Time-resolved Cathodoluminescence Research Articles

Electron beam probing of non-equilibrium carrier dynamics in 18 MeV alpha particle- and 10 MeV proton-irradiated Si-doped β -Ga2O3 Schottky rectifiers

Minority hole diffusion length and lifetime were measured in independent experiments by electron beam-induced current and time-resolved cathodoluminescence in Si-doped β-Ga2O3 Schottky rectifiers irradiated with 18 MeV alpha particles and 10 MeV protons. Both diffusion length and lifetime exhibited a decrease with increasing temperature. The non-equilibrium minority hole mobility was calculated from the independently measured diffusion length and lifetime, indicating that the so-called hole self-trapping is most likely irrelevant in the 77–295 K temperature range.

Using pulsed mode scanning electron microscopy for cathodoluminescence studies on hybrid perovskite films

The use of pulsed mode scanning electron microscopy cathodoluminescence (CL) for both hyperspectral mapping and time-resolved measurements is found to be useful for the study of hybrid perovskite films, a class of ionic semiconductors that have been shown to be beam sensitive. A range of acquisition parameters is analysed, including beam current and beam mode (either continuous or pulsed operation), and their effect on the CL emission is discussed. Under optimized acquisition conditions, using a pulsed electron beam, the heterogeneity of the emission properties of hybrid perovskite films can be resolved via the acquisition of CL hyperspectral maps. These optimized parameters also enable the acquisition of time-resolved CL of polycrystalline films, showing significantly shorter lived charge carriers dynamics compared to the photoluminescence analogue, hinting at additional electron beam-specimen interactions to be further investigated. This work represents a promising step to investigate hybrid perovskite semiconductors at the nanoscale with CL.

Excited states of modified oxygen-deficient centers and Si quantum dots in Gd-implanted silica glasses: emission dynamics and lifetime distributions.

The emission centers and excited state characteristics of silica glasses implanted with Gd ions were studied by time-resolved pulsed cathodoluminescence. It was found that in the process of ion implantation, two types of new emission centers associated with Gd ions as well as Si quantum dots are formed in glassy silica. The distributions of excited states over the lifetime were found for both new centers and Si quantum dots. The nature of dispersion of the emission decay time was discussed in terms of structural disorder in the matrix. Thermal annealing and an increase in the ion fluence lead to the stimulation of the formation of Gd-related new centers and Si quantum dots. The micromechanisms for the formation of new Gd-related centers and two types of Si quantum dots were proposed on the basis of two scenarios for the introduction of Gd ions into the SiO2 network: insertion of Gd into interstitial voids near oxygen-deficient centers and Gd → Si substitution with subsequent expulsion of Si atoms to the interstitial voids. New emission oxygen-deficient centers and quantum dots created by ion-beam technology in silica glasses are of interest for the development of new functional materials for photonics, and micro- and opto-electronics.

Effect of Electron Injection on Minority Carrier Transport Properties in Unintentionally Doped GaN

GaN is a robust and stable wide bandgap material with a bandgap of 3.4eV. It is extensively studied for applications in light emitting diodes, high-power electronics and optoelectronics. Radiation hardness is another attractive attribute of GaN due to its atomic structure and wide bandgap with possible electronic applications in lower Earth satellite orbits. Like other wide bandgap materials, GaN also suffers from short diffusion length, which has been earlier reported to be ~100-300 nm. Minority carrier transport properties such as carrier lifetime (τ) and diffusion length (L) are of vital importance in bipolar and minority-carrier devices. Previously, it was shown that low energy electron beam irradiation (up to 30 keV) for extended duration (up to 3000 seconds) can be used to enhance L by a factor of 4 at room temperature in other wide bandgap materials like p-ZnO and β-Ga2O3 [1-3] . It was suggested that the increase in L is associated with trapping of non-equilibrium electrons on meta-stable trap levels acting as recombination centers. Dependence of L on τ is given by the relation L=√(Dτ) , where D is the diffusion coefficient. Therefore, removal of recombination centers, due to electron trapping on them would, in turn, increase τ, and hence L. Another effect of low energy electron irradiation, apart from increasing τ, is manifested in decrease in the continuous CL intensity. In this work, unintentionally doped GaN was studied using Electron Beam-Induced Current (EBIC), Continuous (CL) and Time-Resolved Cathodoluminescence (TRCL) techniques to independently measure L and τ, and verify the validity of the proposed model[4]. Measurements were conducted on GaN Schottky rectifiers (~400 µm GaN layer grown by Halide Vapor Phase Epitaxy on sapphire) with electron concentration of ~1x1017 cm-3. L was found to increase from 306 nm to 347 nm for a maximum electron injected charge density of 117.5 nC/µm3 and saturating at 60 nC/µm3. For the same maximum and saturation injected charge densities, τ was found to increase from 77 ps to 101 ps. Fig. 1a shows a plot of TRCL streaks for bare region and the region with maximum injected charge density. Slower decay of streak signal indicates longer lifetime in the electron-injected region. Fig. 1b depicts the plot of L and √τ as a function of injected charge density at room temperature. A clear linear dependence (L=√(Dτ)) is seen till saturation charge density of ~60 nC/µm3. Furthermore, mobility values (from the diffusion coefficient) for various charge injection doses were obtained for the ultrafast regime of TRCL spectroscopy.

Impact of electron injection on carrier transport and recombination in unintentionally doped GaN

The impact of electron injection on minority carrier (hole) diffusion length and lifetime at variable temperatures was studied using electron beam-induced current, continuous, and time-resolved cathodoluminescence techniques. The hole diffusion length increased from 306 nm to 347 nm with an electron injection charge density up to 117.5 nC/μm3, corresponding to the lifetime changing from 77 ps to 101 ps. Elongation of the diffusion length was attributed to the increase in the non-equilibrium carrier lifetime, which was determined using ultrafast time-resolved cathodoluminescence and related to non-equilibrium carrier trapping on gallium vacancy levels in the GaN forbidden gap.

Time-resolved Cathodoluminescence in a Transmission Electron Microscope Applied to NV Centers in Diamond

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Resolving Enhanced Mn2+ Luminescence near the Surface of CsPbCl3 with Time-Resolved Cathodoluminescence Imaging.

Mn2+ doping of lead halide perovskites has garnered recent interest because it produces stable orange luminescence in tandem with perovskite emission. Here, we observe enhanced Mn2+ luminescence at the edges of Mn2+-doped CsPbCl3 perovskite microplates and suggest an explanation for its origin using the high spatiotemporal resolution of time-resolved cathodoluminescence (TRCL) imaging. We reveal two luminescent decay components that we attribute to two different Mn2+ populations. While each component appears to be present both near the surface and in the bulk, the origin of the intensity variation stems from a higher proportion of the longer lifetime component near the perovskite surface. We suggest that this higher emission is caused by an increased probability of electron-hole recombination on Mn2+ near the perovskite surface due to an increased trap concentration there. This observation suggests that such surface features have yet untapped potential to enhance emissive properties via control of surface-to-volume ratio.

Time-resolved cathodoluminescence of DNA triggered by picosecond electron bunches

Despite the tremendous importance of so-called ionizing radiations (X-rays, accelerated electrons and ions) in cancer treatment, most studies on their effects have focused on the ionization process itself, and neglect the excitation events the radiations can induce. Here, we show that the excited states of DNA exposed to accelerated electrons can be studied in the picosecond time domain using a recently developed cathodoluminescence system with high temporal resolution. Our study uses a table-top ultrafast, UV laser-triggered electron gun delivering picosecond electron bunches of keV energy. This scheme makes it possible to directly compare time-resolved cathodoluminescence with photoluminescence measurements. This comparison revealed qualitative differences, as well as quantitative similarities between excited states of DNA upon exposure to electrons or photons.

Beam displacement and blur caused by fast electron beam deflection

Electrostatic beam blankers are an alternative to photo-emission sources for generating pulsed electron beams for Time-resolved Cathodoluminescence and Ultrafast Electron Microscopy. While the properties of beam blankers have been extensively investigated in the past for applications in lithography, characteristics such as the influence of blanking on imaging resolution have not been fully addressed. We derive general analytical expressions for the spot displacement and loss in resolution induced by deflecting the electron beam in a blanker. In particular, we analyze the sensitivity of both measures to how precise the conjugate focus is aligned in between the deflector plates. We then work out the specific case of a beam blanker driven by a linear voltage ramp as was used in recent studies by others and by us. The result shows that the spot displacement and focus blur can be reduced to the same order as the electron beam probe size, even when using a beam blanker of millimeter or larger scale dimensions. An interesting result is that, by the right choice of the focus position in the deflector, either the spot displacement from the stationary position can be minimized, or the blur can be made zero but not both at the same time. Our results can be used both to characterize existing beam blanker setups and to design novel blankers. This can further develop the field of time-resolved electron microscopy by making it easier to generate pulses with a typical duration of tens of picoseconds in a regular scanning electron microscope at high spatial resolution.

Time-resolved cathodoluminescence spectroscopy of YAG and YAG:Ce3+ phosphors

The phosphor powders, both undoped and Ce3+ doped with different concentration Y3Al5O12 (YAG), were synthesized by the solid-state reaction method with addition of BaF2 flux. SEM and XRD characterization of the samples were performed. The spectral and luminescence decay kinetic characteristics under the electron beam irradiation with nano- and picoseconds pulse duration and the electron energies of 250 keV and 55 keV were studied, respectively. Two bands in the cathodoluminescence spectrum of YAG:Ce3+ phosphors were observed with maxima at 2.19 ± 0.05 and 2.4 eV. The intensity ratio of these two bands depends on the electron energy and the duration of the excitation pulse. Instead, only one band at 2.12 ± 0.05 eV in the luminescence spectrum of undoped YAG phosphor. It is shown that cerium ions doping increases in the number of various hole centers.

Optical and structural properties of dislocations in InGaN

Threading dislocations in thick layers of InxGa1−xN (5% < x < 15%) have been investigated by means of cathodoluminescence, time-resolved cathodoluminescence, and molecular dynamics. We show that indium atoms segregate near dislocations in all the samples. This promotes the formation of In-N-In chains and atomic condensates, which localize carriers and hinder nonradiative recombination at dislocations. We note, however, that the dark halo surrounding the dislocations in the cathodoluminescence image becomes increasingly pronounced as the indium fraction of the sample increases. Using transmission electron microscopy, we attribute the dark halo to a region of lower indium content formed below the facet of the V-shaped pit that terminates the dislocation in low composition samples (x < 12%). For x > 12%, the facets of the V-defect featured dislocation bundles instead of the low indium fraction region. In this sample, the origin of the dark halo may relate to a compound effect of the dislocation bundles, of a variation of surface potential, and perhaps, of an increase in carrier diffusion length.

Relaxation of intrinsic and extrinsic electronic excitations in nano- and micro-size alumina

Nanopowders consisting of mixed α-alumina and transition alumina phases were prepared by combustion synthesis and investigated using low temperature time-resolved cathodoluminescence and photoluminescence spectroscopy under VUV excitation. The onsets of the intrinsic absorption for different alumina phases were revealed in mixed phase nanopowders by analysing luminescence excitation spectra. All synthesized nanopowders possessed the intrinsic luminescence band with a maximum at 4.6 eV, which is assigned to the radiative decay of triplet self-trapped excitons with ∼750 μs decay time at 78 K. A red shift by 0.3 eV was revealed for the peak of the O2− – Cr3+ charge transfer band near 7 eV as a function of particle size. This shift is correlated with the decrease of α-alumina particle size from 180 to 80 nm. Its origin is discussed in the framework of the Kroning-Penney model.

A high sensitivity system for luminescence measurement of materials.

A unique combined and multi-disciplinary wavelength multiplexed spectrometer is described. It is furnished with high-sensitivity imaging plate detectors, the power to which can be gated to provide time-resolved data. The system is capable of collecting spectrally resolved luminescence data following X-ray excitation [radioluminescence (RL) or X-ray excited optical luminescence (XEOL)], electron irradiation [cathodoluminescence (CL)] and visible light from light emitting diodes (LEDs) [photoluminescence (PL)]. Time-resolved PL and CL data can be collected to provide lifetime estimates with half-lives from microsecond timeframes. There are temperature stages for the high and low temperature experiments providing temperature control from 20 to 673K. Combining irradiation, time resolved (TR) and TR-PL allows spectrally-resolved thermoluminescence (TL) and optically stimulated luminescence (OSL). The design of two detectors with matched gratings gives optimum sensitivity for the system. Examples which show the advantages and multi-use of the spectrometer are listed. Potential future experiments involving lifetime analysis as a function of irradiation, dose and temperature plus pump-probe experiments are discussed.

Energy conversion in LiSrPO4 doped with Pr3+ ions

We report on the time-resolved luminescence spectroscopic characterization of LiSrPO4 doped with Pr3+ ions, that we found potentially attractive for scintillation applications. The spectroscopic study included measurements of photoluminescence, X-ray excited luminescence, thermally stimulated luminescence and time-resolved pulse cathodoluminescence spectra. In addition, luminescence decay kinetics were studied upon high-frequency X-ray and pulse cathode beam excitation. LiSrPO4:Pr3+ showed Pr3+ emission connected with intraconfigurational 4f2→4f2 and interconfigurational 4f15d→4f2 transitions. The presence of defects was shown with thermoluminescence measurements and suggested to be the main reason for delayed recombination of charge carriers on Pr3+ 4f15d states. Some peculiarities of host-to-impurity energy transfer are discussed.

Complementary cathodoluminescence lifetime imaging configurations in a scanning electron microscope

Cathodoluminescence (CL) spectroscopy provides a powerful way to characterize optical properties of materials with deep-subwavelength spatial resolution. While CL imaging to obtain optical spectra is a well-developed technology, imaging CL lifetimes with nanoscale resolution has only been explored in a few studies. In this paper we compare three different time-resolved CL techniques and compare their characteristics. Two configurations are based on the acquisition of CL decay traces using a pulsed electron beam that is generated either with an ultra-fast beam blanker, which is placed in the electron column, or by photoemission from a laser-driven electron cathode. The third configuration uses measurements of the autocorrelation function g(2) of the CL signal using either a continuous or a pulsed electron beam. The three techniques are compared in terms of complexity of implementation, spatial and temporal resolution, and measurement accuracy as a function of electron dose. A single sample of InGaN/GaN quantum wells is investigated to enable a direct comparison of lifetime measurement characteristics of the three techniques. The g(2)-based method provides decay measurements at the best spatial resolution, as it leaves the electron column configuration unaffected. The pulsed-beam methods provide better detail on the temporal excitation and decay dynamics. The ultra-fast blanker configuration delivers electron pulses as short as 30 ps at 5 keV and 250 ps at 30 keV. The repetition rate can be chosen arbitrarily up to 80 MHz and requires a conjugate plane geometry in the electron column that reduces the spatial resolution in our microscope. The photoemission configuration, pumped with 250 fs 257 nm pulses at a repetition rate from 10 kHz to 25 MHz, allows creation of electron pulses down to a few ps, with some loss in spatial resolution.

Reducing Zn diffusion in single axial junction InP nanowire solar cells for improved performance

In this work axial n-i-p junction InP nanowires were grown by selective-area metal organic vapor phase epitaxy (SA-MOVPE) technique with the growth sequence starting from n-segment. The optical properties and carrier lifetimes of the n-, i- and p-type segments were studied and compared using time-resolved photoluminescence (PL) and cathodoluminescence (CL) measurements. We demonstrate for the first time that CL is capable of resolving the electrical profile of the nanowires, namely the varied lengths of the n-, i- and p-segments, providing a simple and effective approach for nanowire growth calibration and optimization. The CL result was further confirmed by electron beam induced current (EBIC) and photocurrent mapping measurements performed from the fabricated single nanowire solar cell devices. It is revealed that despite a non-optimized device structure (very long n-region and short i-region), the n-i-p nanowire solar cells show improved power conversion efficiency (PCE) than the previously reported p-i-n (growth starts with p-segment) single nanowire solar cells due to reduced p-type dopant (Zn) diffusion during the growth of n-i-p solar cell structure.

Effect of 1.5 MeV electron irradiation on β-Ga2O3 carrier lifetime and diffusion length

The influence of 1.5 MeV electron irradiation on minority transport properties of Si doped β-Ga2O3 vertical Schottky rectifiers was observed for fluences up to 1.43 × 1016 cm−2. The Electron Beam-Induced Current technique was used to determine the minority hole diffusion length as a function of temperature for each irradiation dose. This revealed activation energies related to shallow donors at 40.9 meV and radiation-induced defects with energies at 18.1 and 13.6 meV. Time-resolved cathodoluminescence measurements showed an ultrafast 210 ps decay lifetime and reduction in carrier lifetime with increased irradiation.

Exciton diffusion coefficient measurement in ZnO nanowires under electron beam irradiation

In semiconductor nanowires (NWs) the exciton diffusion coefficient can be determined using a scanning electron microscope fitted with a cathodoluminescence system. High spatial and temporal resolution cathodoluminescence experiments are needed to measure independently the exciton diffusion length and lifetime in single NWs. However, both diffusion length and lifetime can be affected by the electron beam bombardment during observation and measurement. Thus, in this work the exciton lifetime in a ZnO NW is measured versus the electron beam dose (EBD) via a time-resolved cathodoluminescence experiment with a temporal resolution of 50 ps. The behavior of the measured exciton lifetime is consistent with our recent work on the EBD dependence of the exciton diffusion length in similar NWs investigated under comparable SEM conditions. Combining the two results, the exciton diffusion coefficient in ZnO is determined at room temperature and is found constant over the full span of EBD.

Spatially dependent carrier dynamics in single InGaN/GaN core-shell microrod by time-resolved cathodoluminescence

The optical properties of InGaN/GaN core-shell microrods are studied by time-resolved cathodoluminescence. Probing the carrier dynamics along the length of the rod from 4 to 300 K enables us to decompose radiative (τr) and non-radiative (τnr) lifetimes. At 300 K, τnr decreases from 500 at the bottom of the rod to 150 ps at its top. This variation results from an increased In-content in the upper part of the rod that causes a higher density of point defects. We further observe that thanks to the use of nonpolar m-plane growth, τr remains below 1.5 ns up to room temperature even with a thick active layer, which is promising for pushing the onset of the efficiency droop to higher current densities.

Microrod carrier dynamics map out potential ability to offset LED efficiency losses at high current

Time-resolved cathodoluminescence measurements reveal short radiative lifetimes of individual core-shell microrods, even at room temperatures, and their potential for improving LED efficiency.