Equilibrium and kinetic surface segregation in binary alloy thin films

A general theoretical analysis of the effect of film thickness on equilibrium and kinetic surface segregation in binary alloy thin films is presented. In this analysis, a constrained condition that represents the finite size of thin film system has been introduced to the modified Darken model, which has been used to describe both equilibrium and kinetic surface segregation in bulk materials. Simulation of surface segregation for alloy thin films can be carried out for all composition ranges and all film thicknesses if only knowing the surface segregation parameters for bulk materials. Simulations of equilibrium and kinetic surface segregation in Cu(1 1 1)Ag binary alloy thin film are presented.     

Effect of calcination temperature on the morphology and surface properties of TiO2 nanotube arrays

Well-ordered TiO₂ nanotube arrays were prepared by electrochemical anodization of titanium in aqueous electrolyte solution of H₃PO₄ + NH₄F at a constant voltage of 20 V for 3 h, followed by calcined at various temperatures. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) were used to characterize the samples. The results showed that the as-prepared nanotube arrays before being calcined were amorphous and could transform to anatase phase at a heat treatment temperature higher than 400 °C. As the calcination temperatures increased, crystallization of anatase phase enhanced and rutile phase appeared at 600 °C. However, further increasing the calcination temperature would cause the collapse of nanotube arrays. PL intensity of the nanotube arrays annealed at 500 °C was the lowest, which was probably ascribed to better crystallization together with fewer surface defects of the nanotube arrays.     

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.     

Theoretical study of Ti and Fe surface alloys on Al(0 0 1) substrate

Accurate density-functional calculations are performed to investigate the formation of Ti and Fe ultrathin alloys on Al(0 0 1) surface. It is demonstrated that a deposition of Ti monolayer on Al(0 0 1) substrate leads to the formation of Al₃Ti surface alloy with Ti atoms arranged according to the L1₂ stacking, distinct from the D0₂₂ structure characteristic of a bulk Al₃Ti compound. A quest for the reason of this distinct atomic arrangement led us to the study of the surface structure of Al₃Ti(0 0 1) compound. It is concluded that even the Al₃Ti(0 0 1) surface is terminated with three layers assuming a L1₂ stacking and hence this stacking fault can be classified as a surface-induced stacking fault. Several possibilities of Fe atoms distributed in the surface region of Al(0 0 1) have been examined. The most stable configuration is the one with the compact Fe monolayer on Al(0 0 1) and covered by one Al monolayer. Lastly, our calculations show that there is no barrier for the penetration of Fe adatoms below the Al(0 0 1) surface; however, such a barrier is present for a Ti-alloyed Al(0 0 1) surface.     

The influence of substrate on the properties of Er2O3 films grown by magnetron sputtering

The structural properties and the room temperature luminescence of Er₂O₃ thin films deposited by RF magnetron sputtering have been studied. Films characterized by good morphological properties have been obtained by using a SiO₂ interlayer between the film and the Si substrate. The evolution of the properties of the Er₂O₃ films due to rapid thermal annealing processes in O₂ ambient performed at temperatures in the range 800-1200 °C has been investigated in details. The existence of well-defined annealing conditions (temperature of 1100 °C or higher) allowing to avoid the occurrence of extensive chemical reactions with the oxidized substrate has been demonstrated and an increase of the photoluminescence (PL) intensity by about a factor of 40 with respect to the as deposited material has been observed. The enhanced efficiency of the photon emission process has been correlated with the longer lifetime of the PL signal. The same annealing processes are less effective when Er₂O₃ is deposited on Si. In this latter case interfacial reactions and pit formation occur, leading to a material characterized by stronger non-radiative phenomena that limit the PL efficiency.     

Supramolecular motif and macroscopic pattern in alpha-methylferrocenemethanol films cast from organic solution

The macroscopic patterns were formed in alpha-methylferrocenemethanol films cast from organic solutions. The macroscopic pattern was composed of concentric rings in the solid film. The concentric rings consist of convex ridges and concave valleys; the ordered phase constitutes the convex ridges, while the concave valleys barely contain anything. It has been found that, as for the solvent which can form hydrogen bonding with the solute and has suitable evaporation rate, macroscopic pattern could be observed in the solid film; while as for the solvent that cannot form hydrogen bonding with the solute, no macroscopic pattern would appear. It was suggested that, intermolecular hydrogen bonding and aromatic π stacking interactions of the solute is responsible for the formation of the microscopic crystalline structure; while the hydrogen bonding between the solute and the solvent, and the solvent-evaporation-induced crystallization process, as well as the solvent-evaporation-induced convections are responsible for the formation of the macroscopic pattern. The results could offer a facile way to the electronic material films with well-defined spatial alignment.     

The influence of substrate temperature variation on tungsten oxide thin film growth in an HFCVD system

Tungsten oxide (WO₃) thin films were deposited by a modified hot filament chemical vapor deposition (HFCVD) technique using Si (1 0 0) substrates. The substrate temperature was varied from room temperature to 430 °C at an interval of 100 °C. The influence of the substrate temperature on the structural and optical properties of the WO₃ films was studied. X-ray diffraction and Raman spectra show that as substrate temperature increases the film tends to crystallize from the amorphous state and the surface roughness decreases sharply after 230 °C as confirmed from AFM image analysis. Also from the X-ray analysis it is evident that the substrate orientation plays a key role in growth. There is a sharp peak for samples on Si substrate due to texturing. The film thickness also decreases as substrate temperature increases. UV-vis spectra show that as substrate temperature increases the film property changes from metallic to insulating behavior due to changing stoichiometry, which was confirmed by XPS analysis.     

Current induced resistance change of magnetic tunnel junctions with ultra-thin MgO tunnel barriers

Ultra-thin magnetic tunnel junctions with low resistive MgO tunnel barriers are prepared to examine their stability under large current stress. The devices show magnetoresistance ratios of up to 110% and an area resistance product of down to . If a large current is applied, a reversible resistance change is observed, which can be attributed to two different processes during stressing and one relaxation process afterwards. Here, we analyze the time dependence of the resistance and use a simple model to explain the observed behavior. The explanation is further supported by numerical fits to the data in order to quantify the timescales of the involved phenomena.     

Structural changes of diamond-like carbon films due to atomic hydrogen exposure during annealing

We have deposited diamond-like carbon (DLC) films by radio-frequency magnetron sputtering, and have annealed the films under various conditions to investigate the effects of annealing on the structural properties by visible Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. The structural ordering of hydrogenated DLC films occurs during annealing below 400 °C in a vacuum and a hydrogen gas atmosphere, while unhydrogenated DLC films are not ordered during annealing even at 700 °C. On the other hand, the ordering and the decrease of the sp³ content are observed for both the films after annealing under an atomic hydrogen exposure. The ordering progresses as the annealing temperature and time are increased. The reduction of the film thickness after annealing is suppressed with increasing annealing temperature. The results suggest that both the preferential etching by atomic hydrogen and the hydrogen evolution encourage the structural changes under an atomic hydrogen exposure.     

Enhanced electrical properties of pentacene-based organic thin-film transistors by modifying the gate insulator surface

A reliable surface treatment for the pentacene/gate dielectric interface was developed to enhance the electrical transport properties of organic thin-film transistors (OTFTs). Plasma-polymerized fluorocarbon (CFx) film was deposited onto the SiO₂ gate dielectric prior to pentacene deposition, resulting in a dramatic increase of the field-effect mobility from 0.015 cm²/(V s) to 0.22 cm²/(V s), and a threshold voltage reduction from −14.0 V to −9.9 V. The observed carrier mobility increase by a factor of 10 in the resulting OTFTs is associated with various growth behaviors of polycrystalline pentacene thin films on different substrates, where a pronounced morphological change occurs in the first few molecular layers but the similar morphologies in the upper layers. The accompanying threshold voltage variation suggests that hole accumulation in the conduction channel-induced weak charge transfer between pentacene and CFx.     

Influence of substrate morphology on Pb growth

The crystallographic structure and morphology of Pb layers in their early stage of growth on Si(3 3 5) surface are studied with Reflection High Electron Energy Diffraction (RHEED) and specific resistivity techniques. The vicinal Si(3 3 5), with different surface morphology controlled by the amount of predeposited Au, was used as a substrate. Changes in the substrate morphology, from disordered step distribution through a perfectly ordered Si(3 3 5) to a hill-and-valley structure consisting of wide (1 1 1) terraces and high Miller index facets, cause switching between one- and two-dimensional growth of the Pb structures.     

In situ measurement of the surface stress evolution during magnetron sputter-deposition of Ag thin film

We measured the evolution of in situ surface stress of Ag thin film during the magnetron sputter deposition. The measurement of force per width of Ag thin film showed that both the surface state and surface stress of Ag layer can be controlled through the variation of the deposition conditions such as the deposition temperature and rate. At room temperature, the force per width curve of Ag film deposited to 1 Å/s showed a typical curve consisting of three stages of surface stress. A brief presence of initial compressive stage and broad tensile maximum resulting in a compressive state had a tendency to disappear with increasing the deposition temperature. Meanwhile, a development of final compressive stage was more at higher temperature. Similar effect was observed but less obvious on increasing the deposition rate.     

New magnetic crystal,metastable metallic alloys Co1−xCux, prepared at strongly non-equilibrium conditions

Magnetic Co_1−xCu_x alloys in the form of single-crystal and polycrystalline films were grown under strongly non-equilibrium conditions using magnetron and triode sputtering techniques. It was found that these alloys could be obtained not only in the expected face-centered cubic structure, but also in a tetragonal phase, undetected earlier for present alloys. Results comparing some structural, magnetic and electric properties of these two phases are also presented here.     

The effect of substrate material on pulsed laser deposition of HgCdTe films

This paper describes some recent results of the HgCdTe thin film grown directly on different substrates (sapphire, GaAs and Si) by pulsed laser deposition (PLD). The influences of the substrate material on the properties of HgCdTe thin films were investigated by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). It was found that the quality of the HgCdTe film has a strong relation to the structure and properties of the substrate. The experiment results indicate that the HgCdTe epitaxial thin films grown directly on the sapphire substrates have a high quality, and the composition of the films is close to that of the target. While the quality of the HgCdTe films deposited on the Si and GaAs substrates are not very good.     

Influence of substrate temperature on the texture of barium ferrite film by magnetron sputtering

Barium ferrite thin films have been prepared by radio frequency magnetron sputtering on a sapphire (0 0 1) substrate at substrate temperature of 500 °C and 650 °C, respectively. The films were further annealed in air at 1000 °C for 5 h. X-ray diffraction shows that the films at the lower substrate temperatures have a good epitaxial relation with respect to the substrate, while the samples under the higher substrate temperatures have (1 0 9) planes parallel to the substrate. The remanence ratio decreases from 0.82 to 0.47 when the substrate temperature is increased. We attribute the variation of the growth direction to the enhanced vertical mobility of the deposited atoms when the substrate temperature is increased.     

Depth profile and interface analysis in the nm-range

In modern technology, thin films are shrinking more and more to a thickness of few nanometers. Analytical investigations of such thin films using the traditional sputter depth profiling, sputtering in combination with surface-analytical techniques, have limitations due to physical effects especially for very thin films. These limitations are pointed out and some alternatives are discussed. Non-destructive analysis with angle-resolved X-ray photoelectron spectroscopy is demonstrated to be a useful method for such investigations. Both qualitative and quantitative results can be obtained even for complex layer structures. Nevertheless, there are also limitations of this method and some alternatives or complementary methods are considered.     

Controlling the orientation and coverage of silica-MFI zeolite films by surface modification

The silica-MFI (Si-MFI) zeolite films are fabricated on α-Al₂O₃ supported silica-zirconia layers. The roughness and chemistry of the substrate surface are changed by surface modification with hydrogen peroxide and carboxymethyl chitosan (CMCS) solution to investigate their effects on the formation and orientation control of Si-MFI zeolite films. The AFM images reveal that the roughness of the silica-zirconia surface can be increased under the treatment of hydrogen peroxide. The Si-MFI zeolite films grown on the rough substrate surface are also b-oriented. Diffuse-reflectance FT-IR studies demonstrate that the abundance of functional groups such as -OH and -COOH can be successfully seeded onto the α-Al₂O₃ supported silica-zirconia layer through modification with CMCS solution. Continuous b-oriented Si-MFI zeolite films can be fabricated on the CMCS-modified α-Al₂O₃ supported silica-zirconia layer. It is evident that the orientation and microstructure of Si-MFI zeolite films on α-Al₂O₃ supported silica-zirconia layers are dominantly controlled by the chemical nature of the substrate surface, where the functional groups serve as the structure-directing matrix to induce the orientation and growth of the zeolite crystals with their b-axes perpendicular to the substrate surface.     

Stabilization of discotic liquid organic thin films by ITO surface treatment

Discotic liquid crystals (LCs) are promising materials in the field of electronic components and, in particular, to make efficient photovoltaic cells due to their good charge transport properties. These materials generally exhibit a mesophase in which the disk-shaped molecules can self-assemble into columns, which favorize charge displacement, and may align themselves uniformly on surfaces to form well-oriented thin films. In order to orientate such a columnar thin film on an indium tin oxide (ITO) substrate, the film is heated up to the temperature range of the isotropic liquid phase and subsequently cooled down again. This treatment may lead not only to the desired alignment, but also to dewetting, which leads to an appreciable inhomogeneity in film thickness and to short circuits during the realization of photovoltaic cells. In this article, we describe how this dewetting and the film morphology can be influenced by ITO surface treatments. The chemical modifications of the surface by these treatments were studied by X-ray photoelectron spectroscopy (XPS). Such ITO treatments are shown to be efficient to prevent thin film dewetting when combined with rapid cooling through the isotropic-to-LC phase transition.     

Structure, magnetic and electrical transport properties of cosputtered Fe0.5Ge0.5 nanocomposite films

Fe_0.5Ge_0.5 nanocomposite films with different film thicknesses were fabricated using cosputtering. The films are composed of Ge, Fe and Fe₃Ge₂, and are ferromagnetic at room temperature. The saturation magnetization and magnetic interaction including dipolar interaction and exchange coupling increase with the increasing film thickness. The electrical conductance mechanism turns from metallic to semiconducting and the saturation Hall resistivity ρ_xys increases with the decreasing film thickness. At 28 nm, ρ_xys is ∼137 μΩ cm at 2 K, about 150 times larger than that of pure Fe film (0.9 μΩ cm) and four orders larger than that of bulk Fe. The ρ_xy-H curves of all the films show the same linearity character in low-field range even though the temperature-independent slope is different at different film thicknesses. At high temperatures, the skew scattering mechanism is dominant. At low temperatures, side-jump effect should be dominant at large resistivity ρ_xx regime for the thin films, and the skew scattering is dominant at small ρ_xx regime for the thick films.     

Long-term stability of soft magnetic properties of amorphous and nanocrystalline alloys based on iron

In the present paper long-term stability of magnetic properties of different amorphous and nanocrystalline alloys was studied. Magnetic properties were measured for annealed samples (300<Ta<900 K) directly after annealing and after long-term aging at room temperature. It was shown that for the Fe_75.3Cu₁Zr_1.7Si₁₃B₉ alloy magnetic permeability of the optimized samples is stable during 8 years aging. For Fe_86−xNb_xB₁₄ alloys the observed long-term instability (3 years aging) is due to annealing out of free volume leading to formations of small iron clusters coherent with the amorphous surroundings.