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Abstract:

2D lead halide perovskites (2DPs) offer chemical compatibility with 3D perovskites and enhanced stability, which are attractive for applications in photovoltaic and light‐emitting devices. However, such lowered structural dimensionality causes increased excitonic effects and highly anisotropic charge‐carrier transport. Determining the diffusivity of excitations, in particular for out‐of‐plane or inter‐layer transport, is therefore crucial, yet challenging to achieve. Here, an effective method is demonstrated for monitoring inter‐layer diffusion of photoexcitations in (PEA)2PbI4 thin films by tracking time‐dependent changes in photoluminescence spectra induced by photon reabsorption effects. Selective photoexcitation from either substrate‐ or air‐side of the films reveals differences in diffusion dynamics encountered through the film profile. Time‐dependent diffusion coefficients are extracted from spectral dynamics through a 1D diffusion model coupled with an interference correction for refractive index variations arising from the strong excitonic resonance of 2DPs. Such analysis, together with structural probes, shows that minute misalignment of 2DPs planes occurs at distances far from the substrate, where efficient in‐plane transport consequently overshadows the less efficient out‐of‐plane transport in the direction perpendicular to the substrate. Through detailed analysis, a low out‐of‐plane excitation diffusion coefficient of (0.26 ± 0.03) ×10−4 cm2 s−1 is determined, consistent with a diffusion anisotropy of ≈4 orders of magnitude.

Abstract:

Doping with small densities of foreign ions is an essential strategy for tuning the optoelectronic properties of semiconductors, but the effects of doping are not well-understood in halide perovskites. We investigate the effect of Bi3+ and Sb3+ doping in lead–tin perovskites. Films doped with small amounts of BiI3 and SbI3 show greatly increased non-radiative recombination at precursor doping concentrations as low as 1 ppm for Bi3+ and 1000 ppm for Sb3+. We rationalize such behaviour by density functional theory (DFT) simulations, showing that these metal ions can be incorporated in the perovskite crystal by introducing deep trap levels in the band gap. Having found that very small amounts of Bi3+ greatly reduce the optoelectronic quality of lead–tin perovskite films, we investigate the presence of Bi impurities in perovskite precursor chemicals and find quantities approaching 1 ppm in some. In response, we introduce a facile method for removing Bi3+ impurities and demonstrate removal of 100 ppm Bi from a perovskite ink. This work demonstrates how the incorporation of small concentrations of foreign metal ions can severely affect film quality, raising the importance of precursor chemical purity.

Abstract:

Metal-halide perovskites are emerging as promising semiconductors for next-generation (opto)electronics. Due to their excellent optoelectronic and physical properties, as well as their processing capabilities, the past decades have seen significant progress and success in various device applications, such as solar cells, photodetectors, light-emitting diodes, and transistors. Despite their performance now rivaling or surpassing that of silicon counterparts, halide-perovskite semiconductors still face challenges for commercialization, particularly in terms of toxicity, stability, reliability, reproducibility, and lifetime. In this Roadmap, we present comprehensive discussions and perspectives from leading experts in the perovskite research community, covering various perovskite (opto)electronics, fundamental material properties and fabrication methods, photophysical characterizations, computing science, device physics, and the current challenges in each field. We hope this article provides a valuable resource for researchers and fosters the development of halide perovskites from basic to applied science.

Abstract:

Substantial VOC loss and halide segregation in wide-bandgap (WBG) perovskite sub-cells pose significant challenges for advancing all-perovskite tandem solar cells (APTSCs). Regarding this, one of the most impactful developments is the application of hole-selective self-assembled monolayers (SAMs), leading to the advancement in APTSC technology. However, SAMs with poor polar-solvent resistance would be inevitably delaminated from substrates during perovskite precursor coating, remaining great challenge in achieving a complete SAMs coverage with derivatization issues, e.g. defective perovskite and considerable interface energy loss. Here, we introduced an in-situ molecular compensation strategy to address the inherent flaw of SAMs within WBG perovskites via incorporating 5-ammonium valeric acid iodide (5-AVAI). The larger-dipole 5-AVAI spontaneously accumulates toward the buried interface to compensate the SAMs-deficient sites when depositing WBG perovskite, effectively minimizing interfacial energy loss. Simultaneously, amphoteric 5-AVAI with amino and carboxyl groups can compensate the defects at grain boundaries for solid passivation. Consequently, a champion efficiency of 20.23% with a record VOC of 1.376 V was realized on WBG devices, enabling an efficiency of 28.9% for the APTSCs. Encouragingly, the tandems showed good operational stability and retained 87.3% of their efficiency after 800 hours of tracking.