Nonradiative Auger Recombination Research Articles

Weakly Confined Semiconductor Nanocrystals Excel in Photochemical and Optoelectronic Properties: Evidence from Single-Dot Studies.

Single-molecule spectroscopy offers state-resolved measurements on charge-transfer reactions of single semiconductor nanocrystals, leading to the discovery of up to six single-charge transfer reactions with seven transient states for single CdSe/CdS core/shell nanocrystals with water (or oxygen) as the hole (or electron) acceptors. Kinetic rates of three photoinduced single-hole transfer reactions decrease significantly upon increasing the number of excess electrons in a nanocrystal, mainly due to efficient Auger nonradiative recombination of the charged single excitons. Conversely, the kinetic rates of three single-electron transfer reactions of an unexcited nanocrystal increase proportionally to the number of excess electrons in it. Results here reveal that charge-transfer reactions of nanocrystals, at the center of nearly all their functions, could only be deciphered at a state-resolved level on a single nanocrystal. Size-dependent studies validate the weakly confined semiconductor nanocrystals, instead of strongly confined ones (quantum dots), as optimal candidates for photochemical and optoelectronic applications.

Random lasers with controlled emission modes by colloidal semiconductor quantum dots coupled to plasmonic nanorod arrays

Random lasers based on scattering for light amplification have gained extensive attention due to their simple structures. Colloidal semiconductor quantum dots (CSQDs) are excellent candidates as active media for random lasing. However, achieving CSQDs-based random lasers is challenging because the non-radiative Auger recombination produces a remarkable carrier loss. Here, we report random lasers with low thresholds based on the CSQDs coupled to the plasmonic nanorod arrays. The random lasers result from the enhancing excitation and emission rates of the CSQDs through plasmon resonance energy transfer induced by the spectral overlap between the resonant cavity modes of the plasmonic nanorod arrays and the excitons of the CSQDs, which reduces the carrier loss and establishes the optical gain in the CSQDs. Moreover, the incoherent and coherent emission modes can be controlled by varying the filling configurations (i.e., full-filling and partial-filling) of the plasmonic nanorods embedded in anodic aluminum oxide templates. Consequently, the incoherent random laser with a threshold of 19.3 μJ/mm2 and coherent random lasers with a threshold of 13.5 μJ/mm2 are performed, respectively. The proposed system provides a feasible method for low-threshold CSQDs-based random lasers with controlled emission modes, showing a promising avenue for potential applications.

Intraband Cooling and Auger Recombination in Weakly to Strongly Quantum-Confined CsPbBr3 Perovskite Nanocrystals.

Semiconductor nanocrystals (NCs) with size-tuned energy gaps present unique and desirable properties for optoelectronic applications. Recent synthetic advancements offer routes to spheroidal CsPbBr3 perovskite NCs in the strong quantum confinement regime with narrow size dispersion. Using tunable femtosecond laser pulses, we examine intraband carrier relaxation using transient absorption spectroscopy and show that, across the transition from weak to strong confinement, hot carrier lifetime increases compared to larger bulk-like particles. However, further increases of confinement subsequently lead to a reduction of the hot carrier lifetime and increase of the non-radiative Auger recombination rate. Finally, we show that hot carrier lifetimes increase as a function of excess energy above the band gap less sensitively under high confinement in comparison to the bulk. Understanding such unique trends is important for maximizing hot carrier lifetimes for use in next-generation hot carrier devices as well as evaluating the transition from weak to strong confinement.

Weakly Confined Organic-Inorganic Halide Perovskite Quantum Dots as High-Purity Room-Temperature Single Photon Sources.

Colloidal perovskite quantum dots (PQDs) have emerged as highly promising single photon emitters for quantum information applications. Presently, most strategies have focused on leveraging quantum confinement to increase the nonradiative Auger recombination (AR) rate to enhance single-photon (SP) purity in all-inorganic CsPbBr3 QDs. However, this also increases the fluorescence intermittency. Achieving high SP purity and blinking mitigation simultaneously remains a significant challenge. Here, we transcend this limitation with room-temperature synthesized weakly confined hybrid organic-inorganic perovskite (HOIP) QDs. Superior single photon purity with a low g(2)(0) < 0.07 ± 0.03 and a nearly blinking-free behavior (ON-state fraction >95%) in 11 nm FAPbBr3 QDs are achieved at room temperature, attributed to their long exciton lifetimes (τX) and short biexciton lifetimes (τXX). The significance of the organic A-cation is further validated using the mixed-cation FAxCs1-xPbBr3. Theoretical calculations utilizing a combination of the Bethe-Salpeter (BSE) and k·p approaches point toward the modulation of the dielectric constants by the organic cations. Importantly, our findings provide valuable insights into an additional lever for engineering facile-synthesized room-temperature PQD single photon sources.

Space charge region recombination in highly efficient silicon solar cells

The recombination rate in the space charge region (SCR) of a silicon-based barrier structure with a long Shockley–Reed–Hall lifetime is calculated theoretically by taking into account the concentration gradient of excess electron-hole pairs in the base region. Effects of the SCR lifetime and applied voltage on the structure ideality factor have been analyzed. The ideality factor is significantly reduced by the concentration gradient of electron-hole pairs. This mechanism provides an increase of the effective lifetime compared to the case when it is insignificant, which is realized at sufficiently low pair concentrations. The theoretical results have been shown to be in agreement with experimental data. A method of finding the experimental recombination rate in SCR in highly efficient silicon solar cells (SCs) has been proposed and implemented. It has been shown that at the high excess carrier concentration exceeding 1015 cm–3 the contribution to the SCR recombination velocity from the initial region of SCR that became neutral is significant. From a comparison of theory with experiment, the SCR lifetime and the ratio of the hole to the electron capture cross sections are determined for a number of silicon SCs. The effect of SCR recombination on the key characteristics of highly efficient silicon SCs, such as photoconversion efficiency and open-circuit voltage, has been evaluated. It has been shown that they depend not only on the charge carrier lifetime in SCR, but also on the ratio of hole to electron capture cross sections σp /σn. When σp /σn &lt; 1, this effect is significantly strengthened, while in the opposite case σp /σn &gt; 1 it is weakened. It has been ascertained that in a number of highly efficient silicon SCs, the distribution of the inverse lifetime in SCR is described by the Gaussian one. The effect described in the paper is also significant for silicon diodes with a thin base, p-i-n structures, and for silicon transistors with p-n junctions. In Appendix 2, the need to take into account the lifetime of non-radiative excitonic Auger recombination with participation of deep impurities in silicon is analyzed in detail. It has been shown, in particular, that considering it enables to reconcile the theoretical and experimental dependences for the effective lifetime in the silicon bulk.

Enhancement of Optical Gain in Colloidal CdSe/CdS/ZnS Quantum Dots through Nanosecond Optical Pumping.

Optical gain and lasing in colloidal nanocrystals are often hindered by sub-nanosecond rapid Auger non-radiative recombination, especially under continuous wave optical or electrical excitation. This study demonstrates amplified spontaneous emission (ASE) from CdSe/CdS/ZnS quantum dot (QD) solids through prolonged pulsed optical pumping over 10 ns. The incorporation of CdS and ZnS double shells on CdSe QDs effectively decelerates the Auger process in multiexcitonic states by extending the electron wave function and enhancing dielectric screening. Furthermore, we engineer smooth, densely packed QD solid films that efficiently guide the optical mode, achieving substantial net gain values under nanosecond pumping. The proposed approach helps observe ASE with gain thresholds of 0.84 and 1.5 mJ/cm2 under optical pumping pulse widths of 6 and 15 ns, respectively. This advancement can promote continuous pumping in colloidal QD gain systems, opening new avenues for optoelectronic applications.

Carrier density dependent Auger recombination in c-plane (In,Ga)N/GaN quantum wells: insights from atomistic calculations

Understanding Auger recombination in (In,Ga)N-based quantum wells is of central importance to unravelling the experimentally observed efficiency ‘droop’ in modern (In,Ga)N light emitting diodes (LEDs). While there have been conflicting results in the literature about the importance of non-radiative Auger recombination processes for the droop phenomenon, it has been discussed that alloy fluctuations strongly enhance the Auger rate. However, these studies were often focused on bulk systems, not quantum wells, which lie at the heart of (In,Ga)N-based LEDs. In this study, we present an atomistic analysis of the carrier density dependence of the Auger recombination coefficients in (In,Ga)N/GaN quantum wells. The model accounts for random alloy fluctuations, the connected carrier localisation effects, and carrier density dependent screening of the built-in polarisation fields. Our studies reveal that at low temperatures and low carrier densities the calculated Auger coefficients are strongly dependent on the alloy microstructure. However, at elevated temperatures and carrier densities, where the localised states are starting to be saturated, the different alloy configurations studied give (very) similar Auger coefficients. We find that over the range of carrier densities investigated, the contribution of the electron-electron–hole related Auger process is of secondary importance compared to the hole-hole-electron process. Overall, for higher temperatures and carrier densities, our calculated total Auger coefficients are in excess of 10−31 cm6 s−1 and may reach 10−30 cm6 s−1, which, based on current understanding in the literature, is sufficient to result in a significant efficiency droop. Thus, our results are indicative of Auger recombination being an important contributor to the efficiency droop in (In,Ga)N-based light emitters even without defect-assisted processes.

Theory and optimisation of radiative recombination in broken-gap InAs/GaSb superlattices

We present a theoretical analysis of mid-infrared radiative recombination in InAs/GaSb superlattices (SLs). We employ a semi-analytical plane wave expansion method in conjunction with an 8-band Hamiltonian to compute the SL electronic structure, paying careful attention to the identification and mitigation of spurious solutions. The calculated SL eigenstates are used directly to compute spontaneous emission spectra and the radiative recombination coefficient . We elucidate the origin of the relatively large coefficients in InAs/GaSb SLs which, despite the presence of spatially indirect (type-II-like) carrier confinement, are close to that of bulk InAs and compare favourably to those calculated for mid-infrared type-I pseudomorphic and metamorphic quantum well structures having comparable emission wavelengths. Our analysis explicitly quantifies the roles played by carrier localisation (specifically, partial delocalisation of bound electron states) and miniband formation (specifically, miniband occupation and optical selection rules) in determining the magnitude of and its temperature dependence. We perform a high-throughput optimisation of the room temperature coefficient in InAs/GaSb SLs across the 3.5–7 m wavelength range, quantifying the dependence of on the relative thickness of the electron-confining InAs and hole-confining GaSb layers. This analysis provides guidance for the growth of optimised SLs for mid-infrared light emitters. Our results, combined with the expected low non-radiative Auger recombination rates in structures having spatially indirect electron and hole confinement, corroborate recently observed high output power in prototype InAs/GaSb SL inter-band cascade light-emitting diodes.

Non-Blinking Luminescence from Charged Single Graphene Quantum Dots.

Photoluminescence blinking behavior from single quantum dots under steady illumination is an important but controversial topic. Its occurrence has impeded the use of single quantum dots in bioimaging. Different mechanisms have been proposed to account for it, although controversial, the most important of which is the non-radiative Auger recombination mechanism whereby photocharging of quantum dots can lead to the blinking phenomenon. Here, the singly charged trion, which maintains photon emission, including radiative recombination and non-radiative Auger recombination, leads to fluorescence non-blinking which is observed in photocharged single graphene quantum dots (GQDs). This phenomenon can be explained in terms of different energy levels in the GQDs, caused by various oxygen-containing functional groups in the single GQDs. The suppressed blinking is due to the filling of trap sites owing to a Coulomb blockade. These results provide a profound understanding of the special optical properties of GQDs, affording a reference for further in-depth research.

Impact of fin aspect ratio on enhancement of external quantum efficiency in single AlGaN fin light-emitting diodes pixels

Previously, we showed within a sub-micron fin shape heterojunction, as current density increases, the non-radiative Auger recombination saturates mediated by the extension of the depletion region into the fin, resulting in a droop-free behavior. Here, we investigate the dependence of the fin aspect ratio (height to width ratio) on external quantum efficiency (EQE) of single n-AlGaN fin/p-GaN heterojunctions. Fins are arranged in an array format varying in width from 3000 to 200 nm. In this architecture, an n-metal contact is interfaced with the non-polar side facet of the fin. At a fixed current density, as the aspect ratio increases from 0.2 to 3 (the fin width reduces), we systematically observe an increase in the ultraviolet (UV) excitonic emission of the AlGaN fin and a 7× enhancement in the EQE. We explain this phenomenon by conserving the volume of the carrier depletion region within a fin. As the fin gets thinner, the base area of the depletion volume shrinks, whereas its height increases within the fin. This geometrical advantage allows a 200 nm wide fin to operate at 1/3rd the current density compared to a 3000 nm wide fin while generating a UV emission with a comparable power of 1 μW. These findings show additional parameters that can be used for developing brighter light sources, including the shape and aspect ratio of a heterojunction at the micro- or nano-scale.

An efficient green-emitting quantum dot with near-unity quantum yield and suppressed Auger recombination for high-performance light-emitting diodes

Near 100% photoluminescence quantum yield (PL QY) is the first target for designing luminescent quantum dots (QDs). Here, an alloyed QD with a core/shell structure of Cd0.194Zn0.806Se0.406S0.594/ZnS is synthesized and characterized by the feature of large core size (about 10 nm) and thin shell (around three ZnS monolayers). It exhibits an efficient green emission with the PL QY of 99.8% and ultra-fast radiative transition rate (kr) of 4.16 × 107 s−1. It demonstrates that the excited state will be rapidly decayed to its ground state through a radiative channel and less vulnerable to non-radiative processes. Under a high pump intensity (254.65 μJ cm−2), the Cd0.194Zn0.806Se0.406S0.594/ZnS QD still owns a long biexciton decay lifetime (τxx) of 1.05 ns and high biexciton QYxx of 25.1%, corresponding to a suppressed non-radiative Auger recombination. The Cd0.194Zn0.806Se0.406S0.594/ZnS QD based light-emitting diode exhibits a peak external quantum efficiency of 20.1% and brightness of over 105 cd m−2 at 5.2 V. We believe that the Cd0.194Zn0.806Se0.406S0.594/ZnS QD not only provides a near-unity QY but also ensures its QD based light-emitting diode (QLED) with an excellent performance, which could be an excellent QD material for QLED applications.

Surface-Ligand-Modified CdSe/CdS Nanorods for High-Performance Light-Emitting Diodes.

Colloidal nanocrystals (NCs) play an important role in the field of optoelectronic devices such as photovoltaic cells, photodetectors, and light-emitting diodes (LEDs). The properties of NC films are strongly affected by ligands attached to them, which constitute a barrier for charge transport between adjacent NCs. Therefore, the method of surface modification by ligand exchange has been used to improve the electrical conductivity of NC films. However, surface modification to NCs in LEDs can also affect emission characteristics. Among NCs, nanorods have unique properties, such as suppression of nonradiative Auger recombination and linearly polarized light emission. In this work, CdSe/CdS nanorods (NRs) were prepared by the hot injection method. To increase the charge transport into CdSe/CdS NRs, we adopted ligand modification to CdSe/CdS NRs. Using this technique, we could shorten the injection barrier length between CdSe/CdS NRs and adjacent layers. It leads to a more balanced charge injection of electron/hole and a greatly increased current efficiency of CdSe/CdS NR-LEDs. In the NR-LEDs, the ligand exchange boosted the electroluminance, reaching a sixfold increase from 848 cd/m2 of native surfactants to 5600 cd/m2 of the exchanged n-octanoic acid ligands at 12 V. The improvement of CdSe/CdS NR-LED performance is closely correlated to the efficient control of charge balance via ligand modification strategy, which is expected to be indispensable to the future NR-LED-based optoelectronic system.

Terahertz cyclotron emission from two-dimensional Dirac fermions

Since the emergence of graphene, we have seen several proposals for the realization of Landau lasers tunable over the terahertz frequency range. The hope was that the non-equidistance of the Landau levels from Dirac fermions would suppress the harmful non-radiative Auger recombination. Unfortunately, even with this non-equidistance an unfavorable non-radiative process persists in Landau-quantized graphene, and so far no cyclotron emission from Dirac fermions has been reported. One way to eliminate this last non-radiative process is to sufficiently modify the dispersion of the Landau levels by opening a small gap in the linear band structure. A proven example of such gapped graphene-like materials are HgTe quantum wells close to the topological phase transition. In this work, we experimentally demonstrate Landau emission from Dirac fermions in such HgTe quantum wells, where the emission is tunable by both the magnetic field and the carrier concentration. Consequently, these results represent an advance in the realization of terahertz Landau lasers tunable by magnetic field and gate-voltage.

Suppressed Auger recombination and enhanced emission of InP/ZnSe/ZnS quantum dots through inner shell manipulation.

Understanding the influence of the inner shell on fluorescence blinking and exciton dynamics is essential to promote the optical performances of InP-based quantum dots (QDs). Here, the fluorescence blinking, exciton dynamics, second-order correlation function g2(τ), and ultrafast carrier dynamics of InP/ZnSe/ZnS QDs regulated by the inner ZnSe shell thickness varying from 2 to 7 monolayers (MLs) were systematically investigated. With an inner ZnSe shell thickness of 5 MLs, the photoluminescence quantum yield (PL QY) can reach 98% due to the suppressed blinking and increased probability of multiphoton emission. The exciton dynamics of InP/ZnSe/ZnS QDs with different inner shells indicates that two decay components of neural excitons and charged trions are competitive to affect the photon emission behavior. The probability density distributions of the ON and OFF state duration in the blinking traces demonstrate an effective manipulation of the inner ZnSe shell in the non-radiative processes via defect passivation. Accordingly, the radiative recombination dominates the exciton deactivation and the non-radiative Auger recombination rate is remarkably reduced, leading to a QY close to unity and a high PL stability for InP/ZnSe/ZnS QDs with 5 MLs of the ZnSe shell. These results provide insights into the photophysical mechanism of InP-based QDs and are significant for developing novel semiconductor PL core/shell QDs.

К вопросу о механизмах разогрева светодиодов на основе p-InAsSbP/n-InAs(Sb)

Three main reasons for a temperature increase in activated p-InAsSbP/n-InAs/n-InAsSbP and p-InAsSbP/n-InAsSb/n-InAs double heterostructures has been considered. Contribution of nonradiative Auger recombination, electron-phonon interaction and Joule heating to diode temperature increase in single element LEDs and flip-chip diode arrays (1×3) were evaluated at forward and reverse bias using data on spatial distribution of the mid-IR radiation intensity and current-voltage characteristics.

On heating mechanisms in LEDs based on p-InAsSbP/n-InAs(Sb)

Three main reasons for a temperature increase in activated p-InAsSbP/n-InAs/n-InAsSbP and p-InAsSbP/ n-InAsSb/n-InAs double heterostructures has been considered, contribution of nonradiative Auger recombination, electron-phonon interaction and Joule heating to diode temperature increase in single element LEDs and flip-chip diode arrays (1x3) were evaluated at forward and reverse bias using data on spatial distribution of the mid-IR radiation intensity and current-voltage characteristics. Keywords: IR LED, IR diode array, Joule heating, Auger recombination, electron-phonon interaction.

Defect passivation and electron band energy regulation of a ZnO electron transport layer through synergetic bifunctional surface engineering for efficient quantum dot light-emitting diodes.

Zinc oxide nanoparticles (ZnO NPs) have been actively pursued as the most effective electron transport layer for quantum-dot light-emitting diodes (QLEDs) in light of their unique optical and electronic properties and low-temperature processing. However, the high electron mobility and smooth energy level alignment at QDs/ZnO/cathode interfaces cause electron over-injection, which aggravates non-radiative Auger recombination. Meanwhile, the abundant defects hydroxyl group (-OH) and oxygen vacancies (OV) in ZnO NPs act as trap states inducing exciton quenching, which synergistically reduces the effective radiation recombination for degrading the device performance. Here, we develop a bifunctional surface engineering strategy to synthesize ZnO NPs with low defect density and high environmental stability by using ethylenediaminetetraacetic acid dipotassium salt (EDTAK) as an additive. The additive effectively passivates surface defects in ZnO NPs and induces chemical doping simultaneously. Bifunctional engineering alleviates electron excess injection by elevating the conduction band level of ZnO to promote charge balance. As a result, state-of-the-art blue QLEDs with an EQE of 16.31% and a T50@100 cd m-2 of 1685 h are achieved, providing a novel and effective strategy to fabricate blue QLEDs with high efficiency and a long operating lifetime.

Superior External Quantum Efficiency of LEDs via Quasi-2D Perovskite Crystals Implanted with Phenethylammonium Acetate.

The multiple quantum well structure of a quasi-two-dimensional (quasi-2D) perovskite leads to nonradiative Auger recombination (AR). This is due to high local carrier density in recombination centers, although the radiative recombination is improved by efficient energy transfer. In this study, we suppress the AR by introducing phenethylammonium acetate (PEAAc) into the quasi-2D PEA2Csn-1PbnBr3n+1 perovskite. The recombination centers of n ≥ 4 phases can be promoted because the COO- preferentially coordinates with Pb2+, inhibiting the fast formation of n = 1, 2, 3 phases with phenethylammonium anion (PEA+). Thus, the AR is suppressed due to the lower density of local charge carriers. To balance the AR suppression and decreasing binding energy in promoting the n ≥ 4 phases, the PEAAc:PEABr molar ratios are adjusted. At the optimal molar ratio, perovskite light-emitting diodes (PeLEDs) with a maximum luminescence of ∼29942 cd m-2 and a maximum external quantum efficiency of ∼20.2% are achieved. These results confirm the most efficient PeLEDs based on PEA2Csn-1PbnBr3n+1 without passivation. Moreover, the efficiency roll off is significantly mitigated with a high threshold of over 3.51 mA/cm2. This study develops high-efficiency PeLEDs with a low efficiency rolloff.

Enhanced scintillation performance of β-Ga2O3 single crystals by Al3+ doping and its physical mechanism

β-Ga2O3 is a potential fast semiconductor scintillator with no significant self-absorption and excellent stability. However, the relatively low light yield of β-Ga2O3 at room temperature limits its practical application. In order to improve its scintillation performance, Al3+ doped β-Ga2O3 single crystals are investigated. By doping 5%Al3+ (atomic concentration), the light yield of β-Ga2O3 is increased from 4394 to 6816 ph/MeV. The increased light yield may be attributed to the decreased free electron concentration and inhibition of Auger nonradiative recombination. The thermal quenching effect can also be moderated by the increase in the thermal activation energy induced by Al3+ doping. The results indicate that Al3+ doping is an effective method to increase the light yield of β-Ga2O3.

Double-crowned 2D semiconductor nanoplatelets with bicolor power-tunable emission

Nanocrystals (NCs) are now established building blocks for optoelectronics and their use as down converters for large gamut displays has been their first mass market. NC integration relies on a combination of green and red NCs into a blend, which rises post-growth formulation issues. A careful engineering of the NCs may enable dual emissions from a single NC population which violates Kasha’s rule, which stipulates that emission should occur at the band edge. Thus, in addition to an attentive control of band alignment to obtain green and red signals, non-radiative decay paths also have to be carefully slowed down to enable emission away from the ground state. Here, we demonstrate that core/crown/crown 2D nanoplatelets (NPLs), made of CdSe/CdTe/CdSe, can combine a large volume and a type-II band alignment enabling simultaneously red and narrow green emissions. Moreover, we demonstrate that the ratio of the two emissions can be tuned by the incident power, which results in a saturation of the red emission due to non-radiative Auger recombination that affects this emission much stronger than the green one. Finally, we also show that dual-color, power tunable, emission can be obtained through an electrical excitation.