Thermally unstable nature of hybrid organic-inorganic perovskites has been a major obstacle to fabricating the long-term operational device. A cesium lead halide perovskite has been suggested as an alternative light absorber, due to its superb thermal stability. However, the phase instability and poor performance are hindering the further progress. Here, cesium lead halide perovskite solar cells with enhanced performance and stability are demonstrated via incorporating potassium cations. Based on CsKPbIBr, the planar-architecture device achieves a power conversion efficiency of 10.0%, which is a remarkable record in the field of inorganic perovskite solar cells. In addition, the device shows an extended operational lifetime against air. Our research will stimulate the development of cesium lead halide perovskite materials for next-generation photovoltaics.

Thermal instability of organic-inorganic hybrid perovskites will be an inevitable hurdle for commercialization. Recently, all-inorganic cesium lead halide perovskites, in particular, CsPbIBr, have emerged as thermally stable and efficient photovoltaic light absorbers. However, the fundamental properties of this material have not been studied in detail. The crystal formation behavior of CsPbIBr is investigated by examining the surface morphology, crystal structure, and chemical state of the perovskite films. We discover a previously uncharacterized feature that the formation of black polymorph through optimal annealing temperature proves to be critical to both solar cell efficiency and phase stability. Our optimized planar heterojunction solar cell exhibits a J-V scan efficiency of 10.7% and open-circuit voltage of 1.23 V, which far outperforms the preceding literature.

A general methodology is reported to create organic–inorganic hybrid metal halide perovskite films with enlarged and preferred‐orientation grains. Simply pressing polyurethane stamps with hexagonal nanodot arrays on partially dried perovskite intermediate films can cause pressure‐induced perovskite crystallization. This pressure‐induced crystallization allows to prepare highly efficient perovskite solar cells (PSCs) because the preferred‐orientation and enlarged grains with low‐angle grain boundaries in the perovskite films exhibit suppressed nonradiative recombination. Consequently, the photovoltaic response is dramatically improved by the uniaxial compression in both inverted‐planar PSCs and normal PSCs, leading to power conversion efficiencies of 19.16%.

To further increase the open‐circuit voltage (V oc) of perovskite solar cells (PSCs), many efforts have been devoted to doping the TiO2 electron transport/selective layers by using metal dopants with higher electronegativity than Ti. However, those dopants can introduce undesired charge traps that hinder charge transport through TiO2, so the improvement in the V oc is often accompanied by an undesired photocurrent density–voltage (J–V) hysteresis problem. Herein, it is demonstrated that the use of a rapid flame doping process (40 s) to introduce cobalt dopant into TiO2 not only solves the J–V hysteresis problem but also increases the V oc and power conversion efficiency of both mesoscopic and planar PSCs. The reasons for the simultaneous improvements are two fold. First, the flame‐doped Co‐TiO2 film forms Co‐Ov (cobalt dopant‐oxygen vacancy) pairs and hence reduces the number density of Ti3+ trap states. Second, Co doping upshifts the band structure of TiO2, facilitating efficient charge extraction. As a result, for planar PSCs, the flame doping of Co increases the efficiency from 17.1% to 18.0% while reducing the hysteresis from 16.0% to 1.7%. Similarly, for mesoscopic PSCs, the flame doping of Co increases the efficiency from 18.5% to 20.0% while reducing the hysteresis from 7.0% to 0.1%.

Although organic–inorganic halide perovskite (OIHP)-based photovoltaics have high photoconversion efficiency (PCE), their poor humidity stability prevents commercialization. To overcome this critical hurdle, focusing on the grain boundary (GB) of OIHPs, which is the main humidity penetration channel, is crucial. Herein, pressure-induced crystallization of OIHP films prepared with controlled mold geometries is demonstrated as a GB-healing technique to obtain high moisture stability. When exposed to 85% RH at 30 °C, OIHP films fabricated by pressure-induced crystallization have enhanced moisture stability due to the enlarged OIHP grain size and low-angle GBs. The crystallographic and optical properties indicate the effect of applying pressure onto OIHP films in terms of moisture stability. The photovoltaic devices with pressure-induced crystallization exhibited dramatically stabilized performance and sustained over 0.95 normalized PCE after 200 h at 40% RH and 30 °C.