Nonradiative Recombination Rate Research Articles

In Situ Photochemical Surface Passivation of CdSe/ZnS Quantum Dots for Quantitative Light Emission and Enhanced Photocurrent Response in Solar Cells

Suppression of energy-wasting nonradiative carrier relaxation in photoactivated semiconductor quantum dots (QDs) is an essential requirement for applications such as QD-sensitized solar cell (QDSSC). Here we report that in situ surface passivation of CdSe/ZnS QDs using dithiothreitol (DTT) results in the 4-fold enhancement of photoluminescence (PL) quantum efficiency of QDs. By the analyses of PL intensities and blinking statistics of single QDs, the PL enhancement is assigned to a combination of processes such as unexpected appearance of bright QDs, gradual increase in the PL intensity of QDs, and substantial suppression of blinking. These processes not only suggest the suppression of nonradiative carrier recombination in QDs passivated with DTT molecules but also enable us to classify the nonradiative carrier recombination centers in QDs into low-density defects in which the rates of nonradiative recombination largely exceed the rates of radiative relaxation and high-density defects in which the rates of nonradiative carrier recombination are comparable to the rates of radiative relaxations. In the former case, passivation of the defects by the spontaneous addition of one or a few DTT molecules to QDs with PL intensity below the detection limit results in the formation of highly luminescent QD-(DTT)n adducts. In the latter case, highly luminescent QD-(DTT)n adducts are formed from already luminescent QDs by the relatively slow addition of DTT molecules. These two types of surface passivation reactions are governed by both chemical and photochemical processes. Overall, the passivation of defects in QD by DTT results in the suppression of energy-wasting nonradiative relaxations, which enables us to drive ca. 33% excess photocurrent in a photoelectrochemical cell constructed using QD-(DTT)n as the sensitizer.

The role of polarization fields in Auger-induced efficiency droop in nitride-based light-emitting diodes

The rates of non-radiative Auger recombination (AR) and radiative recombination (RR) in polar GaN/AlN quantum wells (QWs) are calculated. It is shown that in these QWs the polarization field not only suppresses the RR but also strongly enhances the rate of AR. As a result, the polarization field triggers the Auger-induced efficiency droop, which, according to the calculations, does not exist in non-polar GaN/AlN QWs. We demonstrate that in polar QWs the droop can be overcome by suppression of AR using a gradual variation of the QW layer composition, which compensates the effect of the electric field acting on holes.

Time-resolved photoluminescence of silicon microstructures fabricated by femtosecond laser in air

Green photoluminescence (PL) from silicon microstructures fabricated by femtosecond laser in air was studied at different temperature by time-resolved spectroscopy. The PL decay profiles are well fitted by a stretched exponential function: I(t)=I(0)*exp[-(t/τ)β]. The dependence of the decay time constant τ and of the stretching index β on PL photon energy and on the temperature is investigated. A model of transport and recombination of the carriers is introduced as a possible explanation of the stretched exponential decay. The nonradiative recombination rate of the localized carriers, which is dependent on the carrier density and influenced by the trapping site density and the temperature, is deduced to be responsible for this kind of decay.

Development of nanoimprinted InP QDs decorated polyaniline solar cell with conversion efficiency 3%

Organic–inorganic hybrid materials received considerable attention due to promising industrial applications. The originality of novel chemical recipes, allowing incorporation of well-defined nanoparticle structures into complex hybrid architectures, opens new possibilities for multidisciplinary fields and in particular in optoelectronic devices. The rate of non-radiative recombination and energy transfer through a hybrid inorganic/organic nanocomposite is mainly governing the ability of charge transfer from semiconductor quantum dots to conjugated polymers. Herein, we report that the electron–hole non-radiative recombination in polymer can be constricted by funneling the diffusion of exciton by engineering a proper morphology of a hybrid nanostructure. InP quantum dots have been selected due to their efficient exciton generation and polyaniline as a conjugated polymer for its potency to suppress non-radiative recombination by restraining exciton diffusion. The hole transfer was monitored via bi-exponential kinetic model and time of flight method. The conversion efficiency of the prepared films increased from 0.23% to 3.1% when the thickness is increased from 14nm to 157nm.

Suppression of Nonradiation Recombination by Selected Si Doping in AlGaN Barriers for Ultraviolet Light-Emitting Diodes

The effect of selective Si doping on the emission efficiency in ultraviolet (UV) light-emitting diodes (LEDs) is investigated both experimentally and theoretically. The results show that the light output power increases with the number of Si-doped barriers (QBs). Experimental results indicate that compared with an all-undoped-QB LED, a factor of 3.17 can be achieved for the output power of an all-doped-QB LED at 350 mA. Detailed analysis on this phenomenon shows that the Si-doped QB is beneficial to suppress the nonradiative recombination rate by excess electrons in doped barriers.

Impact of Diffusivity to Carrier Recombination Rate in Nitride Semiconductors: From Bulk GaN to (In,Ga)N Quantum Wells

We combined light induced transient grating and free carrier absorption techniques to investigate temporal and spatial carrier dynamics in nitrides. Inverse correlation of diffusivity and nonradiative recombination rate in GaN epilayers was ascribed to carrier diffusive flow to the internal boundaries of hexagonal grains and recombination on dislocations there, while the similar dependence in InGaN quantum wells (QWs) was a consequence of carrier delocalization caused either by carrier injection or thermal escape. Numerical modeling of recombination rates in light emitting diode structures with In content up to 13% revealed increasing with excitation nonradiative recombination rate which is a consequence of higher overall carrier mobility at higher densities. We propose the injection-enhanced in-plane diffusivity as the most probable mechanism explaining the increase of non-radiative losses in high power light emitting diodes (LEDs).

Influence of defect reduction and strain relaxation on carrier dynamics in InGaN-based light-emitting diodes on cone-shaped patterned sapphire substrates

This study investigates optical properties and carrier dynamics of InGaN-based light-emitting diodes grown on cone-shaped patterned sapphire (CSPS) and planar sapphire substrates. Edge-type threading dislocations were dramatically reduced in InGaN multiple quantum wells (MQWs) on CSPS substrates compared to the case of planar substrates. We observed a smaller Stokes shift and enhanced quantum efficiency for CSPS substrates. From time-resolved optical analysis, we found that the non-radiative (radiative) recombination rate of MQWs on CSPS is lower (higher) than that of MQWs on planar substrates, which is consistent with improved crystal quality (strain relaxation) of the MQWs on CSPS.

Observation of photo darkening in self assembled InGaAs/GaAs quantum dots

Photo darkening was observed in epitaxial InGaAs/GaAs quantum dots (QDs). The photoluminescence (PL) intensity of the QDs showed a non-reversible decrease under continuous laser irradiation. The time constants varied from tens of minutes to several hours, depending on the applied laser power. Based on the spectral evolution, it was concluded that the observed phenomenon should originate from laser induced structural damage and a sustained increase of non-radiative recombination rate in the wetting layer. Additionally, according to the PL decay dynamics at different laser powers, it is argued that there should exist other processes that hinder PL degradation at a high laser power.

Controlled Alloying of the Core–Shell Interface in CdSe/CdS Quantum Dots for Suppression of Auger Recombination

The influence of a CdSexS1-x interfacial alloyed layer on the photophysical properties of core/shell CdSe/CdS nanocrystal quantum dots (QDs) is investigated by comparing reference QDs with a sharp core/shell interface to alloyed structures with an intermediate CdSexS1-x layer at the core/shell interface. To fully realize the structural contrast, we have developed two novel synthetic approaches: a method for fast CdS-shell growth, which results in an abrupt core/shell boundary (no intentional or unintentional alloying), and a method for depositing a CdSexS1-x alloy layer of controlled composition onto the CdSe core prior to the growth of the CdS shell. Both types of QDs possess similar size-dependent single-exciton properties (photoluminescence energy, quantum yield, and decay lifetime). However the alloyed QDs show a significantly longer biexciton lifetime and up to a 3-fold increase in the biexciton emission efficiency compared to the reference samples. These results provide direct evidence that the structure of the QD interface has a significant effect on the rate of nonradiative Auger recombination, which dominates biexciton decay. We also observe that the energy gradient at the core-shell interface introduced by the alloyed layer accelerates hole trapping from the shell to the core states, which results in suppression of shell emission. This comparative study offers practical guidelines for controlling multicarrier Auger recombination without a significant effect on either spectral or dynamical properties of single excitons. The proposed strategy should be applicable to QDs of a variety of compositions (including, e.g., infrared-emitting QDs) and can benefit numerous applications from light emitting diodes and lasers to photodetectors and photovoltaics.

Multiple Exciton Generation and Recombination in Carbon Nanotubes and Nanocrystals

Semiconducting nanomaterials such as single-walled carbon nanotubes (SWCNTs) and nanocrystals (NCs) exhibit unique size-dependent quantum properties. They have therefore attracted considerable attention from the viewpoints of fundamental physics and functional device applications. SWCNTs and NCs also provide an excellent new stage for experimental studies of many-body effects of electrons and excitons on optical processes in nanomaterials. In this Account, we discuss multiple exciton generation and recombination in SWCNTs and NCs for next-generation photovoltaics. Strongly correlated ensembles of conduction-band electrons and valence-band holes in semiconductors are complex quantum systems that exhibit unique optical phenomena. In bulk crystals, the carrier recombination dynamics can be described by a simple model, which includes the nonradiative single-carrier trapping rate, the radiative two-carrier recombination rate, and the nonradiative three-carrier Auger recombination rate. The nonradiative Auger recombination rate determines the carrier recombination dynamics at high carrier density and depends on the spatial localization of carriers in two-dimensional quantum wells. The Auger recombination and multiple exciton generation rates can be advantageously manipulated by nanomaterials with designated energy structures. In addition, SWCNTs and NCs show quantized recombination dynamics of multiple excitons and carriers. In one-dimensional SWCNTs, excitons have large binding energies and are very stable at room temperature. The extremely rapid Auger recombination between excitons determines the photoluminescence (PL) intensity, the PL linewidth, and the PL lifetime. SWCNTs can undergo multiple exciton generation, while strong exciton-exciton interactions and complicated exciton structures affect the quantized Auger rate and the multiple exciton generation efficiency. Interestingly, in zero-dimensional NC quantum dots, quantized Auger recombination causes unique optical phenomena. The breakdown of the k-conversion rule and strong Coulomb interactions between carriers in NCs enhance Auger recombination rate and decrease the energy threshold for multiple exciton generation. We discuss this impact of the k-conservation rule on two-carrier radiative recombination and the three-carrier Auger recombination processes in indirect-gap semiconductor Si NCs. In NCs and SWCNTs, multiple exciton generation competes with Auger recombination, surface trapping of excitons, and cooling of hot electrons or excitons. In addition, we explore heterostructured NCs and impurity-doped NCs in the context of the optimization of charge carrier extraction from excitons in NCs.

Characterization of MBE‐grown AlGaN layers heavily doped using silane

AbstractThe Alx Ga1–xN layers with a wide range of AlN molar fraction (0 < x < 0.6) were grown by ammonia MBE on (0001)‐oriented sapphire substrates using silane as the silicon dopant. The structural, electrical and optical properties of the layers were investigated by atomic force microscopy, X‐ray diffraction, Hall, Raman, photoluminescence and cathodoluminescence measurements. It was found that doping affects surface morphology, dislocation density and luminescence intensity of the Alx Ga1–xN layers. A sharp decrease of the luminescence intensity for the heavily doped GaN and Al0.3Ga0.7N layers was explained by enhancement of the nonradiative recombination rate in degenerate GaN layers and by an increase in the defect concentration in AlGaN layers. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Ultrafast Spectral Migration of Photoluminescence in Graphene Oxide

We use subpicosecond time-resolved photoluminescence measurements to study the nature of photoluminescence in graphene oxide and reduced graphene oxide. Our data indicate that, in contrast to prior suggestions, the photoluminescence spectra of graphene oxide and reduced graphene oxide are inhomogeneously broadened. We observe substantial energy redistribution and relaxation among the emitting states within the first few picoseconds, leading to a progressive red shift of the emission spectrum. Blue shifts that arise in time-integrated spectra upon photothermal reduction are easily understood within this dynamical context without invoking a modified distribution of dipole-coupled states. Rather, reduction increases the nonradiative electron-hole recombination rate and curtails the red-shifting process, which is consistent with an increase in quenching through the introduction of larger and/or more numerous sp(2) clusters. Polarization memory measurements show energetic signatures of electron-hole correlations, established on a subpicosecond time scale and developing little thereafter.

Suppression of Auger-stimulated efficiency droop in nitride-based light emitting diodes

We calculate the rate of nonradiative Auger recombination in InGaN/GaN quantum wells with rectangular and smooth confining potentials. The calculations show that the rate of Auger recombination in rectangular quantum wells is sufficiently high to explain the efficiency droop in nitride-based light emitting diodes (LEDs). This rate, however, can be reduced by softening of the confining potential and a three-fold suppression is demonstrated in the studied quantum wells. The suppression of the Auger recombination rate improves LED radiative efficiency and reduces the droop effect, as we show using the standard recombination (ABC) model.

Time-resolved and temperature-dependent photoluminescence studies on CdTe/ZnTe quantum dots with different ZnTe capping layer thicknesses

We investigate the effects of the capping layer thickness on the optical properties of CdTe/ZnTe quantum dots (QDs). The time-resolved photoluminescence (PL) measurements used to study the carrier dynamics show a shorter decay time for CdTe/ZnTe QDs with decreasing thickness of the ZnTe cap layer due to an increase in the nonradiative surface recombination rate. The activation energy of the electrons confined in the CdTe/ZnTe QDs, as obtained from the temperature-dependent PL spectra, decreases with the thickness of the ZnTe cap layer. These results indicate that the carrier dynamics and activation energy of CdTe/ZnTe QDs are affected by the thickness of the ZnTe cap layer.

Ab initioCalculations of Deep-Level Carrier Nonradiative Recombination Rates in Bulk Semiconductors

Nonradiative carrier recombination is of both applied and fundamental interest. Here a novel algorithm is introduced to calculate such a deep level nonradiative recombination rate using the ab initio density functional theory. This algorithm can calculate the electron-phonon coupling constants all at once. An approximation is presented to calculate the phonon modes for one impurity in a large supercell. The neutral Zn impurity site together with a N vacancy is considered as the carrier-capturing deep impurity level in bulk GaN. Its capture coefficient is calculated as 5.57 × 10(-10)cm(3)/s at 300 K. We found that there is no apparent onset of such a nonradiative process as a function of temperature.

Interplay of polarization fields and Auger recombination in the efficiency droop of nitride light-emitting diodes

We use theoretical modeling to investigate the effect of polarization fields and non-radiative Auger recombination on the efficiency-droop and green-gap problems of polar and nonpolar nitride light-emitting diodes. The dependence of radiative and nonradiative recombination rates on electron-hole wave-function overlap is analyzed. Device designs that minimize the polarization fields lead to higher efficiency, not because the internal quantum efficiency is improved at a given carrier density but because they can be operated at a lower carrier density for a given current density.

Temperature variation of non‐radiative recombination rate in a‐Si:H films

AbstractTemperature variation of the recombination rates has been investigated for the electron‐hole pairs responsible for defect PL in a defective a‐Si:H film as grown. The results are compared with those obtained for a high‐quality a‐Si:H film after illumination. The results of the nonradiative recombination rate are fitted by a theoretical prediction for the case of strong electron‐phonon coupling in the case of the defective a‐Si:H film similarly to the case of the illuminated high‐quality a‐Si:H film.Difference between the frequency of the phonon associated with the non‐radiative recombination process in the defective a‐Si:H film and that in the illuminated highquality a‐Si:H film is discussed by considering the influence of the amorphous network in the a‐Si:H films affected by the preparation conditions and the nature of the native and photo‐created defects.

Picosecond strain pulses generated by a supersonically expanding electron-hole plasma in GaAs

Strain pulses with picosecond duration are generated directly in GaAs by optical excitation from a femtosecond laser. The photons are absorbed in a 15-nm layer near the surface, creating the electron-hole plasma, which diffusively expands into the bulk of the GaAs. At an early time, the drift velocity of the expanding plasma exceeds the speed of longitudinal sound, and the generated strain pulses cannot escape the plasma cloud. Such supersonic generation of strain pulses results in specific temporal and spatial shapes of the generated strain pulses, where the compression part has a much lower amplitude than the tensile part. This phenomenon is studied experimentally at low temperatures and analyzed theoretically based on the wave and diffusion equations for strain and plasma density, respectively. Two mechanisms, deformation potential and thermoelasticity, are responsible for the experimental observations. The relative contributions from these mechanisms are governed by the nonradiative recombination rate in the plasma and depend on the optical excitation density, inducing such nonlinear optoacoustic effects as shortening of the leading strain front and a superlinear/quadratic increase in its amplitude with the rise of pump laser fluence.

Optical properties and effect of carrier tunnelling in CdSe colloidal quantum dots: A comparative study with different ligands

We studied both cw and time-resolved photoluminescence of colloidal CdSe/ZnS core-shell quantum dots capped with chemical ligands. For the trioctylphosphine oxide capped CdSe/ZnS QDs, both the luminescence intensity and lifetime were found to be increased with increasing temperatures, which can be explained by the thermal activation of the carriers trapped at shallow trapping centers. After the ligand exchange into 3-mercaptopropionic acid, the non-radiative recombination rate was increased and the luminescence efficiency was decreased at room temperature. When the QDs were employed in photovoltaic devices, photocurrent was found to be increased after the ligand exchange. The improved photocurrents observed in photovoltaic devices can be explained by the improved tunnelling probability between the neighbouring QDs.

Radiative and nonradiative recombination rates in cubic SiC

Investigation of carrier dynamics in highly excited 3C–SiC by free-carrier absorption and photoluminescence (PL) techniques allowed determination of nonradiative and radiative recombination rates. Free carrier decay kinetics at various injection levels provided nonradiative recombination coefficients: bimolecular Bnr and Auger, C. By modelling carrier in-depth diffusion and taking into account nonlinear recombination rates, we fitted the experimental PL injection dependence and determined radiative bimolecular coefficient at room temperature, Brad=2.05×10−15cm3/s. A theoretically calculated value was found rather similar (2.38×10−15cm3/s). Numerical analysis of the injection-dependent PL spectra exhibited effects of bandgap filling and bandgap renormalisation (BGR), providing the BGR coefficient aBGR=1.2×10−6eVcm3/4 and low injection bandgap value Eg0=2.374eV of a cubic SiC at room temperature.