Photoelectrochemical water splitting and CO₂ reduction provide an attractive route to produce solar fuels while reducing the level of CO₂ emissions. Metal halide perovskites (MHPs) have been extensively studied for this purpose in recent years due to their suitable optoelectronic properties. In this review, we survey the recent achievements in the field. After a brief introduction to photoelectrochemical (PEC) processes, we discussed the properties, synthesis, and application of MHPs in this context. We also survey the state-of-the-art findings regarding significant achievements in performance, and developments in addressing the major challenges of toxicity and instability toward water. Efforts have been made to replace the toxic Pb with less toxic materials like Sn, Ge, Sb, and Bi. The stability toward water has been also improved by using various methods such as compositional engineering, 2D/3D perovskite structures, surface passivation, the use of protective layers, and encapsulation. In the last part, considering the experience gained in photovoltaic applications, we provided our perspective for the future challenges and opportunities. We place special emphasis on the improvement of stability as the major challenge and the potential contribution of machine learning to identify the most suitable formulation for halide perovskites with desired properties.

Double perovskites are a promising family of lead-free materials that not only replace lead but also enable new optoelectronic applications beyond photovoltaics. Recently, a titanium (Ti)-based vacancy-ordered double perovskite, Cs₂TiBr₆, has been reported as an example of truly sustainable and earth-abundant perovskite with controversial results in terms of photoluminescence and environmental stability. Our work looks at this material from a new perspective, i.e., at the nanoscale. We demonstrate the first colloidal synthesis of Cs₂TiX₆ nanocrystals (X = Br, Cl) and observe tunable morphology and size of the nanocrystals according to the set reaction temperature. The Cs₂TiBr₆ nanocrystals synthesized at 185 °C show a bandgap of 1.9 eV and are relatively stable up to 8 weeks in suspensions. However, they do not display notable photoluminescence. The centrosymmetric crystal structure of Cs₂TiBr₆ suggests that this material could enable third-harmonic generation (THG) responses. Indeed, we provide a clear evidence of THG signals detected by the THG microscopy technique. As only a few THG-active halide perovskite materials are known to date and they are all lead-based, our findings promote future research on Cs₂TiBr₆ as well as on other lead-free double perovskites, with stronger focus on currently unexplored nonlinear optical applications.

The perovskite-inspired Cu₂AgBiI₆ (CABI) absorber shows promise for low-toxicity indoor photovoltaics. However, the carrier self-trapping in this material limits its photovoltaic performance. Herein, we examine the self-trapping mechanism in CABI by analyzing the excited-state dynamics of its absorption band at 425 nm, which is responsible for the self-trapped exciton emission, using a combination of photoluminescence and ultrafast transient absorption spectroscopies. Photoexcitation in CABI rapidly generates charge carriers in the silver iodide lattice sites, which localize into the self-trapped states and luminesce. Furthermore, a Cu-Ag-I-rich phase that exhibits similar spectral responses as CABI is synthesized, and a comprehensive structural and photophysical study of this phase provides insights into the nature of the excited states of CABI. Overall, this work explains the origin of self-trapping in CABI. This understanding will play a crucial role in optimizing its optoelectronic properties. It also encourages compositional engineering as the key to suppressing self-trapping in CABI.

Indoor photovoltaic (IPV) technology has emerged as an effective strategy to sustainably power batteryless Internet of Things (IoT) devices. Though tin perovskite solar cells offer competitive IPV performance, their effectiveness is often compromised by Sn²⁺ oxidation, particularly when processed with dimethyl sulfoxide (DMSO) solvent. This work explored the IPV performance of DMSO-free tin perovskites FASnI_3–x Br _x by tuning the halide composition. Notably, X-ray photoelectron spectroscopy confirms no traces of Sn⁴⁺, highlighting the critical role of eliminating DMSO. Under 1000 lx indoor illumination, the power conversion efficiency (PCE) increases with Br content, reaching a maximum of 11.1% for FASnI₂Br without introducing any reducing agent. Remarkably, after six months of storage, it exhibited an impressive indoor PCE of 11.9%, demonstrating the effectiveness of the DMSO-free processing route for the intrinsic stability of the tin perovskite. These findings provide crucial insights for developing high-performance, lead-free perovskite materials for sustainable energy applications and IoT devices.

Cu₂AgBiI₆ (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br^–) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE). By introducing Br^– in the synthetic route of CABI thin films, we identify the optimum composition as CABI-10Br (with 10% Br at the halide site). The tailored composition appears to reduce the deep trap density as shown by time-resolved photoluminescence and transient absorption spectroscopy characterizations. This leads to a dramatic increase in the lifetime of charge carriers, which therefore improves both the external quantum efficiency and the integrated short-circuit current. The photovoltaic performance shows a significant boost since the PCE under standard 1 sun illumination increases from 1.32 to 1.69% (∼30% relative enhancement). Systematic theoretical and experimental characterizations were employed to investigate the effect of Br^– incorporation on the optoelectronic properties of CABI. Our results highlight the importance of mitigating trap states in lead-free perovskite-inspired materials and that Br^– incorporation at the halide site is an effective strategy for improving the device performance.