Hybrid Metal Halide Research Articles

Tunable Blue-Light-Emitting Organic-Inorganic Zinc Halides with Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence.

Hybrid metal halides have received great interests in the field of solid-state lighting technologies due to their diverse structures and excellent emission properties. In this work, we report the synthesis and characterization of four blue-emitting zero-dimensional hybrid metal halides, namely, (2HP)2ZnCl2, (2HP)2ZnBr2, (2TP)2ZnCl2, and (2TP)2ZnBr2 (2HP = 2-hydroxypyridine, 2TP = pyridine-2-thiol). By changing the ligands and halides, a remarkable increase in the photoluminescence quantum yield of (2HP)2ZnCl2 (44.7%) compared to (2TP)2ZnBr2 (1.8%) is realized. The 2HP series features excitation-dependent emission characteristics, whereas the 2TP series does not due to the effect of a different organic ligand. Utilizing time-resolved and temperature-dependent photoluminescence spectroscopies, all four compounds exhibit both thermally activated delayed fluorescence and room-temperature phosphorescence properties. These materials have excellent ambient and thermal stabilities and are solution-processable. Our work shows the importance of carefully incorporating organic ligands with the appropriate inorganic metal center to achieve tunable emission properties.

Solution Processed Bilayer Metal Halide White Light Emitting Diodes.

Metal halide perovskites and perovskite-related organic metal halide hybrids (OMHHs) have recently emerged as a new class of luminescent materials for light emitting diodes (LEDs), owing to their unique and remarkable properties, including near-unity photoluminescence quantum efficiencies, highly tunable emission colors, and low temperature solution processing. While substantial progress has been made in developing monochromatic LEDs with electroluminescence across blue, green, red, and near-infrared regions, achieving highly efficient and stable white electroluminescence from a single LED remains a challenging and under-explored area. Here, a facile approach to generating white electroluminescence is reported by combining narrow sky-blue emission from metal halide perovskites and broadband orange/red emission from zero-dimensional (0D) OMHHs. For the proof of concept, utilizing TPPcarz+ passivated two-dimensional (2D) CsPbBr3 nanoplatelets (NPLs) as sky blue emitter and 0D TPPcarzSbBr4 as orange/red emitter (TPPcarz+ = triphenyl (9-phenyl-9H-carbazol-3-yl) phosphonium), white LEDs (WLEDs) with a solution processed bilayer structure have been fabricated to exhibit a peak external quantum efficiency (EQE) of 4.8% and luminance of 1507 cd m-2 at the Commission Internationale de L'Eclairage (CIE) coordinate of (0.32, 0.35). This work opens a new pathway for creating highly efficient and stable WLEDs using metal halide perovskites and related materials.

Tunable double emission of Sb3+/Mn2+ doping stabilized organic-inorganic hybrid zinc-based halides

Low-dimensional organic-inorganic hybrid metal halides (OIHMHs) have attracted much attention lately in contrast to all-inorganic metal halides because of their excellent photophysical properties and tunable emission wavelengths. Zn-based metal halides have the following advantages: simplicity of synthesis, wide bandgap, and excellent chemical stability. Therefore, they are well-suited as host materials for photoluminescence by cation ion doping. We have successfully synthesized intrinsically non-emissive 0D (PPZ)ZnCl4 [PPZ (1-phenylpiperazine) = C10H14N2], and by mono/co-doping with Mn2+ and Sb3+, interesting luminescence phenomena have been produced. Single-doped Mn2+ / Sb3+ shows distinctive green and single orange emission, respectively. However, the co-doped Mn2+ and Sb3+ appeared as dynamic double emission peaks at 530nm and 670nm. Therefore, the co-doped crystals showed luminescence from two different luminescence centers ([MnCl4]2- and [SbCl4]-). We used DFT to calculate the DOS (density of states) of co-doped crystals, which results in energy transfer between Mn2+ and Sb3+. All of the above samples showed high stability after being left for two months. In addition, two different luminescence centers can be produced by the adjustment of the excitation of the co-doped (PPZ)ZnCl4: Sb0.12Mn0.08 samples, which is a distinguishable and obvious photoluminescence phenomenon having great potential preparation of advanced anti-counterfeiting materials in the future.

Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy-Ordered Double Perovskite Derivatives.

Vacancy-ordered perovskites and derivatives represent an important subclass of hybrid metal halides with promise in applications including light emitting devices and photovoltaics. Understanding the vacancy-property relationship is crucial for designing related task-specific materials, yet research in this field remains sporadic. For the first time, we use the Connolly surface to quantitatively calculate the volume of vacancy (V□, □=vacancy) in vacancy-ordered double perovskite derivatives (VDPDs). A relationship between void fraction and the structure, photoluminescent properties and humidity stability was established based on zero-dimensional (0-D) [N(alkyl)4]2Sb□Cl5□'-type VDPDs. Compared with the more commonly studied A2M(IV)X6□-type double perovskite (A=cation, M=metal ion, X=halide), [N(alkyl)4]2Sb□Cl5□' features double vacancy sites. Our results demonstrate an inverse relationship between the photoluminescent quantum yield and V□ in 0-D VDPDs. Additionally, structural transformation from A2SbCl5 to A3Sb2Cl9 was first reported, during which the novel 'gate-opening' gas adsorption phenomenon was observed in VDPDs for the first time, as evidenced by 'S'-shaped sorption isotherms for water vapor, indicating a cation-controlled water-vapor response behavior. A mixed-cation strategy was developed to modulate the humidity stability of VDPDs. Characterized by controllable water-responsive behavior and unique 'on-off-on' luminescent switching, A2M(III)□X5□'-type materials show great promise for multi-level information anti-counterfeiting applications.

Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy‐Ordered Double Perovskite Derivatives

AbstractVacancy‐ordered perovskites and derivatives represent an important subclass of hybrid metal halides with promise in applications including light emitting devices and photovoltaics. Understanding the vacancy‐property relationship is crucial for designing related task‐specific materials, yet research in this field remains sporadic. For the first time, we use the Connolly surface to quantitatively calculate the volume of vacancy (V□, □=vacancy) in vacancy‐ordered double perovskite derivatives (VDPDs). A relationship between void fraction and the structure, photoluminescent properties and humidity stability was established based on zero‐dimensional (0‐D) [N(alkyl)4]2Sb□Cl5□′‐type VDPDs. Compared with the more commonly studied A2M(IV)X6□‐type double perovskite (A=cation, M=metal ion, X=halide), [N(alkyl)4]2Sb□Cl5□′ features double vacancy sites. Our results demonstrate an inverse relationship between the photoluminescent quantum yield and V□ in 0‐D VDPDs. Additionally, structural transformation from A2SbCl5 to A3Sb2Cl9 was first reported, during which the novel ‘gate‐opening’ gas adsorption phenomenon was observed in VDPDs for the first time, as evidenced by ‘S’‐shaped sorption isotherms for water vapor, indicating a cation‐controlled water‐vapor response behavior. A mixed‐cation strategy was developed to modulate the humidity stability of VDPDs. Characterized by controllable water‐responsive behavior and unique ‘on‐off‐on’ luminescent switching, A2M(III)□X5□′‐type materials show great promise for multi‐level information anti‐counterfeiting applications.

Remote chirality transfer in low-dimensional hybrid metal halide semiconductors.

In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (gCD) of up to 10-2. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. This concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality.

Simultaneous achieving color‐tuning long persistent luminescence and phosphorescent quantum yield of 81.05% in 2D organic metal halide perovskite

AbstractIonically bonded organic metal halide perovskite‐like luminescent materials, which incorporate organic cations and metal halides, have emerged as a versatile multicomponent material system. However, these materials still face challenges in terms of low phosphorescence quantum yields and limited long persistent luminescence (LPL) colors. Herein, we present the design and synthesis of an intraligand charge‐transfer organic‐based metal halide perovskite‐like material, in which organic cations form a compact supramolecular hydrogen‐bonded organic framework (HOF) structure, exhibiting crystallization‐induced phosphorescence emission of ligand, while metal halides form a unique two‐dimensional (2D) structure that displays intrinsic self‐trapped excitons (STE) emission under the radiation of UV light. Notably, the metal halide hybrid is found to exhibit enhanced phosphorescent photoluminescence efficiency of up to 81.05% and tunable LPL from cyan to orange compared to the pristine organic phosphor, due to the structural distortion and scaffolding effects of 2D metal halides as well as a well‐packed HOF structure. Optical characterizations and theoretical calculations reveal that charge transfer from organic cations and halogen to ligand as well as STE from inorganic layers are responsible for the tunable LPL. Meanwhile, the high‐efficiency phosphorescent quantum yield is attributed to stronger hydrogen bond stacking as well as structural distortion of metal halogen bands. Thus, the obtained LPL provides potentials in anti‐counterfeiting, security systems, and so on.

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.

Unveiling Mechanism of Temperature‐Dependent Self‐Trapped Exciton Emission in 1D Hybrid Organic–Inorganic Tin Halide for Advanced Thermography

AbstractLead‐free hybrid metal halide phosphors/crystals showing self‐trapped exciton (STE) emission have been recently explored for thermography due to the strong temperature dependence of their photoluminescence (PL) lifetime (τ). However, realizing high‐spatial‐resolution thermography using polycrystalline powders or crystals presents a challenge. Moreover, the underlying mechanism of temperature‐dependent STE remains elusive. Herein, a homogeneous 1D ODASn2I6 (ODA, 1,8‐octanediamine) nm‐scale thin film exhibiting efficient STE emission is investigated. The PL decay shows a strong temperature dependence from 275 K (τ ≈ 1.31 µs) to 350 K (τ ≈ 0.65 µs) yielding a thermal sensitivity of 0.014 K−1. By employing temperature‐dependent transient absorption spectroscopy, detailed information is obtained about the relaxation processes prior to the STE formation. Simultaneous analyses of steady‐state and time‐resolved spectroscopies lead to a self‐consistent model where the thermally activated phonon‐assisted nonradiative pathway explains the temperature dependence of the PL lifetime via a conical intersection between the ground state and STE potential energy surfaces. Finally, a discernible 50 ns variation in PL lifetimes across different heated regimes over a distance of 1.15 mm is successfully demonstrated with fluorescence lifetime imaging microscopy, underscoring the substantial potential of ODASn2I6 thin film for high‐spatial‐resolution thermography.

Chemically functionalized diamanes - A new class of hybrid 2D materials: DFT insight into crystal, mechanical, and electronic properties

This work describes crystal and electronic structures of a new class of 2D hybrid organic-inorganic compounds based on AB-stacked diamane. Seven members thereof are considered: methyl-, pyrrolyl-, 1,2,4-triazolyl-, phenyl-, pyridinyl-, and pyrimidinyl-substituted (two isomers) diamane. DFT calculations show that an electronic structure of diamane can be modulated by organic functional groups. The chemically functionalized diamanes are semiconductors with HSE06 electronic bandgaps falling in the range [2.09–4.91] eV. Other means of diamane electronic structure tuning include variation of coverage of a diamane surface by substituents, mixing of substituents and changing their mutual orientation. Based on the obtained results we conclude that the functionalized diamanes may serve as photovoltaic materials operable in Vis and near UV spectral regions. Owing to a similarity of the aromatics-substituted diamanes to low-dimensional hybrid metal halide perovskites with aromatic organic cations the former could be photoluminescent. An enhanced resistance of the investigated materials to water is expected.

Dynamic Phosphorescence/Fluorescence Switching in Hybrid Metal Halides Toward Time‐Resolved Multi‐Level Anti‐Counterfeiting

AbstractHybrid metal halides (HMHs) with time‐resolved luminescence behavior promise to be a breakthrough in multi‐level anti‐counterfeiting, but controlling the dynamic switching between phosphorescence and fluorescence is extremely challenging. Herein, an array of 0D HMHs is constructed by screening the π‐conjugated ligand with room‐temperature phosphorescence (RTP). Compared to the organic chromophore, (ETPP)2ZrCl6 possesses a misaligned stacking and rigid structure, contributing to an improved phosphorescence quantum yield (ΦP = 27.50%) and an extended phosphorescence lifetime (τ = 0.6234 s), as the intervening of inorganic unit [ZrCl6]2− suppresses the energy losses caused by nonradiative relaxation and prompts the intersystem crossover (ISC) process. Not only that, the interplay of phosphorescence‐fluorescence dual‐mode emission can be intelligently controlled by doping the active metal Te4+, resulting in a dynamic switching between RTP phosphorescence and self‐trapped exciton (STE) fluorescence. DFT calculations reveal the governing origins of RTP‐STE from the intermolecular ISC channels and spin‐orbit coupling (SOC) coefficients. These precise images into periodic pixelated arrays enable the multi‐level anti‐counterfeiting and information encryption. This work proposes a fluorescence‐phosphorescence co‐modulating strategy under the premise of dissecting the structural origins for optimizing RTP phosphorescence, which paves the way for designing high‐security‐level anti‐counterfeiting materials.

Multimode Luminescence Tailoring in PMA4Na(In,Sb)Cl8 Organic–inorganic Hybrid Metal Halide via Rigid Benzene Ring Induced Local Lattice Distortion

AbstractLow dimensional organic‐inorganic hybrid metal halide materials have attracted extensive attention due to their superior optoelectronic properties. However, low photoluminescence quantum yields (PLQYs) caused by parity‐forbidden transition hinder their further application in optoelectronic devices. Herein, a novel yellow‐emitting PMA4Na(In,Sb)Cl8 (C7H10N+, PMA+) low‐dimensional OIMHs single crystal with a PLQY as high as 88 % was successfully designed and synthesized, originating from the fact that the doping of Sb3+ effectively relaxes the parity‐forbidden transition by strong spin‐orbit (SO) coupling and Jahn‐Teller (JT) interaction. The as‐prepared crystal shows an efficient dual emission peaking 495 and 560 nm at low temperature, which are ascribed to different levels of 3P1→1S0 transitions of Sb3+ in [SbCl6]3− octahedral caused by JT deformation. Moreover, wide‐range luminescence tailoring from cyan to orange can be achieved through adjusting excitation energy and temperature because of flexible [SbCl6]3− octahedral in the PNIC lattice. Based on a relative stiff lattice environment, the 560 nm yellow emission under 350 nm light excitation exhibits abnormal anti‐thermal quenching from 8 to 400 K owing to the suppression of non‐radiative transition. The multimode luminescence regulation enriches PMA4Na(In,Sb)Cl8 great potential in the field of optoelectronics such as temperature sensing, low temperature anti‐counterfeiting and WLED applications.

Identifying Practical DFT Functionals for Predicting 0D and 1D Organic Metal-Halide Hybrids

Identifying Practical DFT Functionals for Predicting 0D and 1D Organic Metal-Halide Hybrids

Precisely Regulating Photoactivated Dynamic Room Temperature Phosphorescence by Alkyl Chain‐Induced Lattice‐Softening

AbstractDynamic response room temperature phosphorescence (RTP) is a hot topic in smart materials research due to its unique RTP‐response characteristics under external stimuli. However, its precisely control are currently challenging. Here, an alkyl chain‐induced lattice‐softening strategy is proposed to precisely regulate photoactivated dynamic RTP (PDRTP). By adjusting the alkyl chain flexibility of hybrid metal halide matrices, oxygen permeability can be adjusted, thereby achieving finely manipulate of the photoactivation equilibrium time, RTP lifetime, and RTP wavelength of the resulted host–guest doped materials within the ranges of 10–600 s, 0.05‐1.62 s, and 405–595 nm, respectively. It is also demonstrated the potential application of the PDRTP materials in afterglow oxygen sensing and multi‐level information encryption. This study not only proposes an effective method for regulating the photosensitivity of PDRTP materials, but also points out a new direction for exploring gas permeability in dense‐packed crystalline materials.

A Highly Optical Anisotropic Hybrid Metal Halide for Modulation and Generation of Polarized Light

AbstractPolarized light is critical for a wide range of applications in modern optics. However, its generation and modulation typically require additional optical comments, which hinders device compactness. Herein, an air‐stable Tin(IV)‐based hybrid metal halide, (C10H9N2O)2SnCl6, composed of [C10H9N2O]+ cations and isolated [SnCl6]2− octahedra is reported. Notably, (C10H9N2O)2SnCl6 exhibits a robust birefringence of 0.50@550 nm that is evidently larger than those of commercially used crystals, which enables efficient modulation of polarized light. Moreover, it possesses a broad polarized blue emission in the range of 374–600 nm with a peak at 426 nm. Theoretical and structural studies reveal that the high optical anisotropy for large birefringence and directly polarized emission of (C10H9N2O)2SnCl6 is ascribed to the cooperative effect of distortion of [SnCl6]2− and high π‐conjugation of [C10H9N2O]+ in parallel arrangement. This work may provide new thoughts on designing and realizing the miniaturization of polarization‐resolved optoelectronic devices.

Oriented Growth of Highly Emissive Manganese Halide Microrods for Dual‐Mode Low‐Loss Optical Waveguides

Zero‐dimensional (0D) structured lead‐free metal halides have recently attracted widespread attention due to their high photoluminescence quantum yield (PLQY) and negligible self‐absorption, showing enormous potential as optical waveguides towards miniaturized photonic devices. However, due to the great difficulty in growth of rod‐like nano/micro‐sized morphologies, such applications have been less explored. Herein, a new‐type emissive organic‐inorganic manganese (II) halide crystal (TPS2MnCl4, TPS = C18H15S, triphenylsulfonium) in the form of microrods is synthesized via a facile chloride ion (Cl‐) induced oriented growth method. Due to a combination of attractive features such as a high PLQY of 86%, negligible self‐absorption and smooth crystal surface, TPS2MnCl4 microrods are well suited for use in optical waveguide with an ultra‐low optical loss coefficient of 1.20·10‐4 dB μm‐1, superior to that of most organic‐inorganic metal halide hybrids, organic materials, polymers and metal nanoclusters to the best of our knowledge. Importantly, TPS2MnCl4 microrods can further work as dual‐mode optical waveguides, combining active and passive light transmission functionalities in one single crystal. In addition, TPS2MnCl4 microrods also display remarkable performance in lighting and anti‐counterfeiting due to their distinct optical properties and commendable stability.

Reversible Local Protonation-Deprotonation: Tuning Stimuli-Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti-Counterfeiting and Encryption.

Precise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli-responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)-C12H16N2)ZnBr4 ((R/S-LH2)ZnBr4) and monoprotonated ((R/S)-C12H15N2)2ZnBr4 ((R/S-LH1)2ZnBr4), derived from the chiral organic amine (R/S)-2,3,4,9-Tetrahydro-1H-carbazol-3-amine ((R/S)-C12H14N2). These compounds showcase luminescent properties; the zero-dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo-layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation-deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation-deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli-responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications in information storage, anti-counterfeiting, and information encryption.

Reversible Local Protonation‐Deprotonation: Tuning Stimuli‐Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti‐Counterfeiting and Encryption

AbstractPrecise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli‐responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)‐C12H16N2)ZnBr4 ((R/S‐LH2)ZnBr4) and monoprotonated ((R/S)‐C12H15N2)2ZnBr4 ((R/S‐LH1)2ZnBr4), derived from the chiral organic amine (R/S)‐2,3,4,9‐Tetrahydro‐1H‐carbazol‐3‐amine ((R/S)‐C12H14N2). These compounds showcase luminescent properties; the zero‐dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo‐layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation‐deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation‐deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli‐responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications in information storage, anti‐counterfeiting, and information encryption.

Oriented Growth of Highly Emissive Manganese Halide Microrods for Dual-Mode Low-Loss Optical Waveguides.

Zero-dimensional (0D) structured lead-free metal halides have recently attracted widespread attention due to their high photoluminescence quantum yield (PLQY) and negligible self-absorption, showing enormous potential as optical waveguides towards miniaturized photonic devices. However, due to the great difficulty in growth of rod-like nano/micro-sized morphologies, such applications have been less explored. Herein, a new-type emissive organic-inorganic manganese (II) halide crystal (TPS2MnCl4, TPS = C18H15S, triphenylsulfonium) in the form of microrods is synthesized via a facile chloride ion (Cl-) induced oriented growth method. Due to a combination of attractive features such as a high PLQY of 86%, negligible self-absorption and smooth crystal surface, TPS2MnCl4 microrods are well suited for use in optical waveguide with an ultra-low optical loss coefficient of 1.20·10-4 dB μm-1, superior to that of most organic-inorganic metal halide hybrids, organic materials, polymers and metal nanoclusters to the best of our knowledge. Importantly, TPS2MnCl4 microrods can further work as dual-mode optical waveguides, combining active and passive light transmission functionalities in one single crystal. In addition, TPS2MnCl4 microrods also display remarkable performance in lighting and anti-counterfeiting due to their distinct optical properties and commendable stability.

Mechanical and Ionic Characterization for Organic Semiconductor-Incorporated Perovskites for Stable 2D/3D Heterostructure Perovskite Solar Cells.

Hybrid metal halide perovskite (MHP) materials, while being promising for photovoltaic technology, also encounter challenges related to material stability. Combining 2D MHPs with 3D MHPs offers a viable solution, yet there is a gap in the understanding of the stability among various 2D materials. The mechanical, ionic, and environmental stability of various 2D MHP ligands are reported, and an improvement with the use of a quater-thiophene-based organic cation (4TmI) that forms an organic-semiconductor incorporated MHP structure is demonstrated. It is shown that the best balance of mechanical robustness, environmental stability, ion activation energy, and reduced mobile ion concentration under accelerated aging is achieved with the usage of 4TmI. It is believed that by addressing mechanical and ion-based degradation modes using this built-in barrier concept with a material system that also shows improvements in charge extraction and device performance, MHP solar devices can be designed for both reliability and efficiency.