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Next-generation low-cost semiconductors such as halide perovskites exhibit optoelectronic properties dominated by nanoscale variations in their structure, composition and photophysics. While microscopy provides a proxy for ultimate device function, past works have focused on neat thin-films on insulating substrates, missing crucial information about charge extraction losses and recombination losses introduced by transport layers. Here we use a multimodal operando microscopy toolkit to measure nanoscale current-voltage curves, recombination losses and chemical composition in an array of state-of-the-art perovskite solar cells before and after extended operational stress. We apply this toolkit to the same scan areas before and after extended operation to reveal that devices with the highest performance have the lowest initial performance spatial heterogeneity - a crucial link that is missed in conventional microscopy. We find that subtle compositional engineering of the perovskite has surprising effects on local disorder and resilience to operational stress. Minimising variations in local efficiency, rather than compositional disorder, is predictive of improved performance and stability. Modulating the interfaces with different contact layers or passivation treatments can increase initial performance but can also lead to dramatic nanoscale, interface-dominated degradation even in the presence of local performance homogeneity, inducing spatially varying transport, recombination, and electrical losses. These operando measurements of full devices act as screenable diagnostic tools, uniquely unveiling the microscopic mechanistic origins of device performance losses and degradation in an array of halide perovskite devices and treatments. This information in turn reveals guidelines for future improvements to both performance and stability., Comment: Main text and supplementary information. Main text 26 pages, 4 figures. Supplementary information 79 pages, 76 figures. Kyle Frohna and Cullen Chosy contributed equally

In recent years, the field of metal-halide perovskite emitters has rapidly emerged as a new community in solid-state lighting. Their exceptional optoelectronic properties have contributed to the rapid rise in external quantum efficiencies (EQEs) in perovskite light-emitting diodes (PeLEDs) from <1% (in 2014) to approaching 30% (in 2023) across a wide range of wavelengths. However, several challenges still hinder their commercialization, including the relatively low EQEs of blue/white devices, limited EQEs in large-area devices, poor device stability, as well as the toxicity of the easily accessible lead components and the solvents used in the synthesis and processing of PeLEDs. This roadmap addresses the current and future challenges in PeLEDs across fundamental and applied research areas, by sharing the community's perspectives. This work will provide the field with practical guidelines to advance PeLED development and facilitate more rapid commercialization., Comment: 103 pages, 29 figures. This is the version of the article before peer review or editing, as submitted by an author to Journal of Physics: Photonics. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it

Tandem perovskite solar cells beckon as lower cost alternatives to conventional single junction solar cells, with all-perovskite tandem photovoltaic architectures showing power conversion efficiencies up to 26.4%. Solution-processing approaches for the perovskite layers have enabled rapid 2optimization of perovskite solar technologies, but new deposition routes are necessary to enable modularity and scalability, facilitating further efficiency improvements and technology adoption. Here, we utilise a 4-source vacuum deposition method to deposit FA$_{0.7}$ Cs$_{0.3}$Pb(I$_x$Br$_{1-x}$)$_3$ perovskite, where the bandgap is widened through fine control over the halide content. We show how the combined use of a MeO-2PACz self-assembled monolayer as hole transporting material and passivation of the perovskite absorber with ethylenediammonium diiodide reduces non-radiative losses, with this dual-interface treatment resulting in efficiencies of 17.8% in solar cells based on vacuum deposited perovskites with bandgap of 1.76 eV. By similarly passivating a narrow bandgap FA$_{0.75}$Cs$_{0.25}$Pb$_{0.5}$Sn$_{0.5}$I$_3$ perovskite and combining it with sub-cells of evaporated FA$_{0.7}$Cs$_{0.3}$Pb(I$_{0.64}$Br$_{0.36}$)$_3$, we report a 2-terminal all-perovskite tandem solar cell with champion open circuit voltage and power conversion efficiency of 2.06 V and 24.1%, respectively. The implementation of our dry deposition method enables high reproducibility in complex device architectures, opening avenues for modular, scalable multi-junction devices where the substrate choice is unrestricted., Comment: 28 pages, 5 figures

With rapidly growing photoconversion efficiencies, hybrid perovskite solar cells have emerged as promising contenders for next generation, low-cost photovoltaic technologies. Yet, the presence of nanoscale defect clusters, that form during the fabrication process, remains critical to overall device operation, including efficiency and long-term stability. To successfully deploy hybrid perovskites, we must understand the nature of the different types of defects, assess their potentially varied roles in device performance, and understand how they respond to passivation strategies. Here, by correlating photoemission and synchrotron-based scanning probe X-ray microscopies, we unveil three different types of defect clusters in state-of-the-art triple cation mixed halide perovskite thin films. Incorporating ultrafast time-resolution into our photoemission measurements, we show that defect clusters originating at grain boundaries are the most detrimental for photocarrier trapping, while lead iodide defect clusters are relatively benign. Hexagonal polytype defect clusters are only mildly detrimental individually, but can have a significant impact overall if abundant in occurrence. We also show that passivating defects with oxygen in the presence of light, a previously used approach to improve efficiency, has a varied impact on the different types of defects. Even with just mild oxygen treatment, the grain boundary defects are completely healed, while the lead iodide defects begin to show signs of chemical alteration. Our findings highlight the need for multi-pronged strategies tailored to selectively address the detrimental impact of the different defect types in hybrid perovskite solar cells., Comment: 23 pages

Halide perovskites excel in the pursuit of highly efficient thin film photovoltaics, with power conversion efficiencies reaching 25.5% in single junction and 29.5% in tandem halide perovskite/silicon solar cell configurations. Operational stability of perovskite solar cells remains a barrier to their commercialisation, yet a fundamental understanding of degradation processes, including the specific sites at which failure mechanisms occur, is lacking. Recently, we reported that performance-limiting deep sub-bandgap states appear in nanoscale clusters at particular grain boundaries in state-of-the-art $Cs_{0.05}FA_{0.78}MA_{0.17}Pb(I_{0.83}Br_{0.17})_{3}$ (MA=methylammonium, FA=formamidinium) perovskite films. Here, we combine multimodal microscopy to show that these very nanoscale defect clusters, which go otherwise undetected with bulk measurements, are sites at which degradation seeds. We use photoemission electron microscopy to visualise trap clusters and observe that these specific sites grow in defect density over time under illumination, leading to local reductions in performance parameters. Scanning electron diffraction measurements reveal concomitant structural changes at phase impurities associated with trap clusters, with rapid conversion to metallic lead through iodine depletion, eventually resulting in pinhole formation. By contrast, illumination in the presence of oxygen reduces defect densities and reverses performance degradation at these local clusters, where phase impurities instead convert to amorphous and electronically benign lead oxide. Our work shows that the trapping of charge carriers at sites associated with phase impurities, itself reducing performance, catalyses redox reactions that compromise device longevity. Importantly, we reveal that both performance losses and intrinsic degradation can be mitigated by eliminating these defective clusters., Comment: 23 pages, 3 figures, Stuart Macpherson and Tiarnan A. S. Doherty contributed equally

Halide perovskites perform remarkably in optoelectronic devices including tandem photovoltaics. However, this exceptional performance is striking given that perovskites exhibit deep charge carrier traps and spatial compositional and structural heterogeneity, all of which should be detrimental to performance. Here, we resolve this long-standing paradox by providing a global visualisation of the nanoscale chemical, structural and optoelectronic landscape in halide perovskite devices, made possible through the development of a new suite of correlative, multimodal microscopy measurements combining quantitative optical spectroscopic techniques and synchrotron nanoprobe measurements. We show that compositional disorder dominates the optoelectronic response, while nanoscale strain variations even of large magnitude (~1 %) have only a weak influence. Nanoscale compositional gradients drive carrier funneling onto local regions associated with low electronic disorder, drawing carrier recombination away from trap clusters associated with electronic disorder and leading to high local photoluminescence quantum efficiency. These measurements reveal a global picture of the competitive nanoscale landscape, which endows enhanced defect tolerance in devices through spatial chemical disorder that outcompetes both electronic and structural disorder., Comment: 26 pages, 4 figures

Here we use time-resolved and steady-state optical spectroscopy on state-of-the-art low- and high-bandgap perovskite films for tandems to quantify intrinsic recombination rates and absorption coefficients. We apply these data to calculate the limiting efficiency of perovskite-silicon and all-perovskite two-terminal tandems employing currently available bandgap materials as 42.0 % and 40.8 % respectively. By including luminescence coupling between sub-cells, i.e. the re-emission of photons from the high-bandgap sub-cell and their absorption in the low-bandgap sub-cell, we reveal the stringent need for current matching is relaxed when the high-bandgap sub-cell is a luminescent perovskite compared to calculations that do not consider luminescence coupling. We show luminescence coupling becomes important in all-perovskite tandems when charge carrier trapping rates are < 10$^{6}$ s$^{-1}$ (corresponding to carrier lifetimes longer than 1 ${\mu}$s at low excitation densities) in the high-bandgap sub-cell, which is lowered to 10$^{5}$ s$^{-1}$ in the better-bandgap-matched perovskite-silicon cells. We demonstrate luminescence coupling endows greater flexibility in both sub-cell thicknesses, increased tolerance to different spectral conditions and a reduction in the total thickness of light absorbing layers. To maximally exploit luminescence coupling we reveal a key design rule for luminescent perovskite-based tandems: the high-bandgap sub-cell should always have the higher short-circuit current. Importantly, this can be achieved by reducing the bandgap or increasing the thickness in the high-bandgap sub-cell with minimal reduction in efficiency, thus allowing for wider, unstable bandgap compositions (>1.7 eV) to be avoided. Finally, we experimentally visualise luminescence coupling in an all-perovskite tandem device stack through cross-section luminescence images., Comment: 20 pages, 5 figures

Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behaviour is still to be understood. Here, a combination of atomic-force, optical and compositional X-ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. We reveal mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus than the bulk parent material. These mechanical boundaries are associated with the presence of bromide-rich clusters as visualized by nano-X-ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties towards the bulk Young's Modulus. We attribute this behaviour to light-induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. Our work highlights critical links between mechanical, chemical and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity., Comment: 16 pages, 4 figures

Perovskite nanoplatelets (NPls) hold great promise for light-emitting applications, having achieved high photoluminescence quantum efficiencies (PLQEs) approaching unity in the blue wavelength range, where other metal-halide perovskites have typically been ineffective. However, the external quantum efficiency (EQE) of blue-emitting NPl light-emitting diodes (LEDs) have only reached 0.12%, with typical values well below 0.1%. In this work, we show that the performance of NPl LEDs is primarily hindered by a poor electronic interface between the emitter and hole-injector. Through Kelvin Probe and X-ray photoemission spectroscopy measurements, we reveal that the NPls have remarkably deep ionization potentials (>=6.5 eV), leading to large barriers for hole injection, as well as substantial non-radiative decay at the interface between the emitter and hole-injector. We find that an effective way to reduce these non-radiative losses is by using poly(triarylamine) interlayers. This results in an increase in the EQE of our blue LEDs emitting at 464 nm wavelength to 0.3%. We find that our results can be generalized to thicker sky-blue-emitting NPls, where we increase the EQE to 0.55% using the poly(triarylamine) interlayer. Our work also identifies the key challenges for further efficiency increases.

With the rapid progress of perovskite photovoltaics (PV), further challenges arise to meet meet the minimum standards required for commercial deployment. Along with the push towards higher efficiencies, we identify a need to improve the quality and uniformity of reported research data and to focus efforts upon understanding and overcoming failures during operation. In this perspective, as a large and representative consortium of researchers active in this field, we discuss which methods require special attention and issue a series of recommendations to improve research practices and reporting.

Halide perovskites have shown great potential for light emission and photovoltaic applications due to their remarkable electronic properties and compatibility with cost-effective fabrication techniques. Although the device performances are promising, they are still limited by microscale heterogeneities in their photophysical properties. In particular, the relation between local heterogeneities and the diffusion of charge carriers at the surface and in the bulk, crucial for efficient collection of charges in a light harvesting device, is not well understood. Here, a photoluminescence tomography technique is developed in a confocal microscope using one- and two-photon excitation to distinguish between local surface and bulk diffusion of charge carriers in methylammonium lead bromide single crystals. The local temporal diffusion is probed at various excitation depths to build statistics of local electronic diffusion coefficients. The measured values range between 0.3 to 2 $cm^2.s^{-1}$ depending on the local trap density and the morphological environment - a distribution that would be missed from analogous macroscopic or surface-measurements. Tomographic images of carrier diffusion were reconstructed to reveal buried crystal defects that act as barriers to carrier transport. This work reveals a new framework to understand and homogenise diffusion pathways, which are extremely sensitive to local properties and buried defects., Comment: C.S. and G.D. contributed equally to this work * corresponding author sds65@cam.ac.uk