Bimolecular Radiative Recombination Research Articles

Understanding the Role of Ion Migration in the Operation of Perovskite Light-Emitting Diodes by Transient Measurements.

Perovskite light-emitting diodes have been gaining attention in recent years due to their high efficiencies. Despite of the recent progress made in device efficiency, the operation mechanisms of these devices are still not well understood, especially the effects of ion migration. In this work, the role of ion migration is investigated by measuring the transient electroluminescence and current responses, with both the current and efficiency showing a slow response in a time scale of tens of milliseconds. The results of the charge injection dynamics show that the slow response of the current is attributed to the migration and accumulation of halide ions at the anode interface, facilitating hole injection and leading to a strong charge imbalance. Further, the results of the charge recombination dynamics show that the slow response of the efficiency is attributed to enhanced charge injection facilitated by ion migration, which leads to an increased carrier density favoring bimolecular radiative recombination. Through a combined analysis of both charge injection and recombination dynamics, we finally present a comprehensive picture of the role of ion migration in device operation.

Enhanced red light emission from dense Si quantum dot-based silicon oxynitride light-emitting diodes with reduced efficiency droop

Strong red light emission from silicon oxynitride-based (SiOxNy-based) light-emitting diodes (LEDs) was investigated. The introduction of dense Si quantum dots (Si QDs) into SiOxNy not only increases carrier injection efficiency but also results in a significant enhancement of more than 300% in the light emission efficiency compared with SiOxNy-based LEDs without Si QDs. Moreover, the efficiency droop phenomenon is remarkably suppressed in the SiOxNy-based LED containing dense Si QDs. Analysis of the dominant recombination process indicates that the improved performance of the SiOxNy-based LEDs results from the increased bimolecular radiative recombination probability.

Effective Control of the Growth and Photoluminescence Properties of CsPbBr3/Cs4PbBr6 Nanocomposites by Solvent Engineering.

Metal halide perovskites exhibit small exciton binding energy, which leads to a low electron–hole capture rate for radiative recombination and accordingly decreases the luminescence efficiency. Reducing the thickness of the perovskite film or the size of the perovskite crystal is found to be an effective method to spatially confine the electrons and holes to promote the bimolecular radiative recombination. Here, we fabricate CsPbBr3/Cs4PbBr6 nanocomposites, applicable for light emission diodes, by a simple self-assembly method. We effectively reduce the critical size of the CsPbBr3 nanocrystals in the CsPbBr3/Cs4PbBr6 nanocomposites by adding a certain amount of dimethyl sulfoxide into the perovskite precursor solution. Accordingly, the photoluminescence quantum yield of the CsPbBr3/Cs4PbBr6 nanocomposites increased from 56 to 91% due to the quantum size effect. In situ observation of the growth of CsPbBr3/Cs4PbBr6 nanocomposites reveals that the reduction of the CsPbBr3 crystal size is due to the change of the chemical reaction speed during the two-step growth process of the CsPbBr3/Cs4PbBr6 nanocomposites.

Room-temperature stability of excitons and transverse-electric polarized deep-ultraviolet luminescence in atomically thin GaN quantum wells

We apply first-principles calculations to study the effects of extreme quantum confinement on the electronic, excitonic, and radiative properties of atomically thin (1–4 atomic monolayers) GaN quantum wells embedded in AlN. We determine the quasiparticle bandgaps, exciton energies and wave functions, radiative lifetimes, and Mott critical densities as a function of well and barrier thickness. Our results show that quantum confinement in GaN monolayers increases the bandgap up to 5.44 eV and the exciton binding energy up to 215 meV, indicating the thermal stability of excitons at room temperature. Exciton radiative lifetimes range from 1 to 3 ns at room temperature, while the Mott critical density for exciton dissociation is approximately 1013 cm−2. The luminescence is transverse-electric polarized, which facilitates light extraction from c-plane heterostructures. We also introduce a simple approximate model for calculating the exciton radiative lifetime based on the free-carrier bimolecular radiative recombination coefficient and the exciton radius, which agrees well with our results obtained with the Bethe–Salpeter equation predictions. Our results demonstrate that atomically thin GaN quantum wells exhibit stable excitons at room temperature for potential applications in efficient light emitters in the deep ultraviolet as well as room-temperature excitonic devices.

Impact of Excess Lead Iodide on the Recombination Kinetics in Metal Halide Perovskites

Fundmental comprehension of light-induced processes in perovskites are still scarce. One active debate surrounds the influence of excess lead iodide (PbI2) on device performance, as well as optoelectronic properties, where both beneficial and detrimental traits have been reported. Here, we study its impact on charge carrier recombination kinetics by simultaneously acquiring the photoluminescence quantum yield and time-resolved photoluminescence as a function of excitation wavelength (450–780 nm). The presence of PbI2 in the perovskite film is identified via a unique spectroscopic signature in the PLQY spectrum. Probing the recombination in the presence and absence of this signature, we detect a radiative bimolecular recombination mechanism induced by PbI2. Spatially resolving the photoluminescence, we determine that this radiative process occurs in a small volume at the PbI2/perovskite interface, which is only active when charge carriers are generated in PbI2, and therefore provide deeper insight into how excess PbI2 may improve the properties of perovskite-based devices.

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 (NiOx) and poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate hole injection interfaces are investigated. The better interface formed between the NiOx/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.

Charge traps in lead-halide perovskites with different grain sizes

It is crucially required to understand charge traps in CH3NH3PbI3 perovskites, which severely affect the charge recombination mechanism and hence have a critical impact on photovoltaic performance. Herein, we studied the photoexcited dynamics of CH3NH3PbI3 perovskites with different grain sizes by measuring the intensity dependence of time-resolved photoluminescence (PL). As a result, we found that the PL decay for all the samples can be well analyzed using bimolecular radiative recombination and trap-assisted Shockely–Read–Hall recombination models. We discuss how the PL dynamics impact the photovoltaic performance of CH3NH3PbI3 perovskite solar cells on the basis of the recombination analysis.

Highly Efficient Visible Colloidal Lead-Halide Perovskite Nanocrystal Light-Emitting Diodes.

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 (enabling a photoluminescence quantum yield of 71% in solid film), unlike in the case of bulk perovskites with slow electron-hole bimolecular radiative recombination (a second-order process). In these PeLEDs, by reaching charge balance in the recombination zone, we find that the Auger nonradiative recombination, with its significant role in emission quenching, is effectively suppressed in low driving current density range. In consequence, these devices reach a maximum external quantum efficiency of 12.9% and a power efficiency of 30.3 lm W-1 at luminance levels above 1000 cd m-2 as required for various applications. These findings suggest that, with feasible levels of device performance, the PeNCs hold great promise for their use in LED lighting and displays.

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%.

Bimolecular recombination in methylammonium lead triiodide perovskite is an inverse absorption process

Photovoltaic devices based on metal halide perovskites are rapidly improving in efficiency. Once the Shockley–Queisser limit is reached, charge-carrier extraction will be limited only by radiative bimolecular recombination of electrons with holes. Yet, this fundamental process, and its link with material stoichiometry, is still poorly understood. Here we show that bimolecular charge-carrier recombination in methylammonium lead triiodide perovskite can be fully explained as the inverse process of absorption. By correctly accounting for contributions to the absorption from excitons and electron-hole continuum states, we are able to utilise the van Roosbroeck–Shockley relation to determine bimolecular recombination rate constants from absorption spectra. We show that the sharpening of photon, electron and hole distribution functions significantly enhances bimolecular charge recombination as the temperature is lowered, mirroring trends in transient spectroscopy. Our findings provide vital understanding of band-to-band recombination processes in this hybrid perovskite, which comprise direct, fully radiative transitions between thermalized electrons and holes.

Photon Reabsorption Masks Intrinsic Bimolecular Charge-Carrier Recombination in CH3NH3PbI3 Perovskite.

An understanding of charge-carrier recombination processes is essential for the development of hybrid metal halide perovskites for photovoltaic applications. We show that typical measurements of the radiative bimolecular recombination constant in CH3NH3PbI3 are strongly affected by photon reabsorption that masks a much larger intrinsic bimolecular recombination rate constant. By investigating a set of films whose thickness varies between 50 and 533 nm, we find that the bimolecular charge recombination rate appears to slow by an order of magnitude as the film thickness increases. However, by using a dynamical model that accounts for photon reabsorption and charge-carrier diffusion we determine that a single intrinsic bimolecular recombination coefficient of value 6.8 × 10-10 cm3s-1 is common to all samples irrespective of film thickness. Hence, we postulate that the wide range of literature values reported for such coefficients is partly to blame on differences in photon out-coupling between samples with crystal grains or mesoporous scaffolds of different sizes influencing light scattering, whereas thinner films or index-matched surrounding layers can reduce the possibility for photon reabsorption. We discuss the critical role of photon confinement on free charge-carrier retention in thin photovoltaic layers and highlight an approach to assess the success of such schemes from transient spectroscopic measurement.

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites’ outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 1015 cm−3, defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence.

Radiative Monomolecular Recombination Boosts Amplified Spontaneous Emission in HC(NH2)2SnI3 Perovskite Films.

Hybrid metal-halide perovskites have potential as cost-effective gain media for laser technology because of their superior optoelectronic properties. Although lead-halide perovskites have been most widely studied to date, tin-based perovskites have been proposed as a less toxic alternative. In this Letter, we show that amplified spontaneous emission (ASE) in formamidinium tin triiodide (FASnI3) thin films is supported by an observed radiative monomolecular charge recombination pathway deriving from its unintentional doping. Such a radiative component will be active even at the lowest charge-carrier densities, opening a pathway for ultralow light-emission thresholds. Using time-resolved THz photoconductivity analysis, we further show that the material has an unprecedentedly high charge-carrier mobility of 22 cm2 V-1 s-1 favoring efficient transport. In addition, FASnI3 exhibits strong radiative bimolecular recombination and Auger rates that are over an order of magnitude lower than for lead-halide perovskites. In combination, these properties reveal that tin-halide perovskites are highly suited to light-emitting devices.

Nongeminate radiative recombination of free charges in cation-exchanged PbS quantum dot films

Using photoluminescence (PL) spectroscopy we explore the radiative recombination pathways in PbS quantum dots (QDs) synthesized by two methods. We compare conventionally synthesized PbS from a PbO precursor to PbS synthesized using cation-exchange from CdS QDs. We show that strongly coupled films of PbS QDs from the cation-exchange luminesce with significant efficiency at room temperature. This is in stark contrast to conventional PbS QDs, which have exceedingly weak room temperature emission. Moreover, the power dependence of the emission is quadratic, indicating bimolecular radiative recombination that is reasonably competitive with trap-assisted recombination, a feature previously unreported in coupled PbS QD films. We interpret these results in terms of a greatly reduced defect concentration for cation-exchanged QDs that mitigates the influence of trap-assisted recombination. Cation-exchanged QDs have recently been employed in highly efficient and air-stable lead chalcogenide QD devices, and the reduced number of trap states inferred here may lead to improved current collection and higher open circuit voltage.

Light-Emitting Electrochemical Cells Based on Hybrid Lead Halide Perovskite Nanoparticles

Methylammonium lead bromide (MAPbBr3) perovskite nanoparticles (NPs) have been recently proposed as a new material for light-emitting diodes, as well as a new paradigm to elucidate the operational mechanism in perovskite solar cells. Here, we have expanded the synthesis concept to fabricate NPs based on formamidinium lead bromide (FAPbBr3). Importantly, we have demonstrated that the photophysical features of this novel material can be easily tuned by exchanging the organic cation, achieving lower radiative bimolecular recombination rate for FAPbBr3 NPs. Additionally, we report for the first time light-emitting electrochemical cells (LECs) based on perovskite NPs by an easily up-scalable spray-coating technique. Stable luminance of 1–2 cd/m2 at low driving currents was achieved for both types of materials. Overall, this work opens a new avenue of research into the field of organic–inorganic metal halide nanoparticles bearing different alkyl ammonium groups and their application in the developing field of t...

Efficiency droop and carrier transport in AlGaN epilayers and heterostructures

The photoluminescence (PL) spectroscopy of AlGaN epilayers and heterostructures under quasi‐steady‐state conditions at different excitations in a wide temperature range from 8 to 300 K established the connection between the internal quantum efficiency, efficiency droop, and carrier localization. The carrier localization conditions were estimated from the temperature dependences of the PL band peak positions. The temperature dependences of the PL intensity were fitted using the Arrhenius‐type equation with two activation energies, which were attributed to the carrier redistribution within the localized states and carrier delocalization, respectively. The delocalization of the localized carriers affects the luminescence efficiency via the enhancement of the two mechanisms of opposite signs: the bimolecular radiative recombination and nonradiative recombination due to an increased probability to reach nonradiative recombination centers.

Theoretical Analysis of Nonlinear Recombination Process and Its Influence on Diffraction Efficiency of Steady-State Photocarrier Grating

A theoretical analysis of the steady-state photocarrier grating (SSPCG), which takes the nonlinear carrier recombination processes into account, has been presented. First, the nonlinear diffusion equation, containing the bimolecular radiative recombination and Auger recombination terms, has been numerically solved, and the spatial distribution of the carrier concentration of the SSPCG has been obtained. Second, using Fourier analysis, the amplitude of the carrier concentration is determined based on the numerical results. Finally, using the band-filling theory and rigorous coupled-wave analysis, all the optical parameters of the SSPCG are determined and the diffraction efficiency is estimated. The results show that, for an InP-based SSPCG, the bimolecular radiative recombination plays a dominant role in the diffusion equation at a given excitation level. The +1st-order diffraction efficiency of the SSPCG increased less by the increase of the grating period, and the rising rate was reduced by it. In spite of the diffraction efficiency (about 0.7 %), it has the potential to be an optical signal processing component.

Tuning the Light Emission Properties by Band Gap Engineering in Hybrid Lead Halide Perovskite

We report about the relationship between the morphology and luminescence properties of methylammonium lead trihalide perovskite thin films. By tuning the average crystallite dimension in the film from tens of nanometers to a few micrometers, we are able to tune the optical band gap of the material along with its photoluminescence lifetime. We demonstrate that larger crystallites present smaller band gap and longer lifetime, which correlates to a smaller radiative bimolecular recombination coefficient. We also show that they present a higher optical gain, becoming preferred candidates for the realization of CW lasing devices.

Bright light-emitting diodes based on organometal halide perovskite.

Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI(3-x)Cl(x) perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9'-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr(-1) m(-2) at a current density of 363 mA cm(-2), with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m(-2) at a current density of 123 mA cm(-2), giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.

Suppression of Hole Overflow and Enhancement of Light Emission Efficiency in Si Quantum Dots Based Silicon Nitride Light Emitting Diodes

We present an effective method to suppress the hole overflow in Si quantum dots-based silicon nitride (SiN) light-emitting diodes (LEDs) by employing nanocrystalline Si (nc-Si) layer as hole blocking layer inserted between the SiN luminescent active layer and p-Si anode. The proposed devices exhibit strong white light emission under forward bias conditions. In comparison to the LEDs without nc-Si interlayer, a significant enhancement of more than 200% in light emission efficiency is achieved from the proposed devices. The increment in EL efficiency is found to strongly depend on the thickness of nc-Si interlayer. Besides, the proposed devices show a low turn-on voltage of 6 V, which is the same as that of the device without nc-Si interlayer. The analysis of the dominant recombination process indicates that the improved emission efficiency is resulting from the increased bimolecular radiative recombination probability, which is attributed to the effective hole-blocking effect of nc-Si barrier that mitigates the unbalance injections between electrons and holes in the SiN active layer by suppressing hole overflow.