Zero‐dimensional (0D) organic metal halide hybrids (OMHHs) are emerging materials with significant potential for optoelectronic applications, including direct X‐ray detectors. While 0D OMHH single crystals exhibit excellent X‐ray detection properties, their scalability remains a significant challenge due to the time‐intensive growth process and difficulty in producing large single crystals exceeding a few centimeters. This limitation hinders their practicality for large‐area detector applications. Here, we report for the first time the development of amorphous 0D OMHH films via solution processing for efficient direct X‐ray detection. By reacting a non‐crystalline organic halide, triphenyl(9‐phenyl‐9H‐carbazol‐3‐yl)phosphonium bromide (TPPCarzBr), with zinc bromide (ZnBr2), we have successfully produced amorphous 0D (TPPCarz)2ZnBr4films with controlled thickness via facile solution processing. The organic cations (TPPCarz⁺) feature a lower bandgap than the ZnBr42−anions, enabling efficient molecular sensitization, where ZnBr42−anions serve as X‐ray absorbers and TPPCarz⁺ cations as charge transporters. Direct X‐ray detectors based on 0D (TPPCarz)2ZnBr4films demonstrate outstanding performance, achieving a stable X‐ray detection sensitivity of 2,165 µC Gyair⁻1cm⁻2at 20 V mm⁻¹ and a detection limit of 6.01 nGyair s⁻¹. The amorphous nature of these films enhances their processability, allowing for fabrication in various sizes and shapes, and making them highly adaptable for scalable detector applications.
more »
« less
Solution Processed Bilayer Metal Halide White Light Emitting Diodes
Abstract 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) CsPbBr3nanoplatelets (NPLs) as sky blue emitter and 0D TPPcarzSbBr4as 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−2at 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.
more »
« less
- Award ID(s):
- 2210902
- PAR ID:
- 10654989
- Publisher / Repository:
- Wiley-VCH GmbH
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 37
- Issue:
- 25
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract 0D organic metal halide hybrids (OMHHs) have recently emerged as a new generation of scintillation materials, due to their high luminescence quantum efficiency, sensitivity, stability, and cost‐effectiveness. While numerous 0D OMHH scintillators have been developed to date, most of them are based on solution grown single crystals that require time‐consuming synthesis and are limited in size. Here, high‐performance X‐ray scintillators based on facile solution processed 0D OMHH amorphous films are reported for the first time. By reacting triphenyl(9‐phenyl‐9H‐carbazol‐3‐yl) phosphonium bromide (TPPcarzBr) with manganese bromide (MnBr2), 0D (TPPcarz)₂MnBr₄ amorphous films can be prepared via solution processing with mild thermal annealing, which exhibits green photoluminescence with an emission maximum ≈517 nm and a photoluminescence quantum efficiency of ≈87%. The X‐ray scintillation of 0D (TPPcarz)₂MnBr₄ amorphous films is characterized to exhibit a light yield of 44600 photon MeV−1and an outstanding linearity with a low limit of detection of 32.42 nGyairs−1over a wide range of X‐ray dose rates. The versatile processability of 0D (TPPcarz)₂MnBr₄ is illustrated with remarkable recyclability, high cost‐effectiveness, and scalability for large‐scale production. By taking advantage of the amorphous nature of newly designed OMHHs, the approach opens up new opportunities for developing high‐performance, solution‐processable scintillators.more » « less
-
Abstract Highly sensitive stimuli‐responsive luminescent materials are crucial for applications in optical sensing, security, and anticounterfeiting. Here, we report two zero‐dimensional (0D) copper(I) halides, (TEP)2Cu2Br4, (TEP)2Cu4Br6, and 1D (TEP)3Ag6Br9, which are comprised of isolated [Cu2Br4]2−, [Cu4Br6]2−, and [Ag6Br9]3−polyanions, respectively, separated by TEP+(tetraethylphosphonium [TEP]) cations. (TEP)2Cu2Br4and (TEP)2Cu4Br6demonstrate greenish‐white and orange‐red emissions, respectively, with near unity photoluminescence quantum yields, while (TEP)3Ag6Br9is a poor light emitter. Optical spectroscopy measurements and density‐functional theory calculations reveal that photoemissions of these compounds originate from self‐trapped excitons due to the excited‐state distortions in the copper(I) halide units. Crystals of Cu(I) halides are radioluminescence active at room temperature under both X‐ and γ‐rays exposure. The light yields up to 15,800 ph/MeV under 662 keV γ‐rays of137Cs suggesting their potential for scintillation applications. Remarkably, (TEP)2Cu2Br4and (TEP)2Cu4Br6are interconvertible through chemical stimuli or reverse crystallization. In addition, both compounds demonstrate luminescence on‐off switching upon thermal stimuli. The sensitivity of (TEP)2Cu2Br4and (TEP)2Cu4Br6to the chemical and thermal stimuli coupled with their ultrabright emission allows their consideration for applications such as solid‐state lighting, sensing, information storage, and anticounterfeiting.more » « less
-
Reduced Energetic Disorders in Dion–Jacobson Perovskites for Efficient and Spectral Stable Blue LEDsAbstract Metal halide perovskites have witnessed great success in green, red, and near‐infrared light‐emitting diodes (LEDs), yet blue LEDs still lag behind. Reducing undesired energetic disorders – broad n ‐phases and halide segregation – is considered as the most critical strategy to further improve the performances. Here, the study reports a newly designed and synthesized di‐ammonium ligand with rigid π ‐conjugated rings and additional methyl groups to construct Dion–Jacobson (DJ) structure. Augmented coordination from the extra ammonium site and increased effective bulkiness from methyl groups lead to better distribution control over conventional mono‐ammonium ligands. This enhances the radiative recombination of blue emissions in the film with homogeneous energy landscape and improved surface morphology, as evidenced by a series of imaging and mapping techniques. As a result, it demonstrates DJ perovskite LEDs (PeLEDs) with peak external quantum efficiencies of ≈4% at 484 nm and ≈11% at 494 nm, which are among the top reported for pure DJ phase‐based PeLEDs in the corresponding wavelength regions. The results deepen the understanding of regulating energetic disorders in perovskite materials via molecular engineering.more » « less
-
Metal halide perovskites have emerged as the next generation of light emitting semiconducting materials due to their excellent properties such as tunable bandgaps, high photoluminescence quantum yield, and high color purity. Nickel oxide is a hole transport material that has been used in planar light emitting diodes (LEDs). In this paper, we develop a novel method for the large scale fabrication of metal halide perovskite nanowire arrays encapsulated inside nickel oxide nanotubes. We study the structural and spectral properties of these infiltrated perovskites nanowires and, to the best of our knowledge, for the first time report on a working LED device consisting of perovskites encapsulated inside nickel oxide nanotubes. Finally, we study the photoluminescence and electroluminescence of an LED with MAPbBr 3 inside nickel oxide nanotubes and obtain an outstanding current efficiency of 5.99 Cd A −1 and external quantum efficiency of 3.9% for the LED device.more » « less
An official website of the United States government

