Multifunctional Conjugated Molecular Additives for Highly Efficient Perovskite Light-Emitting Diodes.

Further optimization of perovskite light-emitting diodes (PeLEDs) is impeded by crystal deformation caused by residual stress and defect formation with subsequent non-radiative recombination. Molecular additives for defect passivation are widely studied; however, the majority have insulating properties that hinder charge injection and transport. Herein, highly efficient green-emitting PeLEDs are reported by introducing semiconducting molecular additives (Fl-OEGA and Fl-C8A). Transmission electron microscopy shows that conjugated additives exist primarily at the grain boundaries of perovskite, and Kelvin probe force microscopy confirms that the variation in contact potential difference between grain boundaries and perovskite crystal domains is significantly reduced. The residual tensile stress is reduced by 13% and the activation energy for ion migration increases in the Fl-OEGA-treated perovskite film, compared to those of the film without additives. Compared to insulating 2,2'-(ethylenedioxy)diethylamine (EDEA), the introduction of semiconducting additives prevents a significant reduction in the charge-transport capability. Furthermore, the PeLEDs with Fl-OEGA show a negligible shift in the turn-on voltage and a significantly smaller decrease in the current density with increasing Fl-OEGA compared to the devices with EDEA. Finally, the 3D CsPbBr3 -PeLEDs show the highest external quantum efficiency of 21.3% by the incorporation of semiconducting Fl-OEGA as a new multifunctional additive.

Multifunctional Charge Transporting Materials for Perovskite Light-Emitting Diodes.

Despite their low exciton-binding energies, metal halide perovskites are extensively studied as light-emitting materials owing to narrow emission with high color purity, easy/wide color tunability, and high photoluminescence quantum yields. To improve the efficiency of perovskite light-emitting diodes (PeLEDs), much effort has been devoted to controlling the emitting layer morphologies to induce charge confinement and decrease the nonradiative recombination. The interfaces between the emitting layer and charge transporting layer (CTL) are vulnerable to various defects that deteriorate the efficiency and stability of the PeLEDs. Therefore, the establishment of multifunctional CTLs that can improve not only charge transport but also critical factors that influence device performance, such as defect passivation, morphology/phase control, ion migration suppression, and light outcoupling efficiency, are highly required. Herein, the fundamental limitations of perovskites as emitters (i.e., defects, morphological and phase instability, high refractive index with poor outcoupling) and the recent developments with regard to multifunctional CTLs to compensate such limitations are summarized, and their device applications are also reviewed. Finally, based on the importance of multifunctional CTLs, the outlook and research prospects of multifunctional CTLs for the further improvement of PeLEDs are discussed.

Sky-Blue-Emissive Perovskite Light-Emitting Diodes: Crystal Growth and Interfacial Control Using Conjugated Polyelectrolytes as a Hole-Transporting Layer.

A series of poly(fluorene-co-phenylene)-based anionic conjugated polyelectrolytes (CPEs) are prepared with varying sizes of counterions (tetramethylammonium, tetraethylammonium, and tetrabutylammonium (TBA+)) and studied as a hole-transporting layer (HTL) for sky-blue-emissive perovskite light-emitting diodes (PeLEDs). Ionic CPE HTLs improve the wettability, compatibility, and nucleation of perovskite crystals at interfaces, enabling highly crystalline perovskite crystal growth with enhanced light-emitting properties. By incorporating the CPE HTLs containing bulky TBA+ counterions (MPS2-TBA) in place of PEDOT:PSS, the decreased phonon-electron coupling and increased exciton binding energy in perovskites are measured by temperature-dependent photoluminescence (PL) measurements. By increasing the size of counterions in CPE interlayers, the PL intensities and lifetimes of perovskite films increase. Through space-charge-limited current measurements, the lowest trap density is measured in the perovskite film on MPS2-TBA, emphasizing a critical role of larger counterions. Using density functional theory, MPS2-TBA is calculated to show the strongest adsorption affinity toward the interstitial defect of lead ions, explaining its pronounced interfacial defect passivation. The counterion size in CPE interlayers is interpreted as a main factor to determine the adsorption affinity onto perovskite, which determines the interacted area as noncovalent adsorption occurs. Finally, the sky-blue-emissive quasi-2D PeLED with MPS2-TBA shows the highest luminance efficiency (a peak EQE of 2.6% at 489 nm) and significantly improved spectral stability.

Multiply Charged Conjugated Polyelectrolytes as a Multifunctional Interlayer for Efficient and Scalable Perovskite Solar Cells.

A series of anionic conjugated polyelectrolytes (CPEs) is synthesized based on poly(fluorene-co-phenylene) by varying the side-chain ionic density from two to six per repeat units (MPS2-TMA, MPS4-TMA, and MPS6-TMA). The effect of MPS2, 4, 6-TMA as interlayers on top of a hole-extraction layer of poly(bis(4-phenyl)-2,4,6-trimethylphenylamine (PTAA) is investigated in inverted perovskite solar cells (PeSCs). Owing to the improved wettability of perovskites on hydrophobic PTAA with the CPEs, the PeSCs with CPE interlayers demonstrate a significantly enhanced device performance, with negligible device-to-device dependence relative to the reference PeSC without CPEs. By increasing the ionic density in the MPS-TMA interlayers, the wetting, interfacial defect passivation, and crystal growth of the perovskites are significantly improved without increasing the series resistance of the PeSCs. In particular, the open-circuit voltage increases from 1.06 V for the PeSC with MPS2-TMA to 1.11 V for the PeSC with MPS6-TMA. The trap densities of the PeSCs with MPS2,4,6-TMA are further analyzed using frequency-dependent capacitance measurements. Finally, a large-area (1 cm2 ) PeSC is successfully fabricated with MPS6-TMA, showing a power conversion efficiency of 18.38% with negligible hysteresis and a stable power output under light soaking for 60 s.

Conjugated Polyelectrolytes as Multifunctional Passivating and Hole-Transporting Layers for Efficient Perovskite Light-Emitting Diodes.

Metal halide perovskites (MHPs) have attracted significant attention as light-emitting materials owing to their high color purities and tunabilities. A key issue in perovskite light-emitting diodes (PeLEDs) is the fabrication of an optimal charge transport layer (CTL), which has desirable energy levels for efficient charge injection while blocking opposite charges and enabling perovskite layer growth with reduced interfacial defects. Herein, two poly(fluorene-phenylene)-based anionic conjugated polyelectrolytes (CPEs) with different counterions (K+ and tetramethylammonium (TMA+ )) are presented as multifunctional passivating and hole-transporting layers (HTLs). The crystal growth of MHPs grown on different HTLs is investigated through X-ray photoelectron spectroscopy, X-ray diffraction, and density functional theory calculation. The CPE bearing the TMA+ counterions remarkably improves the growth of perovskites with suppressed interfacial defects, leading to significantly enhanced emission properties and device performance. The luminescent properties are further enhanced via aging and electrical stress application with effective rearrangement of the counterions on the interfacial defects in the perovskites. Finally, efficient formamidinium lead tribromide-based quasi-2D PeLEDs with an external quantum efficiency of 10.2% are fabricated. Using CPEs with varying counterions as a CTL can serve as an effective method for controlling the interfacial defects and improving perovskite-based optoelectronic device properties.

Versatile Defect Passivation Methods for Metal Halide Perovskite Materials and their Application to Light-Emitting Devices.

Metal halide perovskites (MHPs) have emerged as promising emitters because of their excellent optoelectronic properties, including high photoluminescence quantum yields (PLQYs), wide-range color tunability, and high color purity. However, a fundamental limitation of MHPs is their low exciton binding energy, which results in a low radiative recombination rate and the dependence of PLQY on the excitation intensity. Under the operating conditions of light-emitting diodes (LEDs), the injected current densities are typically lower than the trap density, leading to a low actual PLQY. Moreover, the defects not only initiate the decomposition of MHPs caused by extrinsic factors, but also intrinsically stimulate ion migration across the interface and lead to the corrosion of electrodes due to interaction between those electrodes, even under inert conditions. The passivation of defects has proven to be effective for mitigating the effects of defects in MHPs. Herein, the origins and theoretical calculations of the defect tolerance in MHPs and the impact of defects on both the performance and stability of perovskite LEDs are reviewed. The passivation methods and materials for MHP bulk films and nanocrystals are discussed in detail. Based on the currently reported advances, specific requirements and future research directions for display applications are suggested.

Control of Interface Defects for Efficient and Stable Quasi-2D Perovskite Light-Emitting Diodes Using Nickel Oxide Hole Injection Layer.

Metal halide perovskites (MHPs) have emerged as promising materials for light-emitting diodes owing to their narrow emission spectrum and wide range of color tunability. However, the low exciton binding energy in MHPs leads to a competition between the trap-mediated nonradiative recombination and the bimolecular radiative recombination. Here, efficient and stable green emissive perovskite light-emitting diodes (PeLEDs) with an external quantum efficiency of 14.6% are demonstrated through compositional, dimensional, and interfacial modulations of MHPs. The interfacial energetics and optoelectronic properties of the perovskite layer grown on a nickel oxide (NiO x ) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate hole injection interfaces are investigated. The better interface formed between the NiO x /perovskite layers in terms of lower density of traps/defects, as well as more balanced charge carriers in the perovskite layer leading to high recombination yield of carriers are the main reasons for significantly improved device efficiency, photostability of perovskite, and operational stability of PeLEDs.

Conjugated Polyelectrolytes Bearing Various Ion Densities: Spontaneous Dipole Generation, Poling-Induced Dipole Alignment, and Interfacial Energy Barrier Control for Optoelectronic Device Applications.

Conjugated polyelectrolytes (CPEs) with π-delocalized main backbones and ionic pendant groups are intensively studied as interfacial layers for efficient polymer-based optoelectronic devices (POEDs) because they facilitate facile control of charge injection/extraction barriers. Here, a simple and effective method of performing precise interfacial energy level adjustment is presented by employing CPEs with different thicknesses and various ion densities under electric poling to realize efficient charge injection/extraction of POEDs. The effects of the CPE ion densities and electric (positive or negative) poling on the energy level tuning process are investigated by measuring the open-circuit voltages and current densities of devices with the structure indium tin oxide/zinc oxide/CPE/organic active layer/molybdenum oxide/gold while changing the CPE film thickness. The performances of inverted polymer light-emitting diodes and inverted polymer solar cells are remarkably improved by precisely controlling the interfacial energy level matching using optimum CPE conditions.