Halide Sites Research Articles

Site Disorder Drives Cyanide Dynamics and Fast Ion Transport in Li6PS5CN.

Halide argyrodite solid-state electrolytes of the general formula Li6PS5 X exhibit complex static and dynamic disorder that plays a crucial role in ion transport processes. Here, we unravel the rich interplay between site disorder and dynamics in the plastic crystal argyrodite Li6PS5CN and the impact on ion diffusion processes through a suite of experimental and computational methodologies, including temperature-dependent synchrotron powder X-ray diffraction, AC electrochemical impedance spectroscopy, 7Li solid-state NMR, and machine learning-assisted molecular dynamics simulations. Sulfide and (pseudo)halide site disorder between the two anion sublattices unilaterally improves long-range lithium diffusion irrespective of the (pseudo)halide identity, which demonstrates the importance of site disorder in dictating bulk ionic conductivity in the argyrodite family. Furthermore, we find that anion site disorder modulates the presence and time scales of cyanide rotational dynamics. Ordered configurations of anions enable fast, quasi-free rotations of cyanides that occur on time scales of 1011 Hz at T = 300 K. In contrast, we find that cyanide dynamics are slow or frozen in Li6PS5CN when site disorder between the cyanide and sulfide sublattices is present at T = 300 K. We rationalize the observed differences in cyanide dynamics in the context of elastic dipole interactions between neighboring cyanide anions and local strain induced by the configurations of site disorder that may impact the energetic landscape for cyanide rotational dynamics. Through this study, we find that anion disorder plays a decisive role in dictating the extent and time scales of both lithium ion and cyanide dynamics in Li6PS5CN.

(Invited) Dynamics of Photoluminescence in Mn-Doped Pb-Halide Perovskite Nanocrystals

Nanocrystals of lead halide perovskites have been shown to have extraordinary photoluminescence properties, spanning the entire visible range achieved by the composition tuning via solid solutions at the halide site. Taking cues from Mn doping of traditional Group II-VI semiconductor quantum dots, Mn doping of the lead halide perovskites has been extensively explored by the community, establishing intense Mn-dopant induced emission that is significantly Stokes shifted from the excitonic emissions of the host. While all reports agree on the essential features of this emission, such as the peak position and the width of the Mn photoluminescence, there appears to be little agreement on the microscopic processes by which the host sensitizes Mn following its photoexcitation and the steps that control the deexcitation leading to the Mn emission. There are even reports of disagreement between different reports on the temperature dependence of the Mn emission and its origin. I shall discuss the present status of this field and establish, with the help of new experimental data as well as the already reported ones, what appears to be the microscopic processes controlling the excited dynamics in the Mn-doped lead halide perovskites.

Long-lasting renewable antibacterial N-halamine coating enable dental unit waterlines to prevention and control of contamination of dental treatment water

Developing bacterial biofilm on the dental unit waterlines increases the risk of cross-infection among oral patients. Although chemical disinfectants can achieve disinfection effects in a short period of time, corrosion damage of dental unit waterlines and water contamination can also occur after continuous use of it. Herein, this study explored a one-step deposition method to prepare a durable and renewable antibacterial N-halamine polymeric coating on polyurethane waterlines. The method utilized polyelectrolyte complexes formed with polyethylenimine (PEI) and phytic acid (PA), followed by chlorination to activate the antibacterial properties. The N-halamine polymeric coating reduces the polyurethane waterline’s water contact angle, thus reducing biofouling deposits and the obstruction of the active halide site on the waterlines, thereby facilitating the maintenance of the cleanliness of the coating. In addition, benefiting both from the active chlorine release and the high density of positive charges on the coating, the polyurethane waterline antimicrobial activity is significantly enhanced. Besides, the N-halamine polymeric coating is biocompatible. This study showed that long-lasting and renewable antimicrobial requirements can be achieved by simple surface modification of N-halamine polymer coatings, which provides a practicable strategy for the production of long-term and reproducible antibacterial dental unit waterlines to reduce the incidence of hospital infection in oral department.

Cobalt(III) Halide Metal-Organic Frameworks Drive Catalytic Halogen Exchange.

The selective halogenation of complex (hetero)aromatic systems is a critical yet challenging transformation that is relevant to medicinal chemistry, agriculture, and biomedical imaging. However, current methods are limited by toxic reagents, expensive homogeneous second- and third-row transition metal catalysts, or poor substrate tolerance. Herein, we demonstrate that porous metal-organic frameworks (MOFs) containing terminal Co(III) halide sites represent a rare and general class of heterogeneous catalysts for the controlled installation of chlorine and fluorine centers into electron-deficient (hetero)aryl bromides using simple metal halide salts. Mechanistic studies support that these halogen exchange (halex) reactions proceed via redox-neutral nucleophilic aromatic substitution (SNAr) at the Co(III) sites. The MOF-based halex catalysts are recyclable, enable green halogenation with minimal waste generation, and facilitate halex in a continuous flow. Our findings represent the first example of SNAr catalysis using MOFs, expanding the lexicon of synthetic transformations enabled by these materials.

Halide Engineering in Mixed Halide Perovskite-Inspired Cu2AgBiI6 for Solar Cells with Enhanced Performance.

Cu2AgBiI6 (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br-) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE). By introducing Br- in the synthetic route of CABI thin films, we identify the optimum composition as CABI-10Br (with 10% Br at the halide site). The tailored composition appears to reduce the deep trap density as shown by time-resolved photoluminescence and transient absorption spectroscopy characterizations. This leads to a dramatic increase in the lifetime of charge carriers, which therefore improves both the external quantum efficiency and the integrated short-circuit current. The photovoltaic performance shows a significant boost since the PCE under standard 1 sun illumination increases from 1.32 to 1.69% (∼30% relative enhancement). Systematic theoretical and experimental characterizations were employed to investigate the effect of Br- incorporation on the optoelectronic properties of CABI. Our results highlight the importance of mitigating trap states in lead-free perovskite-inspired materials and that Br- incorporation at the halide site is an effective strategy for improving the device performance.

Unraveling Loss Mechanisms Arising from Energy‐Level Misalignment between Metal Halide Perovskites and Hole Transport Layers

AbstractMetal halide perovskites are promising light absorbers for multijunction photovoltaic applications because of their remarkable bandgap tunability, achieved through compositional mixing on the halide site. However, poor energy‐level alignment at the interface between wide‐bandgap mixed‐halide perovskites and charge‐extraction layers still causes significant losses in solar‐cell performance. Here, the origin of such losses is investigated, focusing on the energy‐level misalignment between the valence band maximum and the highest occupied molecular orbital (HOMO) for a commonly employed combination, FA0.83Cs0.17Pb(I1‐xBrx)3 with bromide content x ranging from 0 to 1, and poly[bis(4‐phenyl)(2,4,6‐trimethylphenyl)amine] (PTAA). A combination of time‐resolved photoluminescence spectroscopy and numerical modeling of charge‐carrier dynamics reveals that open‐circuit voltage (VOC) losses associated with a rising energy‐level misalignment derive from increasing accumulation of holes in the HOMO of PTAA, which then subsequently recombine non‐radiatively across the interface via interfacial defects. Simulations assuming an ideal choice of hole‐transport material to pair with FA0.83Cs0.17Pb(I1‐xBrx)3 show that such VOC losses originating from energy‐level misalignment can be reduced by up to 70 mV. These findings highlight the urgent need for tailored charge‐extraction materials exhibiting improved energy‐level alignment with wide‐bandgap mixed‐halide perovskites to enable solar cells with improved power conversion efficiencies.

Axial–Equatorial Halide Ordering in Layered Hybrid Perovskites from Isotropic–Anisotropic 207Pb NMR

AbstractBandgap‐tuneable mixed‐halide 3D perovskites are of interest for multi‐junction solar cells, but suffer from photoinduced spatial halide segregation. Mixed‐halide 2D perovskites are more resistant to halide segregation and are promising coatings for 3D perovskite solar cells. The properties of mixed‐halide compositions depend on the local halide distribution, which is challenging to study at the level of single octahedra. In particular, it has been suggested that there is a preference for occupation of the distinct axial and equatorial halide sites in mixed‐halide 2D perovskites. 207Pb NMR can be used to probe the atomic‐scale structure of lead‐halide materials, but although the isotropic 207Pb shift is sensitive to halide stoichiometry, it cannot distinguish configurational isomers. Here, we use 2D isotropic–anisotropic correlation 207Pb NMR and relativistic DFT calculations to distinguish the [PbX6] configurations in mixed iodide–bromide 3D FAPb(Br1−xIx)3 perovskites and 2D BA2Pb(Br1−xIx)4 perovskites based on formamidinium (FA+) and butylammonium (BA+), respectively. We find that iodide preferentially occupies the axial site in BA‐based 2D perovskites, which may explain the suppressed halide mobility.

Axial-Equatorial Halide Ordering in Layered Hybrid Perovskites from Isotropic-Anisotropic 207 Pb NMR.

Bandgap-tuneable mixed-halide 3D perovskites are of interest for multi-junction solar cells, but suffer from photoinduced spatial halide segregation. Mixed-halide 2D perovskites are more resistant to halide segregation and are promising coatings for 3D perovskite solar cells. The properties of mixed-halide compositions depend on the local halide distribution, which is challenging to study at the level of single octahedra. In particular, it has been suggested that there is a preference for occupation of the distinct axial and equatorial halide sites in mixed-halide 2D perovskites. 207 Pb NMR can be used to probe the atomic-scale structure of lead-halide materials, but although the isotropic 207 Pb shift is sensitive to halide stoichiometry, it cannot distinguish configurational isomers. Here, we use 2D isotropic-anisotropic correlation 207 Pb NMR and relativistic DFT calculations to distinguish the [PbX6 ] configurations in mixed iodide-bromide 3D FAPb(Br1-x Ix )3 perovskites and 2D BA2 Pb(Br1-x Ix )4 perovskites based on formamidinium (FA+ ) and butylammonium (BA+ ), respectively. We find that iodide preferentially occupies the axial site in BA-based 2D perovskites, which may explain the suppressed halide mobility.

Halide Ordering Enables Superior Charge Transport in 3D (NMPDA)Pb2 I4 Br2 Perovskitoid Single Crystal.

Halide composition engineering has been demonstrated as an effective strategy for optical and electronic properties modulation in 3D perovskites. While the impact of halide mixing on the structural and charge transport properties of 3D perovskitoids remains largely unexplored. Herein, it is demonstrated that bromine (Br) mixing in 3D (NMPDA)Pb2 I6 (NMPDA = N-methyl-1,3-propane diammonium) perovskitoid yields stabilized (NMPDA)Pb2 I4 Br2 with specific ordered halide sites, where Br ions locate at the edge-sharing sites. The halide ordered structure enables stronger H-bonds, shorter interlayer distance, and lower octahedra distortion in (NMPDA)Pb2 I4 Br2 with respect to the pristine (NMPDA)Pb2 I6 . These attributes further result in high ion migration activation energy, low defect states density, and enhanced carrier mobility-lifetime product (µτ), as underpinned by the electrical properties investigation and DFT calculations. Remarkably, the parallel configured photodetector based on (NMPDA)Pb2 I4 Br2 single crystal delivers a high on/off current ratio of 3.92×103 , a satisfying photoresponsivity and detectivity of 0.28 AW-1 and 3.05×1012 Jones under 10.94 µWcm-2 irradiation, superior to that of (NMPDA)Pb2 I6 and the reported 3D perovskitoids. This work sheds novel insight on exploring 3D mixed halide perovskitoids toward advanced and stable optoelectronic devices.

Advancing Efficiency and Stability of Lead, Tin, and Lead/Tin Perovskite Solar Cells: Strategies and Perspectives

Halide‐perovskite‐based solar cells (HPSCs) have established themselves as a promising photovoltaic (PV) technology in a remarkably short time. The rapid improvement in HPSCs can be attributed to the unique material and optoelectronic properties of metal halide perovskite semiconductors coupled with a very knowledgeable and experienced PV community. This review briefly summarizes the chemistry of halide perovskites, delving into the fundamental aspects of crystal structure and optical bandgap, followed by a more in‐depth report on the advancements in HPSCs efficiencies, thanks to structural regulation, interfacial modulation, and thin‐film engineering. It is mainly focused on three metal halide perovskites topics: 1) high‐performance Pb‐based perovskites, 2) Sn‐based perovskites and their associated challenges, and 3) emerging work on mixed composition Pb–Sn perovskites. For each of these domains, the effects stemming from the tuning of the monovalent A‐site and the halide site are examined. Additionally, various approaches aimed at passivating defects in the bulk film and at the interface, along with carrier transport engineering, are discussed. The discussions also encompass the broader implications for device performance, stability, and material toxicity. Finally, perspectives on the future directions and the commercial feasibility of perovskite photovoltaic technologies are provided.

Halide alloying and role of central atom on the structural and optical properties of decylammonium germanium 2D perovskites

We report here a novel series of halide alloyed Ge-containing 2D perovskites including decylammonium as organic spacer, namely DA2Ge(Br1−xIx)4. This system forms a continuous solid solution on the halide site with a modulation of the bandgap from 2.74 to 2.17 eV with a rapid decrease up to x = 0.5 followed by a plateau. Iodide-rich compositions show enhanced broad room temperature (RT) photoluminescence (PL) that narrows at low temperature with maximum quantum yields for mixed compositions. The replacement of Ge with Pb and Sn in DA2GeBr4 and DA2GeI4 provides a tuning of the bandgap in the whole visible spectrum with a marked blue-shift when lead is present and, opposite, a red-shift for Sn replacement. The RT PL progressively broadens moving from Pb to Sn and to Ge covering an emission range from 400 to 800 nm. Finally, the air stability of lead-free 2D perovskites of this work has been determined indicating its improvement by increasing the hardness of the halide.

Real-Time Visualization of Photobrightening in Lead Halide Perovskites Using Confocal Laser Scanning Microscopy

Light induced changes in the optoelectronic properties affect the performance and the stability of halide perovskites. In this work, we report the real-time visualization of the photobrightening (PLB) effect using confocal laser scanning microscopy wherein the photon induced enhancement in photoluminescence is observed and their role in conductivity and photovoltaic properties are studied. The methodology is inspired from the Fluorescence Recovery After Photobleaching (FRAP) technique that is traditionally used to study biological cells. The role of composition, and surface/grain boundaries of perovskites, wavelengths, and intensity of illuminating photons, and time of illumination on the photobrightening or photobleaching is thoroughly investigated. The CH3NH3PbI3 exhibits a dominant photobrightening effect, with green photons showing more PLB than blue or red photons. The study of PLB between films and single crystals clearly shows the effect is a surface phenomenon. The presence of mixed iodide/bromide or pure bromide in the halide site and formamidinium or cesium in the A site suppressed the PLB. The strain relaxation in the organic site is found to be responsible for the PLB effect, and it enhanced the overall conductivity in material leading to better photovoltaic performance.

Resolving Oxidation States and X–site Composition of Sn Perovskites through Auger Parameter Analysis in XPS

AbstractReliable chemical state analysis of Sn semiconductors by XPS is hindered by the marginal observed binding energy shift in the Sn 3d region. For hybrid Sn‐based perovskites especially, errors associated with charge referencing can easily exceed chemistry‐related shifts. Studies based on the modified Auger parameter α ′ provide a suitable alternative and have been used previously to resolve different chemical states in Sn alloys and oxides. However, the meaningful interpretation of Auger parameter variations on Sn‐based perovskite semiconductors requires fundamental studies. In this work, a comprehensive Auger parameter study is performed through systematic compositional variations of Sn halide perovskites. It is found that in addition to the oxidation state, α ′ is highly sensitive to the composition of the halide site, inducing shifts of up to Δα ′ = 2 eV between ASnI3 and ASnBr3 type perovskites. The reported dependencies of α ′ on the Sn oxidation state, coordination and local chemistry provide a framework that enables reliable tracking of degradation as well as X‐site composition for Sn‐based perovskites and related compounds. The higher robustness and sensitivity of such studies not only enables more in‐depth surface analysis of Sn‐based perovskites than previously performed, but also increases reproducibility across laboratories.

Are Mixed-Halide Ruddlesden-Popper Perovskites Really Mixed?

Mixing bromine and iodine within lead halide perovskites is a common strategy to tune their optical properties. This comes at the cost of instability, as illumination induces halide segregation and degrades device performances. Hence, understanding the behavior of mixed-halide perovskites is crucial for applications. In 3D perovskites such as MAPb(Br x I1-x )3 (MA = methylammonium), all of the halide crystallographic sites are similar, and the consensus is that bromine and iodine are homogeneously distributed prior to illumination. By analogy, it is often assumed that Ruddlesden-Popper layered perovskites such as (BA)2MAPb2(Br x I1-x )7 (BA = butylammonium) behave alike. However, these materials possess a much wider variety of halide sites featuring diverse coordination environments, which might be preferentially occupied by either bromine or iodine. This leaves an open question: are mixed-halide Ruddlesden-Popper perovskites really mixed? By combining powder and single-crystal diffraction experiments, we demonstrate that this is not the case: bromine and iodine in RP perovskites preferentially occupy different sites, regardless of the crystallization speed.

Acid‐ and Base‐Stable Cs2Pt(Cl,Br)6 Vacancy‐Ordered Double Perovskites and Their Core–Shell Heterostructures for Solar Water Oxidation

The stability of the absorber materials in an aqueous medium is the key to developing successful photoelectrochemical (PEC) solar fuel devices. The halide perovskite materials provide an opportunity to tune desired optoelectronic properties and show very high photovoltaic power conversion efficiency. However, their stability is poor as they decompose instantly in an aqueous electrolyte medium. Here the most stable vacancy ordered double perovskites Cs2PtCl6 and Cs2PtBr6, which remain intact in a wide range of pH values between 1 and 13 is reported. These materials also possess excellent absorption properties covering a significant portion of the visible spectrum. Like conventional ABX3 materials, these ultrastable materials offer tunability in optical properties via mixed halide sites. Through anion exchange, the conversion of Cs2PtCl6 to Cs2PtBr6 through core–shell conversion mechanism is shown. The latter led to the formation of type‐II heterostructures. The electrochemical properties of these materials are investigated in detail and their ability to carry out solar water oxidation on an unprotected photoanode, with photocurrent density of >0.2 mA cm−2 at 1.23 V (vs. RHE) is demonstrated.

Cover Feature: Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon (ChemPlusChem 10/2021)

The Cover Feature shows the Group 14 elements M=C, Si, and Ge in order of the effective electron-withdrawing power of the −MF3 fragment. C and Ge far outperform Si in mediating polarization of a fourth substituent such as I in F3M−I in the gas and solution phases. Thus, polarized germanium halide sites in molecules and solids (but not Si alternatives) may form strong halogen bonds that are comparable to those formed by their organic analogues. More information can be found in the Full Paper by K. J. Donald and co-workers.

Alleviating halide perovskite surface defects

Alleviating halide perovskite surface defects

Structure, Morphology, and Photovoltaic Implications of Halide Alloying in Lead‐Free Cs3Sb2ClxI9–x 2D‐Layered Perovskites

Compositional tuning is a major driving force behind the excellent optoelectronic properties observed in typical Pb‐based perovskites. For lead‐free perovskite derivatives, a challenge to understand the connection between compositional tuning and intrinsic optoelectronic properties, hence a barrier toward boosting their performance, comes from the fact that multiple crystalline substructures can form based on composition, film processing, or both. Especially with lower dimensional (0D, 1D, and 2D) substructures, the particular polymorph present in the film can be a greater determinant of optoelectronic properties than the composition itself. Herein, a simple method to alloy the halide site in all‐inorganic lead‐free Cs3Sb2I9 films is reported while maintaining a consistent 2D‐layered substructure, as a means to independently study the photovoltaic implications of halide substitution. A broad suite of spectroscopy and device measurements is used to identify an optimal stoichiometric substitution of chloride for iodide (≈8 mol%, measured) that balances both intrinsic and bulk optoelectronic properties to achieve a top power conversion efficiency of 2.2%. This work underscores the importance of controlling substructure while investigating the impacts of compositional tuning for the development of lead‐free perovskites and more broadly validates the approach toward realizing lead‐free alternative perovskite solar technologies.

Induced Vacancy-Assisted Filamentary Resistive Switching Device Based on RbPbI3-xClx Perovskite for RRAM Application.

Halide perovskite (HP) materials are actively researched for resistive switching (RS) memory devices due to their current-voltage hysteresis along with low-temperature processability, superior charge mobility, and simple fabrication. In this study, all-inorganic RbPbI3 perovskite has been doped with Cl in the halide site and incorporated as a switching media in the Ag/RbPbI3-xClx/ITO structure, since pure RbPbI3 is nonswitchable. Five compositions of the RbPbI3-xClx (x = 0, 0.3, 0.6, 0.9, and 1.2) films are fabricated, and the conductivity was found to be increasing upon increase in Cl concentration, as revealed by dielectric and I-V measurements. The device with a 20% chloride-substituted film exhibits a higher on/off ratio, extended endurance, long retention, and high-density storage ability. Finally, a plausible explanation of the switching mechanism from iodine vacancy-mediated growth of conducting filaments (CFs) is provided using conductive atomic force microscopy (c-AFM). The c-AFM measurements reveal that pure RbPbI3 is insulating in nature, whereas Cl-doped films demonstrate resistive switching behavior.

Effects of Organic Cations on Carrier Transport at the Interface between Perovskites and Electron Transport Layers in (FA,MA)SnI3 Solar Cells

Charge extraction at carrier transport layers adjacent to perovskites is crucial for the optimization of perovskite solar cells. In particular, Sn-perovskites with no lead elements are known to struggle from charge extraction. Here, we report the effects of organic ligands such as FA and MA (FA = HC(NH2)2+; MA = CH3NH3+) on charge separation at the interface between electron transport layers and perovskites. TiO2 mesoporous covering the tin-perovskites show significant changes in the electronic structure and built-in potentials according to the ratio of FA to MA. Through a local probe with potential and current mapping, charge transport has been intensively examined. The best cell in this study is obtained as 5.37% at FA/MA = 3:1 with only iodine at the halide sites. Even though the value itself is not comparable with lead halides, it could pave a new direction to improve lead-free perovskite solar cells.