Defect Tolerance Research Articles

Prediction of ternary alkaline-earth metal Sn(II) and Pb(II) chlorides with potential applications as p-type transparent conductors.

Non-metallic Sn(II) and Pb(II) compounds, particularly those with p-type properties, are essential functional materials due to their notable electronic arrangement and chemical characteristics. The presence of additional Sn(II) and Pb(II) chlorides is suggested by the existence of known Sn(II) and Pb(II) compounds. By utilizing first-principles calculations and swarm intelligence structure search techniques, we have predicted the existence of up to seven new ternary alkaline-earth metal chlorides: ABCl4 (where A = Sr and B = Sn or Pb) and AB2Cl6 (where A = Mg, Ca, or Ba and B = Sn, or A = Ca or Sr and B = Pb). These seven chlorides are in the divalent state. The interaction between Sn-5s (or Pb-6s) and Cl-3p in these compounds creates an anti-bonding effect in the upper valence bands, which enhances defect tolerance and promotes high p-type conductivity. These stable chlorides exhibit notable electronic properties, including wide band gaps ranging from 3.91 to 4.94 eV, broad hole effective masses ranging from 0.93 to 5.62 m0, and high valence band alignments ranging from 6.83 to 8.38 eV under vacuum. In particular, Ca/BaSn2Cl6 and CaPb2Cl6 have the potential to be used as p-type transparent conductors due to their favorable properties, including a lower hole effective mass (0.93 m0 for CaPb2Cl6) and higher ionization potentials (6.83/7.05 eV for Ba/CaSn2Cl6). Furthermore, the predicted CaPb2Cl6 crystal exhibits attenuated negative linear compressibility and negative zero-linear-compressibility along the c-axis in different pressure ranges due to its wine-rack structure. This report highlights potential applications for alkaline-earth metal Sn(II) and Pb(II) chlorides, including their use as transparent conductors, particularly p-type conductors.

High defect tolerance β-CsSnI3 perovskite light-emitting diodes.

All-inorganic lead-free CsSnI3 has shown promising potential in optoelectronic applications, particularly in near-infrared perovskite light-emitting diodes (Pero-LEDs). However, non-radiative recombination induced by defects hinders the optoelectronic properties of CsSnI3-based Pero-LEDs, limiting their potential applications. Here, we uncovered that β-CsSnI3 exhibits higher defect tolerance compared to orthorhombic γ-CsSnI3, offering a potential for enhancing the emission efficiency. We further reported on the deposition and stabilization of highly crystalline β-CsSnI3 films with the assistance of cesium formate to suppress electron-phonon scattering and reduce nonradiative recombination. This leads to an enhanced photoluminescence quantum yield up to ∼10%. As a result, near-infrared LEDs based on β-CsSnI3 emitters are achieved with a peak external quantum efficiency of 1.81% and excellent stability under a high current injection of 1.0 A cm-2.

Design for Increased Defect Tolerance in Metamorphic GaAsP-on-Si Top Cells

Design for Increased Defect Tolerance in Metamorphic GaAsP-on-Si Top Cells

Alleviating nanostructural phase impurities enhances the optoelectronic properties, device performance and stability of cesium-formamidinium metal-halide perovskites.

The technique of alloying FA+ with Cs+ is often used to promote structural stabilization of the desirable α-FAPbI3 phase in halide perovskite devices. However, the precise mechanisms by which these alloying approaches improve the optoelectronic quality and enhance the stability have remained elusive. In this study, we advance that understanding by investigating the effect of cationic alloying in CsxFA1-xPbI3 perovskite thin-films and solar-cell devices. Selected-area electron diffraction patterns combined with microwave conductivity measurements reveal that fine Cs+ tuning (Cs0.15FA0.85PbI3) leads to a minimization of stacking faults and an increase in the photoconductivity of the perovskite films. Ultra-sensitive external quantum efficiency, kelvin-probe force microscopy and photoluminescence quantum yield measurements demonstrate similar Urbach energy values, comparable surface potential fluctuations and marginal impact on radiative emission yields, respectively, irrespective of Cs content. Despite this, these nanoscopic defects appear to have a detrimental impact on inter-grains'/domains' carrier transport, as evidenced by conductive-atomic force microscopy and corroborated by drastically reduced solar cell performance. Importantly, encapsulated Cs0.15FA0.85PbI3 devices show robust operational stability retaining 85% of the initial steady-state power conversion efficiency for 1400 hours under continuous 1 sun illumination at 35 °C, in open-circuit conditions. Our findings provide nuance to the famous defect tolerance of halide perovskites while providing solid evidence about the detrimental impact of these subtle structural imperfections on the long-term operational stability.

Guidelines derived from biomineralized tissues for design and construction of high-performance biomimetic materials: from weak to strong.

Living organisms in nature have undergone continuous evolution over billions of years, resulting in the formation of high-performance fracture-resistant biomineralized tissues such as bones and teeth to fulfill mechanical and biological functions, despite the fact that most inorganic biominerals that constitute biomineralized tissues are weak and brittle. During the long-period evolution process, nature has evolved a number of highly effective and smart strategies to design chemical compositions and structures of biomineralized tissues to enable superior properties and to adapt to surrounding environments. Most biomineralized tissues have hierarchically ordered structures consisting of very small building blocks on the nanometer scale (nanoparticles, nanofibers or nanoflakes) to reduce the inherent weaknesses and brittleness of corresponding inorganic biominerals, to prevent crack initiation and propagation, and to allow high defect tolerance. The bioinspired principles derived from biomineralized tissues are indispensable for designing and constructing high-performance biomimetic materials. In recent years, a large number of high-performance biomimetic materials have been prepared based on these bioinspired principles with a large volume of literature covering this topic. Therefore, a timely and comprehensive review on this hot topic is highly important and contributes to the future development of this rapidly evolving research field. This review article aims to be comprehensive, authoritative, and critical with wide general interest to the science community, summarizing recent advances in revealing the formation processes, composition, and structures of biomineralized tissues, providing in-depth insights into guidelines derived from biomineralized tissues for the design and construction of high-performance biomimetic materials, and discussing recent progress, current research trends, key problems, future main research directions and challenges, and future perspectives in this exciting and rapidly evolving research field.

Templated Synthesis of CsPbBr3 Nanowire Arrays Toward Low Current Drift and Stable X-ray Detector

All-inorganic halide perovskite CsPbBr3 with superior environmental stability, remarkable radiation hardness and great defect tolerance has emerged as a competitive material in radiation detection. However, the operation stability of CsPbBr3...

Reducing Wall Shelf Product Defects Using the DMAIC Method in Furniture Industry Companies

The object of research is a place of business that produces household needs and wood-based industries. One of the products it produces is a minimalist wall shelf. In the period January –December 2021 minimalist wall shelf products are the products with the most defects. Manufacturing companies in this study have a product defect tolerance limit of 5% of the total production, but minimalist wall shelf products have a defect of 5.64%. This study aims to determine the types of defects that occur in wall shelf products, identify the causes of defects minimalist wall shelves and provide suggestions for improvements to reduce the number of future defects. In this research the method used is DMAIC. In the minimalist wall shelf production process, 4 types of defects were found. Based on the Pareto diagram, it was determined that the type of lacquer defect was not suitable to be the most dominant type of defect, namely 80.1%, it was also found that the DPMO value and sigma value on minimalist wall shelves were 14,100 and 3.69. Based on the analysis of the fishbone diagram method and Failure Mode and Effect Analysis (FMEA), it is known that the main root cause of product defects is a dirty, dusty and windy environment with an RPN (Risk Priority Number) value of 448. Analysis was carried out using the 5W + 1H approach to find improvements to overcome the problems that occur, obtained suggestions for improvements for the company, namely making work area picket schedules, making closed work areas, daily and monthly check sheetforms for maintenance of work tools, making varnish process work instructions, making training schedules for operators and submitting additional goods forms.

The luminescence modulation of rare earth-doped/containing lead-free double perovskites toward multifunctional applications: a review.

Lead-free double perovskites (DPs) with superior environmental stability and high defect tolerance have attracted considerable attention and exhibit great promise in photodetectors, solar cells, lighting devices, etc. However, achieving optical modulation and high photoluminescence quantum yield using this kind of material remains a challenge. Rare earth ions feature abundant energy levels and outstanding photophysical properties. Incorporating rare earth ions into lead-free DPs is an effective strategy to improve their optical performances, which have great effects on night-vision and light emitting diodes. Consequently, in this mini-review, we summarize the synthesis methods, optical properties, issues, and multifunctional applications of lead-free DPs described in recent years. The performances of DPs can be modulated via rare earth doping, which involves the extension of luminescence range, the improvement of PLQY, the realization of multi-mode excitation, and the regulation of luminescence color. We hope that this review will provide some insights into luminescence modulation and applications of lead-free DPs.

Exotic hexagonal NaCl atom-thin layer on methylammonium lead iodide perovskite: new hints for perovskite solar cells from first-principles calculations.

Alkali halides are simple inorganic compounds extensively used as surface modifiers in optoelectronic devices. In perovskite solar cells (PSCs), they act as interlayers between the light absorber material and the charge selective layers improving their contact quality. They introduce surface dipoles that enable the fine tuning of the relative band alignment and passivate surface defects, a well-known drawback of hybrid organic-inorganic perovskites, that is responsible for most of the issues hampering the long-term performances. Reducing the thickness of such salt-based insulating layer might be beneficial in terms of charge transfer between the perovskite and the electron/hole transport layers. In this context, here we apply density functional theory (DFT) to characterize the structure and the electronic features of atom-thin layers of NaCl adsorbed on the methylammonium lead iodide (MAPI) perovskite. We analyze two different models of MAPI surface terminations and find unexpected structural reconstructions arising at the interface. Unexpectedly, we find an exotic honeycomb-like structuring of the salt, also recently observed in experiments on a diamond substrate. We also investigate how the salt affects the perovskite electronic properties that are key to control the charge dynamics at the interface. Moreover, we also assess the salt ability to improve the defect tolerance of the perovskite surface. With these results, we derive new hints regarding the potential benefits of using an atom-thin layer of alkali halides in PSCs.

Photocatalysis Based on Metal Halide Perovskites for Organic Chemical Transformations.

Heterogeneous photocatalysts incorporating metal halide perovskites (MHPs) have garnered significant attention due to their remarkable attributes: strong visible-light absorption, tuneable band energy levels, rapid charge transfer, and defect tolerance. Additionally, the promising optical and electronic properties of MHP nanocrystals can be harnessed for photocatalytic applications through controlled crystal structure engineering, involving composition tuning via metal ion and halide ion variations, dimensional tuning, and surface chemistry modifications. Combination of perovskites with other materials can improve the photoinduced charge separation and charge transfer, building heterostructures with different band alignments, such as type-II, Z-scheme, and Schottky heterojunctions, which can fine-tune redox potentials of the perovskite for photocatalytic organic reactions. This review delves into the activation of organic molecules through charge and energy transfer mechanisms. The review further investigates the impact of crystal engineering on photocatalytic activity, spanning a diverse array of organic transformations, such as C-X bond formation (X = C, N, and O), [2 + 2] and [4 + 2] cycloadditions, substrate isomerization, and asymmetric catalysis. This study provides insights to propel the advancement of metal halide perovskite-based photocatalysts, thereby fostering innovation in organic chemical transformations.

Detrimental Effects of Metal Foil’s Surface Imperfections on Metal Plating/Stripping and Facile Solutions

Rechargeable metal batteries have attracted great interest and are considered one of the most promising high-energy density storage systems. These devices benefit from the large specific volumetric capacities and high specific gravimetric capacities of metal anodes. Foils or sheets are the most common form of anode for metal batteries since they are massively manufactured and readily accessible. But short circuits from dendrites grown on metal foil anodes can dramatically decrease the cycling stability and lead to premature failure of the batteries.Homogeneous metal plating/stripping is the key to avoiding dendrite formation. And the surface uniformity of metal electrodes is crucial for the initial nucleation and growth, which greatly affects the subsequent deposition. Here, we show that manufacturing-induced defects, including surface imperfections such as a roughened surface, orange peel features, microcracks, scratches, or fold lines, and unpolished edges from cutting can all promote local dendrite growth, leading to drastically decreased cycling stability of the demonstrated Zn metal batteries and K metal batteries. Polishing the metal electrodes on both sides and edges is shown to be effective to improve the electrochemical homogeneity of the metal anode and extend the cycling lifespan by over 700% in the demonstrated Zn metal cells. Finally, we demonstrate a simple and rapid surface passivation strategy that drastically increases the tolerance of such defects in Zn metal batteries. Also, we proposed a scalable, easily automated, and facile metallic K manufacturing with robust performance in K metal batteries.Since such imperfections are ubiquitous in commercially available metal foil products. Our results remind researchers about the significant detrimental effects of these very common defects introduced by metal manufacturing and processing, which should be taken into consideration evaluating metal battery performances. Furthermore, we call for research efforts to develop effective strategies that are scalable, easily automated, and cost-effective to increase the tolerance of batteries over such defects, which will be very important for large-scale, cost-effect energy storage hubs.References Pan He and Jiaxing Huang. "Detrimental effects of surface imperfections and unpolished edges on the cycling stability of a zinc foil anode." ACS Energy Letters, 2021,6,1990-1995.Pan He and Jiaxing Huang. "Chemical passivation stabilizes Zn anode." Advanced Materials, 2022, 34, 2109872.Pan He and Yang Xu. "Facile manufacturing potassium metal anode with robust performance". In preparation. Figure 1

A COMPASS histone H3K4 trimethyltransferase pentamer transactivates drought tolerance and growth/biomass production in Populus trichocarpa.

Histone H3 lysine-4 trimethylation (H3K4me3) activating drought-responsive genes in plants for drought adaptation has long been established, but the underlying regulatory mechanisms are unknown. Here, using yeast two-hybrid, bimolecular fluorescence complementation, biochemical analyses, transient and CRISPR-mediated transgenesis in Populus trichocarpa, we unveiled in this adaptation a regulatory interplay between chromatin regulation and gene transactivation mediated by an epigenetic determinant, a PtrSDG2-1-PtrCOMPASS (complex proteins associated with Set1)-like H3K4me3 complex, PtrSDG2-1-PtrWDR5a-1-PtrRbBP5-1-PtrAsh2-2 (PtrSWRA). Under drought conditions, a transcription factor PtrAREB1-2 interacts with PtrSWRA, forming a PtrSWRA-PtrAREB1-2 pentamer, to recruit PtrSWRA to specific promoter elements of drought-tolerant genes, such as PtrHox2, PtrHox46, and PtrHox52, for depositing H3K4me3 to promote and maintain activated state of such genes for tolerance. CRISPR-edited defects in the pentamer impaired drought tolerance and elevated expression of PtrHox2, PtrHox46, or PtrHox52 improved the tolerance as well as growth in P. trichocarpa. Our findings revealed the identity of the underlying H3K4 trimethyltransferase and its interactive arrangement with the COMPASS for catalysis specificity and efficiency. Furthermore, our study uncovered how the H3K4 trimethyltransferase-COMPASS complex is recruited to the effector genes for elevating H3K4me3 marks for improved drought tolerance and growth/biomass production in plants.

Enhancing Multiexcitonic Emission in Metal-Halide Perovskites by Quantum Confinement.

Semiconductor metal halide perovskite nanocrystals have been under intense investigation for their promise in a variety of optoelectronic applications, which arises from their remarkable properties of defect tolerance and efficient light emission. Recently, quantum dot versions of perovskite nanocrystals have been available, enabling investigation of how quantum size effects control optical function and performance in these quantum dots (QD), past their well-known covalent II-VI analogues. We perform time-resolved photoluminescence (t-PL) experiments on CsPbBr3 perovskite nanocrystals spanning in diameter from 5.8 nm strongly confined quantum dots to 18 nm weakly confined quantum dots. Experiments are performed with sufficient time resolution of 3 ps to observe the interaction energies and recombination kinetics from excitons to multiexcitons. Comparing the same sized QD reveals that perovskite QD have a larger radiative rate constant for emission from X than CdSe QD due to a larger oscillator strength. The multiexciton (MX) regime reveals that perovskite QD emit brightly and with more focused bandwidth than equivalent sized CdSe QD enabling more spectrally pure brightness. The MX kinetics reveals that the perovskite QD maintain efficient radiative decay, effectively competing with Auger recombination. These experiments reveal that the strongly confined QD of perovskites can be efficient multiexcitonic emitters, such as in high brightness light emitting diodes, especially in the blue.

Fatigue performance of laser powder bed fusion manufactured TiB2/AlSi10Mg composite: Experimental investigation and fracture mechanics-based life prediction model for defect tolerance analysis

The fatigue performance of AlSi10Mg composites decorated with nano-TiB2 particles fabricated through laser powder bed fusion (LPBF) was first experimentally investigated at room temperature and it exhibited superior fatigue resistance compared with other LPBF AlSi10Mg alloys and other reinforced AlSi10Mg composites. Then the fractography was examined and a fracture mechanics-based life prediction method was proposed to correlate the critical defect information (size and location) and fatigue life. To assess the crack growth driving force for critical defects, we employed Murakami's concept of the maximum stress intensity factor (SIF). The modification was made to include the effect of specimen cross-sectional geometry and initiation location since Murakami’s method would underestimate the maximum SIF in some cases. Meanwhile, the process of small crack propagation was also considered in modeling, and a unified model to describe crack arrest, small crack growth, and long crack growth was established. By inputting information about defect size and location and external loading conditions, the fatigue life could be evaluated and our results demonstrated good estimation within the [1/4,2] scatter band. Furthermore, an unbroken specimen subjected to the highest external loading was examined using X-ray computed tomography (CT) to characterize the defect population. By incorporating the CT statistical results into our life prediction model, outcomes such as non-propagating cracks or small crack growth without leading to ultimate failure could be obtained, which was consistent with CT findings. Concurrently, CT analysis revealed that the detrimental effect of large inner defects could be less significant than that of small surface defects. Therefore, we propose a novel strategy that combines defect size and location to enhance defect tolerance in additive manufacturing (AM) materials.

Three-dimensional perovskite-based photonic structures made by two-step crystallization

Three-dimensional (3D) photonic structure made of light-emitting materials is a prospective platform for designing lasers and 3D displays, where directivity and efficiency of the emission are highly demanded. While the fabrication of two-dimensional (2D) light-emitting photonic structures is a well-developed technology, the extension of dimensionality up to 3D requires complex and multistep approaches. In this regard, solution-processible halide perovskites are promising materials, which can be easily integrated with various scaffolds supporting optical modes. Here we demonstrate a novel simple two-step technique for fabrication of halide perovskite-based light-emitting 2D and 3D photonic structures based on femtosecond laser photopolymerization and further perovskite growth inside the structures. High defect tolerance of halide perovskites supports synthesis of high-quality material inside the photonic structures, which demonstrate amplified spontaneous emission and stable laser generation. Moreover, we show that the developed method is rather universal and allows for the successful fabrication of photonic structures filled by the various halide perovskites like all-inorganic, organic–inorganic, bromide, and chlorine ones.

Halide Perovskites and Their Derivatives for Efficient, High-Resolution Direct Radiation Detection: Design Strategies and Applications.

The past decade has witnessed a rapid rise in the performance of optoelectronic devices based on lead-halide perovskites (LHPs). The large mobility-lifetime products and defect tolerance of these materials, essential for optoelectronics, also make them well-suited for radiation detectors, especially given the heavy elements present, which is essential for strong X-ray and γ-ray attenuation. Over the past decade, LHP thick films, wafers, and single crystals have given rise to direct radiation detectors that have outperformed incumbent technologies in terms of sensitivity (reported values up to 3.5×106 µC Gyair -1 cm-2 ), limit of detection (directly measured values down to 1.5 nGyair s-1 ), along with competitive energy and imaging resolution at room temperature. At the same time, lead-free perovskite-inspired materials (e.g., methylammonium bismuth iodide), which have underperformed in solar cells, have recently matched and, in some areas (e.g., in polarization stability), surpassed the performance of LHP detectors. These advances open up opportunities to achieve devices for safer medical imaging, as well as more effective non-invasive analysis for security, nuclear safety, or product inspection applications. Herein, the principles behind the rapid rises in performance of LHP and perovskite-inspired material detectors, and how their properties and performance link with critical applications in non-invasive diagnostics are discussed. The key strategies to engineer the performance of these materials, and the important challenges to overcome to commercialize these new technologies are also discussed.

The Gβ-like protein Bcgbl1 regulates development and pathogenicity of the gray mold Botrytis cinerea via modulating two MAP kinase signaling pathways.

The fungal Gβ-like protein has been reported to be involved in a variety of biological processes, such as mycelial growth, differentiation, conidiation, stress responses and infection. However, molecular mechanisms of the Gβ-like protein in regulating fungal development and pathogenicity are largely unknown. Here, we show that the Gβ-like protein gene Bcgbl1 in the gray mold fungus Botrytis cinerea plays a pivotal role in development and pathogenicity by regulating the mitogen-activated protein (MAP) kinases signaling pathways. The Bcgbl1 deletion mutants were defective in mycelial growth, sclerotial formation, conidiation, macroconidial morphogenesis, plant adhesion, and formation of infection cushions and appressorium-like structures, resulting in a complete loss of pathogenicity. Bcgbl1 interacted with BcSte50, the adapter protein of the cascade of MAP kinase (MAPK). Bcgbl1 mutants had reduced phosphorylation levels of two MAPKs, namely Bmp1 and Bmp3, thereby reducing infection. However, deletion of Bcgbl1 did not affect the intracellular cAMP level, and exogenous cAMP could not restore the defects. Moreover, Bcgbl1 mutants exhibited defects in cell wall integrity and oxidative stress tolerance. Transcriptional profiling revealed that Bcgbl1 plays a global role in regulation of gene expression upon hydrophobic surface induction. We further uncovered that three target genes encoding the hydrophobic surface binding proteins (HsbAs) contributed to the adhesion and virulence of B. cinerea. Overall, these findings suggest that Bcgbl1 had multiple functions and provided new insights for deciphering the Bcgbl1-mediated network for regulating development and pathogenicity of B. cinerea.

Exploring the Potential of MXene Contacts on Wide‐Bandgap Dion–Jacobson Perovskite Solar Cell: A Numerical Study

The stability and performance challenges in conventional 3D perovskite solar cells (PSCs), attributed to perovskite structure and transport layers, prompt the exploration of 2D perovskites. However, the presence of transport layers and conventional contacts is still challenging as it creates interface defects and pinholes. In this study, a new transport‐layer‐free device structure, i.e., MXene–2D perovskites–MXene‐based metal–semiconductor–metal PSCs, is introduced to resolve the stability‐ and performance‐related issues. The proposed solar cell incorporates PeDAMAPb2I7 as the absorber layer and MXenes (Hf2NF2/Ta4C3F2) as electrodes. The Dion–Jacobson perovskites solar cell is also investigated for optimum thickness and defect tolerance level of PeDAMAPb2I7. In the results, it is indicated that the device delivered the maximum efficiency of 5.63% at a 500 nm thick absorber layer with a defect density of 1 × 1013 cm−3. Further, the quest to find suitable MXene contact for electron extraction is met by analyzing the proposed solar cell with nine different MXene layers (Hf2NF2, Hf2CF2, Zr2NF2, Ta2CF2, Ti4C3, Ti3C2, Zr2C, Sc2C, Ti2C). In the results, it is indicated that Hf2NF2 has a 3.2 eV work function, making it the optimal choice, achieving 5.63% efficiency.

Exciton-polaron interactions in metal halide perovskite nanocrystals revealed via two-dimensional electronic spectroscopy.

Metal halide perovskite nanocrystals have been under intense investigation for their promise in optoelectronic devices due to their remarkable physics, such as liquid/solid duality. This liquid/solid duality may give rise to their defect tolerance and other such useful properties. This duality means that the electronic states are fluctuating in time, on a distribution of timescales from femtoseconds to picoseconds. Hence, these lattice induced energy fluctuations that are connected to polaron formation are also connected to exciton formation and dynamics. We observe these correlations and dynamics in metal halide perovskite nanocrystals of CsPbI3 and CsPbBr3 using two-dimensional electronic (2DE) spectroscopy, with its unique ability to resolve dynamics in heterogeneously broadened systems. The 2DE spectra immediately reveal a previously unobserved excitonic splitting in these 15nm NCs that may have a coarse excitonic structure. 2D lineshape dynamics reveal a glassy response on the 300fs timescale due to polaron formation. The lighter Br system shows larger amplitude and faster timescale fluctuations that give rise to dynamic line broadening. The 2DE signals enable 1D transient absorption analysis of exciton cooling dynamics. Exciton cooling within this doublet is shown to take place on a slower timescale than within the excitonic continuum. The energy dissipation rates are the same for the I and Br systems for incoherent exciton cooling but are very different for the coherent dynamics that give rise to line broadening. Exciton cooling is shown to take place on the same timescale as polaron formation, revealing both as coupled many-body excitation.

Phase Transitions, Dielectric Response, and Nonlinear Optical Properties of Aziridinium Lead Halide Perovskites.

Hybrid organic-inorganic lead halide perovskites are promising candidates for next-generation solar cells, light-emitting diodes, photodetectors, and lasers. The structural, dynamic, and phase-transition properties play a key role in the performance of these materials. In this work, we use a multitechnique experimental (thermal, X-ray diffraction, Raman scattering, dielectric, nonlinear optical) and theoretical (machine-learning force field) approach to map the phase diagrams and obtain information on molecular dynamics and mechanism of the structural phase transitions in novel 3D AZRPbX3 perovskites (AZR = aziridinium; X = Cl, Br, I). Our work reveals that all perovskites undergo order-disorder phase transitions at low temperatures, which significantly affect the structural, dielectric, phonon, and nonlinear optical properties of these compounds. The desirable cubic phases of AZRPbX3 remain stable at lower temperatures (132, 145, and 162 K for I, Br, and Cl) compared to the methylammonium and formamidinium analogues. Similar to other 3D-connected hybrid perovskites, the dielectric response reveals a rather high dielectric permittivity, an important feature for defect tolerance. We further show that AZRPbBr3 and AZRPbI3 exhibit strong nonlinear optical absorption. The high two-photon brightness of AZRPbI3 emission stands out among lead perovskites emitting in the near-infrared region.