Transmission Electron Energy Loss Spectroscopy Research Articles

Potassium-intercalated bulk HfS2 and HfSe2 : Phase stability, structure, and electronic structure

We have studied potassium-intercalated bulk HfS$_2$ and HfSe$_2$ by combining transmission electron energy loss spectroscopy, angle-resolved photoemission spectroscopy and density functional theory calculations. Calculations of the formation energies and the evolution of the energies of the charge carrier plasmons as a function of the potassium content show that certain, low potassium concentrations $x$ are thermodynamically unstable. This leads to the coexistence of undoped and doped domains if the provided amount of the alkali metal is insufficient to saturate the whole crystal with the minimum thermodynamically stable potassium stoichiometry. Beyond this threshold concentration the domains disappear, while the alkali metal and charge carrier concentrations increase continuously upon further addition of potassium. At low intercalation levels, electron diffraction patterns indicate a significant degree of disorder in the crystal structure. The initial order in the out-of-plane direction is restored at high $x$ while the crystal layer thicknesses expand by 33-36%. Superstructures emerge parallel to the planes which we attribute to the distribution of the alkali metal rather than structural changes of the host materials. The in-plane lattice parameters change by not more than 1%. The introduction of potassium causes the formation of charge carrier plasmons. The observation of this semiconductor-to-metal transition is supported by calculations of the density of states (DOS) and band structures as well as angle-resolved photoemission spectroscopy. The calculated DOS hint at the presence of an almost ideal two-dimensional electron gas at the Fermi level for $x<0.6$. The plasmons exhibit quadratic momentum dispersions which is in agreement with the behavior expected for an ideal electron gas.

Investigation of potassium-intercalated bulkMoS2using transmission electron energy-loss spectroscopy

We have investigated the effect of potassium (K) intercalation on $2H$-MoS$_2$ using transmission electron energy-loss spectroscopy. For K concentrations up to approximately 0.4, the crystals appear to be inhomogeneous with a mix of structural phases and irregular potassium distribution. Above this intercalation level, MoS$_2$ exhibits a $2a \times 2a$ superstructure in the $ab$ plane and unit cell parameters of a = 3.20 $\unicode{x212B}$ and c = 8.23 $\unicode{x212B}$ indicating a conversion from the $2H$ to the $1T'$ or $1T''$ polytypes. The diffraction patterns also show a $\sqrt{3}a \times \sqrt{3}a$ and a much weaker $2\sqrt{3}a \times 2\sqrt{3}a$ superstructure that is very likely associated with the ordering of the potassium ions. A semiconductor-to-metal transition occurs signified by the disappearance of the excitonic features from the electron energy-loss spectra and the emergence of a charge carrier plasmon with an unscreened plasmon frequency of 2.78 eV. The plasmon has a positive, quadratic dispersion and appears to be superimposed with an excitation arising from interband transitions. The behavior of the plasmon peak energy positions as a function of potassium concentration shows that potassium stoichiometries of less than $\sim 0.3$ are thermodynamically unstable while higher stoichiometries up to $\sim 0.5$ are thermodynamically stable. Potassium concentrations greater than $\sim 0.5$ lead to the decomposition of MoS$_2$ and the formation of K$_2$S. The real part of the dielectric function and the optical conductivity of K$_{0.41}$MoS$_2$ were derived from the loss spectra via Kramers-Kronig analysis.

Spin-Orbit Torque in a Perpendicularly Magnetized Ferrimagnetic Tb - Co Single Layer

Spin-orbit torque (SOT) has been studied extensively in a heavy-metal (HM)/ferromagnet (FM) bilayer structure, where a HM is an essential ingredient because a spin current is generated via the spin Hall effect within the HM layer and/or the Rashba-Edelstein effect from the HM/FM interface. Here, we report the observation of SOT in a ferrimagnetic $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ single layer with perpendicular magnetic anisotropy without a HM layer. Using harmonic Hall voltage measurements, we investigate the SOT-induced dampinglike effective field $({B}_{\mathrm{DL}})$ in a $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ layer; the sign of ${B}_{\mathrm{DL}}$ is opposite from that of a $\mathrm{Pt}/\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ bilayer, and the magnitude of ${B}_{\mathrm{DL}}$ increases as the $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ composition approaches its magnetization compensation point. Moreover, we analyze the elemental composition of $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ as a function of film thickness using scanning transmission electron microscopy and electron energy-loss spectroscopy, indicating that the sign and magnitude of the SOT are virtually insensitive to the vertical composition gradient within the $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ layer. Our results demonstrate that the bulk spin-orbit interaction within the $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ layer itself plays a major role in generating SOT in a $\mathrm{Tb}\text{\ensuremath{-}}\mathrm{Co}$ single layer.

Magneto-dielectric effect in relaxor superparaelectric Tb2CoMnO6 film

We report magneto-dielectric properties of partially B-site ordered monoclinic Tb2CoMnO6 double perovskite thin film epitaxially grown by metalorganic aerosol deposition technique. Transmission electron microscopy and electron energy loss spectroscopy mapping shows the presence and distribution of both Co2+ and Co3+ ions in the film, evidencing a partial B-site disorder, which was further confirmed by the observation of reduced saturation magnetization at low temperatures. The ferromagnetic Curie temperature, TC=110 K, is slightly higher as compared to the bulk value (100 K) probably due to an in plane tensile strain. Remarkably, a short range ordering of spins at T*~190 K>>TC was established and assigned to the B-site disorder in the film. Two different dielectric relaxation peaks have been observed; they merge at the same temperature T* of short range spin correlations. Moreover, an unexpected high temperature dipolar relaxor-glass-like transition at T~T* was observed, at which a coupling to short range magnetic correlations results in a 4% magneto-dielectric coupling.

Characterization of He Bubbles in Irradiated Aluminium with High Resolution Transmission Electron Microscopy and Electron Energy Loss Spectroscopy

Characterization of He Bubbles in Irradiated Aluminium with High Resolution Transmission Electron Microscopy and Electron Energy Loss Spectroscopy

The Effect of Pt Loading on Catalytic Activity of Pb0.25@Ptx/C Nanocomposites Toward Ethanol Oxidation.

Here, we study the influence of the Pt loading and the particle size of Pb0.25@Ptx/C catalysts on their specific activity toward ethanol oxidation in acid media. High angle annular dark field-scanning transmission electron microscopy and electron energy loss spectroscopy data indicate the formation of Pb0.25@Ptx/C core-shell structures, which are well dispersed on carbon support, with spherical shapes and small particle sizes (2.9-6.6 nm). Cyclic voltammetry experiments confirm characteristic profiles of polycrystalline Pt for Pb0.25@Ptx/C structures. The specific activity of the catalysts toward ethanol oxidation reaction greatly depends on the Pt content on Pb core, and consequently, depends on the size of the nanoparticles. The optimum activity occurs with the lowest Pt load in the shell and smaller particle size. Enhancements in specific activity result from the higher number of nanoparticles available for the ethanol oxidation reaction and the tensile strain effect of Pt atoms on the surface expanded in Pb0.25@Pt0.75/C. The lower activity observed for the catalysts with loads of 35 and 50% wt. (Pb0.25@Pt1.5 and Pb0.25@Pt2.25/C, respectively) in comparison to Pt/C, could be explain by the larger particle sizes obtained at these catalysts. Moreover, the Pb0.25@Pt0.75/C catalyst has high electrochemical stability and should be more stable in direct ethanol fuel cells systems than monolithic Pt catalysts. This is because the Pt shell in Pb0.25@Pt0.75/C exhibits lower chemical potential (p < 0) than at Pt/C and at the other core-shell catalysts studied; thus, reducing its tendency to dissolve. The developed core-shell nanostructure is thus a potential candidate as high-performance anode catalyst for application in direct ethanol fuel cells.

HRTEM‐EELS cross‐sectional structural analyses of glassy carbon substrate irradiated by platinum ions using a coaxial arc plasma gun

A glassy carbon (GC) substrate was irradiated by Pt ions using a coaxial arc plasma gun in vacuum. The structure of the substrate was studied in the atomic scale using high‐resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) with a thin foil specimen prepared by cross‐sectioning using focused ion beam milling. HRTEM combined with the EELS measurements of the cross‐sectioned sample indicated a disordering of the GC substrate surface and the detection of phenol‐type species, carbon atoms in aliphatic chain molecules, and carboxyl groups, which are considered to have been formed by chemical reaction between the carbon atoms of the GC substrate surface and hydrogen or oxygen atoms. Penetrated Pt atoms were observed inside the GC substrate, and the surface position of the GC substrate was located from the depth profiles of the EELS spectra. STEM‐EELS analyses of a pristine GC substrate without Pt ion irradiation were also conducted for reference.

Fabrication of diamond/Cu direct bonding interface for power device applications

Direct bonding of diamond and Cu was successfully conducted by the surface activated bonding method at room temperature. The structure of the diamond/Cu bonding interface was investigated by transmission electron microscopy and electron energy-loss spectroscopy. The effect of heat treatment temperature on the interface structure was also investigated. A 4-nm-thick damaged layer was formed at the as-bonded interface, and the damaged layer’s thickness decreased with an annealing temperature rise. It was found that the atomic ratio of sp2 bonding in the bonding interface was larger than that of the diamond separated from the interface by approximately 50 nm, which indicates that the damaged layer was composed of amorphous carbon or graphite and diamond. After annealing at 700 °C, a composite layer about 2 nm thick was observed at the interface. There were no nano-voids or micro-cracks observed at the interface with annealing at a temperature as high as 700 °C. These results indicate that the diamond/Cu bonding interface has high thermal stability and can withstand the temperature rise of power devices during operation.

Interstitial Boron Atoms in the Palladium Lattice of an Industrial Type of Nanocatalyst: Properties and Structural Modifications.

It is well-established that the inclusion of small atomic species such as boron (B) in powder metal catalysts can subtly modify catalytic properties, and the associated changes in the metal lattice imply that the B atoms are located in the interstitial sites. However, there is no compelling evidence for the occurrence of interstitial B atoms, and there is a concomitant lack of detailed structural information describing the nature of this occupancy and its effects on the metal host. In this work, we use an innovative combination of high-resolution 11B magic-angle-spinning (MAS) and 105Pd static solid-state NMR nuclear magnetic resonance (NMR), synchrotron X-ray diffraction (SXRD), in situ X-ray pair distribution function (XPDF), scanning transmission electron microscopy-annular dark field imaging (STEM-ADF), electron ptychography, and electron energy loss spectroscopy (EELS) to investigate the B atom positions, properties, and structural modifications to the palladium lattice of an industrial type interstitial boron doped palladium nanoparticle catalyst system (Pd-intB/C NPs). In this study, we report that upon B incorporation into the Pd lattice, the overall face centered cubic (FCC) lattice is maintained; however, short-range disorder is introduced. The 105Pd static solid-state NMR illustrates how different types (and levels) of structural strain and disorder are introduced in the nanoparticle history. These structural distortions can lead to the appearance of small amounts of local hexagonal close packed (HCP) structured material in localized regions. The short-range lattice tailoring of the Pd framework to accommodate interstitial B dopants in the octahedral sites of the distorted FCC structure can be imaged by electron ptychography. This study describes new toolsets that enable the characterization of industrial metal nanocatalysts across length scales from macro- to microanalysis, which gives important guidance to the structure-activity relationship of the system.

Strain-driven lattice distortion and the resultant magnetic properties of La0.7Sr0.3MnO3/BaTiO3 superlattices

We report on the artificial manipulation of interfacial magnetism in the superlattices (SLs) of ([La0.7Sr0.3MnO3]30/[BaTiO3]25)n (1 ≤ n ≤ 10) fabricated by pulsed laser deposition. The thicker 30 uc-La0.7Sr0.3MnO3 and 25 uc-BaTiO3 layers are designed as a single period of SLs in order to eliminate the interaction between two adjacent interfaces that could contribute to a polar phase transition and the corresponding magnetism. We use aberration-corrected scanning transmission electron microscopy and electron energy-loss spectroscopy to demonstrate that epitaxial-strain-driven lattice distortion renders the emergence of divalent Mn at the La0.7Sr0.3MnO3/BaTiO3 interfaces. The saturated magnetization decreases and the magnetic easy axis becomes more in-plane inclined as the interfacial strain of the SLs increases.

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Studies of Hole-Selective Molybdenum Oxide Contacts in Silicon Solar Cells.

In this study, substochiometric hole-selective molybdenum oxide (MoOx) contacts in crystalline silicon (c-Si) solar cells were investigated by a combination of transmission electron microscopy (TEM) and spatially resolved electron energy-loss spectroscopy (SR-EELS). It was observed that a ≈ 4 nm SiOx interlayer grows at the MoOx/c-Si interface during the evaporation of MoOx over a c-Si substrate. SR-EELS analyses revealed the presence of a 1.5 nm diffused MoOx/indium tin oxide (ITO) interface in both as-deposited and annealed samples. Moreover, the presence of a 1 nm thin layer with a lower oxidation state of Mo was detected at the SiOx/MoOx interface in an as-deposited state, which disappears upon annealing. Overall, it was evident that no hole-blocking interlayer is formed at the MoOx/ITO interface during annealing and homogenization of the MoOx layer takes place during the annealing process. Furthermore, device simulations revealed that efficient hole collection is dependent on MoOx work function and that reduction in the work function of MoOx results in loss of band bending and negatively impacts hole selectivity.

Growth behavior of β-Ga2O3 nanowires synthesized by chemical vapor deposition

Gallium oxide (Ga2O3) nanowires deposited on Si substrates were synthesized by chemical vapor deposition (CVD) of Ga powders with assisted catalyzed by nickel chloride (NiCl2). The microstructure of these nanowires was investigated using high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). Four major types of morphology were observed for these Ga2O3 nanomaterials, namely, the particle-fused nanowires, single-crystal nanowires, nanorods and core–shell nanowires. Single crystal and core–shell nanowires were mainly studied. EELS indicated that the amorphous shell was Ga2O3. Because metal catalysts were introduced in the growth process, a vapor-solid (VS) growth mechanism was proposed to explain the single crystal Ga2O3 nanowires.

Emerging Electron Microscopy Techniques for Probing Functional Interfaces in Energy Materials.

Interfaces play a fundamental role in many areas of chemistry. However, their localized nature requires characterization techniques with high spatial resolution in order to fully understand their structure and properties. State-of-the-art atomic resolution or in situ scanning transmission electron microscopy and electron energy-loss spectroscopy are indispensable tools for characterizing the local structure and chemistry of materials with single-atom resolution, but they are not able to measure many properties that dictate function, such as vibrational modes or charge transfer, and are limited to room-temperature samples containing no liquids. Here, we outline emerging electron microscopy techniques that are allowing these limitations to be overcome and highlight several recent studies that were enabled by these techniques. We then provide a vision for how these techniques can be paired with each other and with in situ methods to deliver new insights into the static and dynamic behavior of functional interfaces.

On the thermal stability of mesoporous metal oxide systems decorated with metallic nanoparticles for gas sensing applications

Mesoporous metal oxide systems decorated with metallic nanoparticles are among the most studied functional materials for their applications as chemo-resistive gas sensors. The temperature at which such materials are supposed to operate as gas sensors in real working conditions for an optimum device sensitivity ranges around 150-300oC. In our work, SnO2 mesoporous systems have been prepared by solvothermal methods. As a method for tailoring the chemo-resistive properties, the obtained mesoporous matrix has been further decorated with metallic Fe nanoparticles by wet spraying methods. The as-prepared systems have been extensively investigated by analytical transmission electron microscopy using a JEOL ARM200F instrument equipped with X-ray Energy Dispersive and Electron Energy Loss spectrometers (EDS/EELS). Our work has been focused on the morphological and structural aspects of the above mentioned system under the influence of in-situ heating up to 550oC (a meaningful temperature from the point of view of sample preparation). The morpho-structural evolution with temperature has been emphasized by High Resolution Transmission Electron Microscopy (HRTEM), Selected Area Electron Diffraction (SAED), Scanning Transmission Electron Microscopy (STEM) and Electron Energy Loss Spectroscopy Spectrum Imaging (EELS-SI).

STEM‐EELS analysis of the interface structures of composite ASS‐LIB electrodes fabricated via aerosol deposition

AbstractAll‐solid‐state (ASS) lithium‐ion batteries (LIBs) are conventionally fabricated by sintering the component materials at high temperatures. However, interdiffusion between the two phases can give rise to problematic interfacial chemical compounds; therefore, an alternative fabrication method such as aerosol deposition (AD), which works near room temperature, is highly desirable in the ASS‐LIB research field. Herein, we examined the nanometric interface structures of composite ASS‐LIB electrodes fabricated using an AD method, with a particular focus on the structures of Li+‐conductive glass‐ceramic solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 (LATP), which we analyzed using a non‐negative matrix factorization technique. We applied this technique to datasets obtained by combined scanning transmission electron microscopy and electron energy loss spectroscopy. The interface structure of a nonannealed composite could not be explained by the main crystal phase of pristine LATP particles or their surface structure, which should reflect a deposition process specific to the AD method. A composite annealed at 400°C exhibited an LATP/LCO interface structure, providing superior contact and possibly improving the electrochemical properties of the ASS‐LIB composite accordingly.

Optical properties of meteoric smoke analogues

Abstract. Accurate determination of the optical properties of analogues for meteoric smoke particles (MSPs), which are thought to be composed of iron-rich oxides or silicates, is important for their observation and characterization in the atmosphere. In this study, a photochemical aerosol flow system (PAFS) has been used to measure the optical extinction of iron oxide MSP analogues in the wavelength range 325–675 nm. The particles were made photochemically and agglomerate into fractal-like particles with sizes on the order of 100 nm. Analysis using transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) suggested the particles were most likely maghemite-like (γ-Fe2O3) in composition, though a magnetite-like composition could not be completely ruled out. Assuming a maghemite-like composition, the optical extinction coefficients measured using the PAFS were combined with maghemite absorption coefficients measured using a complementary experimental system (the MICE-TRAPS) to derive complex refractive indices that reproduce both the measured absorption and extinction.

Momentum-Resolved Dielectric Response of Free-Standing Mono-, Bi-, and Trilayer Black Phosphorus.

Black phosphorus (BP), a 2D semiconducting material of interest in electronics and photonics, exhibits physical properties characterized by strong anisotropy and band gap energy that scales with reducing layer number. However, the investigation of its intrinsic properties is challenging because thin-layer BP is photo-oxidized under ambient conditions and the energy of its electronic states shifts in different dielectric environments. We prepared free-standing samples of few-layer BP under glovebox conditions and probed the dielectric response in a vacuum using scanning transmission electron microscopy and electron energy loss spectroscopy (STEM-EELS). Thresholds of the excitation energy are measured at 1.9, 1.4, and 1.1 eV for the mono-, bi-, and trilayer BP, respectively, and these values are used to estimate the corresponding optical band gaps. A comparison of our results with electronic structure calculations indicates that the variation of the quasi-particle gap is larger than that of the exciton binding energy. The dispersion of the plasmons versus momentum for one- to three-layer BP and bulk BP highlights a deviation from parabolic to linear dispersion and strong anisotropic fingerprints.

Role of disorder and correlations in the metal-insulator transition in ultrathinSrVO3films

Metallic oxide SrVO3 represents a prototype system for the study of the mechanism behind thickness-induced metal-to-insulator transition (MIT) or crossover in thin films due to its simple cubic symmetry with one electron in the 3d state in the bulk. Here we report a deviation of chemical composition and distortion of lattice structure existing in the initial 3 unit cells of SrVO3 films grown on SrTiO3 (001) from its bulk form, which shows a direct correlation to the thickness-dependent MIT. In-situ photoemission and scanning tunneling spectroscopy indicate a MIT at the critical thickness of ~3 unit cell (u.c.), which coincides with the formation of a (root2Xroot2)R45 surface reconstruction. However, atomically resolved scanning transmission electron microscopy and electron energy loss spectroscopy show depletion of Sr, change of V valence, thus implying the existence of a significant amount of oxygen vacancies in the 3 u.c. of SrVO3 near the interface. Transport and magneto-transport measurements further reveal that disorder, rather than electron correlations, is likely to be the main cause for the MIT in the SrVO3 ultrathin films.

Formation of Interstellar C60 from Silicon Carbide Circumstellar Grains

Abstract We have conducted laboratory experiments with analog crystalline silicon carbide (SiC) grains using transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). The 3C polytype of SiC was used—the type commonly produced in the envelopes of asymptotic giant branch (AGB) stars. We rapidly heated small (∼50 nm) synthetic SiC crystals under vacuum to ∼1300 K and bombarded them with 150 keV Xe ions. TEM imaging and EELS spectroscopic mapping show that such heating and bombardment leaches silicon from the SiC surface, creating layered graphitic sheets. Surface defects in the crystals were found to distort the six-membered rings characteristic of graphite, creating hemispherical structures with diameters matching that of C60. Such nonplanar features require the formation of five-membered rings. We also identified a circumstellar grain, preserved inside the Murchison meteorite, that contains the remnant of an SiC core almost fully encased by graphite, contradicting long-standing thermodynamic predictions of material condensation. Our combined laboratory data suggest that C60 can undergo facile formation from shock heating and ion bombardment of circumstellar SiC grains. Such heating/bombardment could occur in the protoplanetary nebula phase, accounting for the observation of C60 in these objects, in planetary nebulae (PNs) and other interstellar sources receiving PN ejecta. The synthesis of C60 in astronomical sources poses challenges, as the assembly of 60 pure carbon atoms in an H-rich environment is difficult. The formation of C60 from the surface decomposition of SiC grains is a viable mechanism that could readily occur in the heterogeneous, hydrogen-dominated gas of evolved circumstellar shells.

Lattice disorder and N elemental segregation in ion implanted GaN epilayer

The lattice disorder and elemental distribution in He-implanted GaN epilayer at a fluence of 4 × 1016 He+/cm2 at 450 °C have been investigated by a combination of conventional, high resolution transmission electron microscopy and electron energy loss spectroscopy. High resolution transmission electron microscopy shows interstitial-type dislocation loops attached to He bubbles. The nature of dislocation loops and stacking faults are carefully investigated by high resolution transmission electron microscopy. Electron energy loss spectroscopy shows the deficit of N atoms and enriched Ga nanocrystals formed in the damage region, which is comparable with the previous reports. In addition, the chemical environment of nitrogen upon He+ implantation is first investigated in the present experimental results. The research results will be used for understanding ion irradiation-induced damage in GaN.