Metal Halide Research Articles

Space-Charge-Limited Current Measurements: A Problematic Technique for Metal Halide Perovskites.

Space-charge-limited current (SCLC) measurements play a crucial role in the electrical characterization of semiconductors, particularly for metal halide perovskites. Accurate reporting and analysis of SCLC are essential for gaining meaningful insights into charge transport and defect density in these systems. Unfortunately, performing SCLC measurements on perovskites is complicated by their mixed electronic-ionic conductivity. This complexity led to SCLC data often being incorrectly analyzed using simplified models unsuitable for these materials and reported without essential information about how the measurements were performed. In light of recently published SCLC data, common challenges in using SCLC measurements on perovskite materials are addressed, and solutions are discussed in this paper. The applicability of the often-used analytical models, the overlooked issues related to the mixed ionic-electronic conductivity of perovskites, and the complexity of creating single-carrier devices are investigated using drift-diffusion simulations. Finally, guidelines for more accurate reporting and improved analysis are provided.

Advances and Challenges in Large-Area Perovskite Light-Emitting Diodes.

Metal halide perovskite light-emitting diodes (PeLEDs) have shown promise for high-definition displays and flat-panel lighting because of their wide color gamut, narrow emission band, and high brightness. The external quantum efficiency of PeLEDs increased rapidly from ≈1% to more than 25% in the past few years. However, most of these high-performance devices are fabricated using a spin coating method with a small device area of <0.1 cm2, limiting their commercial applications. Recently, large-area PeLEDs have attracted growing attention and significant breakthroughs have been reported. This perspective first introduces the pros and cons of each technique in making large-area PeLEDs. The advances in the fabrication of large-area PeLEDs are then summarized using spin coating and mass-production methods such as inkjet printing, blade coating, and thermal evaporation. Moreover, the challenging issues will be discussed that are urgent to be solved for large-area PeLEDs.

Structural Stability of Mixed‐Halide Perovskite Nanocrystals in Energy Storage: The Role of Iodine Expulsion

AbstractIn the pursuit of efficient optoelectronics devices, hybrid lead halide perovskite quantum dots (PQDs) have emerged as highly promising semiconductor materials due to their intriguing properties. While these materials have been used in many applications, the fundamental understanding of their behavior remains relatively unexplored, especially for the mixed halide perovskite samples. To facilitate the advancement of PQD technologies for commercial applications, it is essential to gain insights into the role of ion migration. This study delves into the fundamental aspects of ion migration in halide perovskite nanocrystals. Porous electrodes for supercapacitor application were fabricated using CsPbBr3–xIx (x=0,1,2) nanocrystals prepared via the ligand‐assisted re‐precipitation (LARP) method. Three‐electrode electrochemical measurements and several other characterizations were conducted under dark conditions to evaluate device performance and elucidate the impact of mixed halides on device kinetics and stability. X‐ray photoelectron spectroscopy before and after the electrochemical measurement reveals intriguing findings. Notably, the analysis uncovered the phase segregation in the metal halide perovskite nanocrystals with particular emphasis on CsPbBr2I due to its distinctive mixed‐halide behavior. The specific capacitance increases with the increasing cycles. Interestingly, as the iodide content increases, there is no selective halide expulsion as the structure collapses rapidly.

Highly stable and self-powered ultraviolet photodetector based on Dion-Jacobson phase lead-free double perovskite

Metal halide perovskite materials present a wide array of opportunities for the development of high-performance optoelectronic devices, owing to their outstanding photoelectric properties. Compared with the lead-containing perovskites, stable and non-toxic organic-inorganic hybrid perovskites exhibit enhanced potential for future commercial applications. In this work, we developed a self-powered UV photodetector based on 2D Dion−Jacobson (DJ) phase lead-free double perovskite HAAg0.5Bi0.5Br4 (HA2+ = histammonium) perovskite with an on-off ratio up to 2.66 × 106, excellent specific detectivity of 6 × 1012 Jones, and response speed of 1.32 ms/118.4 μs. The light intensity related pyro-phototronic effect on 2D perovskite is thoroughly investigated. Temperature and light detection are realized through multi-energy coupling, which greatly improves the detection performance. Coupled pyro-phototronic current is calculated nearly 75 folds higher than that from the photoelectronic merely. As-prepared photodetector film shows excellent stability in normal environment, maintaining a value of 90 % to the initial performance after 500 cycles and 90 days. This work provides a new self-powered, stable and non-toxic candidate for the future UV photodetectors.

UV-Curing Resin-Assisted Facile Synthesis of Lead-Free Zero-Dimensional Organic–Inorganic Hybrid Metal Halide Quantum Dots for Light-Emitting Application

UV-Curing Resin-Assisted Facile Synthesis of Lead-Free Zero-Dimensional Organic–Inorganic Hybrid Metal Halide Quantum Dots for Light-Emitting Application

Sb3+ dopant triggered highly efficient emission in zero-dimensional organic-inorganic hybrid metal halides.

Hybrid luminescent metal halides have attracted considerable attention for their structural diversity and versatility in photonic applications. Herein, we fabricate Sb3+ doped organic-inorganic hybrid metal halides (DMA)2CsInCl6 (DMA = [CH3NH2CH3]+) single crystal. Under ultraviolet light excitation, the crystals yield bright green emission at 550 nm with near-unity photoluminescence quantum efficiency (PLQY), which is attributed to the strong electronegativity and ns2 lone pairs of Sb3+ dopants. Given the slender rod-shaped semblance, bright green emission, near-unity PLQY, and large Stokes shift, Sb3+-doped (DMA)2CsInCl6 allows the potential optical waveguide applications.

Ions-induced Assembly of Perovskite Nanocomposites for Highly Efficient Light-Emitting Diodes with EQE Exceeding 30.

Metal halide perovskites, a cost-effective class of semiconductos, hold great promise for display technologies that demand high-efficiency, color-pure light-emitting diodes (LEDs). Early research on three-dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non-radiative recombination. Here, an ions-induced growth method is employed to assembe lattice-anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr3 and its variant of zero-dimensional (0D) Cs4PbBr6, to feature significant low trap-assisted nonradiative recombination, enhanced light out-coupling with a corrugated surface, and well-balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half-maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach.

Unlocking Enhanced Light Harvesting in Perovskites: A Light‐Mediated Ligand Management Approach

AbstractInterfaces between nanocrystals and their stabilizing ligands in light‐harvesting devices are crucial for mediating energy transfer, essential for efficient solar energy conversion. In metal halide perovskites, a promising material for these devices, Förster resonance energy transfer (FRET) within perovskite/acceptor‐molecule complexes offers a pathway for optimized energy transfer. However, traditional methods for optimizing FRET in perovskite‐chromophore hybrids are based on static modifications. This study presents an innovative approach for light‐driven dynamic control of FRET, achieving an ≈14% enhancement in efficiency between CsPbBr3 nanocrystals (CPB NCs) and rhodamine B isothiocyanate (RITC) dye. UV light is utilized to reversibly regulate NC‐ligand binding and thus control the coupling between CPB NCs and RITC at their interface. This approach critically relies on strong NC–ligand interactions, such as the Pb─S bond between CPB NCs and RITC. Light exposure weakens the binding of surface ligands, allowing RITC, with its strong bond, to attach more effectively and promote enhanced energy transfer. This light‐activated control is absent with Rhodamine B (RhB) lacking ─NCS group, a strong binding motif. The findings reveal the importance of NC–ligand interactions in dynamically manipulating FRET with light. This pioneering method for nanoscale FRET control paves the way for more efficient light‐harvesting devices.

Multicolor and multimode luminescent lanthanide-doped Cs2NaInCl6:Sb3+ from visible to near infrared for versatile applications

Double halide perovskites have shown admirable potential in promising optoelectronic applications due to simple synthesis, good stability and high structural tolerance. However, the poor optical properties caused by the parity-forbidden transitions posts a stringent limitation on their potential applications. Herein, we dope the lanthanide (Ln3+) ions with abundant energy levels into the Cs2NaInCl6:Sb3+ single crystals, which not only achieve multicolor visible emissions spectra from blue to red light, but also expand to the near infrared region from 800 to 1900 nm. In addition, the phosphors enable the multimode emissions with the up-conversion and down-conversion photoluminescence. Intriguingly, the excitation source, and the excitation light intensity also endow the multicolor emissions. Thus, combining with the multicolor and multimode luminescent properties, Cs2NaInCl6:Sb3+/Ln3+ could be applied to night vision imaging, substance detection, optical thermometry, white-light-emitting diodes (WLEDs) and anti-counterfeiting. The maximum value of relative temperature sensitivity reaches as high as 1.207 % K−1, which is relatively higher than those of most metal halide perovskites. Moreover, the single-source WLED displays Commission Internationale de L'Eclairage color coordinates (0.32, 0.31), a correlated color temperature of 6673 K, and color rendering index of 81.7. These results demonstrate the potential applications in the multifunctional photoelectric applications.

Modulation of electronic and magnetic characteristics of Ni and Cr-based transition metal halide monolayers using strain engineering

Modulation of electronic and magnetic characteristics of Ni and Cr-based transition metal halide monolayers using strain engineering

Experimental study on Na+ conductivity in NaAlBr4 and atomic-scale investigation of Na+ conduction

AbstractThe ionic conduction properties of Li/Na metal halides have been extensively studied, with recent attention turning towards Al-based systems. However, limited studies have focused on alkali Al bromides. In this study, we explored the Na+ conduction properties of NaAlBr4. Conductivity measurements at 30 °C revealed a Na+ conductivity of 1.2 × 10−5 S/cm, surpassing that of isostructural NaAlCl4 threefold. Molecular dynamics (MD) simulations to elucidate the conduction mechanisms revealed that Na+ conduction was not observed in stoichiometric NaAlBr4, which has high formation energies of Na+ vacancies and interstitials (0.88 eV and 0.73 eV, respectively). Nevertheless, a conductivity of 1.2 × 10−5 S/cm was observed. The activation energy for ion conduction was experimentally determined as 0.43 eV, and the migration energies were calculated as 0.26 eV (Na+ vacancies) and 0.16 eV (Na+ interstitials) by MD simulations. These discrepancies in ion conduction were partially explained by the role of transient defects enriched via ball milling in facilitating Na+ conduction on the particle surface, offering insights into the complex ion conduction of ball-milled NaAlBr4.

Antiferromagnetic Ordering in A One-Dimensional Organic Copper Chloride Hybrid Insulator.

Low dimensional (LD) organic metal halide hybrids (OMHHs) have recently emerged as new generation functional materials with exceptional structural and property tunability. Despite the remarkable advances in the development of LD OMHHs, optical properties have been the major functionality extensively investigated for most of LD OMHHs developed to date, while other properties, such as magnetic and electronic properties, remain significantly under-explored. Here, we report for the first time the characterization of the magnetic and electronic properties of a 1D OMHH, organic-copper (II) chloride hybrid (C8H22N2)Cu2Cl6. Owing to the antiferromagnetic coupling between Cu atoms through chloride bridges in 1D [Cu2Cl6 2-]∞ chains, (C8H22N2)Cu2Cl6 is found to exhibit antiferromagnetic ordering with a Néel temperature of 24 K. The two-terminal (2T) electrical measurement on a (C8H22N2)Cu2Cl6 single crystal reveals its insulating nature. This work shows the potential of LD OMHHs as a highly tunable quantum material platform for spintronics.

Semi-Opaque Perovskite Solar Cells.

Transparent photovoltaics are garnering significant interest for power generation in applications where light transmission is required. Metal halide perovskites have emerged as one of the most lucrative material classes for such device architectures due to their exceptional optoelectronic properties, and compositional versatility enabling a wide range of transparency levels. While research has primarily focused on semitransparent solar cell architectures, their colored appearance, and efficiency limitations hinder their practical applicability. In this perspective, we look at semiopaque perovskite solar cells as an alternative technological approach that comprises partially covered surfaces to enable light transmission. Our comparative analysis reveals that such semiopaque devices have the potential for superior efficiencies while maintaining a color-neutral appearance. These benefits are met with a number of hurdles, which provide key areas for future innovation to see the realization of such devices in real world applications.

In-Situ Surface Repair of FAPbBr3 Quantum Dots toward High-Performance Pure-Green Perovskite Light-Emitting Diodes.

Metal halide perovskite light-emitting diodes (PeLEDs) are ideal for high-resolution displays due to their tunable emission, narrow spectra, and low-cost processing. Colloidal FAPbBr3 perovskite quantum dots (PeQDs) enhance radiative recombination, making them efficient for pure-green PeLEDs. However, their low stability and surface defects limit their practical application. Here, we address these challenges by proposing an in situ surface repair strategy using benzhydroxamic acid (BHA) as a modifier. We demonstrated that BHA can coordinate with Pb2+ ions and form hydrogen bonds with FA+ and halide ions, effectively reducing nonradiative recombination and maintaining the integrity of the PeQDs. High-quality FAPbBr3 PeQDs with a photoluminescence quantum yield (PLQY) of up to 92.5% were achieved, leading to pure-green PeLEDs with an external quantum efficiency (EQE) of 24.8% and a maximum luminance of 40,231 cd m-2, providing a feasible and promising perspective for advanced solid-state lighting and displays.

Dual-Template-Directed Zero-Dimensional Bismuth Chlorides: Structures, Luminescence, Photoinduced Chromism, and Enhanced Proton Conductivity.

Zero-dimensional (0D) hybrid organic-inorganic bismuth halides have attracted immense scientific interest as promising candidates for lead-free materials. Here, by using a typical solvothermal method, two mixed-cation-phase 0D hybrid bismuth chlorides of [HPDA][H2PDA]BiCl6 (1) and [Hbzim][H2PA]BiCl6 (2) (PDA = bis(4-pyridyl)amine, bzim = benzimidazole, PA = 2-picolylamine) have been assembled based on a series of organic amine guests. Both compounds exhibit interesting photoluminescence phenomena, in which compound 1 exhibits a double emission property of blue fluorescence and yellow-green phosphorescence simultaneously, while compound 2 exhibits wide-band yellow-green emission under visible light excitation. The luminescence mechanism is explained by experiments and theoretical calculations. In view of the fact that halometallate units and the conjugated nitrogen heterocyclic systems can act as electron donors and electron acceptors, respectively, both compounds exhibit free radical-driven photochromism induced by electron transfer under xenon lamp irradiation at room temperature. In addition, benefiting from abundant hydrogen bond networks in structures, the two compounds show significant temperature-dependent proton conduction behavior in the range of 298-343 K, and the proton conductivity of both compounds is significantly improved after light irradiation. Our study demonstrates two novel hybrid mixed-cation-phase 0D hybrid bismuth halides with photoluminescence, photochromism, and photomodulated proton conduction properties, which enriches the dual-template-directed metal halide system and provides a feasible scheme for the synthesis of photoresponsive smart materials.

Antiferromagnetic Ordering in A One‐Dimensional Organic Copper Chloride Hybrid Insulator

AbstractLow dimensional (LD) organic metal halide hybrids (OMHHs) have recently emerged as new generation functional materials with exceptional structural and property tunability. Despite the remarkable advances in the development of LD OMHHs, optical properties have been the major functionality extensively investigated for most of LD OMHHs developed to date, while other properties, such as magnetic and electronic properties, remain significantly under‐explored. Here, we report for the first time the characterization of the magnetic and electronic properties of a 1D OMHH, organic‐copper (II) chloride hybrid (C8H22N2)Cu2Cl6. Owing to the antiferromagnetic coupling between Cu atoms through chloride bridges in 1D [Cu2Cl62−]∞ chains, (C8H22N2)Cu2Cl6 is found to exhibit antiferromagnetic ordering with a Néel temperature of 24 K. The two‐terminal (2T) electrical measurement on a (C8H22N2)Cu2Cl6 single crystal reveals its insulating nature. This work shows the potential of LD OMHHs as a highly tunable quantum material platform for spintronics.

Ion Leakage Current Control for Polycrystalline Metal Halide Perovskite Direct X-ray Detectors.

Metal halide perovskites have emerged as promising materials for X-ray detection due to their high X-ray attenuation coefficients, defect tolerance, and suitability for large-area, low-temperature fabrication. However, the intrinsic high ion conductivity of these materials presents challenges, such as high dark current density and current drift, which impair the stability and sensitivity of perovskite X-ray detectors. This study introduces an approach to mitigating these issues by incorporating 2,2,3,3,3-pentafluoropropylamine hydrochloride (PFH) into polycrystalline MAPbI3-xClx films using a one-step blade-coating method. PFH aggregates at grain boundaries, raising local vacuum energy levels and passivating surface defects, thereby reducing ion conductivity without affecting electron conductivity. As a result, this approach significantly reduces the dark current and enhances sensitivity, achieving a low detection limit of 14.7 nGyair/s. Additionally, it improves signal stability, consistency, and response speed of the detector. These findings suggest that PFH is a promising additive for advancing the performance and practical application of polycrystalline metal halide perovskite-based X-ray detectors.

Reduced-Dimensional Perovskites: Quantum Well Thickness Distribution and Optoelectronic Properties.

Reduced-dimensional perovskites (RDPs), a large category of metal halide perovskites, have attracted considerable attention and shown high potential in the fields of solid-state displays and lighting. RDPs feature a quantum-well-based structure and energy funneling effects. The multiple quantum well (QW) structure endows RDPs with superior energy transfer and high luminescence efficiency. The effect of QW confinement directly depends on the number of inorganic octahedral layers (QW thickness, i.e., n value), so the distribution of n values determines the optoelectronic properties of RDPs. Here, it is focused on the QW thickness distribution of RDPs, detailing its effect on the structural characteristics, carrier recombination dynamics, optoelectronic properties, and applications in light-emitting diodes. The reported distribution control strategies is also summarized and discuss the current challenges and future trends of RDPs. This review aims to provide deep insight into RDPs, with the hope of advancing their further development and applications.

Hydroxyl-driven construction of dual-emitting CsPbBr3/EuWO4(OH) composite for radiometric thermometer and information encryption applications

Self-assembled inorganic metal halide perovskite composites with high emitting efficiency, tunable multimode emission and stimuli-responsive luminescence demonstrated great potential in diversified luminescence applications. Here, a novel CsPbBr3/EuWO4(OH) composite was successfully prepared through the surface adsorption of Pb2+ ions on hydroxylated EuWO4(OH) microsheets and subsequent nucleation of CsPbBr3 peroviskite quantum dots (PQDs) by the anti-solvent crystallization in CsBr containing N,N-dimethylformamide (DMF) solution. Due to the distinct fluorescent thermochromic switching properties of temperature-insensitive Eu3+ and sensitive CsPbBr3 PQDs emitting centers, the resultant CsPbBr3/EuWO4(OH) composite exhibits excellent ratiometric temperature sensing performance. The CsPbBr3/EuWO4(OH) thermometer based on the fluorescence intensity ratio (FIR) technique originating from emissions of Eu3+ to CsPbBr3 PQDs was then explored with a high temperature sensitivity (Sr) of 5.8 % ℃−1 at 54 ℃. In addition, a high-security-level information encryption scheme was proposed by utilizing the excitation-wavelength-dependent switchable fluorescence of CsPbBr3/EuWO4(OH) composite. This study provides a simple and feasible strategy for assembling dual-emission CsPbBr3/EuWO4(OH) composite, showing potential applications in optical ratiometric thermometry and information encryption fields.

Interface Energy-Level Reorganization for Efficient Perovskite γ-Ray Detectors.

Metal halide perovskites are promising candidates for γ-rayspectrum detectors. However, achieving high-resolution energy spectra in single-photon pulse-height analysis mode remains challenging, due to the inevitable leakage currents degrade the recognizable fingerprint energies which is critical for resolving γ-ray spectroscopy. We demonstrate under high bias voltage, a deficient contact barrier can lead to excessive surface charge injection, thereby increasing leakage current from electrodes to perovskites. Hence, we conceive to employ surface ligand engineering on perovskite single crystals to manipulate energy levels to suppress leakage current. In particular, anchoring a strong dipole ligand onto the perovskite induced surface charge-density displacement, leading to a downward band bending and heightened the corresponding contact barrier. Consequently, the strategy minimized the detectors'leakage current by an order of magnitude, to as low as 44 nA cm-2. The resulting detectors show a significant improvement in energy resolution, 3.9% for 22Na 511 keV γ-rays has been achieved at room temperature. The resulting detector further resolves each fingerprint energy for 152Eu γ-spectrum, representing one of the best γ-rays perovskite detectors reported to date. Moreover, the detectors exhibited stabilized energy resolution without any degradation under a continuous electric fieldfor over 300 minutes, representing the longest longevity reported to date.