Quantum Efficiency Enhancement of Lead-Halide Perovskite Nanocrystal LEDs by Organic Lithium Salt Treatment
Tassilo Naujoks, Roshini Jayabalan, Christopher Kirsch, Fengshuo Zu, Mukunda Mandal, Jan Wahl, Martin Waibel, Andreas Opitz, Norbert Koch, Denis Andrienko, Marc… 展开作者
Tassilo Naujoks, Roshini Jayabalan, Christopher Kirsch, Fengshuo Zu, Mukunda Mandal, Jan Wahl, Martin Waibel, Andreas Opitz, Norbert Koch, Denis Andrienko, Marcus Scheele, Wolfgang Brütting
Surface-defect passivation is key to achieving high photoluminescence quantum yield in lead halide perovskite nanocrystals. However, in perovskite light-emitting diodes these surface ligands also have to enable balanced charge injection into the nanocrystals to yield high efficiency and operational lifetime. In this respect, alkaline halides have been reported to passivate surface trap states and increase the overall stability of perovskite light emitters. On the one side, the incorporation of alkaline ions into the lead halide perovskite crystal structure is considered to counterbalance cation vacancies, while, on the other side, the excess halides are believed to stabilise the colloids. Here, we report an organic lithium salt, viz. LiTFSI, as a halide-free surface passivation on perovskite nanocrystals. We show that the treatment LiTFSI has multiple beneficial effects on lead halide perovskite nanocrystals and LEDs derived from them. We obtain higher photoluminescence quantum yield and longer exciton lifetime, and a radiation pattern that is more favourable for light outcoupling. The ligand-induced dipoles on the nanocrystal surface shift their energy levels toward lower hole-injection barrier. Overall, these effects add up to a four- to seven-fold boost of the external quantum efficiency in proof-of-concept LED structures, depending on the color of the used lead halide perovskite nanocrystal emitters.
Previous theoretical calculations show azetidinium has the right radial size to form a 3D perovskite with lead halides [1], and has been shown to impart, as the A-site cation of ABX3 unit, beneficial properties to ferroelectric perovskites [2]. However, there has been very limited research into its use as the cation in lead halide perovskites to date. In this communication we report the synthesis and characterization of azetidinium-based lead mixed halide perovskite colloidal nanocrystals. The mixed halide system is iodine and chlorine unlike other reported nanocrystals in the literature where…
Perovskite nanocrystal light-emitting diodes (LEDs) employing architecture comprising a ZnO nanoparticles electron-transport layer and a conjugated polymer hole-transport layer have been fabricated. The obtained LEDs demonstrate a maximum external-quantum-efficiency of 6.04%, luminance of 12998 Cd/m2 and stable electroluminescence at 519 nm. Importantly, such high efficiency and brightness have been achieved by employing solution processed transport layers, formamidinium lead bromide nanocrystals (CH(NH2)2PbBr3 NCs) synthesized at room-temperature and in air without the use of a Schlenk line, …
Lead halide perovskite nanocrystals (NCs) are currently emerging as one of the most interesting solution processed semiconductors since they possess high photoluminescence quantum yield (PLQY), and colour tunability through anion exchange reactions or quantum confinement. Here, we show efficient solar cells based on mixed halide (CsPbBrI2) NCs obtained via anion exchange reactions in ambient conditions. We performed anion exchange reactions in concentrated NC solutions with I-, thus inducing a PL red-shift up to 676 nm, and obtaining a high PLQY in film (65%). Solar cell devices operating in t…
All-inorganic lead halide perovskite nanocrystals (NCs) show potential in optoelectronic devices, though their stability and efficiency have yet to improve. In this work, we explore the effect of bivalent metal site doping on the optoelectronic properties of CsPbX$_3$ (X = Br, Cl) perovskite NCs. First, the Pb$^{2+}$ ions in pristine CsPbBr$_3$ NC are partially substituted by Mn$^{2+}$ ions, and the alkaline earth metal strontium is then doped on both pristine and Mn$^{2+}$-substituted particles. The structural and photophysical properties of the pristine and the three doped NC variants have b…
Light-emitting diodes based on perovskite nanocrystals (PNCs-LEDs) have gained great interest for next-generation display and lighting technologies prized for their color purity, high brightness and luminous efficiency approaching the intrinsic limit imposed by extraction of electroluminescence from the device structure. Although the time is ripe for the development of effective light outcoupling strategies to further boost the device performance, this technologically relevant aspect of PNC-LEDs is still without a definitive solution. Here, following theoretical guidelines and without the inte…
The optoelectric applications, light emitters and photovoltaics, with organometallic halide perovskite materials have been decided by dynamics of charge carriers in grains on the polycrystalline thin films. Especially, polar solvent vapour recrystallizes perovskites and changes their grain sizes. In this paper, various polar solvents were evaluated with density functional theory calculation. And a stociometric treatment with these solvents which enhanced photoluminescence intensity was established. The properties of solvents which caused dramatic photoluminescence enhancement and quantum confi…
Dark ground state exciton in semiconductor nanocrystals has been a subject of much interest due to its long lifetime attractive for applications requiring long-lived electronic or spin states. Significant effort has been made recently to explore and access the dark exciton level in metal halide perovskite nanocrystals, which are emerging as a superior source of photons and charges compared to other existing semiconductor nanocrystals. However, the direct observation of long-lived photoluminescence from dark exciton has remained elusive in metal halide perovskite nanocrystals. Here, we report t…
Electroluminescence (EL) of colloidal nanocrystals promises a new generation of high-performance and solution-processable light-emitting diodes (LEDs). The operation of nanocrystal-based LEDs relies on the recombination of electrically-generated excitons. However, a fundamental question, i.e, how excitons are electrically generated in individual nanocrystals, remains unanswered. Here, we reveal a molecular mechanism of sequential electron-hole injection for the exciton generation in nanocrystal-based EL devices. To decipher the corresponding elementary processes, we develop electrically-pumped…
Halide perovskite nanocrystals (NCs) have shown impressive advances, exhibiting optical properties that outpace conventional semiconductor NCs, such as near-unity quantum yields and ultrafast radiative decay rates. Nevertheless, the NCs suffer even more from stability problems at ambient conditions and due to moisture than their bulk counterparts. Herein, we report a strategy of employing polymer micelles as nanoreactors for the synthesis of methylammonium lead trihalide perovskite NCs. Encapsulated by this polymer shell, the NCs display strong stability against water degradation and halide io…
Lead-halide perovskites have been attracting attention for potential use in solid-state lighting. Following the footsteps of solar cells, the field of perovskite light-emitting diodes (PeLEDs) has been growing rapidly. Their application prospects in lighting, however, remain still uncertain due to a variety of shortcomings in device performance including their limited levels of luminous efficiency achievable thus far. Here we show high-efficiency PeLEDs based on colloidal perovskite nanocrystals (PeNCs) synthesized at room temperature possessing dominant first-order excitonic radiation (enabli…
Halide perovskite nanocrystals (NCs) have emerged as a promising material for applications ranging from light-emitting diodes (LEDs) to solar cells and photodetectors. Still, several issues impede the realization of the nanocrystals' full potential, most notably their susceptibility to degradation from environmental stress. This work demonstrates highly stable perovskite nanocrystals (NCs) with quantum yields as high as 95 % by exploiting a ligand-assisted copolymer nanoreactor-based synthesis. The organic ligands thereby serve a dual function by enhancing the uptake of precursors and passivat…
Organic-inorganic halide perovskites recently have emerged as a promising material for highly effective light-emitting diodes (LEDs) and solar cells (SCs). Despite efficiencies of both perovskite SCs and LEDs are already among the best, the development of a perovskite dual functional device that is capable of working in these two regimes with high efficiencies is still challenging. Here we demonstrate that the dual functional device based on mixed halide perovskite CH3NH3PbBr2I can be switched from SC to LED with low threshold voltage Vth < 2 V by exposing to Sun at open circuit Voc or at smal…
The dynamical and static Rashba effects in hybrid methylammonium (MA) lead halide perovskites have recently been theoretically predicted. However, only the static effect was experimentally confirmed so far. Here we report on the dynamical Rashba effect observed using snapshot transient absorption spectral imaging with 400 nm pumping for a fully encapsulated film of 20-nm-sized 3D MAPbBr3 nanocrystals. The effect causes a 240 meV splitting of the lowest-energy absorption bleaching band, initially appearing over sub-ps timescale and progressively stabilizing to 60 meV during 500 ps. The integrat…
The radiative recombination of injected charge carriers gives rise to electroluminescence (EL), a central process for light-emitting diode (LED) operation. It is often presumed in some emerging fields of optoelectronics, including perovskite and organic LEDs, that the minimum voltage required for light emission is the semiconductor bandgap divided by the elementary charge. Here we show for many classes of LEDs, including those based on metal halide perovskite, organic, chalcogenide quantum-dot and commercial III-V semiconductors, photon emission can be generally observed at record-low driving …
We study the nature of photo-excited charge carriers in CsPbBr3 nanocrystal thin films by ultrafast optical pump - THz probe spectroscopy. We observe a deviation from a pure Drude dispersion of the THz dielectric response that is ascribed to the polaronic nature of carriers; a transient blueshift of observed phonon frequencies is indicative of the coupling between photogenerated charges and stretching-bending modes of the deformed inorganic sublattice, as confirmed by DFT calculations.
Metal-halide perovskite nanocrystals have demonstrated excellent optoelectronic properties for light-emitting applications. Isovalent doping with various metals (M2+) can be used to tailor and enhance their light emission. Although crucial to maximize performance, an understanding of the universal working mechanism for such doping is still missing. Here, we directly compare the optical properties of nanocrystals containing the most commonly employed dopants, fabricated under identical synthesis conditions. We show for the first time unambiguously and supported by first principles calculations …
2D quantum confined hybrid materials are of great interest from a solid state physics standpoint because of the rich multibody phenomena hosted, their tunability and easy synthesis allowing to create material libraries. In addition, from a technological standpoint, 2D hybrids are promising candidates for efficient, tunable, low cost materials impacting a broad range of optoelectronic devices. Different approaches and materials have therefore been investigated, with the notable example of 2D metal halide hybrid perovskites. Despite the remarkable properties of such materials, the presence of to…
Unbalanced charge injection is deleterious for the performance of colloidal quantum dot (CQD) light emitting diodes (LEDs) as it deteriorates the quantum efficiency (QE), brightness and operational lifetime. CQD LEDs emitting in the infrared have previously achieved high quantum efficiencies but only when driven to emit in the low radiance regime. At higher radiance levels, required for practical applications, the efficiency decreased dramatically in view of the notorious efficiency droop. Here we report a novel methodology to regulate charge supply in multinary bandgap CQD composites that fac…
Exploring epitaxial structures for electrically pumped perovskite lasers: a study of CsPb(Br,I)$_3$ based on the \textit{ab initio} Bethe-Salpeter equation
Transition between cooperative emission regimes in giant perovskite nanocrystals
IBM Research Europe – Zurich（IBM欧洲苏黎世研究中心）；Institute of Inorganic Chemistry, Department of Chemistry and Applied Bioscience, ETH Zurich（苏黎世联邦理工学院应用化学与生物科学系无机化学研究所）；Laboratory of Thin Films and Photovoltaics, Empa — Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科技与测试研究院薄膜与光伏实验室）
Although the structural phase transitions in single-crystal hybrid methyl-ammonium (MA) lead halide perovskites (MAPbX3, X = Cl, Br, I) are common phenomena, they have never been observed in the corresponding nanocrystals. Here we demonstrate that two-photon-excited photoluminescence (PL) spectroscopy is capable of monitoring the structural phase transitions in MAPbX3 nanocrystals because nonlinear susceptibilities govern the light absorption rates. We provide experimental evidence that the orthorhombic-to-tetragonal structural phase transition in a single layer of 20-nm-sized 3D MAPbBr3 nanoc…
The relaxation of high-energy "hot" carriers in semiconductors is known to involve the redistribution of energy between (i) hot and cold carriers and (ii) hot carriers and phonons. Over the past few years, these two processes have been identified in lead-halide perovskites (LHPs) using ultrafast pump-probe experiments, but the interplay between these processes is not fully understood. Here we present a comprehensive kinetic model to elucidate the individual effects of the hot and cold carriers in bulk and nanocrystal $CsPbBr_{3}$ films obtained from "pump-push-probe" measurements. In accordanc…
Metal halide perovskites (MHPs) based phosphor-converted light-emitting diodes (pc-LEDs) are limited by the low MHP stability under storage/operation conditions. A few works have recently stablished the in-situ synthesis of MHPs into polymer matrices as an effective strategy to enhance MHPs stability with a low-cost fabrication. However, this is limited within petrochemical-based polymers. Herein, the first in-situ ambient preparation of highly luminescent and stable MHPs-bio-polymer filters (MAPbBr3 nanocrystals as emitter and poly(L-lactide acid) (PLLA) as matrix) with arbitrary areas (up to…
Perovskite nanoplatelets (NPls) hold great promise for light-emitting applications, having achieved high photoluminescence quantum efficiencies (PLQEs) approaching unity in the blue wavelength range, where other metal-halide perovskites have typically been ineffective. However, the external quantum efficiency (EQE) of blue-emitting NPl light-emitting diodes (LEDs) have only reached 0.12%, with typical values well below 0.1%. In this work, we show that the performance of NPl LEDs is primarily hindered by a poor electronic interface between the emitter and hole-injector. Through Kelvin Probe and…
The low efficiency of metal halide perovskite light-emitting diodes (PeLEDs) with blue emission block their potential applications in large-area full-color displays and solid-state lighting. A delicate control over the entire electroluminescence process is indispensable to overcome the efficiency limitations of blue PeLEDs. Here, we demonstrate an efficient device architecture to synergistically reduce the energetic losses during electron-photon conversion and boost the extraction of trapped light in the device. An interfacial nucleation seeding scheme is proposed to control the crystallizatio…
Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light emitting applications. In addition, they can be used as components to create a variety of materials through physical and chemical transformations. Recent studies focused on nanoplatelets that are able to self-assemble and transform on solid substrates. Yet, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present the transformation of self-assembled stacks of CsPbBr$_3$ nanoplatelets in solution, capturing the different stages of the process by keep…
Perovskite light-emitting diodes (PeLEDs) have emerged as a strong contender for next-generation display and information technologies. However, similar to perovskite solar cells, the poor operational stability remains the main obstacle toward commercial applications. Here we demonstrate ultra-stable and efficient PeLEDs with extraordinary operational lifetimes (T50) of 1.0x10^4 h, 2.8x10^4 h, 5.4x10^5 h, and 1.9x10^6 h at initial radiance (or current densities) of 3.7 W/sr/m2 (~5 mA/cm2), 2.1 W/sr/m2 (~3.2 mA/cm2), 0.42 W/sr/m2 (~1.1 mA/cm2), and 0.21 W/sr/m2 (~0.7 mA/cm2) respectively, and ex…
