Cathodoluminescence Measurements Research Articles

Spatial correlation of defect-selective etching and dark luminescence spots in Al x Ga1−x N

Defect-selective etching with molten Ba(OH)2/MgO etch drops was performed on c-plane AlGaN layers covering the entire composition range between GaN and AlN. Regardless of the aluminum content, the etchant produced shallow, hexagonal etch pits with depth-to-diameter ratios of 1/10–1/100. Two predominant types of etch pits were observed, which differed in size. In addition, the etch rate decreased from the center to the edge of the area exposed to the etch drops, providing a radially symmetric variation in etch pit size. For all AlGaN compositions, the positions of the etch pits correlate perfectly with the positions of the dark luminescence spots in cathodoluminescence measurements. Areas on the AlGaN samples that were not exposed to the etching procedure showed identical dark spots with the same size and density as those in the etched regions. Additionally, the density of etch pits and dark spots corresponded to the density of threading dislocations in the AlGaN layers. These observations demonstrate that the density of threading dislocations in c-plane AlGaN layers can be determined by destructive defect-selective etching with Ba(OH)2/MgO and etch pit counting, as well as by nondestructive counting of the dark spots in cathodoluminescence images.

Metal-modulated epitaxy of Mg-doped Al0.80In0.20N-based layer for application as the electron blocking layer in deep ultraviolet light-emitting diodes

This work reports the growth and characterization of p-AlInN layers doped with Mg by plasma-assisted molecular beam epitaxy (PAMBE). AlInN was grown with an Al molar fraction of 0.80 by metal-modulated epitaxy (MME) with a thickness of 180 nm on Si(111) substrates using AlN as buffer layers. Low substrate temperatures were used to enhance the incorporation of indium atoms into the alloy without clustering, as confirmed by X-ray diffraction (XRD). Cathodoluminescence measurements revealed ultraviolet (UV) range emissions. Meanwhile, Hall effect measurements indicated a maximum hole mobility of 146 cm2/(V∙s), corresponding to a free hole concentration of 1.23 × 1019 cm−3. The samples were analyzed by X-ray photoelectron spectroscopy (XPS) estimating the alloy composition and extracting the Fermi level by valence band analysis. Mg-doped AlInN layers were studied for use as the electron-blocking layer (EBL) in LED structures. We varied the Al composition in the EBL from 0.84 to 0.96 molar fraction to assess its theoretical effects on electroluminescence, carrier concentration, and electric field, using SILVACO Atlas. The results from this study highlight the importance and capability of producing high-quality Mg-doped p-AlInN layers through PAMBE. Our simulations suggest that an Al content of 0.86 is optimal for achieving desired outcomes in electroluminescence, carrier concentration, and electric field.

Carrier tunneling and transport in coupled quantum wells: Modeling and experimental verification

We propose an approach to elucidate carrier dynamics by developing a robust rate equation model capable of explaining carrier dynamics in a dual-well system. To experimentally validate the accuracy and reliability of our model, we utilized a combination of time-resolved photoluminescence and spatially resolved cathodoluminescence measurements. The integration of these complementary techniques allowed us to thoroughly investigate the spectral characteristics in both wells, revealing distinct features attributed to carrier tunneling and transport effects and verifying the predictive ability of the model. This validation process not only confirms the model's accuracy under both coupled and uncoupled conditions but also highlights its potential applicability to quantum-well-based semiconductor lasers. Overall, our study not only advances our understanding of carrier dynamics in quantum wells but also introduces a versatile and reliable tool for designing and simulating ultrafast semiconductor lasers.

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.

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.

Closed-loop electron-beam-induced spectroscopy and nanofabrication around individual quantum emitters

Abstract Color centers in diamond play a central role in the development of quantum photonic technologies, and their importance is only expected to grow in the near future. For many quantum applications, high collection efficiency from individual emitters is required, but the refractive index mismatch between diamond and air limits the optimal collection efficiency with conventional diamond device geometries. While different out-coupling methods with near-unity efficiency exist, many have yet to be realized due to current limitations in nanofabrication methods, especially for mechanically hard materials like diamond. Here, we leverage electron-beam-induced etching to modify Sn-implanted diamond quantum microchiplets containing integrated waveguides with a width and thickness of 280 nm and 200 nm, respectively. This approach allows for simultaneous high-resolution imaging and modification of the host matrix with an open geometry and direct writing. When coupled with the cathodoluminescence signal generated from the electron–emitter interactions, we can monitor the enhancement of the quantum emitters in real-time with nanoscale spatial resolution. The operando cathodoluminescence measurement and fabrication around single photon emitters demonstrated here provide a new foundation for the potential control of emitter–cavity interactions in integrated quantum photonics.

Simultaneous enhancements on emissions from quantum dot and quantum well by Ag nanoparticles for color conversion

Quantum dots (QDs) have been paid much attention on the color conversion for light-emitting diode (LED) in micro-display recently. However, it is hard to achieve high color conversion efficiency in a thin QD layer. In this paper, we fabricated silver nanoparticles (Ag NPs) with radii ranging mostly from 25 to 35 nm on a blue LED with a peak wavelength of 450 nm, then spin-coated QDs with a peak wavelength of 565 nm. Scanning electron microscopy, cathodoluminescence, photoluminescence (PL), and time-resolved PL measurements were performed. The PL emissions from quantum wells (QWs) of blue LED and QDs were enhanced by 10% and 32%, respectively, when the Ag NPs were included. The PL lifetimes of QWs and QDs were reduced by 10 and 6 times, respectively, compared to their initial states. Finite difference time domain software and the perturbation method were used to simulate the PL measurements and variable separation. It was concluded that the coupling of QDs and QWs with localized surface plasmon improves the external quantum efficiency and enhances the spontaneous emission rate in both QWs and QDs. This paper provides a new idea for designing high-efficiency color conversion micro-LED.

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.

Low-Leakage Current Core-Shell AlGaN Nanorod LED Device Operating in the Ultraviolet-B Band.

Despite the considerable potential of AlGaN-based ultraviolet-B light-emitting diodes (UV-B LEDs) in various applications such as phototherapy, UV curing, plant growth, and analytical technology, their development is still ongoing due to low luminescence efficiency. In this study, we introduced a novel epitaxial growth mechanism to effectively control the height and thickness of AlGaN multiple wells (MWs) on AlGaN nanorod structures using horizontal reactor-based metal-organic chemical vapor deposition (MOCVD). By adjusting the H2 carrier gas flow rate, we could control the growth boundary layer's thickness, successfully separating the AlGaN well and p-AlGaN layer from the substrate. Cathodoluminescence (CL) measurements confirmed the stability of the core-shell AlGaN quantum wells as a highly stable nonpolarized structure, with the wavelength peak remaining almost unchanged under various injection currents. Furthermore, transmission electron microscopy (TEM) provided clear evidence of differentiation, highlighting the distinct formation of the 275 nm AlGaN core and the 295 nm AlGaN shell structure. The developed AlGaN MW structure, characterized by these rectification features, not only demonstrated a significantly improved electroluminescence (EL) peak intensity but also exhibited a much lower leakage current compared to the conventional core-shell AlGaN structure. The newly proposed growth mechanism and advanced nonpolarized core-shell AlGaN structure are expected to serve as excellent alternatives for substantially enhancing the efficiency of the next generation of high-efficiency UV LEDs.

Origin of the parasitic luminescence of 235 nm UVC LEDs grown on different AlN templates

AlN layers annealed at high temperatures offer low threading dislocation densities of mid 108 cm−2 and are therefore increasingly used as base layers in ultraviolet (UV) light emitting diode (LED) heterostructure growth. These LEDs, just like those grown on conventional metalorganic vapor phase epitaxy (MOVPE) AlN templates, often suffer from long-wavelength parasitic luminescence. In this work, luminescence properties of far-UVC LED heterostructures grown on MOVPE-AlN/sapphire templates and high-temperature annealed AlN/sapphire templates are compared. To investigate the origin of parasitic emission with high spatial resolution, cross section scanning transmission electron microscopy was combined with cathodoluminescence measurements. As a result, the main origin of the parasitic luminescence band centered at 3.5 eV (354 nm) for the heterostructure grown on annealed AlN is assigned to point defects related to oxygen in the AlN template layer. The defect band centered at 3.0 eV (413 nm) for the heterostructure grown on MOVPE-AlN was found to be related to self-compensating VAl-Si point defect complexes in the n-AlGaN layer and oxygen incorporation close to the AlN/sapphire interface. The results also suggest that the type of AlN template determines the kind of parasitic luminescence from the n-AlGaN layer.

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.

Analysis of Nanowire pn-Junction with Combined Current-Voltage, Electron-Beam-Induced Current, Cathodoluminescence, and Electron Holography Characterization.

We present the characterization of a pn-junction GaAs nanowire. For the characterization, current-voltage, electron-beam-induced current, cathodoluminescence, and electron holography measurements are used. We show that by combining information from these four methods, in combination with drift-diffusion modelling, we obtain a detailed picture of how the nanowire pn-junction is configured and how the recombination lifetime varies axially in the nanowire. We find (i) a constant doping concentration and 600 ps recombination lifetime in the n segment at the top part of the nanowire; (ii) a 200-300 nm long gradient in the p doping next to the pn-junction; and (iii) a strong gradient in the recombination lifetime on the p side, with 600 ps lifetime at the pn-junction, which drops to 10 ps at the bottom of the p segment closest to the substrate. We recommend such complementary characterization with multiple methods for nanowire-based optoelectronic devices.

Degree of Polarization of Cathodoluminescence from a (100) GaAs Substrate with SiN Stripes

Notes on fits of analytic estimations, 2D finite element method (FEM), and 3D FEM simulations to measurements of the cathodoluminescence (CL) and to the degree of polarization (DOP) of the CL from the top surface of a (100) GaAs substrate with a 6.22 μm wide SiN stripe are presented. Three interesting features are found in the DOP of CL data. Presumably these features are noticeable owing to the spatial resolution of the CL measurement system. Comparisons of both strain and spatial resolutions obtained by CL and photoluminescence (PL) systems are presented. The width of the central feature in the measured DOP is less than the width of the SiN, as measured from the CL. This suggests horizontal cracks or de-laminations into each side of the SiN of about 0.7 μm. In addition, it appears that deformed regions of widths of ≈1.5 μm and adjacent to the SiN must exist to explain some of the features.

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.

Size-dependent cathodoluminescence properties of 5,5′-di(4-biphenylyl)-2,2′-bithiophene nanocrystals

Crystal-size-dependent cathodoluminescence measurements demonstrated that 0-1 band peak energy of BP2T nanocrystals gradually blue-shifted compared to that of the bulk crystal as the nanocrystal size decreased below 560 nm.

Exploring Al2O3 blister evolution through cathodoluminescence and attenuated total reflectance infrared analyses

This work focuses on the morphological and optical evolution of Al2O3 thick films grown by atomic layer deposition on Si-SiO2 substrates. Blister formation has been the subject of extensive research in the literature; our work fills a crucial gap in the optical characterization of areas inside and outside blisters. Morphological studies were carried out by scanning electron microscopy; we found a reciprocal relationship between the density of the blisters and their diameter. The thickness and refractive index were studied by ellipsometry, revealing a systematic increase in the refractive index with increasing annealing temperature. In addition, we observed the hydrophobic behavior in all films using the water contact angle technique, which suggests that even with blisters, this material can be used in waterproof coatings. Using Auger spectroscopy, we confirmed that delamination occurs completely once the blisters are broken. In this work, we perform cathodoluminescence measurements outside and inside the ampoules. In the area outside the blisters, we observe emissions attributed to the F centers, and the change from the main peaks of 2.8 and 3.4 eV for the as-deposited film to the dominance of emissions centered at 3.4 and 3.7 eV is clearly observed. Furthermore, we observed a strong increase in the cathodoluminescence signal at higher annealing temperatures. On the other hand, we also observed the evolution of the blisters through the cathodoluminescence spectra; in that area, we observed the radical change in the spectrum once the blister is broken, giving rise to the SiO2 signals. We also observed this rupture through a new absorption band in the attenuated total reflectance IR spectra.

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.

Simultaneous Growth Strategy of High-Optical-Efficiency GaN NWs on a Wide Range of Substrates by Pulsed Laser Deposition.

Here, we explore a catalyst-free single-step growth strategy that results in high-quality self-assembled single-crystal vertical GaN nanowires (NWs) grown on a wide range of common and novel substrates (including GaN, Ga2O3, and monolayer two-dimensional (2D) transition-metal dichalcogenide (TMD)) within the same chamber and thus under identical conditions by pulsed laser deposition. High-resolution transmission electron microscopy and scanning transmission electron microscopy (HR-STEM) and grazing incidence X-ray diffraction measurements confirm the single-crystalline nature of the obtained NWs, whereas advanced optical and cathodoluminescence measurements provide evidence of their high optical quality. Further analyses reveal that the growth is initiated by an in situ polycrystalline layer formed between the NWs and substrates during growth, while as its thickness increases, the growth mode transforms into single-crystalline NW nucleation. HR-STEM and corresponding energy-dispersive X-ray compositional analyses indicate possible growth mechanisms. All samples exhibit strong band edge UV emission (with a negligible defect band) dominated by radiative recombination with a high optical efficiency (∼65%). As all NWs have similar structural and optical qualities irrespective of the substrate used, this strategy will open new horizons for developing III-nitride-based devices.

Activated Single Photon Emitters And Enhanced Deep‐Level Emissions in Hexagonal Boron Nitride Strain Crystal

AbstractThe peculiar defect‐related photon emission processes in 2D hexagonal boron nitride (hBN) have become a topic of intense research due to their potential applications in quantum information and sensing technologies. Here, it is reported on exotic single photons and enhanced deep‐level emissions in 2D hBN strain crystal, which is fabricated by transferring multilayer hBN onto hexagonal close‐packed silica spheres on a silica substrate. Effective activation of single photon emission is realized from the defect ensembles in the multilayer hBN at positions that are in contact with the apex of the SiO2 spheres. At these points, the local tensile strain‐induced overall blue shift of the SPE ensembles is up to 12 nm. Furthermore, high spatial resolution cathodoluminescence measurements show remarkable strain‐enhanced deep‐level emissions in the multilayer hBN with the emission intensity distribution following the periodic hexagonal pattern of the strain crystal. The maximum deep‐level emission enhancement is up to 350% with an energy redshift of 6 nm. These results provide a simple on‐chip compatible method for activating and tuning the defect‐related photon emissions in multilayer hBN, demonstrating the potential of hBN strain crystal as a building block for future on‐chip quantum nanophotonic devices.

Structural, morphological and luminescence properties of hafnia nanoparticles obtained by hydrothermal synthesis

Hafnia is a novel material for optoelectronic applications, fabrication methods are focused to obtain hafnium oxide nanomaterials included thin films and nanoparticles. HfO2 nanoparticles synthesized and studied in this work are crystalline without subsequent heat treatment and were processed by hydrothermal method at 200 °C during 1.3, 2 and 4 h. SEM and TEM analysis revealed the presence of spherical and oval nanoparticles, with range size from 60 to 70 nm and 90–110 nm for spherical and oval nanoparticles, respectively. Raman spectroscopy and X-ray diffraction confirmed that nanoparticles exhibit a stable monoclinic phase. Crystal growth is typical with the presence of the characteristic monoclinic plane (1‾11) but for reaction times of 2 and 4 h and pH over 12 it turns in the plane (220) which is perpendicular to typical growth. Cathodoluminescence measurements revealed strong blue emission intensity showing a broadband in all visible range and a maximum peak at 460 nm. The presences of VO3 and VO4 in HfO2 crystalline structure are responsible for this inherent CL emission corroborated by photoluminescence studies.