Radiative Recombination Centers Research Articles

Redistribution of radiative recombination centers in the SiC/por-SiC/Dy2O3 structure under the influence of athermal microwave irradiation

In this work, the authors have considered the effect of short-term nonthermal action of microwave radiation on the distribution of radiative recombination centers in SiC/por-SiC/Dy2O3 structures. The analysis of photoluminescence spectra of these structures excited by the radiation with an energy lower than the band gap in the 4H-SiC crystalline substrate has shown that the short-term action of microwave radiation leads to the migration of dislocations and, as a consequence, to redistribution of radiative recombination centers and local symmetry change.

Impacts of vacancy complexes on the room-temperature photoluminescence lifetimes of state-of-the-art GaN substrates, epitaxial layers, and Mg-implanted layers

For rooting the development of GaN-based optoelectronic devices, understanding the roles of midgap recombination centers (MGRCs), namely, nonradiative recombination centers and deep-state radiative recombination centers, on the carrier recombination dynamics is an essential task. By using the combination of time-resolved photoluminescence and positron annihilation spectroscopy (PAS) measurements, the origins of major MGRCs in the state-of-the-art GaN epilayers, bulk crystals, and Mg-implanted layers were identified, and their concentrations were quantified for deriving the capture coefficients of minority carriers. In this article, potential standardization of the room-temperature photoluminescence lifetime for the near-band-edge emission (τPLRT) as the concentration of major MGRCs well below the detection limit of PAS is proposed. For n-GaN substrates and epilayers grown from the vapor phase, τPLRT was limited by the concentration of carbon on N sites or divacancies comprising a Ga vacancy (VGa) and a N vacancy (VN), [VGaVN], when carbon concentration was higher or lower, respectively, than approximately 1016 cm−3. Here, carbon and VGaVN act as major deep-state radiative and nonradiative recombination centers, respectively, while major MGRCs in bulk GaN crystals were identified as VGa(VN)3 vacancy clusters in Na-flux GaN and VGa or VGaVN buried by a hydrogen and/or VGa decorated with oxygen on N sites, VGa(ON)3–4, in ammonothermal GaN. The values of τPLRT in n-GaN samples are compared with those of p-GaN, in which τPLRT was limited by the concentration of VGa(VN)2 in Mg-doped epilayers and by the concentrations of VGaVN and (VGaVN)3 in Mg-implanted GaN right after the implantation and after appropriate activation annealing, respectively.

Improved midgap recombination lifetimes in GaN crystals grown by the low-pressure acidic ammonothermal method

To investigate the carrier recombination processes in GaN crystals grown by the low-pressure acidic ammonothermal (LPAAT) method, the photoluminescence (PL) spectra and PL lifetimes of LPAAT GaN crystals grown on acidic ammonothermal (AAT) GaN seed crystals were correlated with the growth polarity and species/concentration of point defects. The PL spectra of LPAAT GaN grown toward the (0001¯) direction (−c region), which provided the highest growth rate, exhibited a predominant near-band edge (NBE) emission. Neither bandgap narrowing nor Burstein–Moss shifts due to high concentration residual impurities were observed in the NBE emissions, indicating higher purity than the previously reported AAT GaN crystals. In addition, strain-induced energy shift or energy broadening of excitonic emission peaks was not observed, indicating excellent crystal coherency. Because of the reduced concentration of midgap recombination centers, a record-long room-temperature PL lifetime for the NBE emission of ammonothermal GaN (40 ps) was obtained from the −c region. Meanwhile, the PL spectra also exhibited the yellow and blue luminescence bands originating from particular deep-state radiative recombination centers. The major vacancy-type defects acting as midgap recombination centers are identified as vacancy complexes comprising a Ga vacancy (VGa) and a few N vacancies (VN), namely, VGa(VN)n buried by H and/or O, where n is an integer. Further reduction of such defect complexes will allow less compensated stable carrier concentration in the LPAAT GaN crystals.

Thermally stable radiative recombination centers within trench structures of red multi-quantum wells

High-Indium (In)-content multi-quantum wells (MQWs) are generally thermally unstable due to poor crystal quality resulting from low-temperature growth. In this study, red emission was achieved by modulating trench structures using dual-colour MQW structures. Impressively, the red MQWs inside deep trenches showed excellent thermal stability despite being grown at low temperatures. After high-temperature annealing at 950 °C for 30 min, the photoluminescence (PL) intensity of red MQWs exhibited a significant reduction of 91.9% outside trenches, while it dropped by only 9.3% inside trenches, as confirmed by confocal PL mapping. Transmission electron microscopy results show that massive In-rich phases and stacking faults appeared in the MQWs outside trenches after annealing. By contrast, the red MQWs inside deep trenches remained intact in lattice arrangement without being significantly damaged. The superior thermal stability of red MQWs inside deep trenches was mainly attributed to the low-defect-density epitaxy of InGaN layers in strain-relaxed states.

Influence of thermal annealing on silicon negative ion implanted SiO2 thin films

SiO2 thin film of thickness 300 nm grown on p-type silicon substrate was implanted with 100 keV silicon negative ions with fluences varying from 5×1015 to 1×1017 ions cm−2. The implanted samples were annealed at the temperature of 500 °C under N2 ambient. Electron spin resonance (ESR), Fourier transform infrared (FTIR), Photoluminescence (PL), and glancing angle X-ray diffraction (GXRD) techniques have been used to investigate the implanted SiO2 thin film after thermal annealing. ESR studies revealed the absence of vacancy defects after thermal annealing. FTIR studies showed variations in the vibrational modes, attributed to the formation of new structures after annealing at 500 °C. PL studies showed the presence of a peak at 720 nm with an intensity higher than that observed for the unannealed SiO2 samples. This effect showed a decrease in the non-radiative defect centers with an increase in the radiative Si:SiO2 interface states after thermal annealing. The presence of an additional peak at 692 nm may be attributed to the radiative recombination centers associated with silicon nanoclusters formed after annealing at 500 °C. GXRD studies showed a decrease in the intensity of the spectra for the samples implanted with 1×1016 and 5×1016 ions cm−2 after thermal annealing at 500 °C. This result reveals the formation of new SiOx structures in SiO2 thin film.

Inhomogeneous spatial distribution of non radiative recombination centers in GaN/InGaN nanowire heterostructures studied by cathodoluminescence

In order to elucidate the mechanisms responsible for cathodoluminescence intensity variations at the scale of single InGaN/GaN nanowire heterostructures, a methodology is proposed based on a statistical analysis on ensembles of several hundreds of nanowires exhibiting a diameter of 180, 240 and 280 nm. For 180 nm diameter, we find that intensitiy variations are consistent with incorporation of point defects obeying Poisson’s statistics. For wider diameters, intensity variations at the scale of single NWs are observed and assigned to local growth conditions fluctuations. Finally, for the less luminescent nanowires, a departure from Poisson’s statistics is observed suggesting the possible clustering of non independent point defects.

Vegetal melanin-induced radiative recombination centers in porous silicon

Melanin has attracted significant attention in recent years due to its optoelectronic properties exploited in micro and nano-bioelectronic applications. Herein, were report on the photoluminescence tuning of porous silicon (PSi) functionalized with melanin. PSi was prepared through an electrochemical etching process applying a density current of 2.8 mA/cm2 to a silicon wafer using an electrolyte composed of HF and ethanol (1:1). The melanin/PSi heterojunction interface was created by drop casting a melanin solution (0.1 mg/mL in dimethyl sulfoxide) using different volumes of 10, 30 and 50 μl onto a PSi wafer. A remarkable increment of the photoluminescence intensity in the melanin/PSi interface as compared to the pristine PSi was observed through steady-state experiments. Moreover, a pronounced blue-shift (50 nm) of pristine PSi emission maximum as compared to melanin/PSi interfaces was also recorded. This behavior could be ascribed to the generation of radiative recombination centers as indicated by an increment of silicon-hydrogen (Si–H) and silicon-oxygen (Si–O) defects formed in the PSi upon interaction with the melanin, as proven by infrared (FT-IR) experiments. Time-resolved experiments revealed a remarkable decrease in the decay times of the melanin/PSi composites moving from microsecond-time components in the pristine PSi towards nanosecond decay times when the highest amount of melanin was employed, indicative of an increment of radiative recombination centers. Surface morphology changes of the composites were monitored by scanning electron microscopy (SEM), displaying the formation of small grains of melanin on the surface of the PSi up to the appearance of a melanin thin film when low and high amounts of melanin were used, respectively. This study demonstrates the enormous potential of melanin-PSi heterojunctions to provide a novel and sustainable solution for developing (bio)optoelectronic devices.

Polishing and etching damages of ZnO single crystals studied using time-resolved photoluminescence spectroscopy

Controlled thinning of wide bandgap semiconductors by chemo-mechanical polishing (CMP) and/or reactive ion etching (RIE) has been one of the versatile methods for various optoelectronic applications. The influences of CMP and subsequent wet chemical etching, as well as independent RIE, on the room-temperature photoluminescence lifetime for the near-band-edge emission [τPLNBE(RT)] of O-polarity c-plane ZnO single crystals were examined by using time-resolved photoluminescence measurements. τPLNBE(RT) decreased from a nanosecond range to a few picoseconds (ps) by a conventional CMP, indicating a generation of high-concentration midgap recombination centers, such as nonradiative recombination centers and deep radiative recombination centers. τPLNBE(RT) was progressively regained up to 600 ps by a subsequent etching using HCl aqueous solution. However, the recovery saturated at the etching depth of about 200 nm and τPLNBE(RT) was not restored even after etching by 350 nm. The results indicate the introduction of certain structural deformations during the CMP. Because x-ray diffraction measurement revealed the presence of incoherent surface domains right after the CMP and the HCl etching gave rise to inhomogeneously etched canyons, nonradiative recombination centers, such as dislocations and vacancy clusters, are likely generated by mechanical shear stresses. τPLNBE(RT) also decreased by the RIE. However, the degradation was less significant than the case for the CMP, because RIE scarcely gives mechanical stresses. Interestingly, τPLNBE(RT) for the samples etched under higher plasma power was longer than the lower power cases. From the results of x-ray photoelectron spectroscopy measurements, unintentionally deposited oxide films containing Si are proposed to act as an attenuating layer for the introduction of nonradiative recombination centers.

P‐11.6: Efficient radiative recombination centers induced by trench defects in multiple‐quantum wells of red InGaN light‐emitting diodes

P‐11.6: Efficient radiative recombination centers induced by trench defects in multiple‐quantum wells of red InGaN light‐emitting diodes

Understanding native defect induced photoluminescence in Zn2SnO4

Simulation of photoluminescence spectroscopy from first principles provides a powerful approach for predicting the experimental spectrum and understanding the origin of the luminescence of materials. We show here that the use of the hybrid-exchange correlation functional combined with first-principles molecular dynamics can simulate the defect-induced photoluminescence spectrum of zinc stannate $({\mathrm{Zn}}_{2}{\mathrm{SnO}}_{4})$ in good agreement with the experiment. The calculations were carried out for 12 different point defects of ${\mathrm{Zn}}_{2}{\mathrm{SnO}}_{4}$, and show that the green-to-red photoluminescence emissions obtained in the experiment are mainly contributed by the oxygen vacancy defects. These defect states play the roles of deep donors and radiative recombination centers during the photoluminescence mechanism. In particular, their electronic properties are significantly affected by temperature, which is related to the strong fluctuation of the nearest-neighbor Sn atoms relative to the vacancy center.

Crystal structure and photoluminescence of ZnSe and ZnSe:Mn nanocrystals obtained by combustion synthesis

ZnSe and ZnSe:Mn nanocrystals were obtained by combustion synthesis (self-propagating high-temperature synthesis) using current pulses to initiate a reaction with amplitudes of ∼35 A and ∼40 A. The magnitude of the amplitude of the current pulse affects the size of the nanocrystals, their phase composition, the ratio of the cubic and hexagonal phases, the degree of microstresses and the density of dislocations. The inclusion of Mn dopants into ZnSe has little effect on the nanocrystal morphology and strongly influences the morphology of polycrystals. An EPR spectrum of Mn2+ ions with a hyperfine structure constant A = 6.55 mТ and a g-factor g = 2.0055, which is due to Mn2+ ions in a cubic environment, was found in self-activated and doped ZnSe and ZnSe: Mn nanocrystals. It was found that increasing the amplitude of the current pulse, which initiates the combustion synthesis reaction, increases the intensity of the diffusion processes and more effective isovalent substitution of Zn2+ ions by Mn2+ ions in the crystal lattice of ZnSe nanocrystals. The photoluminescence spectra of ZnSe and ZnSe:Mn nanocrystals were investigated, and individual emission bands were detected in the integral spectra. There were three such individual bands in the photoluminescence spectrum of ZnSe nanocrystals. Their maxima were characterized using the following parameters: λ max = 592 nm (E = 2.095 eV), λ max = 543 nm (E = 2.282 eV), and λ max = 505 nm (E = 2.455 eV). Six individual emission bands were detected in the photoluminescence spectra of ZnSe:Mn nanocrystals with the parameters: λ max = 675. 5 nm (E = 1.835 eV), λ max = 642.5 nm (E = 1.929 eV), λ max = 613 nm (E = 2.022 eV), λ max = 583.5 nm (E = 2.124 eV), λ max = 550 nm (E = 2.255 eV), λ max = 528.5 nm (E = 2.345 eV). This paper discusses the nature of the centers of radiative recombination of individual bands.

Lateral surface passivation of CdSe nanoplatelets through crown management.

Two-dimensional colloidal CdSe nanoplatelets (NPLs) have been considered as ideal emitting materials for high performance light-emitting devices due to their excellent optical properties. However, the understanding of defect related radiative and nonradiative recombination centers in CdSe NPLs is still far from sufficient, especially their physical distribution locations. In this work, CdSe core and CdSe/CdS core/crown NPLs have been successfully synthesized and their optical properties have been characterized by laser spectroscopies. It is found that the photoluminescence quantum yield of CdSe NPLs is improved by a factor of 4 after the growth of the CdS crown. At low temperatures, the change in the ratio of low and high energy emission intensities from NPLs suggests that the radiative recombination centers are mainly located on the lateral surface of the samples. This finding is further confirmed by the surface passivation experiment. Meanwhile, the nonradiative recombination centers of NPLs located on the lateral surface are also confirmed by ligand exchange. These results demonstrate the importance of understanding the optical properties of the lateral surface of NPLs, which are important for the design of material structures for optoelectronic applications.

Redistribution of centers responsible for radiative recombination in SiC/por-SiC and SiC/por-SiC/Er2O3 structures under nonthermal action of microwave radiation

In this work, the authors have considered the effect of short-term nonthermal action of microwave radiation on the photoluminescent characteristics of SiC/por-SiC/Er2O3 and SiC/por-SiC structures. The analysis of photoluminescence spectra of these structures, which are excited by radiation with an energy lower than the band gap in the 4H-SiC crystalline substrate, has shown that short-term action of microwave radiation leads to redistribution of radiative recombination centers, which is caused by surface states in the por-SiC layer.

New perspectives on traps and radiative recombination centers for optically stimulated luminescence in LiF:Mg,Cu,P

LiF:Mg,Cu,P (MCP) is well-known for its high thermoluminescence (TL) sensitivity and is widely used for TL dosimetry. Following recent studies, highlighting its optically stimulated luminescence (OSL), the properties of MCP have been studied for OSL-based 2D and 3D dosimetry. Here, we have measured the spectrally resolved OSL emission as a function of stimulation time, identifying the peak of the emission band to be at ∼355 nm during the early stimulation period before shifting to peaking at ∼382 nm during the remaining part of the experiment. By assuming the spectra to originate from radiative recombination centers with Gaussian emission bands, we identified two recombination centers with emission centered at ∼355 nm (RC1) and ∼394 nm (RC2), respectively. From the OSL decay curves, we have identified two dominating types of OSL traps (fast and slowly decaying OSL traps). We provide indicative values for the photoexcitation cross section of these OSL traps. The fast-decaying OSL traps were found to predominantly emit OSL through RC1. By depleting the fast-decaying OSL traps before TL measurements, we have identified these traps to be associated with a previously undetected TL peak at ∼87 ° C (1 °C/s heating rate), located between the TL peaks usually denoted as peaks one and two. We further found that the features related to the fast-decaying OSL traps were not observable for powder samples without a heat treatment at ∼560–700 °C. Pellet samples show these features without the heat treatment, but could potentially have undergone a similar treatment during sintering.

Spectral and kinetic properties of silver sulfide quantum dots in an external electric field

The effect of an external electric field on the luminescence characteristics of silver sulfide nanoparticles embedded in a film based on an optically passive dielectric matrix has been studied. The luminescence characteristics were studied using methods of optical and time-resolved spectroscopy involving the time-correlated single-photon counting technique. The morphology of the nanoparticles was studied using transmission electron microscopy. It was shown that in an external electric field, an increase in the intensity of the recombination luminescence band is observed for silver sulfide nanoparticles, together with an increase in the electronic relaxation rate. This effect is explained by the fact that the electric field enhances the transport of free holes to electron traps which are radiative recombination centers. The observed effects indicate that silver sulfide nanoparticles can be effectively used as active layers of organic light-emitting diodes, where an external field of the order of 500 kV/cm will not lead to a deterioration in their operating luminescence characteristics.

Concentric core-shell tracks and spectroscopic properties of SrTiO3 under intense electronic excitation

A deeper understanding of the intrinsic link between the irradiation-induced microstructures and the corresponding spectroscopic properties is becoming increasingly attractive for the research fields of materials science, physics, and information technology. In this work, the structural damage response, spectroscopic features, and associated physical mechanisms of SrTiO3 single crystals under swift heavy ion irradiation were comparatively analyzed using a combination of experimental and theoretical approaches. Corresponding to 0.11–5.00 MeV/u ion irradiation with electronic energy loss ranging from 4.0 to 29.3 keV/nm, the inelastic thermal spike calculations combined with molecular dynamics simulations are compared with the experimental observations, revealing the track fine structures (individual spherical defects with a disordered region, and discontinuous and continuous tracks consisting of an amorphous core and a disordered outer shell) and demonstrating the dominant effects of the deposition energy and lattice temperature on track damage formation and evolution; thus, two essential thresholds for defect formation of ∼0.60 eV/atom and amorphous region formation of ∼1.81 eV/atom were identified to better describe the concentric core-shell track structure. The enhanced nanohillock formation in the surface region is attributed to the combined action of kinetic and potential energy depositions, and the fluence dependence in regulating the hillock dimensions is also presented. The measured refractive index profiles along different crystal axes further indicate the anisotropy of irradiation-induced lattice expansion. With increasing ion fluence and damage level, the intrinsic bandgap gradually decreased, and the concentration of additional radiative recombination centers (1.81 eV, 2.31 eV, and 2.42 eV) accordingly increased in the SrTiO3 crystal, providing the possibility of regulating related defects to achieve tunable/selective photon emission for more critical technological applications.

Ultra-broadband light-emitting diodes from co-evaporated lead-free CsCu2I3

• CsCu 2 I 3 films were prepared by vacuum co-evaporation method. • Co-evaporated CsCu 2 I 3 film exhibits self-trapped exciton behavior. • LEDs using the CsCu 2 I 3 films show red-shifted and ultra-broad EL. As an alternative to the conventional solution-processing, a vacuum co-evaporation method is developed to prepare CsCu 2 I 3 thin film, for fabricating light-emitting diodes (LEDs). LEDs using the co-evaporated lead-free CsCu 2 I 3 films exhibit ultra-broad warm-white emission. We found that the LEDs using the CsCu 2 I 3 thin films have red-shift and broadened electroluminescence (EL) with a full width at half-maximum of 245 nm in contrast to 132 nm from photoluminescence (PL) spectra for the CsCu 2 I 3 films. The current hysteresis of LEDs using the CsCu 2 I 3 films indicates that the migration of ions provides a new radiative-recombination center and further resulting in EL change and broadening. The experimental work presented here gains insight on broadening EL spectra for the LEDs with self-trapped exciton materials.

Carbon Nanodots with Nearly Unity Fluorescent Efficiency Realized via Localized Excitons.

Carbon nanodots (CDs) have emerged as an alternative option for traditional nanocrystals due to their excellent optical properties and low toxicity. Nevertheless, high emission efficiency is a long‐lasting pursuit for CDs. Herein, CDs with near‐unity emission efficiency are prepared via atomic condensation of doped pyrrolic nitrogen, which can highly localize the excited states thus lead to the formation of bound excitons and the symmetry break of the π–electron conjugation. The short radiative lifetimes (<8 ns) and diffusion lengths (<50 nm) of the CDs imply that excitons can be efficiently localized by radiative recombination centers for a defect‐insensitive emission of CDs. By incorporating the CDs into polystyrene, flexible light‐converting films with a high solid‐state quantum efficiency of 84% and good resistance to water, heating, and UV light are obtained. With the CD–polymer films as light conversion layers, CD‐based white light‐emitting diodes (WLEDs) with a luminous efficiency of 140 lm W−1 and a flat‐panel illumination system with lighting sizes of more than 100 cm2 are achieved, matching state‐of‐the‐art nanocrystal‐based LEDs. These results pave the way toward carbon‐based luminescent materials for solid‐state lighting technology.

Electric-Field-Induced Ion Migration Behavior in Methylammonium Lead Iodide Perovskite.

Ionic movement inside organometal halide perovskites (OMHP) materials has been widely reported to be linked with stability issues in the perovskite-based optoelectronic devices. However, the dynamic processes of the ionic movement and how they influence the devices are still not well-understood. In this work, we applied an external electric field to the CH3NH3PbI3 crystal and simultaneously monitored the PL behaviors. Two successive PL responses were observed in the same location of the crystal. First, an irreversible PL quenching was observed caused by the photo-annealing effect under an electric field accompanied by a permanent morphology change. The annealed area also showed reversible PL variation, which was attributed to the activation-deactivation of the radiative recombination centers induced by the migration of the iodine ions. Such results can help us gain a deep insight into how the ionic movements in OMHPs influence the performance of the perovskite-based optoelectronic devices under working conditions.

Transient absorption spectral dynamics of hybrid associates of CdS quantum dots and methylene blue dye

The transient absorption spectra dynamics for hybrid associates of colloidal CdS quantum dots, passivated by thioglycolic acid (CdS/TGA QDs), and methylene blue cationic dye molecules (MB+) were studied by femtosecond spectroscopy. It was established that one of the main channels of relaxation of the CdS/TGA QDs excitation energy in hybrid associates based on CdS/TGA QDs and MB+ is a fast energy transfer to the reduced forms of MB+ (MBOH•, MB•) that are formed still at the synthesis stage of samples. This channel strongly competes with the resonant energy transfer from the centers of radiative recombination in quantum dots to MB+. Therefore, for hybrid associates based on QDs/TGA and methylene blue, there is no any noticeable signal of the transient absorption corresponding to the triplet state of MB+ dye, which is then known to be actively involved in charge transfer.