal stability of the inverted PSCs.

The two-dimensional Ruddlesden-Popper (RP) phases are an important class of halide perovskites with versatile optoelectronic properties. So far, only organic-inorganic hybrid RP phases involving long organic spacers were reported in this class. Here, we report an all-inorganic RP phase lead halide perovskite, CsPbICl (1, I4/ mmm space group; a = 5.6385(8) Å, c = 18.879(4) Å), synthesized by a solid-state method. The compound exhibits a band gap of E ∼ 3.04 eV and photoconductivity. We find an anomalous band gap evolution in CsPbSn ICl solid solutions. Our combined density functional theory and experimental study supports the thermodynamically stable nature of 1 as a unique ordered phase in the CsPbX (X = Cl, Br, I) system. The calculations suggest that 1 is a direct bandgap semiconductor with relatively small effective carrier mass along the in-plane direction, consistent with the experimentally observed in-plane UV-light photoresponse. We also demonstrate that 1 is promising for radiation detection capable of α-particle counting. Moreover, 1 shows markedly ambient and thermal stability.

A stable α/δ phase junction of formamidinium lead iodide perovskites was realized via controllable precursors at a low annealing temperature for enhanced near-infrared emission.