Solution-processed, high-performance light-emitting diodes based on quantum dots
TL;DR: This optoelectronic performance is achieved by inserting an insulating layer between the quantum dot layer and the oxide electron-transport layer to optimize charge balance in the device and preserve the superior emissive properties of the quantum dots.
Abstract: Solution-processed optoelectronic and electronic devices are attractive owing to the potential for low-cost fabrication of large-area devices and the compatibility with lightweight, flexible plastic substrates. Solution-processed light-emitting diodes (LEDs) using conjugated polymers or quantum dots as emitters have attracted great interest over the past two decades. However, the overall performance of solution-processed LEDs--including their efficiency, efficiency roll-off at high current densities, turn-on voltage and lifetime under operational conditions-remains inferior to that of the best vacuum-deposited organic LEDs. Here we report a solution-processed, multilayer quantum-dot-based LED with excellent performance and reproducibility. It exhibits colour-saturated deep-red emission, sub-bandgap turn-on at 1.7 volts, high external quantum efficiencies of up to 20.5 per cent, low efficiency roll-off (up to 15.1 per cent of the external quantum efficiency at 100 mA cm(-2)), and a long operational lifetime of more than 100,000 hours at 100 cd m(-2), making this device the best-performing solution-processed red LED so far, comparable to state-of-the-art vacuum-deposited organic LEDs. This optoelectronic performance is achieved by inserting an insulating layer between the quantum dot layer and the oxide electron-transport layer to optimize charge balance in the device and preserve the superior emissive properties of the quantum dots. We anticipate that our results will be a starting point for further research, leading to high-performance, all-solution-processed quantum-dot-based LEDs ideal for next-generation display and solid-state lighting technologies.
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TL;DR: In this article, the authors describe visible-light-emitting perovskite LEDs that surpass the quantum efficiency milestone of 20.3 per cent, which is achieved by a new strategy for managing the compositional distribution in the device.
Abstract: Metal halide perovskite materials are an emerging class of solution-processable semiconductors with considerable potential for use in optoelectronic devices1–3. For example, light-emitting diodes (LEDs) based on these materials could see application in flat-panel displays and solid-state lighting, owing to their potential to be made at low cost via facile solution processing, and could provide tunable colours and narrow emission line widths at high photoluminescence quantum yields4–8. However, the highest reported external quantum efficiencies of green- and red-light-emitting perovskite LEDs are around 14 per cent7,9 and 12 per cent8, respectively—still well behind the performance of organic LEDs10–12 and inorganic quantum dot LEDs13. Here we describe visible-light-emitting perovskite LEDs that surpass the quantum efficiency milestone of 20 per cent. This achievement stems from a new strategy for managing the compositional distribution in the device—an approach that simultaneously provides high luminescence and balanced charge injection. Specifically, we mixed a presynthesized CsPbBr3 perovskite with a MABr additive (where MA is CH3NH3), the differing solubilities of which yield sequential crystallization into a CsPbBr3/MABr quasi-core/shell structure. The MABr shell passivates the nonradiative defects that would otherwise be present in CsPbBr3 crystals, boosting the photoluminescence quantum efficiency, while the MABr capping layer enables balanced charge injection. The resulting 20.3 per cent external quantum efficiency represents a substantial step towards the practical application of perovskite LEDs in lighting and display. A strategy for managing the compositional distribution in metal halide perovskite light-emitting diodes enables them to surpass 20% external quantum efficiency—a step towards their practical application in lighting and displays.
2,346 citations
TL;DR: The demonstration of these novel quantum-dot light-emitting diodes based on all-inorganic perovskite CsPbX3 (X = Cl, Br, I) nanocrystals opens a new avenue toward designing optoelectronic devices, such as displays, photodetectors, solar cells, and lasers.
Abstract: Novel quantum-dot light-emitting diodes based on all-inorganic perovskite CsPbX3 (X = Cl, Br, I) nanocrystals are reported. The well-dispersed, single-crystal quantum dots (QDs) exhibit high quantum yields, and tunable light emission wavelength. The demonstration of these novel perovskite QDs opens a new avenue toward designing optoelectronic devices, such as displays, photodetectors, solar cells, and lasers.
2,311 citations
TL;DR: In this paper, a room-temperature (RT) synthesis of CsPbX3@X quantum-well band alignment is proposed to guarantee the excitons generation and high-rate radiative recombination at RT.
Abstract: Recently, Kovalenko and co-workers and Li and co-workers developed CsPbX3 (X = Cl, Br, I) inorganic perovskite quantum dots (IPQDs), which exhibited ultrahigh photoluminescence (PL) quantum yields (QYs), low-threshold lasing, and multicolor electroluminescence. However, the usual synthesis needs high temperature, inert gas protection, and localized injection operation, which are severely against applications. Moreover, the so unexpectedly high QYs are very confusing. Here, for the first time, the IPQDs' room-temperature (RT) synthesis, superior PL, underlying origins and potentials in lighting and displays are reported. The synthesis is designed according to supersaturated recrystallization (SR), which is operated at RT, within few seconds, free from inert gas and injection operation. Although formed at RT, IPQDs' PLs have QYs of 80%, 95%, 70%, and FWHMs of 35, 20, and 18 nm for red, green, and blue emissions. As to the origins, the observed 40 meV exciton binding energy, halogen self-passivation effect, and CsPbX3@X quantum-well band alignment are proposed to guarantee the excitons generation and high-rate radiative recombination at RT. Moreover, such superior optical merits endow them with promising potentials in lighting and displays, which are primarily demonstrated by the white light-emitting diodes with tunable color temperature and wide color gamut.
1,932 citations
TL;DR: Perovskite quantum wells yield highly efficient LEDs spanning the visible and near-infrared as discussed by the authors. But their performance is not as good as those of traditional LEDs, and their lifetime is shorter.
Abstract: Perovskite quantum wells yield highly efficient LEDs spanning the visible and near-infrared.
1,419 citations
TL;DR: The formation of submicrometre-scale structure in perovskite light-emitting diodes can raise their external quantum efficiency beyond 20%, suggesting the possibility of both high efficiency and high brightness.
Abstract: Light-emitting diodes (LEDs), which convert electricity to light, are widely used in modern society—for example, in lighting, flat-panel displays, medical devices and many other situations. Generally, the efficiency of LEDs is limited by nonradiative recombination (whereby charge carriers recombine without releasing photons) and light trapping1–3. In planar LEDs, such as organic LEDs, around 70 to 80 per cent of the light generated from the emitters is trapped in the device4,5, leaving considerable opportunity for improvements in efficiency. Many methods, including the use of diffraction gratings, low-index grids and buckling patterns, have been used to extract the light trapped in LEDs6–9. However, these methods usually involve complicated fabrication processes and can distort the light-output spectrum and directionality6,7. Here we demonstrate efficient and high-brightness electroluminescence from solution-processed perovskites that spontaneously form submicrometre-scale structures, which can efficiently extract light from the device and retain wavelength- and viewing-angle-independent electroluminescence. These perovskites are formed simply by introducing amino-acid additives into the perovskite precursor solutions. Moreover, the additives can effectively passivate perovskite surface defects and reduce nonradiative recombination. Perovskite LEDs with a peak external quantum efficiency of 20.7 per cent (at a current density of 18 milliamperes per square centimetre) and an energy-conversion efficiency of 12 per cent (at a high current density of 100 milliamperes per square centimetre) can be achieved—values that approach those of the best-performing organic LEDs. The formation of submicrometre-scale structure in perovskite light-emitting diodes can raise their external quantum efficiency beyond 20%, suggesting the possibility of both high efficiency and high brightness.
1,404 citations
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TL;DR: Research in the use of organic polymers as active semiconductors in light-emitting diodes has advanced rapidly, and prototype devices now meet realistic specifications for applications.
Abstract: Research in the use of organic polymers as the active semiconductors in light-emitting diodes has advanced rapidly, and prototype devices now meet realistic specifications for applications. These achievements have provided insight into many aspects of the background science, from design and synthesis of materials, through materials fabrication issues, to the semiconductor physics of these polymers.
5,653 citations
TL;DR: A class of metal-free organic electroluminescent molecules in which the energy gap between the singlet and triplet excited states is minimized by design, thereby promoting highly efficient spin up-conversion from non-radiative triplet states to radiative singlet states while maintaining high radiative decay rates.
Abstract: The inherent flexibility afforded by molecular design has accelerated the development of a wide variety of organic semiconductors over the past two decades. In particular, great advances have been made in the development of materials for organic light-emitting diodes (OLEDs), from early devices based on fluorescent molecules to those using phosphorescent molecules. In OLEDs, electrically injected charge carriers recombine to form singlet and triplet excitons in a 1:3 ratio; the use of phosphorescent metal-organic complexes exploits the normally non-radiative triplet excitons and so enhances the overall electroluminescence efficiency. Here we report a class of metal-free organic electroluminescent molecules in which the energy gap between the singlet and triplet excited states is minimized by design, thereby promoting highly efficient spin up-conversion from non-radiative triplet states to radiative singlet states while maintaining high radiative decay rates, of more than 10(6) decays per second. In other words, these molecules harness both singlet and triplet excitons for light emission through fluorescence decay channels, leading to an intrinsic fluorescence efficiency in excess of 90 per cent and a very high external electroluminescence efficiency, of more than 19 per cent, which is comparable to that achieved in high-efficiency phosphorescence-based OLEDs.
5,297 citations
TL;DR: In this paper, the excited electronic states of semiconductor crystallites sufficiently small (∼50 A diam) that the electronic properties differ from those of bulk materials were modeled, and an approximate formula was given for the lowest excited electronic state energy.
Abstract: We model, in an elementary way, the excited electronic states of semiconductor crystallites sufficiently small (∼50 A diam) that the electronic properties differ from those of bulk materials. In this limit the excited states and ionization processes assume a molecular‐like character. However, diffraction of bonding electrons by the periodic lattice potential remains of paramount importance in the crystallite electronic structure. Schrodinger’s equation is solved at the same level of approximation as used in the analysis of bulk crystalline electron‐hole states (Wannier excitons). Kinetic energy is treated by the effective mass approximation, and the potential energy is due to high frequency dielectric solvation by atomic core electrons. An approximate formula is given for the lowest excited electronic state energy. This expression is dependent upon bulk electronic properties, and contains no adjustable parameters. The optical f number for absorption and emission is also considered. The same model is applied to the problem of two conduction band electrons in a small crystallite, in order to understand how the redox potential of excess electrons depends upon crystallite size.
4,322 citations
TL;DR: In this article, solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤ 5%, are presented.
Abstract: ▪ Abstract Solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤5%, are presented. Preparation of monodisperse samples enables systematic characterization of the structural, electronic, and optical properties of materials as they evolve from molecular to bulk in the nanometer size range. Sample uniformity makes it possible to manipulate nanocrystals into close-packed, glassy, and ordered nanocrystal assemblies (superlattices, colloidal crystals, supercrystals). Rigorous structural characterization is critical to understanding the electronic and optical properties of both nanocrystals and their assemblies. At inter-particle separations 5–100 A, dipole-dipole interactions lead to energy transfer between neighboring nanocrystals, and electronic tunneling between proximal nanocrystals gives rise to dark and photoconductivity. At separations <5 A, exchange interactions cause otherwise insulating ass...
4,116 citations
TL;DR: In this article, a hybrid organic/inorganic electroluminescent device was constructed based on the recombination of holes injected into a layer of semiconducting p-paraphenylene vinylene (PPV) with electrons injected into the multilayer film of cadmium selenide nanocrystals.
Abstract: ELECTROLUMINESCENT devices have been developed recently that are based on new materials such as porous silicon1 and semiconducting polymers2,3. By taking advantage of developments in the preparation and characterization of direct-gap semiconductor nanocrystals4–6, and of electroluminescent polymers7, we have now constructed a hybrid organic/inorganic electroluminescent device. Light emission arises from the recombination of holes injected into a layer of semiconducting p-paraphenylene vinylene (PPV)8–10 with electrons injected into a multilayer film of cadmium selenide nanocrystals. Close matching of the emitting layer of nanocrystals with the work function of the metal contact leads to an operating voltage11 of only 4V. At low voltages emission from the CdSe layer occurs. Because of the quantum size effect19–24 the colour of this emission can be varied from red to yellow by changing the nanocrystal size. At higher voltages green emission from the polymer layer predominates. Thus this device has a degree of voltage tunability of colour.
3,783 citations