Optical and structural properties of pulsed laser ablation deposited ZnO thin film

A limited number of reports exists in the literature concerning the systematic study of the structural and optical properties of ZnO thin films, produced by pulsed laser ablation, in correlation with the deposition parameters adopted. In this paper we present a characterization of a sample prepared by this technique and studied by photoelectron spectroscopy and X-ray diffraction. The dielectric function of both target and films has been deduced by reflection electron energy loss spectroscopy.     

Microstructural studies of bulk and thin film GDC

Ceria rare earth solid solutions are known as solid electrolyte with potential application in oxygen sensors and solid oxide fuel cells. We report the preparation of gadolinia-doped ceria, Ce_0.90Gd_0.10O_1.95, by the conventional solid-state reaction method and the preparation of thin films from a sintered pellet of gadolinia-doped ceria by the pulsed laser deposition technique. The effect of process conditions, such as substrate temperature, oxygen partial pressure, and laser energy on microstructural properties of these films are examined using powder X-ray diffraction, scanning electron microscopy, atomic force microscopy, and Raman spectroscopy.     

Micro-structural characterization of precipitation-synthesized fluorapatite nano-material by transmission electron microscopy using different sample preparation techniques

Fluorapatite is a naturally occurring mineral of the apatite group and it is well known for its high physical and chemical stability. There is a recent interest in this ceramic to be used as a radioactive waste form material due to its intriguing chemical and physical properties. In this study, the nano-sized fluorapatite particles were synthesized using a precipitation method and the material was characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Two well-known methods, called solution-drop and the microtome cutting, were used to prepare the sample for TEM analysis. It was found that the microtome cutting technique is advantageous for examining the particle shape and cross-sectional morphology as well as for obtaining ultra-thin samples. However, this method introduces artifacts and strong background contrast for high-resolution transmission electron microscopy (HRTEM) observation. On the other hand, phase image simulations showed that the solution-drop method is reliable and stable for HRTEM analysis. Therefore, in order to comprehensively analyze the microstructure and morphology of the nano-material, it is necessary to combine both solution-drop and microtome cutting techniques for TEM sample preparation.     

High-resolution transmission electron microscopy investigation of the nanostructure of undoped and Pt-doped nanocrystalline pulsed laser deposited SnO2 thin films

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto alumina substrates. The reactive PLD process was carried out at different substrate deposition temperatures (T_d) between 20 and 600 °C under an oxygen background pressure of 150 mtorr. The same PLD technique was used to produce SnO₂ films in situ-doped with Pt (at the level of ∼2 at. %) through the concomitant ablation of both SnO₂ target and Pt strips. Conventional and high-resolution transmission electron microscopy (HRTEM) observations have revealed that the microstructure of the PLD SnO₂ films is highly sensitive to their deposition temperature. Indeed, its changes from a porous granular structure with extremely fine equiaxed grains (∼4 nm diameter), at T_d=20 °C to a very compact and textured columnar structure characterized by SnO₂ columns (∼25 nm diameter) composed of grains of ∼12 nm of diameter, at T_d=600 °C. In addition, the PLD SnO₂ films were found to exhibit the highest nanoporosity at T_d=300 °C which also coincides with the granular-to-columnar microstructural transition. On the other hand, the microstructure of the Pt-doped SnO₂ films, deposited at 300 °C, was found to contain a high density of defects, such as twin boundaries and edge dislocations. By combining HRTEM and EDS microanalysis, we were able to show that the Pt-dopant self-organizes into spherical nanoparticles (1-2 nm diameter) randomly distributed at the SnO₂ grain boundaries. Finally, doping the films with such platinum nanoclusters is found to affect the SnO₂ nanostructure by particularly reducing the SnO₂ mean grain size (from ∼10 nm when undoped to ∼6 nm for the doped films).     

Metal interface formation studied by high-energy reflection energy loss spectroscopy and electron Rutherford backscattering

We demonstrate that high-energy, high-resolution reflection electron energy loss spectroscopy can provide unique insights into interface formation, especially for the case where an extended interface is formed. By changing the geometry and/or electron energy the electronic structure can be probed over a range of thicknesses (from 10s of Å to more than 1000 Å). At the same time one resolves the elastically scattered electrons into different components, corresponding to scattering of atoms with different mass (so-called ‘electron Rutherford backscattering’). Thus these high-energy REELS/elastic scattering experiments obtain information on both the electronic structure and the atomic composition of the overlayer formed.     

Optical properties and electronic transitions of SnO2 thin films by reflection electron energy loss spectroscopy

Optical properties of SnO₂ thin films in the 4–60 eV energy range are determined by reflection electron energy loss spectroscopy. Bulk and surface electron loss functions, real and imaginary parts of the dielectric function, refraction index, extinction and absorption coefficients are obtained from the analysis of the electron energy loss spectra. Electronic transitions are identified through the interpretation of the optical data. The samples (250–500 nm thick) were produced by ion beam-induced chemical vapor deposition. It is found that the compacity of the SnO₂ thin films affects their optical properties and therefore the relative intensity of the observed electronic transitions. The advantages of this method to determine optical properties of thin films are discussed. Inelastic mean free paths (6.2, 17 and 41 Å for electrons traveling in SnO₂ with kinetic energies of 300, 800 and 2000 eV, respectively) are obtained from the corresponding inelastic electron scattering cross-sections.     

Interaction of doxorubicin with the subcellular structures of the sensitive and Bcl-xL-overexpressing MCF-7 cell line: Confocal and low-energy-loss transmission electron microscopy

The present investigation was directed to examine the interaction of the anti-cancer agent doxorubicin (DOX) with the subcellular compartments of the drug sensitive and Bcl-xL-overexpressing (Bcl-xL) MCF-7 cells using confocal and low-energy-loss transmission electron microscopy (LELTEM). Intracellular detection of DOX with LELTEM was carried out without specific antibodies or heavy metal stains but via the electron-induced molecular orbital excitation of the drug. Cells were incubated with 10 μM DOX for 1 min, 1, 24, and 48 h and then examined live by confocal microscope and as very thin sections in an electron microscope equipped with an energy filter having an energy resolution of 1 eV. Ultrastructural localization of DOX, obtained from pairs of images taken at energy losses of 3 ± 1 and 10 ± 1 eV, were analyzed and correlated with the confocal observations. When the sensitive and Bcl-xL cells were examined under the confocal microscope after 1 min, DOX uptake could not be detected in the nuclei nor in the cytoplasm whereas LELTEM observation revealed that at this stage of incubation the drug has already been incorporated by both cell types and that the nuclear membrane, nucleolus, and mitochondria of the Bcl-xL cells were temporally less DOX-responsive as compared to the sensitive cells. As the incubation time increased, nuclear membranes and nucleoli of both cell types appeared equally sensitive to DOX, nonetheless, mitochondria of the Bcl-xL cells remained invulnerable to DOX for 24 h. The results point to LELTEM feasibility to better characterize yet unresolved cellular events caused by DOX and suggest a transitory role for Bcl-xL overexpression in protecting the cellular compartments from DOX invasion.     

原子尺度材料三维结构、磁性及动态演变的透射电子显微学表征

原子表征与操控是实现原子制造必须突破的物理瓶颈之一.像差校正电子显微学方法因其优异的空间分辨率,为实现原子精细制造提供了有力的表征手段.因此,利用电子显微学手段,在原子尺度对原子制造的材料及器件进行三维结构和性能的协同表征,对于深入理解原子水平材料操控的物理机理具有非常重要的意义.纳米团簇及纳米颗粒是原子制造材料与器件研究的主要对象之一,具有丰富的物理化学性质和较高的可操纵性.本文探讨纳米团簇/颗粒结构三维定量表征、使役条件下纳米团簇/颗粒结构演变定量表征、纳米颗粒/晶粒结构-成分-磁性协同定量表征等诸多方法与实例,阐明了电子显微学表征手段的突破和发展为实现精细控制的原子制造材料提供了坚实基础.     

Visualisation of liposomes prepared from skin and stratum corneum lipids by transmission electron microscopy

Transmission electron microscopy was used to visualize the liposomes prepared from total lipids extracted from mouse, human and porcine skin and stratum corneum. The total lipid composition was monitored by high precision thin layer chromatography coupled with a flame identification detector (HPTLC/FID, Iatroscan) and the fatty acid content of the samples was monitored by gas chromatography. The liposomes were prepared by the thin lipid film hydration method and they were visualized by transmission electron microscopy after negative staining using uranyl acetate. The structure of the vesicular structures present in the formulations largely depended on the lipid composition of the samples. The liposomes with high ceramide content were drop like vesicles with sharp tips, whereas the presence of excessive phospholipid content lead to bag like liposomes with two hemispheres divided by a membrane. Finally, the tendency of triacylglycerides to accumulate in the lipophylic region of the lipid bilayer, forms membranes with uneven thickness, resulting in structures with undulated membranes. A degree of fusion depending on the phospholipid content was also observed.     

Characterization of magnetic core-shell nanoparticles by fluxgate magnetorelaxometry, ac susceptibility, transmission electron microscopy and photon correlation spectroscopy—A comparative study

We have compared the structure parameters of magnetic core-shell nanoparticles determined from fluxgate magnetorelaxometry measurements applying the moment superposition model with the results from other methods. For the characterization of the magnetic cores, the nanoparticles are immobilized by freeze-drying. The core size distribution estimated for superparamagnetic Fe₃O₄ magnetic nanoparticles (MNPs) with polyacrylic acid shell agrees well with that from transmission electron microscopy measurements. The distribution of hydrodynamic diameters of nanoparticle suspensions estimated from magnetorelaxometry measurements is in good agreement with that obtained from ac susceptibility and photon correlation spectroscopy measurements. Advantages of magnetorelaxometry compared to the other two integral techniques are that it is fast and the signal is less dominated by larger particles.     

Cytochemical localization of calcium and X-ray microanalysis of Catharanthus roseus L. infected with phytoplasmas

The potassium pyroantimonate (KPA) Ca²⁺ precipitation technique, X-ray microanalysis and Electron Energy Loss Spectroscopy carried out by transmission electron microscopy were used to analyze the Ca²⁺ distribution in Catharanthus roseus L. leaves infected with phytoplasmas belonging to different taxonomic groups, and in phytoplasma cells. The analysis revealed that the distribution of Ca²⁺ was different in healthy and diseased plants (where the KPA deposits were numerous) and no differences were observed in the tissues of the three types of infected C. roseus L. Since no KPA precipitates were visible in the phloem and on phytoplasma cells, it is likely that Ca²⁺ ions are not directly involved in phytoplasma replication, but, in infected cells is a response to the pathogen indicative of a higher Ca²⁺ in the plasmalemma.     

The sp2 and sp3 fractions of unknown carbon materials: electron energy-loss near-edge structure analysis of C-K spectra acquired under the magic-angle condition by the electron nanobeam technique

A method is described for the quantification of the sp², sp³ and intermediate hybridizations in several carbon (C) material samples. Electron energy-loss near-edge spectra were acquired using fast electrons (120 keV) in an electron microscope in nanobeam configuration under the so-called ”magic-angle” condition, and were analysed to extract the sp² and sp³ fractions, and identify the possible mixed sp^2+ε hybridizations. The method consists in projecting the unknown spectra on a basis made up of pure sp² and sp³ spectra, obtained under the same experimental conditions from graphite and diamond crystals, respectively. The residual spectra contain information about the intermediate hybridizations sp^2+ε occurring in the samples. The method was successfully tested on “ab initio” numerically generated spectra relative to amorphous C materials. Finally, it was applied to actual C amorphous and pyrolytic samples, and results were compared to those obtained by the most commonly used, conventional ”three-Gaussian” method. The combined application of electron diffraction and spectroscopy, in the nanobeam configuration, yielded useful information about the atomic and electronic structure from very small volumes of the unknown C material.     

Yttrium nitride thin films grown by reactive laser ablation

Yttrium nitride thin films were grown on silicon substrates by laser ablating an yttrium target in molecular nitrogen environments. The composition and chemical state were determined with Auger electron, X-Ray photoelectron, and energy loss spectroscopies. The reaction between yttrium and nitrogen is very effective using this method. Ellipsometry measurements indicate that the films are metallic. We attribute this behavior to a small oxygen contamination. Each oxygen atom introduces two additional electrons to the unit cell, resulting in a complex semiconductor-ionic-metallic system. These results are corroborated by first principles total energy calculations of clean and oxygen doped YN.     

High-resolution study of quasi-elastic electron scattering from a two-layer system

In large-angle elastic scattering events of keV electrons a significant amount of momentum is transferred from the electron to a nucleus in the target. As a consequence kinetic energy is transferred from the energetic electron to the nucleus, and hence these processes can be referred to as ‘quasi-elastic’. How much energy is transferred depends on the mass of the nucleus. In this paper, we present measurements from a two-layer system (a germanium layer and a carbon layer), and at high energies the quasi-elastic peaks of Ge and C are clearly resolved. It is demonstrated that the sample geometry has a huge effect on the observed relative intensities. It is shown that the intensities are influenced by the elastic scattering cross-section of the atoms in the film, film composition and selective attenuation, due to varying amount of inelastic scattering for layers of the film. However truly quantitative agreement is not obtained.     

Cr掺杂锐钛矿型TiO2（001）薄膜中Cr原子的直接观测

Imaging the doping elements is critical for understanding the photocatalytic activity of doped TiO₂ thin film. But it is still a challenge to characterize the interactions between the dopants and the TiO₂ lattice at the atomic level. Here, we use high angle annular dark-field/annular bright-field scanning transmission electron microscope (HAADF/ABF-STEM) combined with electron energy loss spectroscopy (EELS) to directly image the individual Cr atoms doped in anatase TiO₂(001) thin film from [100] direction. The Cr dopants, which are clearly imaged through the atomic-resolution EELS mappings while can not be seen by HADDF/ABF-STEM, occupy both the substitutional sites of Ti atoms and the interstitial sites of TiO₂ matrix. Most of them preferentially locate at the substitutional sites of Ti atoms. These results provide the direct evidence for the doping structure of Cr-doped A-TiO₂ thin film at the atomic level and also prove the EELS mapping is an excellent technique for characterizing the doped materials.     

Structure and orbital ordering of ultrathin LaVO3 probed by atomic resolution electron microscopy and Raman spectroscopy

Orbital ordering has been less investigated in epitaxial thin films, due to the difficulty to evidence directly the occurrence of this phenomenon in thin film samples. Atomic resolution electron microscopy enabled us to observe the structural details of the ultrathin LaVO₃ films. The transition to orbital ordering of epitaxial layers as thin as ≈4 nm was probed by temperature‐dependent Raman scattering spectroscopy of multilayer samples. From the occurrence and temperature dependence of the 700 cm^–1 Raman active mode it can be inferred that the structural phase transition associated with orbital ordering takes place in ultrathin LaVO₃ films at about 130 K.     

X-ray and electron spectroscopy investigation of the core-shell nanowires of ZnO:Mn

ZnO/ZnO:Mn core-shell nanowires were studied by means of X-ray absorption spectroscopy of the Mn K- and L_2,3-edges and electron energy loss spectroscopy of the O K-edge. The combination of conventional X-ray and nanofocused electron spectroscopies together with advanced theoretical analysis turned out to be fruitful for the clear identification of the Mn phase in the volume of the core-shell structures. Theoretical simulations of spectra, performed using the full-potential linear augmented plane wave approach, confirm that the shell of the nanowires, grown by the pulsed laser deposition method, is a real dilute magnetic semiconductor with Mn²⁺ atoms at the Zn sites, while the core is pure ZnO.     

Electronic, chemical and structural characterization of CNTs grown by acetylene decomposition over MgO supported Fe-Co bimetallic catalysts

The electronic and chemical structure of carbon nanotubes synthesized by decomposition of acetylene over Fe-Co bimetallic catalysts in different growth conditions, were analyzed by valence band photoelectron spectroscopy and scanning electron microscopy. A clear relationship between the bonding features and the growth condition allowed us to determine the key parameters in terms of temperature, growth time and catalyst content. Furthermore, the analysis allowed a determination of the byproducts.     

Effect of the laser fluence on structural and optical characterization of thin CdS films synthesized by femtosecond pulsed laser deposition

CdS thin films have been grown on Si(1 1 1) and quartz substrates using femtosecond pulsed laser deposition. X-ray diffraction, atomic force microscopy, photoluminescence measurement, and optical transmission spectroscopy were used to characterize the structure and optical properties of the deposited CdS thin films. The influence of the laser fluence (laser incident energy in the range 0.5–1.5 mJ/pulse) on the structural and optical characterizations of CdS thin films has been studied. The results indicate that the structure and optical properties of the CdS thin films can be improved as increasing the per pulse output energy of the femtosecond laser to 1.2 mJ. But when the per pulse output energy of the femtosecond laser is further increased to 1.5 mJ, which leads to the degradation of the structure and optical properties of the CdS thin films.     

Structural characterization of Al_(0.55)Ga_(0.45)N epitaxial layer determined by high resolution x-ray diffraction and transmission electron microscopy

Structural characteristics of Alo.55 Gao.45N epilayer were investigated by high resolution x-ray diffraction(HRXRD)and transmission electron microscopy(TEM);the epilayer was grown on GaN/sapphire substrates using a high-temperature A1 N interlayer by metal organic chemical vapor deposition technique.The mosaic characteristics including tilt,twist,heterogeneous strain,and correlation lengths were extracted by symmetric and asymmetric XRD rocking curves as well as reciprocal space map(RSM).According to Williamson-Hall plots,the vertical coherence length of AlGaN epilayer was calculated,which is consistent with the thickness of AlGaN layer measured by cross section TEM.Besides,the lateral coherence length was determined from RSM as well.Deducing from the tilt and twist results,the screw-type and edge-type dislocation densities are 1.0×10~8 cm~(-2) and 1.8×10~(10) cm~(-2),which agree with the results observed from TEM.