It is well known that the surface trap states and electronic disorders in the solution-processed CH NH PbI perovskite film affect the solar cell performance significantly and moisture sensitivity of photoactive perovskite material limits its practical applications. Herein, we show the surface modification of a perovskite film with a solution-processable hydrophobic polymer (poly(4-vinylpyridine), PVP), which passivates the undercoordinated lead (Pb) atoms (on the surface of perovskite) by its pyridine Lewis base side chains and thereby eliminates surface-trap states and non-radiative recombination. Moreover, it acts as an electron barrier between the perovskite and hole-transport layer (HTL) to reduce interfacial charge recombination, which led to improvement in open-circuit voltage (V ) by 120 to 160 mV whereas the standard cell fabricated in same conditions showed V as low as 0.9 V owing to dominating interfacial recombination processes. Consequently, the power conversion efficiency (PCE) increased by 3 to 5 % in the polymer-modified devices (PCE=15 %) with V more than 1.05 V and hysteresis-less J-V curves. Advantageously, hydrophobicity of the polymer chain was found to protect the perovskite surface from moisture and improved stability of the non-encapsulated cells, which retained their device performance up to 30 days of exposure to open atmosphere (50 % humidity).

Metal halide perovskite solar cells, despite achieving high power conversion efficiency (PCE), need to demonstrate high stability prior to be considered for industrialization. Prolonged exposure to heat, light, and moisture is known to deteriorate the perovskite material owing to the breakdown of the crystal structure into its non-photoactive components. In this study, we show that by combining the organic ligand 1-naphthylmethylammonium iodide (NMAI) with methylammonium (MA) to form a mixed dimensional (NMA)2(MA)n−1PbnI3n+1 perovskite the optical, crystallographic and morphological properties of the newly formed mixed dimensional perovskite films under thermal ageing can be retained. Indeed, under thermal ageing at 85 °C, the best performing (NMA)2(MA)n−1PbnI3n+1 perovskites films show a stable morphology, a low PbI2 formation rate and a significantly reduced variation of both MA-specific vibrational modes and fluorescence lifetimes as compared to the pristine MAPbI3 films. These results highlight the role of the bulky NMA+ organic cation in mixed dimensional perovskites to both inhibit the MA+ diffusion and reduce the material defects, which act as non-radiative recombination centres. As a result, the thermal stability of metal halide perovskites has been substantially improved.

Thermal stability is a critical criterion for assessing the long-term stability of perovskite solar cells (PSCs). Here, it is shown that un-encapsulated co-evaporated MAPbI 3 (TE_MAPbI 3 ) PSCs demonstrate remarkable thermal stability even in an n-i-p structure that employs Spiro-OMeTAD as hole transport material (HTM). TE_MAPbI 3 PSCs maintain over ≈95% and ≈80% of their initial power conversion efficiency (PCE) after 1000 and 3600 h respectively under continuous thermal aging at 85 °C. TE_MAPbI 3 PSCs demonstrate remarkable structural robustness, absence of pinholes, or significant variation in grain sizes, and intact interfaces with the HTM, upon prolonged thermal aging. Here, the main factors driving TE_MAPbI 3 stability are assessed. It is demonstrated that the excellent TE_MAPbI 3 thermal stability is related to the perovskite growth process leading to a compact and almost strain-stress-free film. On the other hand, un-encapsulated PSCs with the same architecture, but incorporating solutionprocessed MAPbI 3 or Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 as active layers, show a complete PCE degradation after 500 h under the same thermal aging condition. These results highlight that the control of the perovskite growth process can substantially enhance the PSCs thermal stability, besides the chemical composition. The TE_MAPbI 3 impressive long-term thermal stability features the potential for field-operating conditions.

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Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr 3 to a ⟨110⟩ oriented FA n+2 Pb n Br 3n+2 structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate n phase in the FA n+2 Pb n Br 3n+2 structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented monohalide/cation perovskite. Proton transfer reaction-mass spectroscopy carried out to precisely quantify the decomposition product reveals that the organic solvent in the film is a key contributor to the structural transformation and, therefore, the chromism in the ⟨110⟩ structure. These intermediate n phases (2 ≤ n ≤ ∞) stabilize in metastable states in the FA n+2 Pb n Br 3n+2 system, which is accessible via strain or optical or thermal input. The structure reversibility in the ⟨110⟩ perovskite allowed us to demonstrate a class of photochromic sensors capable of self-adaptation to lighting.