Snaith group

Abstract:

Monolithic perovskite/c-Si tandem solar cells have attracted enormous research attention and have achieved efficiencies above 30%. This work describes the development of monolithic tandem solar cells based on silicon heterojunction (SHJ) bottom- and perovskite top-cells and highlights light management techniques assisted by optical simulation. We first engineered (i)a-Si:H passivating layers for (100)-oriented flat c-Si surfaces and combined them with various (n)a-Si:H, (n)nc-Si:H, and (n)nc-SiO_x:H interfacial layers for SHJ bottom-cells. In a symmetrical configuration, a long minority carrier lifetime of 16.9 ms was achieved when combining (i)a-Si:H bilayers with (n)nc-Si:H (extracted at the minority carrier density of 10¹⁵ cm^-3). The perovskite sub-cell uses a photostable mixed-halide composition and surface passivation strategies to minimize energetic losses at charge-transport interfaces. This allows tandem efficiencies above 23% (a maximum of 24.6%) to be achieved using all three types of (n)-layers. Observations from experimentally prepared devices and optical simulations indicate that both (n)nc-SiO_x:H and (n)nc-Si:H are promising for use in high-efficiency tandem solar cells. This is possible due to minimized reflection at the interfaces between the perovskite and SHJ sub-cells by optimized interference effects, demonstrating the applicability of such light management techniques to various tandem structures.

Abstract:

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.

Abstract:

Tin-containing metal halide perovskites have enormous potential as photovoltaics, both in narrow band gap mixed tin–lead materials for all-perovskite tandems and for lead-free perovskites. The introduction of Sn(II), however, has significant effects on the solution chemistry, crystallization, defect states, and other material properties in halide perovskites. In this perspective, we summarize the main hurdles for tin-containing perovskites and highlight successful attempts made by the community to overcome them. We discuss important research directions for the development of these materials and propose some approaches to achieve a unified understanding of Sn incorporation. We particularly focus on the discussion of charge carrier dynamics and nonradiative losses at the interfaces between perovskite and charge extraction layers in p-i-n cells. We hope these insights will aid the community to accelerate the development of high-performance, stable single-junction tin-containing perovskite solar cells and all-perovskite tandems.

Abstract:

2H-Benzotriazol-2-ylethylammonium bromide and iodide and its difluorinated derivatives are synthesized and employed as interlayers for passivation of formamidinium lead triiodide (FAPbI₃) solar cells. In combination with PbI₂ and PbBr₂, these benzotriazole derivatives form two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs) as evidenced by their crystal structures and thin film characteristics. When used to passivate n-i-p FAPbI₃ solar cells, the power conversion efficiency improves from 20% to close to 22% by enhancing the open-circuit voltage. Quasi-Fermi level splitting experiments and scanning electron microscopy cathodoluminescence hyperspectral imaging reveal that passivation provides a reduced nonradiative recombination at the interface between the perovskite and hole transport layer. Photoluminescence spectroscopy, angle-resolved grazing-incidence wide-angle X-ray scattering, and depth profiling X-ray photoelectron spectroscopy studies of the 2D/three-dimensional (3D) interface between the benzotriazole RPP and FAPbI₃ show that a nonuniform layer of 2D perovskites is enough to passivate defects, enhance charge extraction, and decrease nonradiative recombination.