This review provides an update on the progress in understanding formation and degradation mechanisms in halide perovskites for photovoltaic applications, as supported by in situ and operando X‐ray ...scattering techniques. The value of these real‐time analyses is particularly high for gaining insights into the structural evolution during crystal formation and decomposition upon exposure to external stress factors. This type of analysis reveals the pathways between starting and end points of a process rather than being limited to comparing states before and after the process. Special attention is put on the successful efforts toward upscaling including deposition techniques that are compatible to roll‐to‐roll processing. These processes are realized using fast annealing procedures. The development of these processes strongly benefited from in situ studies exploring the direct transition from precursor to perovskite without going through observable crystalline intermediate phases. A particular focus of this review is the benefit of using in situ and operando X‐ray scattering techniques to better understand and ultimately improve device stability. The difference between structural stability of thin films and structural stability under device operation is highlighted, convincingly demonstrating the indispensability of operando studies.
In this review, the recent developments in understanding the structural evolution of halide perovskites during both formation and degradation using in situ and operando X‐ray scattering techniques are discussed. The benefit of this experimental approach in contrast to ex situ characterization is highlighted and emphasis is laid on the encouraging progress made in terms of upscaling and stability.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The performance of three-dimensional (3D) organic-inorganic halide perovskite solar cells (PSCs) can be enhanced through surface treatment with 2D layered perovskites that have efficient charge ...transport. We maximized hole transport across the layers of a metastable Dion-Jacobson (DJ) 2D perovskite that tuned the orientational arrangements of asymmetric bulky organic molecules. The reduced energy barrier for hole transport increased out-of-plane transport rates by a factor of 4 to 5, and the power conversion efficiency (PCE) for the 2D PSC was 4.9%. With the metastable DJ 2D surface layer, the PCE of three common 3D PSCs was enhanced by approximately 12 to 16% and could reach approximately 24.7%. For a triple-cation–mixed-halide PSC, 90% of the initial PCE was retained after 1000 hours of 1-sun operation at ~40°C in nitrogen.
Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is ...challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation-from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
CsPbI3 nanocrystals with narrow size distributions were prepared to study the size-dependent properties. The nanocrystals adopt the perovskite (over the nonperovskite orthorhombic) structure with ...improved stability over thin-film materials. Among the perovskite phases (cubic α, tetragonal β, and orthorhombic γ), the samples are characterized by the γ phase, rather than α, but may have a size-dependent average tilting between adjacent octahedra. Size-dependent lattice constants systematically vary 3% across the size range, with unit cell volume increasing linearly with the inverse of size to 2.1% for the smallest size. We estimate the surface energy to be from −3.0 to −5.1 eV nm–2 for ligated CsPbI3 nanocrystals. Moreover, the size-dependent bandgap is best described using a nonparabolic intermediate confinement model. We experimentally determine the bulk bandgap, effective mass, and exciton binding energy, concluding with variations from the bulk α-phase values. This provides a robust route to understanding γ-phase properties of CsPbI3.
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IJS, KILJ, NUK, PNG, UL, UM
Abstract
Metal halide perovskites feature crystalline-like electronic band structures and liquid-like physical properties. The crystal–liquid duality enables optoelectronic devices with unprecedented ...performance and a unique opportunity to chemically manipulate the structure with low energy input. In this work, we leverage the low formation energy of metal halide perovskites to demonstrate multicolor reversible chromism. We synthesized layered Ruddlesden-Popper FA
n+1
Pb
n
X
3n+1
(FA = formamidinium, X = I, Br;
n
= number of layers = 1, 2, 3 … ∞) and reversibly tune the dimensionality (
n
) by modulating the strength and number of H-bonds in the system. H-bonding was controlled by exposure to solvent vapor (solvatochromism) or temperature change (thermochromism), which shuttles FAX salt pairs between the FA
n+1
Pb
n
X
3n+1
domains and adjacent FAX “reservoir” domains. Unlike traditional chromic materials that only offer a single-color transition, FA
n+1
Pb
n
X
3n+1
films reversibly switch between multiple colors including yellow, orange, red, brown, and white/colorless. Each colored phase exhibits distinct optoelectronic properties characteristic of 2D superlattice materials with tunable quantum well thickness.
Hydrothermal synthesis is challenging in metal oxide systems with diverse polymorphism, as reaction products are often sensitive to subtle variations in synthesis parameters. This sensitivity is ...rooted in the non-equilibrium nature of low-temperature crystallization, where competition between different metastable phases can lead to complex multistage crystallization pathways. Here, we propose an ab initio framework to predict how particle size and solution composition influence polymorph stability during nucleation and growth. We validate this framework using in situ X-ray scattering, by monitoring how the hydrothermal synthesis of MnO
proceeds through different crystallization pathways under varying solution potassium ion concentrations (K
= 0, 0.2, and 0.33 M). We find that our computed size-dependent phase diagrams qualitatively capture which metastable polymorphs appear, the order of their appearance, and their relative lifetimes. Our combined computational and experimental approach offers a rational and systematic paradigm for the aqueous synthesis of target metal oxides.
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)
Cs
Pb(I
Br
)
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.
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GEOZS, IJS, IMTLJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK, ZAGLJ
The low formation energies inherent in metal halide perovskites enable the structure to be easily broken and remade with little energy input. In this work, we leverage low formation energy to ...demonstrate 0D/3D structural transformations induced by reversible intercalation of methanol to yield dramatic control of visible light absorption. We identify a methanolated structure that features sheets of 0D isolated PbI64– octahedra separated by MAI and methanol. Methanol and water reversibly displace each other in the 0D complex by controlling the chemical potential of the system via Le Chatelier’s principle. The weaker H-bonding of methanol compared to water effectively reduces the complex dissociation temperature from 70 to 50 °C, rendering the methanol complex more desirable for an array of next-generation applications spanning low-power-consumption memory to switchable photovoltaics.
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IJS, KILJ, NUK, PNG, UL, UM
Adhesion measurements and chemical characterization of the encapsulant/silver metallization interface of a photovoltaic (PV) module through temperature, humidity, and voltage bias exposures were ...conducted. Results demonstrate two independent degradation mechanisms: (a) with voltage bias, the ionic conduction of Na+ ions through the encapsulant results in the formation of sodium silicate at the silver metallization surface, thereby weakening that interface and (b) with moisture ingress, dissociation of the silane bonding to silver in the silver oxide similarly weakens this interface resulting in significantly lower debond energies.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
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 (
), 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
of 2.2 volts.
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