All‐inorganic perovskite CsPbI2Br is emerging as a promising absorber material for perovskite solar cells (PSCs) due to its superior photophysical properties and thermal stability. However, there are still many great challenges to obtaining high‐quality, phase‐stable, thick CsPbI2Br films in ambient air to promote further development of the PSCs. Herein, for the first time, an intermediate phase‐assisted sequential deposition for desired CsPbI2Br films is proposed. It is carried out by sequentially spin‐coating PbBr2 and CsI precursors onto the substrate in ambient air, during which a Ruddlesden–Popper (R–P) perovskite intermediate phase film composed of a Cs‐Pb‐I‐Br complex is produced. After annealing, the intermediate phase film is transformed into a CsPbI2Br film consisting of CsPbI2Br grains and CsBr species through a spinodal decomposition reaction. The as‐obtained CsPbI2Br film holds full coverage, micro‐sized grains, and excellent phase stability. Moreover, the CsBr species located at grain boundaries can effectively passivate the defects. Therefore, a carbon‐electrode PSC with such a desired CsPbI2Br film yields the optimized efficiency of 15.24%, coupled with a remarkable photovoltage of 1.312 V and excellent stability in ambient air with relative humidity of 60–70%. The efficiency achieved herein is among the record efficiencies for carbon‐electrode PSCs based on various all‐inorganic perovskites reported currently.

Low‐temperature, ambient processing of high‐quality CsPbBr3 films is demanded for scalable production of efficient, low‐cost carbon‐electrode perovskite solar cells (PSCs). Herein, we demonstrate a crystal orientation engineering strategy of PbBr2 precursor film to accelerate its reaction with CsBr precursor during two‐step sequential deposition of CsPbBr3 films. Such a novel strategy is proceeded by adding CsBr species into PbBr2 precursor, which can tailor the preferred crystal orientation of PbBr2 film from [020] into [031], with CsBr additive staying in the film as CsPb2Br5 phase. Theoretical calculations show that the reaction energy barrier of (031) planes of PbBr2 with CsBr is lower about 2.28 eV than that of (020) planes. Therefore, CsPbBr3 films with full coverage, high purity, high crystallinity, micro‐sized grains can be obtained at a low temperature of 150 °C. Carbon‐electrode PSCs with these desired CsPbBr3 films yield the record‐high efficiency of 10.27% coupled with excellent operation stability. Meanwhile, the 1 cm2 area one with the superior efficiency of 8.00% as well as the flexible one with the champion efficiency of 8.27% and excellent mechanical bending characteristics are also achieved.

Photodetectors with excellent high-temperature performance and facile fabrication are desired for harsh environment applications. Herein, we report the high-temperature, self-powered PDs by adopting 0D-3D mixed-dimensionality perovskite Cs4Pb(BrCl)6-CsPbBr2-xCl1+x films and simple...