Activation Energy For Migration Research Articles

Bromine‐Substituted Cation Anchoring to Suppress Ion Migration in Alternating Cations Intercalation‐Type Perovskite for Stable X‐Ray Detection

Metal halide perovskites have emerged as excellent direct X‐ray detection materials owing to their large mobility‐lifetime product, strong radiation absorption, and low‐cost preparation. However, it is still a challenge to achieve stable X‐ray detection due to the limitations associated with severe ion migration under high voltage bias. Herein, based on a bromine substitution strategy to suppress ion migration, a 2D alternating cations intercalation‐type (ACI) perovskite, (R‐MPA)(BrEA)PbBr4 (1, R‐MPA = methylphenethylamm‐onium; BrEA = 2‐bromoethylamine) is reported to achieve X‐ray detection. Specifically, introducing Br atom forms additional intermolecular interactions (i.e., Br···π) and enhances hydrogen bonding interactions, greatly improving the structure stability. Based on this enhanced interaction, 1 presents a higher activation energy of ion migration (1.05 eV) than that of (R‐MPA)EAPbBr4 resulting in a lower dark current drift of 9.17 × 10−8 nA cm−1 s−1 V−1, revealing that suppression of ion migration. Consequently, the 1‐based detector shows a high sensitivity of 2653.7 μC Gy−1 cm−2 and, most importantly, outstanding operational and environmental stability, maintaining ≈91% of its initial sensitivity at 50 V bias after 90 days in the air. This work demonstrates an efficient strategy for introducing halogen interactions via ACI to suppress ion migration for stable X‐ray detection.

Experimental and Theoretical Investigation of Anisotropic Proton Conduction in Two-Dimensional Metal-Organic Frameworks.

Two-dimensional (2D) materials are known for their potential to exhibit anisotropic transport properties due to their layered structures. However, the anisotropic ion conduction of 2D metal-organic frameworks (MOFs) has been rarely explored. In this study, we investigated the anisotropic proton conduction along the in-plane and stacking directions of two analogs of undulating 2D MOFs: [Mn(salen)]2[Pt(CN)4]·H2O (MnPt) and [Mn(salen)]2[PtI2(CN)4]·H2O (MnPtI). This investigation was conducted using both experimental methods, involving single crystals, and theoretical calculations. Compared to the relatively isotropic proton conduction of MnPt at 85 °C and 95% relative humidity (RH), with a stacking direction conductivity (σstacking) of 1.8 × 10-5 S/cm, which is approximately 2.9 times the in-plane conductivity (σin-plane), MnPtI exhibited highly anisotropic proton conduction. The σstacking of MnPtI under the same conditions (85 °C, 95% RH) was 1.5 × 10-4 S/cm, which is 83 times higher than its σin-plane. Additionally, the activation energy for proton conduction in MnPtI ranged from 0.65 to 0.73 eV, which is higher than the 0.48 eV observed for MnPt. Theoretical calculations confirmed that slight differences in local structures, including node distortions between MnPt and MnPtI, significantly influenced the activation energies for water migration. This was attributed to the formation of hydrogen bonds between layers and water molecules.

Enhanced Electric Field Minimizing Quasi-Fermi Level Splitting Deficit for High-Performance Tin-Lead Perovskite Solar Cells.

The quasi-Fermi level splitting (QFLS) deficit caused by the non-radiative recombination at the interface of perovskite/electron transport layer (ETL) can lead to severe open-circuit voltage (VOC) loss and thus decreases the efficiency of perovskite solar cells (PSCs), however, has received limited attention in inverted tin-lead PSCs. Herein, the strategy of constructing an extra-electric field is presented by introducing ferroelectric polymer dipoles (FPD)-β-poly(1,1-difluoroethylene)-to suppress the QFLS deficit. The directional polarization of FPD can enhance the built-in electric field (BEF) and thus promote the charge transfer at the perovskite/ETL interface, which effectively suppresses non-radiative recombination. Furthermore, the incorporation of FPD facilitates high-quality crystallization of perovskite and reduces the surface energetic disorder. Therefore, the QFLS deficit in the perovskite/ETL half-stacked device is reduced from 62 to 27 meV after incorporating FPD, and the optimized device achieves an efficiency of 23.44% with a high VOC of 0.88V. Additionally, the addition of FPD increases the activation energy for ion migration, which can reduce the effect of ion migration on the long-term stability of the device. Consequently, the FPD-incorporated device retains 88% of the initial efficiency after 1100h of continuous illumination at the maximum power point (MPP).

Low Temperature Sintering Al-B Doped-LLZO for All-Solid-State Lithium Battery

This research synthesizes a double Al-B doped LLZO following a composition of Li7+0.5xLa1.14Al1.43xB0.5xZr2-3xO12-δ through a solid-state reaction. The materials were sintered at a low temperature of 900 °C, giving an advantage in reducing Li loss. The material was analyzed to understand the phase content, the crystal structure and cell parameters, the surface morphology, the impedance, the electrical conductivity, and the activation energy for ionic migration. As a result, the Al-B doped-LLZO with x composition of 0.3 (Li7.15La1.14Al0.429B0.15Zr1.1O12-) and ball milling time of 120 h, LLZBAO(0.3)120 h, provides the highest ionic conductivity of 6.898×10–4 Scm–1 at room temperature, and it increases as the temperature increases confirming activation energy of 0.135 eV. A prototype of LCO-LLZBAO(0.3)120h-Li metal battery was produced and tested to investigate the solid electrolyte performance. A cyclic voltammetry analysis confirms a quasi-reversible reaction involving extraction-insertion of Li ions into LiCoO2. However, the excess capacity and a long plateau at low voltage also indicate the reduced Li+ into zero valent-metal, which is poorly reversible, causing the battery capacity to decrease and become stable after 20 cycles.

Recycling Single‐Crystal Perovskite Solar Cells With Improved Efficiency and Stability

AbstractMetal halide perovskite single crystals are promising for photovoltaic applications due to their outstanding properties. However, the high surface trap density causes severe nonradiative recombination and ion migration, hindering device performance and stability. Herein, mitigation of the deficient crystal surface is reported by optimized polishing engineering, resulting in stoichiometric lead‐iodine ratio with reduced iodide ion vacancies, increased ion migration activation energy, and suppressed nonradiative recombination. As a result, Cs0.05FA0.95PbI3 (FA = formamidinium) devices exhibit an impressive efficiency of 23.1%, which is one of the highest values for single‐crystal perovskite solar cells (PSCs). Moreover, multiple recycling of the degraded single‐crystal PSCs with higher efficiency and stability is achieved by removing the deteriorated surface, validating crystal surface dominates device degradation while the role of bulk and buried interface is negligible, which is different from polycrystalline devices. The T85 lifetime (remain 85% of initial efficiency) of Cs0.05FA0.95PbI3 devices increases to 1150 h after the recycling process, which is much better than that of previously reported single‐crystal PSCs. Since deficient crystal surface and ion migration are universal issues of perovskite materials, this work will promote the development of stable single‐crystal PSCs and other optoelectronic devices, such as X‐ray detectors, light‐emitting diodes, etc.

Rational Tailored Polyfluorosubstituted Amide Molecule for Stabilizing PbI6 Framework and Inhibiting Ion Migration Toward Highly Efficient and Stable Perovskite Solar Cells

AbstractPerovskite solar cells (PSCs), while highly efficient, face stability challenges that hinder their commercial application. These instability issues mainly arise from the fragile nature of Pb─I bonds in perovskites, which easily break under environmental stresses such as heat and light, leading to the breakdown of the [PbI6] framework and irreversible degradation. To address these issues, a multifunctional molecule, N1,N4‐bis(2,3,5,6‐tetrafluoro‐4‐iodophenyl)terephthalamide (FIPh‐A), is designed and synthesized to enhance the stability of perovskite films and devices. FIPh‐A molecule possesses carbonyl, amino, and iodotetrafluorophenyl groups that bind and stabilize Pb2+ ions and [PbI6]4− octahedra structure, preventing ion migration in perovskite films. The activation energy of ion migration increases obviously from 0.28 eV to 0.39 eV by adding FIPh‐A verified by experiment results. The residual strain is also released efficiently by introducing FIPh‐A molecule into perovskite films characterized by grazing incidence X‐ray diffraction. The champion PSC with FIPh‐A achieves a power conversion efficiency of 24.60%. After 500 h of continuous illumination (ISOS‐L‐1) and 300 h of thermal aging at 80 °C (ISOS‐D‐2I), these PSCs with FIPh‐A maintained 93% and 77% of their initial efficiency, respectively. These results emphasize the potential of multifunctional additives in overcoming the stability challenges of PSCs, thereby facilitating their commercial advancement.

Stabilization of Organic Cations in Lead Halide Perovskite Solar Cells Using Phosphine Oxides Derivatives.

Preventing ion migration in perovskite photovoltaics is key to achieving stable and efficient devices. The activation energy for ion migration is affected by the chemical environment surrounding the ions. Thus, the migration of organic cations in lead halide perovskites can be mitigated by engineering their local interactions, for example through hydrogen bonding. Ion migration also leads to ionic losses via interfacial reactions. Undesirable reactivities of the organic cations can be eliminated by introducing protecting groups. In this work, we report bis(2-oxo-3-oxazolidinyl) phosphinic chloride (BOP-Cl) as a perovskite ink additive with the following benefits: (1) The phosphoryl and two oxo groups form six-membered intermolecular hydrogen-bonded rings with the formamidinium cation (FA), mitigating ion migrations. (2) The hydrogen bonding reduces the electrophilicity of the ammonium protons by donating electron density, therefore reducing its reactivity with the surface oxygen on the metal oxide. Furthermore, the molecule can react to form a protecting group on the nucleophilic oxygen at the tin oxide transport layer surface through the elimination of chlorine. As a result, we achieve perovskite solar cells with an efficiency of 25.0% and improved MPP stability T93 = 1200 h at 40-45 °C compared to a control device (T86 = 550 h). In addition, we show a negative correlation between the strength of hydrogen bonding of different phosphine oxide derivatives to the organic cations and the degree of metastable behavior (e.g., initial burn-in) of the device.

Mitigating Noise Current in 2D Perovskite Single Crystal Photodetectors for Imaging under Black‐Light Condition

AbstractWeak‐light imaging plays a pivotal role in various fields such as astronomical photography, military nighttime surveillance, and biomedical imaging. The capability of photodetectors (PDs) in detecting weak‐light relies heavily on minimizing their noise current. In this study, the weak‐light detection performances of PDs constructed from PEA2MAn‐1PbnI3n+1 (n = 1, 2, 3) 2D perovskite single crystals are presented. Among these, the n = 1 PD showcases incredibly low noise current that induces an ultra‐low detection limit of 14 pW cm−2 under 532 nm light illumination, and a high detectivity of 3.25 × 1015 Jones. The n = 1 PD also meets imaging requirements even under black‐level illumination conditions of 75 pW cm−2. The investigation reveals that decreasing n value corresponds to an increase in the PEA+ ratios of cations, resulting in reduced defects and enhanced ion migration activation energy and exciton binding energy. These reduce noise current of devices from electron/hole, ion, and exciton dynamic behaviors. Notably, inhibiting ion migration can significantly improve the stability of the noise current baseline and facilitate the stable detection of weak signals. This study underscores the potential of 2D perovskites for advancing weak‐light imaging technologies, offering valuable insights for future development in this field.

Sensitivity enhancement of hydrogen-gas sensor by sub nm Au on Pd surface of a wireless quartz resonator

Hydrogen (H2) is an important source of next-generation energy production. The various H2 sensors developed to date cannot easily detect very low concentrations of H2 (<10 ppm) at room temperature within 100 s. In this study, we develop H2 sensors by depositing a 200 nm thick palladium (Pd) film on AT-cut quartz resonators and adding a sub nm gold (Au) layer on the Pd surface. Moderate Au deposition on the Pd surface improves the sensitivity of the sensor by decreasing the activation energy of atomic-hydrogen migration from the surface to the subsurface. The optimal Au thickness that minimizes the activation energy is 0.5 nm. Finally, we show that the approximate detection limit at room temperature is 5 ppm.

Ion migration and dark current suppression in quasi-2D perovskite-based X-ray detectors.

Cesium-based lead-free double perovskite materials (Cs2AgBiBr6) have garnered significant attention in the X-ray detection field due to their environment friendly characteristics. However, their substantial ion migration properties lead to large dark currents and detection limits in Cs2AgBiBr6-based X-ray detectors, restricting the detection performance of the device. In terms of process technology, ultrasonic spraying is more suitable than a spin-coating method for fabricating large-area, micron-scale perovskite thick films, with higher cost-effectiveness, which is crucial for X-ray detection. This work introduces a BA+ (BA+ = CH3CH2CH2CH2NH3 +, n-butyl) source into the precursor solution and employs ultrasonic spraying to fabricate quasi-two-dimensional structured polycrystalline (BA)2Cs9Ag5Bi5Br31 perovskite thick films, developing a low-cost, eco-friendly X-ray detector with low dark current density and low detection limit. Characterization results reveal that the ion migration activation energy of (BA)2Cs9Ag5Bi5Br31 reaches 419 meV, approximately 17% higher than that of traditional three-dimensional perovskites, effectively suppressing perovskite ion migration and subsequently reducing the dark current. The (BA)2Cs9Ag5Bi5Br31-based X-ray detectors exhibit high resistivity (about 1.75 × 1010 Ω cm), low dark current density (66 nA cm-2), minimal dark current drift (0.016 pA cm-1 s-1 V-1), and detection limit (138 nGyair s-1), holding considerable promise for applications in low-noise, low-dose X-ray detection.

Revealing the Role of Polyacrylonitrile for Highly Efficient and Stable Perovskite Solar Cells at Extremely Low Temperatures

AbstractPerovskite solar cells (PSCs) are considered to be a promising candidate for near‐space applications due to their high specific power, excellent radiation resistance, and compatibility with flexible substrates. Nevertheless, the low‐temperature cycles impose considerable challenges to their long‐term stability. Herein, the extremely low‐temperature photovoltaic process of PSCs is investigated and the effect mechanisms of PAN (Polyacrylonitrile) as an additive are revealed. It is found that the additive PAN regulates perovskite lattice stress and stabilizes perovskite lattice structure and thus retards perovskite phase transition at low temperatures. Moreover, the PAN improves perovskite dielectric properties and ion migration activation energy and effectively passivates perovskite defects at low temperatures. Therefore, the carrier transport/extraction/collection abilities at low temperatures are enhanced effectively by alleviating exciton effect and increasing dielectric screening effect. Benefiting from these positive effects of PAN, the PAN‐modified device achieves a maximum efficiency of 24.34% at 150K and maintains 72% of its initial value after 120 thermal cycles (290‐130K). Also, the PAN‐modified flexible devices exhibit excellent bending stability and thermal cycle stability. This study provides a deep insight into understanding the extremely low‐temperature photovoltaic behavior of PSCs and demonstrates the potentiality of PAN additive strategy for achieving efficient and stable PSCs at low temperatures.

Dual‐Doping Strategy of Metal Chlorides in Ambient Air with High Humidity for Achieving Highly Air‐Stable All‐Inorganic Perovskite Solar Cells

It is fundamentally challenging to achieve stable and efficient all‐inorganic perovskite solar cells (PSCs) in ambient air conditions for low‐cost commercial manufacturing, as the crystallinity, surface morphology, and optical activity of all‐inorganic perovskites exhibit high sensitivity to environmental factors such as moisture and illumination. Herein, a dual‐doping strategy is presented to prepare high‐quality dual‐doping CsPbI2Br films under ambient air with relative humidity of 70% (70% RH) by introducing CaCl2 and InCl3 additives into precursor solution. The results from the experiments and calculations reveal that the CaCl2 additive can isolate moisture by forming hydrates at the surface and grain boundary of perovskites. Meanwhile, the addition of InCl3 can significantly improve the optoelectronic properties via the heterovalent substitution of Pb2+ by a small amount of In3+. Moreover, the phase segregation can be significantly suppressed in the dual‐doping CsPbI2Br films owing to decreasing the electron–phonon coupling strength and increasing the activation energy of ion migration. The unencapsulated dual‐doping CsPbI2Br PSC with the power conversion efficiency (PCE) of 15.51% (70% RH) demonstrates high humidity storage and long‐term optical stability, remaining 90% of the original PCE after aging 2400 h under ambient air (50% RH) and 1500 h under continuous illumination, respectively.

Migration of polydimethylsiloxane chain segments toward the surface of UV-cured waterborne poly(urethane-acrylate) films

Waterborne polyurethane (WPU) has poor water resistance and low surface hydrophobicity due to the incorporation of hydrophilic chain-extender. The water resistance and the surface hydrophobicity can be improved by incorporation of polydimethylsiloxane (PDMS), which is attributed to the migration of PDMS chain segments toward the surface of WPU film. However, whether the PDMS chain segments can migrate toward the surface of WPU film after UV-curing, resulting in higher hydrophobicity, needs further investigation? We prepared the different WPUA films by changing the molar ratio of aminopropyl-terminated polydimethylsiloxane (APT-PDMS) to hydroxyethyl acrylate (HEA), to deeply understand the migrating phenomenon of PDMS chain segments toward the surface of WPUA films. The migration cause of PDMS chain segments and the influence of chemical cross-linking on the migration were investigated by thermal annealing and solvent immersion of WPUA films. In addition, the migration activation energy and the relaxation time were studied by the migration rate of PDMS chain segments in the thermal annealing and the rheological behavior of WPUA film, aiming to elucidate the migration of PDMS chain segments depending on the chain motion and the fractional free volume. This investigation provides a simple and feasible strategy for improving the hydrophobicity of waterborne polyurethane.

An ab initio molecular dynamics investigation of the behaviour of amorphous substances in anodic aluminium oxide under electric field

In order to elucidate the diffusion behaviour of ions in alumina during the anodic alumina process, the effects of electric field strength, hydration content, and electrolyte on amorphous alumina and hydrated alumina were studied using ab initio molecular dynamics. The results show that the diffusion rate of ions in alumina increases with the increase in electric field strength, but there is an extreme value. The maximum diffusion rate of Al ions in alumina monohydrate is 21.8 μm2/ms/V, while in alumina trihydrate, it is 16.7 μm2/ms/V. The ionic diffusion rate of hydrated alumina is one to two orders of magnitude larger than that of anhydrous amorphous alumina due to the effect of the drag of H ions, which reduces the migration activation energy. Electrolytes also affect the diffusion rate of alumina through the action of H ions. The increase in H ions will not only enhance the diffusion rate of hydrated alumina but also render the hydrous compound more vulnerable to breakdown.

Migration roles of different oxygen species over Cu/CeO2 for propane and soot combustion

Determining the migration rules of oxygen species in catalytic combustion, especially for catalysts composed of transition metal oxides, is essential yet challenging. This study hydrothermally synthesized nanosphere-structured cerium dioxide (CeO2) and its copper-loaded catalysts (Cu/CeO2) to identify the distinct functions of superficial oxygen species (O) and lattice oxygen (O2–). The presence of Cu-Ce solid solution at the Cu/CeO2 interface lowered the apparent activation energy for the catalytic combustion of propane and soot. The catalytic combustion of propane followed the Mars-van Krevelen mechanism, with O2– serving as the dominant reactive phase while O played a subordinate role. The solid–solid reaction between soot and superficial oxygen of the catalyst was responsible for catalyzed soot combustion. The O species produced by surface defective sites exhibited higher activity than O2–, which drained easily at the beginning of the reactions. The isotopic oxygen exchange tests revealed the mechanism of metal oxide (CuO/CeO2) interactions for active oxygen species migration, with the results demonstrating the solid solution at the phase interface as portholes for oxygen migration, thus increasing oxygen mobility between the gaseous phase and the surface by lowering the migration activation energy. In situ, infrared results showed that the reaction path of soot catalytic combustion was single, without any intermediate production formation, compared to multiple paths in the propane oxidation process. This study provided an easily implemented and widely applicable method, which deepens our understanding of the characterization of the function and migration of predominant oxygen species in diverse combustion reactions involving oxide-based catalysts. Additionally, this study clarified differences and similarities between the reaction mechanisms of solid–solid and solid–gas catalysis.

Nanosurface-reconstructed perovskite for highly efficient and stable active-matrix light-emitting diode display.

Perovskite quantum dots (QDs) are promising for various photonic applications due to their high colour purity, tunable optoelectronic properties and excellent solution processability. Surface features impact their optoelectronic properties, and surface defects remain a major obstacle to progress. Here we develop a strategy utilizing diisooctylphosphinic acid-mediated synthesis combined with hydriodic acid-etching-driven nanosurface reconstruction to stabilize CsPbI3 QDs. Diisooctylphosphinic acid strongly adsorbs to the QDs and increases the formation energy of halide vacancies, enabling nanosurface reconstruction. The QD film with nanosurface reconstruction shows enhanced phase stability, improved photoluminescence endurance under thermal stress and electric field conditions, and a higher activation energy for ion migration. Consequently, we demonstrate perovskite light-emitting diodes (LEDs) that feature an electroluminescence peak at 644 nm. These LEDs achieve an external quantum efficiency of 28.5% and an operational half-lifetime surpassing 30 h at an initial luminance of 100 cd m-2, marking a tenfold improvement over previously published studies. The integration of these high-performance LEDs with specifically designed thin-film transistor circuits enables the demonstration of solution-processed active-matrix perovskite displays that show a peak external quantum efficiency of 23.6% at a display brightness of 300 cd m-2. This work showcases nanosurface reconstruction as a pivotal pathway towards high-performance QD-based optoelectronic devices.

Influence of nano-crystallization on Li-ion conductivity in glass Li3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}PS4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}: a molecular dynamics study

Understanding the ionic conduction mechanisms in solid electrolyte glasses and glass-ceramics is an important task for improving the performance of next-generation all-solid-state batteries. Although many ionic conduction mechanisms have been proposed, the mechanism of increased ionic conductivity in partially crystallized glass is not fully understood. In this study, molecular dynamics was used to analyze the strain and local ion mobility in the glass around the crystal nano-particles of Li3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}PS4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}, which is a promising material for solid electrolytes. From the analysis of the results, we find that a local strain field is generated around the crystal particles and that the tensile strain field decreases the activation energy of ion migration and increases the ionic conductivity. This study opens the possibility of improving the ionic conductivity of glass-ceramics by controlling crystallization and dispersing the tensile strain field, even though the crystalline phase is not a high ionic conducting phase.

Ordered Perovskite Structure with Functional Units for High Performance and Stable Solar Cells.

Ion migration is one of the most critical challenges that affects the stability of metal-halide perovskite solar cells (PSCs). However, the current arsenal of available strategies for solving this issue is limited. Here, novel perovskite active layers following the concept of ordered structures with functional units (OSFU) to intrinsically suppress ion migration, in which a three-dimensional (3D) perovskite layer is deposited by vapor deposition for light absorption and a 2D layer is deposited by solution process for ion inhibition, are constructed. As a promising result, the activation energy of ion migration increases from 0.36 eV for the conventional perovskite to 0.54 eV for the OSFU perovskite. These devices exhibit substantially enhanced operational stability in comparison with the conventional ones, retaining >85% of their initial efficiencies after 1200 h under ISOS-L-1. Moreover, the OSFU devices show negligible fatigue behavior with a robust performance under light/dark cycling aging test (ISOS-LC-1 protocol), which demonstrates the promising application of functional motif theory in this field.

Defect Modulation via SnX2 Additives in FASnI3 Perovskite Solar Cells.

Tin halide perovskites suffer from high defect densities compared with their lead counterparts. To decrease defect densities, SnF2 is commonly used as an additive in tin halide perovskites. Herein, we investigate how SnF2 compares to other SnX2 additives (X = F, Cl, Br) in terms of electronic and ionic defect properties in FASnI3. We find that FASnI3 films with SnF2 show the lowest Urbach energies (EU) of 19 meV and a decreased p-type character, as probed with ultraviolet photoemission spectroscopy. The activation energy of ion migration, as probed with thermal admittance spectroscopy, for FASnI3 with SnF2 is 1.33 eV, which is higher than with SnCl2 and SnBr2, which are 1.22 and 0.79 eV, respectively, resulting in less ion migration. Because of improved defect passivation, the champion power conversion efficiency of FASnI3 with SnF2 is 7.47% and only 1.84% and 1.20% with SnCl2 and SnBr2, respectively.

Meliorative dielectric properties in core@double-shell structured Al@Al2O3@PDA/PVDF nanocomposites via decoupling the intra-particle polarization and inter-particle polarization

Percolating polymeric composites present enormous potential owing to high dielectric constant (ε) which can be realized near the percolation threshold, but the accompanied large loss forbids their extensive use in practice. Great efforts have been devoted to coat conductive particles with an insulating shell for constrained dielectric loss, yet they markedly reduce ε. In this work, we explore poly(vinylidene fluoride) (PVDF) composites with a serial of core@double-shell Al@Al2O3@PDA (polydopamine) nanoparticles with various PDA shell thicknesses. It reveals that the high ε of the nanocomposites results from a fast intra-particle polarization and a slow inter-particle polarization. The formation of double-shell enables the independent control of the two polarizations always coupled in traditional percolating composites. Through facilitating intra-particle polarization and repressing inter-particle polarization, Al@Al2O3@PDA/PVDF can achieve a much higher ε and lower dielectric loss simultaneously, far exceeding the unmodified Al@Al2O3/PVDF. Moreover, the calculated activation energy of carrier migration in Al@Al2O3@PDA/PVDF is obviously higher than that in untreated nanocomposites, indicating enhanced charge-trapping capability in the core@double-shell nanofiller composites. This core@double-shell strategy offers a new paradigm for the design and preparation of percolating composites with desirable dielectric performances.