Cathodoluminescence Spectroscopy Research Articles

Investigation of Emission Heterogeneity in InGaN/GaN Micro-Light-Emitting Diodes by Photon-Correlation Cathodoluminescence Spectroscopy

Investigation of Emission Heterogeneity in InGaN/GaN Micro-Light-Emitting Diodes by Photon-Correlation Cathodoluminescence Spectroscopy

Free Electron-Plasmon Coupling Strength and Near-Field Retrieval through Electron Energy-Dependent Cathodoluminescence Spectroscopy.

Tightly confined optical near fields in plasmonic nanostructures play a pivotal role in important applications ranging from optical sensing to light harvesting. Energetic electrons are ideally suited to probing optical near fields by collecting the resulting cathodoluminescence (CL) light emission. Intriguingly, the CL intensity is determined by the near-field profile along the electron propagation direction, but the retrieval of such field from measurements has remained elusive. Furthermore, the conditions for optimum electron near-field coupling in plasmonic systems are critically dependent on such field and remain experimentally unexplored. In this work, we use electron energy-dependent CL spectroscopy to study the tightly confined dipolar mode in plasmonic gold nanoparticles. By systematically studying gold nanoparticles with diameters in the range of 20-100 nm and electron energies from 4 to 30 keV, we determine how the coupling between swift electrons and the optical near fields depends on the energy of the incoming electron. The strongest coupling is achieved when the electron speed equals the mode phase velocity, meeting the so-called phase-matching condition. In aloof experiments, the measured data are well reproduced by electromagnetic simulations, which explain that larger particles and faster electrons favor a stronger electron near-field coupling. For penetrating electron trajectories, scattering at the particle produces severe corrections of the trajectory that defy existing theories based on the assumption of nonrecoil condition. Therefore, we develop a first-order recoil correction model that allows us to account for inelastic electron scattering, rendering better agreement with measured data. Finally, we consider the albedo of the particles and find that, to approach unity coupling, a highly confined electric field and very slow electrons are needed, both representing experimental challenges. Our findings explain how to reach unity-order coupling between free electrons and confined excitations, helping us understand fundamental aspects of light-matter interaction at the nanoscale.

Improved Sequentially Processed Cu(In,Ga)(S,Se)2 by Ag Alloying

Alloying small quantities of silver into Cu(In,Ga)Se2 is shown to improve the efficiency for wide and low bandgap solar cells. Low bandgap industrial Cu(In,Ga)(S,Se)2 absorbers are studied, substituting less than 10% of the copper with silver, using absolute photoluminescence and cathodoluminescence spectroscopy. Silver improves the grain size and promotes the interdiffusion of Ga and In across the depth of the absorber, resulting in a smoother bandgap gradient. However, a certain lateral inhomogeneity is observed near the front and back sides. The nonradiative losses in the bare absorbers are reduced by up to 30 meV.

Integration of layered group IV selenides: From SnSe–SnSe2-xSx core-shell crystals to complex (SnSe–SnSe2-xSx)-GeSe van der waals heterostructures

The layered semiconductor tin selenide (SnSe) has received extensive interest due to its promising thermoelectric and ferroelectric properties. Integrating SnSe with other layered crystals in heterostructures can enable the modification of charge- and thermal transport, electrical polarization, and other properties such as chemical stability, optoelectronics, and photonics. Here, we demonstrate the vapor transport synthesis of single-crystalline SnSe monochalcogenide flakes that are spontaneously encapsulated in a thin layered SnSe2-xSx dichalcogenide shell. In a second growth step, such SnSe–SnSe2-xSx heterostructures are integrated with the monochalcogenide GeSe, which is laterally stitched to the SnSe side facets while preserving the dichalcogenide shell across the basal facets. This architecture is confirmed by optical microscopy, electron microscopy and diffraction, energy dispersive X-ray and Raman spectroscopies, as well as cathodoluminescence spectroscopy. The results extend our capabilities for materials integration by forming complex heterostructures with both vertical van der Waals interfaces and covalent lateral interfaces between layered semiconductors.

Investigation of optical polarization characteristics of ultraviolet-C AlGaN multiple quantum wells by angle-resolved cathodoluminescence

AlGaN-based ultraviolet-C (UV-C) light-emitting diodes (LEDs) face challenges related to their extremely low external quantum efficiency, which is predominantly attributed to the remarkably inadequate transverse magnetic (TM) light extraction efficiency (LEE). In this study, we employ angle-resolved cathodoluminescence (ARCL) spectroscopy to assess the optical polarization of (0001)-oriented AlGaN multiple quantum well (MQW) structures in UV-C LEDs, in conjunction with a focused ion beam and scanning electron microscopy (FIB/SEM) system to etch samples with various inclination angles (θ) of sidewall. This technique effectively distinguishes the spatial distribution of TM- and transverse electric (TE)-polarized photons contributing to the luminescence of the MQW structure. CL spectroscopy confirms that UV-C LEDs with a θ of 35° exhibit the highest CL signal compared to samples with other θ. Furthermore, we establish a model using finite difference time domain (FDTD) simulation to validate the mechanism of the outcomes. The complementary contribution of TM and TE photons at different specific angles are distinguished by ARCL and confirmed by simulation. At angles near the sidewall, the CL is dominated by the TM photons, which mainly contribute to the increased LEE and the decreased degree of polarization (DOP) to make the spatial distribution of CL more uniform. Additionally, this method allows us to analyze the polarization of light without the need for polarizers, enabling the differentiation of TE and TM modes. This distinction provides flexibility for selecting different emission mode based on various application requirements. The presented approach not only opens up new opportunities for enhanced UV-C light extraction but also provides valuable insights for future endeavors in device fabrication and epitaxial film growth.

Cathodoluminescence emission and electron energy loss absorption from a 2D transition metal dichalcogenide in van der Waals heterostructures.

Nanoscale variations of optical properties in transition metal dichalcogenide (TMD) monolayers can be explored with cathodoluminescence (CL) and electron energy loss spectroscopy (EELS) using electron microscopes. To increase the CL emission intensity from TMD monolayers, the MoSe2flakes are encapsulated in hexagonal boron nitride (hBN), creating van der Waals (VdW) heterostructures. Until now, the studies have been exclusively focused on scanning transmission electron microscopy (STEM-CL) or scanning electron microscopy (SEM-CL), separately. Here, we present results, using both techniques on the same sample, thereby exploring a large acceleration voltage range.
We correlate the CL measurements with STEM-EELS measurements acquired with different energy dispersions, to access both the low-loss region at ultra-high spectral resolution, and the core-loss region. This provides information about the weight of the various absorption phenomena including the direct TMD absorption, the hBN interband transitions, the hBN bulk plasmon, and the core losses of the atoms present in the heterostructure. The S(T)EM-CL measurements from the TMD monolayer only show emission from the A exciton. Combining the STEM-EELS and S(T)EM-CL measurements, we can reconstruct different decay pathways leading to the A exciton CL emission. The comparison with SEM-CL shows that this is also a good technique for TMD heterostructure characterization, where the reduced demands on sample preparation are appealing. To demonstrate the capabilities of SEM-CL imaging, we also measured on a SiO2/Si substrate, quintessential in the sample preparation of two-dimensional materials, which is electron-opaque and can only be measured in SEM-CL. The CL-emitting defects of SiO2make this substrate challenging to use, but we demonstrate that this background can be suppressed by using lower electron energy.

Unraveling sources of emission heterogeneity in Silicon Vacancy color centers with cryo-cathodoluminescence microscopy

Diamond color centers have proven to be versatile quantum emitters and exquisite sensors of stress, temperature, electric and magnetic fields, and biochemical processes. Among color centers, the silicon-vacancy (SiV[Formula: see text]) defect exhibits high brightness, minimal phonon coupling, narrow optical linewidths, and high degrees of photon indistinguishability. Yet the creation of reliable and scalable SiV[Formula: see text]-based color centers has been hampered by heterogeneous emission, theorized to originate from surface imperfections, crystal lattice strain, defect symmetry, or other lattice impurities. Here, we advance high-resolution cryo-electron microscopy combined with cathodoluminescence spectroscopy and 4D scanning transmission electron microscopy (STEM) to elucidate the structural sources of heterogeneity in SiV[Formula: see text] emission from nanodiamond with sub-nanometer-scale resolution. Our diamond nanoparticles are grown directly on TEM membranes from molecular-level seedings, representing the natural formation conditions of color centers in diamond. We show that individual subcrystallites within a single nanodiamond exhibit distinct zero-phonon line (ZPL) energies and differences in brightness that can vary by 0.1 meV in energy and over 70% in brightness. These changes are correlated with the atomic-scale lattice structure. We find that ZPL blue-shifts result from tensile strain, while ZPL red shifts are due to compressive strain. We also find that distinct crystallites host distinct densities of SiV[Formula: see text] emitters and that grain boundaries impact SiV[Formula: see text] emission significantly. Finally, we interrogate nanodiamonds as small as 40 nm in diameter and show that these diamonds exhibit no spatial change to their ZPL energy. Our work provides a foundation for atomic-scale structure-emission correlation, e.g., of single atomic defects in a range of quantum and two-dimensional materials.

Composition and optical properties of (In, Ga)As nanowires grown by group-III-assisted molecular beam epitaxy.

(In, Ga) alloy droplets are used to catalyse the growth of (In, Ga)As nanowires by molecular beam epitaxy on Si(111) substrates. The composition, morphology and optical properties of these nanowires can be tuned by the employed elemental fluxes. To incorporate more than 10% of In, a high In/(In+Ga) flux ratio above 0.7 is required. We report a maximum In content of almost 30% in bulk (In, Ga)As nanowires for an In/(In+Ga) flux ratio of 0.8. However, with increasing In/(In+Ga) flux ratio, the nanowire length and diameter are notably reduced. Using photoluminescence and cathodoluminescence spectroscopy on nanowires covered by a passivating (In, Al)As shell, two luminescence bands are observed. A significant segment of the nanowires shows homogeneous emission, with a wavelength corresponding to the In content in this segment, while the consumption of the catalyst droplet leads to a spectrally-shifted emission band at the top of the nanowires. The (In,Ga)As nanowires studied in this work provide a new approach for the integration of infrared emitters on Si platforms.

Optical Properties of Low‐Defect Large‐Area Hexagonal Boron Nitride for Quantum Applications

Intrinsic defects and their concentrations in hexagonal boron nitride (h‐BN) play a key role in single‐photon emission. In this study, the optical properties of large‐area multilayer h‐BN‐on‐sapphire grown by metal‐organic chemical vapor deposition are explored. Based on the detailed spectroscopic characterization using both cathodoluminescence (CL) and photoluminescence (PL) measurements, the material is devoid of random single‐point defects instead of a few clustered complex defects. The emission spectra of the measurements confirm a record‐low‐defect concentration of ≈104 cm−2. Post‐annealing, no significant changes are observed in the measured spectra and the defect concentrations remain unaltered. Through CL and PL spectroscopy, an optically active boron vacancy spin defect is identified and a novel complex defect combination arising from carbon impurities is revealed. This complex defect, previously unreported, signifies a unique aspect of the material. In these findings, the understanding of defect‐induced optical properties in h‐BN films is contributed, providing insights for potential applications in quantum information science.

Diffusion-Dominated Luminescence Dynamics of CsPbBr3 Studied Using Cathodoluminescence and Microphotoluminescence Spectroscopy.

Time-resolved or time-correlation measurements using cathodoluminescence (CL) reveal the electronic and optical properties of semiconductors, such as their carrier lifetimes, at the nanoscale. However, halide perovskites, which are promising optoelectronic materials, exhibit significantly different decay dynamics in their CL and photoluminescence (PL). We conducted time-correlation CL measurements of CsPbBr3 using Hanbury Brown-Twiss interferometry and compared them with time-resolved PL. The measured CL decay time was on the order of subnanoseconds and was faster than PL decay at an excited carrier density of 2.1 × 1018 cm-3. Our experiment and analytical model revealed the CL dynamics induced by individual electron incidences, which are characterized by highly localized carrier generation followed by a rapid decrease in carrier density due to diffusion. This carrier diffusion can play a dominant role in the CL decay time for undoped semiconductors, in general, when the diffusion dynamics are faster than the carrier recombination.

Germanium Fabry-Perot nanoresonators investigated by cathodoluminescence spectroscopy

We report on the experimental investigation, by means of spatially-resolved cathodoluminescence spectroscopy, of rectangular all-dielectric Ge nanoantennas sustaining Fabry-Perot resonances. The combination of spatial and spectral resolution allows us to directly image the standing-wave pattern of the local density of optical states inside the nanoantennas, which is the fingerprint of the resonant Purcell contribution to the overall emission enhancement previously reported in the literature for the same structures. Our results confirm that the emission properties of Ge nanostructures can be effectively tuned by engineering the local density of optical states and that cathodoluminescence provides valuable information to experimentally address such modulation in their emission properties.

Investigation of the surface band structure and the evolution of defects in β-(AlxGa1−x)2O3

This study examines the electronic and luminescent properties of β-(AlxGa1−x)2O3 (0 ≤ x ≤ 0.42) thin films grown on (0001) sapphire using laser-MBE, with a focus on the evolution of defect energy levels and their impact on surface Fermi level pinning and luminescence. X-ray photoelectron spectroscopy (XPS) and cathodoluminescence (CL) have been employed to analyze surface band bending and defect evolution as a function of aluminum content. The results have revealed a pinned Fermi level at 3.6 eV above the valence band maximum despite the increase in the bandgap. The consequent upward band bending has been confirmed by a peak shift in the core level XPS. The defects that lead to the Fermi level pinning effect are attributed to E2*, which is related to a Ga vacancy or Ga vacancy-O vacancy complex. In addition, CL spectroscopy and depth-resolved CL have demonstrated consistent blue and ultraviolet emissions across the Al content range and a similar suppression of electron concentration on blue and ultraviolet emissions in β-(AlxGa1−x)2O3 and β-Ga2O3. Based on the observed evolution of defects with Al content, the blue band emission is attributed to electron transition in the donor–accepter pair.

Tunable yellow and orange emission of Ce, Eu doped multilayered YSZ/YAG ceramics

Eu3+ and Ce3+ doped YSZ/YAG multilayered luminescent ceramics were consolidated by the Spark Plasma Sintering (SPS) method. The optimal modes were explored during the SPS process for functionally graded ceramics (FGCs) structure fabrication. The introduction of rare-earth (RE) oxides into FGCs with different concentration leads to a shift in the temperature range of intense shrinkage to lower temperatures from 1280 °C to 1100–1190 °C and a decrease in the relative shrinkage during the SPS process by 3–6%. Morphological, optical and luminescent properties have been investigated in detail for fabricated YSZ/YAG ceramics with different arrangement of the layers. The nature of luminescent centers in FGCs was studied using time-resolved cathodoluminescent and steady-state photoluminescent (PL) spectroscopy. The PL efficiency of YSZ/YAG ceramics were analyzed and optimal compositions of the FGCs layers were determined. The YSZ/YAG novel functional multilayered ceramics could be promising candidate for light-emitting devices application.

Electron-assisted probing of polaritonic light–matter states

Abstract Thanks to their exceptional spatial, spectral and temporal resolution, highly-coherent free-electron beams have emerged as powerful probes for material excitations, enabling their characterization even in the quantum regime. Here, we investigate strong light–matter coupling through monochromatic and modulated electron wavepackets. In particular, we consider an archetypal target, comprising a nanophotonic cavity next to a single two-level emitter. We propose a model Hamiltonian describing the coherent interaction between the passing electron beam and the hybrid photonic–excitonic target, which is constructed using macroscopic quantum electrodynamics and fully parameterized in terms of the electromagnetic dyadic Green’s function. Using this framework, we first describe electron-energy-loss and cathodoluminescence spectroscopies, and photon-induced near-field electron emission microscopy. Finally, we show the power of modulated electrons beams as quantum tools for the manipulation of polaritonic targets presenting a complex energy landscape of excitations.

Nanoscale Cathodoluminescence Thermometry with a Lanthanide-Doped Heavy-Metal Oxide in Transmission Electron Microscopy.

When navigated by the available energy of a system, often provided in the form of heat, physical processes or chemical reactions fleet on a free-energy landscape, thus changing the structure. In in situ transmission electron microscopy (TEM), where material structures are measured and manipulated inside the microscope while being subjected to external stimuli such as electrical fields, laser irradiation, or mechanical stress, it is necessary to precisely determine the local temperature of the specimen to provide a comprehensive understanding of material behavior and to establish the relationship among energy, structure, and properties at the nanoscale. Here, we propose using cathodoluminescence (CL) spectroscopy in TEM for in situ measurement of the local temperature. Gadolinium oxide particles doped with emissive europium ions present an opportunity to utilize them as a temperature probe in CL measurements via a ratiometric approach. We show the thermometric performance of the probe and demonstrate a precision of ±5 K in the temperature range from 113 to 323 K with the spatial resolution limited by the size of the particles, which surpasses other methods for temperature determination. With the CL-based thermometry, we further demonstrate measuring local temperature under laser irradiation.

3D structure of threading screw dislocation at a deep location in 4H-SiC using 3D micro-X-ray topography

We used 3D micro-X-ray topography (3D μ-XRT) to construct a 3D structure of the threading screw dislocations (TSDs) in 4H-SiC. The 00012 diffraction condition, which can observe the strain field at a deep location in the sample, was employed in the 3D μ-XRT geometry. The dislocation core-lines of TSDs propagating from the surface to the interior of the sample were successfully captured spatially, and TSDs parallel to and inclined from the 〈0001〉 axis were both confirmed. Either the component 〈〉 or 〈〉 of the Burgers vector is considered to be mixed in the inclined TSD. To verify this suggestion, scanning electron microscopy (SEM) and cathodoluminescence (CL) spectroscopy were performed on the molten-alkali-etched TSDs. Both the SEM shapes and CL intensities of the TSD etch pits with inclination showed the features of the mixed component, supporting the correlation between the inclination and mixed component in TSD.

Cathodoluminescence spectroscopy of monolayer hexagonal boron nitride

Cathodoluminescence (CL) spectroscopy is a suitable technique for studying the luminescent properties of optoelectronic materials because CL has no limitation on the excitable bandgap energy and eliminates ambiguous signals due to simple light scattering and resonant Raman scattering potentially involved in the photoluminescence spectra. However, direct CL measurements of atomically thin two-dimensional materials have been difficult due to the small excitation volume that interacts with high-energy electron beams. Herein, distinct CL signals from a monolayer hexagonal BN (hBN), namely mBN, epitaxial film grown on a graphite substrate are shown by using a CL system capable of large-area and surface-sensitive excitation. Spatially resolved CL spectra at 13 K exhibited a predominant 5.5-eV emission band, which has been ascribed to originate from multilayered aggregates of hBN, markedly at thicker areas formed on the step edges of the substrate. Conversely, a faint peak at 6.04 ± 0.01 eV was routinely observed from atomically flat areas, which is assigned as being due to the recombination of phonon-assisted direct excitons of mBN. The CL results support the transition from indirect bandgap in bulk hBN to direct bandgap in mBN. The results also encourage one to elucidate emission properties of other low-dimensional materials by using the present CL configuration.

The 450 nm (2.8 eV) cathodoluminescence emission in quartz and its relation to structural defects and Ti contents

Abstract The origin of the common blue 450 nm (2.8 eV) cathodoluminescence (CL) emission in natural and synthetic quartz has been investigated using a combination of CL microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and trace-element analysis by electron micro-probe analysis as well as inductively coupled plasma-mass spectrometry (ICP-MS). The study shows that the appearance of the ~450 nm emission band can be attributed to two different defects in quartz. First, a transient luminescence can be explained by structural defects in oxygen deficient quartz. The luminescence model implies self-trapped exciton (STE) emission related to oxygen vacancies. This type of CL emission is frequent in high-purity synthetic quartz and natural quartz of hydrothermal origin. Second, in Ti-rich quartz from natural samples (e.g., quartz phenocrysts in rhyolites) and synthetic quartz of Ti-diffusion experiments, an additional 450 nm (2.8 eV) emission was detected, which is stable under the electron beam. The intensity of this ~450 nm emission band correlates with the concentration of trace Ti in quartz, and substitutional Ti4+ at the Si4+ position was proved by EPR spectroscopy. In quartz crystals with elevated Ti concentrations both intrinsic and extrinsic blue CL emissions at ~450 nm can coexist, hindering a thorough characterization and quantification of the CL signal. A reliable distinction of the two different CL emission bands is possible by fitting the peaks of the CL spectra, and the peak width of the 450 nm emission can be used to differentiate the STE from the Ti4+ emission. However, the definitive technique is through the observation of CL peak shape change over time at a point by collecting a time series of CL spectra in conjunction with EPR spectroscopy and trace-element analysis of the Ti concentration.

Defects distribution and evolution in selected-area helium ion implanted 4H–SiC

An experimental demonstration of the generation of VSi, CSiVC, and NCVSi color centers in 4H–SiC using helium ion microscope irradiation of 5 × 5 μm2 areas with subsequent annealing treatment is presented. With the aid of transmission electron microscopy (TEM), photoluminescence (PL) and cathodoluminescence (CL) spectroscopy and Raman stress analysis, the evolution and distribution of color centers were thoroughly investigated. Cross-sectional TEM revealed the presence of helium bubbles in the center of the regions implanted with high doses which account for the observed quench of PL emission in the center of the implanted regions in both PL and CL measurements. PL spectra from the virgin, implanted and annealed samples proved the appearance of VSi after implantation and the transformation from VSi to CSiVC and NCVSi centers after annealing at 1000 °C. Moreover, with the increase of the implantation dose, the area of NCVSi centers increases whereas that of CSiVC decreases, which provide the first evidence of the competitive relationship between the formation of CSiVC and NCVSi defects. The comparison between stress distribution and CSiVC defect distribution illustrated that CSiVC centers predominantly distributed around the surface rupture region after thermal annealing where significant stress repair occurred. The results show that focused helium ion implantation holds promise for the precise coupling of VSi, CSiVC and NCVSi centers in predefined locations in integrated photonics applications.

Processes controlling rare earth element distribution in sedimentary apatite: Insights from spectroscopy, in situ geochemistry and O and Sr isotope composition

ABSTRACTIn phosphorites, the content and distribution of rare earth elements are linked to the environment of phosphogenesis. This paper focuses on the question of sources and processes controlling the rare earth element content of apatite from Belgian phosphorites formed during three major phosphogenic events in the Lower Palaeozoic, Late Cretaceous and Cenozoic. To constrain sources and processes, new data include petrological, mineralogical (including cathodoluminescence and Raman spectroscopy) and in situ trace element and Sr and O isotope analyses of apatite. Fluorapatite from Lower Palaeozoic P‐rich conglomerates has the greatest rare earth element enrichment. It is affected by metamorphism that led to deformation of apatite nodules and formation of garnet porphyroblast inclusions. The role of Fe‐oxyhydroxides in element scavenging is highlighted by some apatite nodules that maintain their primary middle rare earth element enrichment, while others are characterized by altered rare earth element patterns resulting from competition for these elements between co‐crystallizing minerals during deformation. A systematic shift towards lower δ18O and radiogenic Sr isotopic composition compared to contemporaneous seawater indicate interaction with 18O‐depleted meteoric fluids and a crustal component. By contrast, carbonate‐rich fluorapatite from the Late Cretaceous phosphatic chalk mostly keeps its primary trace element and isotopic signatures (close to seawater), although an external rare earth element addition is noted, as well as rare earth element redistribution induced by diagenetic alteration. Cenozoic carbonate fluorapatite nodules mostly present flat rare earth element patterns that are indicative of a detrital influence. Slight changes in rare earth element distribution are assigned to post‐depositional alteration, which also led to an increase in radiogenic Sr, with unchanged δ18O compared to seawater. The methodology followed here efficiently helps in deciphering the processes that modified the chemistry of apatite in the frame of major phosphogenic events.