Search Results (42)

Low-dimensional organic–inorganic hybrid metal halides (OIMHs) have garnered significant research attention due to their remarkable optical, electrical, and mechanical properties. These materials feature tunable optoelectronic characteristics, high photovoltaic efficiency, exceptional scalability and processability and ease of fabrication. By selecting appropriate organic and inorganic components, it is possible to achieve molecular-level dimensional control of the metal halides. Here, this review provides an in-depth analysis of the structure and synthesis methods of OIMHs materials, explores their optical properties, and summarizes their current applications in areas such as white-light LEDs, X-ray detectors, sensors, and solar cells. Finally, we also discuss the challenges faced by these materials and offer a perspective on their future development, aiming to serve as a reference for advancing research in OIMHs. Full article

Stimulus-responsive inorganic–organic hybrid metal halides (IOMHs) have shown great potential in applications such as sensing and anti-counterfeiting. IOMHs can undergo a variety of structural changes when triggered by humidity; however, relevant reports of structural dimensionality change from zero dimension (0D) to one dimension (1D) are rare. This study investigates the synthesis, structure, and properties of two antimony-based IOMHs, namely 0D-(Mp)₃SbCl₆·MeCN and 1D-(Mp)₂SbCl₅ (Mp = protonated morpholine; MeCN = acetonitrile). Photophysical characterizations show that (Mp)₃SbCl₆·MeCN, when being excited at 375 nm, exhibits typical self-trapped exciton triplet state broad-band emission, with a peak at 620 nm and a quantum yield as high as 75.06%. Under humid conditions, the 0D structure of (Mp)₃SbCl₆·MeCN undergoes a phase transition, leading to the 1D structure of (Mp)₂SbCl₅. This transition is accompanied by fluorescence quenching. X-ray powder diffraction, Raman spectroscopy, and thermogravimetric analysis confirm the phase transition process and its reversibility. Based on the high contrast of fluorescence before and after phase transition, (Mp)₃SbCl₆·MeCN is demonstrated as an ideal material for fluorescence water sensing, capable of detecting trace amounts of water in tetrahydrofuran with a detection limit of 0.2% v/v. Full article

The reaction between the iminophosphorane ligand N-phenyl-1,1,1-triphenylphosphanimine (NPh=PPh₃) and anhydrous manganese(II) halides allowed the isolation of complexes with the general formula [MnX₂(NPh=PPh₃)₂] (X = Cl, Br, I). The compounds showed luminescence in the green region attributed to the ⁴T₁(⁴G)→⁶A₁(⁶S) transition of the metal centre in the tetrahedral field, which was superimposed in the cases of X = Cl and X = Br on weak ligand-centred fluorescence. The emission and excitation spectra were compared with those of the free ligand and of the related zinc(II) bromo-complex. DFT calculations on the free ligand and on the manganese(II) bromo-complex helped to rationalise the experimental data. The protonation of NPh=PPh₃ led to the formation of the iminium cation [NHPh=PPh₃]⁺, which was used as a building block for the synthesis of organic–inorganic hybrids with the general formula [NHPh=PPh₃]₂[MnX₄] (X = Cl, Br, I). The crystal structure of [NHPh=PPh₃]₂[MnBr₄] was determined by means of X-ray diffraction. Green photoluminescence associated with the metal-centred transition was also observed for the organic–inorganic hybrids, with higher quantum yields with respect to the neutral [MnX₂(NPh=PPh₃)₂] complexes. In the case of X = I, luminescence from the cation was superimposed on that from the tetraiodomanganate anion upon excitation of the compound with near–UV light. Full article

Metallosurfactants combine the unique soft-matter properties of surfactants with magnetic functionalities of metal ions. The inclusion of iron-based species, in particular, can further boost the functionality of the material, owing to iron’s ability to adopt multiple oxidation states and form both high-spin and low-spin complexes. Motivated by this, a series of hybrid inorganic-organic dodecylpyridinium metallosurfactants with iron-containing counterions was developed. It was established that using either divalent or trivalent iron halides in a straightforward synthetic procedure yields C₁₂Py-metallosurfactants with distinct complex counterions: (C₁₂Py)₂[Fe₂X₆O] and (C₁₂Py)[FeX₄] (X = Cl or Br), respectively. A combination of techniques—including conductometry, dynamic and electrophoretic light scattering, single-crystal and thermogravimetric analysis, and magnetic measurements—provided in-depth insights into their solution and solid-state properties. The presence of different iron-based counterions significantly influences the crystal structure (interdigitated vs. non-interdigitated bilayers), magnetic properties (paramagnetic vs. nonmagnetic singlet ground state), and self-assembly (vesicles vs. micelles) of the dodecylpyridinium series. To our knowledge, this is the first report on the synthesis and characterization of hybrid organic-inorganic metallosurfactants containing the μ-oxo-hexahalo-diferrate anion. Full article

Dosimetry is crucial in radiotherapy to warrant safe and correct treatment. In FLASH radiotherapy, where ultra-high dose rates (UHDRs) are used, the dosimetric demands are more stringent, requiring the development and investigation of new dosemeters. In this study, three prototype fiber-optic dosemeters (FODs)—an inorganic, an organic–inorganic hybrid metal halide, and an organic (plastic) scintillator are optimized and investigated for UHDR electron irradiations. The plastic FOD is developed by Medscint, whereas the others are in-house made. The stem signal is minimized by spectral decomposition for the plastic scintillator, and by band-pass wavelength filters for the inorganic and organic–inorganic hybrid metal halide FOD. All prototypes are tested for the dose rate defining parameters. The optimal band-pass wavelength filters are found to be centered around 500 nm and 425 nm for the inorganic and organic–inorganic hybrid metal halide FODs, respectively. A sampling frequency of 1000 Hz is chosen for the inorganic and organic–inorganic hybrid metal halide FODs. The plastic FOD shows to be the least dose rate dependent with maximum deviations of 3% from the reference for the relevant beam settings. The inorganic and organic–inorganic hybrid metal halide FODs, in contrast, show large deviations of >10% from the reference and require more investigation. The current FOD prototypes are insufficient for application in UHDR electron beams, and require further development and investigation. Full article

Organic–inorganic hybrid metal halide perovskites are poised to revolutionize the next generation of photovoltaics with their exceptional optoelectronic properties and compatibility with low-cost and large-scale fabrication methods. Since perovskite tends to degrade over short time intervals due to various parameters (oxygen, humidity, light, and temperature), advanced characterization methods are needed to understand their degradation mechanisms. In this context, investigation of the electrical and optoelectronic properties of several perovskite mini-modules was performed by means of photo- and electroluminescence imaging as well as Dark Lock-In Thermography methods. Current–voltage curves at periodic time intervals and External Quantum Efficiency measurements were implemented alongside other measurements to reveal correlations between the electrical and radiative properties of the solar cells. The different imaging techniques used in this study reveal the changes in radiative emission processes and how those are correlated with performance. Alongside the indoor optoelectronic characterization of perovskite reference samples, the outdoor monitoring of two perovskite modules of the same structure for 23 weeks is reported. Significant performance degradation is presented outdoors from the first week of testing for both samples under test. The evolution of the major electrical characteristics of the mini-modules and the diurnal changes were studied in detail. Finally, dark storage recovery studies after outdoor exposure were implemented to investigate changes in the major electrical parameters. Full article

Recently, the utilization of metal halide perovskites in sensing and their application in environmental studies have reached a new height. Among the different metal halide perovskites, cesium lead halide perovskites (CsPbX₃; X = Cl, Br, and I) and composites have attracted great interest in sensing applications owing to their exceptional optoelectronic properties. Most CsPbX₃ nanostructures and composites possess great structural stability, luminescence, and electrical properties for developing distinct optical and photonic devices. When exposed to light, heat, and water, CsPbX₃ and composites can display stable sensing utilities. Many CsPbX₃ and composites have been reported as probes in the detection of diverse analytes, such as metal ions, anions, important chemical species, humidity, temperature, radiation photodetection, and so forth. So far, the sensing studies of metal halide perovskites covering all metallic and organic–inorganic perovskites have already been reviewed in many studies. Nevertheless, a detailed review of the sensing utilities of CsPbX₃ and composites could be helpful for researchers who are looking for innovative designs using these nanomaterials. Herein, we deliver a thorough review of the sensing utilities of CsPbX₃ and composites, in the quantitation of metal ions, anions, chemicals, explosives, bioanalytes, pesticides, fungicides, cellular imaging, volatile organic compounds (VOCs), toxic gases, humidity, temperature, radiation, and photodetection. Furthermore, this review also covers the synthetic pathways, design requirements, advantages, limitations, and future directions for this material. Full article

Perovskite-based metal oxide phototransistors have emerged as promising photodetection devices owing to the superior optoelectronic properties of perovskite materials and the high carrier mobility of metal oxides. However, high dark current has been one major problem for this type of device. Here, we studied the dark current behaviors of phototransistors fabricated based on the Indium Gallium Zinc Oxide (IGZO) channel and different perovskite materials. We found that depositing organic–inorganic hybrid perovskites materials (MAPbI₃/FAPbI₃/FA_0.2MA_0.8PbI₃) on top of IGZO transistor can increase dark current from ~10⁻⁶ mA to 1~10 mA. By contrast, we observed depositing an inorganic perovskite material, CsPbI₃, incorporated with PCBM additive can suppress the dark current down to ~10⁻⁶ mA. Our study of ion migration reveals that ion migration is pronounced in organic–inorganic perovskite films but is suppressed in CsPbI₃, particularly in CsPbI₃ mixed with PCBM additive. This study shows that ion migration suppression by the exclusion of organic halide and the incorporation of PCBM additive can benefit low dark current in perovskite phototransistors. Full article

As derivatives of metal halide perovskite materials, low-dimensional metal halide materials have become important materials that have attracted much attention in recent years. As one branch, zinc-based metal halides have the potential for practical applications due to their lead-free, low-toxicity and high-stability characteristics. However, pure zinc-based metal halide materials are still limited by their poor optical properties and cannot achieve large-scale practical applications. Therefore, in this work, we report an organic–inorganic hybrid zero-dimensional zinc bromide, (TDMP)ZnBr₄, using transition metal Mn²⁺ ions as dopants and incorporating them into the (TDMP)ZnBr₄ lattice. The original non-emissive (TDMP)ZnBr₄ exhibits bright green emission under the excitation of external UV light after the introduction of Mn²⁺ ions with a PL peak position located at 538 nm and a PLQY of up to 91.2%. Through the characterization of relevant photophysical properties and the results of theoretical calculations, we confirm that this green emission in Mn²⁺:(TDMP)ZnBr₄ originates from the ⁴T₁ → ⁶A₁ optical transition process of Mn²⁺ ions in the lattice structure, and the near-unity PLQY benefits from highly localized electrons generated by the unique zero-dimensional structure of the host material (TDMP)ZnBr₄. This work provides theoretical guidance and reference for expanding the family of zinc-based metal halide materials and improving and controlling their optical properties through ion doping. Full article

Organic–inorganic hybrid halides and their analogs that exhibit efficient broadband emission from self-trapped excitons (STEs) offers an unique pathway towards realization of highly efficient white light sources for lighting applications. An appropriate dilution of ns² ions into a halide host is essential to produce auxiliary emissions. However, the realization of ns² cation-based halides phosphor that can be excited by blue light-emitting diode (LED) is still rarely reported. In this study, a zero-dimensional Te-based single crystal (C₈H₂₀N)₂TeCl₆ was synthesized, which exhibits a yellow-orange emission centered at 600 nm with a full width at half maximum of 130 nm upon excitation under 437 nm. Intense electron–phonon coupling was confirmed in the (C₈H₂₀N)₂TeCl₆ single crystal and the light emitting mechanism is comprehensively discussed. The results of this study are pertinent to the emissive mechanism of Te-based hybrid halides and can facilitate discovery of unidentified metal halides with broadband excitation features. Full article

Organometal halide perovskites have achieved great success in solution-processed photovoltaics. The explorations quickly expanded into other optoelectronic applications, including light-emitting diodes, lasers, and photodetectors. An in-depth analysis of the special scale effects is essential to understand the working mechanisms of devices and optimize the materials towards an enhanced performance. Generally speaking, organometal halide perovskites can be classified in two ways. By controlling the morphological dimensionality, 2D perovskite nanoplatelets, 1D perovskite nanowires, and 0D perovskite quantum dots have been studied. Using appropriate organic and inorganic components, low-dimensional organic–inorganic metal halide hybrids with 2D, quasi-2D, 1D, and 0D structures at the molecular level have been developed and studied. This provides opportunities to investigate the scale-dependent properties. Here, we present the progress on the characteristics of scale effects in organometal halide perovskites in these two classifications, with a focus on carrier diffusion, excitonic features, and defect properties. Full article

Organic–inorganic metal halide perovskite (OIMHP) has emerged as a promising material for solar cell application due to their outstanding optoelectronics properties. The perovskite-based solar cell (PSC) demonstrates a significant enhancement in efficiency of more than 20%, with a certified efficiency rating of 23.13%. Considering both the Shockley limit and bandgap, there exists a substantial potential for further efficiency improvement. However, stability remains a significant obstacle in the commercialization of these devices. Compared to organic carrier transport layers (CTLs), inorganic material such as ZnO, TiO₂, SnO₂, and NiO_X offer the advantage of being deposited using atomic layer deposition (ALD), which in turn improves the efficiency and stability of the device. In this study, methylammonium lead iodide (MAPbI₃)-based cells with inorganic CTL layers of SnO₂ and NiO_X are simulated using SCAPS-1D software. The cell structure configuration comprises ITO/SnO₂/CH₃NH₃PbI₃/NiO_X/Back contact where SnO₂ and NiO_X act as ETL and HTL, respectively, while ITO is a transparent front-end electrode. Detailed investigation is carried out into the influence of various factors, including MAPbI₃ layer size, the thickness of CTLs, operating temperature parasitic resistance, light intensity, bulk defects, and interfacial defects on the performance parameters. We found that the defects in layers and interface junctions greatly influence the performance parameter of the cell, which is eliminated through an ALD deposition approach. The optimum size of the MAPbI₃ layer and CTL was found to be 400 nm and 50 nm, respectively. At the optimized configuration, the PSC demonstrates an efficiency of 22.13%, short circuit current (JSC) of 20.93 mA/m², open circuit voltage (V_OC) of 1.32 V, and fill factor (FF) of 70.86%. Full article

In recent years, all-inorganic cesium lead halide perovskite quantum dots have emerged as promising candidates for various optoelectronic applications, including sensors, light-emitting diodes, and solar cells, owing to their exceptional photoelectric properties. However, their commercial utilization has been limited by stability issues. In this study, we addressed this challenge by passivating the surface defects of CsPbBr₃ quantum dots using indium acetate, a metal–organic compound. The resulting CsPbBr₃ quantum dots exhibited not only high photoluminescence intensity, but also a remarkably narrow half-peak width of 19 nm. Furthermore, by embedding the CsPbBr₃ quantum dots in ethylene-vinyl acetate, we achieved stretchability and significantly enhanced stability while preserving the original luminous intensity. The resulting composite film demonstrated the potential to improve the power conversion efficiency of crystalline silicon solar cells and enabled the creation of excellent white light-emitting diodes with coordinates of (0.33, 0.31). This co-passivation strategy, involving surface passivation and polymer packaging, provides a new idea for the practical application of CsPbBr₃ quantum dots. Full article

Hybrid organic–inorganic iodides based on Bi(III) and Sb(III) provide integrated functionalities through the combination of high dielectric constants, semiconducting properties and ferroic phases. Here, we report a pyrrolidinium-based bismuth (1) and antimony (2) iodides of (NC₄H₁₀)₃[M₂I₉] (M: Bi(III), Sb(III)) formula which are ferroelastic at room temperature. The narrow band gaps (~2.12 eV for 1 and 2.19 eV for 2) and DOS calculations indicate the semiconducting characteristics of both materials. The crystal structure consists of discrete, face-sharing bioctahedra [M₂I₉]³⁻ and disordered pyrrolidinium amines providing charge balance and acting as spacers between inorganic moieties. At room temperature, 1 and 2 accommodate orthorhombic Cmcm symmetry. 1 displays a complex temperature-induced polymorphism. It is stable up to 525 K and undergoes a sequence of low-temperature phase transitions (PTs) at 221/222 K (I ↔ II) and 189/190 K (II ↔ III) and at 131 K (IV→III), associated with the ordering of pyrrolidinium cations and resulting in Cmcm symmetry breaking. 2 undergoes only one PT at T = 215 K. The dielectric studies disclose a relaxation process in the kilohertz frequency region, assigned to the dynamics of organic cations, described well by the Cole–Cole relation. A combination of single-crystal X-ray diffraction, synchrotron powder diffraction, spin–lattice relaxation time of ¹H NMR, dielectric and calorimetric studies is used to determine the structural phase diagram, cation dynamics and electric properties of (NC₄H₁₀)₃[M₂I₉]_. Full article

In metal halide perovskites, charge transport in the bulk of the films is influenced by trapping and release and nonradiative recombination at ionic and crystal defects. Thus, mitigating the formation of defects during the synthesis process of perovskites from precursors is required for better device performance. An in-depth understanding of the nucleation and growth mechanisms of perovskite layers is crucial for the successful solution processing of organic–inorganic perovskite thin films for optoelectronic applications. In particular, heterogeneous nucleation, which occurs at the interface, must be understood in detail, as it has an effect on the bulk properties of perovskites. This review presents a detailed discussion on the controlled nucleation and growth kinetics of interfacial perovskite crystal growth. Heterogeneous nucleation kinetics can be controlled by modifying the perovskite solution and the interfacial properties of perovskites adjacent to the underlaying layer and to the air interface. As factors influencing the nucleation kinetics, the effects of surface energy, interfacial engineering, polymer additives, solution concentration, antisolvents, and temperature are discussed. The importance of the nucleation and crystal growth of single-crystal, nanocrystal, and quasi-two-dimensional perovskites is also discussed with respect to the crystallographic orientation. Full article