The technique of alloying FA+ with Cs+ is often used to promote structural stabilization of the desirable α-FAPbI3 phase in halide perovskite devices. However, the precise mechanisms by which these alloying approaches improve the optoelectronic quality and enhance the stability have remained elusive. In this study, we advance that understanding by investigating the effect of cationic alloying in CsxFA1−xPbI3 perovskite thin-films and solar-cell devices. Selected-area electron diffraction patterns combined with microwave conductivity measurements reveal that fine Cs+ tuning (Cs0.15FA0.85PbI3) leads to a minimization of stacking faults and an increase in the photoconductivity of the perovskite films. Ultra-sensitive external quantum efficiency, kelvin-probe force microscopy and photoluminescence quantum yield measurements demonstrate similar Urbach energy values, comparable surface potential fluctuations and marginal impact on radiative emission yields, respectively, irrespective of Cs content. Despite this, these nanoscopic defects appear to have a detrimental impact on inter-grains’/domains’ carrier transport, as evidenced by conductive-atomic force microscopy and corroborated by drastically reduced solar cell performance. Importantly, encapsulated Cs0.15FA0.85PbI3 devices show robust operational stability retaining 85% of the initial steady-state power conversion efficiency for 1400 hours under continuous 1 sun illumination at 35 °C, in open-circuit conditions. Our findings provide nuance to the famous defect tolerance of halide perovskites while providing solid evidence about the detrimental impact of these subtle structural imperfections on the long-term operational stability.

Full-area passivating contacts based on SiOx/poly-Si stacks are key for the new generation of industrial silicon solar cells substituting the passivated emitter and rear cell (PERC) technology. Demonstrating a potential efficiency increase of 1 to 2% compared to PERC, the utilization of n-type wafers with an n-type contact at the back and a p-type diffused boron emitter has become the industry standard in 2024. In this work, variations of this technology are explored, considering p-type passivating contacts on p-type Si wafers formed via a rapid thermal processing (RTP) step. These contacts could be useful in conjunction with n-type contacts for realizing solar cells with passivating contacts on both sides. Here, a particular focus is set on investigating the influence of the applied thermal treatment on the interfacial silicon oxide (SiOx) layer. Thin SiOx layers formed via ultraviolet (UV)–O3 exposure are compared with layers obtained through a plasma treatment with nitrous oxide (N2O). This process is performed in the same plasma enhanced chemical vapor deposition (PECVD) chamber used to grow the Si-based passivating layer, resulting in a streamlined process flow. For both oxide types, the influence of the RTP thermal budget on passivation quality and contact resistivity is investigated. Whereas the UV–O3 oxide shows a pronounced degradation when using high thermal budget annealing (T > 860 °C), the N2O–plasma oxide exhibits instead an excellent passivation quality under these conditions. Simultaneously, the contact resistivity achieved with the N2O-plasma oxide layer is comparable to that yielded by UV–O3-grown oxides. To unravel the mechanisms behind the improved performance obtained with the N2O-plasma oxide at high thermal budget, characterization by high-resolution (scanning) transmission electron microscopy (HR-(S)TEM), X-ray reflectometry (XRR) and X-ray photoelectron spectroscopy (XPS) is conducted on layer stacks featuring both N2O and UV–O3 oxides after RTP. A breakup of the UV–O3 oxide at high thermal budget is observed, whereas the N2O oxide is found to maintain its structural integrity along the interface. Furthermore, chemical analysis reveals that the N2O oxide is richer in oxygen and contains a higher amount of nitrogen compared to the UV–O3 oxide. These distinguishing characteristics can be directly linked to the enhanced stability exhibited by the N2O oxide under higher annealing temperatures and extended dwell times.

This work presents a study of p-type passivating contacts based on SiC_x formed via a rapid thermal processing (RTP) step, using conditions compatible with the firing used to sinter screen-printed metallization pastes in industry. The contributions of the two interfaces (wafer/contact and contact/metal) to the contact resistivity are first decorrelated, identifying tunnelling at the wafer interface as the main contribution. We then investigate the influence of the active dopant concentration on the contact resistivity and the SiC_x sheet resistance and propose strategies to reduce both resistances by increasing the thermal budget applied during RTP. Lastly, we discuss potentials and limitations of implementing the investigated stacks as rear side contacts of p-type devices with localized metallization. We demonstrate that increasing the thermal budget during RTP can effectively mitigate resistive losses and enhance contact performance and we show that an oxide layer that can withstand high thermal budgets is the key factor for obtaining simultaneously high passivation quality and good electrical properties. We investigate three different oxide types grown by HNO₃ immersion, UV-O₃ exposure and N₂O plasma oxidation. The latter is demonstrated to be a promising candidate for an application in devices fabricated with high RTP thermal budget.