Trap-assisted Auger Recombination Research Articles

Optical Absorption, Photocarrier Recombination Dynamics and Terahertz Dielectric Properties of Electron-Irradiated GaSe Crystals

Optical absorption spectra of 9 MeV electron-irradiated GaSe crystals were studied. Two absorption bands with the low-photon-energy threshold at 1.35 and 1.73 eV (T = 300 K) appeared in the transparency region of GaSe after the high-energy-electron irradiation. The observed absorption bands were attributed to the defect states induced by Ga vacancies in two charge states, having the energy positions at 0.23 and 0.61 eV above the valence band maximum at T = 300 K. The optical pump-terahertz probe technique (OPTP) was employed to study the dark and photoexcited terahertz conductivity and charge carrier recombination dynamics at two-photon excitation of as-grown and 9 MeV electron-irradiated GaSe crystals. The measured values of the differential terahertz transmission at a specified photoexcitation condition were used to extract the terahertz charge carrier mobilities. The determined terahertz charge carrier mobility values were ~46 cm2/V·s and ~14 cm2/V·s for as-grown and heavily electron-irradiated GaSe crystals, respectively. These are quite close to the values determined from the Lorentz–Drude–Smith fitting of the measured dielectric constant spectra. The photo-injection-level-dependent charge carrier lifetimes were determined from the measured OPTP data, bearing in mind the model injection-level dependencies of the recombination rates governed by interband and trap-assisted Auger recombination, bulk and surface Shockley–Read–Hall (SRH) recombination and interband radiative transitions in the limit of a high injection level. It was found that GaSe possesses a long charge carrier lifetime (a~1.9 × 10−6 ps−1, b~2.7 × 10−21 cm3ps−1 and c~1.3 × 10−37 cm6ps−1), i.e., τ~0.53 μs in the limit of a relatively low injection, when the contribution from SRH recombination is dominant. The electron irradiation of as-grown GaSe crystals reduced the charge carrier lifetime at a high injection level due to Auger recombination through radiation-induced defects. It was found that the terahertz spectra of the dielectric constants of as-grown and electron-irradiated GaSe crystals can be fitted with acceptable accuracy using the Lorentz model with the Drude–Smith term accounting for the free-carrier conductivity.

Electrical Relaxation and Transport Properties of ZnGeP2 and 4H-SiC Crystals Measured with Terahertz Spectroscopy

Terahertz photoconductivity and charge carrier recombination dynamics at two-photon (ZnGeP2) and three-photon (4H-SiC) excitation were studied. Thermally annealed, high-energy electron-irradiated and Sc-doped ZnGeP2 crystals were tested. The terahertz charge carrier mobilities were extracted from both the differential terahertz transmission at a specified photoexcitation condition and the Drude–Smith fitting of the photoconductivity spectra. The determined terahertz charge carrier mobility values are ~453 cm2/V·s for 4H-SiC and ~37 cm2/V·s for ZnGeP2 crystals. The charge carrier lifetimes and the contributions from various recombination mechanisms were determined at different injection levels using the model, which takes into account the influence of bulk and surface Shockley–Read–Hall (SRH) recombination, interband radiative transitions and interband and trap-assisted Auger recombination. It was found that ZnGeP2 possesses short charge carrier lifetimes (a~0.01 ps−1, b~6 × 10−19 cm3·ps−1 and c~7 × 10−40 cm6·ps−1) compared with 4H-SiC (a~0.001 ps−1, b~3 × 10−18 cm3·ps−1 and c~2 × 10−36 cm6·ps−1), i.e., τ~100 ps and τ~1 ns at the limit of relatively low injection, when the contribution from Auger and interband radiative recombination is small. The thermal annealing of as-grown ZnGeP2 crystals and the electron irradiation reduced the charge carrier lifetime, while their doping with 0.01 mass % of Sc increased the charger carrier lifetime and reduced mobility. It was found that the dark terahertz complex conductivity of the measured crystals is not fitted by the Drude–Smith model with reasonable parameters, while their terahertz photoconductivity can be fitted with acceptable accuracy.

Ultrafast carrier dynamics of PbS quantum dots in glasses for light amplification

Lead sulfide quantum dots (PbS QDs) have a unique performance in the near-infrared (NIR) range. In-situ precipitation of PbS QDs in glass not only improves the stability, but also is easy to be fabricated fiber compatible with silicon photonics. In this work, we reveal that absorption cross sections of PbS QDs at 1040 nm are 4–13 × 10−16 cm2, the bi- and tri-excitons lifetime are∼60 and ∼10 ps due to the trap-assisted Auger recombination using transient absorption (TA). Furthermore, we demonstrate the broadband net gain in 1500–1600 nm in single PbS QDs embedded glass with a gain threshold of <N>= 4.1 (averaged number of excitons), and achieve the maximum gain time of ∼20 ps and gain coefficient of >120 cm−1. These results illustrate the existing obstacles to achieve the net gain in PbS QDs embedded glass, which is important for applications on fiber amplifiers, NIR laser and high-capacity telecommunication.

Influence of the Surface Modification on Carrier Kinetics and ASE of Evaporated Perovskite Film

All inorganic cesium lead halide perovskite has emerged as promising optical gain materials due to its excellent optical properties. Carrier recombination and amplified spontaneous emissions (ASE) threshold affect their performance on lasing applications. Herein, CsPbBr3 films were prepared using thermally evaporated method with uniform and high coverage surface. Ammonium salt (PABr) was used to further modify the film. The modified sample exhibited flattened surface morphology, enhanced light-emission, suppressed trap-assisted recombination and Auger recombination, thus improving the efficiency of radiation recombination. It was found that the PABr modified CsPbBr3 exhibit an ASE threshold of 25.45 uJ cm−2 which is lower than that of pure CsPbBr3 with 31.5 uJ cm−2. This work suggest that the thermally evaporated method interfacial modification could provide an effective strategy to ameliorate the room-temperature stimulated emission of CsPbBr3.

Detection of hot electrons originating from an upper valley at ∼1.7eV above the Γ valley in wurtzite GaN using electron emission spectroscopy

Using electron emission spectroscopy, measurement and analysis were conducted on the energy distribution of vacuum emitted electrons from electrically driven InGaN/GaN green (peak wavelengths $\ensuremath{\lambda}\ensuremath{\approx}515\phantom{\rule{0.16em}{0ex}}\mathrm{nm}$) light-emitting diodes (LEDs) with and without a prewell superlattice (SL). We report on the detection of a high-energy upper valley at $\ensuremath{\sim}1.7\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ above the $\mathrm{\ensuremath{\Gamma}}$ valley from samples with no prewell SL. We propose that these upper valley electrons originate predominantly from trap-assisted Auger recombination (TAAR) in green LEDs, as the intensity of these peaks is found to have quadratic dependence on the carrier density $n$ [see Espenlaub et al., J. Appl. Phys. 126, 184502 (2019)]. The high-energy upper valley peak was not observed in the sample with a prewell SL which is attributed to gettering by the prewell SL of still unidentified impurities that act as TAAR centers.

Investigation of self-trapped excitonic dynamics in hematite nanoforms through non-degenerate pump–probe transmission spectroscopy

Non-degenerate pump–probe transmission spectroscopy is used to examine the ultrafast dynamics of photo-excited carriers in hematite nanoforms at various pump fluences. Using coupled rate equations, the kinetics of self-trapped exciton (STE) formation and its interaction with free excitons resulting in exciton annihilation were studied. It is shown from this model that the majority of the excitons were trapped by polaronic trap states to form self-trapped excitons within ∼3.5 ps. The findings indicate that free excitons and STEs interact non-linearly, similar to trap-assisted bi-molecular Auger recombination to annihilate one another. It is observed that there is substantial dependence of kinetics of STE formation and exciton decay on photo-excited exciton density, and the nature of this dependence indicates the reduced screening of electron–phonon interaction. Using the screening model applied to the rate constants of STE formation and decay, we estimate the saturation exciton density to be ∼3.3 × 1017 cm−3 and the average STE density to be ∼3.8 × 1018 cm−3 in the hematite nanoforms. We also noticed that doping K and Ni to hematite nanoforms up to 5% did not remarkably change the nature of the exciton dynamics.

Photoexcited carrier dynamics in semi-insulating 4H-SiC by Raman spectroscopy

The photoexcited carrier dynamics of high-purity (HPSI) and vanadium-doped semi-insulating (VDSI) 4H-SiC irradiated by lasers with different wavelengths and powers were investigated. Raman spectra were measured at room temperature and the photoexcited carrier concentrations were extracted from the Raman line shape analysis of longitudinal optical phonon–plasmon coupled mode. It was found that the longitudinal optical (LO) peaks of HPSI and VDSI did not shift with laser power variations, due to a low concentration of photoexcited carriers, when a 532- nm laser was used. However, when a 355- nm laser was adapted, the relationship between the photoexcited carrier concentrations and the laser power was found to be nonlinear because of the dominance of trap-assisted Auger (TAA) recombination. The coefficient of TAA recombination was laser power–dependent. The proposed carrier dynamic model deepens the understanding of the physical mechanism of semi-insulating SiC irradiated by nanosecond laser and provides an insight into the interpretation of experimental phenomena related to laser energy in optoelectronic devices.

Optical Pump–Terahertz Probe Study of HR GaAs:Cr and SI GaAs:EL2 Structures with Long Charge Carrier Lifetimes

The time dynamics of nonequilibrium charge carrier relaxation processes in SI GaAs:EL2 (semi-insulating gallium arsenide compensated with EL2 centers) and HR GaAs:Cr (high-resistive gallium arsenide compensated with chromium) were studied by the optical pump–terahertz probe technique. Charge carrier lifetimes and contributions from various recombination mechanisms were determined at different injection levels using the model, which takes into account the influence of surface and volume Shockley–Read–Hall (SRH) recombination, interband radiative transitions and interband and trap-assisted Auger recombination. It was found that, in most cases for HR GaAs:Cr and SI GaAs:EL2, Auger recombination mechanisms make the largest contribution to the recombination rate of nonequilibrium charge carriers at injection levels above ~(0.5–3)·1018 cm−3, typical of pump–probe experiments. At a lower photogenerated charge carrier concentration, the SRH recombination prevails. The derived charge carrier lifetimes, due to the SRH recombination, are approximately 1.5 and 25 ns in HR GaAs:Cr and SI GaAs:EL2, respectively. These values are closer to but still lower than the values determined by photoluminescence decay or charge collection efficiency measurements at low injection levels. The obtained results indicate the importance of a proper experimental data analysis when applying terahertz time-resolved spectroscopy to the determination of charge carrier lifetimes in semiconductor crystals intended for the fabrication of devices working at lower injection levels than those at measurements by the optical pump–terahertz probe technique. It was found that the charge carrier lifetime in HR GaAs:Cr is lower than that in SI GaAs:EL2 at injection levels &gt; 1016 cm−3.

Low-Threshold, Highly Stable Colloidal Quantum Dot Short-Wave Infrared Laser enabled by Suppression of Trap-Assisted Auger Recombination.

Pb-chalcogenide colloidal quantum dots (CQDs) are attractive materials to be used as tuneable laser media across the infrared spectrum. However, excessive nonradiative Auger recombination due to the presence of trap states outcompetes light amplification by rapidly annihilating the exciton population, leading to high gain thresholds. Here, a binary blend is employed of CQDs and ZnO nanocrystals in order to passivate the in-gap trap states of PbS-CQD gain medium. Using transient absorption, a fivefold increase is measured in Auger lifetime demonstrating the suppression of trap-assisted Auger recombination. By doing so, a twofold reduction is achieved in amplified spontaneous emission (ASE) threshold. Finally, by integrating the proposed binary blend to a distributed feedback (DFB) resonator, single-mode lasing emission is demonstrated at 1650nm with a linewidth of 1.23nm (0.62 meV), operating at a low lasing threshold of ≈385 μJ cm-2 . The Auger suppression in this system has allowed to achieve unprecedented lasing emission stability for a CQD laser with recorded continuous operation of 5 h at room temperature and ambient conditions.

Simulation and characterization of planar high-efficiency back contact silicon solar cells

Short-circuit current, open-circuit voltage, and photoconversion efficiency of silicon high-efficiency solar cells with all back contact (BCSC) with planar surfaces have been calculated theoretically. In addition to the recombination channels usually considered in this kind of modeling, namely, radiative, Auger, Shockley–Read–Hall, and surface recombination, the model also takes into account the nonradiative trap-assisted exciton Auger recombination and recombination in the space charge region. It is ascertained that these two recombination mechanisms are essential in BCSCs in the maximum power operation regime. The model results are in good agreement with the experimental results from the literature.

The Measurement of Charge Carrier Lifetime in SIGaAs: Cr and EL2-GaAs by Pump-Probe Terahertz Spectroscopy

In the present work, the temporal dynamics of relaxation of a nonequilibrium concentration of charge carriers in SI-GaAs:Cr and EL2-GaAs semiconductor crystals has been studied using pump-probe terahertz spectroscopy. The obtained experimental data were analyzed taking into account the mechanisms of surface and bulk Shockley–Reed–Hall recombination, radiative recombination, interband and trap assisted Auger recombination. It was found that at injection levels arising upon excitation of samples by laser radiation with a pulse duration of 35 fs and an energy of 0.1 mJ per pulse at a central wavelength of 791 nm, Auger recombination mechanisms have a significant effect. Auger recombination mechanisms make a dominant contribution to the recombination rate of nonequilibrium charge carriers at injection levels above 2·1018 cm–3 for SI-GaAs:Cr and above 1018 cm–3 for EL2-GaAs. At lower injection levels, the bulk and surface Shockley-Reed-Hall recombination are the dominant recombination mechanisms.

Thermal droop in III-nitride based light-emitting diodes: Physical origin and perspectives

This tutorial paper focuses on the physical origin of thermal droop, i.e., the decrease in the luminescence of light-emitting diodes (LEDs) induced by increasing temperature. III-nitride-based LEDs are becoming a pervasive technology, covering several fields from lighting to displays, from automotive to portable electronics, and from horticulture to sensing. In all these environments, high efficiency is a fundamental requirement, for reducing power consumption and system cost. Over the last decade, a great deal of effort has been put in the analysis of the efficiency droop, the decrease in LED internal quantum efficiency (IQE) induced by high current density. On the other hand, an IQE decrease is observed also for increasing temperature, a phenomenon usually referred to as thermal droop. For commercial LEDs, the IQE decrease related to thermal droop can be comparable to that of efficiency droop: for this reason, understanding thermal droop is a fundamental step for making LEDs capable of operating at high temperature levels. In several fields (including street lighting, automotive, photochemical treatments, projection, entertainment lighting, etc.), compact and high-flux light sources are required: typically, to reduce the size, weight, and cost of the systems, LEDs are mounted in compact arrays, and heat sinks are reduced to a minimum. As a consequence, LEDs can easily reach junction temperatures above 85–100 °C and are rated for junction temperatures up to 150–175 °C (figures from commercially available LED datasheets: Cree XHP70, Osram LUW HWQP, Nichia NVSL219CT, Samsung LH351B, and LedEngin LZP-00CW0R) and this motivates a careful analysis of thermal droop. This paper discusses the possible physical causes of thermal droop. After an introduction on the loss mechanisms in junctions, we will individually focus on the following processes: (i) Shockley–Read–Hall (SRH) recombination and properties of the related defects; (ii) Auger recombination and its temperature dependence, including the discussion of trap-assisted Auger recombination; (iii) impact of carrier transport on the thermal droop, including a discussion on carrier delocalization, escape, and freeze out; (iv) non-SRH defect-related droop mechanisms. In addition, (v) we discuss the processes that contribute to light emission at extremely low current levels and (vi) the thermal droop in deep ultraviolet LEDs, also with reference to the main parasitic emission bands. The results presented within this paper give a tutorial perspective on thermal droop; in addition, they suggest a pathway for the mitigation of this process and for the development of LEDs with stable optical output over a broad temperature range.

Absorption enhancement and efficiency improvement of an organic solar cell embedded with core–shell Au@ITO nanoparticles

In this paper, we propose a new design of plasmonic organic solar cells (OSCs). It consists of a protective layer of SiO2, an anti-reflective glass of ITO, a compact buffer of PEDOT:PSS, an absorbing organic material of P3HT:PCBM, and a reflective layer of Al. A square periodic array of core–shell nanoparticles (Au@ITO NPs) is embedded in the active layer of P3HT:PCBM in order to enhance the absorption of OSC. Although ITO coating slightly reduces efficiency, it prevents the oxidation of gold NPs and increases the OSC lifetime. We study the effect of numerous parameters such as the core radius, shell thickness, and core material on the optical absorption by solving Maxwell’s equations using the three-dimensional finite-difference time-domain method. The drift–diffusion and Poisson’s equations are solved with an in-house software tool by discretizing the solar cell using the finite element method. To the best of our knowledge, this paper is the first to apply the real model of trap-assisted recombination and Auger recombination of used materials to the simulations to match them with the experimental results. The numerical results show the proposed OSC embedded with Au@ITO NPs has the built-in potential of 2.9 V, short-circuit current of 16.63 mA/cm2, the open-circuit voltage of 1.14 V, maximum power of 17.25 mW/cm2, fill-factor of 0.91, the conduction band of 2.8 eV, electron quasi-Fermi level of 2.35 eV, hole quasi-Fermi level of 0.6 eV and an efficiency of 17.25%. Furthermore, the performance of the proposed OSC has an improvement of 25% compared to conventional OSCs.

Evidence for trap-assisted Auger recombination in MBE grown InGaN quantum wells by electron emission spectroscopy

We report on the direct measurement of hot electrons generated in the active region of blue light-emitting diodes grown by ammonia molecular beam epitaxy by electron emission spectroscopy. The external quantum efficiency of these devices is &amp;lt;1% and does not droop; thus, the efficiency losses from the intrinsic, interband, electron–electron–hole, or electron–hole–hole Auger should not be a significant source of hot carriers. The detection of hot electrons in this case suggests that an alternate hot electron generating process is occurring within these devices, likely a trap-assisted Auger recombination process.

Evidence of trap-assisted Auger recombination in low radiative efficiency MBE-grown III-nitride LEDs

By studying low radiative efficiency blue III-nitride light emitting diodes (LEDs), we find that the ABC model of recombination commonly used for understanding efficiency behavior in LEDs is insufficient and that additional effects should be taken into account. We propose a modification to the standard recombination model by incorporating a bimolecular nonradiative term. The modified model is shown to be in much better agreement with the radiative efficiency data and to be more consistent than the conventional model with very short carrier lifetimes measured by time-resolved photoluminescence in similar, low radiative efficiency material. We present experimental evidence that a hot carrier-generating process is occurring within these devices, in the form of measurements of forward photocurrent under forward bias. The forward photocurrent, due to hot carrier generation in the active region, is present despite the lack of any “efficiency droop”—the usual signature of band-to-band Auger recombination in high-quality III-nitride LEDs. Hot carrier generation in the absence of band-to-band Auger recombination implies that some other source of hot carriers exists within these low radiative efficiency devices, such as trap-assisted Auger recombination.

Direct measurement of hot-carrier generation in a semiconductor barrier heterostructure: Identification of the dominant mechanism for thermal droop

Energy measurements of electrons emitted from a semiconductor can reveal internal physical processes hitherto elusive. Signatures of hot-electron processes in heterostructures have been observed from cesiated, light-emitting, and p-i-n diodes. In p-i-n devices with AlGaN barriers, a high-energy peak was measured and ascribed to a trap-assisted Auger recombination process. Temperature dependent measurements of light-emitting diodes with AlGaN electron blocking layers also show such hot carriers when electrons thermally reach these barriers, identifying carrier escape as the mechanism of thermal droop and demonstrating the efficacy of such barriers to partially mitigate thermal droop.

Identification of the mechanism responsible for the boron oxygen light induced degradation in silicon photovoltaic cells

Silicon solar cells containing boron and oxygen are one of the most rapidly growing forms of electricity generation. However, they suffer from significant degradation during the initial stages of use. This problem has been studied for 40 years resulting in over 250 research publications. Despite this, there is no consensus regarding the microscopic nature of the defect reactions responsible. In this paper, we present compelling evidence of the mechanism of degradation. We observe, using deep level transient spectroscopy and photoluminescence, under the action of light or injected carriers, the conversion of a deep boron-di-oxygen-related donor state into a shallow acceptor which correlates with the change in the lifetime of minority carriers in the silicon. Using ab initio modeling, we propose structures of the BsO2 defect which match the experimental findings. We put forward the hypothesis that the dominant recombination process associated with the degradation is trap-assisted Auger recombination. This assignment is supported by the observation of above bandgap luminescence due to hot carriers resulting from the Auger process.

Statistics of the Auger Recombination of Electrons and Holes via Defect Levels in the Band Gap-Application to Lead-Halide Perovskites.

Recent evidence for bimolecular nonradiative recombination in lead-halide perovskites poses the question for a mechanistic origin of such a recombination term. A possible mechanism is Auger recombination involving two free charge carriers and a trapped charge-carrier. To study the influence of trap-assisted Auger recombination on bimolecular recombination in lead-halide perovskites, we combine estimates of the transition rates with a detailed balance compatible approach of calculating the occupation statistics of defect levels using a similar approach as for the well-known Shockley–Read–Hall recombination statistics. We find that the kinetics resulting from trap-assisted Auger recombination encompasses three different regimes: low injection, high injection, and saturation. Although the saturation regime with a recombination rate proportional to the square of free carrier concentration might explain the nonradiative bimolecular recombination in general, we show that the necessary trap density is higher than reported. Thus, we conclude that Auger recombination via traps is most likely not the explanation for the observed nonradiative bimolecular recombination in CH3NH3PbI3 and related materials.

Interplay of bimolecular and Auger recombination in photoexcited carrier dynamics in silicon nanocrystal/silicon dioxide superlattices

We report results of investigating carrier recombination in silicon nanocrystal/silicon dioxide superlattices. The superlattices prepared by nitrogen-free plasma enhanced chemical vapour deposition contained layers of silicon nanocrystals. Femtosecond transient transmission optical spectroscopy was used to monitor carrier mechanisms in the samples. The three-particle Auger recombination was observed in accord with previous reports. However, under high pump intensities (high photoexcited carrier densities) the bimolecular process dominated the recombination. Detailed analysis of measured data and fitting procedure made it possible to follow and quantify the interplay between the two recombination processes. The bimolecular recombination was interpreted in terms of the trap-assisted Auger recombination.

Photodoping and Transient Spectroscopies of Copper-Doped CdSe/CdS Nanocrystals.

Colloidal Cu+-doped CdSe/CdS core/shell semiconductor nanocrystals (NCs) are investigated in their as-prepared and degenerately n-doped forms using time-resolved photoluminescence and transient-absorption spectroscopies. Photoluminescence from Cu+:CdSe/CdS NCs is dominated by recombination of delocalized conduction-band (CB) electrons with copper-localized holes. In addition to prominent bleaching of the first excitonic absorption feature, transient-absorption measurements show bleaching of the sub-bandgap copper-to-CB charge-transfer (MLCBCT) absorption band and also reveal a photoinduced midgap valence-band (VB)-to-copper charge-transfer (LVBMCT) absorption band that extends into the near-infrared, as predicted by recent computations. The photoluminescence of these NCs is substantially diminished upon introduction of excess CB electrons via photodoping. Time-resolved photoluminescence measurements reveal that the MLCBCT excited state is still formed upon photoexcitation of the n-doped Cu+:CdSe/CdS NCs, but its luminescence is quenched by a fast (picosecond) three-carrier trap-assisted Auger recombination process involving two CB electrons and one copper-bound hole.