Showing papers on "Cathodoluminescence published in 2019"

Electron-beam spectroscopy for nanophotonics.

Abstract: Progress in electron-beam spectroscopies has recently enabled the study of optical excitations with combined space, energy and time resolution in the nanometre, millielectronvolt and femtosecond domain, thus providing unique access into nanophotonic structures and their detailed optical responses. These techniques rely on ~1–300 keV electron beams focused at the sample down to sub-nanometre spots, temporally compressed in wavepackets a few femtoseconds long, and in some cases controlled by ultrafast light pulses. The electrons undergo energy losses and gains (also giving rise to cathodoluminescence light emission), which are recorded to reveal the optical landscape along the beam path. This Review portraits these advances, with a focus on coherent excitations, emphasizing the increasing level of control over the electron wavefunctions and ensuing applications in the study and technological use of optically resonant modes and polaritons in nanoparticles, 2D materials and engineered nanostructures. Spatially resolved electron microscopy techniques, such as cathodoluminescence and electron energy-loss spectroscopy can provide high space, energy and time resolutions for the structural and optical characterization of materials; this Review discusses recent progress and future directions in the field of nanophotonics.

Revealing multiple classes of stable quantum emitters in hexagonal boron nitride with correlated cathodoluminescence, photoluminescence, and strain mapping

Abstract: Single photon emitters (SPEs) in solids have emerged as promising candidates for quantum photonic sensing, communications, and computing. Defects in hexagonal boron nitride (hBN) exhibit high-brightness, room-temperature quantum emission, but their large spectral variability and unknown local structure significantly challenge their technological utility. Here, we directly correlate hBN quantum emission with the material's local strain using a combination of photoluminescence (PL), cathodoluminescence (CL) and nano-beam electron diffraction. Across 40 emitters and 15 samples, we observe zero phonon lines(ZPLs) in PL and CL ranging from 540-720 nm. CL mapping reveals that multiple defects and distinct defect species located within an optically-diffraction-limited region can each contribute to the observed PL spectra. Local strain maps indicate that strain is not required to activate the emitters and is not solely responsible for the observed ZPL spectral range. Instead, four distinct defect classes are responsible for the observed emission range. One defect class has ZPLs near 615 nm with predominantly matched CL-PL responses; it is not a strain-tuned version of another defect class with ZPL emission centered at 580 nm. A third defect class at 650 nm has low visible-frequency CL emission; and a fourth defect species centered at 705 nm has a small, ~10 nm shift between its CL and PL peaks. All studied defects are stable upon both electron and optical irradiation. Our results provide an important foundation for atomic-scale optical characterization of color centers, as well as a foundation for engineering defects with precise emission properties.

Electron Beam Spectroscopy for Nanophotonics

Abstract: Progress in electron-beam spectroscopies has recently enabled the study of optical excitations with combined space, energy and time resolution in the nanometer, millielectronvolt and femtosecond domain, thus providing unique access into nanophotonic structures and their detailed optical responses. These techniques rely on $\approx$ 1-300 keV electron beams focused at the sample down to sub-nanometer spots, temporally compressed in wavepackets a few femtoseconds long, and in some cases controlled by ultrafast light pulses. The electrons undergo energy losses and gains, also giving rise to cathodoluminescence light emission, which are recorded to reveal the optical landscape along the beam path. This review portraits these advances, with a focus on coherent excitations, emphasizing the increasing level of control over the electron wave functions and ensuing applications in the study and technological use of optically resonant modes and polaritons in nanoparticles, 2D materials and engineered nanostructures.

Recombination and bandgap engineering in CdSeTe/CdTe solar cells

Abstract: Selenium compositional grading in CdTe-based thin-film solar cells substantively improves carrier lifetime and performance. However, where and how recombination lifetime improves has not been studied significantly. Here, we deposit a CdSexTe1−x/CdTe bilayer on MgZnO/SnO2/glass, which achieves a short-circuit current density greater than 28 mA/cm2 and carrier lifetimes as long as 10–20 ns. We analyze the grain structure, composition, and recombination through the thickness of the absorber using electron backscatter diffraction, Auger-electron spectroscopy, cathodoluminescence spectrum imaging, and time-resolved photoluminescence microscopy. Despite small CdSeTe grains near the pn-junction and significantly larger CdTe grains in the rest of the film, both time-resolved photoluminescence and cathodoluminescence reveal that the carrier lifetime in CdSeTe alloy regions is longer than in CdTe regions. The results indicate that Se both passivates grain boundaries and improves grain-interior carrier lifetime. However, these effects occur only where there is significant alloying, which is important for bandgap engineering.

Fe-TiO2 Nanoparticles Synthesized by Green Chemistry for Potential Application in Waste Water Photocatalytic Treatment

Abstract: Anatase TiO2 nanoparticles doped with iron ions have been synthesized via the green chemistry method using aqueous extract of lemongrass (Cymbopogon citratus) obtained from Soxhlet extraction and doped by wet impregnation. The TiO2 anatase phase has been doped with Fe3+ (0.05, 0.075, and 0.1 Fe3+ : Ti molar ratio) at 550°C and 350°C, respectively. The scanning electron microscopy with energy-dispersive X-ray (SEM-EDS) shows nanoparticle clusters and efficiencies of impregnations between 66.5 and 58.4% depending on the theoretical dopant amount. The electron transmission microscopy (TEM) reveals final particle sizes ranging between 7 and 26 nm depending on the presence or not of the dopant. The cathodoluminescence (CL) and photoluminescence (PL) studies of the doped and undoped nanoparticles show a luminescence signal attributed to surface oxygen vacancies (visible CL emission 380–700 nm and PL emission 350–800 nm); additionally, a decrease in emission intensity is observed due the inhibition of the recombination of the photogenerated electron-holes pairs; moreover, nanopowders were analyzed by UV-Vis spectrophotometry of diffuse reflectance, and the absorption edge of the Fe-TiO2 in comparison to undoped TiO2 is extended greatly toward the visible light. The six bands (A1g + 2B1g + 3Eg) found by Raman spectroscopy and the x-ray diffraction pattern (XRD) confirm that synthesized TiO2 is only anatase phase, which is commonly used as a catalyst in waste water treatment, specifically in heterogeneous photocatalytic processes.

On the origins of the green luminescence in the "zero-dimensional perovskite" Cs4PbBr6: conclusive results from cathodoluminescence imaging.

Abstract: There is great interest in the use of highly-efficient all-inorganic halide perovskites CsnPbBr2+n for optoelectronic applications. There however remains considerable debate as to the origins of the green luminescence in the zero-dimensional phase of the perovskite Cs4PbBr6, with theories suggesting it originates either from defects in the Cs4PbBr6 lattice or CsPbBr3 impurities/inclusions. The confusion has arisen due to the two phases being miscible and typically co-existing. Moreover, low impurity levels of CsPbBr3 in Cs4PbBr6 are difficult to detect by XRD measurements, yet have much stronger photoluminescence than bulk CsPbBr3 that exhibits quenching, further contributing to the confusion as to the origins of the green photoluminescence. With the rise of significant debate and misconceptions, we provide conclusive evidence that the green emission from Cs4PbBr6 is indeed due to nanocrystalline CsPbBr3 impurities. This is demonstrated by undertaking cathodoluminescence and EDX measurements on samples prepared mechanochemically by ball-milling. Cathodoluminescence imaging clearly shows the presence of small crystals embedded in/or between larger crystallites of Cs4PbBr6 and they emit around 520 nm. EDX shows that the smaller crystal inclusions have a Pb : Br ratio that is approximately 2 times higher, confirming the CsPbBr3 phase, which has the expected size-dependent shift to shorter wavelengths (about 528 to 515 nm). These studies make significant inroads into understanding these lead halide perovskites for their use in a variety of optoelectronic and photovoltaic applications.

Vertical GaN Nanowires and Nanoscale Light-Emitting-Diode Arrays for Lighting and Sensing Applications

Abstract: For various lighting and monolithic sensor systems application, vertically aligned three-dimensional (3D) gallium nitride (GaN)- and indium gallium nitride (InGaN)/GaN-based LED nanowire arrays with sub-200 nm feature sizes (down to 35 nm) were fabricated using a nanosphere lift-off lithography (NSLL) technique combined with hybrid top-down etching (i.e., inductively coupled plasma dry reactive ion etching (ICP-DRIE) and wet chemical etching). Owing to the lithographic opening and well-controlled surface functionalization prior to the polystyrene nanosphere (PN) deposition, vertical GaN nanowire arrays with an area density of 9.74 × 108 cm–2 and an aspect ratio of >10 could be realized in a specified large area of 1.5 × 1.5 mm2. Optoelectrical characteristics of the nanoLEDs were further investigated in cathodoluminescence (CL) measurements, in which multiquantum well (MQW) shows a clear CL-emission at a wavelength of 465 nm. Thus, using NSLL to manufacture low-cost but highly ordered 3D GaN-based nanowir...

Imaging of Plasmonic Chiral Radiative Local Density of States with Cathodoluminescence Nanoscopy.

Abstract: Chiral light-matter interactions as an emerging aspect of quantum optics enable exceptional physical phenomena and advanced applications in nanophotonics through the nanoscale exploitation of photo...

Crystal structure, vibrational spectroscopy and optical properties of a one-dimensional organic-inorganic hybrid perovskite of [NH3CH2CH(NH3)CH2]BiCl5.

Abstract: In this work the crystal structure by single crystal X-ray measurement and optical properties of 1D propane-1,2-di­ammonium penta­chlorobis­muthate [NH3CH2CH(NH3)CH3]BiCl5 organic–inorganic hybrid perovskite are presented. It is prepared by mixing ethano­lic solution of equimolar ratios (1:1) of its basic components. The title compound crystallized in the noncentrosymmetric orthorhombic space group Pca21 with Z = 8 molecules per unit cell. The unit-cell parameters are a = 19.8403 (7) A, b = 6.3303 (2) A, c = 19.0314 (7) A. The vibrational spectra are studied by Raman and infrared spectroscopy. The optical properties show a strong absorption in the ultraviolet region, the band gap energy Eg is found to be 3.15 eV. Cathodoluminescence measurements are also discussed.

Luminescence reveals variations in local structural order of calcium carbonate polymorphs formed by different mechanisms.

Abstract: In nature, calcium carbonate (CaCO3) in the form of calcite and aragonite nucleates through different pathways including geogenic and biogenic processes. It may also occur as pyrogenic lime plaster and laboratory-precipitated crystals. All of these formation processes are conducive to different degrees of local structural order in CaCO3 crystals, with the pyrogenic and precipitated forms being the least ordered. These variations affect the manner in which crystals interact with electromagnetic radiation, and thus formation processes may be tracked using methods such as X-ray diffraction and infrared spectroscopy. Here we show that defects in the crystal structure of CaCO3 may be detected by looking at the luminescence of crystals. Using cathodoluminescence by scanning electron microscopy (SEM-CL) and laser-induced fluorescence (LIF), it is possible to discern different polymorphs and their mechanism of formation. We were thus able to determine that pyrogenic calcite and aragonite exhibit blue luminescence due to the incorporation of distortions in the crystal lattice caused by heat and rapid precipitation, in agreement with infrared spectroscopy assessments of local structural order. These results provide the first detailed reference database of SEM-CL and LIF spectra of CaCO3 standards, and find application in the characterization of optical, archaeological and construction materials.

Carrier localization structure combined with current micropaths in AlGaN quantum wells grown on an AlN template with macrosteps

Abstract: The microscopic structural and optical characteristics of AlGaN-based light-emitting diodes grown on AlN templates with macrosteps were evaluated. Cross-sectional transmission electron microscopy in the high-angle annular dark field scanning mode and microscopic energy dispersive X-ray spectroscopy reveal that the AlGaN cladding layer under the AlGaN quantum wells (QWs) has microscopic compositional modulations originating from the macrosteps at the AlN template surface. The Ga-rich oblique zones in the cladding layer likely behave as current micropaths. These micropaths are connected to the carrier localization structure, which is formed by the modulation of both the well widths and the compositions of the QWs. In-plane spatially-resolved cathodoluminescence (CL) spectroscopy indicated significant inhomogeneity of the CL characteristics: the brighter emission with a lower peak photon energy confirms the existence of the carrier localization structure in the QWs. Carrier localization in the QWs along with the current micropaths in the AlGaN cladding layer appears to increase the external quantum efficiency of AlGaN LEDs.

Growth and characterization of β-Ga2O3 thin films on different substrates

Abstract: β-Ga2O3 thin films were grown on the substrates of sapphire, GaN, and single crystals of β-Ga2O3, using plasma-assisted molecular beam epitaxy. By varying deposition conditions, pure-phase epitaxial β-Ga2O3 thin films were obtained, and the crystal quality of the as-grown films was optimized. A systematic characterization and a detailed analysis were performed on the films, including the nucleation process, surface morphology, crystal quality, thermal stability, as well as electrical and optical properties. Optical absorption was investigated using photothermal deflection spectroscopy, which provides detailed information about sub-gap optical absorption. Photocurrent measurements indicated a pronounced persistent photo-conductivity of β-Ga2O3. A blue-UV emission with an energy of 3–3.5 eV was observed by cathodoluminescence spectroscopy. The Fermi level position of the as-grown film was determined based on temperature-dependent electrical conductivity measurements. It is proposed that oxygen vacancies in the film form a defect band at around E c-0.8 eV that pins the Fermi level and is related to the observed photocurrent and cathodoluminescence characteristics.

Strong Cathodoluminescence and Fast Photoresponse from Embedded CH3NH3PbBr3 Nanoparticles Exhibiting High Ambient Stability.

Abstract: This study presents a comprehensive analysis of the strong cathodoluminescence (CL), photoluminescence (PL), and photoresponse characteristics of CH3NH3PbBr3 nanoparticles (NPs) embedded in a mesoporous nanowire (NW) template. Our study revealed a direct correlation between the CL and PL emissions from the perovskite NPs (Per NPs), for the first time. Per NPs are fabricated by a simple spin-coating of a perovskite precursor on the surface of metal-assisted chemically etched mesoporous Si NW arrays. The Per NPs confined in the mesopores show blue-shifted and enhanced CL emission as compared to the bare perovskite film, while the PL intensity of Per NPs is dramatically high compared to that of their bulk counterpart. A systematic analysis of the CL/PL spectra reveals that the quantum confinement effect and ultralow defects in Per NPs are mainly responsible for the enhanced CL and PL emissions. Low-temperature PL and time-resolved PL analysis confirm the high exciton binding energy and radiative recombination in Per NPs. The room temperature PL quantum yield of the Per NP film on the NW template was found to be 40.5%, while that of Per film was 2.8%. The Per NPs show improved ambient air stability than the bare film due to the protection provided by the dense NW array, since a dense NW array can slow down the lateral diffusion of oxygen and water molecules in Per NPs. Interestingly, the Si NW/Per NP junction shows superior visible light photodetection and the prototype photodetector shows a high responsivity (0.223 A/W) with response speeds of 0.32 and 0.28 s of growth and decay in photocurrent, respectively, at 2 V applied bias, which is significantly better than the reported photodetectors based on CH3NH3PbBr3 nanostructures. This work demonstrates a low-cost fabrication of CH3NH3PbBr3 NPs on a novel porous NW template, which shows excellent photophysical and optoelectronic properties with superior ambient stability.

Mechanism analysis of a narrow-band ultra-bright green phosphor with its prospect in white light-emitting diodes and field emission displays

Abstract: In the current study, aiming to get brighter green phosphors for LEDs and FEDs, Ce3+ and Tb3+ were successfully co-doped into the newly discovered matrix, [Mg1.25Si1.25Al2.5]O3N3 through solid-state reaction. The sample presents a broad excitation band covering (n-)UV region from 240 to 420 nm and a sharp green Tb3+ characteristic emission with negligible Ce3+ emission. The efficient energy transfer mechanism from Ce3+ to Tb3+ has been calculated to be dipole–dipole interaction, which leads to a 13% higher brightness at its optimum excitation than the green phosphor of BaSrSiO4:Eu2+ commodity. The gentle thermal quenching trend and relatively high quantum yield of the sample is also remarkable. A LED lamp fabricated by the sample and the commercial phosphors demonstrated better performances than the traditional one with a color rendering index of 84.5 and CIE coordinate of (0.3190, 0.3290). Additionally, the cathodoluminescence spectra of the sample display an outstanding unsaturated peak intensity and anti-degradation as well. The results indicate that [Mg1.25Si1.25Al2.5]O3N3:Ce3+,Tb3+ could be considered as a promising green-emitting material for white LEDs and FEDs application.

Vacancy cluster in ZnO films grown by pulsed laser deposition

Abstract: Undoped and Ga-doped ZnO films were grown on c-sapphire using pulsed laser deposition (PLD) at the substrate temperature of 600 °C. Positron annihilation spectroscopy study (PAS) shows that the dominant VZn-related defect in the as-grown undoped ZnO grown with relative low oxygen pressure P(O2) is a vacancy cluster (most likely a VZn-nVO complex with n = 2, 3) rather than the isolated VZn which has a lower formation energy. Annealing these samples at 900 °C induces out-diffusion of Zn from the ZnO film into the sapphire creating the VZn at the film/sapphire interface, which favors the formation of vacancy cluster containing relatively more VZn. Increasing the P(O2) during growth also lead to the formation of the vacancy cluster with relatively more VZn. For Ga-doped ZnO films, the oxygen pressure during growth has significant influence on the electron concentration and the microstructure of the VZn-related defect. Green luminescence (GL) and yellow luminescence (YL) were identified in the cathodoluminescence study (CL) study, and both emission bands were quenched after hydrogen plasma treatment. The origin of the GL is discussed.

Study on Dislocation Annihilation Mechanism of the High-Quality GaN Grown on Sputtered AlN/PSS and Its Application in Green Light-Emitting Diodes

Abstract: GaN was grown on the sputtered AlN/patterned sapphire substrate under two growth modes by metal–organic chemical vapor deposition, which was named as “rising tide” and “tsunami” growth modes, respectively, due to different characteristics of the GaN growth process. High-quality GaN epilayer was obtained under “tsunami” growth mode, and the full-width at half-maximums of GaN (002)/(102) high-resolution X-ray diffraction rocking curves were 58/90 arcsec. The green InGaN/GaN light-emitting diodes fabricated on GaN under “tsunami” growth mode exhibited both higher light output power and external quantum efficiency. By monitoring the GaN films at different growth stages using the scanning electron microscope and the transmission electron microscope as well as cathodoluminescence, the dislocation annihilation mechanisms were researched. Under “tsunami” growth mode, GaN grew into the shape of a truncated pyramid that promoted dislocations originated from flat area bend toward the inclined planes, and it was noteworthy that the propagation of dislocations in grains on the conical surface was inhibited. While under “rising tide” growth mode, the dislocations on the conical surface had chances to extend.

Mapping the Origins of Luminescence in ZnO Nanowires by STEM-CL.

Abstract: In semiconductor nanowires, understanding both the sources of luminescence (excitonic recombination, defects, etc.) and the distribution of luminescent centers (be they uniformly distributed, or concentrated at structural defects or at the surface) is important for synthesis and applications. We develop scanning transmission electron microscopy–cathodoluminescence (STEM-CL) measurements, allowing the structure and cathodoluminescence (CL) of single ZnO nanowires to be mapped at high resolution. Using a CL pixel resolution of 10 nm, variations of the CL spectra within such nanowires in the direction perpendicular to the nanowire growth axis are identified for the first time. By comparing the local CL spectra with the bulk photoluminescence spectra, the CL spectral features are assigned to internal and surface defect structures. Hyperspectral CL maps are deconvolved to enable characteristic spectral features to be spatially correlated with structural features within single nanowires. We have used these maps...

Non-radiative recombination at dislocations in InAs quantum dots grown on silicon

Abstract: We study the impact of misfit dislocations on the luminescence from InAs quantum dots (QDs) grown on Si substrates. Electron channeling contrast imaging is used together with cathodoluminescence mapping to locate misfit dislocations and characterize the resulting nonradiative recombination of carriers via near-infrared light emission profiles. With a 5 kV electron beam probe, the dark line defect width due to a typical misfit dislocation in a shallow QD active layer is found to be approximately 1 μm, with a 40%–50% peak emission intensity loss at room temperature. Importantly, we find that at cryogenic temperatures, the dislocations affect the QD ground state and the first excited state emission significantly less than the second excited state emission. At the same time, the dark line defect width, which partially relates to carrier diffusion in the system, is relatively constant across the temperature range of 10 K–300 K. Our results suggest that carrier dynamics in the QD wetting layer control emission intensity loss at dislocations, and that these defects reduce luminescence only at those temperatures where the probability of carriers thermalizing from the dots into the wetting layer becomes significant. We discuss the implications of these findings toward growing dislocation-tolerant, reliable quantum dot lasers on silicon.

Spatial Resolution of Coherent Cathodoluminescence Super-Resolution Microscopy.

Abstract: We investigate the nanoscale excitation of Ag nanocubes with coherent cathodoluminescence imaging spectroscopy (CL) to resolve the factors that determine the spatial resolution of CL as a deep-subwavelength imaging technique. The 10-30 keV electron beam coherently excites localized plasmons in 70 nm Ag cubes at 2.4 and 3.1 eV. The radiation from these plasmon modes is collected in the far-field together with the secondary electron intensity. CL line scans across the nanocubes show exponentially decaying tails away from the cube that reveal the evanescent coupling of the electron field to the resonant plasmon modes. The measured CL decay lengths range from 8 nm (10 keV) to 12 nm (30 keV) and differ from the calculated ones by only 1-3 nm. A statistical model of electron scattering inside the Ag nanocubes is developed to analyze the secondary electron images and compare them with the CL data. The Ag nanocube edges are derived from the CL line scans with a systematic error less than 3 nm. The data demonstrate that CL probes the electron-induced plasmon fields with nanometer accuracy.

Effect of AlGaN undershell on the cathodoluminescence properties of coaxial GaInN/GaN multiple-quantum-shells nanowires.

Abstract: Coaxial GaInN/GaN multiple-quantum-shells (MQSs) nanowires (NWs) were grown on an n-type GaN/sapphire template employing selective growth by metal–organic chemical vapour deposition (MOCVD). To improve the cathodoluminescence (CL) emission intensity, an AlGaN shell was grown underneath the MQS active structures. By controlling the growth temperature and duration, an impressive and up to 11-fold enhancement of CL intensity is achieved at the top area of the GaInN/GaN MQS NWs. The spatial distribution of Al composition in the AlGaN undershell was assessed as a function of position along the NW and analysed by energy-dispersive X-ray measurement and CL characterisation. By introducing an AlGaN shell underneath GaInN/GaN MQS, the diffusion of point defects from the n-core to MQS is effectively suppressed because of the lower formation energy of vacancies-complexes in AlGaN in comparison to GaN. Moreover, the spatial distribution of Al and In was attributed to the insufficient delivery of gas precursors to the bottom of the NWs and the anisotropy diffusion on the nonpolar m-planes. This investigation can shed light on the effect of the AlGaN undershell on improving the emission efficiency of NW-based white and micro-light-emitting diodes (LEDs).

Electron-induced state conversion in diamond NV centers measured with pump-probe cathodoluminescence spectroscopy

Abstract: Nitrogen-vacancy (NV) centers in diamond are reliable single-photon emitters, with applications in quantum technologies and metrology. Two charge states are known for NV centers: NV$^0$ and NV$^-$, with the latter being mostly studied due to its long electron spin coherence time. Therefore, control over the charge state of the NV centers is essential. However, an understanding of the dynamics between the different states still remains challenging. Here, conversion from NV$^-$ to NV$^0$ due to electron-induced carrier generation is shown. Ultrafast pump-probe cathodoluminescence spectroscopy is presented for the first time, with electron pulses as pump, and laser pulses as probe, to prepare and read out the NV states. The experimental data is explained with a model considering carrier dynamics (0.8 ns), NV$^0$ spontaneous emission (20 ns) and NV$^0$ $\rightarrow$NV$^-$ back transfer (500 ms). The results provide new insights into the NV$^-$$\leftrightarrow$NV$^0$ conversion dynamics, and into the use of pump-probe cathodoluminescence as a nanoscale NV characterization tool.