Electrochemical Impedance Spectroscopy of All-Perovskite Tandem Solar Cells.

This work explores electrochemical impedance spectroscopy to study recombination and ionic processes in all-perovskite tandem solar cells. We exploit selective excitation of each subcell to enhance or suppress the impedance signal from each subcell, allowing study of individual tandem subcells. We use this selective excitation methodology to show that the recombination resistance and ionic time constants of the wide gap subcell are increased with passivation. Furthermore, we investigate subcell-dependent degradation during maximum power point tracking and find an increase in recombination resistance and a decrease in capacitance for both subcells. Complementary optical and external quantum efficiency measurements indicate that the main driver for performance loss is the reduced capacity of the recombination layer to facilitate recombination due to the formation of a charge extraction barrier. This methodology highlights electrochemical impedance spectroscopy as a powerful tool to provide critical feedback to unlock the full potential of perovskite tandem solar cells.

Substitution of lead with tin suppresses ionic transport in halide perovskite optoelectronics.

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development.

Identification and Mitigation of Transient Phenomena That Complicate the Characterization of Halide Perovskite Photodetectors.

Halide perovskites have shown promise to advance the field of light detection in next-generation photodetectors, offering performance and functionality beyond what is currently possible with traditional inorganic semiconductors. Despite a relatively high density of defects in perovskite thin films, long carrier diffusion lengths and lifetimes suggest that many defects are benign. However, perovskite photodetectors show detection behavior that varies with time, creating inconsistent device performance and difficulties in accurate characterization. Here, we link the changing behavior to mobile defects that migrate through perovskites, leading to detector currents that drift on the time scale of seconds. These effects not only complicate reproducible device performance but also introduce characterization challenges. We demonstrate that such transient phenomena generate measurement artifacts that mean the value of specific detectivity measured can vary by up to 2 orders of magnitude even in the same device. The presence of defects can lead to photoconductive gain in photodetectors, and we show batch-to-batch processing variations in perovskite devices gives varying degrees of charge carrier injection and photocurrent amplification under low light intensities. We utilize the passivating effect of aging to reduce the impact of defects, minimizing current drifts and eliminating the gain. This work highlights the potential issues arising from mobile defects, which lead to inconsistent photodetector operation, and identifies the potential for defects to tune photodetection behavior in perovskite photodetectors.

Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.

The family of hybrid organic-inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore the optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-Ci molecules, where Ci indicates an alkylammonium chain and i indicates the number of CH2 units in the chain, varying from 3 to 5, as cations in the two-dimensional (2D) perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-Ci)2PbI4, we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C3)2PbI4, where photothermal deflection spectroscopy results remarkably reveal an organic-inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-Ci molecules, the efficiency of which increases by varying the chain length from i = 5 to i = 3. The charge transfer results in long-lived carriers (10-100 ns) and quenched emission, in stark contrast to the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA)2PbI4, in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i = 5 to i = 3. This study paves the way for the rational design of 2D perovskites with combined inorganic-organic electronic properties through the wide range of functionalities available in the world of organics.

Local symmetry breaking drives picosecond spin domain formation in polycrystalline halide perovskite films.

Photoinduced spin-charge interconversion in semiconductors with spin-orbit coupling could provide a route to optically addressable spintronics without the use of external magnetic fields. However, in structurally disordered polycrystalline semiconductors, which are being widely explored for device applications, the presence and role of spin-associated charge currents remains unclear. Here, using femtosecond circular-polarization-resolved pump-probe microscopy on polycrystalline halide perovskite thin films, we observe the photoinduced ultrafast formation of spin domains on the micrometre scale formed through lateral spin currents. Micrometre-scale variations in the intensity of optical second-harmonic generation and vertical piezoresponse suggest that the spin-domain formation is driven by the presence of strong local inversion symmetry breaking via structural disorder. We propose that this leads to spatially varying Rashba-like spin textures that drive spin-momentum-locked currents, leading to local spin accumulation. Ultrafast spin-domain formation in polycrystalline halide perovskite films provides an optically addressable platform for nanoscale spin-device physics.

Vacuum-Deposited Wide-Bandgap Perovskite for All-Perovskite Tandem Solar Cells.

All-perovskite tandem solar cells beckon as lower cost alternatives to conventional single-junction cells. Solution processing has enabled rapid optimization of perovskite solar technologies, but new deposition routes will enable modularity and scalability, facilitating technology adoption. Here, we utilize 4-source vacuum deposition to deposit FA0.7Cs0.3Pb(IxBr1-x)3 perovskite, where the bandgap is changed through fine control over the halide content. We show how using MeO-2PACz as a hole-transporting material and passivating the perovskite with ethylenediammonium diiodide reduces nonradiative losses, resulting in efficiencies of 17.8% in solar cells based on vacuum-deposited perovskites with a bandgap of 1.76 eV. By similarly passivating a narrow-bandgap FA0.75Cs0.25Pb0.5Sn0.5I3 perovskite and combining it with a subcell of evaporated FA0.7Cs0.3Pb(I0.64Br0.36)3, we report a 2-terminal all-perovskite tandem solar cell with champion open circuit voltage and efficiency of 2.06 V and 24.1%, respectively. This dry deposition method enables high reproducibility, opening avenues for modular, scalable multijunction devices even in complex architectures.

Charge transport in mixed metal halide perovskite semiconductors.

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm2 V-1 s-1. The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

Tunable Multiband Halide Perovskite Tandem Photodetectors with Switchable Response.

Photodetectors with multiple spectral response bands have shown promise to improve imaging and communications through the switchable detection of different photon energies. However, demonstrations to date have been limited to only two bands and lack capability for fast switching in situ. Here, we exploit the band gap tunability and capability of all-perovskite tandem solar cells to demonstrate a new device concept realizing four spectral bands of response from a single multijunction device, with fast, optically controlled switching between the bands. The response to monochromatic light is highly selective and narrowband without the need for additional filters and switches to broader response bands on applying bias light. Sensitive photodetection above 6 × 1011 Jones is demonstrated in all modes, with rapid switching response times of <250 ns. We demonstrate proof of principle on how the manipulation of the modular multiband detector response through light conditions enables diverse applications in optical communications with secure encryption.

Local nanoscale phase impurities are degradation sites in halide perovskites.

Understanding the nanoscopic chemical and structural changes that drive instabilities in emerging energy materials is essential for mitigating device degradation. The power conversion efficiency of halide perovskite photovoltaic devices has reached 25.7 per cent in single-junction and 29.8 per cent in tandem perovskite/silicon cells1,2, yet retaining such performance under continuous operation has remained elusive3. Here we develop a multimodal microscopy toolkit to reveal that in leading formamidinium-rich perovskite absorbers, nanoscale phase impurities, including hexagonal polytype and lead iodide inclusions, are not only traps for photoexcited carriers, which themselves reduce performance4,5, but also, through the same trapping process, are sites at which photochemical degradation of the absorber layer is seeded. We visualize illumination-induced structural changes at phase impurities associated with trap clusters, revealing that even trace amounts of these phases, otherwise undetected with bulk measurements, compromise device longevity. The type and distribution of these unwanted phase inclusions depends on the film composition and processing, with the presence of polytypes being most detrimental for film photo-stability. Importantly, we reveal that both performance losses and intrinsic degradation processes can be mitigated by modulating these defective phase impurities, and demonstrate that this requires careful tuning of local structural and chemical properties. This multimodal workflow to correlate the nanoscopic landscape of beam-sensitive energy materials will be applicable to a wide range of semiconductors for which a local picture of performance and operational stability has yet to be established.

Optoelectronic Properties of Low-Bandgap Halide Perovskites for Solar Cell Applications.

Riding on the coat tails of rapid developments in single-junction halide perovskite solar cells, all-perovskite multijunction solar cells have recently garnered significant attention, with the highest power-conversion efficiency already reaching 25.6%. Much of this progress has been fueled by the rapid rise in the photovoltaic performance of low-bandgap halide perovskite absorbers, materials, which, to date, have only been achievable by the partial or complete substitution of lead with tin. However, much room still exists to develop a more critical understanding of key material properties in these low-bandgap perovskites. Herein, the key optoelectronic properties of absorption, carrier generation, recombination, and transport in these tin-containing perovskites are discussed, showing that intrinsic doping distinctively impacts many of these properties, thereby rendering this class of halide perovskites unique within the family. Current understanding of the mechanisms that degrade optoelectronic performance in these materials and the corresponding devices are also summarized. These collective results highlight an important interplay between doping, defects, and degradation that will need to be controlled. Finally, the current gaps in understanding of these low-bandgap perovskites are outlined, thereby providing guidelines for further research, which will unlock their full potential for realizing a plethora of high-performance optoelectronic devices.

Ion migration drives self-passivation in perovskite solar cells and is enhanced by light soaking.

Perovskite solar cells have rapidly become the most promising emerging photovoltaic technology. This is largely due to excellent self-passivating properties of the perovskite absorber material, allowing for a remarkable ease of fabrication. However, the field is plagued by poor reproducibility and conflicting results. This study finds that dynamic processes (ion migration) taking place after fabrication (without external stimuli) have a large influence on materials properties and need to be controlled to achieve reproducible results. The morphological and optoelectronic properties of triple cation perovskites with varying halide ratios are studied as they evolve over time. It is found that ion migration is essential for self-passivation, but can be impeded by low ion mobility or a low number of mobile species. Restricted ion movement can lead to crack formation in strained films, with disastrous consequences for device performance. However, a short light soaking treatment after fabrication helps to mobilize ions and achieve self-passivation regardless of composition. The community should adopt this treatment as standard practice to increase device performance and reproducibility.

Critical Assessment of the Use of Excess Lead Iodide in Lead Halide Perovskite Solar Cells.

It is common practice in the lead halide perovskite solar cell field to add a small molar excess of lead iodide (PbI2) to the precursor solution to increase the device performance. However, recent reports have shown that an excess of PbI2 can accelerate performance loss. In addition, PbI2 is photoactive (band gap ∼2.3 eV), which may lead to parasitic absorption losses in a solar cell. Here we show that devices using small quantities of excess PbI2 exhibit better device performance as compared with stoichiometric devices, both initially and for the duration of a stability test under operating conditions, primarily by enhancing the charge extraction. However, the photolysis of PbI2 negates the beneficial effect on charge extraction by leaving voids in the perovskite film and introduces trap states that are detrimental for device performance. We propose that although excess PbI2 provides a good template for enhanced performance, the community must continue to seek other additives or synthesis routes that fulfill the same beneficial role as excess PbI2, but without the photolysis that negates these beneficial effects under long-term device operation.

Comparing the excited-state properties of a mixed-cation-mixed-halide perovskite to methylammonium lead iodide.

Organic-inorganic perovskites are one of the most promising photovoltaic materials for the design of next generation solar cells. The lead-based perovskite prepared with methylammonium and iodide was the first in demonstrating high power conversion efficiency, and it remains one of the most used materials today. However, perovskites prepared by mixing several halides and several cations systematically yield higher efficiencies than "pure" methylammonium lead iodide (MAPbI3) devices. In this work, we unravel the excited-state properties of a mixed-halide (iodide and bromide) and mixed-cation (methylammonium and formamidinium) perovskite. Combining time-resolved photoluminescence, transient absorption, and optical-pump-terahertz-probe experiments with density functional theory calculations, we show that the population of higher-lying excited states in the mixed material increases the lifetime of photogenerated charge carriers upon well above-bandgap excitation. We suggest that alloying different halides and different cations reduces the structural symmetry of the perovskite, which partly releases the selection rules to populate the higher-energy states upon light absorption. Our investigation thus shows that mixed halide perovskites should be considered as an electronically different material than MAPbI3, paving the way toward further materials optimization and improved power conversion efficiency of perovskite solar cells.

Unraveling the Effect of Crystal Structure on Degradation of Methylammonium Lead Halide Perovskite.

Despite the remarkable efficiencies of perovskite solar cells, moisture instability has still been the major constraint in the technology deployment. Although, some research groups have discussed the possible mechanisms involved in the perovskite degradation, no broader understanding has been developed so far. Here, we demonstrate that the crystal orientation of perovskite film plays a major role in its degradation. We observed that the films fabricated via different routes led to different degradation behaviors and unraveled that diversity in the degradation rate arises due to the difference in crystallographic characteristics of the films. Using optical and electrical measurements, we show that the film prepared via a single-step (lead chloride precursor based) route undergoes a much faster degradation rate as compared with films prepared using single step (acetate precursor based) and two-step (or sequential deposition) routes. Although the resulting film is methylammonium lead iodide (MAPbI3) regardless of processing via different routes, their respective crystal orientation is different. In this manuscript, we correlate crystal orientation of MAPbI3 with their degradation pattern. Our studies also suggest a possible way to make stable perovskite film.

Cesium-Incorporated Triple Cation Perovskites Deliver Fully Reversible and Stable Nanoscale Voltage Response.

Perovskite solar cells that incorporate small concentrations of Cs in their A-site have shown increased lifetime and improved device performance. Yet, the development of fully stable devices operating near the theoretical limit requires understanding how Cs influences perovskites' electrical properties at the nanoscale. Here, we determine how the chemical composition of three perovskites (MAPbBr3, MAPbI3, and Cs-mixed) affects their short- and long-term voltage stabilities, with <50 nm spatial resolution. We map an anomalous irreversible electrical signature on MAPbBr3 at the mesoscale, resulting in local V oc variations of ∼400 mV, and in entire grains with negative contribution to the V oc. These measurements prove the necessity of high spatial resolution mapping to elucidate the fundamental limitations of this emerging material. Conversely, we capture the fully reversible voltage response of Cs-mixed perovskites, composed by Cs0.06(MA0.17FA0.83)0.94Pb(I0.83Br0.17)3, demonstrating that the desired electrical output persists even at the nanoscale. The Cs-mixed material presents no spatial variation in V oc, as ion motion is restricted. Our results show that the nanoscale electrical behavior of the perovskites is intimately connected to their chemical composition and macroscopic response.

Partial oxidation of the absorber layer reduces charge carrier recombination in antimony sulfide solar cells.

We investigate the effect of a post heat treatment of the absorber layer in air for antimony sulfide (Sb2S3) sensitized solar cells. Phenomenologically, exposing the Sb2S3 surface of sensitised solar cells to air at elevated temperatures is known to improve device performance. Here, we have investigated the detailed origins of this improvement. To this end, samples were annealed in air for different time periods and the build-up of an antimony oxide layer was monitored by XPS. A very short heat treatment resulted in an increase in power conversion efficiency from η = 1.4% to η = 2.4%, while longer annealing decreased the device performance. This improvement was linked to a reduction in charge carrier recombination at the interface of Sb2S3 with the organic hole conductor, arising from the oxide barrier layer, as demonstrated by intensity modulated photovoltage spectroscopy (IMVS).

Optical analysis of CH3NH3Sn x Pb1-x I3 absorbers: a roadmap for perovskite-on-perovskite tandem solar cells.

Organic-inorganic perovskite structures in which lead is substituted by tin are exceptional candidates for broadband light absorption. Herein we present a thorough analysis of the optical properties of CH3NH3Sn x Pb1-x I3 films, providing the field with definitive insights about the possibilities of these materials for perovskite solar cells of superior efficiency. We report a user's guide based on the first set of optical constants obtained for a series of tin/lead perovskite films, which was only possible to measure due to the preparation of optical quality thin layers. According to the Shockley-Queisser theory, CH3NH3Sn x Pb1-x I3 compounds promise a substantial enhancement of both short circuit photocurrent and power conversion efficiency in single junction solar cells. Moreover, we propose a novel tandem architecture design in which both top and bottom cells are made of perovskite absorbers. Our calculations indicate that such perovskite-on-perovskite tandem devices could reach efficiencies over 35%. Our analysis serves to establish the first roadmap for this type of cells based on actual optical characterization data. We foresee that this study will encourage the research on novel near-infrared perovskite materials for photovoltaic applications, which may have implications in the rapidly emerging field of tandem devices.

Doping of TiO2 for sensitized solar cells.

This review gives a detailed summary and evaluation of the use of TiO2 doping to improve the performance of dye sensitized solar cells. Doping has a major effect on the band structure and trap states of TiO2, which in turn affect important properties such as the conduction band energy, charge transport, recombination and collection. The defect states of TiO2 are highly dependent on the synthesis method and thus the effect of doping may vary for different synthesis techniques, making it difficult to compare the suitability of different dopants. High-throughput methods may be employed to achieve a rough prediction on the suitability of dopants for a specific synthesis method. It was however found that nearly every employed dopant can be used to increase device performance, indicating that the improvement is not so much caused by the dopant itself, as by the defects it eliminates from TiO2. Furthermore, with the field shifting from dye sensitized solar cells to perovskite solar cells, the role doping can play to further advance this emerging field is also discussed.

Efficient room temperature aqueous Sb2S3 synthesis for inorganic-organic sensitized solar cells with 5.1% efficiencies.

Sb2S3 sensitized solar cells are a promising alternative to devices employing organic dyes. The manufacture of Sb2S3 absorber layers is however slow and cumbersome. Here, we report the modified aqueous chemical bath synthesis of Sb2S3 absorber layers for sensitized solar cells. Our method is based on the hydrolysis of SbCl3 to complex antimony ions decelerating the reaction at ambient conditions, in contrast to the usual low temperature deposition protocol. This simplified deposition route allows the manufacture of sensitized mesoporous-TiO2 solar cells with power conversion efficiencies up to η = 5.1%. Photothermal deflection spectroscopy shows that the sub-bandgap trap-state density is lower in Sb2S3 films deposited with this method, compared to standard deposition protocols.