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At least 235 records · Page 13

Halide perovskites as disposable epitaxial templates for the phase-selective synthesis of lead sulfochloride nanocrystals

Colloidal chemistry grants access to a wealth of materials through simple and mild reactions. However, even few elements can combine in a variety of stoichiometries and structures, potentially resulting in impurities or even wrong products. Similar issues have been long addressed in organic chemistry by using reaction-directing groups, that are added to a substrate to promote a specific product and are later removed. Inspired by such approach, we demonstrate the use of CsPbCl 3 perovskite nanocrystals to drive the phase-selective synthesis of two yet unexplored lead sulfochlorides: Pb 3 S 2 Cl 2 and Pb 4 S 3 Cl 2 . When homogeneously nucleated in solution, lead sulfochlorides form Pb 3 S 2 Cl 2 nanocrystals. Conversely, the presence of CsPbCl 3 triggers the formation of Pb 4 S 3 Cl 2 /CsPbCl 3 epitaxial heterostructures. The phase selectivity is guaranteed by the continuity of the cationic subnetwork across the interface, a condition not met in a hypothetical Pb 3 S 2 Cl 2 /CsPbCl 3 heterostructure. The perovskite domain is then etched, delivering phase-pure Pb 4 S 3 Cl 2 nanocrystals that could not be synthesized directly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two-Factor Phase Separations in Mixed-Halide Quasi-2D Perovskite LEDs: Dimensionality and Halide Segregations

Quasi-2D halide perovskites have attracted much interest as a promising material for light-emitting diodes (LEDs) due to their tunability in quantum confinement and halide alloy formation to modulate the energy bandgap and emission color. However, two-factor phase separations with respect to heterogeneous quantum-well thicknesses and halide segregation are still crucial issues in quasi-2D perovskite LEDs, leading to low external quantum efficiencies (EQEs) and color shifts. In this work, we compare quasi-2D perovskite films using different cations to unveil the key contributions from the chemical design of organic cations. While mixing halide ions in conventional quasi-2D perovskite films induces micrometer-scale heterogeneity, new extended and twisted conjugated cations suppress the two-factor phase separations, leading to high EQEs of over 25% and controllable emission wavelengths across red and near-infrared regions. The fundamental insights in this work will provide guidance for advancing materials design and device performance in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On-demand formation of Lewis bases for efficient and stable perovskite solar cells

In the fabrication of FAPbI 3 -based perovskite solar cells, Lewis bases play a crucial role in facilitating the formation of the desired photovoltaic α-phase. However, an inherent contradiction exists in their role: they must strongly bind to stabilize the intermediate δ-phase, yet weakly bind for rapid removal to enable phase transition and grain growth. To resolve this conflict, we introduced an on-demand Lewis base molecule formation strategy. This approach utilized Lewis-acid-containing organic salts as synthesis additives, which deprotonated to generate Lewis bases precisely when needed and could be reprotonated back to salts for rapid removal once their role is fulfilled. This method promoted the optimal crystallization of α-phase FAPbI 3 perovskite films, ensuring the uniform vertical distribution of A-site cations, larger grain sizes and fewer voids at buried interfaces. Perovskite solar cells incorporating semicarbazide hydrochloride achieved an efficiency of 26.1%, with a National Renewable Energy Laboratory-certified quasi-steady-state efficiency of 25.33%. These cells retained 96% of their initial efficiency after 1,000 h of operation at 85 °C under maximum power point tracking. Additionally, mini-modules with an aperture area of 11.52 cm 2 reached an efficiency of 21.47%. This strategy is broadly applicable to all Lewis-acid-containing organic salts with low acid dissociation constants and offers a universal approach to enhance the performance of perovskite solar cells and modules.

14 SOLAR ENERGY↗

Thermal tolerance of perovskite quantum dots dependent on A-site cation and surface ligand

A detailed picture of temperature dependent behavior of Cs x FA 1-x PbI 3 perovskite quantum dots across the composition range is constructed by performing in situ optical spectroscopic and structural measurements, supported by theoretical calculations that focus on the relation between A-site chemical composition and surface ligand binding. The thermal degradation mechanism depends not only on the exact chemical composition, but also on the ligand binding energy. The thermal degradation of Cs-rich perovskite quantum dots is induced by a phase transition from black γ-phase to yellow δ-phase, while FA-rich perovskite quantum dots with higher ligand binding energy directly decompose into PbI 2 . Quantum dot growth to form large bulk size grain is observed for all Cs x FA 1-x PbI 3 perovskite quantum dots at elevated temperatures. In addition, FA-rich quantum dots possess stronger electron-longitudinal optical phonon coupling, suggesting that photogenerated excitons in FA-rich quantum dots have higher probability to be dissociated by phonon scattering compared to Cs-rich quantum dots.

14 SOLAR ENERGY↗

Combined Precursor Engineering and Grain Anchoring Leading to MA‐Free, Phase‐Pure, and Stable α‐Formamidinium Lead Iodide Perovskites for Efficient Solar Cells

Abstract α‐Formamidinium lead iodide (α‐FAPbI 3 ) is one of the most promising candidate materials for high‐efficiency and thermally stable perovskite solar cells (PSCs) owing to its outstanding optoelectrical properties and high thermal stability. However, achieving a stable form of α‐FAPbI 3 where both the composition and the phase are pure is very challenging. Herein, we report on a combined strategy of precursor engineering and grain anchoring to successfully prepare methylammonium (MA)‐free and phase‐pure stable α‐FAPbI 3 films. The incorporation of volatile FA‐based additives in the precursor solutions completely suppresses the formation of non‐perovskite δ‐FAPbI 3 during film crystallization. Grains of the desired α‐phase are anchored together and stabilized when 4‐ tert ‐butylbenzylammonium iodide is permeated into the α‐FAPbI 3 film interior via grain boundaries. This cooperative scheme leads to a significantly increased efficiency close to 21 % for FAPbI 3 perovskite solar cells. Moreover, the stabilized PSCs exhibit improved thermal stability and maintained ≈90 % of their initial efficiency after storage at 50 °C for over 1600 hours.

Ling, Xufeng↗

Metastable Phase Relations in the System Ca(sub O)-Al2(sub O)3-MgO-TiO(sub 2): Applications to Ca- And Al-Rich Inclusions

Introduction: High temperature phases such as corundum, hibonite, grossite, and perovskite are among the earliest phases that condensed in the early solar nebula. Recent work has shown that defect-structured phases occur in some ultrarefractory inclusions as metastable, possibly more kinetically-favored alternatives to the thermodynamically predicted stable phase assemblages [1-4]. For example, Han et al. have shown that non-stoichiometry in hibonite is accommodated by extra "spinel" blocks in the structure instead of the equilibrium assemblages hibonite+corundum or hibonite+spinel. To explore these relations, we have conducted a series of experiments in the system CaO-Al2O3- MgO-TiO2. Here we discuss the compositions and mineralogy of the experimental samples and how they relate to phases in refractory inclusions with a focus on perovskite and spinel. Methods: For the series of annealing studies, a CaO-Al2O3 eutectic melt is allowed to react with a pure alumina crucible at 1,530degC for either 4 hours or 5 days, followed by quenching in air. Later experiments were similar except that additions of 5 wt% MgO, and CaTiO(sub 3) were used to explore the effect of minor elements on the phase assemblages. The experimental conditions resulted in reaction zones approximately 100-300 m wide consisting of a hibonite layer immediately adjacent to the corundum, followed by a grossite layer, and finally krotite with residual quenched melt. For the experiments with Mg, spinel is distributed in all layers but is mainly concentrated in the krotite layer. In the Ti-bearing experiments, perovskite precipitated in association with the krotite and residual melt. In addition to the experiments, we also analyzed perovskite grains in the FUN inclusion SHAL [5] and a large compact type A CAI from Allende. The experiments and refractory inclusions were analyzed using a JEOL 7600F SEM and quantitative analyses were obtained using the JEOL 8530F field-emission electron microprobe.

Keller, L. P.↗

Origins of the Pressure-Induced Phase Transition and Metallization in the Halide Perovskite (CH 3 NH 3 )PbI 3

Hybrid halide perovskites are promising for applications because of their favorable optoelectronic properties and low cost. Here we investigate the effects of hydrostatic pressure on the structural and electronic properties of (MA)PbI 3 (MA = CH 3 NH 3 + ) using first-principles density functional theory calculations. Our calculations predict that at a pressure of 0.23 GPa, the orthorhombic Fmmm phase becomes unstable with respect to a cubic Im$\bar{3}$ phase, in good agreement with room-temperature experiments (~0.3 GPa). At higher pressures, about 6 GPa, we predict the onset of pronounced intra- and interoctahedral distortions. This symmetry lowering leads to the introduction of I 5p–I 5p* antibonding and Pb 6p–Pb 6p bonding character into the valence band maximum (VBM) and the conduction band minimum (CBM) states, respectively. We find this change in bond character explains the evolution of the VBM and CBM states under compression, trends that ultimately lead to metallization at significantly higher pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Synthesis of Single-Layer Quasi-Ruddlesden–Popper Phase Bismuth-Based Two-Dimensional Perovskite Nanosheets with Controllable Optoelectronic Properties

Single- and few-layered two-dimensional (2D) nanomaterials have attracted intense research interest in the last two decades due to their unique electronic and optoelectronic properties leading to various potential applications. Herein, we report the colloidal synthesis of Bi-based 2D perovskite nanosheets (PEG6-NH 3 +) n Cs 3-n Bi 2 X 9 , where X = CI, Br, and I, through careful design of reaction conditions and selection of poly(ethylene glycol) (PEG6) surface passivating ligands. The 2D nanosheets are similar to 5 nm in thickness with micron-sized lateral dimensions and display composition-dependent band gap and work function modulation. Furthermore, small-angle X-ray scattering analysis substantiates that the individual inorganic crystal layer, Cs 3-n Bi 2 X 9 , is separated by the spacer, PEG6 ligand. Additionally, we determined that PEG6-NH 2 is an essential passivating ligand and spacer for the formation of Bi-based 2D nanosheets. Most importantly, controlled crystallization of the colloidal dispersion of nanosheets results in the formation of superlattice microstructures of the quasi-Ruddlesden-Popper phase. These microstructures can be exfoliated to ultrathin nanosheets by overcoming the van der Waals interaction between the organic passivating layers. The controlled synthesis of lead-free 2D perovskite nanosheets presented here can expand their utility to photocatalytic and optoelectronic applications with reduced toxicity.

36 MATERIALS SCIENCE↗

Subduction and volatile recycling in Earth's mantle

The subduction of water and other volatiles into the mantle from oceanic sediments and altered oceanic crust is the major source of volatile recycling in the mantle. Until now, the geotherms that have been used to estimate the amount of volatiles that are recycled at subduction zones have been produced using the hypothesis that the slab is rigid and undergoes no internal deformation. On the other hand, most fluid dynamical mantle flow calculations assume that the slab has no greater strength than the surrounding mantle. Both of these views are inconsistent with laboratory work on the deformation of mantle minerals at high pressures. We consider the effects of the strength of the slab using two-dimensional calculations of a slab-like thermal downwelling with an endothermic phase change. Because the rheology and composition of subducting slabs are uncertain, we consider a range of Clapeyron slopes which bound current laboratory estimates of the spinel to perovskite plus magnesiowustite phase transition and simple temperature-dependent rheologies based on an Arrhenius law diffusion mechanism. In uniform viscosity convection models, subducted material piles up above the phase change until the pile becomes gravitationally unstable and sinks into the lower mantle (the avalanche). Strong slabs moderate the 'catastrophic' effects of the instabilities seen in many constant-viscosity convection calculations; however, even in the strongest slabs we consider, there is some retardation of the slab descent due to the presence of the phase change.

King, S. D.↗

Energy-harvesting chromogenic devices

The present disclosure relates to devices that include a perovskite, where, when a first condition is met, at least a portion of the perovskite is in a first phase that substantially transmits light, when a second condition is met, at least a portion of the perovskite is in a second phase that substantially absorbs light, and the perovskite is reversibly switchable between the first phase and the second phase by reversibly switching between the first condition and the second condition.

Wheeler, Lance Michael↗

Energy-harvesting chromogenic devices

The present disclosure relates to devices that include a perovskite, where, when a first condition is met, at least a portion of the perovskite is in a first phase that substantially transmits light, when a second condition is met, at least a portion of the perovskite is in a second phase that substantially absorbs light, and the perovskite is reversibly switchable between the first phase and the second phase by reversibly switching between the first condition and the second condition.

Wheeler, Lance Michael↗

La 0.6 Sr 0.4 CoO 3−δ Films Under Deoxygenation: Magnetic And Electronic Transitions Are Apart from The Structural Phase Transition

Abstract Topotactic phase transitions induced by changes in the oxygen vacancy concentration can largely alter the physical properties of complex oxides, including electronic and magnetic phases, while maintaining the structural integrity of the crystal lattice. An oxygen‐vacancy‐induced topotactic phase transition from perovskite (PV) to brownmillerite (BM) is achieved in epitaxial La 0.6 Sr 0.4 CoO 3−δ (LSCO) thin films. Two novel intermediate states with different oxygen content are identified by X‐ray diffraction, which involves a single‐phase reduced PV state and a mixed state of co‐existing PV and BM. The combination of depth‐sensitive polarized neutron reflectometry (PNR) and Rutherford backscattering (RBS) allows a quantitative determination of magnetization and the mean oxygen content in all states, revealing a continuous transition from La 0.6 Sr 0.4 CoO 2.97 to La 0.6 Sr 0.4 CoO 2.5 . BM formation is observed for an LSCO layer with an oxygen content of 2.67, while the magnetic and electronic transition already occurs for a layer with a higher oxygen content of 2.77 (and above) and in the absence of a BM signature. These results demonstrate that the physics of electronic metal‐to‐insulator transition (MIT), magnetic ferromagnet‐to‐non‐ferromagnet transition (FM‐to‐non‐FM), and structural PV‐to‐BM phase transition should be considered within the framework of separate but interrelated processes.

36 MATERIALS SCIENCE↗

Tunable ferroelectricity in oxygen-deficient perovskites with Grenier structure

Using first-principles calculations, we predict that tunable ferroelectricity can be realized in oxide perovskites with the Grenier structure and ordered oxygen vacancies. Specifically, we show that R 1/3 A 2/3 FeO 2.67 solids (where R is a rare-earth ion and A an alkaline-earth cation) exhibit polar phases, with a spontaneous polarization tunable by an appropriate choice of R and A. We find that larger cations combined with small R elements lead to a maximum in the polarization and to a minimum in the energy barriers required to switch the sign of the polarization. Ferroelectricity arises from cooperative distortions of octahedral and tetrahedral units, where a combination of rotational and sliding modes controls the emergence of polarization within three-dimensional connected layers. Our results indicate that polar Grenier phases of oxide perovskites are promising materials for microelectronic applications and, in general, for the study of phenomena emerging from breaking inversion symmetry in solids.

Electronic devices↗

Cold air quench control of local crystallization environment in fully air-processed carbon-based perovskite solar cells

Carbon-based perovskite solar cells (C-PSCs) present a low-cost route to efficient photovoltaic technology. Gas quenching is an essential process commonly used for solvent extraction in scalable module fabrication using solution processes, but film quality remains highly sensitive to the localized environmental processing temperature, especially during intermediate phase transitions before perovskite film high temperature annealing. In this study, we introduce a cold air quench strategy to precisely control the local crystallization temperature that simultaneously promotes uniform crystallization and facilitates strain relaxation in fully air-processed C-PSCs. It is found that implementing dry air at 10 °C as the quenching gas yields a champion power conversion efficiency (PCE) of 20.52 %, with preferential (110) orientation and reduced, homogenized in-plane strain. This newly developed technique of a cost-effective low temperature air quenching process also enhances carrier lifetime, reduces interface recombination, and improves charge extraction. Furthermore, this work presents cold air quenching as a scalable, economic method to control perovskite crystallization and strain in C-PSC fabrication, advancing the industrial viability of high-performance perovskite modules.

14 SOLAR ENERGY↗