Cost management and toxic waste generation are two key issues that must be addressed before the commercialization of perovskite optoelectronic devices. We report a groundbreaking strategy for eco-friendly and cost-effective fabrication of highly efficient perovskite solar cells. This strategy involves the usage of a high volatility co-solvent, which dilutes perovskite precursors to a lower concentration (<0.5 M) while retaining similar film quality and device performance as a high concentration (>1.4 M) solution. More than 70% of toxic waste and material cost can be reduced. Mechanistic insights reveal ultra-rapid evaporation of the co-solvent together with beneficial alteration of the precursor colloidal chemistry upon dilution with co-solvent, which in-situ studies and theoretical simulations confirm. The co-solvent tuned precursor colloidal properties also contribute to the enhancement of the stability of precursor solution, which extends its processing window thus minimizing the waste. This strategy is universally successful across different perovskite compositions, and scales from small devices to large-scale modules using industrial spin-coating, potentially easing the lab-to-fab translation of perovskite technologies.

There is an ongoing surge of interest in the use of formamidinium (FA) lead iodide perovskites in photovoltaics due to their exceptional optoelectronic properties. However, thermodynamic instability of the desired cubic perovskite (α-FAPbI 3 ) phase at ambient conditions leads to the formation of a yellow non-perovskite (δ-FAPbI 3 ) phase that compromises its utility. A stable α-FAPbI 3 perovskite phase is achieved by employing benzylammonium iodide (BzI) and the microscopic structure is elucidated by using solid-state NMR spectroscopy and X-ray scattering measurements. Perovskite solar cells based on the FAPbI 3 (BzI) 0.25 composition achieve power conversion efficiencies exceeding 20%, which is accompanied by enhanced shelf-life and operational stability, maintaining 80% of the performance after one year at ambient conditions.

The performance of perovskite solar cells is highly dependent on the fabrication method; thus, controlling the growth mechanism of perovskite crystals is a promising way towards increasing their efficiency and stability. Herein, a multi‐cation halide composition of perovskite solar cells is engineered via the two‐step sequential deposition method. Strikingly, it is found that adding mixtures of 1D polymorphs of orthorhombic δ‐RbPbI3 and δ‐CsPbI3 to the PbI2 precursor solution induces the formation of porous mesostructured hexagonal films. This porosity greatly facilitates the heterogeneous nucleation and the penetration of FA (formamidinium)/MA (methylammonium) cations within the PbI2 film. Thus, the subsequent conversion of PbI2 into the desired multication cubic α‐structure by exposing it to a solution of formamidinium methylammonium halides is greatly enhanced. During the conversion step, the δ‐CsPbI3 also is fully integrated into the 3D mixed cation perovskite lattice, which exhibits high crystallinity and superior optoelectronic properties. The champion device shows a power conversion efficiency (PCE) over 22%. Furthermore, these devices exhibit enhanced operational stability, with the best device retaining more than 90% of its initial value of PCE under 1 Sun illumination with maximum power point tracking for 400 h.

Low-dimensional hybrid perovskites have emerged as promising materials for optoelectronic applications. Although these materials have already demonstrated enhanced stability as compared to their three-dimensional perovskite analogues, their functionality has been limited by the insulating character of the organic moieties that primarily play a structure-directing role. This is particularly the case for the layered (2D) perovskite materials based on formamidinium lead iodide (FAPbI3) that remain scarce. We demonstrate a low-dimensional hybrid perovskite material based on a SPbI4 composition incorporating an electroactive naphthalenediimide (NDI) moiety as an organic spacer (S) between the perovskite slabs and evidence the propensity of the spacer to stabilize the α-FAPbI3 perovskite phase in hybrid low-dimensional SFA n–1Pb n I3n+1 perovskite compositions. This has been investigated by means of solid-state nuclear magnetic resonance spectroscopy in conjunction with molecular dynamics simulations and density functional theory calculations. Theoretical calculations suggest an electronic contribution of the organic spacer to the resulting optoelectronic properties, which was confirmed by transient absorption spectroscopy. We have further analyzed these materials by time-resolved microwave conductivity measurements, revealing challenges for their application in photovoltaics.

Arene–perfluoroarene moieties are used to assemble Dion-Jacobson perovskite phases, revealing nanosegregation and enhanced environmental stabilities relevant to their application.