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The development of highly stable and efficient wide-bandgap (WBG) perovskite solar cells (PSCs) based on bromine-iodine (Br–I) mixed-halide perovskite (with Br greater than 20%) is critical to create tandem solar cells. However, issues with Br–I phase segregation under solar cell operational conditions (such as light and heat) limit the device voltage and operational stability. This challenge is often exacerbated by the ready defect formation associated with the rapid crystallization of Br-rich perovskite chemistry with antisolvent processes. We combined the rapid Br crystallization with a gentle gas-quench method to prepare highly textured columnar 1.75–electron volt Br–I mixed WBG perovskite films with reduced defect density. With this approach, we obtained 1.75–electron volt WBG PSCs with greater than 20% power conversion efficiency, approximately 1.33-volt open-circuit voltage ( V oc ), and excellent operational stability (less than 5% degradation over 1100 hours of operation under 1.2 sun at 65°C). When further integrated with 1.25–electron volt narrow-bandgap PSC, we obtained a 27.1% efficient, all-perovskite, two-terminal tandem device with a high V oc of 2.2 volts.

Achieving the long-term stability of perovskite solar cells is arguably the most important challenge required to enable widespread commercialization. Understanding the perovskite crystallization process and its direct impact on device stability is critical to achieving this goal. The commonly employed dimethyl-formamide/dimethyl-sulfoxide solvent preparation method results in a poor crystal quality and microstructure of the polycrystalline perovskite films. In this work, we introduce a high-temperature dimethyl-sulfoxide-free processing method that utilizes dimethylammonium chloride as an additive to control the perovskite intermediate precursor phases. By controlling the crystallization sequence, we tune the grain size, texturing, orientation (corner-up versus face-up) and crystallinity of the formamidinium (FA)/caesium (FA)yCs1–yPb(IxBr1–x)3 perovskite system. A population of encapsulated devices showed improved operational stability, with a median T80 lifetime (the time over which the device power conversion efficiency decreases to 80% of its initial value) for the steady-state power conversion efficiency of 1,190 hours, and a champion device showed a T80 of 1,410 hours, under simulated sunlight at 65 °C in air, under open-circuit conditions. This work highlights the importance of material quality in achieving the long-term operational stability of perovskite optoelectronic devices.

Deciphering the atomic and electronic structures of interfaces is key to developing state-of-the-art perovskite semiconductors. However, conventional characterization techniques have limited previous studies mainly to grain-boundary interfaces, whereas the intragrain-interface microstructures and their electronic properties have been much less revealed. Herein using scanning transmission electron microscopy, we resolved the atomic-scale structural information on three prototypical intragrain interfaces, unraveling intriguing features clearly different from those from previous observations based on standalone films or nanomaterial samples. These intragrain interfaces include composition boundaries formed by heterogeneous ion distribution, stacking faults resulted from wrongly stacked crystal planes, and symmetrical twinning boundaries. The atomic-scale imaging of these intragrain interfaces enables us to build unequivocal models for the ab initio calculation of electronic properties. Our results suggest that these structure interfaces are generally electronically benign, whereas their dynamic interaction with point defects can still evoke detrimental effects. This work paves the way toward a more complete fundamental understanding of the microscopic structure–property–performance relationship in metal halide perovskites.

Metal halide perovskites (MHPs) combine extraordinary optoelectronic properties with chemical and mechanical properties not found in their semiconductor counterparts. For instance, they exhibit optoelectronic properties on par with single-crystalline gallium arsenide yet exhibit near-zero formation energies. The small lattice energy of MHPs means they undergo a rich diversity of polymorphism near standard conditions similar to organic materials. MHPs also demonstrate ionic transport as high as state-of-the-art battery electrodes. The most widespread applications for metal halide perovskites (e.g. photovoltaics and solid-state lighting) typically view low formation energies, polymorphism, and high ion transport as a nuisance that should be eliminated. Here, we put these properties into perspective by comparing them to other technologically relevant semiconductors in order to highlight how unique this combination of properties is for semiconductors and to illustrate ways to leverage these properties in emerging applications.

Summary Polycrystalline photovoltaic materials offer low costs and good scalability; however, grain boundaries in these materials are extended defects, which can drastically increase carrier recombination. Interestingly, three leading polycrystalline thin-film technologies—cadmium telluride (CdTe), CuIn1-xGaxSe2 (CIGS), and perovskite solar cells (PSCs)—passivate absorber surfaces in the same way: via formation of low-dimensional, typically two-dimensional (2D), van der Waals materials. This has primarily occurred serendipitously through process optimization, but in some cases, 2D capping layers are intentionally incorporated to improve device performance. Here, evidence compiled from the literature, supplemented with new data where necessary, is presented to illustrate the existence of 3D/2D interfaces in CdTe, CIGS, and PSCs, and their correlation with improved passivation and device performance. This suggests that 3D/2D passivation might be a heretofore unappreciated key to successful polycrystalline thin-film photovoltaics. Finally, the desired attributes of successful low-dimensional layers are presented with rational design strategies for next-generation polycrystalline solar cells.

Summary The development of mixed tin-lead (Sn-Pb)-based perovskite solar cells (PSCs) with low band gap (1.2–1.4 eV) has become critical not only for pushing single-junction devices toward the maximum efficiency given by the Shockley-Queisser limit, but also for enabling all-perovskite tandem devices beyond this limit. However, achieving high power-conversion efficiency (PCE) and long-term device operation stability simultaneously remains a significant challenge for Sn-Pb-based PSCs. Here, we demonstrate near ideal-band-gap (∼1.34 eV) methylammonium-free Sn-Pb-based PSCs with high efficiency (∼20%) and promising operational stability of maintaining >80% of initial PCE over 750 h under maximum-power-point tracking. The key to this success is the use of a SnCl2⋅3FACl complex additive that improves the microstructure and reduces the development of residual stress in the Sn-Pb perovskite thin films, which in turn enhances the efficiency and stability of the Sn-Pb-based ideal-band-gap PSCs.

While research on derivatives of both bulk and low-dimensional metal halide perovskite (MHP) semiconductors has grown exponentially over the past decade, the understanding and intentional applicati...

Summary Surface modification of organic-inorganic halide perovskite thin films represents a promising approach to enhance the efficiency and stability of perovskite solar cells. Here, we synthesized N-methyl-1,3-propane diammonium diiodide (Me-PDAI2) and found that Me-PDA2+ can template a three-dimensional “perovskitoid” structure (Me-PDA)Pb2I6. Simple surface treatment with Me-PDAI2 on top of a standard (FAPbI3)0.85(MAPbI2Br)0.10(CsPbI3)0.05 perovskite induces the formation of a thin (Me-PDA)Pb2I6 perovskitoid surface layer, leading to smoother surface texture, longer charge-carrier lifetime, higher charge-carrier mobility, and a reduced surface-defect density. With the perovskitoid surface modification, the device efficiency is significantly improved from 20.3% to 22.0% along with enhanced stability in both shelf life (ISOS-D-1 stability) and operation (ISOS-L-1 stability). We further demonstrated that the perovskitoid surface engineering approach is applicable to various perovskite compositions, including CsFAMA-, FAMA-, and MA-based lead halide perovskites, making perovskitoid an important design motif for perovskite surface engineering for enhanced device performance and stability.

Summary Inorganic perovskite solar cells (PSCs) are promising for achieving long-term operational stability with good device performance. Here, we report the fabrication of inorganic CsPbI2Br-based perovskite thin films with a well-defined CsPbI3−xBrx composition gradient in the surface region by a scalable, orthogonal processable spray-coating approach. The graded structure broadens absorption wavelength range and increases carrier lifetime, but it also causes electrical field redistribution within a device stack for more efficient charge separation and collection. With this approach, we obtained a power conversion efficiency of 16.81% for a 0.096-cm2 PSC. We further demonstrated a monolithically integrated perovskite submodule based on the graded CsPbI3−xBrx by spray coating with an efficiency of 13.82% (112-cm2 aperture area) and ∼9% degradation over 1,000-h continuous 1-sun light soaking.

Cost-effective, high-throughput industrial applications of metal-halide perovskites require a highly tolerant method (i.e., wide process window) that produces high-quality materials with a short an...

Using time-resolved in situ X-ray photoelectron spectroscopy, we identify and suppress rapid degradation mechanisms for cesium-stabilized formamidinium lead iodide perovskite materials used in stat...

The constituent ions of halide perovskite materials are mobile in the solid state and known to participate in reduction/oxidation reactions. Yet few parameters related to electrochemical processes ...

Mixed tin–lead halide perovskite solar cells have promising power conversion efficiencies, but long-term stability is still a challenge. Herein we examine the stability of a 60:40 tin–lead perovski...

Summary Nickel oxide (NiOx) hole transport layers (HTLs) are desirable contacts for perovskite photovoltaics because they are low cost, stable, and readily scalable; however, they deliver lower open-circuit voltages (VOCs) compared to organic HTLs. Here, we characterize and mitigate electron transfer-proton transfer reactions between NiOx HTLs and perovskite precursors. Using XPS and UPS characterization, we identify that Ni≥3+ metal cation sites in NiOx thin films act both as Bronsted proton acceptors and Lewis electron acceptors, deprotonating cationic amines and oxidizing iodide species, forming PbI2−xBrx-rich hole extraction barriers at the perovskite-NiOx interface. Titrating reactive Ni≥3+ surface states with excess A-site cation salts during perovskite active layer deposition yielded an increase in VOC values to 1.15 V and power conversion efficiencies of ∼20%. This may be a general finding for metal oxide contacts that act as Bronsted and Lewis acid-base reactants toward perovskite precursors, an observation that has also been made recently for TiO2 and SnO2 contacts.

We report on the improved operational stability of unencapsulated perovskite solar cells (PSCs) aged in ambient atmosphere at elevated temperatures (70 C) for >1000 hours under constant illuminati...

Halide perovskites with bandgaps of 1.70–1.85 eV are of interest for multijunction photovoltaics. Mixing halides on the X site of the ABX3-structured perovskite system is a common way to reach thes...

Engineering perovskites with anions The bandgap of the perovskite top layer in tandem silicon solar cells must be tuned to ∼1.7 electron volts. Usually, the cation composition is varied because the bromine-rich anion compositions with wide bandgaps are structurally unstable. Kim et al. show that by using phenethylammonium as a two-dimensional additive, along with iodine and thiocyanate, bromine-rich perovskite films can be stabilized. A tandem silicon cell delivered >26% certified power conversion efficiency, and a perovskite device maintained 80% of its initial power conversion efficiency of >20% after 1000 hours under illumination. Science , this issue p. 155

Low-bandgap Sn/Pb ABX3 perovskites have reached photovoltaic power conversion efficiencies >20%, but they usually have poor stability due to the common use of acidic poly(3,4-ethylenedioxythiophene...

Tuning band gaps with three halides Tandem solar cells can boost solar cell efficiency by using two active layers to absorb the solar spectrum more completely, provided that the two cells are current-matched. Inorganic-organic perovskites tuned to the appropriate wide band gap (∼1.7 electron volts) as top cells that contained iodine and bromine or bromine and chlorine have short carrier diffusion lengths and undergo photo-induced phase segregation. Xu et al. now report a method for incorporating chloride that allows for fabrication of stable triple-halide perovskites with a band gap of 1.67 electron volts. Two-terminal tandem silicon solar cells made with this material had a power conversion efficiency of 27%. Science , this issue p. 1097

The optoelectronic properties of lead halide perovskite thin films can be tuned through compositional variations and strain, but the associated nanocrystalline structure makes it difficult to untangle the link between composition, processing conditions, and ultimately material properties and degradation. Here, we study the effect of processing conditions and degradation on the local photoconductivity dynamics in [(CsPbI

Herein, we subject formamidinium lead iodide films to oxygen-containing gases (flowing O

Narrow-bandgap (NBG) tin (Sn)-lead (Pb) perovskites generally have a high density of unintentional p-type self-doping, which reduces the charge-carrier lifetimes, diffusion lengths, and device efficiencies. Here, a p-n homojunction across the Sn-Pb perovskite is demonstrated, which results from a gradient doping by barium ions (Ba

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Directing efficient hole transport Surface defects in three-dimensional perovskites can decrease performance but can be healed with coatings based on two-dimensional (2D) perovskite such as Ruddlesden-Popper phases. However, the bulky organic groups of these 2D phases can lead to low and anisotropic charge transport. F. Zhang et al . show that a metastable polymorph of a Dion-Jacobson 2D structure based on asymmetric organic molecules reduced the energy barrier for hole transport and their transport through the layer. When used as a top layer for a triple-cation mixed-halide perovskite, a solar cell retained 90% of its initial power conversion efficiency of 24.7% after 1000 hours of operation at approximately 40°C in nitrogen. —PDS