Metal halide perovskites have emerged as exceptional semiconductors for optoelectronic applications. Substitution of the monovalent cations has advanced luminescence yields and device efficiencies. ...Here, we control the cation alloying to enhance optoelectronic performance through alteration of the charge carrier dynamics in mixed-halide perovskites. In contrast to single-halide perovskites, we find high luminescence yields for photoexcited carrier densities far below solar illumination conditions. Using time-resolved spectroscopy we show that the charge carrier recombination regime changes from second to first order within the first tens of nanoseconds after excitation. Supported by microscale mapping of the optical bandgap, electrically gated transport measurements and first-principles calculations, we demonstrate that spatially varying energetic disorder in the electronic states causes local charge accumulation, creating p- and n-type photodoped regions, which unearths a strategy for efficient light emission at low charge-injection in solar cells and light-emitting diodes.Localized photodoping in mixed-cation perovskites is shown to modify charge-carrier recombination and thus offer a route for more efficient light emission.
The success of halide perovskites in a host of optoelectronic applications is often attributed to their long photoexcited carrier lifetimes, which has led to charge-carrier recombination processes ...being described as unique compared to other semiconductors. Here, we integrate recent literature findings to provide a critical assessment of the factors we believe are most likely controlling recombination in the most widely studied halide perovskite systems. We focus on four mechanisms that have been proposed to affect measured charge carrier recombination lifetimes, namely: (1) recombination via trap states, (2) polaron formation, (3) the indirect nature of the bandgap (e.g., Rashba effect), and (4) photon recycling. We scrutinize the evidence for each case and the implications of each process on carrier recombination dynamics. Although they have attracted considerable speculation, we conclude that multiple trapping or hopping in shallow trap states, and the possible indirect nature of the bandgap (e.g., Rashba effect), seem to be less likely given the combined evidence, at least in high-quality samples most relevant to solar cells and light-emitting diodes. On the other hand, photon recycling appears to play a clear role in increasing apparent lifetime for samples with high photoluminescence quantum yields. We conclude that polaron dynamics are intriguing and deserving of further study. We highlight potential interdependencies of these processes and suggest future experiments to better decouple their relative contributions. A more complete understanding of the recombination processes could allow us to rationally tailor the properties of these fascinating semiconductors and will aid the discovery of other materials exhibiting similarly exceptional optoelectronic properties.
Methylammonium lead iodide perovskite (MAPbI
) exhibits long charge carrier lifetimes that are linked to its high efficiency in solar cells. Yet, the mechanisms governing these unusual carrier ...dynamics are not completely understood. A leading hypothesis-disproved in this work-is that a large, static bulk Rashba effect slows down carrier recombination. Here, using second harmonic generation rotational anisotropy measurements on MAPbI
crystals, we demonstrate that the bulk structure of tetragonal MAPbI
is centrosymmetric with I4/mcm space group. Our calculations show that a significant Rashba splitting in the bandstructure requires a non-centrosymmetric lead iodide framework, and that incorrect structural relaxations are responsible for the previously predicted large Rashba effect. The small Rashba splitting allows us to compute effective masses in excellent agreement with experiment. Our findings rule out the presence of a large static Rashba effect in bulk MAPbI
, and our measurements find no evidence of dynamic Rashba effects.
Halide perovskites perform remarkably in optoelectronic devices. 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 visualization 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 over a weaker influence of nanoscale strain variations even of large magnitude. Nanoscale compositional gradients drive carrier funnelling 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.
Perovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto‐electronic properties and ...their successful integration into multijunction cells. However, the performance of single‐ and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/C60 interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first‐principle numerical simulations. It is found that the most significant contribution to the total C60‐induced recombination loss occurs within the first monolayer of C60, rather than in the bulk of C60 or at the perovskite surface. The experiments show that the C60 molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of C60, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.
Nonradiative recombination induced by C60 is limiting the performance of pin type perovskite solar cells and remains poorly understood. In this manuscript, the possible recombination pathways are systematically examined and it is discovered that across‐interface recombination dominates. A point contact strategy is suggested to circumvent the loss, paving the way to improved pin type perovskite solar cells.
Efforts to stabilize photoactive formamidinium (FA)–based halide perovskites for perovskite photovoltaics have focused on the growth of cubic formamidinium lead iodide (α-FAPbI
) phases by ...empirically alloying with cesium, methylammonium (MA) cations, or both. We show that such stabilized FA-rich perovskites are noncubic and exhibit ~2° octahedral tilting at room temperature. This tilting, resolvable only with the use of local nanostructure characterization techniques, imparts phase stability by frustrating transitions from photoactive to hexagonal phases. Although the bulk phase appears stable when examined macroscopically, heterogeneous cation distributions allow microscopically unstable regions to form; we found that these transitioned to hexagonal polytypes, leading to local trap-assisted performance losses and photoinstabilities. Using surface-bound ethylenediaminetetraacetic acid, we engineered an octahedral tilt into pure α-FAPbI
thin films without any cation alloying. The templated photoactive FAPbI
film was extremely stable against thermal, environmental, and light stressors.
The rapid rise in efficiency and tunable bandgap of metal-halide perovskites makes them highly attractive for use in tandems on silicon. Recently we demonstrated a perovskite–silicon monolithic ...two-terminal tandem with 23.6% power conversion efficiency. Here, we present work on optical optimization to improve light harvesting that includes thinning out the top transparent electrode to reduce front-surface reflection and parasitic absorption; introducing metal fingers to minimize series resistance losses; and further minimizing reflection loss with a polydimethylsiloxane (PDMS) stamp with random, pyramidal texture. Additionally, to reduce voltage loss while achieving current matching, we employ polybis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA) as a hole transport material instead of NiO x and a wider 1.68 eV bandgap perovskite composition. These optimizations boost the open-circuit voltage to 1.77 V and the short-circuit current density to 18.4 mA/cm2, culminating in a 25% efficient perovskite–silicon tandem with a 1 cm2 active area.
Radiation‐resistant but cost‐efficient, flexible, and ultralight solar sheets with high specific power (W g−1) are the “holy grail” of the new space revolution, powering private space exploration, ...low‐cost missions, and future habitats on Moon and Mars. Herein, this study investigates an all‐perovskite tandem photovoltaic (PV) technology that uses an ultrathin active layer (1.56 µm) but offers high power conversion efficiency, and discusses its potential for high‐specific‐power applications. This study demonstrates that all‐perovskite tandems possess a high tolerance to the harsh radiation environment in space. The tests under 68 MeV proton irradiation show negligible degradation (<6%) at a dose of 1013 p+ cm−2 where even commercially available radiation‐hardened space PV degrade >22%. Using high spatial resolution photoluminescence (PL) microscopy, it is revealed that defect clusters in GaAs are responsible for the degradation of current space‐PV. By contrast, negligible reduction in PL of the individual perovskite subcells even after the highest dose studied is observed. Studying the intensity‐dependent PL of bare low‐gap and high‐gap perovskite absorbers, it is shown that the VOC, fill factor, and efficiency potentials remain identically high after irradiation. Radiation damage of all‐perovskite tandems thus has a fundamentally different origin to traditional space PV.
Efficient all‐perovskite‐based tandem photovoltaics (PV) are shown to be radiation hard, surpassing state‐of‐the‐art industry‐standard space PV. Combining high specific power with good resilience to the harsh radiation environment in space, they promise a next‐generation of lightweight and cost‐efficient solutions to power private space exploration, low‐cost missions as well as future habitats on the Moon and Mars.
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