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At least 19 records

Evaluating Brightness and Stability of Cathodoluminescence from Colloidal Semiconductor Nanocrystals

Cathodoluminescence offers promise as a technique for correlation of atomic structure with electronic structure at the level of individual nanoparticles or even defects, with the ability to analyze complex nanostructures at length-scales far below those typically available to optical spectroscopy. Unlike other forms of electron microscopy, cathodoluminescence offers direct insights into the electronic structure of the visualized sample. Despite reports more than 10 years ago of individual nanoparticle cathodoluminescence, effective cathodoluminescence collection from colloidal semiconductor materials is relatively rare and remains challenging due to the instability of materials under the conditions of electron beam irradiation. In this work, to clarify the roadblocks for cathodoluminescence analysis of colloidal nanocrystals, we attempt a comprehensive study of the cathodoluminescence properties of semiconductor quantum shells, which have a thin concentric CdSe shell surrounding CdS nanoparticles, then surrounded by a further concentric CdS shell. These same materials were recently demonstrated to show promising scintillation performance in radioluminescence measurements, including high brightness (up to 100 ph/keV) and excellent durability. Comparative quantum yield measurements are designed to assess the brightness of semiconductor nanocrystal films, which show that the quantum shells are much less bright under electron irradiation compared to X-ray photons. Instability of CL emission is assigned to charging effects on the samples—and not thermal effects—through a series of voltage, current, dwell time, and atmospheric pressure experiments.

cathodoluminescence↗

A Review and Perspective on Cathodoluminescence Analysis of Halide Perovskites

Halide perovskite solar cells have achieved a certified efficiency of 25.2%, surpassing CdTe and CuInGaSe 2 , which have long been regarded as the most-efficient thin-film photovoltaic materials. As this exciting class of materials continues to mature, researchers will require characterization techniques capable of exposing the interplay among structure, chemistry, and optoelectronic properties to inform processing strategies and increase both device efficiencies and long-term stability. Cathodoluminescence microscopy is an ideal technique to provide such information due to the high spatial resolution and robust optical information acquired. Here, the current body of work related to cathodoluminescence analysis of halide perovskite materials for optoelectronic applications is surveyed. This review demonstrates how cathodoluminescence can monitor degradation due to environmental stressors, phase segregation resulting from material processing, and other halide perovskite-centric material issues. A persistent concern associated with e-beam-based analysis of halide perovskites is what effect the electron beam has on the material properties being probed. Addressing this, a detailed discussion is provided on the origin of the cathodoluminescence signal and a review of studies focused on revealing changes in the properties of halide perovskites resulting from e-beam excitation. Finally, a perspective on future opportunities to expand the role of cathodoluminescence analysis for halide perovskites is provided.

14 SOLAR ENERGY↗

Single Particle Cathodoluminescence Spectroscopy with Sub-20 nm, Electron-Stable Phosphors

Lanthanide-doped nanophosphors have emerged as promising optical labels for high-resolution, "multicolor"electron microscopy. Here, we develop a library of 11 unique lanthanide-doped nanophosphors with average edge lengths of 15.2 ± 2.0 nm (N = 4284). These nanophosphors consist of an electron-stable BaYF5 host lattice doped at 25% atomic concentration with the lanthanides Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , Ce 3+ , Ho 3+ , Er 3+ , Tm 3+ , and Yb 3+ . Under ~100 pA/nm 2 beam beam current in a transmission electron microscope, each nanophosphor species exhibits strong cathodoluminescence spectra with sharp characteristic emission lines for each lanthanide. The bright emission and stability of these nanoparticles enable not only ensemble, but also single-particle cathodoluminescence spectroscopy, which we demonstrate with BaYF 5 :Ln 3+ , where Ln 3+ = Tb 3+ , Ho 3+ , Er 3+ , Sm 3+ , Eu 3+ , or Pr 3+ . Single-particle cathodoluminescence corresponds directly with HAADF intensity across nanoparticles, confirming high spatial localization of the measured cathodoluminescence signal of lanthanide-doped nanophosphors. Furthermore, our synthesis and characterization of sub-20 nm, electron-stable nanophosphors provides a robust material platform to achieve single-molecule labeled correlative cathodoluminescence electron microscopy, a critical foundation for high-resolution correlation of single molecules within the context of cellular ultrastructure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanometer Resolution Structure‐Emission Correlation of Individual Quantum Emitters via Enhanced Cathodoluminescence in Twisted Hexagonal Boron Nitride

Understanding the atomic structure of quantum emitters, often originating from point defects or impuritie, is essential for designing and optimizing materials for quantum technologies such as quantum computing, communication, and sensing. Despite the availability of atomic-resolution scanning transmission electron microscopy and nanoscale cathodoluminescence microscopy, experimentally determining the atomic structure of individual emitters is challenging due to the conflicting needs for thick samples to generate strong cathodoluminescence signals and thin samples for structural analysis. To overcome this challenge, significantly enhanced cathodoluminescence at twisted interfaces is leveraged to achieve sub-nanometer localization precision for the first time in mapping individual quantum emitters in carbon-implanted hexagonal boron nitride. This unprecedent spatial sensitivity, together with correlative electron energy loss spectroscopy quantitative scanning transmission electron microscopy imaging, and first principles density functional theory calculations, enables the identification of the atomic structure of the 440 nm blue emitter in hexagonal boron nitride as a substituted vertical carbon dimer. Building on the atomic structure insights, nanoscale spatially precise creation of blue emitters is demonstrated by electron beam irradiation of carbon-coated hexagonal boron nitride. This advancement in correlating atomic structures with optical properties lays the foundation for a deeper understanding and precise engineering of quantum emitters, significantly advancing the development of cutting-edge quantum information technologies.

2D material↗

Non-perturbative cathodoluminescence microscopy of beam-sensitive materials

Cathodoluminescence microscopy is now a wellestablished and powerful tool for probing the photonic properties of nanoscale materials, but in many cases, nanophotonic materials are easily damaged by the electronbeam doses necessary to achieve reasonable cathodoluminescence signal-to-noise ratios. Two-dimensional materials have proven particularly susceptible to beam-induced modifications, yielding both obstacles to high spatial-resolution measurement and opportunities for beam-induced patterning of quantum photonic systems. Here pan-sharpening techniques are applied to cathodoluminescence microscopy in order to address these challenges and experimentally demonstrate the promise of pan-sharpening for minimally-perturbative high-spatial-resolution spectrum imaging of beam-sensitive materials.

2D materials↗

Rare-earth-doped electrospun scheelite CaWO 4 nanofibers with excitation-dependent photoluminescence and high-linearity cathodoluminescence for ratiometric UV wavelength and radiation sensors

Scheelite structured AWO 4 compounds (A = Ba, Ca, Pb and Sr) are efficient hosts for rare-earth dopants. In this work, high-aspect-ratio AWO 4 (A = Ba, Ca, Pb and Sr) nanofibers, doped with 5 mol.% Tb and 5 mol.% Eu on A site, were synthesized using a sol-gel electrospinning technique, and their performances as a ratiometric sensor for the detection of UV light wavelength were comparatively studied. High-resolution electron microscopy reveals the presence of nanosized grains composing the nanofibers. The AWO 4 :5Tb-5Eu nanofibers exhibit strong characteristic photoluminescence (PL) and cathodoluminescence (CL) emission from both Tb 3+ and Eu 3+ ions. In the case of CaWO 4 lattice, the emission intensity ratio of Tb 3+ /Eu 3+ is found to show a linear relationship with the excitation wavelength in the tested range of 240–330 nm, with efficient energy transfer from host lattice to rare-earth ions. However, a similar result is not observed in other scheelite structured BaWO 4 , PbWO 4 , and SrWO 4 nanofibers. Here, the unique PL emission characteristics of CaWO 4 :5Tb-5Eu under different UV excitation wavelengths are due to its unique excitation band. This study reveals a potential new application of CaWO 4 :5Tb-5Eu as a fluorescent probe for UV wavelength detection. Additionally, the CL intensities from CaWO 4 :5Tb-5Eu nanofibers exhibit highly linear dependences on the applied voltage and current without saturation, which can be utilized for radiation detection.

36 MATERIALS SCIENCE↗

Nanoscale depth and lithiation dependence of V 2 O 5 band structure by cathodoluminescence spectroscopy

Vanadium pentoxide (V 2 O 5 ) is a very well-known cathode material that has attracted considerable interest for its potential use in solid-state lithium-ion batteries. We pioneer the use of depth-resolved cathodoluminescence spectroscopy (DRCLS) to monitor the changes in the electronic structure of lithiated V 2 O 5 from the free surface to the thin film bulk several hundred nm below as a function of lithiation. DRCLS measurements of V 2 O 5 interband transitions are in excellent agreement with density functional theory (DFT) calculations. The direct measure of V 2 O 5 's electronic band structure as a function of lithiation level provided by DRCLS can help inform solid-state battery designs to further withstand degradation and increase efficiency. In particular, these unique electrode measurements may reveal physical mechanisms of lithiation that change V 2 O 5 irreversibly, as well as methods to mitigate them in solid-state batteries.

25 ENERGY STORAGE↗

Quantitative assessment of selenium diffusion and passivation in CdSeTe solar cells probed by spatially resolved cathodoluminescence

The introduction of selenium in CdSeTe/CdTe solar cells has led to improved device performances attributed to the passivation of bulk defects. In this work, high-resolution cathodoluminescence experiments are performed on a series of CdSeTe/CdTe thin films with different Se concentrations to quantify the mechanisms and the passivation role of Se. We demonstrate a universal dependence between the Se concentration and the radiative efficiency and a ten-fold enhancement of the luminescence between CdTe and CdSe 0.4 Te 0.6 . Raw luminescence maps are converted into maps of the Se concentration, revealing its graded profile within the stack. We demonstrate the diffusion of Se along CdTe grain boundaries induced by the cadmium chloride annealing treatment and determine the diffusion coefficients, which are more than eight times higher at grain boundaries than in grain interiors. These results provide microscopic insights into the distribution of Se and its impact on the passivation of CdSeTe/CdTe solar cells.

14 SOLAR ENERGY↗

Electric field dependence of nanoscale cathodoluminescence inside Cr doped β-Ga 2 O 3 interfaces

Chromium (Cr) is a common impurity in β-Ga 2 O 3 crystals, where its characteristic R1 and R2 luminescence lines are susceptible to both the host crystal field and externally applied fields. Here, in this work, we demonstrate that the Cr cathodoluminescence (CL) quenches toward the bulk of the crystal but enhances with applied reverse bias, reflecting the effect of free carrier depletion with increasing electric field. Furthermore, we illustrate that the R1/R2 CL intensity ratio, measured as the integrated area ratio of R1 to R2, can be used as a direct probe of the electric field in a Ni-β-Ga 2 O 3 : Cr Schottky diode. This optical calibration method provides a complementary approach to conventional C–V and I–V measurements for determining electric field strength in the depletion region of β-Ga 2 O 3 -based Schottky diodes and can be extended to other semiconductors and multilayer device structures.

36 MATERIALS SCIENCE↗

Imaging CdCl 2 defect passivation and formation in polycrystalline CdTe films by cathodoluminescence

Polycrystalline thin-film solar cells are attractive for low-cost photovoltaics, but their efficiencies are hindered by material quality issues. State-of-the-art CdTe solar cells use CdCl 2 annealing treatments whose effects are still being discovered at a fundamental level. Here, a series of CdTe samples with different annealing temperatures is investigated with high-resolution hyperspectral cathodoluminescence mapping measured at both room temperature and low temperature on the same microscopic areas. A statistical analysis over a large number of grains is combined with a local analysis at grain boundaries. The results elucidate the dynamic interplay between grain boundary and intragrain defect passivation and formation, in the midst of grain growth. The CdCl 2 annealing initially contributes to an increase of the grain size and the passivation of both grain boundaries and grain interiors, increasing the overall luminescence and diffusion length. For higher annealing temperatures, a further increase of grain size is counterbalanced by the rise of bulk defects. The results illustrate the tradeoffs that lead to an optimal annealing temperature, as well as new methods for understanding defect passivation and creation in thin film solar cells.

14 SOLAR ENERGY↗

Spatially and Spectrally Resolved Defects in Polycrystalline CdTe Thin Films Revealed by Quantitative Cathodoluminescence

Increasing the grain size is a potential strategy to reduce grain-boundary recombination and improve performance of thin-film solar cells. Here, CdTe thin films with a range of grain sized were produced by varying the CdC1 2 post-deposition treatment temperature. We use high-resolution cathodoluminescence (CL) microscopy to study recombination and shallow defect levels in detail. Intensities from room temperature CL maps were compared across samples. We find that the CL intensity initially increases with grain size, as expected, but then plateaus as the grain size is increased further. The plateau is correlated with a decrease in the characteristic length-related to the carrier diffusion length-determined from CL intensity profiles near grain boundaries. In addition, low-temperature CL measurements demonstrate the evolution of the defect levels with CdC1 2 temperature.

cadmium telluride thin films↗

Depth-resolved cathodoluminescence and surface photovoltage spectroscopies of gallium vacancies in β-Ga 2 O 3 with neutron irradiation and forming gas anneals

The gallium vacancy is one of the dominant native point defects in β-Ga 2 O 3 , one that, together with its complexes, can have a major effect on free carrier densities and transport in this wide bandgap semiconductor. We used a combination of depth-resolved cathodoluminescence spectroscopy and surface photovoltage spectroscopy to identify the optical and energy-level properties of these defects as well as how their defect densities and spatial distributions vary with neutron irradiation and temperature-dependent-forming gas anneals. These studies reveal optical signatures that align closely with theoretical energy-level predictions. Likewise, our optical techniques reveal variations in these defect densities that are consistent with hydrogen passivation of gallium vacancies as a function of temperature and depth from the free Ga 2 O 3 surface. These techniques can help guide the understanding and control of dominant native point defects in Ga 2 O 3 .

42 ENGINEERING↗

Hyperspectral Cathodoluminescence of Bastnäsite at the Mountain Pass Mine, USA: Implications for REE Mineralisation and Mining

This study uses micro-analyses including hyperspectral cathodoluminescence to image and obtain mineral spectral to help evaluate REE deportment via from Mountain Pass Mine in California. It presents the first known CL-based spectra for bastnäsite, new information regarding baryte CL spectra, providing insights on the coeval and spatial relationship between REE, Ba, and S in carbonatite systems. Bastnäsite, baryte, and monazite are often intergrown in both brecciated, “blue ore” samples, and these minerals occur as an apparent intercumulus texture in the dolomite-rich, “white ore” samples. Bastnäsite luminescence is present, but very low compared to baryte in the visible spectrum. Bastnäsite illustrates some textural variability related to its main luminescent peak ~1.4 eV, which is indicative of Nd3+. It also exhibits several other small peaks comprised of multiple activators related to various REE, including Ce3+, Sm3+, Eu3+, and potentially Eu2+. Baryte displays textures of variable complexity but often with darker rims near crystal margins. It luminesces mainly at 1.4-1.52 eV, 2.05 eV, and 3.59-4.08 eV. The 2.05 eV peak is likely attributed to Ag+, but the other peaks are more enigmatic.

58 - GEOSCIENCES↗

Cathodoluminescence of Ultrathin Twisted Ge 1–x Sn x S van der Waals Nanoribbon Waveguides

Ultrathin van der Waals semiconductors have shown extraordinary optoelectronic and photonic properties. Propagating photonic modes make layered crystal waveguides attractive for photonic circuitry and for studying hybrid light-matter states. Accessing guided modes by conventional optics is challenging due to limited spatial resolution and poor out-of-plane far field coupling. Scanning near-field optical microscopy (SNOM) can overcome these issues and can characterize waveguide modes down to tens of nm resolution, albeit for planar samples or nanostructures with moderate height variations. Electron microscopy provides atomic-scale localization also for more complex geometries, and recent advances extended the accessible excitations from interband transitions to phonons. In this work, bottom-up synthesized layered semiconductor (Ge 1-x Sn x S) nanoribbons with axial twist and deep sub-wavelength thickness are demonstrated as a platform for realizing waveguide modes, and cathodoluminescence (CL) spectroscopy is introduced as a tool to characterize them. Combined experiments and simulations show the excitation of guided modes by the electron beam and their efficient detection via photons emitted in the ribbon plane, which enables measuring key properties such as the evanescent field into the vacuum cladding with nanometer resolution. The results identify van der Waals waveguides operating in the infrared and highlight an electron microscopy-based approach for probing complex-shaped nanophotonic structures.

36 MATERIALS SCIENCE↗

Resolving Enhanced Mn 2+ Luminescence near the Surface of CsPbCl 3 with Time-Resolved Cathodoluminescence Imaging

Mn 2+ doping of lead halide perovskites has garnered recent interest because it produces stable orange luminescence in tandem with perovskite emission. In this work, we observe enhanced Mn 2+ luminescence at the edges of Mn 2+ -doped CsPbCl 3 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 Mn 2+ 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. Overall, we suggest that this higher emission is caused by an increased probability of electron-hole recombination on Mn 2+ 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxygen Vacancy Evolution at Li x V 2 O 5 /LiPON Solid State Electrochemical Interfaces Using Depth Resolved Cathodoluminescence Spectroscopy

The formation of oxygen vacancies at buried LiPON/ Li x V 2 O 5 interfaces has been observed on a near-nanometer scale and nondestructively using depth-resolved cathodoluminescence spectroscopy (DRCLS) and interfacial markers. Before electrochemical cycling, as-deposited LiPON/Li x V 2 O 5 exhibits a 1.6 eV defect optical emission, which density functional theory calculations identify as originating from oxygen vacancies. This defect appears first within a few nanometers of the buried LiPON/Li x V 2 O 5 interface without cycling, indicating that spontaneous O diffusion from the Li x V 2 O 5 lattice into LiPON may have caused these interface-localized oxygen vacancy defects. DRCLS measured the intensity and spatial distribution of this oxygen vacancy signal as a function of electrochemical cycling in a LiPON/Li x V 2 O 5 half-cell, showing oxygen vacancy signal increasing and moving deeper into the electrode with increased cycle number. Significant electrochemical irreversibility was also observed, with poor Coulombic efficiency and a 15% drop in capacity over 50 cycles. Theoretical simulations predict that the presence of oxygen vacancies increases the energy barrier for lithium diffusion significantly, indicating that this aggregation of oxygen vacancies could be another battery degradation mechanism accompanying lithiation induced phase changes.

36 MATERIALS SCIENCE↗

Visualizing Electric and Magnetic Field Coupling in Au-Nanorod Trimer Structures via Stimulated Electron Energy Gain and Cathodoluminescence Spectroscopy: Implications for Meta-Atom Imaging

In this work, trimer meta-atoms composed of three gold rods in an equilateral triangular geometry were fabricated, and their near-field plasmonic responses were characterized via electron energy loss (EEL), cathodoluminescence (CL), and stimulated electron energy loss/gain (sEEL/sEEG) spectroscopy. The trimer structure hybridizes into a low-energy mode with all three rods coupling in-phase, which produces a circulating current and thus a magnetic field. The next highest-energy mode consists of two rods coupling out-of-phase and produces a net electric dipole. We investigate the near fields of hybridized magnetic and electric modes via EEL and CL and correlate their spectral characteristics and intensity maps. Then, by changing the length of the trimer rods, we tune the magnetic and electric modes to our laser energy and characterize the excited state via sEEL/sEEG spectroscopy. Exploration of the tilt dependence, relative to the optical source, of the two modes reveals that the electric mode sEEG intensity increases more than the expected sin 2 (θ) dependence of the optical electric field coupling (see the Supporting Information for a detailed description). After correcting for the tail of the close-proximity electric mode, we demonstrate sEEG via coupling of the magnetic component of the optical field to the magnetic meta-atoms, which has the expected cos 2 (θ) tilt dependence. This realization opens the possibility to explore the nanoscale excited-state near-field imaging of other magnetic meta-atom structures.

36 MATERIALS SCIENCE↗