Bright and Stable Red Perovskite LEDs under High Current Densities.

Perovskite LEDs (PeLEDs) have emerged as a next-generation light-emitting technology. Recent breakthroughs were made in achieving highly stable near-infrared and green PeLEDs. However, the operational lifetimes (T50) of visible PeLEDs under high current densities (>10 mA cm-2) remain unsatisfactory (normally <100 h), limiting the possibilities in solid-state lighting and AR/VR applications. This problem becomes more pronounced for mixed-halide (e.g., red and blue) perovskite emitters in which critical challenges such as halide segregation and spectral instability are present. Here, we demonstrate bright and stable red PeLEDs based on mixed-halide perovskites, showing measured T50 lifetimes of up to ∼357 h at currents of ≥25 mA cm-2, a record for the operational stability of visible PeLEDs under high current densities. The devices produce intense and stable emission with a maximum luminance of 28,870 cd m-2 (radiance: 1584 W sr-1 m-2), which is record-high for red PeLEDs. Key to this demonstration is the introduction of sulfonamide, a dipolar molecular stabilizer that effectively interacts with the ionic species in the perovskite emitters. It suppresses halide segregation and migration into the charge-transport layers, resulting in enhanced stability and brightness of the mixed-halide PeLEDs. These results represent a substantial step toward bright and stable PeLEDs for emerging applications.

Light management for perovskite light-emitting diodes.

Perovskite light-emitting diodes (LEDs) have reached external quantum efficiencies of over 20% for various colours, showing great potential for display and lighting applications. Despite the internal quantum efficiencies of the best-performing devices already approaching unity, around 80% of the internally generated photons are trapped in the devices and lose energy through a variety of lossy channels. Significant opportunities for improving efficiency and maximizing photon extraction lie in the effective management of light. In this Review we analyse light management strategies based on the intrinsic optical properties of the perovskite materials and the extrinsic properties related to device structures. These approaches should allow the external quantum efficiencies of perovskite LEDs to substantially exceed the conventional limits of planar organic LED devices. By revisiting lessons learned from organic LEDs and perovskite solar cells, we highlight possible directions of future research towards perovskite LEDs with ultrahigh efficiencies.

Advances in the Application of Perovskite Materials.

Nowadays, the soar of photovoltaic performance of perovskite solar cells has set off a fever in the study of metal halide perovskite materials. The excellent optoelectronic properties and defect tolerance feature allow metal halide perovskite to be employed in a wide variety of applications. This article provides a holistic review over the current progress and future prospects of metal halide perovskite materials in representative promising applications, including traditional optoelectronic devices (solar cells, light-emitting diodes, photodetectors, lasers), and cutting-edge technologies in terms of neuromorphic devices (artificial synapses and memristors) and pressure-induced emission. This review highlights the fundamentals, the current progress and the remaining challenges for each application, aiming to provide a comprehensive overview of the development status and a navigation of future research for metal halide perovskite materials and devices.

Stabilizing FASnI3-based perovskite light-emitting diodes with crystallization control.

The toxicity of lead presents a critical challenge for the application of perovskite optoelectronics. Lead-free perovskite solar cells were achieved with formamidinium tin iodide (FASnI3) perovskites, exhibiting decent power-conversion efficiencies (PCEs) of up to 14%, with >98% of the initial PCE retained after 3000 h of storage. However, when employed in light-emitting applications, FASnI3-based perovskite LEDs (PeLEDs) show limited stability, with T50 lifetimes of up to 0.25 h at 10 mA cm-2. Here, we improve the stability of FASnI3-based PeLEDs through the inclusion of a two-dimensional precursor phenethylamine iodide (PEAI), allowing controlled crystallization of the mixed-dimensional perovskite emitters. The density of defects is found to be reduced, accompanied by the suppression of oxidation from Sn2+ to Sn4+. Using an optimized perovskite composition, we achieve an EQE of 1.5% (a ∼10-fold improvement over the control devices), a maximum radiance of 145 W sr-1 m-2, and a record-long T50 lifetime of 10.3 h at 100 mA cm-2 for FASnI3-based PeLEDs. Our results illuminate an alternative path toward lead-free PeLED applications.

Efficient Near-Infrared Electroluminescence from Lanthanide-Doped Perovskite Quantum Cutters.

Perovskite nanocrystals (PeNCs) deliver size- and composition-tunable luminescence of high efficiency and color purity in the visible range. However, attaining efficient electroluminescence (EL) in the near-infrared (NIR) region from PeNCs is challenging, limiting their potential applications. Here we demonstrate a highly efficient NIR light-emitting diode (LED) by doping ytterbium ions into a PeNCs host (Yb3+ : PeNCs), extending the EL wavelengths toward 1000 nm, which is achieved through a direct sensitization of Yb3+ ions by the PeNC host. Efficient quantum-cutting processes enable high photoluminescence quantum yields (PLQYs) of up to 126 % from the Yb3+ : PeNCs. Through halide-composition engineering and surface passivation to improve both PLQY and charge-transport balance, we demonstrate an efficient NIR LED with a peak external quantum efficiency of 7.7 % at a central wavelength of 990 nm, representing the most efficient perovskite-based LEDs with emission wavelengths beyond 850 nm.

Ultralow-voltage operation of light-emitting diodes.

For a light-emitting diode (LED) to generate light, the minimum voltage required is widely considered to be the emitter's bandgap divided by the elementary charge. Here we show for many classes of LEDs, including those based on perovskite, organic, quantum-dot and III-V semiconductors, light emission can be observed at record-low voltages of 36-60% of their bandgaps, exhibiting a large apparent energy gain of 0.6-1.4 eV per photon. For 17 types of LEDs with different modes of charge injection and recombination (dark saturation currents of ~10-39-10-15 mA cm-2), their emission intensity-voltage curves under low voltages show similar behaviours. These observations and their consistency with the diode simulations suggest the ultralow-voltage electroluminescence arises from a universal origin-the radiative recombination of non-thermal-equilibrium band-edge carriers whose populations are determined by the Fermi-Dirac function perturbed by a small external bias. These results indicate the potential of low-voltage LEDs for communications, computational and energy applications.

Tuning Precursor-Amine Interactions for Light-Emitting Lead Bromide Perovskites.

Organic additives with amino moieties are effective in improving the properties of archetypical formamidinium (FA)-based hybrid perovskites for photovoltaic and light-emitting applications. However, a detailed understanding of how amino additives affect the perovskite materials is lacking, impeding developments in this area. Here, by investigating the interactions of lead bromide perovskite precursors with phenethylamine (PEA) and its derivatives with small variations in chemical structure, we reveal that only the secondary amine (N-methyl-2-phenylethylamine (N-PEA)) results in strengthened hydrogen bonds with FABr in precursor solutions, allowing the formation of high-quality perovskite films. The photoluminescence quantum efficiencies (PLQEs) of the resultant perovskite samples on widely used charge-transport substrates are retained to 82% of their original values, indicating reduced sensitivity to interfacial nonradiative traps critical to device applications. Using a standard device structure, green perovskite light-emitting diodes with peak external quantum efficiencies of 12.7% at ∼500 cd m-2 and operational lifetimes (T50) exceeding 10 h (at 100 cd m-2) are obtained.

Efficient light-emitting diodes based on oriented perovskite nanoplatelets.

Solution-processed planar perovskite light-emitting diodes (LEDs) promise high-performance and cost-effective electroluminescent devices ideal for large-area display and lighting applications. Exploiting emission layers with high ratios of horizontal transition dipole moments (TDMs) is expected to boost the photon outcoupling of planar LEDs. However, LEDs based on anisotropic perovskite nanoemitters remain to be inefficient (external quantum efficiency, EQE <5%) due to the difficulties of simultaneously controlling the orientations of TDMs, achieving high photoluminescence quantum yields (PLQYs) and realizing charge balance in the films of assembled nanostructures. Here, we demonstrate efficient electroluminescence from an in situ grown perovskite film composed of a monolayer of face-on oriented nanoplatelets. The ratio of horizontal TDMs of the perovskite nanoplatelet film is ~84%, which leads to a light-outcoupling efficiency of ~31%, substantially higher than that of isotropic emitters (~23%). In consequence, LEDs with a peak EQE of 23.6% are achieved, representing highly efficient planar perovskite LEDs.

Germanium-lead perovskite light-emitting diodes.

Reducing environmental impact is a key challenge for perovskite optoelectronics, as most high-performance devices are based on potentially toxic lead-halide perovskites. For photovoltaic solar cells, tin-lead (Sn-Pb) perovskite materials provide a promising solution for reducing toxicity. However, Sn-Pb perovskites typically exhibit low luminescence efficiencies, and are not ideal for light-emitting applications. Here we demonstrate highly luminescent germanium-lead (Ge-Pb) perovskite films with photoluminescence quantum efficiencies (PLQEs) of up to ~71%, showing a considerable relative improvement of ~34% over similarly prepared Ge-free, Pb-based perovskite films. In our initial demonstration of Ge-Pb perovskite LEDs, we achieve external quantum efficiencies (EQEs) of up to ~13.1% at high brightness (~1900 cd m-2), a step forward for reduced-toxicity perovskite LEDs. Our findings offer a new solution for developing eco-friendly light-emitting technologies based on perovskite semiconductors.

Lanthanide-doped inorganic nanoparticles turn molecular triplet excitons bright.

The generation, control and transfer of triplet excitons in molecular and hybrid systems is of great interest owing to their long lifetime and diffusion length in both solid-state and solution phase systems, and to their applications in light emission1, optoelectronics2,3, photon frequency conversion4,5 and photocatalysis6,7. Molecular triplet excitons (bound electron-hole pairs) are 'dark states' because of the forbidden nature of the direct optical transition between the spin-zero ground state and the spin-one triplet levels8. Hence, triplet dynamics are conventionally controlled through heavy-metal-based spin-orbit coupling9-11 or tuning of the singlet-triplet energy splitting12,13 via molecular design. Both these methods place constraints on the range of properties that can be modified and the molecular structures that can be used. Here we demonstrate that it is possible to control triplet dynamics by coupling organic molecules to lanthanide-doped inorganic insulating nanoparticles. This allows the classically forbidden transitions from the ground-state singlet to excited-state triplets to gain oscillator strength, enabling triplets to be directly generated on molecules via photon absorption. Photogenerated singlet excitons can be converted to triplet excitons on sub-10-picosecond timescales with unity efficiency by intersystem crossing. Triplet exciton states of the molecules can undergo energy transfer to the lanthanide ions with unity efficiency, which allows us to achieve luminescent harvesting of the dark triplet excitons. Furthermore, we demonstrate that the triplet excitons generated in the lanthanide nanoparticle-molecule hybrid systems by near-infrared photoexcitation can undergo efficient upconversion via a lanthanide-triplet excitation fusion process: this process enables endothermic upconversion and allows efficient upconversion from near-infrared to visible frequencies in the solid state. These results provide a new way to control triplet excitons, which is essential for many fields of optoelectronic and biomedical research.

Circularly Polarized Photoluminescence from Chiral Perovskite Thin Films at Room Temperature.

Hybrid organic-inorganic perovskites allow the synthesis of high-quality, nanostructured semiconducting films via easily accessible solution-based techniques. This has allowed tremendous development in optoelectronic applications, primarily solar cells and light-emitting diodes. Allowed by the ease of access to nanostructure, chirality has recently been introduced in semiconducting perovskites as a promising way to obtain advanced control of charge and spin and for developing circularly polarized light sources. Circular polarization of photoluminescence (CPL) is a powerful tool to probe the electronic structure of materials. However, CPL in chiral perovskites has been scarcely investigated, and a study in bulk thin films and at room temperature is still missing. In this work, we fabricate bromine-based chiral perovskites by using a bulky chiral organic cation mixed with CsBr, resulting in Ruddlesden-Popper perovskite thin films. We measure CPL on these films at room temperature and, by using unpolarized photoexcitation, we record a degree of circular polarization of photoluminescence in the order of 10-3 and provide a full spectral characterization of CPL. Our results show that chirality is imparted on the electronic structure of the semiconductor; we hypothesize that the excess in polarization of emitted light originates from the charge in the photogenerated Wannier exciton describing an orbit in a symmetry-broken environment. Furthermore, our experiments allow the direct measurement of the magnetic dipole moment of the optical transition, which we estimate to be ≥0.1 µB. Finally, we discuss the implications of our findings on the development of chiral semiconducting perovskites as sources of circularly polarized light.

The role of photon recycling in perovskite light-emitting diodes.

Perovskite light-emitting diodes have recently broken the 20% barrier for external quantum efficiency. These values cannot be explained with classical models for optical outcoupling. Here, we analyse the role of photon recycling (PR) in assisting light extraction from perovskite light-emitting diodes. Spatially-resolved photoluminescence and electroluminescence measurements combined with optical modelling show that repetitive re-absorption and re-emission of photons trapped in substrate and waveguide modes significantly enhance light extraction when the radiation efficiency is sufficiently high. In this manner, PR can contribute more than 70% to the overall emission, in agreement with recently-reported high efficiencies. While an outcoupling efficiency of 100% is theoretically possible with PR, parasitic absorption losses due to absorption from the electrodes are shown to limit practical efficiencies in current device architectures. To overcome the present limits, we propose a future configuration with a reduced injection electrode area to drive the efficiency toward 100%.

Triple-Cation-Based Perovskite Photocathodes with AZO Protective Layer for Hydrogen Production Applications.

Metal halide perovskites are actively pursued as photoelectrodes to drive solar fuel synthesis. However, currently, these photocathodes suffer from limited stability in water, which hampers their practical application. Here, we report a high-performance solution-processable photocathode composed of cesium formamidinium methylammonium triple-cation lead halide perovskite protected by an Al-doped ZnO (AZO) layer combined with a Field's metal encapsulation. Careful selection of charge transport layers resulted in an improvement in photocurrent, fill factor, device stability and reproducibility. The dead pixels count reduced from 25 to 6% for the devices with an AZO layer, and in photocathodes with an AZO layer the photocurrent density increased by almost 20% to 14.3 mA cm-2. In addition, we observed a 5-fold increase in the device lifetime for photocathodes with AZO, which reached up to 18 h before complete failure. Finally, the photocathodes are fabricated using low-cost and scalable methods, which have promise to become compatible with standard solution-based processes.

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.

In Situ Atmospheric Deposition of Ultrasmooth Nickel Oxide for Efficient Perovskite Solar Cells.

Organic-inorganic perovskite solar cells have attracted significant attention due to their remarkable performance. The use of alternative metal-oxide charge-transport layers is a strategy to improving device reliability for large-scale fabrication and long-term applications. Here, we report solution-processed perovskite solar cells employing nickel oxide hole-extraction layers produced in situ using an atmospheric pressure spatial atomic-layer deposition system, which is compatible with high-throughput processing of electronic devices from solution. Our sub-nanometer smooth (average roughness of ≤0.6 nm) oxide films enable the efficient collection of holes and the formation of perovskite absorbers with high electronic quality. Initial solar-cell experiments show a power-conversion efficiency of 17.1%, near-unity ideality factors, and a fill factor of >80% with negligible hysteresis. Transient measurements reveal that a key contributor to this performance is the reduced luminescence quenching trap density in the perovskite/nickel oxide structure.

Conjugated Polyelectrolytes as Efficient Hole Transport Layers in Perovskite Light-Emitting Diodes.

Perovskite-based optoelectronic devices have been rapidly developing in the past 5 years. Since the first report, the external quantum efficiency (EQE) of perovskite light-emitting diodes (PeLEDs) has increased rapidly through the control of morphology and structure from 0.1% to more than 11%. Here, we report the use of various conjugated polyelectrolytes (CPEs) as the hole injection layer in PeLEDs. In particular, we find that poly[2,6-(4,4-bis-potassium butanylsulfonate)-4 H-cyclopenta-[2,1- b;3,4- b']-dithiophene)] (PCPDT-K) transfers holes effectively, blocks electron transport from the perovskite to the underlying ITO layer, and reduces luminescence quenching at the perovskite/PCPDT-K interface. Our optimized PeLEDs with PCPDT-K show enhanced EQE by a factor of approximately 4 compared to control PeLEDs with PEDOT:PSS, reaching EQE values of 5.66%, and exhibit improved device stability.

Growth of Nanosized Single Crystals for Efficient Perovskite Light-Emitting Diodes.

Organic-inorganic hybrid perovskites are emerging as promising emitting materials due to their narrow full-width at half-maximum emissions, color tunability, and high photoluminescence quantum yields (PLQYs). However, the thermal generation of free charges at room temperature results in a low radiative recombination rate and an excitation-intensity-dependent PLQY, which is associated with the trap density. Here, we report perovskite films composed of uniform nanosized single crystals (average diameter = 31.7 nm) produced by introducing bulky amine ligands and performing the growth at a lower temperature. By effectively controlling the crystal growth, we maximized the radiative bimolecular recombination yield by reducing the trap density and spatially confining the charges. Finally, highly bright and efficient green emissive perovskite light-emitting diodes that do not suffer from electroluminescence blinking were achieved with a luminance of up to 55 400 cd m-2, current efficiency of 55.2 cd A-1, and external quantum efficiency of 12.1%.

High Circular Polarization of Electroluminescence Achieved via Self-Assembly of a Light-Emitting Chiral Conjugated Polymer into Multidomain Cholesteric Films.

We demonstrate a facile route to obtain high and broad-band circular polarization of electroluminescence in single-layer polymer OLEDs. As a light-emitting material we use a donor-acceptor polyfluorene with enantiomerically pure chiral side-chains. We show that upon thermal annealing the polymer self-assembles into a multidomain cholesteric film. By varying the thickness of the polymer emitting layer, we achieve high levels of circular polarization of electroluminescence (up to 40% excess of right-handed polarization), which are the highest reported for polymer OLEDs not using chiral dopants or alignment layers. Mueller matrix ellipsometry shows strong optical anisotropies in the film, indicating that the circular polarization of luminescence arises mainly after the photon has been generated, through selective scattering and birefringence correlated in the direction of the initial linear polarization of the photon. Our work demonstrates that chirally substituted conjugated polymers can combine photonic and semiconducting properties in advanced optoelectronic devices.

Ultrafast carrier thermalization in lead iodide perovskite probed with two-dimensional electronic spectroscopy.

In band-like semiconductors, charge carriers form a thermal energy distribution rapidly after optical excitation. In hybrid perovskites, the cooling of such thermal carrier distributions occurs on timescales of about 300 fs via carrier-phonon scattering. However, the initial build-up of the thermal distribution proved difficult to resolve with pump-probe techniques due to the requirement of high resolution, both in time and pump energy. Here, we use two-dimensional electronic spectroscopy with sub-10 fs resolution to directly observe the carrier interactions that lead to a thermal carrier distribution. We find that thermalization occurs dominantly via carrier-carrier scattering under the investigated fluences and report the dependence of carrier scattering rates on excess energy and carrier density. We extract characteristic carrier thermalization times from below 10 to 85 fs. These values allow for mobilities of 500 cm2 V-1 s-1 at carrier densities lower than 2 × 1019 cm-3 and limit the time for carrier extraction in hot carrier solar cells.Carrier-carrier scattering rates determine the fundamental limits of carrier transport and electronic coherence. Using two-dimensional electronic spectroscopy with sub-10 fs resolution, Richter and Branchi et al. extract carrier thermalization times of 10 to 85 fs in hybrid perovskites.

High Open-Circuit Voltages in Tin-Rich Low-Bandgap Perovskite-Based Planar Heterojunction Photovoltaics.

Low-bandgap CH3 NH3 (Pbx Sn1-x )I3 (0 ≤ x ≤ 1) hybrid perovskites (e.g., ≈1.5-1.1 eV) demonstrating high surface coverage and superior optoelectronic properties are fabricated. State-of-the-art photovoltaic (PV) performance is reported with power conversion efficiencies approaching 10% in planar heterojunction architecture with small (<450 meV) energy loss compared to the bandgap and high (>100 cm2 V-1 s-1 ) intrinsic carrier mobilities.