Organic–inorganic hybrid perovskite solar cells have resulted in tremendous interest in developing next generation photovoltaics due to high record efficiency exceeding 22%. For inverted structure perovskite solar cells, the hole extraction layers play a significant role in achieving efficient and stable perovskite solar cell by modifying charge extraction, interfacial recombination losses, and band alignment. Here, cesium doped NiOx is selected as a hole extraction layer to study the impact of Cs dopant on the optoelectronic properties of NiOx and the photovoltaic performance. Cs doped NiOx films are prepared by a simple solution‐based method. Both doped and undoped NiOx films are smooth and highly transparent, while the Cs doped NiOx exhibits better electron conductivity and higher work function. Therefore, Cs doping results in a significant improvement in the performance of NiOx‐based inverted planar perovskite solar cells. The best efficiency of Cs doped NiOx devices is 19.35%, and those devices show high stability as well. The improved efficiency in devices with Cs:NiOx is attributed to a significant improvement in the hole extraction and better band alignment compared to undoped NiOx. This work reveals that Cs doped NiOx is very promising hole extraction material for high and stable inverted perovskite solar cells.

Hole‐transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long‐term stability, high‐performance dopant‐free small‐molecule HTMs (SM‐HTMs) are greatly desired. However, such dopant‐free SM‐HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor–acceptor‐type SM‐HTMs (MPA‐BTI and MPA‐BTTI) are devised, which synergistically integrate several design principles for high‐performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant‐free MPA‐BTTI‐based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long‐term stability under illumination, which breaks the long‐time standing bottleneck in the development of dopant‐free SM‐HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well‐aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA‐BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high‐performance dopant‐free SM‐HTMs in PVSCs.

As a key component in perovskite solar cells (PVSCs), hole-transporting materials (HTMs) have been extensively explored and studied. Aiming to meet the requirements for future commercialization of PVSCs, HTMs which can enable excellent device performance with low cost and eco-friendly processability are urgently needed but rarely reported. In this work, a traditional anchoring group (2-cyanoacrylic acid) widely used in molecules for dye-sensitized solar cells is incorporated into donor–acceptor-type HTMs to afford MPA-BT-CA, which enables effective regulation of the frontier molecular orbital energy levels, interfacial modification of an ITO electrode, efficient defect passivation toward the perovskite layer, and more importantly alcohol solubility. Consequently, inverted PVSCs with this low-cost HTM exhibit excellent device performance with a remarkable power conversion efficiency (PCE) of 21.24% and good long-term stability in ambient conditions. More encouragingly, when processing MPA-BT-CA films with the green solvent ethanol, the corresponding PVSCs also deliver a substantial PCE as high as 20.52% with negligible hysteresis. Such molecular design of anchoring group-based materials represents great progress for developing efficient HTMs which combine the advantages of low cost, eco-friendly processability, and high performance. We believe that such design strategy will pave a new path for the exploration of highly efficient HTMs applicable to commercialization of PVSCs.

A series of metal acetylacetonates produced by a full low-temperature (below 100 °C) process are successfully employed to obtain both "multistable" and high-performance planar-inverted perovskite solar cells. All the three kinds of champion cells in small area exhibit over 18% in conversion-efficiency with negligible hysteresis, along with a conversion efficiency above 16% for planar PSCs in an aperture area of over 1 cm .

Black phosphorus, famous as two-dimensional (2D) materials, shows such excellent properties for optoelectronic devices such as tunable direct band gap, extremely high hole mobility (300-1000 cm/(V s)), and so forth. In this Letter, facile processed black phosphorus quantum dots (BPQDs) were successfully applied to enhance hole extraction at the anode side of the typical p-i-n planar hybrid perovskite solar cells, which remarkably improved the performance of devices with photon conversion efficiency ramping up from 14.10 to 16.69%. Moreover, more detailed investigations by c-AFM, SKPM, SEM, hole-only devices, and photon physics measurements discover further the hole extraction effect and work mechanism of the BPQDs, such as nucleation assistance for the growth of large grain size perovskite crystals, fast hole extraction, more efficient hole transfer, and suppression of energy-loss recombination at the anode interface. This work definitely paves the way for discovering more and more 2D materials with high electronic properties to be used in photovoltaics and optoelectronics.