Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2′,7,7′-tetrakis( N , N -di- p -methoxyphenyl-amine)9,9′-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4- tert -butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.

This work summarizes recent progress of low-temperature carbon-based electrodes in perovskite photovoltaic devices and their great up-scalability potential.

The stabilization of grain boundaries and surfaces of the perovskite layer is critical to extend the durability of perovskite solar cells. Here we introduced a sulfonium-based molecule, dimethylphenethylsulfonium iodide (DMPESI), for the post-deposition treatment of formamidinium lead iodide perovskite films. The treated films show improved stability upon light soaking and remains in the black α phase after two years ageing under ambient condition without encapsulation. The DMPESI-treated perovskite solar cells show less than 1% performance loss after more than 4,500 h at maximum power point tracking, yielding a theoretical T₈₀ of over nine years under continuous 1-sun illumination. The solar cells also display less than 5% power conversion efficiency drops under various ageing conditions, including 100 thermal cycles between 25 °C and 85 °C and an 1,050-h damp heat test.

Tremendous efforts have been dedicated toward minimizing the open-circuit voltage deficits on perovskite solar cells (PSCs), and the fill factors are still relatively low. This hinders their further application in large scalable modules. Herein, we employ a newly designed ammonium salt, cyclohexylethylammonium iodide (CEAI), for interfacial engineering between the perovskite and hole-transporting layer (HTL), which enhanced the fill factor to 82.6% and consequent PCE of 23.57% on the target device. This can be associated with a reduction of the trap-assisted recombination rate at the 3D perovskite surface, via formation of a 2D perovskite interlayer. Remarkably, the property of the 2D perovskite interlayer along with the cyclohexylethyl group introduced by CEAI treatment also determines a pronounced enhancement in the surface hydrophobicity, leading to an outstanding stability of over 96% remaining efficiency of the passivated devices under maximum power point tracking with one sun illumination under N₂ atmosphere at room temperature after 1500 h.

The inferior power conversion efficiency (PCE) compared to their regular counterparts (n–i–p) and undesirable stability issues of inverted (p–i–n) perovskite solar cells (PSCs) are the foremost issues hindering their commercialization. Here, for the first time, we demonstrate a polymeric room-temperature molten salt (poly-RTMS), namely poly(1-vinyl-3-ethyl-acetate) imidazole tetrafluoroborate (PEa), as a novel type of additive to modulate the perovskite crystallization and its electronic properties. The PEa poly-RTMS containing multiple chemical anchoring sites along with strong bonding stability can firmly bond to Pb ion defects at grain boundaries and the interface of the perovskite film via coordination bond, which effectively passivates the electronic defects and enhances the photo-, thermal-, and moisture-stability of perovskite films. As a result, the PEa-modified inverted PSCs show striking performance improvements over the control with the PCE exceeding 21.4% and excellent long-term operational stability, maintaining over 92% of the initial efficiency for 1200 hours under continuous full sun illumination at 70–75 °C. This strategy opens a new avenue to modulate the properties of perovskites for optoelectronic applications.

Surface passivation treatment is a widely used strategy to resolve trap‐mediated nonradiative recombination toward high‐efficiency metal‐halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in‐depth understanding of its passivation mechanism. Here, a systematic study on a mixed‐salt passivation strategy of formamidinium bromide (FABr) coupled with different F‐substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F‐substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed‐salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high‐quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed‐salt treatment. In addition, the introduction of the moisture resisted F‐substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long‐term stability under a high humid atmosphere as well as operational conditions.