Characterization of indium tin oxide film and practical ITO film by electron microscopy

In order to clarify the structure of indium oxide film containing tin and tin oxides, various In₂O₃ based films prepared by vacuum evaporation were studied using high-resolution electron microscope (HREM). Indium tin oxide (ITO) film was composed of In₂O₃ and SnO. SnO crystal also contained (110) or (101) crystallographic shear (CS) structures that indicate excess amounts of tin. The CS structure was also found in a commercial ITO film having the resistivity of 2×10⁻⁴ Ω cm.     

Quantitative characterization of clay dispersion in polypropylene-clay nanocomposites by combined transmission electron microscopy and optical microscopy

This paper presents a novel method to describe the microstructure of polymer/clay nanocomposites quantitatively. Based on the image analyses of transmission electron microscopy (TEM) and optical microscopy micrographs, two parameters, degree of dispersion (χ) and mean interparticle distance per unit volume of clay (λ_V) are proposed to describe the level of clay dispersion. The degree of dispersion gives the percentage of exfoliation, and λ_V is a measure of spatial separation between particles relative to clay loading. A polypropylene/clay system was chosen as an example to show the effects of processing conditions and biaxial stretching on clay dispersion using the proposed quantifiers. It provides insights into the ‘real’ clay dispersion using a combination of both microscopical and macroscopical aspects.     

Characterization of organic thin films using transmission electron microscopy and Fourier Transform Infra Red spectroscopy

Organic Light Emitting Diodes (OLEDs) have received much attention for use in display and solid-state lighting applications. Consequently, evaluating materials analyses techniques to better understand potential issues between the different films constituting the OLED device structure becomes important. In particular, film thickness monitoring and control is essential for reproducible and reliable OLED performance. Typically, Quartz Crystal Microbalances (QCMs) are used to monitor the thicknesses in-situ. While QCMs can provide thickness information, they do not provide information about the composition or quality of the deposited films. To overcome these issues, in this paper, we have used Fourier Transform InfraRed Spectroscopy (FT-IR) to measure film thicknesses and compositions in individual as well as stacked organic layers relevant to OLED structures and used cross-sectional Transmission Electron Microscopy imaging to correlate the physical thickness of the organic films to their IR (infrared) absorption peak intensities from FT-IR. We demonstrate that this technique can be used to precisely measure film thicknesses within 5% of the nominal thickness and provide information about film composition.     

Scanning transmission electron microscopy (STEM)-transmission electron microscopy (TEM) analysis of nitrogen ion implanted austenitic 302 stainless steel

The microstructure of nitrogen implanted AISI 302 austenitic stainless steel and the effect of long-term room temperature ageing on it have been studied. Samples were implanted in 1992 with 2.5×10²¹ N₂⁺ m⁻² at 130 keV. The characteristics of the implanted layer and the depth profile have been investigated by scanning transmission electron microscope combined with energy dispersive X-ray spectrometry. Electron diffraction patterns recorded in the implanted layer using transmission electron microscopy confirm the formation of CrN along with the presence of Cr₂N. The identification of phases by glancing angle X-ray diffraction also indicates the formation of Cr₂N and nitrogen solid solutions. The effects of ageing on the microstructure are observed to be small.     

Finestructures study of the diamond/titanium interface by transmission electron microscopy

It is well known that a TiC layer can be formed and should act as a buffer layer in diamond films deposited on Ti alloy. Through our cross-sectional investigation in HRTEM, a thin layer (20–30 nm) was first identified between the outermost diamond film and the inner reactive TiC layer adjacent to the substrate. This layer consists of numerous crystalline nanoparticles with grain sizes of 5–20 nm. Through electron nanodiffraction patterns combined with EDS and EELS analysis, these nanoparticles can be identified as a TiC_1−xO_x phase with a similar structure to cubic TiC. Besides, C atoms and O atoms in TiC_1−xO_x randomly occupy the vacancies of C in TiC. The thickness of this TiC_1−xO_x layer does not change significantly with increasing deposition time, and the diamond phase directly nucleates and grows on it.     

Characterisation of nano-structured titanium and aluminium nitride coatings by indentation, transmission electron microscopy and electron energy loss spectroscopy

Titanium and aluminium nitride Ti_1 − xAl_xN films deposited by radiofrequency magnetron reactive sputtering onto steel substrate are examined by transmission electron microscopy over all the range of composition (x = 0, 0.5, 0.68, 0.86, 1). The deposition parameters are optimised in order to grow nitride films with low stress over all the composition range. Transmission electron microscopy cross-section images of Vickers indentation prints performed on that set of coatings show the evolution of their damage behaviour as increasing x Al content. Cubic Ti-rich nitrides consist of small grains clustered in rather large columns sliding along each other during indentation. Hexagonal Al-rich films grow in thinner columns which can be bent under the Vickers tip. Indentation tests carried out on TiN and AlN films are simulated using finite element modelling. Particular aspects of shear stresses and displacements in the coating/substrate are investigated. The growth mode and the nanostructure of two typical films, TiN and Ti_0.14Al_0.86N, are studied in detail by combining transmission electron microscopy cross-sections and plan views. Electron energy loss spectrum taken across Ti_0.14Al_0.86N film suggests that a part of nitrogen atoms is in cubic-like local environment though the lattice symmetry of Al-rich coatings is hexagonal. The poorly crystallised domains containing Ti and N atoms in cubic-like environment are obviously located in grain boundaries and afford protection of the coating against cracking.     

Transmission electron microscopy characterization of TiN/SiNx multilayered coatings plastically deformed by nanoindentation

Plastic deformation of TiN_5 nm/SiN_0.5 nm multilayers by nanoindentation was investigated by transmission electron microscopy in order to identify deformation mechanisms involved in film failure resulting from severe plastic deformation. The TiN layers exhibited a crystalline fcc structure with a [002] preferential orientation; further crystal growth was interrupted by the amorphous SiN_x layers. After severe plastic deformation collective vertical displacement of slabs of several TiN/SiN_x-bilayers, which resulted from shear sliding at TiN/TiN grain boundaries, was observed. They are, together with horizontal fractures along the SiN_x layers, vertical cracks under the indenter tip following the TiN grain boundaries and delamination from the substrate, the predominant failure mechanisms of these coatings. The deformation behaviour of these films provides an experimental support for the absence of dislocation activity in grains of 5 nm size.     

Structural investigations on nanocrystalline Ni-W alloy films by transmission electron microscopy

Electrodeposited Ni-W alloys have been investigated in the as-deposited state by transmission electron microscopy in order to investigate the microstructural features in dependence of the tungsten content. Within the tungsten content range from 7 at.% up to 12 at.%, the microstructure is nanocrystalline characterized by a bimodal grain size distribution, consisting out of 20 to 200 nm sized grains and also larger grains with several 100 nm characteristic dimension. No clear trend in microstructure formation is visible with W content or deposition conditions in the investigated W content range. Only solid solution phase characteristics were observed. The lattice constant is 0.360 nm for 12 at.% W as derived from electron diffraction for the solid solution face centered cubic structure. Larger grains show twinning and stacking faults. Voids with diameter of a few nm were detected along with some multiple twinned particles, indicating high stress level during growth. About 2 at.% difference in the alloy composition from grain to grain was measured.     

Characterisation of dislocations, nanopipes and inversion domains in GaN by transmission electron microscopy

Transmission electron microscopy is used to analyse a range of defects observed in hexagonal GaN films grown on sapphire and GaN substrates by metalorganic chemical vapour deposition. Large angle convergent beam electron diffraction is used to analyse the Burgers vectors of dislocations and to show that hollow tubes, or nanopipes, are associated with screw dislocations having Burgers vectors±c. Weak-beam electron microscopy shows that dislocations are dissociated into partials in the (0001) basal plane, but that threading segments are generally undissociated. The presence of high densities of inversion domains in GaN/sapphire films is confirmed using convergent beam electron diffraction and the atomic structure of the {

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} inversion domain boundary is determined by an analysis of displacement fringes seen in inclined domains.     

Epitaxial orientation and morphology of β-FeSi2 produced on a flat and a patterned Si(001) substrates

The epitaxial growth of β-FeSi₂ films produced on flat and patterned Si(001) substrates under various substrate temperatures (T_s) with deposition rates of Fe (V_Fe) was investigated by transmission electron microscopy (TEM). In the film deposited on the flat Si(001) substrate, precipitates of flat-bottom shaped β-FeSi₂ and those of round-bottom shaped α-FeSi₂ were formed at T_s = 500 °C and V_Fe = 0.02 nm/s. The β-FeSi₂ adopted the epitaxy to (001)_Si plane, while α-FeSi₂ selected the epitaxy to {111}_Si planes inside the Si matrix. At T_s = 350 °C and V_Fe = 0.01 nm/s, a continuous β-FeSi₂ layer were formed epitaxially on the Si(001) substrate without forming α-FeSi₂. It was found that the lower temperature and the higher Fe-concentration suppress the formation of α-FeSi₂ and promote the formation of β-FeSi₂. In addition, the morphology of β-FeSi₂ changed from fine isolated precipitates (islands) to a continuous layer with increasing the deposition rate and the substrate temperature. In the film deposited on the patterned Si(001) substrate at T_s = 500 °C and V_Fe = 0.02 nm/s, on the other hand, both β- and α-FeSi₂ precipitates were formed on the top-hills and the valleys of the patterned substrate, while only α-FeSi₂ precipitates were formed on the sidewalls. These results demonstrate that not only the growth conditions but also geometric situations affect strongly the epitaxial growth of FeSi₂ precipitates.     

Formation of new carbides with diamond structure from carbon film containing transition metal

New carbide crystallites, which have a solid-solution phase with diamond structure, were formed from amorphous carbon film containing a transition metal such as Fe, Co, Mo or Ti by vacuum heating at 500-800 °C. The lattice constants for each solid-solution phase have been determined from electron diffraction patterns and high-resolution transmission electron microscope images. The formation of carbon polymorphs has been summarized as being dependent on the heat treatment temperature.     

Comparison of glass hydration layer thickness measured by transmission electron microscopy and nanoindentation

The thicknesses of the hydration layers on the surfaces of 2 silicate glasses have been assessed using a) a combination of focused ion beam milling and transmission electron microscopy and b) nanoindentation; the two approaches give consistent layer thicknesses. Lighter contrast of the hydrated layers in TEM suggests that the layers have reduced density when compared to the bulk glasses; this is consistent with the reduced near surface modulus and hardness of hydrated glasses observed in nanoindentation.     

Structure determination of chitosan-stabilized Pt and Pd based bimetallic nanoparticles by X-ray photoelectron spectroscopy and transmission electron microscopy

Chitosan (CTS)-stabilized bimetallic nanoparticles were prepared at room temperature (rt.) in aqueous solution. Palladium (Pd) and platinum (Pt) were selected as the first metals while iron (Fe) and nickel (Ni) functioned as the second metals. In order to obtain the noble metal core-transition metal shell structures, bimetallic nanoparticles were prepared in a two-step process: the preparation of mono noble metallic (Pd or Pt) nanoparticles and the deposition of transition metals (Fe or Ni) on the surface of the monometallic nanoparticles. The structures of the nanoparticles were studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The XPS results show that Pd and Pt exist mainly in zero valences. The presence of Fe and Ni in the bimetallic nanoparticles affects the binding energy of Pd and Pt. Moreover, the studies of O 1s spectra indicate the presence of Fe or Ni shells. The analyses of TEM micrographs give the particle size and size distributions while the high-resolution TEM (HRTEM) micrographs show the existence of noble metal core lattices. The results confirm the formation of noble metal core-transition metal shell structures.     

Structural property of β-FeSi2 layers deposited on FeSi from a molten salt

The microstructural properties of the β-FeSi₂/FeSi structure prepared from a molten salt have been characterized using transmission electron microscopy (TEM). The β-FeSi₂ films were grown on FeSi substrates at the heat treatment temperature of 900 °C from 1 min to 24 h using the molten salt technique. It is found that the films consisted of a thin surface layer and a thick underlying layer with columnar-shaped domains. The crystallographic directions of the domains are mostly randomly oriented. The β-FeSi₂ domains in the film, however, have specific crystallographic orientation relationships with the adjoining domains and the FeSi substrate. A high density of the stacking faults on the β-FeSi₂ (100) planes was also observed through the films. Moreover, the growth evolution of the β-FeSi₂ domains, the defect characteristics and the formation mechanism of the defects are discussed.     

Transmission electron microscopy studies of nanostructured TiO2 films on various substrates

A chemical vapour deposition (CVD) synthetic route to the production of nanocrystalline titanium dioxide has been carefully investigated on various substrates. CVD was performed at a relatively low temperature of 320 °C on KCl crystal, Al foil, KBr pellet and freshly sliced MICA substrates. The influence of substrate material on film formation was studied in order to find a titanium dioxide film with good intercalation properties for an electrode in a dye-sensitized solar cell. Intercalation properties depend on average grain sizes and porosity in nanophased materials. These films were thoroughly characterized with respect to their surface morphology, crystal structure and the phase composition. Transmission electron microscopy (TEM) accompanied by selected area electron diffraction (SAED) was employed for structural characterization of TiO₂ films. The studies showed that films deposited on KCl crystal, KBr pellet and MICA are solely composed of an anatase phase whereas in the film deposited onto Al foil, the brookite phase of TiO₂ is also present. The structural parameters of anatase were determined using the Rietveld refinement of electron diffraction data. By comparison of anatase lattice parameters with their corresponding bulk values, the significant deviation in values of lattice parameters a and c in anatase phase was observed and attributed to the thin-film features. The average grain size and the grain size distribution obtained by TEM were compared for TiO₂ films deposited on different substrates.     

Effect of film thickness and the presence of surface fluorine on the structure of a thin barrier film deposited from tetrakis-(dimethylamino)-titanium onto a Si(100)-2 × 1 substrate

The structure of a thin film deposited using tetrakis-(dimethylamino)-titanium (Ti(N(CH₃)₂)₄) as a precursor onto a Si(100)-2 × 1 substrate at ultra-high-vacuum conditions was investigated as a function of film thickness for the films of 20 and 145 nm in the presence of surface copper and fluorine produced by in situ dosing of a common copper deposition precursor, (hexafluoroacetylacetonate)Cu(vinyltrimethylsilane), (hfac)Cu(VTMS), and a hydrogenated form of the hfac ligand, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, hfacH. A combination of surface, depth-profiling, and microscopy analytical techniques suggests that the structure of the titanium carbonitride film depends profoundly on its thickness. While the composition of the film was relatively constant throughout its whole thickness, the nanometer-scale structure changed from amorphous at the top of a 145-nm-thick film, to having a significant amount of small (∼ 5 nm) crystallites closer to the TiCN/Si interface. These studies also confirmed the absence of microfractures in the film prepared by this approach. The ex situ depth profiling investigation suggested that if (hfac)Cu(VTMS) is deposited on a TiCN-precovered silicon substrate and briefly annealed to 800 K, the film acts as a diffusion barrier for copper, while surface fluorine penetrates the film rather easily, resulting in fluorine that is distributed uniformly throughout the film.     

In situ high resolution transmission electron microscopy investigation of deformation mechanism in sub-10-nm Au crystals

Abstract

In situ high resolution transmission electron microscopy investigations were performed on sub-10-nm Au crystals. The effects of tensile loading direction and crystal size on the deformation mechanism of Au crystals were analysed. For the Au crystals with a width below 2 nm, the surface atom diffusion with a phenomenon of layer by layer peeling is the main deformation mechanism and the tensile loading direction plays negligible effect. For the Au crystals with a width over 7 nm, the dislocations generated form surface and gliding into crystal dominate the plastic deformation and the tensile loading direction plays important role. Lomer dislocations are produced and destructed by dislocation reaction during tensile strain process in <001> oriented Au crystal. The Schmid law is the key intrinsic issue controlling the deformation mechanism for the nanowires with a size larger than 7 nm.     

Synthesis and Characterization of Transition Metals Doped ZnO Nanorods

Different morphologies of undoped and transition metals(Mn,Co and Ni) doped one-dimensional(1D) ZnO nanocrystals were successfully synthesized by chemical method in an air atmosphere using polyvinylpyrrolidone(PVP) as a surfactant.The structure and optical properties were studied by scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),thermal gravimetric analysis(TGA),ultraviolet visible(UV-vis) absorption spectra and photoluminescence(PL) spectra.The doped ZnO nanorods exhibited a blue-shifted band gap and enhanced ultraviolet(UV) emission.In addition defect related emission was observed for the doped ZnO.     

Scanning electron microscopy imaging of single-walled carbon nanotubes on substrates

Scanning electron microscopy (SEM) plays an indispensable role in nanoscience and nanotechnology because of its high efficiency and high spatial resolution in characterizing nanomaterials.Recent progress indicates that the contrast arising from different conductivities or bandgaps can be observed in SEM images if single-walled carbon nanotubes (SWCNTs) are placed on a substrate.In this study,we use SWCNTs on different substrates as model systems to perform SEM imaging of nanomaterials.Substantial SEM observations are conducted at both high and low acceleration voltages,leading to a comprehensive understanding of the effects of the imaging parameters and substrates on the material and surface-charge signals,as well as the SEM imaging.This unified picture of SEM imaging not only furthers our understanding of SEM images of SWCNTs on a variety of substrates but also provides a basis for developing new imaging recipes for other important nanomaterials used in nanoelectronics and nanophotonics.     

Morphological modification of β-FeSi2 on Si(111) by high temperature growth and post-thermal annealing

β-FeSi₂ crystals have been grown on Si(111) substrates, and morphological modification of the β-FeSi₂/Si(111) by high temperature growth and post-thermal annealing was investigated. The morphological feature of the β-FeSi₂ crystals significantly depends on the growth conditions, especially, substrate temperature during growth. The β-FeSi₂ continuous layers with relatively smooth surfaces were grown at the low substrate temperatures of 650-700 °C with exposure of the grown layers to Sb flux during the growth. On the other hand, nano-scaled islands have been grown at the higher substrate temperature of 850 °C. The structural property, interfacial morphology and growth evolution of the β-FeSi₂ islands were examined, and compared with those for the layers grown at a lower substrate temperature. In addition, the morphological evolution of the β-FeSi₂/Si layers by post-thermal annealing was examined, and it was found that the interfacial smoothness between the β-FeSi₂ layers and the Si(111) substrates was improved by the post-thermal annealing on condition that a thin SiO_x amorphous overlayer should be formed on the β-FeSi₂ layer during the post-thermal annealing. The mechanisms of the morphological modification at the β-FeSi₂/Si(111) interface by the post-thermal annealing will also be discussed.