Growth morphology of nanoscale sputter-deposited Au films on amorphous soft polymeric substrates

The growth of a room-temperature sputter-deposited thin Au film on two soft polymeric substrates, polystyrene (PS) and poly(methyl methacrylate) (PMMA), from nucleation to formation of a continuous film is investigated by means of atomic force microscopy. In particular, we studied the surface morphology evolution of the film as a function of the deposition time observing an initial Au three-dimensional island-type growth. Then the Au film morphology evolves, with increasing deposition time, from hemispherical islands to partially coalesced worm-like island structures, to percolation, and finally to a continuous and rough film. The overall Au morphology evolution is discussed in the framework of the interrupted coalescence model, allowing us to evaluate the island critical radius for the partial coalescence R _c=8.7±0.9 nm for Au on PS and R _c=7.6±0.8 nm for Au on PMMA. Furthermore, the application of the kinetic freezing model allows us to evaluate the room-temperature surface diffusion coefficient D _s≈1.8×10⁻¹⁸ m²/s for Au on PS and D _s≈1.1×10⁻¹⁸ m²/s for Au on PMMA. The application of the Vincent model allows us, also, to evaluate the critical coverage (at which the percolation occurs) P _c=61% for Au on PS and P _c=56% for Au on PMMA. Finally, the dynamic scaling theory of a growing interface was applied to characterize the kinetic roughening of the Au film on both PMMA and PS. Such analyses allow us to evaluate the dynamic scaling, growth, and roughness exponents z=3.8±0.4, β=0.28±0.03, α=1.06±0.05 for the growth of Au on PS and z=4.3±0.3, β=0.23±0.03, α=1.03±0.05 for the growth of Au on PMMA, in agreement with a non-equilibrium but conservative and linear growth process in which the surface diffusion phenomenon plays a key role.     

STM study of Au(111) growth on mica

Gold films were thermally evaporated in vacuum on heated cleaved mica substrates. The substrate temperature was immediately decreased after finishing the growth. Samples prepared at various temperatures from 580 K to 890 K and evaporation rates smaller than 1 nm/s were studied by a scanning tunneling microscope (STM) under ambient conditions. Structure and defects of Au(111) surfaces were investigated and discussed with respect to growth conditions.     

The microstructure of SiO thin films: from nanoclusters to nanocrystals

The microstructure and electronic structure of silicon-rich oxide (SRO) films were investigated using transmission electron microscopy and electron energy loss spectroscopy as the main analytical techniques. The as-deposited SRO film was found to be a single phase SiO_1.0, as suggested by its electronic structure characteristics determined by the valence electron energy loss spectrum. This single phase undergoes a continuous but incomplete phase decomposition to Si and SiO₂ for films annealed between 300 and 1100°C. The resulting Si phase first appears as ～2?nm-diameter amorphous clusters which grow to larger sizes at higher annealing temperatures, but only crystallize at a critical temperature between 800 and 900°C. This cluster/matrix configuration of the SRO films is consistent with the appearance of the interface plasmon and its oscillator strength as a function of the nanoparticle size. Three separate stages were identified in the sequence of annealed films that were characterized by the presence of single-phase SiO, amorphous silicon nanoclusters, and silicon nanocrystals, respectively. The presence of amorphous silicon nanoclusters in the intermediate stage, the mean size of which can be controlled via annealing, may offer an alternative to silicon nanocrystal composites for optical applications.     

Kinetic pathways of diffusion and solid-state reactions in nanostructured thin films

Mass transport and solid-state reactions in nanocrystalline thin films are reviewed. It is illustrated that diffusion along different grain boundaries (GBs) can have important effects on the overall intermixing process between two pure films. These processes can be well characterized by a bimodal GB network, with different (fast and slow) diffusivities. First the atoms migrate along fast GBs and accumulate at the film surface. These accumulated atoms form a secondary diffusion source for back diffusion along slow boundaries. Thus the different GBs of the thin films can be gradually filled up with the diffusing atoms and composition depth profiles reflect the result of these processes. Similar processes can be observed in binary systems with intermetallic layers: instead of nucleation and growth of the reaction layer at the initial interface, the reaction takes place in the GBs and the amount of the product phase grows by the motion of its interfaces perpendicular to the GBs. Thus, the entire layer of the pure parent films can be consumed by this GB diffusion-induced solid-state reaction (GBDIREAC), and a fully homogeneous product layer can be obtained.     

Kinetic roughening of laser deposited polymer films: crossover from single particle character to continuous growth

The crossover in kinetic roughening of thin films from a particle-character-dominated regime to continuous growth behavior has been observed in this work. This has been accomplished by atomic force microscopy investigations of pulsed laser deposited amorphous organic films with thicknesses ranging from several nanometers to more than 4 microm. The early-stage random-deposition-like processes end once a closed layer is formed, which grows without saturation on the characteristic length scales. In addition, the influence of oblique film deposition has been examined and interpreted.     

Dielectric properties of anodic films on sputter-deposited Ti-Si porous columnar films

For electrolytic capacitor application of the single-phase Ti alloys containing supersaturated silicon, which form anodic oxide films with superior dielectric properties, porous Ti-7 at% Si columnar films, as well as Ti columnar films, have been prepared by oblique angle magnetron sputtering on to aluminum substrate with a concave cell structure to enhance the surface area and hence capacitance. The deposited films of both Ti and Ti-7 at% Si have isolated columnar morphology with each column revealing nanogranular texture. The distances between columns are ∼500 nm, corresponding to the cell size of the textured substrate and the gaps between columns are 100-200 nm. When the porous Ti-7 at% Si film is anodized at a constant current density in ammonium pentaborate electrolyte, the growth of a uniform amorphous oxide film continues to ∼35 V, while it is limited to less than 6 V on the porous Ti film. The maximum voltage of the growth of uniform amorphous oxide films on the Ti-7 at% Si films is similar for both the flat and porous columnar films, suggesting little influence of surface roughness on the amorphous-to-crystalline transition of growing anodic oxide under the high electric field. Due to the suppression of crystallization to sufficiently high voltages, the anodic oxide films formed on the porous Ti-7 at% Si film shows markedly improved dielectric properties, in comparison with those on the porous Ti film.     

Epitaxial growth of al thin films on mica and investigation of film structure

The temperature dependence of the structure of the aluminium thin film was studied. Reflection and transmission electron diffraction (RED and TED, respectively) patterns show that the changes of the polar orientation (texture) and the azimuthal orientation (due to epitaxy) arise in the film as the temperature of substrate surface is increased. The simultaneous presence of spot patterns at RED and arc or ring patterns at TED in a certain temperature range is explained by the preferred orientation of the film grains in the azimuthal direction and the nearly perfect orientation in the polar direction. The particular changes of the azimuthal orientation became at the temperature of the largest desorption of water molecules from mica so that we deduce that the presence of water molecules is necessary for the particular degree of the azimuthal orientation at lower temperature. At a higher temperature (500°C) of the substrate surface the well-oriented films were prepared with the same diffraction patterns as single crystal with orientation (111)_Al// //(001)_M and (110)_Al//(010)_M (double positioning is present in the films).The author expresses his gratitude to Dr. L.Eckertová and Dr. Z.Hájek for valuable discussions and to Dr. M.Rozsíval and Dr. P.Kratochvíl for their aid at the structure analysis.     

Studies on the properties of sputter-deposited Al-doped ZnO films

ZnO is a well known material; however, the research interest in this material is still high enough because ZnO is one of the materials with the most potential for optoelectronics due to its promising properties of high conductivity as well as good transparency. In this work, aluminum doped zinc oxide films (ZnO:Al) were deposited by RF magnetron sputtering on glass and silicon substrates with different deposition times of 2, 3 and 4 h. The aim of this work is the study of the deposition time effect on the properties of ZnO:Al films. It is shown that films grow with the hexagonal c$c$-axis perpendicular to the substrate surface. The morphological characteristics show a granular and homogenous surface and the cristallinity of the films is enhanced with increased deposition time. The deposited films show good optical transmittance (80%–90%) in the visible and near infrared spectrum. The calculated band gap is about 3.3 eV. The electrical ZnO:Al/Si(p) junction properties were investigated using the Capacitance–Voltage (C–V$C\text{–}V$) dependence. Calculations of the built-in potential from classical 1/C²–V$1/C^2\text{–}V$ characterization give values between 0.54 and 0.71 V.     

Influence of plasma pressure on the growth characteristics and ferroelectric properties of sputter-deposited PZT thin films

PZT thin films of thickness (320-1040) nm were synthesized on Si/SiO₂/Ti/Pt multilayered substrates by radio frequency magnetron sputtering. The influence of plasma pressure in the range of (0.24-4.9) Pa, during deposition, on the structural, electrical and ferroelectric properties of the PZT films was systematically studied. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and cross-sectional transmission electron microscopy (XTEM) were employed for structural study. Nano-probe Energy Dispersive (EDX) line scanning was employed to investigate the elemental distribution across the film-bottom electrode interface. I-V characteristics and polarization-electric field (P-E) hysteresis loop of the films were measured. The study reveals that the plasma pressure has a strong influence on the evolution and texture of the ferroelectric perovskite phase and microstructure of the films. At an optimum plasma pressure of 4.1 Pa, PZT films are grown with 93% perovskite phase with (1 1 1) preferred orientation and uniform granular microstructure. These films show a saturation polarization of 67 μC/cm², remnant polarization of 30 μC/cm² and coercive field of 28 kV/cm which, according to the literature, seem to be suitable for device applications.Transmission electron microscopy (TEM) study shows that at a plasma pressure of 4.1 Pa, the PZT/bottom Pt interface is sharp and no amorphous interlayer is formed at the interface. At a higher plasma pressure of 4.9 Pa, poor I-V and P-E hysteresis loop are observed which are interpreted as due to an amorphous interlayer at the film-bottom electrode interface which is possibly enriched in Pb, Zr, O and Pt.     

CVD diamond films: from growth to applications

The present review provides an up-to-date report on the main potential of CVD diamond films for industrial applications as well as on recent basic research which seeks to understand diamond deposition microwave plasma reactors. This review includes firstly an overview of diamond film applications. Elements which explain variations in diamond film characteristics as a function of synthesis conditions are given. Also experimental results are reported which show variations in diamond characteristics (quality, microstructure, growth rate, growth mechanisms) as four plasma variables (pressure, power, percentage of methane, substrate temperature) are systematically changed. In the second part, we discuss the effects of these variables on local parameters such as electron temperature, gas temperature, carbon-containing species and H-atom densities. Finally, based on these results, relationships between key local parameters and diamond characteristics are established and discussed.     

Self-assembled monolayers of decanethiol on Au(111)/mica

We report here a preparation for thin gold films on mica substrates. We have investigated the influence of the substrate temperature and the evaporation rate on the morphology of the films. After careful outgasing of the substrate, 100 nm of Au is evaporated onto the mica surface maintained at high temperature. After slow cooling, ex situ characterizations are performed using AFM and STM. For our purposes, the best compromise between roughness and grain size is found to occur for an evaporation rate of 2 ?s^-1 onto a mica substrate maintained at 460 C. We have used these substrates for STM and AFM study of decanethiol self-assembled monolayers (SAMs). We present results for gold samples immersed for a few seconds in decanethiol solutions, revealing an incomplete organization of the films. The organization process is discussed through comparison between AFM and STM data recorded on the SAMs. Then we present molecular resolution STM pictures of ordered SAMs for longer immersion times. Received 25 May 1999     

Density functional study of the cysteine adsorption on Au nanoclusters

The adsorption of the cysteine amino acid (H–SC_βH₂–C_αH–NH₂–COOH) on the Au₅₅ cluster is investigated through density functional theory calculations. Two isomers, with icosahedral (I_h) and chiral (C₁) geometries, of the Au₅₅ cluster are used to calculate the adsorption energy of the cysteine on different facets of these isomers. Results, only involving the S(thiolate)-Au bonding show that the higher adsorption energies are obtained when the sulfur atom is bonded to an asymmetrical bridge site at the facet containing Au atoms with the lowest coordination of the C₁ cluster isomer.     

Au cluster growth on ZnO thin films by pulsed laser deposition

Nanostructures formed by Au nanoparticles on ZnO thin film surface are of interest for applications which include medical implants, gas-sensors, and catalytic systems. A frequency tripled Nd:YAG laser (λ = 355 nm, τ_FWHM ∼ 10 ns) was used for the successive irradiation of the Zn and Au targets. The ZnO films were synthesized in 20 Pa oxygen pressure while the subsequent Au coverage was grown in vacuum. The obtained structures surface morphology, crystalline quality, and chemical composition depth profile were investigated by acoustic (dynamic) mode atomic force microscopy, X-ray diffraction, and wavelength dispersive X-ray spectroscopy. The surface is characterized by a granular morphology, with average grain diameters of a few tens of nanometers. The surface roughness decreases with the increase of the number of laser pulses applied for the irradiation of the Au target. The Au coverage reveals a predominant (1 1 1) texture, whereas the underlying ZnO films are c-axis oriented. A linear dependence was established between the thickness of the Au coverage and the number of laser pulses applied for the irradiation of the Au target.     

Reversible switching of nanostructured cobalt hydroxide films from superhydrophobic to superhydrophilic state

Superhydrophobic cobalt hydroxide films with flower-like micro-nano structure prepared by chemical-bath deposition undergo a change in wettability from superhydrophobic to superhydrophilic state either by immersion in ethyl acetate or by heat treatment at 200°C and above. The superhydrophobicity of the film can be regained by immersion in an ethanolic solution of stearic acid. The superhydrophobicity is attributed to the combined effect of micro-nano binary surface morphology and the low surface energy of the self-assembled monolayer of stearic acid. It is proposed that switching from superhydrophobicity to superhydrophilicity is caused by removal of the adsorbed layer of stearic acid by solvent or heat treatment.     

Specific features and mechanisms of photoluminescence of nanostructured silicon carbide films grown on silicon in vacuum

The light-emitting properties of cubic silicon carbide films grown by vacuum vapor phase epitaxy on Si(100) and Si(111) substrates under conditions of decreased growth temperatures (T _gr ∼ 900–700°C) have been discussed. Structural investigations have revealed a nanocrystalline structure and, simultaneously, a homogeneity of the phase composition of the grown 3C-SiC films. Photoluminescence spectra of these structures under excitation of the electronic subsystem by a helium-cadmium laser (λ_excit = 325 nm) are characterized by a rather intense luminescence band with the maximum shifted toward the ultraviolet (∼3 eV) region of the spectral range. It has been found that the integral curve of photoluminescence at low temperatures of measurements is split into a set of Lorentzian components. The correlation between these components and the specific features of the crystal structure of the grown silicon carbide layers has been analyzed.     

A rapid approach to reproducible, atomically flat gold films on mica

A simple and reproducible method for the preparation of gold films on mica with large (typically 0.8-1.0 μm) atomically flat (1 1 1) terraces is described. The procedure involves thin gold film evaporation onto freshly cleaved mica substrates, followed by 1 min annealing at 650 °C under nitrogen. The annealed gold surfaces are compared to those of freshly evaporated gold films on mica using cyclic voltammetry and atomic force microscopy. Our results favorably compare to other published annealing techniques, with minimal equipment and time necessary to reproducibly obtain atomically flat gold terraces.