Auger Recombination Rate Research Articles

Amino‐Arsine and Amino‐Phosphine Based Synthesis of InAs@InP@ZnSe core@shell@shell Quantum Dots

AbstractA colloidal synthesis protocol is demonstrated for InAs@InP core@shell quantum dots (QDs) with a tunable InP shell thickness (ranging from 3 to 8 monolayers), utilizing tris(diethylamino)‐arsine and ‐phosphine. Structural analysis reveals that the InP shell preferentially grows onto the tetrahedral InAs cores along the <‐1‐1‐1> directions, forming tetrapodal‐shaped InAs@InP QDs. Growth of the InP shell causes a red shift in the absorption spectrum of the QDs. This is explained by considering that electrons are delocalized throughout the whole core@shell QDs, while holes preferentially leak along the <‐1‐1‐1> directions, as indicated by the density functional theory calculations. This means such heterostructures cannot be described as type‐I or quasi type‐II, contrary to earlier assumptions. The overlap of carrier wavefunctions throughout the entire InAs@InP QD structure results in no significant reduction of the Auger recombination rate, which remains as fast as in InAs QDs. However, the InP shell enhances photoluminescence (PL) efficiency (up to ≈13%) by passivating surface trap states of the InAs QDs (mainly located close to the top of the valence band). The overgrowth of a ZnSe shell endows the QDs with a high PL efficiency (≈55%) and good stability upon air exposure (≈80% PL intensity retention after 14 days).

Investigation of the mechanism of carrier recombination in GaN-based blue laser diodes before lasing

Abstract The carrier recombination behavior of GaN-based blue laser diodes (LDs) is studied and analyzed by experiments and simulation calculations before lasing, with a particular focus on the role of Auger recombination. It is found that Auger recombination plays a crucial role in the decrease in differential efficiency and threshold current of GaN-based blue LDs. The theoretical calculation results show that a large Auger recombination rate may lead to a dominant recombination channel before lasing, which could exceed the radiation recombination and result in an obvious decrease in the differential efficiency. Such a high Auger recombination will dissipate a large number of carriers in the quantum well, resulting in deterioration of device performance, a higher threshold current and a lower efficiency. This work presents a method to evaluate Auger recombination through differential efficiency and also provides evidence that suppressing the Auger recombination rate is beneficial to improve the performance of blue LDs.

Biexciton Emission in CsPbBr3 Nanocrystals: Polar Facet Matters.

The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.

Towards Large-Area Black Phosphorous Midwave-IR Optoelectronics

High-efficiency mid-wavelength infrared (mid-IR, 3–5 µm) optoelectronics, including light emitting diodes (LEDs) and photodetectors, are of high demand for emerging applications in spectroscopy, imaging, and gas sensing. Black phosphorus (bP) has emerged as a unique optoelectronic material for mid-IR applications with performances surpassing those of conventional III-V and II-VI semiconductors of similar bandgap. In this talk, I will present recent advancements on understanding and controlling the radiative and non-radiative recombination rates as a function of bP thickness. We observe higher photoluminescence quantum yields in bP as compared to conventional III-V and II-VI semiconductors of similar bandgaps due to the smaller Auger recombination rate. As a result, bP mid-IR LEDs with external quantum efficiency of >4% are reported, outperforming the state-of-the-art in this wavelength range. Furthermore, device encapsulation and packaging technologies are explored with extrapolated half lifetime of ~15,000 hours based on accelerated lifetime measurements. Finally, I will present strategies for large-area device fabrication and processing.

Improvement of the Internal Quantum Efficiency of III‐Nitride Blue Micro‐Light‐Emitting Diodes by the Hole Accelerator at the Low Current Density

The hole accelerator is proven to benefit the hole injection for traditional light‐emitting diodes (LEDs) because the induced electric field provides the holes with more kinetic energy to pass through the electron‐blocking layer, enhancing the hole injection efficiency. Herein, the effect of the hole accelerator (HA) layer on the micro‐LEDs by modeling the characteristics of the devices with a current density of lower than 10 A cm−2 is investigated. The simulation results show that the appended HA layer brings a knot of the electric field in the HA layer, leading to higher internal quantum efficiency (IQE) than the device without HA under the low current density. The thickness and composition of HA, the quantum number, and the material of quantum barrier are also simulated and analyzed. The simulated radiative, Shockley–Read–Hall, and Auger recombination rates show that the IQE of the micro‐LED with the HA layer is higher than that without the HA layer under the current density of lower than 10 A cm−2.

Size Uniformity of CsPbBr3 Perovskite Quantum Dots via Manganese-Doping.

The achievement of size uniformity and monodispersity in perovskite quantum dots (QDs) requires the implementation of precise temperature control and the establishment of optimal reaction conditions. Nevertheless, the accurate control of a range of reaction variables represents a considerable challenge. This study addresses the aforementioned challenge by employing manganese (Mn) doping to achieve size uniformity in CsPbBr3 perovskite QDs without the necessity for the precise control of the reaction conditions. By optimizing the Mn:Pb ratio, it is possible to successfully dope CsPbBr3 QDs with the appropriate concentrations of Mn²⁺ and achieve a uniform size distribution. The spectroscopic measurements on single QDs indicate that the appropriate Mn²⁺ concentrations can result in a narrower spectral linewidth, a longer photoluminescence (PL) lifetime, and a reduced biexciton Auger recombination rate, thus positively affecting the PL properties. This study not only simplifies the size control of perovskite QDs but also demonstrates the potential of Mn-doped CsPbBr3 QDs for narrow-linewidth light-emitting diode applications.

Tailoring Auger Recombination Dynamics in CsPbI3 Perovskite Nanocrystals via Transition Metal Doping.

Auger recombination is a pivotal process for semiconductor nanocrystals (NCs), significantly affecting charge carrier generation and collection in optoelectronic devices. This process depends mainly on the NCs' electronic structures. In our study, we investigated Auger recombination dynamics in manganese (Mn2+)-doped CsPbI3 NCs using transient absorption (TA) spectroscopy combined with theoretical and experimental structural characterization. Our results show that Mn2+ doping accelerates Auger recombination, reducing the biexciton lifetime from 146 to 74 ps with increasing Mn doping concentration up to 10%. This accelerated Auger recombination in Mn-doped NCs is attributed to increased band edge wave function overlap of excitons and a larger density of final states of Auger recombination due to Mn orbital involvement. Moreover, Mn doping reduces the dielectric screening of the excitons, which also contributes to the accelerated Auger recombination. Our study demonstrates the potential of element doping to regulate Auger recombination rates by modifying the materials' electronic structure.

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.

Fine-Tuning Crystal Structures of Lead Bromide Perovskite Nanocrystals through Trace Cadmium(II) Doping for Efficient Color-Saturated Green LEDs.

Decreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade-off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7 times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4- octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color-saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n-doped emitters convert into only slightly n-doped ones; this boosts the charge injection efficiency of the corresponding light-emitting diodes. The light-emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123 cd A-1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22 nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color-saturated green emission for the electroluminescence peak centered at 534 nm, thus being fully compliant with the latest standard for wide color gamut displays.

Fine‐Tuning Crystal Structures of Lead Bromide Perovskite Nanocrystals through Trace Cadmium(II) Doping for Efficient Color‐Saturated Green LEDs

AbstractDecreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade‐off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7 times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4− octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color‐saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n‐doped emitters convert into only slightly n‐doped ones; this boosts the charge injection efficiency of the corresponding light‐emitting diodes. The light‐emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123 cd A−1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22 nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color‐saturated green emission for the electroluminescence peak centered at 534 nm, thus being fully compliant with the latest standard for wide color gamut displays.

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.

Study of Laser-Induced Multi-Exciton Generation and Dynamics by Multi-Photon Absorption in CdSe Quantum Dots.

Multi-exciton generation by multi-photon absorption under low-energy photons can be thought a reasonable method to reduce the risk of optical damage, especially in photoelectric quantum dot (QD) devices. The lifetime of the multi-exciton state plays a key role in the utilization of photon-induced carriers, which depends on the dynamics of the exciton generation process in materials. In this paper, the exciton generation dynamics of the photon absorption under low-frequency light in CdSe QDs are successfully detected and studied by the temporal resolution transient absorption (TA) spectroscopy method. Since the cooling time of hot excitons extends while the rate of auger recombination is accelerated when incident energy is increased, the filling time of defect states is irregular, and exciton generation experiences a transition from single-photon absorption to multi-photon absorption. This result shows how to change the excitation. Optical parameters can prolong the lifetime of excitons, thus fully extracting excitons and improving the photoelectric conversion efficiency of QD optoelectronic devices, which provides theoretical and experimental support for the development of QD optoelectronic devices.

Charge Injection and Auger Recombination Modulation for Efficient and Stable Quasi-2D Perovskite Light-Emitting Diodes.

The inefficient charge transport and large exciton binding energy of quasi-2D perovskites pose challenges to the emission efficiency and roll-off issues for perovskite light-emitting diodes (PeLEDs) despite excellent stability compared to 3D counterparts. Herein, alkyldiammonium cations with different molecular sizes, namely 1,4-butanediamine (BDA), 1,6-hexanediamine (HDA) and 1,8-octanediamine (ODA), are employed into quasi-2D perovskites, to simultaneously modulate the injection efficiency and recombination dynamics. The size increase of the bulky cation leads to increased excitonic recombination and also larger Auger recombination rate. Besides, the larger size assists the formation of randomly distributed 2D perovskite nanoplates, which results in less efficient injection and deteriorates the electroluminescent performance. Moderate exciton binding energy, suppressed 2D phases and balanced carrier injection of HDA-based PeLEDs contribute to a peak external quantum efficiency of 21.9%, among the highest in quasi-2D perovskite based near-infrared devices. Besides, the HDA-PeLED shows an ultralong operational half-lifetime T50 up to 479h at 20mA cm‒2, and sustains the initial performance after a record-level 30000 cycles of ON-OFF switching, attributed to the suppressed migration of iodide anions into adjacent layers and the electrochemical reaction in HDA-PeLEDs. This work provides a potential direction of cation design for efficient and stable quasi-2D-PeLEDs.

Simultaneous inclusion of quantum dots in multi-functional layers of thin film organic solar cells

The role of quantum dot (QD) decoration in the hole transport buffer layer and the photoactive medium on the photovoltaic parameters of thin film organic solar cells (TFOSCs) was investigated. A cadmium–tellurium-based QD was synthesized successfully and embedded in two of the functional layers of a TFOSC to improve its overall power conversion efficiency. The experimentally determined optimum concentration of the QD was maintained in the interfacial layer to investigate the effect of QD concentration in the active layer. The observed increased short-circuit current density (Jsc) and open circuit voltage (Voc) are attributable to the enhanced energy level tuning, broadened optical absorption, and charge transport process facilitated by the integration of QDs inside the media. Moreover, an improved device efficiency was obtained when the solvent additive was introduced into the bulk heterojunction photoactive layer films to facilitate QD dispersion and increase the interpenetrating network of the active layer blend that reduces the occurrence of trap sites, which, in turn, limits the Auger recombination rates. The QD-doped TFOSCs catalyzed with solvent additives displayed an enhanced overall photovoltaic parameter, which is quite appreciable in comparison with that of the pristine devices.

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.

Unveiling the Impact of Organic Spacer Cations on Auger Recombination in Layered Halide Perovskites

AbstractA library of large organic cation spacers is available for engineering the performance of layered two‐dimensional (2D) halide perovskite devices. Despite extensive photophysics studies, there remains a research gap over the structure‐function relations in 2D perovskites, especially the underlying factors influencing the Auger recombination (AR) process. Herein, the contributions of exciton binding energy, exciton‐phonon coupling, and defects/film morphology to the AR process in 2D perovskites are examined. Phenyl‐alkyl‐ammonium cations with different lengths of attached alkyl groups, commonly used in blue light‐emitting diodes, are investigated. The findings reveal an order of magnitude higher threshold carrier density for the AR onset as well as a reduced AR in cations with longer alkyl chain length. Although possessing similar exciton binding energies, the exciton‐phonon coupling strength is found to play a major role in reducing the AR rate, with a smaller contribution from the defect states/film morphology. The findings can help provide further guidance on organic spacer cation engineering for highly efficient 2D perovskite light emitters.

Effect of hydrostatic pressure on the Auger coefficient of InGaN/GaN multiple-quantum-well laser diode

A numerical model was used to analyze the Auger coefficient in a c-plane InGaN/GaN multiple-quantum-well laser diode (MQWLD) under hydrostatic pressure. Finite difference techniques were employed to acquire energy Eigenvalues and their corresponding Eigenfunctions of InGaN/GaN MQWLD, and the hole Eigenstates were calculated via a 6 × 6 k.p method under applied hydrostatic pressure. It was found that a change in pressure up to 10 GPa increases the carrier density in the quantum well and barriers and the effective band gap. Based on the result, the exaction binding energy decreased, the electric field rate increased up to 0.77 MV / cm, and the Auger coefficient decreased down to 2.1 × 10 − 31 and 0.6 × 10 − 31 cm6 s − 1 in the MQW and barrier regions, respectively. Also, the calculations demonstrated that the hole-hole-electron (CHHS) and electron-electron-hole (CCCH) Auger coefficients had the largest contribution to the Auger coefficient. Our study provides more detailed insight into the origin of the Auger recombination rate drop under hydrostatic pressure in InGaN-based light-emitting diodes.

Direct Assessment of Auger Recombination Rates of Charged Excitons via Opto-Electrical Measurements

Auger recombination (AR), whereby the electron–hole recombination energy is transferred to a third charge carrier, prevails in nanocrystal quantum dots (QDs) and governs the performance of QD-based devices including light-emitting diodes and lasers. Thus, precise AR evaluation of QDs is essential for understanding and improving the characteristics of such applications. So far, conventional charging approaches, such as the stir-versus-static method, photochemistry, or electrochemistry, have been able to assess the AR decay rate of either positively (two holes and one electron, X+) or negatively (one hole and two electrons, X–) charged excitons, and the decay dynamics of the other type of charged exciton is presumably estimated by the superposition principle of the biexciton Auger process. Herein, we demonstrate an opto-electrical method that enables us to precisely assess AR rates of X+ and X– in core/shell heterostructured QDs. Specifically, we devise electron-only devices and hole-only devices to inject extra charge carriers into QDs without unwanted side reactions or degradation of QDs and probe AR characteristics of these charged QDs via time-resolved photoluminescence measurements. We find that AR rates of charged excitons, both X+ and X–, gained from the present method agree well with those attained from conventional approaches and the superposition principle, corroborating the validity of the present approach. This present method permits us to comprehend multicarrier dynamics in QDs, prompting the use of QDs in light-emitting diodes and laser devices based on QDs.

Hot Carrier Cooling and Biexciton Dynamics of Anisotropic-Shaped CsPbBr3 Perovskite Nanocrystals

Fast hot-carrier (HC) cooling and the Auger recombination (AR) rate in solar absorbers act as a fundamental barrier toward the harvest of improved solar-energy efficiency. The recent emergence of lead halide perovskite (LHP) has shown enormous potential in high-performance solar cells; however, they are primarily limited to isotropic cubic shapes. It is thus essential to assess whether other anisotropic shapes can be utilized for improving the device’s functionality. Herein, we have studied HC relaxation and AR rates in hexapod CsPbBr3 NCs using ultrafast transient absorption (TA) spectroscopy. Our results indicate a prolonged HC cooling time and bi-exciton lifetime in a hexapod nanostructure compared to cubic CsPbBr3. In coordination with the HC temperature, we further confirm the slower HC relaxation rate in hexapod CsPbBr3 NCs by employing the electron–phonon coupling model, suggesting a retarded decay of longitudinal optical (LO) phonons. We demonstrate that the delocalization of charge carriers in the shallow trap states leads to a reduced overlap of electron and hole wave functions that is responsible for suppressing the bi-exciton AR rate.

Revealing Ultrafast Carrier Dynamics of Hybrid Perovskites at Various Stages of Nucleation and Growth Kinetics

AbstractWith hybrid organic–inorganic perovskites expanding their technological reach, from photovoltaic solar cells that operate at low carrier densities (1011 − 1013 cm−3) to light‐emitting diodes and lasers that operate at higher carrier densities (1013 − 1019 cm−3), it is critical to know how microstructure dictates carrier dynamics at varying injected carrier densities. For fabrication at scale, it is equally critical to know how quickly during the growth process do hybrid perovskites develop their characteristic optoelectronic properties. This work reports on a facile fabrication method that “freezes” different stages of nucleation and growth kinetics of prototypical hybrid perovskite on the same substrate—providing a unique strategy to assess differences in optoelectronic properties and carrier dynamics from nascent nucleating microcrystals to large‐grain thin films. The solution‐processed fabrication technique, optimized to control the nucleation density of an intermediate phase, successfully decouples the nucleation and growth steps that lead to large‐grain thin films. Ultrafast broadband absorption microscopy finds that the nucleating microcrystals already possess the optoelectronic properties of hybrid perovskites and share similar femtosecond‐to‐nanosecond dynamics as large‐grain thin films. When compared to the large‐grain thin films, the confining microcrystals exhibit enhanced carrier interactions, marked by an increase in bimolecular and Auger recombination rates.