Successful application of spatial difference technique to electron energy-loss spectroscopy studies of Mo/SrTiO3 interfaces

The electron energy‐loss near‐edge structure (ELNES) of Mo/SrTiO₃ interfaces has been studied using high spatial resolution electron energy‐loss spectroscopy (EELS) in a dedicated scanning transmission electron microscope. Thin films of Mo with a thickness of 50 nm were grown on (001)‐orientated SrTiO₃ surfaces by molecular beam epitaxy at 600 °C. High‐resolution transmission electron microscopy revealed that the interfaces were atomically abrupt with the (110)_Mo plane parallel to the substrate surface. Ti‐L_2,3 (～460 eV), O‐K (～530 eV), Sr‐L_2,3 (～1950 eV) and Mo‐L_2,3 (～2500 eV) absorption edges were acquired by using the Gatan Enfina parallel EELS system with a CCD detector. The interface‐specific components of the ELNES were extracted by employing the spatial difference method. The interfacial Ti‐L_2,3 edge shifted to lower energy values and the splitting due to crystal field became less pronounced compared to bulk SrTiO₃, which indicated that the Ti atoms at the interface were in a reduced oxidation state and that the symmetry of the TiO₆ octahedra was disturbed. No interfacial Sr‐L_2,3 edge was observed, which may demonstrate that Sr atoms do not participate in the interfacial bonding. An evident interface‐specific O‐K edge was found, which differs from that of the bulk in both position (0.8 ± 0.2 eV positive shift) and shape. In addition, a positive shift (0.9 ± 0.3 eV) occurred for the interfacial Mo‐L_2,3, revealing an oxidized state of Mo at the interface. Our results indicated that at the interface SrTiO₃ was terminated with TiO₂. The validity of the spatial difference technique is discussed and examined by introducing subchannel drift intentionally.     

On the estimation variance for the specific Euler–Poincaré characteristic of random networks

The factors that determine the local magnetic properties of FeCo/SiO₂ nanocomposite powders and films have been analysed by electron energy‐loss spectroscopy (EELS) and transmission electron microscopy (TEM). Attention has been given to the chemical composition, the local electronic structure and the atomic arrangement. The results show that the nanoparticles from sol‐gel prepared powders are generally Fe‐rich, whereas they are Co‐rich in sol‐gel prepared films. In addition, a subnanometre oxide layer at the surface of the FeCo nanoparticles has been clearly observed in the powder sample. It is found that the magnetic moment should be partly governed by alloying effects. Numerical values of the near‐surface magnetic moment have been obtained using the ab‐initio layer‐KKR method. These values should be helpful in understanding the layer‐by‐layer changes of the white line ratio close to the surface of the nanoparticles.     

Microstructure and interfacial chemistry of pure and La‐doped BiFeO3 thin films

We report on the microstructure and interfacial chemistry of thin films of pure and La‐doped multiferroic bismuth ferrite (Bi_1‐xLa_xFeO₃ or BLFO), synthesized on Indium Tin Oxide‐coated glass substrates by solution‐deposition technique and studied using scanning transmission electron microscopy. Our results show that undoped and La‐doped thin films are polycrystalline with distorted rhombohedral structure without any presence of any line or planar defect in the films. In addition, the films with La doping did not show any structural change and maintain the equilibrium structure. Cross section compositional analysis using X‐ray energy dispersive spectrometry did not reveal either any interdiffusion of chemical species or formation of reaction product at the film‐substrate interface. However, a closer examination of the microstructure of the films shows tiny pores along with the presence of ～2–3 nm thin amorphous layers, which may have significant influence on the functional properties of such films. Microsc. Res. Tech. 76:1304–1309, 2013. © 2013 Wiley Periodicals, Inc.     

Combining Ar ion milling with FIB lift-out techniques to prepare high quality site-specific TEM samples

Focused ion beam (FIB) techniques can prepare site‐specific transmission electron microscopy (TEM) cross‐section samples very quickly but they suffer from beam damage by the high energy Ga⁺ ion beam. An amorphous layer about 20–30 nm thick on each side of the TEM lamella and the supporting carbon film makes FIB‐prepared samples inferior to the traditional Ar⁺ thinned samples for some investigations such as high resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). We have developed techniques to combine broad argon ion milling with focused ion beam lift‐out methods to prepare high‐quality site‐specific TEM cross‐section samples. Site‐specific TEM cross‐sections were prepared by FIB and lifted out using a Narishige micromanipulator onto a half copper‐grid coated with carbon film. Pt deposition by FIB was used to bond the lamellae to the Cu grid, then the coating carbon film was removed and the sample on the bare Cu grid was polished by the usual broad beam Ar⁺ milling. By doing so, the thickness of the surface amorphous layers is reduced substantially and the sample quality for TEM observation is as good as the traditional Ar⁺ milled samples.     

Bandgap measurement of thin dielectric films using monochromated STEM-EELS

High-resolution electron energy-loss spectroscopy (HR-EELS), achieved by attaching electron monochromators to transmission electron microscopes (TEM), has proved to be a powerful tool for measuring bandgaps. However, the method itself is still uncertain, due to Cerenkov loss and surface effects that can potentially influence the quality of EELS data. In the present study, we achieved an energy resolution of about 0.13 eV at 0.1 s, with a spatial resolution of a few nanometers, using a monochromated STEM-EELS technique. We also assessed various methods of bandgap measurement for a-SiNx and SiO₂ thin dielectric films. It was found that the linear fit method was more reliable than the onset reading method in avoiding the effects of Cerenkov loss and specimen thickness. The bandgap of the SiO₂ was estimated to be 8.95 eV, and those of a-SiNx with N/Si ratios of 1.46, 1.20 and 0.92 were measured as 5.3, 4.1 and 2.9 eV, respectively. These bandgap-measurement results using monochromated STEM-EELS were compared with those using Auger electron spectroscopy (AES)-reflective EELS (REELS).     

Detecting single atoms of calcium and iron in biological structures by electron energy-loss spectrum-imaging

As techniques for electron energy‐loss spectroscopy (EELS) reach a higher degree of optimization, experimental detection limits for analysing biological structures are approaching values predicted by the physics of the electron scattering. Theory indicates that it should be possible to detect a single atom of certain elements like calcium and iron contained in a macromolecular assembly using a finely focused probe in the scanning transmission electron microscope (STEM). To test this prediction, EELS elemental maps have been recorded with the spectrum‐imaging technique in a VG Microscopes HB501 STEM coupled to a Gatan Enfina spectrometer, which is equipped with an efficient charge‐coupled device (CCD) array detector. By recording spectrum‐images of haemoglobin adsorbed onto a thin carbon film, it is shown that the four heme groups in a single molecule can be detected with a signal‐to‐noise ratio of ～10 : 1. Other measurements demonstrate that calcium adsorbed onto a thin carbon film can be imaged at single atom sensitivity with a signal‐to‐noise ratio of ～5 : 1. Despite radiation damage due to the necessarily high electron dose, it is anticipated that mapping single atoms of metals and other bound elements will find useful applications in characterizing large protein assemblies.     

EFFECT OF SURFACE ENERGY ON THE GROWTH OF DIAMOND-LIKE CARBON/AMORPHOUS SILICON FILMS ON VARIOUS SUBSTRATES

Diamond-like carbon/amorphous silicon bilayer films were deposited on SiO₂, Ge, and Ta₂O₅ substrates using a pulsed filtered cathodic arc (PFCA) system. Amorphous silicon (a-Si) layer was firstly deposited on three substrates using DC magnetron sputtering, then diamond-like carbon (DLC) film was deposited on a-Si layer via pulsed filtered cathodic arc. The thicknesses of a-Si layer and DLC film as monitored by in-situ ellipsometry during the film deposition were 7 and 10 nm, respectively. The surface energy of SiO₂, Ge, and Ta₂O₅ substrates was determined by measuring the contact angle of water on these substrates. It was found that the contact angles of water on SiO₂, Ge, and Ta₂O₅ substrates were 53°, 63°, and 75°, respectively. This result indicates that SiO₂ has the highest surface energy while Ta₂O₅ has the lowest surface energy. The thickness of the a-Si layer and DLC film was determined from the cross-section transmission electron microscopy (TEM) images. The thinnest a-Si layer of 5.64 nm was obtained from SiO₂ substrate which has the highest surface energy. The thickest a-Si layer of 6.97 nm was obtained from Ta₂O₅ corresponding to the lowest surface energy. This study shows that the thickness of the growth film strongly depends on the surface energy of the substrate. However, the DLC films deposited on each a-Si layer of three substrates have the same thickness approximately of 9.9 nm, because all of them were deposited on a-Si layers having the same surface energy.     

Microstructural characterization of nitrided Timetal 834

The microstructure of Timetal 834, in as‐received condition and after nitriding under glow discharge has been examined by light microscopy and analytical transmission electorn microscopy (TEM) methods (SAED, EDS, EELS and EFTEM). The microstructure of the as‐received alloy consists of the α phase and a small amount of the β phase. Silicide precipitates (Zr₅Si₄) are present both inside the grains and at the grain boundaries. TEM investigations of cross‐sectional thin foils allow for detailed analysis of the nitrided layer microstructure. It was found that the nitrided layer exhibits a graded character with continuously varying nitrogen content. The outermost sublayer consists of nanocrystals of δ‐TiN. The following sublayers consist mainly of δ′‐Ti₂N and ?‐Ti₂N grains. The last sublayer, closest to the substrate, is identified as a nitrogen‐rich α(N) solid solution containing up to 14 at% of nitrogen.     

Interfacial reactions and silicate formation in highly dispersed Lu2O3– SiO2 system

Solid state interface reactions in highly dispersed Lu₂O₃– SiO₂ binary oxide system were studied at 600–1100 °C with X‐ray powder diffraction (XRD), high‐resolution transmission electron microscopy (HRTEM) and Fourier Transform Infrared spectroscopy (FTIR). The results show that at 600–900 °C an amorphous, nanometer thick Lu‐O‐Si layer covering SiO₂ particles exists in the system. At higher temperatures the breakage of the layer into amorphous islands occurs and crystalline silicates with various structures are formed. In particular, Lu₄[Si₃O₁₀][SiO₄] silicate, analogue of B‐type Dy – Tm disilicates, forms at 1000 °C.     

Structural analyses of Nd-doped CeO2 thin films deposited by pulsed laser deposition

CeO₂ thin films doped with neodymium oxides for application to gas sensors have been elaborated by the pulsed laser deposition technique. The films were deposited on orientated Si (100) substrates with variable deposition times (t = 90, 180 and 360 s) and molar fractions of Nd₂O₃ (0, 6.5, 15, 21.5 and 27 at.%). The resulting Nd–CeO₂ thin films were characterized by means of X‐ray diffraction analysis, scanning electron microscopy and transmission electron microscopy equipped with EDS (Energy Dispersive Spectrometer) microanalysis. From X‐ray diffraction analyses, it is clearly established that the texture is modified by Nd additions. The preferred (111) orientations of the CeO₂ crystals change into the (200) orientation. The morphology of the CeO₂ grains changes from triangles, for pure CeO₂ thin films, to spherical grains for Nd‐doped films. In addition, cell parameter analyses from X‐ray diffraction data show that a partial chemical substitution of Ce by Nd should occur in the face‐centred cubic lattice of ceria: this should give rise to Ce_1‐xNd_xO_2?z phases with oxygen non‐stoichiometry.     

Transmission electron microscopy characterization of the erbium silicide formation process using a Pt/Er stack on a silicon-on-insulator substrate

Very thin erbium silicide layers have been used as source and drain contacts to n‐type Si in low Schottky barrier MOSFETs on silicon‐on‐insulator substrates. Erbium silicide is formed by a solid‐state reaction between the metal and silicon during annealing. The influence of annealing temperature (450 °C, 525 °C and 600 °C) on the formation of an erbium silicide layer in the Pt/Er/Si/SiO₂/Si structure was analysed by means of cross‐sectional transmission electron microscopy. The Si grains/interlayer formed at the interface and the presence of Si grains within the Er‐related layer constitute proof that Si reacts with Er in the presence of a Pt top layer in the temperature range 450–600 °C. The process of silicide formation in the Pt/Er/Si structure differs from that in the Er/Si structure. At 600 °C, the Pt top layer vanishes and a (Pt–Er)Si_x system is formed.     

Characterization and tribological investigation of sol–gel ceramic films on Ti–6Al–4V

SiO₂, TiO₂, and hydroxyapatite (HA) thin films with good biocompatibility were grown on Ti–6Al–4V (coded as TC4) substrate by sol–gel and dip-coating processes from specially formulated sols, followed by annealing at 500 °C The chemical states of some typical elements in the target films were detected by means of X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) and high-resolution scanning electron microscopy (SEM) are applied to characterize the original unworn films. The tribological properties of thin films sliding against an AISI52100 steel ball were evaluated on a reciprocating friction and wear tester. As the result, the target films composed of nano-particles ranging from 30 nm to 100 nm around were obtained. All the sol–gel ceramic films are superior in resisting wear compared with the TC4 substrate. Among all, HA film shows the best resistance while SiO₂ film shows the worst wear resistance both under higher (3 N) and lower load (1 N). TiO₂ shows good wear resistance under lower load (1 N). SEM observation of the morphologies of worn surfaces indicates that the wear of TC4 is characteristic of abrasive wear. Differently, abrasion, plastic deformation and micro-fracture dominate the wear of ceramic films. The superior friction reduction and wear resistance of HA film is greatly due to the slight plastic deformation of the film. It is supposed that the deformation of the HA film is closely related to the special arrangement of the nano-particles and microstructure. HA film is recommended for clinical application from the point of wear resistance view.     

Characterization of nitride thin films by electron backscatter diffraction

Thin films incorporating GaN, InGaN and AlGaN are presently arousing considerable excitement because of their suitability for UV and visible light‐emitting diodes and laser diodes. However, because of the lattice mismatch between presently used substrates and epitaxial nitride thin films, the films are of variable quality. In this paper we describe our preliminary studies of nitride thin films using electron backscattered diffraction (EBSD). We show that the EBSD technique may be used to reveal the relative orientation of an epitaxial thin film with respect to its substrate (a 90° rotation between a GaN epitaxial thin film and its sapphire substrate is observed) and to determine its tilt (a GaN thin film was found to be tilted by 13 ± 1° towards [101 0]_GaN), where the tilt is due to the inclination of the sapphire substrate (cut off‐axis by 10° from (0001)_sapphire towards (101 0)_sapphire). We compare EBSD patterns obtained from As‐doped GaN films grown by plasma‐assisted molecular beam epitaxy (PA‐MBE) with low and high As₄ flux, respectively. Higher As₄ flux results in sharper, better defined patterns, this observation is consistent with the improved surface morphology observed in AFM studies. Finally, we show that more detail can be discerned in EBSD patterns from GaN thin films when samples are cooled.     

Optical transition process in AgOx super-resolution near-field structure

A sandwiched 15 nm AgO_x thin film of the super‐resolution, near‐field optical disk was studied using a confocal Z‐scan system. Nonlinear optical properties of quartz glass/ZnS–SiO₂ (170 nm)/AgO_x (15 nm)/ZnS–SiO₂ (40 nm) were measured using a Q‐switch Nd : YAG pulse laser of wavelength 532 nm, pulse width 0.7 ns, and 15.79 kHz repetition rate. Transmittance and reflectance of the sandwiched AgO_x thin film show important optical responses at the focused position of Z‐scan. The dissociation processes of AgO_x, recombination of the silver and oxygen, and the resonance of the localized surface plasmon of the nano‐composites of the AgO_x thin film are correlated to transmittance and reflectance at the focused position of the Z‐scan for different input laser powers. An irreversible upper threshold intensity of 4.40 × 10⁶ mW cm^?2 at the focused position was found. A reversible working window of the focusing intensity between 1.86 × 10⁶ and 4.40 × 10⁶ mW cm^?2 was measured with sandwiched AgO_x thin film alone. The near‐field interactions of the AgO_x thin film and the recording layers of super‐resolution near‐field optical disk are also discussed.     

A tribological study of kinetically influenced ultrathin Au and Cu metal overlayers grown on dendrimer mediated Si

Evidence is presented here for deposition kinetic energy influences on the wear properties of Au and Cu films deposited by evaporation and sputtering on clean and poly(amidoamine) (PAMAM) dendrimer modified SiO _x substrates. Ramped load nanoscratch tests show increased resistance to wear in the presence of the dendrimer monolayer. Nanoscratch profiles indicate that the critical load to failure (scratch bearing capacity) is increased in the presence of a dendrimer interlayer. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis of the wear tracks show that following film failure plowing is the predominant mechanism of wear for sputtered or evaporatively deposited Au. No obvious changes in the wear properties (a pure cutting mechanism) of Cu thin films are observed upon changing the kinetic energy of the incoming metal.     

Energy-filtered transmission electron microscopy of biological samples on highly transparent carbon nanomembranes

Ultrathin carbon nanomembranes (CNM) comprising crosslinked biphenyl precursors have been tested as support films for energy-filtered transmission electron microscopy (EFTEM) of biological specimens. Due to their high transparency CNM are ideal substrates for electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) of stained and unstained biological samples. Virtually background-free elemental maps of tobacco mosaic virus (TMV) and ferritin have been obtained from samples supported by ∼1 nm thin CNM. Furthermore, we have tested conductive carbon nanomembranes (cCNM) comprising nanocrystalline graphene, obtained by thermal treatment of CNM, as supports for cryoEM of ice-embedded biological samples. We imaged ice-embedded TMV on cCNM and compared the results with images of ice-embedded TMV on conventional carbon film (CC), thus analyzing the gain in contrast for TMV on cCNM in a quantitative manner. In addition we have developed a method for the preparation of vitrified specimens, suspended over the holes of a conventional holey carbon film, while backed by ultrathin cCNM.     

Chemical reactions and morphological stability at the Cu/Al2O3 interface

The microstructures of diffusion‐bonded Cu/(0001)Al₂O₃ bicrystals annealed at 1000 °C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high‐resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20–35 nm thick interfacial CuAlO₂ layer formed, which crystallises in the rhombohedral structure. However, the CuAlO₂ layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle‐like structure was observed. The needles are several millimetres long, ～10 µm wide and ～1 µm thick. They consist of CuAlO₂ with alternating rhombohedral and hexagonal structures. Solid‐state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as‐bonded sample.     

Combining FIB milling and conventional Argon ion milling techniques to prepare high‐quality site‐specific TEM samples for quantitative EELS analysis of oxygen in molten iron

This paper reports a procedure to combine the focused ion beam micro‐sampling method with conventional Ar‐milling to prepare high‐quality site‐specific transmission electron microscopy cross‐section samples. The advantage is to enable chemical and structural evaluations of oxygen dissolved in a molten iron sample to be made after quenching and recovery from high‐pressure experiments in a laser‐heated diamond anvil cell. The evaluations were performed by using electron energy‐loss spectroscopy and high‐resolution transmission electron microscopy. The high signal to noise ratios of electron energy‐loss spectroscopy core‐loss spectra from the transmission electron microscopy thin foil, re‐thinned down to 40 nm in thickness by conventional Argon ion milling, provided us with oxygen quantitative analyses of the quenched molten iron phase. In addition, we could obtain lattice‐fringe images using high‐resolution transmission electron microscopy. The electron energy‐loss spectroscopy analysis of oxygen in Fe_0.94O has been carried out with a relative accuracy of 2%, using an analytical procedure proposed for foils thinner than 80 nm. Oxygen K‐edge energy‐loss near‐edge structure also allows us to identify the specific phase that results from quenching and its electronic structure by the technique of fingerprinting of the spectrum with reference spectra in the Fe‐O system.     

Formation of Pentacene wetting layer on the SiO2 surface and charge trap in the wetting layer

We studied the early-stage growth of vacuum-evaporated pentacene film on a native SiO₂ surface using atomic force microscopy and in-situ spectroscopic ellipsometry. Pentacene deposition prompted an immediate change in the ellipsometry spectra, but atomic force microscopy images of the early stage films did not show a pentacene-related morphology other than the decrease in the surface roughness. This suggested that a thin pentacene wetting layer was formed by pentacene molecules lying on the surface before the crystalline islands nucleated. Growth simulation based on the in situ spectroscopic ellipsometry spectra supported this conclusion. Scanning capacitance microscopy measurement indicated the existence of trapped charges in the SiO₂ and pentacene wetting layer.