Metal Halide Perovskite Light-emitting Diodes Research Articles

Regulation of nucleation and crystallization for blade-coating large-area CsPbBr3 perovskite light-emitting diodes

Metal halide perovskite light-emitting diodes (PeLEDs) and large-area perovskite color conversion layers for liquid crystal display exhibit great potential in the field of illumination and display. Blade-coating method stands out as a highly suitable technique for fabricating large-scale films, albeit with challenges such as uneven nucleation coverage and non-uniformity crystallization process. In this work, we developed an in-situ characterization measurement system to monitor the perovskite nucleation, and crystallization process. By incorporating formamidine acetate (FAAc) into perovskite precursor solutions, the nucleation rate and nuclei density of perovskite were increased, leading to more uniform nucleation. In addition, we inserted a layer of [2-(9H-carbazol-9-yl)ethyl] phosphonic acid above the poly(9-vinylcarbazole) hole transport layer. This layer acts as an anchor for the perovskite nano-crystal nuclei formed in the precursor, enhancing the steric hindrance of the solute and subsequently slowing down the crystal growth rate, thereby improving crystal quality. Based on these improvements, large-area perovskite nano-polycrystalline films with significantly improved uniformity and enhanced photoluminescence quantum yield were obtained. A small-area PeLED (2 mm × 2 mm) with a maximum external quantum efficiency of 25.91% was realized, marking the highest record of PeLED prepared by blade-coating method to date. An ultra-large-area PeLED (5 cm × 7 cm) was also prepared, which is the largest PeLED prepared by the solution method reported so far.

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.

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.

Thiourea-Induced Cocrystallization of Mixed-Halide Perovskite Thin Films for High-Performance Pure Blue Perovskite Light Emitting Diodes

Metal halide perovskite light-emitting diodes (PeLEDs) are gaining significant attention towards next-generation display materials owing to their advantageous properties, including color tunability, exceptionally narrow bandwidth, and high luminescence. Recent studies have successfully achieved over 20% external quantum efficiencies (EQE) in green and red PeLEDs. However, the blue PeLEDs lag far behind those of green or red PeLEDs because unstable phase stability in mixed halide perovskite thin films under high turn-on voltage (Von). In specific, the blue emission usually possesses halide ions with smaller ionic radius (Cl- or Br-), which easily migrates under high operative bias generating significant halogen vacancies and phase-transformation. In this context, we suggest thiourea as a promising additive for stabilizing defective perovskite thin films. Thiourea is a well-known hydrogen bond donor to halogens, which allows potential coordination complex of thiourea-halide ions to encompass well-dispersed mixed halides in co-crystallized perovskite lattices. In addition, the strong coordination of the C=S···Pb2+ was also demonstrated the thiourea-incorporated perovskite films, which effectively passivated undercoordinated Pb2+ antisites. Consequently, the thiourea-incorporated perovskite films exhibited stable deep-blue emission within 460 nm, demonstrating excellent luminance and quantum efficiency in pure blue PeLEDs. Moreover, the addition of thiourea achieved decreased Von and excellent spectral stability of pure blue PeLEDs at high applied bias, leading to significant advancements in pure blue perovskite display technology.

Efficient Deep-Blue Light-Emitting Diodes Through Decoupling of Colloidal Perovskite Quantum Dots.

Metal halide perovskite light-emitting diodes (PeLEDs) have exceptional color purity but designs that emit deep-blue color with high efficiency have not been fully achieved and become more difficult in the thin film of confined perovskite colloidal quantum dots (PeQDs) due to particle interaction. Here it is demonstrated that electronic coupling and energy transfer in PeQDs induce redshift in the emission by PeQD film, and consequently hinder deep-blue emission. To achieve deep-blue emission by avoiding electronic coupling and energy transfer, a QD-in-organic solid solution is introduced to physically separate the QDs in the film. This physical separation of QDs reduces the interaction between them yielding a blueshift of ≈7nm in the emission spectrum. Moreover, using a hole-transporting organic molecule with a deep-lying highest occupied molecular orbital (≈6.0eV) as the organic matrix, the formation of exciplex emission is suppressed. As a result, an unprecedently high maximum external quantum efficiency of 6.2% at 462nm from QD-in-organic solid solution film in PeLEDs is achieved, which satisfies the deep-blue color coordinates of CIEy <0.06. This work suggests an important material strategy to deepen blue emission without reducing the particle size to <≈4nm.

Pulsed operation of perovskite LEDs: a study on the role of mobile ions

ABSTRACT Metal halide perovskite light-emitting diodes (PeLEDs) are a promising technology for energy-efficient and cost-effective lighting and displays, thanks to their tunable color emission, high brightness, color purity and low-temperature fabrication. However, the mixed ionic-electronic conductivity of perovskite materials presents unique challenges, as ionic defects can redistribute under operation, affecting the energy landscape and charge recombination mechanisms. Our drift-diffusion simulations establish a connection between the transient electroluminescence (TrEL) signals of PeLEDs under pulsed operation and the influence of mobile ions. We find that the TrEL plateau value’s dependence on the duty cycle and end-of-pulse overshoot can be explained by the time-varying distribution of ionic defects. The inclusion of mobile ions is crucial to understand the TrEL response. Moreover, the simulations highlight injection barriers at the perovskite/charge-transport layer interfaces, such as is the case for the hole transport layer in our example, as a significant source of non-radiative charge recombination. These findings contribute to the understanding of transient ionic processes in perovskite-based devices.

Improving the Operational Lifetime of Metal-Halide Perovskite Light-Emitting Diodes with Dimension Control and Ligand Engineering.

Perovskite light-emitting diodes (LEDs) have emerged as one of the most propitious candidates for next-generation lighting and displays, with the highest external quantum efficiency (EQE) of perovskite LEDs already surpassing the 20% milestone. However, the further development of perovskite LEDs primarily relies on addressing operational instability issues. This Perspective examines some of the key factors that impact the lifetime of perovskite LED devices and some representative reports on recent advancements aimed at improving the lifetime. Our analysis underscores the significance of "nano" strategies in achieving long-term stable perovskite LEDs. Significant efforts must be directed toward proper device encapsulation, perovskite material passivation, interfacial treatment to address environment-induced material instability, bias-induced phase separation, and ion migration issues.

Large-Area Flexible Perovskite Light-Emitting Diodes Enabled by Inkjet Printing.

Metal halide perovskite light-emitting diodes (PeLEDs) are attracting increasing attention due to their potential applications in flat panel lighting and displays. The solution process, large-area fabrication, and flexibility are attractive properties of PeLEDs over traditional inorganic LEDs. However, it is still very challenging to deposit uniform perovskite films on flexible substrates using a blade or slot-die coating, as the flexible substrate is not perfectly flat. Here, the inkjet printing technique is adopted, and the key challenges are overcome step-by-step in preparing large-area films on flexible substrates. Double-hole transporting layers are first used and a wetting interfacial layer to improve the surface wettability so that the printed perovskite droplets can form a continuous wet film. The fluidic and evaporation dynamics of the perovskite wet layer is manipulated to suppress the coffee ring effect by solvent engineering. Uniform perovskite films are obtained finally on flexible substrates with different perovskite compositions. The peak external quantum efficiency of the inkjet-printed PeLEDs reaches 14.3%. Large-area flexible PeLEDs (4×7 cm2 ) also show very uniform emission. This work represents a significant step toward real applications of large-area PeLEDs in flexible flat-panel lighting.

High Curvature PEDOT:PSS Transport Layer Toward Enhanced Perovskite Light-Emitting Diodes.

The rapidly developed metal halide perovskite light-emitting diodes (PeLEDs) are considered as a promising candidate for next-generation display and illumination, but the unbalanced charge transport is still a hard-treat case to restrict its efficiency and operational stability. Here, a high curvature PEDOT:PSS transport layer is demonstrated via the self-assembly island-like structures by the incorporation of alkali metal salts. Benefiting from the dielectric confinement effect of the high curvature surface, the modified CsPbBr3 -based PeLEDs present a 2.1 times peak external quantum efficiency (EQE) from 6.75% to 14.23% and a 3.3 times half lifetime (T50 ) from 3.96 to 13.01h. Besides, the PeLEDs show high luminance up to 44834cdm-2 . Evidently, this work may provide a deep insight into the structure-activity relationship between the micro-structures at the PEDOT:PSS/perovskite interface and the performance of PeLEDs, and crack the codes for ameliorating the performance of PeLEDs via interfacial micro-structured regulation.

Thermal Properties of Polymer Hole-Transport Layers Influence the Efficiency Roll-off and Stability of Perovskite Light-Emitting Diodes.

While the performance of metal halide perovskite light-emitting diodes (PeLEDs) has rapidly improved in recent years, their stability remains a bottleneck to commercial realization. Here, we show that the thermal stability of polymer hole-transport layers (HTLs) used in PeLEDs represents an important factor influencing the external quantum efficiency (EQE) roll-off and device lifetime. We demonstrate a reduced EQE roll-off, a higher breakdown current density of approximately 6 A cm-2, a maximum radiance of 760 W sr-1 m-2, and a longer device lifetime for PeLEDs using polymer HTLs with high glass-transition temperatures. Furthermore, for devices driven by nanosecond electrical pulses, a record high radiance of 1.23 MW sr-1 m-2 and an EQE of approximately 1.92% at 14.6 kA cm-2 are achieved. Thermally stable polymer HTLs enable stable operation of PeLEDs that can sustain more than 11.7 million electrical pulses at 1 kA cm-2 before device failure.

Vacuum-deposited perovskite CsPbBr3 thin-films for temperature-stable Si based pure-green all-inorganic light-emitting diodes

Metal halide perovskite light-emitting diodes (PeLEDs) are excellent candidates in the field of lighting and display due to their outstanding optical-electrical properties. However, the solution-processed technology of perovskite films and the organic electron/hole transport layers of PeLEDs make it still challenging to improve the operational stability of devices. Herein, we successfully prepared highly luminescent CsPbBr3 perovskite films via vacuum-deposited method and then fabricated all-inorganic PeLEDs with the heterostructure of p-NiO/CsPbBr3/n-Si. Our device exhibits pure-green emission with a wavelength of 527 nm, a narrow full width at half-maximum of 18 nm, and a maximum luminance of 51933 cd/m2, representing one of the best brightness pure-green PeLEDs. Most importantly, the PeLEDs exhibited great thermal stability with a heat resistance up to 80 °C. The electroluminescence peak position of the PeLEDs remains consistent when the ambient temperature increases from 40 °C to 110 °C. Moreover, the all-inorganic PeLEDs can maintain their good luminescence performance after seven thermal cycling tests (30 °C–100 °C). This work not only demonstrated a facile strategy to prepare high-quality pure-green CsPbBr3 perovskite films, but also provided an important all-inorganic device structure for high thermal stability of PeLED.

P‐11.1: The interface engineering with quaternary ammonium ionic liquid enabling efficient blue perovskite light‐emitting diode

Metal halide perovskite light-emitting diodes (PeLEDs) have become a rising star in recent years. Interface plays an important role in the development of the PeLEDs performance. In this work, we demonstrate that the interface engineering with quaternary ammonium ionic liquid that could be used to improve the efficiency of the blue PeLEDs. We find the interface engineering can balance hole and electron injection. In addition, quaternary ammonium cation promotes the growth and nucleation of the blue perovskite emitter, improving its film morphology and reducing the occurrence of defects. The use of the ionic liquid interfacial layer is also helpful to inhibit the ion migration in the perovskite under forward bias operation. In conclusion, by exploring the quaternary ammonium ionic liquid interfacial layer, the luminous efficiency can be greatly improved.

Vacuum-Deposited Inorganic Perovskite Light-Emitting Diodes with External Quantum Efficiency Exceeding 10% via Composition and Crystallinity Manipulation of Emission Layer under High Vacuum.

Although vacuum-deposited metal halide perovskite light-emitting diodes (PeLEDs) have great promise for use in large-area high-color-gamut displays, the efficiency of vacuum-sublimed PeLEDs currently lags that of solution-processed counterparts. In this study, highly efficient vacuum-deposited PeLEDs are prepared through a process of optimizing the stoichiometric ratio of the sublimed precursors under high vacuum and incorporating ultrathin under- and upper-layers for the perovskite emission layer (EML). In contrast to the situation in most vacuum-deposited organic light-emitting devices, the properties of these perovskite EMLs are highly influenced by the presence and nature of the upper- and presublimed materials, thereby allowing us to enhance the performance of the resulting devices. By eliminating Pb° formation and passivating defects in the perovskite EMLs, the PeLEDs achieve an outstanding external quantum efficiency (EQE) of 10.9% when applying a very smooth and flat geometry; it reaches an extraordinarily high value of 21.1% when integrating a light out-coupling structure, breaking through the 10% EQE milestone of vacuum-deposited PeLEDs.

Operational Stability Issues and Challenges in Metal Halide Perovskite Light-Emitting Diodes.

Metal halide perovskite light-emitting diodes (Pe-LEDs) have shown promise for high-definition displays because of their wide color gamut (∼140%) and narrow emission band. Although the external quantum efficiency (EQE) of Pe-LEDs increased rapidly from ∼1% to more than 20% in several years, they still suffer from poor operational stability, which has been recognized as the bottleneck for commercial application of Pe-LEDs. Although the environmental sensitivity of perovskites can be avoided by encapsulation approaches, the ion migration of perovskites is easily induced by crystal defects under the action of an electric field in the operating state, thus accelerating irreversible phase transition and physical degradation of the perovskites. Additionally, the unbalanced carrier injection of Pe-LEDs could induce great Auger recombination and Joule heating, which deteriorate the operational stability of devices. Considering these issues, coping strategies, such as surface engineering, ion doping, and quantum confinement control of perovskites and structure design and thermal management of devices, are discussed in this Perspective.

Efficient Inorganic Perovskite Light-Emitting Diodes by Inducing Grain Arrangement via a Multifunctional Interface.

Accumulating evidence shows that metal halide perovskite light-emitting diodes (PeLEDs) are well-described to show broad application prospects in lighting and display due to the wide color gamut and high color purity. However, it is still a great challenge to prepare high-quality all-inorganic PeLEDs by a solution method. For example, it is difficult to obtain all-inorganic perovskite films with good crystallinity and high grain orientation because of too fast and uncontrollable crystallization of all-inorganic perovskite films. Here, we demonstrated a multifunctional interface of formamide (FA)-doped PEDOT:PSS, which improved the crystallinity of all-inorganic perovskite films by inducing grain arrangement. As a result, a highly crystalline, ordered, and defect-passivated CsPbBr3 film was obtained by the multiple roles of FA, and the CsPbBr3-based PeLED treated with FA achieved both high brightness and high efficiency: the peak external quantum efficiency (EQE) reaches 9.61%, and the maximum brightness is 185,000 cd/m2. In addition, Tween 80, used as a passivator of perovskite films, reduced the defect states and suppressed ion migration. Under the synergistic effect of FA interface treatment and Tween 80 passivation treatment, efficient CsPbBr3-based PeLEDs were obtained with an EQE of 15.02% and an operation lifetime of 182.5 min at an initial brightness of 1000 cd/m2, which is among the best reported lifetimes under high brightness. Our study provides a simple and effective strategy for the realization of all-inorganic PeLEDs with high efficiency, high brightness, and ultralong operation lifetime.

Insight into perovskite light-emitting diodes based on PVP buffer layer

Metal halide perovskite light-emitting diodes (PeLEDs) have shown enormous potential in the field of display. Recently, the economical and practical polyvinylpyrrolidone (PVP) has been widely used in perovskite-based optoelectronic devices. However, its comprehensive and complex effects are still lack of in-depth research. In this work, PVP interlayer is experimentally evidenced to play a multi-function role of passivating interface defects between hole transport layer (HTL) and emissive layer (EML), inhibiting grain boundary defects of EML, balancing hole/electron mobilities, and supporting as a hydrophilic interlayer to improve the wettability in PeLEDs. As a result, the hydrophobic poly-TPD HTL based 3D CsPbBr3, quasi-2D PEA2 [CsPbBr3]5PbBr4 and 3D CsPb(Cl0.3Br0.7)3 PeLEDs are successfully demonstrated with the assistance of PVP buffer layer, yielding the optimized luminance, external quantum efficiency, current efficiency and T50 lifetime of 45,582 cd m−2, 2.78%, 8.4 cd A−1 and 2400 s for CsPbBr3 PeLED, 14,074 cd m−2, 5.50%, 17.6 cd A−1 and 7260 s for PEA2 [CsPbBr3]5PbBr4 PeLED, 774 cd m−2, 0.40%, 0.47 cd A−1 and 330 s for 3D CsPb(Cl0.3Br0.7)3 PeLED, respectively. This work provides a deep insight of PVP buffer layer into various HTLs and multi-colored PeLEDs for the first time, which helps to enhance the key optoelectronic performance for PeLEDs.

Perovskite light-emitting diodes with low roll-off efficiency via interfacial ionic immobilization

Metal halide perovskite light-emitting diodes (PeLEDs) are emerging low-cost solution-processable technology with high color purity and tunable emission wavelength. However, the defective interface between perovskite emission layer and charge transport layer substantially limits the improvement of device performance, especially for a device with simultaneously high luminance and decent external quantum efficiency. Herein, we propose a facile and reliable interfacial modification strategy to realize efficient PeLEDs with high external quantum efficiency under high luminance. By modifying the hole transport layer with alkali metal ions (K+, Na+) and weak acid ion (citrate ion), perovskite films with high surface coverage and fewer interface defects are fabricated. As a result, a high brightness of 80,288 cd/m2 and a high external quantum efficiency of 13.02% under continuous current drive are obtained in our PeLEDs. More commendable, our devices show low roll-off behaviors of EQE under high luminance and high current density, because of halide anion and lead cation vacancies at the interface of perovskite and charge transport layer are efficiently suppressed.

Nanosecond-Pulsed Perovskite Light-Emitting Diodes at High Current Density.

While metal-halide perovskite light-emitting diodes (PeLEDs) hold the potential for a new generation of display and lighting technology, their slow operation speed and response time limit their application scope. Here, high-speed PeLEDs driven by nanosecond electrical pulses with a rise time of 1.2ns are reported with a maximum radiance of approximately 480 kW sr-1 m-2 at 8.3 kA cm-2 , and an external quantum efficiency (EQE) of 1% at approximately 10 kA cm-2 , through improved device configuration designs and material considerations. Enabled by the fast operation of PeLEDs, the temporal response provides access to transient charge carrier dynamics under electrical excitation, revealing several new electroluminescence quenching pathways. Finally, integrated distributed feedback (DFB) gratings are explored, which facilitate more directional light emission with a maximum radiance of approximately 1200 kW sr-1 m-2 at 8.5 kA cm-2 , a more than two-fold enhancement to forward radiation output.

The Past, Present, and Future of Metal Halide Perovskite Light‐Emitting Diodes

Metal Halide Perovskite Light-Emitting Diodes Can metal halide perovskite light-emitting diodes (PeLEDs) become one of the next-generation LED technologies for display and lighting applications? In article number 2000072, Biwu Ma and co-workers introduce the major progress achieved in the development of efficient and stable PeLEDs to date, discuss the main issues and challenges in the field, and provide their prospects on addressing these issues and challenges.

Synthesis and Device Optimization of Highly Efficient Metal Halide Perovskite Light-emitting Diodes

Synthesis and Device Optimization of Highly Efficient Metal Halide Perovskite Light-emitting Diodes