Perovskite-based Light-emitting Diodes Research Articles

The Rise of Textured Perovskite Morphology: Revolutionizing the Pathway toward High‐Performance Optoelectronic Devices

AbstractHalide perovskite materials have achieved overwhelming success in various optoelectronic applications, especially perovskite solar cells and perovskite‐based light‐emitting diodes (P‐LEDs), owing to their outstanding optical and electric properties. It is widely believed that flat and mirror‐like perovskite films are imperative for achieving high device performance, while the potential of other perovskite morphologies, such as the emerging textured perovskite, is overlooked, which leaves plenty of room for further breakthroughs. Compared to flat and mirror‐like perovskites, textured perovskites with unique structures, e.g., coral‐like, maze‐like, column‐like or quasi‐core@shell assemblies, are more efficient at light harvesting and charge extraction, thus revolutionizing the pathways toward ultrahigh performance in perovskite‐based optoelectronic devices. Employing a textured perovskite morphology, the record of external quantum efficiency for P‐LEDs is demonstrated as 21.6%. In this research news, recent progress in the utilization of textured perovskite is summarized, with the emphasis on the preparation strategies and prominent optoelectronic properties. The impact of the textured morphology on light harvesting, carrier dynamic management, and device performance is highlighted. Finally, the challenges and great potential of employing these innovative morphologies in fabricating more efficient optoelectronic devices, or creating a new energy harvesting and conversion regime are also provided.

Methylammonium-Mediated Crystallization of Cesium-Based 2D/3D Perovskites toward High-Efficiency Light-Emitting Diodes.

Two-dimensional (2D)/three-dimensional (3D) perovskites have been successfully applied in high-efficiency light-emitting diodes (LEDs) because of their large exciton binding energy (Eb) caused by the quantum and dielectric confinements. Thermal annealing and antisolvent treatments are usually executed in order to promote the crystallization and film quality of perovskites, which add complexity to the device fabrication process. Here, the cesium-based 2D/3D perovskite was prepared by introducing ammonium halide benzamidine hydrochloride (BMCl) as the additive. By further introducing an appropriate amount of MABr and PbBr2, BM2(Cs1-xMAxPbBr3)n-1PbBr4 crystals can be formed rapidly without any additional treatments, while inhibiting the formation of the unfavorable Cs4PbBr6 phase. The optimized 2D/3D perovskite-based LEDs achieved a maximum luminance of 12 367 Cd/m2, a current efficiency of 17.4 Cd/A, and an external quantum efficiency of 5.2%. Our results suggest that appropriate perovskite crystallization can be achieved at room temperature by the regulation of precursor solution, making the perovskite crystallization process easier to control with reduced processing complexity.

Gaining Insight into the Underlayer Treatment for in Situ Fabrication of Efficient Perovskite Nanocrystal-Based Light-Emitting Diodes

The feasibility of in situ fabrication of metal halide perovskite films for optoelectronic devices has attracted increasing research interest as it eliminates the material preparation step and thus simplifies the integration procedure. The success of in situ fabrication requires delicate regulations of the underlayers. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is a universal hole transporting material for solution-processed optoelectronic devices; however, it is usually hard to cast high-quality active layers directly onto the pristine PEDOT:PSS layer due to its unfavored surface properties. The physical changes in the film morphology and optical and electric properties and the chemical change in the molecular composition of the oxygen plasma-treated PEDOT:PSS surface are investigated in this work. It is found that the reduced film thickness and PSS-rich surface after plasma treatment facilitate the growth of upper layers of formamidinium lead bromide (FAPbBr3) nanocrystal films, leading to higher photoluminescence quantum yields. The magnificent performance of perovskite-based light-emitting diodes (Pe-LEDs) with oxygen plasma-treated PEDOT:PSS shows a highest current efficiency of 54.0 cd/A, which is more than 4 times than those of the analogous Pe-LEDs fabricated with pristine PEDOT:PSS.

Effects of Organic Cations on the Structure and Performance of Quasi-Two-Dimensional Perovskite-Based Light-Emitting Diodes.

Quasi-two-dimensional (quasi-2D) perovskites are efficient luminescent materials due to their self-assembled quantum-well structure. We found that the organic cations have a significant effect on the structure and performance of quasi-2D perovskite-based light-emitting diodes (LEDs). Two classic organic cations, formamidinium (FA) and methylammonium (MA), were chosen for investigation. The MA-based quasi-2D perovskite has the largest band-gap n = 1 phase and a photoluminescence quantum yield (PLQY) as high as 85.3%, whereas this n = 1 phase is almost absent in the FA-based quasi-2D perovskite, which shows a moderate PLQY of 73.5%. However, the FA-based perovskite shows a much higher external quantum efficiency (15.4%) than the MA-based perovskite (0.93%) in LEDs. The lower electroluminescence efficiency of the MA-based perovskite could be ascribed to the poor hole injection. These results showed the importance of rational design of the quasi-2D perovskite for efficient LEDs.

Efficient single-layer light-emitting diodes based on organic\u2013inorganic lead halide perovskite and tuning luminescence properties

Because of the interesting features of the organic/inorganic halide perovskite (e.g., CH3NH3PbX3, X = Cl, Br) materials, such as long electron–hole diffusion length, high absorption coefficient and adjustable band gap, they have attracted a great deal of attention. In this research, CH3NH3PbX3 (X = Br, Cl) are synthesized and perovskite-based single-layer and perovskite-based bilayer diodes are fabricated. Using electron beam deposition technique, thin films of CH3NH3PbX3 (X = Br, Cl) hybrids with excellent homogeneity are manufactured. Absorption spectrum, X-ray spectrum and photoluminescence spectrum of organic/inorganic halide perovskites along with electroluminescence spectra, SEM micrographs and current–voltage characteristic of perovskite-based light-emitting diodes are investigated. Perovskite-based bilayer diodes are evaluated for the first time. The difference between the emission wavelengths of single-layer and bilayer diodes is the main characteristic of bilayer diodes.

Metal Halide Perovskite Light‐Emitting Devices: Promising Technology for Next‐Generation Displays

AbstractAs the requirements and expectation for displays in society are growing, higher standards of the display technology are proposed, including wider color gamut, higher color purity, and higher resolution. The recent emergence of light‐emitting halide perovskites has come with numerous advantages, such as high charge‐carrier mobility, tunable emission wavelength, narrow emission linewidth, and intrinsically high photoluminescence quantum yield. Recent advancement of perovskite‐based light‐emitting diodes (PeLEDs) as a promising technology for next‐generation displays is reviewed. Here, how the attractive optical and electrical properties of perovskite materials can be translated into high PeLED performance are discussed, and working mechanisms and optimization approaches of both perovskite materials and the respective devices are analyzed. On the material side this includes the control of size and composition of perovskites grains and nanocrystals, surface and interface passivation, doping and alloying, while on the device side this includes the interfacial engineering and energy level adjustments, and photon emission enhancement. Several challenges such as performance of blue PeLEDs, the environmental and operational stability of PeLEDs, and the toxicity issues of lead halide perovskites are discussed, and perspectives on future developments of perovskite materials and PeLEDs for the display technology are offered.

Doping and Photon Induced Defect Healing of Hybrid Perovskite Thin Films: An Approach Towards Efficient Light Emitting Diodes

AbstractHere, we demonstrate a simple method to improve photoluminescence and electroluminescent properties of MAPbBr3 perovskite thin films by monovalent Cs cation doping and treatment with UV light. It is known that the intermediate species of lead halides, which limits the photoluminescence quantum yield (PLQY) of perovskite thin films, are formed due to the presence of an organic polar solvent. In such cases, coalescence of nanocrystals is unavoidable when the thin‐films are thermally annealed to remove the intermediate phases and solvent residues. We find that PbBr2(DMSO)x complexes can effectively tune the morphology, grain boundary, PLQY, and non‐radiative loss of perovskite thin films under UV light irradiation. Upon UV exposure, highly uniform MA0.87Cs0.13PbBr3 ultra‐thin (45 nm) films with a full surface coverage of neatly packed nanocrystallites are obtained. When these films are integrated into electroluminescent devices, a current efficiency (CE) of 18.71 Cd/A and an external quantum efficiency (EQE) of 5.63% are observed for green perovskite‐based light emitting diodes (PeLEDs). These values of CE and EQE are respectively thirty‐four and forty‐three times higher than those achieved in pure MAPbBr3 based devices.

Improved Hole Injection into Perovskite Light‐Emitting Diodes Using A Black Phosphorus Interlayer

AbstractThe light‐output and efficiency of perovskite based light‐emitting diodes (PeLEDs) is limited by hole injection and high leakage current, generated by a high hole injection barrier and poor perovskite morphology, respectively. Here, a feasible strategy is reported to overcome both constraints by introducing 2D black phosphorus (BP) as hole injection layer in the PeLED stack. A continuous film composed of high‐quality, ultrathin, and large BP sheets on top of poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate simultaneously improves the hole injection and morphology of the green‐emitting inorganic CsPbBr3 perovskite. Inclusion of the BP enhances the external quantum efficiency of CsPbBr3 based PeLEDs from 0.7% to 2.8%.

High-efficiency perovskite–polymer bulk heterostructure light-emitting diodes

Perovskite-based optoelectronic devices have gained significant attention due to their remarkable performance and low processing cost, particularly for solar cells. However, for perovskite light-emitting diodes (LEDs), non-radiative charge carrier recombination has limited electroluminescence (EL) efficiency. Here we demonstrate perovskite-polymer bulk heterostructure LEDs exhibiting record-high external quantum efficiencies (EQEs) exceeding 20%, and an EL half-life of 46 hours under continuous operation. This performance is achieved with an emissive layer comprising quasi-2D and 3D perovskites and an insulating polymer. Transient optical spectroscopy reveals that photogenerated excitations at the quasi-2D perovskite component migrate to lower-energy sites within 1 ps. The dominant component of the photoluminescence (PL) is primarily bimolecular and is characteristic of the 3D regions. From PL quantum efficiency and transient kinetics of the emissive layer with/without charge-transport contacts, we find non-radiative recombination pathways to be effectively eliminated. Light outcoupling from planar LEDs, as used in OLED displays, generally limits EQE to 20-30%, and we model our reported EL efficiency of over 20% in the forward direction to indicate the internal quantum efficiency (IQE) to be close to 100%. Together with the low drive voltages needed to achieve useful photon fluxes (2-3 V for 0.1-1 mA/cm2), these results establish that perovskite-based LEDs have significant potential for light-emission applications.

Stable, Efficient Red Perovskite Light‐Emitting Diodes by (α, δ)‐CsPbI3 Phase Engineering

AbstractRecently, inorganic cesium–lead halide perovskites with high thermal stability have attracted much attention as promising light‐emitting material for research of perovskite‐based light‐emitting diodes (PeLEDs) toward high‐definition displays. However, the CsPbI3‐based red PeLEDs still suffer low external quantum efficiency (EQE) and poor device stability due to the spontaneous phase transition from cubic CsPbI3 (α‐CsPbI3) to nonradiative orthorhombic phase (δ‐CsPbI3) under ambient conditions. Here, a feasible approach is reported on phase engineering by incorporating the long‐chain cation (e.g., 2‐(naphthalene‐1‐yl)ethanamine (NEA)) in CsPbI3 for stable and high‐performance CsPbI3‐based red light‐emitting diodes (LEDs). A high EQE of 8.65% is successfully achieved for the characteristic red emission at ≈682 nm representing the highest value among Cs‐based red PeLEDs up to now. More importantly, the corresponding PeLEDs exhibit outstanding stability with EQE retaining 90% after 3 months of storage. These results verify the potential of using cesium‐based inorganic perovskite as viable alternatives to methylammonium (MA)‐ or formamidinium (FA)‐based perovskite for desirable practical applications.

Carrier cascade: Enabling high performance perovskite light-emitting diodes (PeLEDs)

In recent years, hybrid lead-halide perovskites have emerged as promising solution-processed semiconductors for thin-film optoelectronics with a growing focus on light-emitting diode applications. Perovskites exhibit remarkable flexibilities in structure and composition tuning and possess excellent intrinsic properties such as band gap tunability over a visible range, high colour purity emission, high photoluminescence quantum yield (PLQY) and high exciton binding energies. Recently, perovskite-based light-emitting diodes (PeLEDs) have exhibited external quantum efficiency of 14.36% and revealed the potential for further improvement. High PLQY is a key requirement for better PeLED performance. This can be realised by controlling the grain-size of the perovskite films with optimum active layer thickness and utilising reduced-dimensionality perovskite emitters to spatially confine charge carriers for enhanced radiative recombination. In this short review, we discuss the critical parameters required for efficient PeLEDs, the recent progress mainly highlighting the energy transfer mechanism within Ruddlesden Popper structures and graded size nanoparticle films. We also outline the recommendations and strategies for further improvement.

Boosting Perovskite Light-Emitting Diode Performance via Tailoring Interfacial Contact.

Solution-processed perovskite light-emitting diodes (LEDs) have attracted wide attention in the past several years. However, the overall efficiency and stability of perovskite-based LEDs remain inferior to those of organic or quantum dot LEDs. Nonradiative charge recombination and the unbalanced charge injection are two critical factors that limit the device efficiency and operational stability of perovskite LEDs. Here, we develop a strategy to modify the interface between the hole transport layer and the perovskite emissive layer with an amphiphilic conjugated polymer of poly[(9,9-bis(3'-( N, N-dimethylamino)propyl)-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)] (PFN). We show evidences that PFN improves the quality of the perovskite film, which effectively suppresses nonradiative recombination. By further improving the charge injection balance rate, a green perovskite LED with a champion current efficiency of 45.2 cd/A, corresponding to an external quantum efficiency of 14.4%, is achieved. In addition, the device based on the PFN layer exhibits improved operational lifetime. Our work paves a facile way for the development of efficient and stable perovskite LEDs.

Rapid Crystallization of All-Inorganic CsPbBr3 Perovskite for High-Brightness Light-Emitting Diodes

Research into perovskite-based light-emitting diodes (PeLEDs) has been rapidly gaining momentum since the initial reports of green-emitting methylammonium lead bromide (CH3NH3PbBr3)-based devices were published. However, issues pertaining to its stability and morphological control still hamper progress toward high performing devices. Solvent engineering, a technique typically employed to modulate film crystallization, offers little opportunity for scale-up due to the tendency for inhomogeneous film growth and low degree of reproducibility. Here, we propose and show a simple gas-facilitated process to deposit a stable, all-inorganic perovskite CsPbBr3 film. The formation of smaller and less percolated grains, which gives rise to enhanced optical properties, highlights the importance of spatial charge confinement in the film. Consequently, the performance of our PeLEDs shows great improvement, with luminance as high as 8218 cd m–2 and turn-on voltage as low as 2.4 V. Concomitantly, the current efficiency and EQE of our device were increased to 0.72 cd A–1 and 0.088%, respectively. High reproducibility in the performance of PeLEDs fabricated using this process opens the path for large-area devices.

Kinetic Control of Perovskite Thin-Film Morphology and Application in Printable Light-Emitting Diodes

Highly luminescent methylammonium lead bromide (CH3NH3PbBr3) perovskite fibrous microstructure thin films have been fabricated using a perylene-3,4,9,10-tetracarboxylic dianhydride-containing antisolvent-mediated single-step fabrication method. Confocal microscopy of these thin films reveals homogeneous emission over the entire area, in contrast to the localized emission from the thin films fabricated by conventional methods. The antisolvent treatment produces pinhole-free, mazelike morphology with high photoluminescence yield. These films were incorporated as the emissive layer in thin-film light emitting diodes (LEDs), made using a low-temperature meltable and processable alloy as cathode. These LEDs gave luminescence efficiency of up to 50 Cd/m2. The proposed LED structure highlights the prospects of using low-temperature roll-to-roll processing for manufacturing perovskite-based solar cells and LEDs.

Enhanced Optical and Electrical Properties of Polymer-Assisted All-Inorganic Perovskites for Light-Emitting Diodes.

Highly bright light-emitting diodes based on solution-processed all-inorganic perovskite thin film are demonstrated. The cesium lead bromide (CsPbBr3 ) created using a new poly(ethylene oxide)-additive spin-coating method exhibits photoluminescence quantum yield up to 60% and excellent uniformity of electrical current distribution. Using the smooth CsPbBr3 films as emitting layers, green perovskite-based light-emitting diodes (PeLEDs) exhibit electroluminescent brightness and efficiency above 53 000 cd m-2 and 4%: a new benchmark of device performance for all-inorganic PeLEDs.

NiOx Electrode Interlayer and CH3 NH2 /CH3 NH3 PbBr3 Interface Treatment to Markedly Advance Hybrid Perovskite-Based Light-Emitting Diodes.

The performance of hybrid perovskite-based light-emitting diodes (LEDs) is markedly enhanced by the application of a NiOx electrode interlayer and moderate methylamine treatment. A hybrid perovskite-based LED exhibits a peak luminous efficiency of 15.9 cd A-1 biased at 8.5 V, 407.65 mA cm-2 , and 65 300 cd m-2 , showing a distinctive impact for future applications.

Polymer-Free Films of Inorganic Halide Perovskite Nanocrystals as UV-to-White Color-Conversion Layers in LEDs.

Being considerably more efficient than traditional incandescent bulbs or fluorescent tubes, light-emitting diodes (LEDs) are becoming the main technology for general lighting applications.1,2 In the last years, a variety of white-LEDs have been demonstrated employing, for example, organic molecules (OLEDs)3−7 or inorganic quantum dots (QDs) of different composition.8 A common way of achieving a white-light emission is to couple a near-UV or blue LED with down-conversion materials such as phosphors.9 More recently, QDs have been incorporated into LEDs, replacing conventional phosphors to tune finely the emission spectrum.10 Among the different available QDs, lead halide-based perovskite nanocrystals have recently emerged as very promising candidates for many optoelectronic applications.11−15 Colloidal perovskite nanocrystals can be synthesized and/or transformed postsynthesis, so that samples emitting at different wavelengths throughout the whole visible spectrum, with high photoluminescence quantum yield (PLQY), can be prepared easily. This can be achieved either by changing the chemical composition (by anion-exchange for example)16,17 or the shape (cubes, platelets, sheets, wires).18−21 Also, electroluminescence has been observed from bulk perovskite films,22−25 blended perovskite-in-polymer films,26 as well as from nanocrystals-only films27,28 leading to the first perovskite-based LEDs.

High-performance planar green light-emitting diodes based on a PEDOT:PSS/CH3NH3PbBr3/ZnO sandwich structure.

PSS/CH3NH3PbBr3/ZnO sandwich structures by a spin-coating method combined with a sputtering system. Under forward bias, a dominant emission peak at ∼530 nm with a low full width of half-maximum (FWHM) of 30 nm can be achieved at room temperature. Owing to the high surface coverage of the CH3NH3PbBr3 layer and a device design based on carrier injection and a confinement configuration, the proposed diode exhibits good electroluminescence performance, with an external quantum efficiency of 0.0645%. More importantly, we investigated the working stability of the studied diode under continuous operation to verify the sensitivity of the electroluminescence performance to ambient atmosphere and to assess the suitability of the diode for practical applications. Moreover, the underlying reasons for the undesirable emission decay are tentatively discussed. This demonstration of an effective green electroluminescence based on CH3NH3PbBr3 provides valuable information for the design and development of perovskites as efficient emitters, thus facilitating their use in existing applications and suggesting new potential applications.

Emulsion Synthesis of Size-Tunable CH3NH3PbBr3 Quantum Dots: An Alternative Route toward Efficient Light-Emitting Diodes.

We report a facile nonaqueous emulsion synthesis of colloidal halide perovskite quantum dots by controlled addition of a demulsifier into an emulsion of precursors. The size of resulting CH3NH3PbBr3 quantum dots can be tuned from 2 to 8 nm by varying the amount of demulsifier. Moreover, this emulsion synthesis also allows the purification of these quantum dots by precipitation from the colloidal solution and obtains solid-state powder which can be redissolved for thin film coating and device fabrication. The photoluminescence quantum yields of the quantum dots is generally in the range of 80-92%, and can be well-preserved after purification (∼80%). Green light-emitting diodes fabricated comprising a spin-cast layer of the colloidal CH3NH3PbBr3 quantum dots exhibited maximum current efficiency of 4.5 cd/A, power efficiency of 3.5 lm/W, and external quantum efficiency of 1.1%. This provides an alternative route toward high efficient solution-processed perovskite-based light-emitting diodes. In addition, the emulsion synthesis is versatile and can be extended for the fabrication of inorganic halide perovskite colloidal CsPbBr3 nanocrystals.