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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Layered and Low-Dimensional Lead, Silver, and Bismuth Halide Perovskites Directed by Halogen-Substituted Spacer Cations

Hybrid organic–inorganic metal halides provide a diverse parameter space in which the optoelectronic properties can be tuned through the composition. The compositional tunability extends to the metal site, which can be expanded from single valent metals (e.g., Pb 2+ ) to multivalent metals (e.g., Ag + and Bi 3+ ), and the dimension (2D, 1D, or 0D). However, a deeper understanding of how the organic cations template these metal halide structures is needed. Here, we synthesize and study the structures of a series of new layered and low-dimensional metal (Pb, Ag, and Bi) halides templated by the halogenated aryl spacer cations 2-chlorobenzylammonium (2ClBZ) and 3-chloro-2-fluorobenzylammonium (3Cl2FBZ). We report new lead perovskites, (3Cl2FBZ) 2 PbBr 4 , (2ClBZ) 3 PbI 5 , and (3Cl2FBZ) 2 PbI 4 , and compare them to their silver and/or bismuth analogs (2ClBZ) 4 AgBiBr 8 , (3Cl2FBZ) 4 AgBiBr 8 , (2ClBZ) 3 Bi 2 I 9 , and (3Cl2FBZ) 4 Bi 2 I 10 . In all structures, the halogen-substituted cations result in 2D or “pseudo-2D” layering, but the different halogen substituents introduce different distortions (tilting, octahedral distortion) and dimensional reduction to 1D or 0D depending on the metal and halide compositions. Optical absorption measurements reveal the bandgaps are tunable through metal sites, dimension, and cations to different extents. Furthermore, the 1D (3Cl2FBZ) 4 Bi 2 I 10 crystallizes in the noncentrosymmetric space group Cmc2 1 and exhibits second-harmonic generation (SHG). Furthermore, the organic–inorganic interactions and resultant structural distortions examined here provide insights toward the engineering of noncentrosymmetry and dimensional control in hybrid metal halide perovskites.

Cations↗
DOE OSTI2022

Turn-on Circularly Polarized Luminescence in Chiral Indium Chlorides by 5s 2 Metal Centers

Introducing chirality into the metal-halide hybrids has enabled many emerging properties including chiroptical activity, spin-dependent transport, and ferroelectricity. However, most of the chiral metal-halide hybrids to date are non-emissive, and the underlying mechanism remains elusive. Here, in this study, we show a new strategy to turn on the circularly polarized luminescence (CPL) in chiral metal-halide hybrids. We demonstrate that alloying Sb 3+ into chiral indium-chloride hybrids dramatically increases the photoluminescence quantum yield in two new series of chiral indium-antimony chlorides. These materials exhibit strong CPL signals with tunable energy and a high dissymmetry factor up to 1.5×10 -2 . Mechanistic studies reveal that the emission originates from the self-trapped excitons centered in 5s 2 Sb 3+ . Moreover, near-ultraviolet pumped white light is demonstrated with a polarization up to 6.0 %. Our work demonstrates new strategies towards highly luminescent chiral metal-halide hybrids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

In situ formation of pseudohalide anions induced by humid air and light passivates formamidinium‐based halide perovskites

Abstract Metal halide perovskites based on formamidinium (FA), or FA‐rich compositions have shown great promise for high‐performance photovoltaics. A deeper understanding of the impact of ambient conditions (e.g., moisture, oxygen, and illumination) on the possible reactions of FA‐based perovskite films and their processing sensitivities has become critical for further advances toward commercialization. Herein, we investigate reactions that take place on the surface of the FA 0.7 Cs 0.3 , mixed Br/I wide bandgap perovskite thin films in the presence of humid air and ambient illumination. The treatment forms a surface layer containing O, OH, and N‐based anions. We propose the latter originates from formamidine trapped at the perovskite/oxide interface reacting further to cyanide and/or formamidinate—an understudied class of pseudohalides that bind to Pb. Optimized treatment conditions improve photoluminescence quantum yield owing to both reduced surface recombination velocity and increased bulk carrier lifetime. The corresponding perovskite solar cells also exhibit improved performance. Identifying these reactions opens possibilities for better utilizing cyanide and amidinate ligands, species that may be expected during vapor processing of FA‐based perovskites. Our work also provides new insights into the self‐healing or self‐passivating of MA‐free perovskite compositions where FA and iodide damage could be partially offset by advantageous reaction byproducts. image

14 SOLAR ENERGY↗
DOE OSTI2025

Exploring the Structural Origins of Optically Efficient One-Dimensional Lead Halide Perovskite Nanostructures

Metal halide perovskites have excellent optoelectronic properties. This study aims to determine how the optoelectronic properties of a model perovskite, cesium lead bromide (CsPbBr3), change with length and thickness in one dimension (1D). By examining the photophysics of CsPbBr3 quantum dots (QDs), nanowires (NWs), and nanorods (NRs), we observe the influence of confinement, exciton diffusion, and trapping on their optical properties. Our findings reveal that exciton diffusion to trap states limits the photoluminescence quantum yield (PLQY) of 1D CsPbBr3 in the weakly confined regime (8-14 nm) and explains their long-lived exciton dynamics, while enhanced radiative rates contribute to achieving near-unity PLQY in the strongly confined regime (<7 nm). Consequently, blue-emitting, 2.4 nm-thick CsPbBr3 NRs were 3.6X more emissive than the conventional CsPbBr3 QDs. This study underscores how structural optimization can improve the optoelectronic performance of CsPbBr3 and provides insight into the complex interplay of radiative and nonradiative processes in 1D ionic semiconductors.

Oddo, Alexander M↗
DOE OSTI2025

Layer Number Dependence of Chirality and Spin Polarized Lifetime in Chiral 2D Halide Perovskites

Chiral metal halide perovskite semiconductors (CMHS) are fascinating semiconductors with unique chiroptical properties and spin-polarized charge transport. Achieving long spin lifetimes and high carrier mobility concurrently is essential to realize the true potential of CMHS in manipulating charge, spin, and light. While conventional monolayer n = 1 CMHS possess appreciable anisotropy factors of circular dichroism (g CD ) and photoluminescence (g lum ), imparting chirality to quasi-2D CMHS (n > 1) with enhanced carrier mobilities is underexplored. Herein, we systematically investigate the layer number (n-value) dependence and emergent trade-offs in chiroptical properties, spin-relaxation times, and carrier mobilities in chiral quasi-2D (R/S-MPEA) 2 MA n-1 Pb n I 3n+1 single crystals and thin films (R/S-MPEA: R/S-β-methylphenylethylammonium; MA: methylammonium; n = 1–3). Films with n = 2 exhibited the highest g CD of 8 × 10 –3 , an order of magnitude larger than their n = 1 and n = 3 counterparts. On the other hand, n = 3 films demonstrated enhanced spin lifetimes up to 15 ps along with increased carrier mobility up to 11.6 cm 2 V –1 s –1 . As a result, photodiode-type photodetectors based on n = 3 CMHS reveal high specific detectivity and superior discrimination of circularly polarized light, outperforming n = 1 and 2. These findings highlight the potential of quasi-2D CMHS as tunable, high-performance platforms with longer spin lifetime and diffusion length, enabling new functionalities.

14 SOLAR ENERGY↗
DOE OSTI2023

Octahedral Distortion and Excitonic Behavior of Cs 3 Bi 2 Br 9 Halide Perovskite at Low Temperature

The metal halide ionic octahedron, represented as [MX 6 ] $n$- (M = metal cation, X = halide anion), serves as the basic structural unit in halide perovskites and plays a crucial role in determining their optoelectronic and chemical properties. Thus, it is possible to correlate the responses of metal halide perovskites to various environmental stimuli with the dynamic behaviors of the [MX 6 ] $n$- octahedra. In this study, with the temperature-dependent single-crystal X ray diffraction (SCXRD) measurements on Cs 3 Bi 2 Br 9 2D halide perovskites, we can identify two classes of distortions through the lowering of temperature: intraoctahedral distortion, which is the off-centering of Bi 3+ cation within a [BiBr 6 ] 3– octahedron due to the Bi 3+ 6s 2 lone pair electrons, and interoctahedral distortion, which is the collective misalignments among the [BiBr 6 ] 3– building blocks. Free exciton (FE) and self-trapped exciton (STE) models are used to study the relationship between the distortion of octahedra in Cs 3 Bi 2 Br 9 and the corresponding changes in its optoelectronic properties, which transform from dominating blue emission above 100 K to red emission at 4 K. In conclusion, this work provides new insights into the excitonic behaviors of perovskites and suggests a possibility that we can design and rationalize the optical properties of halide perovskites by regulating the environmental stimuli based on the knowledge of behaviors of the individual [MX 6 ] $n$- building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Investigation of chemical vapor deposition of garnet films for bubble domain memories

The important process parameters and control required to grow reproducible device quality ferrimagnetic films by chemical vapor deposition (CVD) were studied. The investigation of the critical parameters in the CVD growth process led to the conclusion that the required reproducibility of film properties cannot be achieved with individually controlled separate metal halide sources. Therefore, the CVD growth effort was directed toward replacement of the halide sources with metallic sources with the ultimate goal being the reproducible growth of complex garnet compositions utilizing a single metal alloy source. The characterization of the YGdGaIG films showed that certain characteristics of this material, primarily the low domain wall energy and the large temperature sensitivity, severely limited its potential as a useful material for bubble domain devices. Consequently, at the time of the change from halide to metallic sources, the target film compositions were shifted to more useful materials such as YGdTmGaIG, YEuGaIG and YSmGaIG.

Besser, P. J.↗
DOE OSTI2024

Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite

Abstract In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.

25 ENERGY STORAGE↗
DOE OSTI2026

Optimized Photoemission from Organic Molecules in 2D Layered Halide Perovskites

In recent years, hybrid organic−inorganic metal halides have been at the forefront of materials research. Typically, the functional (e.g., optoelectronic) properties of hybrid halides are derived from the inorganic structural part, whereas the organic structural units can add extra advantages in terms of stability, rigidity, and processability. Here, we report the design, synthesis, and characterization of two new hybrid materials in which the outstanding photophysical properties originate from the organic structural part. The new compounds, (C 15 H 16 N) 2 CdCl 4 and ((Br)C 15 H 15 N) 2 CdCl 4 , have 2D layered Ruddlesden−Poppertype perovskite structures. These hybrids are blue-white light emitters just like their corresponding pure organic salts, but with much improved emission efficiencies. Optical spectroscopy and density functional theory (DFT) studies confirm that photoemission comes from the trans-stilbene organic cations. The photoluminescence quantum yield (PLQY) values of these new materials are among the highest known, 50.83% and 26.60% for (C 15 H 16 N) 2 CdCl 4 and ((Br)C 15 H 15 N) 2 CdCl 4 , respectively. This is up to a 5-fold increase as compared to the light emission efficiency of the precursor salt C 15 H 16 NCl (PLQY of 10.33%). Alongside their outstanding optical properties, their environmental and thermal stability allow their consideration for potential practical applications such as radiation detection. This work shows that hybrid metal halides can be compositionally and structurally engineered to have highly efficient photoemission originating from the organic components for fast scintillation applications.

Halogens↗
DOE OSTI2021

Perovskite-Derived Cs 2 SnCl 6 –Silica Composites as Advanced Waste Forms for Chloride Salt Wastes

Advanced materials and processes are required to separate halides and fission products from complex salt waste streams associated with the chemical reprocessing of used nuclear fuels and molten salt reactor technologies for immobilization into chemically durable waste forms. Here, in this work, we explore an innovative concept using metal-halide perovskites as advanced host phases to incorporate Cs and Cl with very high waste loadings. Wet chemistry-synthesized Cs 2 SnCl 6 powders from CsCl salt solutions are successfully encapsulated into a silica matrix to form a composite using low-temperature spark plasma sintering with tunable Cs and Cl loadings up to 31 wt.% and 26 wt.%, respectively. Chemical durability testing of the composite waste forms by semi-dynamic leaching experiments demonstrates that incongruent leaching mechanism dominated. The metal-halide perovskite-silica composite waste forms display exceptional chemical durability with the long-term release rates of Cs and Cl comparable to or outperforming the state-of-the-art waste form materials but with significantly higher waste loadings. The scalable synthesis of the metal-halide perovskite from wet-chemistry processes opens up new opportunities in designing perovskite-glass composite waste forms for salt wastes with very high waste loadings and exceptional chemical durability for the sustainable development of advanced fuel cycles and next-generation reactor technologies.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Method to produce salts containing actinide halides

A method of producing uranium halides is disclosed in which chlorine gas is introduced into a liquid uranium-nickel alloy. NaCl salt is surrounding the crucible containing the liquid uranium-nickel alloy, producing a eutectic mixture of NaCl—UCl3. Upon chlorination, the metal halide dissolves in the matrix salt forming a solution. Adding the reactant metal, uranium to the nickel, the alloy is able to remain molten throughout processing. The liquid metal alloy may be removed from the salt bath, while the halogen gas continues to enter the system through the sparge until the desired composition of NaCl—UCl3—UCl4 is achieved. The method and system can be used to produce other metal halide salts such as actinide, lanthanide or transition metal halides contained in a matrix salt consisting of alkali and/or alkaline earth halides.

Williamson, Mark A.↗
DOE OSTI2020

Method and system for preparing polycrystalline group III metal nitride

A process of preparing polycrystalline group III nitride chunks comprising the steps of (a) placing a group III metal inside a source chamber; (b) flowing a halogen-containing gas over the group III metal to form a group III metal halide; (c) contacting the group III metal halide with a nitrogen-containing gas in a deposition chamber containing a foil, the foil comprising at least one of Mo, W, Ta, Pd, Pt, Ir, or Re; (d) forming a polycrystalline group III nitride layer on the foil within the deposition chamber; (e) removing the polycrystalline group III nitride layer from the foil; and (f) comminuting the polycrystalline group III nitride layer to form the polycrystalline group III nitride chunks, wherein the removing and the comminuting are performed in any order or simultaneously.

36 MATERIALS SCIENCE↗
DOE OSTI2020

From Defects to Degradation: A Mechanistic Understanding of Degradation in Perovskite Solar Cell Devices and Modules

Metal halide perovskite solar cells (PSCs) have risen in efficiency from just 3.81% in 2009 to over 25.2% today. While metal halide perovskites have excelled in efficiency, advances in stability are significantly more complex and have progressed more slowly. The advance of efficiency, which is readily measured, over stability, which can require literally thousands of hours to demonstrate, is to be expected given the rapid rate of innovation in the field. In the face of changing absorber composition, synthetic approaches, and device stack components it is necessary to understand basic material properties to rationalize how to enable stability in devices. In this article the aim is to present an in-depth review of the current understanding of metal halide perovskite devices and module stability by focusing on what is known retarding intrinsic and extrinsic degradation mechanisms at the material, device, and module level. Once these considerations are presented the discussion then moves to connecting different degradation mechanisms to stresses anticipated in operation and how they can impact efficiency of cells and ultimately modules over time.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Efficient and stable perovskite solar cells based on blade-coated CH 3 NH 3 PbI 3 thin films fabricated using “green” solvents under ambient conditions

Metal halide perovskites are considered the most promising candidates for solar cells of the decade due to their exceptional optical and electronic properties. The power conversion efficiency of metal halide perovskites, when incorporated as the active layer of solar cells, has become comparable to that observed for conventional silicon solar cells. However, the stability, scaleup, green solvent usage, and fabrication in ambient conditions of metal halide perovskites need to be solved for commercial applications. Here, in this work, we report the fabrication of blade-coated methylammonium lead iodide (MAPbI 3 ) perovskite thin films using methylamine and acetonitrile as “green” solvents under ambient conditions. Our perovskite films are initially prepared from low purity PbI2 (99%) and are blade-coated in dry air at relative humidity (RH) levels above 30%. A significant advantage of fabricating our perovskite thin films via blade-coating protocols is that there is a minimal amount of precursors (5 μL) used compared to spin-coating methods (50μL–60μL) for a 4 cm 2 substrate. With the addition of a small amount of an organic halide salt, namely, phenethylammonium chloride, the film crystallinity is improved and non-radiative recombination is suppressed, resulting in power conversion efficiencies over 20%. In addition, the device maintains more than 95% of its initial efficiency after 500 h under continuous light illumination of 1-sun at open circuit conditions, 50 °C and 60% RH. The above method leads a path towards the commercial fabrication of perovskite solar cells.

14 SOLAR ENERGY↗
DOE OSTI2023

Thermochromic Halide Perovskite Windows with Ideal Transition Temperatures

Abstract Urban centers across the globe are responsible for a significant fraction of energy consumption and CO 2 emission. As urban centers continue to grow, the popularity of glass as cladding material in urban buildings is an alarming trend. Dynamic windows reduce heating and cooling loads in buildings by passive heating in cold seasons and mitigating solar heat gain in hot seasons. Here, reduced energy consumption in highly glazed buildings in a mesoscopic building energy model is demonstrated when thermochromic windows are employed. Savings are realized across eight disparate climate zones of the United States. The model is used to determine ideal critical transition temperatures of 20–27.5 °C for thermochromic windows based on metal halide perovskite materials. Ideal transition temperatures are realized experimentally in composite metal halide perovskite films composed of perovskite crystals and an adjacent reservoir phase. The transition temperature is controlled by cointercalating methanol, instead of water, with methylammonium iodide and tailoring the hydrogen‐bonding chemistry of the reservoir phase. Thermochromic windows based on metal halide perovskites represent a clear opportunity to mitigate the effects of energy‐hungry buildings.

14 SOLAR ENERGY↗
DOE OSTI2024

Multifunctional Nanofiber Reinforcement for Improved Thermomechanical and Chemical Stability of Perovskite Solar Cells

This project focused on the development of metal halide perovskite-polymeric nanofiber nanocomposites for robust and efficient solar cells. Metal halide perovskite solar cells are a potentially disruptive technology with high efficiencies and low-cost solution processability amenable with roll-to-roll fabrication of flexible devices. However, perovskites exhibit extreme brittleness, high internal film stresses, and chemical instabilities that significantly limit service lifetimes under normal operating conditions. To date, most work addressing these shortcomings has been focused on encapsulating devices between thick layers of rigid materials such as glass, which increases the total weight and cost of devices. Furthermore, these rigid and heavy encapsulants do not translate well to emerging solar markets vital for national security, including integrated mobile power, emergency deployments for disaster relief and military engagement, and lightweight power for space. It is therefore critical to improve the thermomechanical and chemical stability of perovskite devices in a way that is compatible with flexible and lightweight substrates. In this project, we integrated nylon-6,6 nanofibers into MAPbI3 to mechanically reinforce the perovskite, demonstrating films that exhibited fracture energies 5-fold greater than pristine MAPbI3 while also maintaining similar power conversion efficiencies due to beneficial light scattering effects from the polymeric nanofibers. These results required successful development of approaches to control the deposition thickness of nanofiber mats down to 100s of nanometers, and to ensure the polymer nanofibers did not inhibit charge transport to the at the perovskite-transport layer interface.

14 SOLAR ENERGY↗
DOE OSTI2024

Synthetic Control of Water-Stable Hybrid Perovskitoid Semiconductors

Hybrid metal-halide perovskites and their derived materials have emerged as the next-generation semiconductors with a wide range of applications, including photovoltaics, light-emitting devices, and other optoelectronics. Over the past decade, numerous single-crystalline perovskite derivatives have been synthesized and developed. However, the synthetic methods for these derivatives mainly rely on acidic crystallization conditions. This approach leads to crystals comprising metal halide building blocks, which show problematic stability when directly exposed to water. In this study, a methodology is developed for synthesizing hybrid metal-halide compounds using lead iodide and the zwitterionic bifunctional molecule cysteamine (CYS), to form various perovskitoid structures under a broad pH range. Interestingly, the different pH conditions alter the coordination environment of lead halides, leading to lead-sulfide and lead-nitride covalent bond formation. This modification significantly enhances their stability when in direct contact with water, lasting for months. Photoluminescence measurements and first principal density functional theory (DFT) calculations reveal that the perovskitoids synthesized under basic and acidic pH conditions exhibit a direct bandgap nature, while those synthesized under neutral conditions display an indirect bandgap. This approach opens new avenues for manipulating synthetic methods to develop water-stable hybrid semiconductors suitable for a wide range of applications, such as solid-state light emitters.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The Role of SnO2 Processing on Ionic Distribution in Double-Cation-Double Halide Perovskites

Moving toward a future of efficient, accessible, and less carbon-reliant energy devices has been at the forefront of energy research innovations for the past 30 years. Metal-halide perovskite (MHP) thin films have gained significant attention due to their flexibility of device applications and tunable capabilities for improving power conversion efficiency. Serving as a gateway to optimize device performance, consideration must be given to chemical synthesis processing techniques. Therefore, how does common substrate processing techniques influence the behavior of MHP phenomena such as ion migration and strain? Here, we demonstrate how a hybrid approach of chemical bath deposition (CBD) and nanoparticle SnO2 substrate processing significantly improves the performance of (FAPbI3)0.97(MAPbBr3)0.03 by reducing micro-strain in the SnO2 lattice, allowing distribution of K+ from K-Cl treatment of substrates to passivate defects formed at the interface and produce higher current in light and dark environments. X-ray diffraction reveals differences in lattice strain behavior with respect to SnO2 substrate processing methods. Through use of conductive atomic force microscopy (c-AFM), conductivity is measured spatially with MHP morphology, showing higher generation of current in both light and dark conditions for films with hybrid processing. Additionally, time-of-flight secondary ionization mass spectrometry (ToF-SIMS) observed the distribution of K+ at the perovskite/SnO2 interface, indicating K+ passivation of defects to improve the power conversion efficiency (PCE) and device stability. We show how understanding the role of ion distribution at the SnO2 and perovskite interface can help reduce the creating of defects and promote a more efficient MHP device.

conductive atomic force microscopy↗