Berkovich indentation-induced deformation behaviors of GaN thin films observed using cathodoluminescence and cross-sectional transmission electron microscopy

Presented in this study are the Berkovich nanoindentation-induced mechanical deformation mechanisms of metal-organic chemical-vapor deposition (MOCVD) derived GaN thin films, investigated by using the cathodoluminescence (CL) and the cross-sectional transmission electron microscopy (XTEM) techniques. The multiple “pop-in” events were observed in the load-displacement (P-h) curves and appeared to occur randomly with increasing the indentation load. These instabilities are attributed to the dislocation nucleation and propagation. CL images of nanoindentation show a very well-defined rosette structures with the hexagonal system, and clearly display the distribution of deformation-induced extended defects/dislocations which affect CL emission. By using focused ion beam (FIB) milling to accurately position the cross-section of an indented area, XTEM results demonstrate that the major plastic deformation is taking place through the propagation of dislocations. The present observations are in support to the massive dislocations activities occurring underneath the indenter during the loading cycle. No evidence of either phase transformation or formation of micro-cracking was observed by using XTEM observations. We also discuss how these features correlate with Berkovich nanoindentation-induced defects/dislocations microstructures. Finally, this study has significant implications for the extent of contact-induced damage during fabrication of GaN-based optoelectronic devices.     

Structural and optical characterization of undoped, doped, and clustered ZnO thin films obtained by PLD for gas sensing applications

The synthesis by pulsed laser deposition technique of zinc oxide thin films suitable for gas sensing applications is herein reported. The ZnO targets were irradiated by an UV KrF^* (λ = 248 nm, τ_FWHM ∼7 ns) excimer laser source, operated at 2.8 J/cm² incident fluence value, whilst the substrates consisted of SiO₂(0 0 1) wafers heated at 150 °C during the thin films growth process. The experiments were performed in an oxygen dynamic pressure of 10 Pa. Structural and optical properties of the thin films were investigated. The obtained results have demonstrated that the films are c-axis oriented. Their average transmission in the visible-infrared spectral region was found to be about 85%. The equivalent refractive indexes and extinction coefficients were very close to those of the tabulated reference values. Doping with 0.5% Au and coating with 100 pulses of Au clusters caused but a very slight decrease (with a few percent) of both transmission and refractive index values. The coatings with the most appropriate optical properties as waveguides have been selected and their behavior was tested for butane sensing.     

Morphology of sol-gel produced composite films for optical oxygen sensors

The results reported concern the characterization of thin layer SiO₂-based matrices with an oxygen sensing component Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline) immobilized, when a sol-gel process along with dip- and spin-coating deposition methods are used.SEM, TEM and AFM study, assisted by X-ray energy dispersive microanalysis reveals the influence of the precursors used, sol treatment and the coating conditions on the films morphology and Ru distribution in the matrices. Uniform and smooth surface is produced from tetraethoxysilane (TEOS). The presence of ormosils (methyltriethoxysilane, MtEOS and octyltriethoxysilane, OtEOS) significantly increases the surface roughness exhibited as dots on the SEM image. Their surface concentration and size depend on the number of immersions and withdrawal speed at the dip coating. Spin deposition leads to rather different morphology of the films, based on TEOS/OtEOS. Following commonly used sol preparation procedure (with 1.25-2.5 g Ru-complex/dm³ sol) microcrystallization of the complex occurs with formation of randomly distributed crystals 100-400 nm in size. The ultrasound treatment of the sol by means of ultrasound disintegrator leads to homogeneous distribution of the complex without observable crystallization and significant improvement of the film sensing properties (increase of Stern-Volmer constant and better linearity of the Stern-Volmer plots both in gaseous and aqueous media).     

Surface morphology of GaN nanorods grown by catalyst-free hydride vapor phase epitaxy

GaN nanorods were grown on c-plane sapphire substrates by using catalyst-free hydride vapor phase epitaxy (HVPE). The effects of substrate temperature, Ga boat temperature, and Ga pretreatment on the surface morphology of GaN nanorods were investigated. From the dependence of a radial and axial growth rate on the substrate temperature, the kinetically limited process was found to be a rate determining step in the growth of GaN nanorods in HVPE. In addition, the activation energy of the growth along the both axial and radial directions were estimated. The dependence of a Ga boat temperature and the Ga pretreatment effect revealed that the density of nanorods were dependent on the flux of Ga species on the substrate.     

Selective electroplating of copper lines on pre-patterned tantalum oxide thin films

Direct selective metal deposition on semiconductors is of interest to electronic device technology, in particular for interconnects and Schottky devices. In this study, we investigate selective copper electrodeposition on patterned tantalum oxide thin films. Cyclic voltammetry studies show that thick tantalum oxide thin films have insulating properties while oxide films thinner than a critical value are semiconductors. Copper films electrodeposited on tantalum oxide thin films are known to form Schottky contacts. We demonstrate the formation of copper patterns on pre-patterned tantalum oxide films by a simple process: an insulating tantalum oxide film was grown electrochemically, the film was then mechanically scratched followed by mild oxidation to produce a thin tantalum oxide film inside the scratch. Based on the differential behavior of thin and thick tantalum oxide films, metal lines were electrodeposited selectively under formation of Schottky junctions. The process demonstrated in this paper is compatible to standard processes for semiconductor device fabrication while permitting flexible prototyping for research at small scales.     

Atomic layer deposition of PbZrO3 thin films

In this paper, we report on the preparation of lead zirconate films for the first time using atomic layer deposition in an attempt to investigate some of the film properties and also to evaluate possible use of the precursor combination to prepare more complex lead titanate zirconate. In the depositions tetraphenyl lead (Ph₄Pb) was used as the lead and zirconium 2,2,6,6-tetramethyl-3,5-heptadionato (Zr(thd)₄) as the zirconium precursor, while ozone was used as the oxygen source. Film growth, stoichiometry and quality were studied using different pulsing ratios at deposition temperatures of 275 and 300 °C. According to X-ray diffraction, the crystalline perovskite phase was observed when films deposited on SrTiO₃(1 0 0) were annealed at 600 °C. Surface roughness was reduced for lead deficient films as well as in annealed samples.     

Characteristics of low-temperature-grown GaN films on Si(111)

In this paper, we report on the characteristics of GaN films grown on Si(111) at a low temperature (200 °C) by electron cyclotron resonance (ECR) plasma-assisted metalorganic chemical vapor deposition (PA-MOCVD). Structural analysis of the GaN films was performed by using scanning electron microscopy (SEM), atomic force miscroscopy (AFM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), and Rutherford backscattering spectrometry (RBS). Post deposition analysis revealed high quality crystalline GaN was obtained at this low temperature. Electrical analysis of the GaN films was done by using current-voltage (I-V) measurements where electrical characterizations were carried on GaN/Si heterojunction and Schottky barrier diodes. Rectification behaviour was observed for the isotype GaN/Si (n-n) heterojunction. Ideality factors and Schottky barrier heights for Ni and Cr Schottky barriers on GaN, were deduced to be 1.4 and 1.7; and 0.62 and 0.64 eV, respectively.     

Elimination of Crystallographic Wing Tilt of Canti-Bridged Epitaxial Laterally Overgrown GaN Films by Optimizing Growth Procedure

Canti-bridged epitaxial lateral overgrowth （CBELO） of GaN is performed by metalorganic chemical vapour deposition （MOCVD） on maskless V-grooved sapphire substrates prepared by wet chemical etching with different mesa widths. The wing tilt usually observed in ELO is not found in the CBELO GaN with wide mesa widths, while it can be detected obviously in the GaN with narrow mesa widths. The wing tilt of CBELO GaN grown on a grooved sapphire substrate with narrow mesa can be controlled by adjusting the thickness of the nucleation layer. The dependence of the wing tilt on the nucleation layer thickness is studied. Cross-sectional scanning electron microscopy is used to characterize the geometry of the wing regions, and double crystal x-ray diffraction is used to analyse the structural characteristics and to measure the magnitude of the crystalline wing tilt. It is found that the crystalline wing tilt can be eliminated completely by first growth of a thin nucleation GaN layer then the CBELO GaN. Possible reason and the origin of the wing tilt in CBELO GaN films are also discussed.     

Molecular dynamics of contact behavior of self-assembled monolayers on gold using nanoindentation

Molecular dynamics simulation is used to study nanoindentation of the self-assembled monolayers (SAMs) on an Au surface. The interaction of SAM atoms is described by a general universal force field (UFF), the tight-binding second-moment approximation (TB-SMA) is used for Au substrate, and the Lennard-Jones potential function is employed to describe interaction among the indenter, the SAMs, and the Au substrate atoms. The model consists of a planar Au substrate with n-hexadecanethiol SAM chemisorbed to the substrate. The simulation results show that the contact pressure increases as the SAMs temperature increases. In addition, the contact pressure also increases as the depth and velocity of indentation increase.     

Structural characterization of nc-Si films grown by low-energy PECVD on different substrates

The knowledge and control of the structural details (texture, crystallite environment and size) of nanocrystalline silicon films is a prerequisite for their proper application in various technological fields. To this purpose, nanocrystalline silicon films grown by low energy plasma enhanced chemical vapour deposition (LEPECVD) on different kinds of substrates were submitted to a systematic characterization using Raman spectroscopy, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The results showed how the difference in substrate morphology is responsible for a deep difference in the film structural properties, particularly in the case of high silane dilutions.     

Characterization of soft-X-ray detectors fabricated with high-quality CVD diamond thin films

We have characterized the performance of soft-X-ray detectors fabricated with undoped and B-doped homoepitaxial diamond layers of high quality which were grown on a commercially available type Ib (1 0 0) substrate by means of a high-power microwave-plasma chemical-vapor-deposition (CVD) method. The signal currents of the diamond-based detectors with thin TiN electrodes formed vertically (along the homoepitaxial growth direction) were measured at room temperature as a function of the applied voltage, V_a, for irradiations of 500-1200 eV soft-X-ray beams ranging from ≈6 × 10⁹ to ≈1 × 10¹¹ photons/s. The deduced apparent quantum efficiencies increased with the increasing V_a and reached to 2.5 × 10³ at V_a = 60 V. As expected from the device structure, the detector performance depended only very slightly on the applied magnetic field up to 10 T. The excellently high sensitivities attained for soft-X-ray photons are discussed in relation to carrier amplification mechanisms which invested the above diamond detectors.     

Synchrotron radiation assistant MOCVD deposition of ZnO films on Si substrate

The growth of ZnO film on Si(1 0 0) substrate has been studied with synchrotron radiation (SR) assisted MOCVD method. The diethylzinc (DEZn) and CO₂ are used as source materials, while Nitrogen is employed as a carrier gas for DEZn. With the assistance of SR the ZnO film can be deposited even at room temperature. XRD, SEM and photoluminescence (PL) studies show that the crystal quality of ZnO films grown with the assistance of SR is higher than that of those without SR assistance. The growth mechanism of ZnO film with the SR assistant MOCVD system is primarily discussed.     

A nanoindentation analysis of the influence of lattice mismatch on some wide band gap semiconductor films

Nanoindentation studies are carried out on epitaxial ZnO and GaN thin films on (0 0 0 1) sapphire and silicon substrates, respectively. A single discontinuity (‘pop-in’) in the load-indentation depth curve is observed for ZnO and GaN films at a specific depths of 13-16 and 23-26 nm, respectively. The physical mechanism responsible for the ‘pop-in’ event in these epitaxial films may be due to the interaction behavior of the indenter tip with the pre-existing threading dislocations present in the films during mechanical deformation. It is observed that the ‘pop-in’ depth is dependent on lattice mismatch of the epitaxial thin film with the substrate, the higher the lattice mismatch the shallower the critical ‘pop-in’ depth.     

Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition

By electrochemically controlling the structure of the surface aggregates, the grain microstructure has been optimized to yield mesoporous thin films of tungsten oxide (WO₃) at the electrode-electrolyte interface in a peroxotungstate sol in the presence of a structure-directing agent (Triton) at room temperature. Apart from the dominant ultrafine nanocrystallites and pores (5-10 nm), well-developed abutting grains (25-100 nm) and nanofibrils also constitute an integral part of the film matrix. X-ray photoemission spectra reveal the as-deposited film (WO_3−x) to be constituted by a high proportion of W⁶⁺ states with a low oxygen deficiency (x = 0.02). A relatively high W⁵⁺ content in the film, upon intercalation of 18 mC cm⁻² charge translates into a large coloring efficiency (η_VIS ∼ 70 cm² C⁻¹) and transmission modulation. At a lithium intercalation level of 22 mC cm⁻², in addition to W⁵⁺ and W⁶⁺ states, the film also comprises of W⁴⁺ states. The extremely fast color-bleach kinetics (3 and 2 s, respectively, for a 50% change in transmittance) shown by the as-deposited WO₃ film are repercussions of the mesopore morphology, the multiple nanostructures and the sixfold channels of its hexagonal modification. The film shows a high cycling stability as the switching times do not show any significant decline even after 3500 repetitive cycles. Coloration efficiency over the solar and photopic regions and current density for lithium intercalation for the as-deposited film are superior to that observed for the films annealed at 100, 250 and 500 °C. The abysmal electrochromic response of the annealed films is a consequence of surface defects like cracks and uncontrolled densification and pore shrinkage.     

Microstructural and surface property variations due to the amorphous region formed by thermal annealing in Al-doped ZnO thin films grown on n-Si (1 0 0) substrates

X-ray diffraction (XRD) patterns revealed that the as-grown and annealed Al-doped ZnO (AZO) films grown on the n-Si (1 0 0) substrates were polycrystalline. Transmission electron microscopy (TEM) images showed that bright-contrast regions existed in the grain boundary, and high-resolution TEM (HRTEM) images showed that the bright-contrast regions with an amorphous phase were embedded in the ZnO grains. While the surface roughness of the AZO film annealed at 800 °C became smoother, those of the AZO films annealed at 900 and 1000 °C became rougher. XRD patterns, TEM images, selected-area electron diffraction patterns, HRTEM images, and atomic force microscopy (AFM) images showed that the crystallinity in the AZO thin films grown on the n-Si (1 0 0) substrates was enhanced resulting from the release in the strain energy for the AZO thin films due to thermal annealing at 800 °C. XRD patterns and AFM images show that the crystallinity of the AZO thin films annealed at 1000 °C deteriorated due to the formation of the amorphous phase in the ZnO thin films.     

Swift heavy ion induced surface modifications in nano-crystalline Li-Mg ferrite thin films

The swift heavy ion (190 MeV Au¹⁴⁺) induced modifications in surface morphologies of the nanocrystals of ferrite thin films have been extensively studied through the images of atomic force microscopy (AFM). In most of the irradiated films significant features like, the ditch and dike structures, have been observed through out the surface. We try to explain the observed changes on the basis of thermal spike model followed by momentum transfer induced lateral mass transport. In addition to these changes some new and interesting features have been noticed after irradiation in 8F and 9F ferrite thin films. These new features are attributed to sputtering phenomenon due to the presence of defects like latent tracks.     

Atomic force microscopy study of thermal stability of silver selenide thin films grown on silicon

Silver selenide thin films were grown on silicon substrates by the solid-state reaction of sequentially deposited Se and Ag films of suitable thickness. Transmission electron microscopy and particle-induced X-ray emission studies of the as-deposited films showed the formation of single phase polycrystalline silver selenide from the reaction of Ag and Se films. Atomic force microscopy images of the as-deposited and films annealed at different temperatures in argon showed the film morphology to evolve into an agglomerated state with annealing temperature. The results indicate that when annealed above 473 K, silver selenide films on silicon become unstable and agglomerate through holes generated at grain boundaries.     

Environmental transmission electron microscopy observations of the growth of carbon nanotubes under nanotube-nanotube and nanotube-substrate interactions

The growth process of carbon nanotubes (CNTs) under CNT-CNT and CNT-substrate interactions has been observed directly by environmental transmission electron microscopy. Even a free standing CNT occasionally swings during the growth until it touches the substrate. In addition, we show that the growth direction of CNTs changes due to the interaction between CNTs.     

Decomposition of thin titanium deuteride films; thermal desorption kinetics studies combined with microstructure analysis

The thermal evolution of deuterium from thin titanium films, prepared under UHV conditions and deuterated in situ at room temperature, has been studied by means of thermal desorption mass spectrometry (TDMS) and a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The observed Ti film thickness dependent morphology was found to play a crucial role in the titanium deuteride (TiD_y) film formation and its decomposition at elevated temperatures. TDMS heating induced decomposition of fine-grained thin Ti films, of 10-20 nm thickness, proceeds at low temperature (maximum peak temperature T_m about 500 K) and its kinetics is dominated by a low energy desorption (E_D = 0.61 eV) of deuterium from surface and subsurface areas of the Ti film. The origin of this process is discussed as an intermediate decomposition state towards recombinative desorption of molecular deuterium. The TiD_y bulk phase decomposition becomes dominant in the kinetics of deuterium evolution from thicker TiD_y films. The dominant TDMS peak at approx. T_m = 670 K, attributed to this process, is characterized by E_D = 1.49 eV.