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At least 73 records · Page 4

Design principles of spacer cations for suppressing phase segregation in 2D halide perovskites

Suppression of photoinduced halide segregation in mixed halide perovskites remains a significant challenge for their application as wide bandgap semiconductors in solar cells. In addition to stability issues, halide segregation leads to a loss in power conversion efficiency in solar cells and a shift in emission wavelength in light-emitting devices. However, employing low-dimensional halide perovskites, such as two-dimensional (2D) or quasi-2D structures, offers a strategy to mitigate this segregation. Here, we have systematically studied how the molecular structure and binding configuration of spacer cations, ranging from linear alkyl chains to aromatic structures, affect photoinduced halide segregation across both Ruddlesden–Popper (RP) and Dion–Jacobson (DJ) frameworks in 2D mixed halide perovskites (Br : I = 50 : 50). Aromatic spacer cations within the DJ perovskite configuration were found to suppress segregation most effectively. For example, the halide segregation rate in a 2D mixed halide perovskite film with the DJ phase using the aromatic spacer cation 1,4-phenylenedimethanammonium (PDMA) was 9.3 × 10 −4 s −1 —an order of magnitude lower than that observed with linear 2D RP perovskites employing butylammonium (BA) as the spacer cation (6.1 × 10 −3 s −1 ). Spectroscopic studies detailing the influence of spacer cation selection in mixed halide perovskites for suppressing phase segregation are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organo-metal halide perovskites films and methods of making the same

An aspect of the present disclosure is a method that includes applying a solution that includes a first solvent, a halogen-containing precursor, and a metal halide to a substrate to form a coating of the solution on the substrate, contacting the coating with a second solvent to form a first plurality of organo-metal halide perovskite crystals on the substrate, and thermally treating the first plurality of organo-metal halide perovskite crystals, such that at least a portion of the first plurality of organo-metal halide perovskite crystals is converted to a second plurality of organo-metal halide perovskite crystals on the substrate. The halogen-containing precursor and the metal halide are present in the solution at a molar ratio of the halogen-containing precursor to the metal halide between about 1.01:1.0 and about 2.0:1.0, and a property of the second plurality of organo-metal halide perovskite crystals is improved relative to a property of the first plurality of organo-metal halide perovskite crystals.

Zhu, Kai↗

Dehalogenation reactions between halide salts and phosphate compounds

Reactions between phosphoric acid [H 3 PO 4 ] or ammonium hydrogen phosphates [i.e., NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 ] and halide salts can be used to dehalogenate (remove halides from) salt-based waste streams, where the process of removing halides yields products that have more efficient disposal pathways for repository storage. In this context, the term efficiency is defined as higher waste loadings and simplified immobilization processes with potential for recycle of certain salt components (e.g., 37 Cl as H 37 Cl or NH 4 37 Cl). The main streams identified for these processes are nuclear wastes generated during electrochemical reprocessing of used nuclear fuel as well as used halide salts from molten salt reactor operation. The potential byproducts of these reactions are fairly consistent across the range of halide species (i.e., F, Cl, Br, I) where the most common are hydrogen halides [e.g., HCl (g) ] or ammonium halides (e.g., NH 4 Cl). However, trihalide compounds (e.g., NCl 3 ), nitrogen triiodide ammine adducts [NI 3 ·(NH 3 ) x ], and ammonium triiodide (NH 4 I 3 ) are also possible. Several of these byproducts (i.e., NCl 3 , NBr 3 , NI 3 , and NH 4 I 3 ) are shock-sensitive contact explosives so their production in these processes must be tracked and carefully controlled, which includes methods of immediate neutralization upon production such as direct transport to a caustic scrubber for dissolution. Several benefits arise from utilizing H 3 PO 4 as the phosphate additive during dehalogenation reactions for making iron phosphate waste forms including more oxidized iron (higher Fe 3+ :Fe 2+ ratios), higher chemical durabilities, and the avoidance of trihalides, but the byproducts are hydrogen halides, which are corrosive and require special handling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Annealing and Composition on the Crystal Structure of Mixed-Halide, Ruddlesden–Popper Perovskites

Mixed-halide two-dimensional (2D) hybrid organic–inorganic perovskites offer an important opportunity to control the band gap for applications in optoelectronic devices. In this study, we focus on phenethylammonium lead halide [(PEA) 2 Pb(I 1– x Br x ) 4 ] films, the pure iodide form of which is one of the most widely studied optically active 2D perovskite systems. Resonant infrared, matrix-assisted pulsed laser evaporation is used to grow films to explore the effects of post-growth annealing and mixed-halide composition. The composition, crystal structure, and optical properties are studied for as-grown and annealed films of (PEA) 2 Pb(I 1– x Br x ) 4 for x = 0, 0.25, 0.5, 0.75, and 1. First-principles calculations are used in conjunction with the experimental data to explain the mixed-halide behavior that does not trend monotonically with the bromide content. Important results of this work are as follows: (i) X-ray diffraction reveals evidence for halide phase separation around x = 0.25, consistent with first-principles calculations, whereas no phase separation is observed for x = 0.5 and above and (ii) a unique photoluminescence (PL) peak splitting is observed for x = 0.75, a composition for which no compositional phase separation is observed. The PL splitting is tentatively explained by the coexistence of two distinct types of halide short-range ordering at x = 0.75. Overall, this study demonstrates that mixed-halide n = 1 Ruddlesden–Popper perovskites are not simple random alloys but that instead, they display distinct sites and ordering preferences of the different halide anions. These preferences are critical to understand and rationally tune the properties of the materials.

36 MATERIALS SCIENCE↗

A-Site Cation Chemistry in Halide Perovskites

Metal halide perovskites are an important class of semiconductors now being implemented as photovoltaic absorbers and explored for light emission, among other device applications. The semiconducting properties of halide perovskites are deeply intertwined with their composition and structure. Specifically the symmetry, tilting, and distortions of the metal halide octahedra impact the band structure and other optoelectronic properties. In this review, we examine the various compositions of monovalent A-site cations in threedimensional (3D) halide perovskites AMX 3 (M = divalent metal; X = halide). We focus on how the A-site cation templates the inorganic metal-halide perovskite framework, resulting in changes in the crystal structure symmetry, as well as M–X bonding parameters, summarized in a comprehensive table of AMX 3 structures. The A-site cation motion, effects of alloying, and 2D Ruddlesden–Popper perovskite structures with unique A-site cations are further overviewed. Correlations are shown between these A-site cation dominated structural parameters and the resulting optoelectronic properties such as band gap. This review should serve as a reference for the A-site cation structural chemistry of metal halide perovskites and inspire continued research into less explored metal halide perovskite compositions and structures.

14 SOLAR ENERGY↗

Ramifications of Ion Migration in 2D Lead Halide Perovskites

Lower dimensional or 2D halide perovskites with their versatile structural and functional properties, are known to improve the performance and room temperature stability of perovskite solar cells. One would expect 2D perovskites to be more resistant to ion migration compared to their 3D counterparts because of the presence of bulky organic cations. However, recent findings show ion migration indeed is prevalent in 2D halide perovskites similar to 3D perovskites. Halide ion migration in 2D perovskites manifests itself as halide ion segregation under photoirradiation as well as in halide exchange between physically paired films of 2D perovskites with different halide ions. Besides halide ion migration, cation migration of spacer cations and A-site cation is also seen when 2D/3D perovskite films are subjected to light and thermal stress. It is important to recognize the importance of ion migration while incorporating 2D perovskites in solar cells and other optoelectronic devices as it can be detrimental for achieving streamlined performance and long-term stability Furthermore, this perspective discusses recent reports on ion migration in 2D and in 2D/3D halide perovskite films under the operational conditions (at elevated temperature and given in-built bias) and presents a few mitigating strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Halide sublattice dynamics drive Li-ion transport in antiperovskites

Here, in this work, we resolve how proton dynamics and halide mixing enhance or impede ionic conduction in protonated lithium antiperovskites (pLiAP) at compositions near the eutectic points of the halide salts. As a material class, pLiAPs of the form Li 3-x OH x X, (X = Cl, Br) show vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. Proton incorporation and halide mixing stabilize the perovskite cubic phase at low temperatures (<50 °C) and using halide mixtures near the eutectic points (~250 to 300 °C) offer possibilities of lower temperature and faster synthesis and processing conditions (<1 h). Mixed-halide compositions such as Li 2 OHCl 0.37 Br 0.63 lead to a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 × 10 -6 vs. 4.9 × 10 -8 S cm -1 (Li 2 OHCl). We combine infrared spectroscopy and nuclear magnetic resonance with first-principles density functional theory calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. In contrast to what has been supposed, our findings suggest that the halide sublattice dynamics, besides the OH rotation, correlate strongly with the fast-ion conduction at high temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilizing Iodine in 2D Mixed Halide Perovskites: Dion–Jacobson Versus Ruddlesden–Popper Phases

Iodine electrochemistry plays an important role in driving iodide‐oxidation induced halide migration in 3D halide perovskites. When subjected to light illumination or electrochemical bias, mixed halide perovskites undergo halide segregation followed by iodine expulsion from the crystal lattices. To mitigate such intrinsic halide ion mobility in 3D perovskites, lower‐dimensional (2D) perovskites are employed as barriers to stabilize the perovskite layers. Interestingly, 2D halide perovskites also exhibit halide ion mobility that is dependent on the binding configuration, viz., Ruddlesden–Popper (RP) and Dion–Jacobson (DJ) phases. Hybrid RP‐DJ perovskites with a mixed Br:I ratio of 50:50 show increased stability following continuous photoirradiation. Spectroscopic studies that probe iodine migration and expulsion in photoirradiated 2D films of different configurations are presented here. The effective strategy of blending two different 2D phases (RP‐DJ) offers new opportunities to develop stable 2D/3D perovskite interfaces in solar cells.

2D halide perovskites↗

Effect of static local distortions vs. dynamic motions on the stability and band gaps of cubic oxide and halide perovskites

Ternary ABX 3 perovskites made of corner-sharing BX 6 octahedra have long featured prominently in solid-state chemistry and condensed matter physics. Still, the joint understanding of their two main subgroups—halides and oxides—has not been fully developed. Indeed, unlike the case in simpler compounds having a single, robust repeated motif (“monomorphous”), certain cubic perovskites can manifest a non-thermal (= intrinsic) distribution of local motifs (“polymorphous networks”). Such static deformations can include positional degrees of freedom (e.g., atomic displacements and octahedral tilting) or magnetic moment degrees of freedom in paramagnets. Unlike thermal motion, such static distortions do not time-average to zero, being an expression of the intrinsic symmetry breaking preference of the chemical bonding. Here, the present study compares electronic structure features of oxide and halide perovskites starting from the static polymorphous distribution of motifs described by Density Functional Theory (DFT) minimization of the internal energy, continuing to finite temperature thermal disorder modeled via finite temperature DFT molecular dynamics. We find that (i) different oxide vs. halide ABX 3 compounds adopt different energy-lowering symmetry-breaking modes. The calculated pair distribution function (PDF) of SrTiO 3 from the first-principles agrees with recently measured PDF. (ii) In both oxides and halides, such static distortions lead to band gap blueshifts with respect to undistorted cubic Pm-3m structure. (iii) For oxide perovskites, high-temperature molecular dynamics simulations initiated from the statically distorted polymorphous structures reveal that the thermally-induced distortions can lead to a band gap redshift. (iv) In contrast, for cubic halide perovskite CsPbI 3 , both the intrinsic distortions and the thermal distortions contribute in tandem to band gap blueshift, the former, intrinsic effect being dominant. (v) In the oxide SrTiO 3 and CaTiO 3 (but not in halide) perovskites, octahedral tilting leads to the emergence of a distinct Γ–Γ direct band gap component as a secondary valley minimum to the well-known indirect R–Γ gap. Understanding such intrinsic vs. thermal effects on oxide vs. halide perovskites holds the potential for designing target electronic properties.

36 MATERIALS SCIENCE↗

Flash Formation of I-Rich Clusters during Multistage Halide Segregation Studied in MAPbI 1.5 Br 1.5

Wide band gap mixed halide perovskites such as MAPb(I 1–x Br x ) 3 sparked great research interest because of their outstanding optoelectronic properties, ease of fabrication, and band gap tunability. Their application thus far is however limited by light-induced halide segregation in which microscopic clusters with a high iodide content are formed and act as recombination centers. The key mechanism(s) underlying this halide segregation process are still debated. Here, we present a study on the photoluminescence evolution in MAPb(I 1.5 Br 1.5 ) perovskites with varying microstructures under constant illumination at room temperature and at elevated temperature. Our findings reveal a more complicated picture of the segregation mechanism occurring in three stages instead of two as commonly reported. The process starts with a flash formation of I-rich domains. Following is a rapid blue shift before the gradual and typically observed red shift occurs. The evolution of the three stages is fully reversible in the dark and is also present at elevated temperatures (50 °C). We explain the existence of multiple stages during light-induced halide segregation by natural compositional fluctuations of the halides and the formation of halide clusters with a dynamically changing distribution in I–Br content. The variation in the I–Br ratio depends on the grain size and film heterogeneity. Overall, these findings add further details in the quest of unraveling the underlying segregation mechanism(s), which need to be identified to stabilize halides in wide band gap perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Phase Transformation of Colloidal 2D Lead Halide Perovskite Platelets under Photoirradiation

The photostability of lead halide perovskites is an important criterion for their utilization in light harvesting applications. Colloidal two-dimensional mixed halide perovskites offer a convenient approach to probe photoinduced transformations using spectroscopy tools. We employed suspensions of colloidal 2D methylammonium lead halide perovskite platelets with butylammonium and octylammonium as organic spacer cations. Upon irradiation of the mixed halide perovskite (BAOAMAPb 2 (Br 3.5 I 3.5 )) colloidal platelet suspension, we observe a phase transformation, as seen from the formation of bromide rich domains (BAOAMAPb 2 Br 7 ) and an iodide complex (PbI 3 – ). Unlike in the case of 3D mixed halide films, we did not observe the formation of iodide rich domains as part of the photoinduced phase segregation process. Instead, we observed the dissociation of the BAOAMAPb 2 I 7 to form an iodide complex, PbI 3 – . Interestingly, this photoinduced phase transformation was reversible, as the products which were confined in the colloidal core restored the original mixed halide phase upon storage in dark. The spectroscopic measurements that characterize excited states of different colloidal methylammonium lead halide perovskites and kinetics of photoinduced transformation and their dark recovery are presented. Furthermore, these new phototransformations of colloidal perovskite platelets provide new insights into the processes that dictate their overall photostability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A universal wet-chemistry synthesis of solid-state halide electrolytes for all-solid-state lithium-metal batteries

Solid-state halide electrolytes have gained revived research interests owing to their high ionic conductivity and high-voltage stability. However, synthesizing halide electrolytes from a liquid phase is extremely challenging because of the vulnerability of metal halides to hydrolysis. In this work, ammonium-assisted wet chemistry is reported to synthesize various solid-state halide electrolytes with an exceptional ionic conductivity (>1 microsiemens per centimeter). Microstrain-induced localized microstructure change is found to be beneficial to lithium ion transport in halide electrolytes. Furthermore, the interfacial incompatibility between halide electrolytes and lithium metal is alleviated by transforming the mixed electronic/ionic conductive interface into a lithium ion–conductive interface. Such all-solid-state lithium-metal batteries (ASSLMBs) demonstrate a high initial coulombic efficiency of 98.1% based on lithium cobalt oxide and a high discharge capacity of 166.9 microampere hours per gram based on single-crystal LiNi 0.6 Mn 0.2 Co 0.2 O 2 . This work provides universal approaches in both material synthesis and interface design for developing halide-based ASSLMBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroelectrochemical insights into the intrinsic nature of lead halide perovskites

Abstract Lead halide perovskites have emerged as a new class of semiconductor materials with exceptional optoelectronic properties, sparking significant research interest in photovoltaics and light-emitting diodes. However, achieving long-term operational stability remains a critical hurdle. The soft, ionic nature of the halide perovskite lattice renders them vulnerable to various instabilities. These instabilities can be triggered by factors such as photoexcitation, electrical bias, and the surrounding electrolyte/solvent or atmosphere under operating conditions. Spectroelectrochemistry offers a powerful approach to bridge the gap between electrochemistry and photochemistry (or spectroscopy), by providing a comprehensive understanding of the band structure and excited-state dynamics of halide perovskites. This review summarizes recent advances that highlight the fundamental principles, the electronic band structure of halide perovskite materials, and the photoelectrochemical phenomena observed upon photo- and electro-chemical charge injections. Further, we discuss halide instability, encompassing halide oxidation, vacancy formation, ion migration, degradation, and sequential expulsion under electrical bias. Spectroelectrochemical studies that provide a deeper understanding of interfacial processes and halide mobility can pave the way for the design of more robust perovskites, accelerating future research and development efforts. Graphical Abstract

Min, Seonhong↗

A Review and Perspective on Cathodoluminescence Analysis of Halide Perovskites

Halide perovskite solar cells have achieved a certified efficiency of 25.2%, surpassing CdTe and CuInGaSe 2 , which have long been regarded as the most-efficient thin-film photovoltaic materials. As this exciting class of materials continues to mature, researchers will require characterization techniques capable of exposing the interplay among structure, chemistry, and optoelectronic properties to inform processing strategies and increase both device efficiencies and long-term stability. Cathodoluminescence microscopy is an ideal technique to provide such information due to the high spatial resolution and robust optical information acquired. Here, the current body of work related to cathodoluminescence analysis of halide perovskite materials for optoelectronic applications is surveyed. This review demonstrates how cathodoluminescence can monitor degradation due to environmental stressors, phase segregation resulting from material processing, and other halide perovskite-centric material issues. A persistent concern associated with e-beam-based analysis of halide perovskites is what effect the electron beam has on the material properties being probed. Addressing this, a detailed discussion is provided on the origin of the cathodoluminescence signal and a review of studies focused on revealing changes in the properties of halide perovskites resulting from e-beam excitation. Finally, a perspective on future opportunities to expand the role of cathodoluminescence analysis for halide perovskites is provided.

14 SOLAR ENERGY↗

Identifying impacts of process, precursors, and defects in metal halide perovskite solar cells

With efficiencies of halide perovskite solar cells stagnating over the last few years at values above 25% and approaching thermodynamic limits, focus must shift to ensuring stability of these devices over the long term. The overarching goal of this project was to understand the root causes of instability in halide perovskite solar cells. Our approach was rooted in fundamental scientific pursuits, determining at the molecular level those processes responsible for degradation of the metal halide perovskite system, either in the precursor ink, or in the solid state. We then used this understanding to show that degradation leads to midgap states in halide perovskite semiconductors, explaining loss in performance; also, this in-depth understanding allowed us to develop specifically targeted solutions to prevent these degradation mechanisms. These include guidance about amines in perovskite inks, solvents to use (and not to use), and impacts of Cs incorporation to perovskite inks and solids. Finally, we achieved our end-of-project goal and demonstrated an effective lifetime of a halide perovskite solar cell of 5000 h, including measurement of devices over 3000 h, amongst the longest in the field. Overall, this project has considerably pushed forward the science of perovskite degradation and sets examples and groundwork for future studies to enable halide perovskite solar cells to be a successful solar energy conversion technology.

14 SOLAR ENERGY↗

Tuning Solvation Dynamics of Electrolytes at Their Eutectic Point Through Halide Identity

Deep eutectic solvents (DESs) are regarded as highly promising solvent systems for redox flow batteries. DESs, composed of choline halides (ChX, X = F − , Cl − , Br − , I − ) and ethylene glycol (EG), exhibit distinct physicochemical properties at their eutectic points, including halide-dependent phase behavior, viscosity, polarity, conductivity, and solvation dynamics. In this study, we investigate the effects of the halide identity on the solvation properties of ChX:EG mixtures at varying mol % of ChX salt content. The solvatochromic polarity based on ET(30) measurements indicates higher polarity for larger halides (I − > Br − ) than for smaller halides (Cl − > F − ), which exhibit larger compensating solvation shells. The ionic conductivity follows the trend of the solvent fluidity (the inverse of the viscosity), namely ChCl > ChBr > ChI > ChF, influenced by the ion mobility and solvodynamic radii. Measurements of the liquidus temperatures (T L ) reveal that the system with ChCl exhibits the deepest eutectic point (at ~20 mol % ChCl), while ChBr and ChI have shallower minima at ~10 mol % ChBr and ~3 mol % ChI, respectively. ChF does not display a eutectic transition but instead appears to readily supercool at salt concentrations above 30 mol % ChF. Consistent with the phase transition measurements, femtosecond transient absorption spectroscopy shows that in the ChCl system, the solvation dynamics become faster with an increasing salt concentration up to ~16.67 mol %, after which the dynamics slow down with further increases in the salt content. The ChF-based system exhibits similar behavior, though with slower dynamics. In contrast, the solvation dynamics of the systems containing ChBr and ChI monotonously slow down with an increasing salt concentration, in agreement with the phase transition measurements, which show that the eutectic points occur at low salt concentrations. These measurements suggest that the solvent composition and, in particular, the identity of the halide anion play a significant role in the solvation behavior of these ethylene-glycol-based DESs, offering a foundation for tuning the DES properties for specific applications.

Biochemistry & Molecular Biology↗

A thermodynamic evaluation of metal halides for the recrystallization of Cu(In,Ga)Se 2

CdTe films are deposited at low temperatures and recrystallized to photovoltaic device quality using CdCl 2 treatments, leading to competitive manufacturing costs. Cu(In,Ga)Se 2 (CIGS) typically requires high-temperature, low-rate depositions to produce high-efficiency devices, resulting in higher costs. A similar metal halide treatment of CIGS has been demonstrated by us previously for some metal halide sources. To understand and optimize the process, a thermodynamic evaluation of candidate metal halides for such treatments is presented as a guide for their selection. By comparing bond dissociation energies, mono- and di-halide compounds are proposed to be ideal compounds to act as transport agents. Known recrystallization and temperature reduction benefits by Ag alloying suggests that Ag-halides should be used to aid transport of all species. The high vapor pressure and mobility of Ga compounds still poses a problem for metal halide treatment resulting in Ga etching and removal of intentional Ga gradients. Less severe but similar issues with In compounds may occur. As a result, Cu compounds have low vapor pressures which may limit transport, however, Cu is highly mobile in CIGS and recrystallization still occurs.

14 SOLAR ENERGY↗

Halide perovskite-polymer composite film for bright and stable light-emitting devices

Stability is the primary hindrance for the application of halide perovskite material in light-emitting devices, solar cells, and other devices. In this work, halide perovskite and polymer composite film have been prepared for stable and bright light-emitting devices. Pure-phase Cs4PbBr6 crystals have been synthesized, and their photoluminescence (PL) properties and fluorescence lifetimes have been investigated. The Cs 4 PbBr 6 crystals exhibited high uniformity but underwent rapid photodegradation under light irradiation. To address this issue, we prepared bright light-emitting devices using composite of Cs 4 PbBr 6 crystals and polyethylene oxide (PEO) as the emission layer. The aim was to improve the optical and physical properties of halide perovskites, such as photodegradation and stability. PEO, with its excellent film-forming ability, created a uniform and dense film on the halide perovskite surface, filling microscopic defects and providing a protective barrier. FTIR, morphology, and PL analyses confirmed the protective role of the halide perovskite and polymer composite film. The composite film light-emitting devices demonstrated improved stability and higher PL brightness, with a peak brightness approaching 3 × 10 8 cd/m 2 , which was approximately 75% higher than the pure halide perovskite devices.

Composite film↗