Hybrid Organic-inorganic Metal Halide Research Articles

Mn-Doped M2CdCl4 (M = CH3NH3+, C2H8N+, and C3H10N+) Layered Hybrid Perovskite and Its Flexible Film Based on Simple Mechanochemical Synthesis.

Layered hybrid perovskites show significant advantages in the field of optoelectronics. However, the low quantum efficiency and complex preparation methods limit their applications. In this work, we developed a series of perovskite powders with a two-dimensional (2D) layered structure of organic-inorganic hybrid metal halides M2CdCl4:x%Mn (M = CH3NH3+, C2H8N+, C3H10N+) via facile mechanochemical methods. The prepared manganese Mn-doped MA2CdCl4 produces orange emission at 605 nm under both 254 and 420 nm excitation, which originates from a dual excitation channel competition mechanism, and its excitation channel could be changed with the increase of Mn2+ ion concentration. Typically, MA2CdCl4:20%Mn powder exhibits high photoluminescence quantum yield (PLQY) close to 90% at 605 nm due to the organic amine ions enlarging the Mn-Mn interlayer distances. In addition, we prepared MA2CdCl4:x%Mn@PVA flexible films, which also exhibit good luminescence at 254 nm excitation and were unexpectedly found to have a better response to Cs+, which could be a candidate for anticounterfeiting applications.

Near-Unity Green Luminescent Hybrid Manganese Halides as X-ray Scintillators.

The increasing demands in optoelectronic applications have driven the advancement of organic-inorganic hybrid metal halides (OIMHs), owing to their exceptional optical and scintillation properties. Among them, zero-dimensional (0D) low-toxic manganese-based scintillators have garnered significant interest due to their exceptional optical transparency and elevated photoluminescence quantum yields (PLQYs), making them promising for colorful light-emitting diodes and X-ray imaging applications. In this study, two OIMH single crystals of (Br-PrTPP)2MnBr4 (Br-PrTPP = (3-bromopropyl) triphenylphosphonium) and (Br-BuTPP)2MnBr4 (Br-BuTPP = (4-bromobutyl) triphenylphosphonium) were prepared via a facile saturated crystallization method. Benefiting from the tetrahedrally coordinated [MnBr4]2- polyhedron, both of them exhibited strong green emissions peaked at 517 nm owing to the d-d electron transition of Mn2+ with near-unity PLQYs of 99.33 and 86.85%, respectively. Moreover, benefiting from the high optical transparencies and remarkable luminescence properties, these manganese halides also exhibit excellent radioluminescent performance with the highest light yield of up to 68,000 photons MeV-1, negligible afterglow (0.4 ms), and linear response to X-ray dose rate with the lowest detection limit of 45 nGyair s-1. In X-ray imaging, the flexible film made by the composite of (Br-PrTPP)2MnBr4 and PDMS shows an ultrahigh spatial resolution of 12.78 lp mm-1, which provides a potential visualization tool for X-ray radiography.

From C4H7N2Ge0.4Sn0.6Br3 to C6H11N2Ge0.4Sn0.6Br3: Effective Modulation of the Second Harmonic Generation Effect and Optical Band Gap by Planar π-Conjugated Organic Cation Size.

In the search for nonlinear optical (NLO) materials with excellent overall performance, we have devoted ourselves to organic-inorganic hybrids consisting of anionic groups containing stereochemically active lone-pair (SCALP) electron cations and organic planar π-conjugated group cations. Accordingly, in this paper, two novel organic-inorganic hybrid metal halides, C4H7N2Ge0.4Sn0.6Br3 (I) and C6H11N2Ge0.4Sn0.6Br3 (II), have been synthesized. The powder second-harmonic technique shows that both C4H7N2Ge0.4Sn0.6Br3 and C6H11N2Ge0.4Sn0.6Br3 have moderately strong second-order nonlinear optical effects, which are about 2.03 (I) and 1.16 (II) times that of KH2PO4 (KDP), respectively. They also have different optical band gaps of 2.75 (I) and 2.88 eV (II) due to the different sizes of the organic cations, and their photoluminescent and thermal properties were also investigated. This work provides new structural insights for the design and modulation of organic-inorganic hybrid halide materials with multiple excellent optical properties.

Synthesis and Characterization of New Hybrid Organic-Inorganic Metal Halides [(CH3)3SO]M2I3 (M = Cu and Ag).

Recently, all-inorganic copper(I) metal halides have emerged as promising optical materials due to their high light emission efficiencies. This work details the crystal structure of the two hybrid organic-inorganic metal halides [(CH3)3SO]M2I3 (M = Cu and Ag) and their alloyed derivatives [(CH3)3SO]Cu2-xAgxI3 (x = 0.2; 1.25), which were obtained by incorporating trimethylsulfoxonium organic cation (CH3)3SO+ in place of Cs+ in the yellow-emitting all-inorganic CsCu2I3. These compounds are isostructural and centrosymmetric with the space group Pnma, featuring one-dimensional edge-sharing [M2I3]- anionic double chains separated by rows of (CH3)3SO+ cations. Based on density functional theory calculations, the highest occupied molecular orbitals (HOMOs) of [(CH3)3SO]M2I3 (M = Cu and Ag) are dominated by the Cu or Ag d and I p orbitals, while the lowest unoccupied molecular orbitals (LUMOs) are Cu or Ag s and I p orbitals. [(CH3)3SO]Cu2I3 single crystals exhibit a semiconductor resistivity of 9.94 × 109 Ω·cm. Furthermore, a prototype [(CH3)3SO]Cu2I3 single-crystal-based X-ray detector with a detection sensitivity of 200.54 uCGy-1 cm-2 (at electrical field E = 41.67 V/mm) was fabricated, indicating the potential use of [(CH3)3SO]Cu2I3 for radiation detection applications.

Efficient Deep‐Blue Light‐Emitting 2D (100)‐Oriented Perovskites and Spectral Broadening by Exciton Self‐Trapping for White‐light Emissions

AbstractEfficient narrow deep‐blue and broadband emissions in layered 2D organic–inorganic hybrid metal halide perovskites (MHPs) are attracting more attention and need further study. In this work, two (100)‐oriented 2D organic‐inorganic hybrid MHPs of (TFI)2PbBr4 and (TFI)2PbCl4·H2O (TFI = 4‐(trifluoromethyl)‐1H‐imidazole) with efficient deep‐blue and bluish‐white emissions are synthesized and the photoluminescence quantum yields (PLQYs) reached up to 81.21% and 20.23%, respectively. As both intrinsic lattice distortions of two crystals with similar crystal structure are almost negligible, they have theoretical deep‐blue emissions empirically. However, the halogen substitution of chlorine (Cl) by bromine (Br) broadened the deep‐blue photoluminescence to a bluish‐white area. Here, the spectral broadening phenomenon is discussed in detail. The (TFI)2PbBr4 film shows a narrow emission with a 16 nm full width at half maximum (FWHM) peaking at 435 nm upon excitation, and an ultraviolet‐pumped light‐emitting diode (LED) prepared by bluish‐white (TFI)2PbCl4·H2O phosphor shows a color rendering index (CRI) of ≈93 and a related color temperature (CCT) of 4162K, indicating their potential applications in deep‐blue and white LEDs, respectively.

Giant Apparent Optical Circular Dichroism in Thin Films of Bismuth‐Based Hybrid Organic–Inorganic Metal Halide Semiconductor Through Preferred Orientation

AbstractIntroducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self‐assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)‐4‐methoxy‐α‐methylbenzylammonium, is incorporated to synthesize the bismuth‐based hybrid organic–inorganic metal halide semiconductor, (R/S‐MeOMePMA)BiI4. Thin films of this Bi‐based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ≈0.1, close to the highest value observed in another chiral metal‐halide semiconductor, (R‐MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S‐MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin‐film orientation enables the control of gCD, with maximum value observed when its thin film has a well‐crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal–halide materials and provides design rules for achieving large chiroptical response via morphology control.

Antimony Doped Hybrid Zinc Halide Crystals with Tunable Light Emission and Long‐Term Stability

AbstractAs a class of emerging photoluminescent materials, hybrid halide crystals have drawn research attention for their potential application in the fields of light‐emitting, security, and waveguide. Nevertheless, hybrid halide crystals containing antimony with long‐term stability and tunable light emission are still increasingly in demand. In this work, serial new hybrid halide crystals (BZA)2ZnCl4·2H2O:xSb3+ (x = 0–0.2, x represents the reaction ratio) and (BZA)2SbCl5 are synthesized (BZA = 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine). In (BZA)2ZnCl4·2H2O:xSb3+ crystals, Sb3+ cations replace partial Zn2+ cations to form [SbCl4]− tetrahedron. Red light emission caused by the substitution of Sb3+ for Zn2+ enhances as the doping rate increases, resulting in the tunable emission from light blue to pink and finally to dark red. There are two kinds of Sb3+ in (BZA)2SbCl5 crystal. Sb(1) has a sixfold coordination with Cl to form a [Sb(1)Cl5]∞ 1D zigzag chain. Sb(2) atom adopts a fivefold coordination with Cl and is separated from each other by BZA+ cations. (BZA)2SbCl5 crystal shows bright orange‐yellow light emission with a photoluminescence quantum yield of 45%. Moreover, the organic–inorganic hybrid metal halide crystals containing antimony have excellent long‐term stability, with phase and luminescence keeping nearly unchanged after more than six months in ambient air.

Sb3+-Doped Indium-Based Metal Halide (Gua)3InCl6 with Efficient Yellow Emission.

In recent years, low-dimensional organic-inorganic hybrid metal halides (OIHMHs) have shown excellent photophysical properties due to their quantum structure, adjustable energy levels, and energy transfer between inorganic and organic components, which have attracted extensive attention from researchers. Herein, we synthesize a zero-dimensional (0D) OIHMH, Sb3+:(Gua)3InCl6, by introducing Sb3+ into (Gua)3InCl6, which undergoes a significant enhancement of the emission peak at 580 nm with the photoluminescence quantum yield (PLQY) boosted from 17.86 to 95.72% when excited at 340 nm. This boost in photoluminescence of the doped sample was studied by combining ultrafast femtosecond transient absorption, temperature-dependent photoluminescence (PL) spectra, and density functional theory (DFT) calculation, revealing the process of self-trapped exciton (STE) recombination to emit light at both Sb and In sites in this 0D structure simultaneously. This material with the lowest dark STE level at the In site for emission in the undoped sample can amazingly yield very strong emission in the doped sample, which has never been observed before. Finally, we tested its application in a photoelectric device. This work not only helps to gain a deeper understanding of the formation of STEs in In-based halides but also plays a certain guiding role in the design of new luminescent materials.

Recent developments in perovskite materials, fabrication techniques, band gap engineering, and the stability of perovskite solar cells

Organic-inorganic hybrid metal halide perovskite solar cells (PSC) represent a novel class of optoelectronic semiconductors that have garnered significant attention from photovoltaic researchers globally. This is due to their continually improving efficiency, straightforward solution processing methods, use of lightweight and cost-effective materials, and other notable features. The advantageous properties of perovskite materials, such as superior charge transport, tunable band gap, and distinctive electronic structure, contribute to their appeal. Over the past 6 to 7 years, diverse device architectures and fabrication techniques for PSC have emerged, achieving an impressive power conversion efficiency (PCE) of 25.7%. This review article primarily focuses on recent advancements in PSC fabrication techniques, synthesis, device architecture, charge transport mechanisms, band gap engineering, and stability. Additionally, it provides a summary of recently reported materials used in various layers of PSC, including the perovskite layer, as well as electron and hole transport layers. Lastly, the article outlines the challenges faced in the development of PSC, offers recommendations, and suggests potential directions for future research to guide the field forward.

Chiral zero-dimensional hybrid organic–inorganic metal halides based on nipecotic acid and tetrabromocuprate

Chiral 0D hybrid organic–inorganic metal halides with narrow bandgap and high thermal stability have been constructed from chiral amino acids and copper salt.

Highly efficient self-trapped exciton luminescence of Sb3+-doped (CH6N3)3BiCl6 for ethanol detection

Zero-dimensional (0D) organic–inorganic metal halide hybrids (MHHs) are considered promising luminescent materials due to their unique “host–guest” structure and tunable emission spectrum.

High-efficiency color-tunable ultralong room-temperature phosphorescence from organic-inorganic metal halides via synergistic inter/intramolecular interactions.

Materials exhibiting highly efficient, ultralong and multicolor-tunable room-temperature phosphorescence (RTP) are of practical importance for emerging applications. However, these are still very scarce and remain a formidable challenge. Herein, using precise structure design, several novel organic-inorganic metal-halide hybrids with efficient and ultralong RTP have been developed based on an identical organic cation (A). The original organic salt (ACl) exhibits red RTP properties with low phosphorescence efficiency. However, after embedding metals into the organic salt, the changed crystal structure endows the resultant metal-halide hybrids with excellent RTP properties. In particular, A2ZnCl4·H2O exhibits the highest RTP efficiency of up to 56.56% with a long lifetime of up to 159 ms. It is found that multiple inter/intramolecular interactions and the strong heavy-atom effect of the rigid metal-halide hybrids can suppress molecular motion and promote the ISC process, resulting in highly stable and localized triplet excitons followed by highly efficient RTP. More crucially, multicolor-tunable fluorescence and RTP achieved by tuning the metal and halogen endow these materials with wide application prospects in the fields of multilevel information encryption and dynamic optical data storage. The findings promote the development of phosphorescent metal-halide hybrids for potential high-tech applications.

Zero-dimensional hybrid tin halides with stable broadband light emissions.

Considering the instability and toxicity of 3D Pb-based perovskite nanocrystals, lead-free low-dimensional organic-inorganic hybrid metal halides have attracted widespread attention as potential substitutes. Herein, two new tin-based 0D halides [H4BAPP]SnBr5·Br and [H4BAPP]SnCl5·Cl·H2O (BAPP = 1,4-bis(3-aminopropyl)piperazine) were synthesized successfully based on [SnX5]3- as an emission center. Typically, [H4BAPP]SnBr5·Br and [H4BAPP]SnCl5·Cl·H2O display broadband yellow and yellow-green light emissions originating from the radiative recombination of self-trapped excitons (STEs). The photoluminescence quantum yields (PLQYs) of the two compounds were calculated to be 19.27% and 2.36%, respectively. Furthermore, the excellent chemical and thermal stability and broadband light emissions reveal their potential application in solid-state white lighting diodes.

Tellurium(IV) Halide Achieving Effective Nonlinear-Optical Activity: The Role of Chiral Ligands and Lattice Distortion.

Chiral organic-inorganic hybrid metal halides are a promising class of nonlinear-optical materials with unique optical properties and flexible crystal structures. However, the structures and properties of chiral hybrid tellurium halides, especially second harmonic generation (SHG), have not been reported. Here, by introducing chiral organic molecule (R/S)-methylbenzylammonium (R/S-MBA), we synthesized a pair of novel zero-dimensional (0D) chiral tellurium-based hybrid halides with noncentrosymmetric space group C2, (R/S-MBA)2TeCl6 (R/S-Cl). Single-crystal X-ray diffraction analysis and solid-state circular dichroism (CD) spectra confirm that R/S-Cl shows obvious enantiomer enrichment. Moreover, the resulting chiral products present an efficient SHG response. Interestingly, through manipulation of halogen atoms, two pairs of achiral tellurium halides, (R/S-MBA)2TeBr6 (R/S-Br) and (R/S-MBA)2TeI6 (R/S-I), were obtained, both of which crystallize in the centrosymmetric space group R3̅. It is noteworthy that R/S-I has a narrow band gap of 1.55 eV, which is smaller than that of most 0D metal halides and comparable to that of three-dimensional lead halide, showing its potential as a highly efficient light absorber.

Efficient green emission in organic-inorganic hybrid (C13H22N)2MnCl4 metal halides with large Mn–Mn spacing distance

Organic-inorganic hybrid metal halides hold considerable potential for diverse applications, including light-emitting diodes, display diodes, liquid crystal displays, and photodetectors, owing to their exceptional optical properties. Herein, we successfully synthesized lead-free zero-dimensional (0D) (C13H22N)2MnCl4 metal halide single crystals with green emission, employing an anti-solvent method. The (C13H22N)2MnCl4 single crystals, featuring four-coordinated Mn2+, exhibit pronounced green emission at 528 nm and demonstrate a photoluminescence quantum yield (PLQY) of approximately 72 %. This emission is attributed to the 4T1(G)-6A1(S) transition and the considerable Mn–Mn spacing distance between adjacent [MnCl4]2- tetrahedra. The photoluminescence spectra during thermal cycling underscore the exceptional optical stability of the (C13H22N)2MnCl4 material. These organic-inorganic hybrid manganese halides emerge as a compelling and novel candidate for future light-emitting diode materials.

Antimony Bromide Organic-Inorganic Hybrid Compound with a Long-Chain Diamine Showing Switchable Phase Transition and Second-Harmonic Generation Properties.

Organic-inorganic hybrid metal halides have attracted significant attention in recent years due to their excellent optoelectronic properties and potential applications in solar cells. Herein, the organic-inorganic hybrid molecule [N,N-dimethyl-1,3-propanediamine]SbBr5 (1) was synthesized by reacting a long-chain organic diamine N,N-dimethyl-1,3-propanediamine with SbBr3 as a metal halide precursor in HBr aqueous solution. Compound 1 possesses a one-dimensional chainlike structure with the second-harmonic generation switch and two continuous phase transitions above room temperature. The band gap of compound 1 is about 2.62 eV, exhibiting a semiconductive property, which may have important implications for the development of new optoelectronic devices.

Free Halogen Substitution of Chiral Hybrid Metal Halides for Activating the Linear and Nonlinear Chiroptical Properties.

Halogen substitution has been proven as an effective approach to the band gap engineering and optoelectronic modulation of organic-inorganic hybrid metal halide (OIHMH) materials. Various high-performance mixed halide OIHMH film materials have been primarily obtained through the substitution of coordinated halogens in their inorganic octahedra. Herein, we propose a new strategy of substitution of free halogen outside the inorganic octahedra for constructing mixed halide OIHMH single crystals with chiral structures, resulting in a boost of their linear and nonlinear chiroptical properties. The substitution from DMA4[InCl6]Cl (DMA = dimethylammonium) to DMA4[InCl6]Br crystals through a facile antisolvent vaporization method produces centimeter-scale single crystals with high thermal stability along with high quantum yield photoluminescence, conspicuous circularly polarized luminescence, and greatly enhanced second harmonic generation (SHG). In particular, the obtained DMA4[InCl6]Br single crystal features an intrinsic chiral structure, exhibiting a significant SHG circular dichroism (SHG-CD) response with a highest reported anisotropy factor (gSHG-CD) of 1.56 among chiral OIHMH materials. The enhancements in both linear and nonlinear chiroptical properties are directly attributed to the modulation of octahedral distortion. The mixed halide OIHMH single crystals obtained by free halogen substitution confine the introduced halogens within free halogen sites of the lattice, thereby ensuring the stability of compositions and properties. The successful employment of such a free halogen substitution approach may broaden the horizon of the regulation of structures and the optoelectronic properties of the OIHMH materials.

The effect of different halogen atoms on the rigid and energy transfer of organic cations

Low-dimensional organic-inorganic hybrid metal halides (OIMHs) have become an emerging class of light-emitting materials. Two zero-dimensional (0D) lead-free organic (EnrofloH2)4Mn3X12 (X = Cl, Br) has been reported in this work. Upon 338 and 340 nm excitation, (EnrofloH2)4Mn3Cl12·2Cl and (EnrofloH2)4Mn3Br12·2Br exhibit emission peaking at 460, 514 nm and 460, 520 nm respectively. It was noticed that the choice of the halide could profoundly govern the luminescent subjects (ENR or Mn2+) through the altered energy transfer. Different halogens could influence the rigidity of ENR organic cations by changing their stacking patterns and band gaps, thus manipulating their luminescent properties. The bandgap behaviors have been revealed by density functional theory calculations. Based on the results, the emission of both compounds come from organic cations (EnrofloH22+) and 4D-6A1 transition of Mn2+ ions. The spectral interplay of these emission bands is governed by the temperature and the possibility of exchanging mechanisms between two emission centers.

The Scale Effects of Organometal Halide Perovskites.

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.

Preliminary exploration of the influence of N+/NHx+ ions/groups bombardment at TiO2 ETLs on performance of MAPbI3 perovskite solar cells

The service stability of organic–inorganic hybrid metal halide perovskite solar cells (PSCs) is one of most important factors, which is seriously influenced by the decomposition of perovskite layer. Especially, the decomposition of perovskite layer could deteriorate the interface between perovskite layer and TiO2 electron transport layer (ETL). In this work, TiO2 ETLs are prepared by the sputtering technique and traditional spin-coating technique. Then, TiO2 ETLs are bombarded by N+/NHx+ ions/groups. PSCs with all TiO2 ETLs are prepared and measured. The results show that after bombardment, N+/NHx+ ions/groups could chemically react with Ti/O ions at surface of TiO2 ETLs. As a result, the conduction band minimum and transfer resistance of TiO2 ETLs both deteriorate, which decrease the power conversion efficiency of PSCs seriously. While, because anatase TiO2 (001) crystal face consists of saturated O/Ti ions and displays the highest surface free energy, TiO2 ETLs with anatase (001) preferred orientation displays the optimal restraint on deterioration of power conversion efficiency caused by N+/NHx+ ions/groups bombardment. Based on above results, TiO2 ETLs with anatase (001) preferred orientation should be the optimal one for PSCs, which could improve the service stability obviously.