Showing papers on "Cathodoluminescence published in 2022"

Interplay of defect levels and rare earth emission centers in multimode luminescent phosphors

Abstract: Abstract Multimode luminescence generally involves tunable photon emissions in response to various excitation or stimuli channels, which demonstrates high coding capacity and confidentiality abilities for anti-counterfeiting and encryption technologies. Integrating multimode luminescence into a single stable material is a promising strategy but remains a challenge. Here, we realize distinct long persistent luminescence, short-lived down/upconversion emissions in NaGdTi 2 O 6 :Pr 3+ , Er 3+ phosphor by emloying interplay of defect levels and rare earth emission centers. The materials show intense colorful luminescence statically and dynamically, which responds to a wide spectrum ranging from X-ray to sunlight, thermal disturbance, and mechanical force, further allowing the emission colors manipulable in space and time dimensions. Experimental and theoretical approaches reveal that the Pr 3+ ↔ Pr 4+ valence change, oxygen vacancies and anti-site Ti Gd defects in this disordered structure contributes to the multimode luminescence. We present a facile and nondestructive demo whose emission color and fade intensity can be controlled via external manipulation, indicating promise in high-capacity information encryption applications.

Tuning colour centres at a twisted hexagonal boron nitride interface

Abstract: The colour centre platform holds promise for quantum technologies, and hexagonal boron nitride has attracted attention due to the high brightness and stability, optically addressable spin states and wide wavelength coverage discovered in its emitters. However, its application is hindered by the typically random defect distribution and complex mesoscopic environment. Here, employing cathodoluminescence, we demonstrate on-demand activation and control of colour centre emission at the twisted interface of two hexagonal boron nitride flakes. Further, we show that colour centre emission brightness can be enhanced by two orders of magnitude by tuning the twist angle. Additionally, by applying an external voltage, nearly 100% brightness modulation is achieved. Our ab initio GW and GW plus Bethe-Salpeter equation calculations suggest that the emission is correlated to nitrogen vacancies and that a twist-induced moiré potential facilitates electron-hole recombination. This mechanism is further exploited to draw nanoscale colour centre patterns using electron beams.

Cathodoluminescence excitation spectroscopy: Nanoscale imaging of excitation pathways

Abstract: Following optical excitations’ life span from creation to decay into photons is crucial in understanding materials photophysics. Macroscopically, this is studied using optical techniques, such as photoluminescence excitation spectroscopy. However, excitation and emission pathways can vary at nanometer scales, preventing direct access, as no characterization technique has the relevant spatial, spectral, and time resolution. Here, using combined electron spectroscopies, we explore excitations’ creation and decay in two representative optical materials: plasmonic nanoparticles and luminescent two-dimensional layers. The analysis of the energy lost by an exciting electron that is coincident in time with a visible-ultraviolet photon unveils the decay pathways from excitation toward light emission. This is demonstrated for phase-locked (coherent) interactions (localized surface plasmons) and non–phase-locked ones (point defect excited states). The developed cathodoluminescence excitation spectroscopy images energy transfer pathways at the nanometer scale, widening the available toolset to explore nanoscale materials.

Omnibearing Interpretation of External Ions Passivated Ion Migration in Mixed Halide Perovskites.

Abstract: Fundamental understanding of ion migration inside perovskites is of vital importance for commercial advancements of photovoltaics. However, the mechanism for external ions incorporation and its effect on ion migration remains elusive. Herein, taking K+ and Cs+ co-incorporated mixed halide perovskites as a model, the impact of external ions on ion migration behavior has been interpreted via multiple dimensional characterization aspects. The space-effect on phase segregation inhibition has been revealed by the photoluminescence evolution and in situ dynamic cathodoluminescence behaviors. The plane-effect on current suppression along grain boundary has been evidenced via visualized surface current mapping, local current hysteresis, and time-resolved current decay. And the point-effect on activation energy incremental for individual ions has been also probed by cryogenic electronic quantification. All these results sufficiently demonstrate the passivated ion migration results in the eventually improved phase stability of perovskite, of which the origin lies in various ion migration energy barriers.

Variable temperature probing of minority carrier transport and optical properties in p-Ga2O3

Abstract: Electron beam-induced current in the temperature range from 304 to 404 K was employed to measure the minority carrier diffusion length in metal–organic chemical vapor deposition-grown p-Ga2O3 thin films with two different concentrations of majority carriers. The diffusion length of electrons exhibited a decrease with increasing temperature. In addition, the cathodoluminescence emission spectrum identified optical signatures of the acceptor levels associated with the VGa−–VO++ complex. The activation energies for the diffusion length decrease and quenching of cathodoluminescence emission with increasing temperature were ascribed to the thermal de-trapping of electrons from VGa−–VO++ defect complexes.

Free-electron–light interactions in nanophotonics

Abstract: When impinging on optical structures or passing in their vicinity, free electrons can spontaneously emit electromagnetic radiation, a phenomenon generally known as cathodoluminescence. Free-electron radiation comes in many guises: Cherenkov, transition, and Smith–Purcell radiation, but also electron scintillation, commonly referred to as incoherent cathodoluminescence. While those effects have been at the heart of many fundamental discoveries and technological developments in high-energy physics in the past century, their recent demonstration in photonic and nanophotonic systems has attracted a great deal of attention. Those developments arose from predictions that exploit nanophotonics for novel radiation regimes, now becoming accessible thanks to advances in nanofabrication. In general, the proper design of nanophotonic structures can enable shaping, control, and enhancement of free-electron radiation, for any of the above-mentioned effects. Free-electron radiation in nanophotonics opens the way to promising applications, such as widely tunable integrated light sources from x-ray to THz frequencies, miniaturized particle accelerators, and highly sensitive high-energy particle detectors. Here, we review the emerging field of free-electron radiation in nanophotonics. We first present a general, unified framework to describe free-electron light–matter interaction in arbitrary nanophotonic systems. We then show how this framework sheds light on the physical underpinnings of many methods in the field used to control and enhance free-electron radiation. Namely, the framework points to the central role played by the photonic eigenmodes in controlling the output properties of free-electron radiation (e.g., frequency, directionality, and polarization). We then review experimental techniques to characterize free-electron radiation in scanning and transmission electron microscopes, which have emerged as the central platforms for experimental realization of the phenomena described in this review. We further discuss various experimental methods to control and extract spectral, angular, and polarization-resolved information on free-electron radiation. We conclude this review by outlining novel directions for this field, including ultrafast and quantum effects in free-electron radiation, tunable short-wavelength emitters in the ultraviolet and soft x-ray regimes, and free-electron radiation from topological states in photonic crystals.

Composite Detectors Based on Single-Crystalline Films and Single Crystals of Garnet Compounds

Abstract: This manuscript summarizes recent results on the development of composite luminescent materials based on the single-crystalline films and single crystals of simple and mixed garnet compounds obtained by the liquid-phase epitaxy growth method. Such composite materials can be applied as scintillating and thermoluminescent (TL) detectors for radiation monitoring of mixed ionization fluxes, as well as scintillation screens in the microimaging techniques. The film and crystal parts of composite detectors were fabricated from efficient scintillation/TL materials based on Ce3+-, Pr3+-, and Sc3+-doped Lu3Al5O12 garnets, as well as Ce3+-doped Gd3−xAxAl5−yGayO12 mixed garnets, where A = Lu or Tb; x = 0–1; y = 2–3 with significantly different scintillation decay or positions of the main peaks in their TL glow curves. This work also summarizes the results of optical study of films, crystals, and epitaxial structures of these garnet compounds using absorption, cathodoluminescence, and photoluminescence. The scintillation and TL properties of the developed materials under α- and β-particles and γ-quanta excitations were studied as well. The most efficient variants of the composite scintillation and TL detectors for monitoring of composition of mixed beams of ionizing radiation were selected based on the results of this complex study.

Exciton-dielectric mode coupling in MoS2 nanoflakes visualized by cathodoluminescence

Abstract: Abstract Two-dimensional (2D) transition metal dichalcogenides (TMDCs), possessing unique exciton luminescence properties, have attracted significant attention for use in optical and electrical devices. TMDCs are also high refractive index materials that can strongly confine the electromagnetic field in nanoscale dimensions when patterned into nanostructures, thus resulting in complex light emission that includes exciton and dielectric resonances. Here, we use cathodoluminescence (CL) to experimentally visualize the emission modes of single molybdenum disulfide (MoS2) nanoflakes and to investigate luminescence enhancement due to dielectric resonances in nanoscale dimensions, by using a scanning transmission electron microscope. Specifically, we identify dielectric modes whose resonant wavelength is sensitive to the shape and size of the nanoflake, and exciton emission peaks whose energies are insensitive to the geometry of the flakes. Using a four-dimensional CL method and boundary element method simulations, we further theoretically and experimentally visualize the emission polarization and angular emission patterns, revealing the coupling of the exciton and dielectric resonant modes. Such nanoscopic observation provides a detailed understanding of the optical responses of MoS2 including modal couplings of excitons and dielectric resonances which play a crucial role in the development of energy conversion devices, single-photon emitters, and nanophotonic circuits with enhanced light-matter interactions.

Additive Manufacturing of 3D Luminescent ZrO2:Eu3+ Architectures

Abstract: Implementation of more refined structures at the nano to microscale is expected to advance applications in optics and photonics. This work presents the additive manufacturing of 3D luminescent microarchitectures emitting light in the visible range. A tailor‐made organo‐metallic resin suitable for two‐photon lithography is developed, which upon thermal treatment in an oxygen‐rich atmosphere allows the creation of silicon‐free tetragonal (t‐) and monoclinic (m‐) ZrO2. The approach is unique because the tailor‐made Zr‐resin is different from what is achieved in other reported approaches based on sol−gel resins. The Zr‐resin is compatible with the Eu‐rich dopant, a luminescent activator, which enables to tune the optical properties of the ZrO2 structures upon annealing. The emission characteristics of the Eu‐doped ZrO2 microstructures are investigated in detail with cathodoluminescence and compared with the intrinsic optical properties of the ZrO2. The hosted Eu has an orange−red emission showcased using fluorescence microscopy. The presented structuring technology provides a new platform for the future development of 3D luminescent devices.

New Mechanism for Long Photo-Induced Enhanced Raman Spectroscopy in Au Nanoparticles Embedded in TiO2.

Abstract: The photo-induced enhanced Raman spectroscopy (PIERS) effect is a phenomenon taking place when plasmonic nanoparticles deposited on a semiconductor are illuminated by UV light prior to Raman measurement. Results from the literature show that the PIERS effect lasts for about an hour. The proposed mechanism for this effect is the creation of oxygen vacancies in the semiconductor that would create a path for charge transfer between the analyte and the nanoparticles. However, this hypothesis has never been confirmed experimentally. Furthermore, the tested structure of the PIERS substrate has always been composed of plasmonic nanoparticles deposited on top of the semiconductor. Here, gold nanoparticles co-deposited with porous TiO2 are used as a PIERS substrate. The deposition process confers the nanoparticles a unique position half buried in the nanoporous semiconductor. The resulting PIERS intensity is among the highest measured until now but most importantly the duration of the effect is significantly longer (at least 8 days). Cathodoluminescence measurements on these samples show that two distinct mechanisms are at stake for co-deposited and drop-casted gold nanoparticles. The oxygen vacancies hypothesis tends to be confirmed for the latter, but the narrowing of the depletion zone explains the long PIERS effect.

Structural and electrical properties of thick κ-Ga2O3 grown on GaN/sapphire templates

Abstract: Thick (23 µm) films of κ-Ga2O3 were grown by Halide Vapor Phase Epitaxy (HVPE) on GaN/sapphire templates at 630 °C. X-ray analysis confirmed the formation of single-phase κ-Ga2O3 with half-widths of the high-resolution x-ray diffraction (004), (006), and (008) symmetric reflections of 4.5 arc min and asymmetric (027) reflection of 14 arc min. Orthorhombic κ-Ga2O3 polymorph formation was confirmed from analysis of the Kikuchi diffraction pattern in electron backscattering diffraction. Secondary electron imaging indicated a reasonably flat surface morphology with a few (area density ∼103 cm−2) approximately circular (diameter ∼50–100 µm) uncoalesced regions, containing κ-Ga2O3 columns with in-plane dimensions and a height of about 10 µm. Micro-cathodoluminescence (MCL) spectra showed a wide 2–3.5 eV band that could be deconvoluted into narrower bands peaked at 2.59, 2.66, 2.86, and 3.12 eV. Ni Schottky diodes prepared on the films showed good rectification but a high series resistance. The films had a thin near-surface region dominated by Ec − 0.7 eV deep centers and a deeper region (∼2 µm from the surface) dominated by shallow donors with concentrations of ≤1016 cm−3. Photocurrent and photocapacitance spectra showed the presence of deep compensating acceptors with optical ionization energies of ∼1.35 and 2.3 eV, the latter being close to the energy of one of the MCL bands. Deep level transient spectroscopy revealed deep traps with energies near 0.3, 0.6, 0.7, 0.8, and 1 eV from the conduction band edge. The results show the potential of HVPE to grow very thick κ-Ga2O3 on GaN/sapphire templates.

Deconvolution of Light‐Induced Ion Migration Phenomena by Statistical Analysis of Cathodoluminescence in Lead Halide‐Based Perovskites

Abstract: Studying the compositional instability of mixed ion perovskites under light illumination is important to understand the mechanisms underlying their efficiency and stability. However, current techniques are limited in resolution and are unable to deconvolute minor ion migration phenomena. Here, a method that enables ion migration to be studied allowing different segregation mechanisms to be elucidated is described. Statistical analysis is applied to cathodoluminescence data to generate compositional distribution histograms. Using these histograms, two different ion migration phenomena, horizontal ion migration (HIM) and vertical ion migration (VIM), are identified in different perovskite films. It is found that most passivating agents inhibit HIM, but not VIM. However, VIM can be reduced by deposition of imidazolium iodide on the perovskite surface. This method can be used to study perovskite‐based devices efficiency and stability by providing molecular level mechanistic understanding of passivation approaches leading to performance improvement of perovskite solar cells via rational design.

Modulating the growth of chemically deposited ZnO nanowires and the formation of nitrogen- and hydrogen-related defects using pH adjustment

Abstract: ZnO nanowires (NWs) grown by chemical bath deposition (CBD) have received great interest for nanoscale engineering devices, but their formation in aqueous solution containing many impurities needs to be carefully addressed. In particular, the pH of the CBD solution and its effect on the formation mechanisms of ZnO NWs and of nitrogen- and hydrogen-related defects in their center are still unexplored. By adjusting its value in a low- and high-pH region, we show the latent evolution of the morphological and optical properties of ZnO NWs, as well as the modulated incorporation of nitrogen- and hydrogen-related defects in their center using Raman and cathodoluminescence spectroscopy. The increase in pH is related to the increase in the oxygen chemical potential (μO), for which the formation energy of hydrogen in bond-centered sites (HBC) and VZn-NO-H defect complexes is found to be unchanged, whereas the formation energy of zinc vacancy (VZn) and zinc vacancy-hydrogen (VZn-nH) complexes steadily decreases as shown from density-functional theory calculations. Revealing that these VZn-related defects are energetically favorable to form as μO is increased, ZnO NWs grown in the high-pH region are found to exhibit a higher density of VZn-nH defect complexes than ZnO NWs grown in the low-pH region. Annealing at 450 °C under an oxygen atmosphere helps tuning the optical properties of ZnO NWs by reducing the density of HBC and VZn-related defects, while activating the formation of VZn-NO-H defect complexes. These findings show the influence of pH on the nature of Zn(ii) species, the electrostatic interactions between these species and ZnO NW surfaces, and the formation energy of the involved defects. They emphasize the crucial role of the pH of the CBD solution and open new possibilities for simultaneously engineering the morphology of ZnO NWs and the formation of nitrogen- and hydrogen-related defects.

Graphene-based deep-ultraviolet photodetectors with ultrahigh responsivity using chemical vapor deposition of hexagonal boron nitride to achieve photogating

Abstract: This study presents high-responsivity graphene-based deep-ultraviolet (DUV) photodetectors using chemical vapor deposition (CVD)-hexagonal boron nitride (h-BN) photogating. To improve the DUV photoresponse, h-BN was used as a photosensitizer in graphene field-effect transistors (GFETs). The h-BN photosensitizers were synthesized using CVD and then transferred onto a SiO 2 /Si substrate. The behavior of h-BN irradiated with DUV light was investigated using cathodoluminescence and UV–VIS reflectance. Under 260 nm light, it exhibited a clear photoresponse with an ultrahigh responsivity of 19600 AW -1 , which was 460% higher than a GFET device without h-BN photosensitizers. A noise equivalent power of 3.09×10 −13 W/Hz 1/2 was achieved.

Carrier Diffusion in <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" overflow="scroll"><mml:mrow><mml:mi>Ga</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math> : A Cathodoluminescence Study. III. Nature of Nonradiative Recombination at Threading Dislocations

Abstract: We investigate the impact of threading dislocations with an edge component ($a$ or $a+c$ type) on carrier recombination and diffusion in $\mathrm{Ga}\mathrm{N}$(0001) layers close to the surface as well as in the bulk. To this end, we utilize cathodoluminescence imaging of the top surface of a $\mathrm{Ga}\mathrm{N}$(0001) layer with a deeply buried (In,$\mathrm{Ga}$)N quantum well. Varying the acceleration voltage of the primary electrons and comparing the signal from the layer and the quantum well enables us to probe carrier recombination at depths ranging from the close vicinity of the surface to the position of the quantum well. Our experiments are accompanied by fully three-dimensional Monte Carlo simulations of carrier drift, diffusion, and recombination in the presence of the surface, the quantum well, and the dislocation, taking into account the dislocation strain field and the resulting piezoelectric field at the dislocation outcrop. Near the surface, this field establishes an exciton dead zone around the dislocation, the extent of which is not related to the carrier diffusion length. However, reliable values of the carrier diffusion length can be extracted from the dipolelike energy shift observed in hyperspectral cathodoluminescence maps recorded around the dislocation outcrop at low acceleration voltages. For high acceleration voltages, allowing us to probe a depth where carrier recombination is unaffected by surface effects, we observe a much stronger contrast than expected from the piezoelectric field alone. This finding provides unambiguous experimental evidence for the strong nonradiative activity of edge threading dislocations in bulk $\mathrm{Ga}\mathrm{N}$ and hence also in buried heterostructures.

Correlative Nanoscale Imaging of Strained hBN Spin Defects.

Abstract: Spin defects like the negatively charged boron vacancy color center (VB-) in hexagonal boron nitride (hBN) may enable new forms of quantum sensing with near-surface defects in layered van der Waals heterostructures. Here, the effect of strain on VB- color centers in hBN is revealed with correlative cathodoluminescence and photoluminescence microscopies. Strong localized enhancement and redshifting of the VB- luminescence is observed at creases, consistent with density functional theory calculations showing VB- migration toward regions with moderate uniaxial compressive strain. The ability to manipulate spin defects with highly localized strain is critical to the development of practical 2D quantum devices and quantum sensors.

Correlation between electrical properties and growth dynamics for Si-doped Al-rich AlGaN grown by metal-organic chemical vapor deposition

Abstract: Correlation between electrical properties and growth dynamics for Si-doped AlGaN with Al mole fraction above 60% has been investigated. It is found that the electron concentration decreases significantly when decreasing the growth rate, while the electron mobility experiences a non-monotonic process of increasing at first and then decreasing. Combination of secondary ion mass spectroscopy and panchromatic cathodoluminescence results, reveals that the evolution of electrical properties mainly originates from compensation of III vacancy (VIII) to Si dopant, making VIII-nSi complexes, i.e., the concentrations of VIII-nSi complexes increase with decreasing the growth rate, implying high growth rate principle is vital for n-AlGaN.

Zircon classification from cathodoluminescence images using deep learning

Abstract: • An automated zircon classification from cathodoluminescence images. • Deep learning models using over 4000 cathodoluminescence images of igneous, metamorphic, and hydrothermal zircons. • The model facilitates quick and nearly error-free zircon type distributions. Zircon is a widely-used heavy mineral in geochronological and geochemical research because it can extract important information to understand the history and genesis of rocks. Zircon has various types, and an accurate examination of zircon type is a prerequisite procedure before further analysis. Cathodoluminescence (CL) imaging is one of the most reliable ways to classify zircons. However, current CL image examination is conducted by manual work, which is time-consuming, bias-prone, and requires expertise. An automated and bias-free method for zircon classification is absent but necessary. To this end, deep convolutional neural networks (DCNNs) and transfer learning are applied in this study to classify the common types of zircons, i.e., igneous, metamorphic, and hydrothermal zircons. An atlas with over 4000 CL images of these three types of zircons is created, and three DCNNs are trained using these images. The results of this study indicate that the DCNNs can distinguish hydrothermal zircons from other zircons, as indicated by the highest accuracy of 100%. Although similar textures in igneous and metamorphic zircons pose great challenges for zircon classification, the DCNNs successfully classify 95% igneous and 92% metamorphic zircons. This study demonstrates the high accuracy of DCNNs in zircon classification and presents the great potentiality of deep learning techniques in numerous geoscientific disciplines.

Optical emission from focused ion beam milled halide perovskite device cross‐sections

Abstract: Cross‐sectional transmission electron microscopy has been widely used to investigate organic–inorganic hybrid halide perovskite‐based optoelectronic devices. Electron‐transparent specimens (lamellae) used in such studies are often prepared using focused ion beam (FIB) milling. However, the gallium ions used in FIB milling may severely degrade the structure and composition of halide perovskites in the lamellae, potentially invalidating studies performed on them. In this work, the close relationship between perovskite structure and luminescence is exploited to examine the structural quality of perovskite solar cell lamellae prepared by FIB milling. Through hyperspectral cathodoluminescence (CL) mapping, the perovskite layer was found to remain optically active with a slightly blue‐shifted luminescence. This finding indicates that the perovskite structure is largely preserved upon the lamella fabrication process although some surface amorphisation occurred. Further changes in CL due to electron beam irradiation were also recorded, confirming that electron dose management is essential in electron microscopy studies of carefully prepared halide perovskite‐based device lamellae.

Defect Compensation in Nitrogen-Doped β-Ga₂O₃ Nanowires: Implications for Bipolar Nanoscale Devices

Abstract: Nitrogen (N) is a promising candidate currently being pursued for p-type doping in Ga2O3. In this work, the results of detailed investigations into N-doped β-Ga2O3 nanowires using microstructural, chemical, and optical analyses are described. Monoclinic β-Ga2O3 nanowires are grown by chemical vapor deposition using a metallic gallium (Ga) precursor and subsequently doped with N by remote plasma by exploiting their nanoscale cross sections and large surface-to-volume ratios. The N incorporation into β-Ga2O3 is confirmed by X-ray absorption near-edge and Raman spectroscopies without changes in the nanowire morphology. N is found to exist mainly as molecular N2 and N–O chemical states, but a significant portion of N substitutes on oxygen (O) sites. Concurrent temperature-resolved cathodoluminescence measurements of the undoped and N-doped β-Ga2O3 are used to track the temperature dependences of their intrinsic ultraviolet (UV) luminescence and defect-related visible bands from 80 to 480 K. The blue and green bands increase in intensity relative to the UV after N doping; however, their intensity variations with temperature are found to be identical for the undoped and N-doped β-Ga2O3, indicating that these bands originate from existing recombination pathways in Ga2O3 rather than from radiative N-related centers. The enhancement in defect-related luminescence in N-doped β-Ga2O3 is explained by an increase in the concentration of O vacancies as a result of the compensation of NO acceptors.

Non-invasive and non-destructive characterization of MBE-grown CdZnTe/CdTe superlattice-based dislocation filtering layers

Abstract: We report on the structural and optical properties of heteroepitaxial II–VI CdTe (211)B buffer layers with strained CdZnTe/CdTe superlattice layers, investigated by employing non-destructive methods including high-resolution x-ray diffraction, cathodoluminescence, and photoluminescence spectroscopy. X-ray diffraction reciprocal space mapping measurements revealed that the superlattice layers are coherently strained, leading to a spread in x-ray double-crystal rocking curve full-width at half-maximum values but better in-plane lattice-matching with HgCdTe. Both cross-sectional cathodoluminescence and photoluminescence measurements confirm the coherent growth of superlattice layers and their dislocation filtering effects. Both these techniques in CdTe layers are found to be well correlated with the dislocation density as determined by etch pit density measurements. The results indicate the potential of these non-destructive methods to be further developed into general-purpose techniques capable of characterizing the defect evolution in semiconductor heteroepitaxy.