Photovoltaic Performance of FAPbI3 Perovskite Is Hampered by Intrinsic Quantum Confinement.

Formamidinium lead trioiodide (FAPbI3) is a promising perovskite for single-junction solar cells. However, FAPbI3 is metastable at room temperature and can cause intrinsic quantum confinement effects apparent through a series of above-bandgap absorption peaks. Here, we explore three common solution-based film-fabrication methods, neat N,N-dimethylformamide (DMF)-dimethyl sulfoxide (DMSO) solvent, DMF-DMSO with methylammonium chloride, and a sequential deposition approach. The latter two offer enhanced nucleation and crystallization control and suppress such quantum confinement effects. We show that elimination of these absorption features yields increased power conversion efficiencies (PCEs) and short-circuit currents, suggesting that quantum confinement hinders charge extraction. A meta-analysis of literature reports, covering 244 articles and 825 photovoltaic devices incorporating FAPbI3 films corroborates our findings, indicating that PCEs rarely exceed a 20% threshold when such absorption features are present. Accordingly, ensuring the absence of these absorption features should be the first assessment when designing fabrication approaches for high-efficiency FAPbI3 solar cells.

Chloride-Based Additive Engineering for Efficient and Stable Wide-Bandgap Perovskite Solar Cells.

Metal halide perovskite based tandem solar cells are promising to achieve power conversion efficiency beyond the theoretical limit of their single-junction counterparts. However, overcoming the significant open-circuit voltage deficit present in wide-bandgap perovskite solar cells remains a major hurdle for realizing efficient and stable perovskite tandem cells. Here, a holistic approach to overcoming challenges in 1.8 eV perovskite solar cells is reported by engineering the perovskite crystallization pathway by means of chloride additives. In conjunction with employing a self-assembled monolayer as the hole-transport layer, an open-circuit voltage of 1.25 V and a power conversion efficiency of 17.0% are achieved. The key role of methylammonium chloride addition is elucidated in facilitating the growth of a chloride-rich intermediate phase that directs crystallization of the desired cubic perovskite phase and induces more effective halide homogenization. The as-formed 1.8 eV perovskite demonstrates suppressed halide segregation and improved optoelectronic properties.

Understanding the Degradation of Methylenediammonium and Its Role in Phase-Stabilizing Formamidinium Lead Triiodide.

Formamidinium lead triiodide (FAPbI3) is the leading candidate for single-junction metal-halide perovskite photovoltaics, despite the metastability of this phase. To enhance its ambient-phase stability and produce world-record photovoltaic efficiencies, methylenediammonium dichloride (MDACl2) has been used as an additive in FAPbI3. MDA2+ has been reported as incorporated into the perovskite lattice alongside Cl-. However, the precise function and role of MDA2+ remain uncertain. Here, we grow FAPbI3 single crystals from a solution containing MDACl2 (FAPbI3-M). We demonstrate that FAPbI3-M crystals are stable against transformation to the photoinactive δ-phase for more than one year under ambient conditions. Critically, we reveal that MDA2+ is not the direct cause of the enhanced material stability. Instead, MDA2+ degrades rapidly to produce ammonium and methaniminium, which subsequently oligomerizes to yield hexamethylenetetramine (HMTA). FAPbI3 crystals grown from a solution containing HMTA (FAPbI3-H) replicate the enhanced α-phase stability of FAPbI3-M. However, we further determine that HMTA is unstable in the perovskite precursor solution, where reaction with FA+ is possible, leading instead to the formation of tetrahydrotriazinium (THTZ-H+). By a combination of liquid- and solid-state NMR techniques, we show that THTZ-H+ is selectively incorporated into the bulk of both FAPbI3-M and FAPbI3-H at ∼0.5 mol % and infer that this addition is responsible for the improved α-phase stability.

Understanding the impact of surface roughness: changing from FTO to ITO to PEN/ITO for flexible perovskite solar cells.

So far, single-junction flexible PSCs have been lacking in efficiency compared to rigid PSCs. Recently, > 23% have been reported. We therefore focus on understanding the differences between rigid and flexible substrates. One often neglected parameter is the different surface roughness which directly affects the perovskite film formation. Therefore, we adjust the layer thickness of SnO2 and the perovskite layers. Furthermore, we introduce a PMMA layer between the perovskite and the hole transporting material (HTM), spiro-MeOTAD, to mitigate shunting pathways. In addition, the multication perovskite Rb0.02Cs0.05FA0.77MA0.16Pb(I0.83Br0.17)3 is employed, resulting in stabilized performances of 16% for a flexible ITO substrate and 19% on a rigid ITO substrate.

Intermediate-phase engineering via dimethylammonium cation additive for stable perovskite solar cells.

Achieving the long-term stability of perovskite solar cells is arguably the most important challenge required to enable widespread commercialization. Understanding the perovskite crystallization process and its direct impact on device stability is critical to achieving this goal. The commonly employed dimethyl-formamide/dimethyl-sulfoxide solvent preparation method results in a poor crystal quality and microstructure of the polycrystalline perovskite films. In this work, we introduce a high-temperature dimethyl-sulfoxide-free processing method that utilizes dimethylammonium chloride as an additive to control the perovskite intermediate precursor phases. By controlling the crystallization sequence, we tune the grain size, texturing, orientation (corner-up versus face-up) and crystallinity of the formamidinium (FA)/caesium (FA)yCs1-yPb(IxBr1-x)3 perovskite system. A population of encapsulated devices showed improved operational stability, with a median T80 lifetime (the time over which the device power conversion efficiency decreases to 80% of its initial value) for the steady-state power conversion efficiency of 1,190 hours, and a champion device showed a T80 of 1,410 hours, under simulated sunlight at 65 °C in air, under open-circuit conditions. This work highlights the importance of material quality in achieving the long-term operational stability of perovskite optoelectronic devices.

Poly(ethylene glycol)-[60]Fullerene-Based Materials for Perovskite Solar Cells with Improved Moisture Resistance and Reduced Hysteresis.

A series of [60]fullerenes covalently functionalized with the polymer poly(ethylene glycol) is presented. These new [60]fullerene-based materials have been incorporated as additives in CH3 NH3 PbI3 (MAPbI3 ), the most common organic-inorganic perovskite used in perovskite solar cells. The extensive photovoltaic study performed by using these materials shows several beneficial effects on the performance of these cells, including a reduction in hysteresis and an increased stability against moisture, whereby the solar cells retain up to 97 % of their initial power conversion efficiency in an ambient atmosphere.