Ion-beam-induced atomic transport and phase formation in the system nickel/antimony

Nickel-antimony intermetallic compounds of different stoichiometries were studied by means of perturbed angular correlation (PAC) spectroscopy. The hyperfine interaction parameters for ¹¹¹Cd probes in the crystal lattices of NiSb, Ni₅Sb₂, Ni₃Sb and NiSb₂ were determined. The results are discussed in the light of crystallographic data.     

Ion-beam-induced atomic transport and phase formation in the system nickel/antimony

We report on the ion-beam mixing processes of Sb/Ni marker layers and bilayers under the irradiation of ions ranging from He to Pb, at 80 K and at room temperature. The concentration profiles are obtained by Rutherford backscattering spectroscopy with 900 keV -particles. At 80 K, the bilayer mixing rates cannot be reproduced by purely ballistic mixing; the essentially linear scaling of the bilayer mixing rate with the energy F _D deposited at the interface points to local spike formation. A transition to global spike formation seems to be visible for the Pb-irradiations. Additional mixing effects at 300 K are due to radiation enhanced diffusion and scale with F _D. The marker mixing rates at 80 K are reproduced by the ballistic mixing approach, but are equally well described by local spike models. High fluence Xe-irradiations of Sb/Ni bilayers lead to intermetallic phases in the interface region as verified by transmission electron microscopy.     

ZnS thin film prepared through a self-assembled thin film precursor route

Poly(zinc 1,6-hexanedithiolate) thin film, a precursor to prepare ZnS thin film, was self-assembled on a quartz substrate. The UV-vis spectra monitored the annealing process of the poly(zinc 1,6-hexanedithiolate) film, which revealed that the ZnS thin film began to form at approximately 515 K. The result of XRD confirmed the crystallinity of ZnS. With increase of annealing temperature, a red shift of the emission spectra was observed.     

Structure,morphology, and growth dynamics of perfluoro‐pentacene thin films

We report high structural order in thin films of the organic semiconductor perfluoro‐pentacene (PFP), which is a candidate material for n‐type applications, deposited by vacuum sublimation on oxidized silicon wafers. Bragg reflections up to high order in both specular and grazing incidence geometries and a mosaicity of less than 0.01° demonstrate the well defined structure. The thin film entirely consists of crystallites with a structure close to the bulk phase without any contamination with a second phase. Real‐time X‐ray measurements show that PFP grows in a Stranski–Krastanov growth mode with the first monolayer wetting the substrate before 3d‐growth sets in during growth of the second monolayer. Implications for its use are discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Interfacial reaction barriers during thin-film solid-state reactions: The crystallographic origin of kinetic barriers at the NiS2/Si(111) interface

Epitaxial NiSi₂ islands have been grown on Si(111) substrates by the direct reaction of nickel vapour with the silicon substrate in ultra-high vacuum at 400° C. Growth kinetics was shown to depend on the orientation of the islands: A-oriented islands grow about ten times faster than B-oriented ones, with the ratio of the advance rates of the main growth fronts even reaching 30. Applying plan-view transmission electron microscopy and high-resolution electron microscopy of cross sections, a corresponding difference was found in the structure of the NiSi₂/Si(111) growth front: Steps at the B-oriented growth front were of three or six interplanar (111) spacings in height, whereas at the A-oriented growth front step-like defects of less than one interplanar (111) spacing in height were observed. These observations are explained by an atomic-scale model of the solid-state reaction, which involves the diffusion of nickel to the interfaces and the nucleation and subsequent lateral propagation of interfacial steps. The difference in the reaction kinetics originates from the presence of kinetic reaction barriers at the NiSi₂/Si(111) growth fronts, the barrier at the B-front being higher owing to the lower formation rate of steps of triple atomic height than that of steps of lower height at the A-NiSi₂/Si(111) growth front.     

Formation of amorphous layers by solid-state reaction. from thin Ir films on Si(100)

Received: 18 November 1997 / Accepted: 16 October 1998 / Published online: 24 February 1999     

Short-range order in Valenta model of thin films

The present paper deals with the Valenta model for magnetic thin films extended to the entropy construction in its pair representation. The problem of the thin films theory is old, but the Valenta model introduced fifty years ago seems to be still an effective approach requiring however, some modifications. The most important one is connected with the improvement of the entropy construction in the self-consistent way when the correlations are taken into account. The idea is introduced in the present paper and discussed in detail.     

Surface morphology and surface chemical states of epitaxial Pb(Zr0.95Ti0.05)O3 thin films grown on SrTiO3(100) by sputter deposition

0.95 Ti_0.05)O₃ thin films of an orthorhombic perovskite structure were obtained on SrTiO₃(100) substrates by radio frequency sputter deposition. The surface morphology of the films was investigated with atomic force microscopy, scanning electron microscopy, and reflection electron microscopy. It is shown that the film surfaces are rather bumpy. There are undulations of about 400 nm in length in an in-plane direction. The mean roughness perpendicular to the surface is 39.6 nm, for the film thickness of 0.45 μm. The surface roughening was probably caused by island-shaped nucleation and growth during the film growth. It has also been found that some gorges and a number of small pits remain at the film surfaces. The surface chemical states of the films were characterized by using X-ray photoelectron spectroscopy. A Pb enrichment layer and a large amount of adsorbed oxygen have been found at the surfaces of the films. Near the film surface Pb and Zr exist mainly in the forms of, besides Pb(Zr,Ti)0₃, metal Pb, metal Zr, oxygen-chemisorbed Pb, and various lead oxides. In addition, a small amount of lead, whose binding energy of Pb 4f_7/2 is much lower than that of metal Pb, was observed at the film surfaces, but its chemical state is unknown up to now. Received: 2 June 1997/Accepted: 22 September 1997     

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.     

Studies on distribution of element contents in transient layer at interface between boron-doped diamond film electrode and tantalum substrate

The boron-doped diamond film (BDD) grown on tantalum (Ta) substrate as an electrode (BDD/Ta) was prepared by hot filament chemical vapor deposition method. The experimental results demonstrated that our BDD/Ta had high current efficiency, strong ability to degrade wastewater, good corrosion stability and long lifetime. These excellent characteristics of BDD/Ta have been explained in terms of Rutherford backscattering (RBS) experiments. RBS investigation revealed that the continuous transient layer at the interface between boron-doped diamond film and Ta-substrate was formed and the microstructure of the continuous transient layer given by the continuous distribution of all element contents at the interface was obtained. The thicknesses of boron-doped diamond film and the continuous transient layer were about equal to 8000 × 10¹⁵ atoms/cm² and 5800 × 10¹⁵ atoms/cm², respectively. The formation of the continuous transient layer at the interface can eliminate the mismatch of thermal expansion coefficients (TEC) at the interface and only lead to the slow change of TEC because of the continuous distribution of element contents of the film and substrate in the transient layer at the interface. Thus, there is no residual stress to concentrate on the interface and the stress-corrosion delamination of the film disappears. Therefore, the corrosion stability and lifetime of BDD/Ta increase and last well, that have been verified by X-ray diffraction (XRD) experiments.     

Properties of Cu film and Ti/Cu film on polyimide prepared by ion beam techniques

Cu film and Ti/Cu film on polyimide substrate were prepared by ion implantation and ion beam assisted deposition (IBAD) techniques. Three-dimension white-light interfering profilometer was used to measure thickness of each film. The thickness of the Cu film and Ti/Cu film ranged between 490 nm and 640 nm. The depth profile, surface morphology, roughness, adhesion, nanohardness, and modulus of the Cu and Ti/Cu films were measured by scanning Auger nanoprobe (SAN), atomic force microscopy (AFM), and nanoindenter, respectively. The polyimide substrates irradiated with argon ions were analyzed by scanning electron microscopy (SEM) and AFM. The results suggested that both the Cu film and Ti/Cu film were of good adhesion with polyimide substrate, and ion beam techniques were suitable to prepare thin metal film on polyimide.     

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.     

Phase transitions in metals on metals

Phase transitions in two-dimensional metal layers on metal surfaces are discussed, with emphasis on systems with attractive lateral interactions on densely packed surfaces. The experimental tools which give information on these transitions are described briefly and the results obtained with them are illustrated by examples of various metals on W and Mo surfaces.     

Shear-induced adhesive failure of a rigid slab in contact with a thin confined film

A rigid-glass prism (square or rectangular base, rectangular cross-section) is sheared off a thin film of silicone elastomer bonded to a glass plate by applying a tangential force at various distances above the prism/elastomer interface. At a given tangential force, the prism starts to slide on the elastomeric film. As the sliding velocity, thus the frictional force, is progressively increased, an elastic instability develops at the interface that results in the formation of numerous bubbles. These bubbles, the lateral dimension of which is comparable to the thickness of the film, move across the interface with speeds 1000 times faster than the overall sliding speed of the glass prism against the PDMS film. It is found that the glass prism continues to slide on the elastomeric film as long as the applied shear stress is less than a critical value. During sliding, however, a normal stress is developed at the interface that decays from the front (i.e. where the force is applied) to the rear end of the prism. When the normal stress reaches a critical value, the prism comes off the film. The critical shear stress of fracture increases with the modulus of the film, but decreases with the thickness following a square root relationship, as is the case with the removal of rigid punches from thin elastomeric films by normal pull-off forces.     

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.     

Aluminium diffusion in titanium nitride films. Efficiency of TiN barrier layers

Two kinds of reactively evaporated titanium nitride films with columnar (B ₀ films) and fine-grained (B ₊ films) film structures, respectively, have been examined as diffusion barriers for preventing aluminium diffusion. The aluminium diffusion profiles have been investigated by 2 MeV ⁴He⁺ Rutherford backscattering spectrometry (RBS) at temperatures up to 550° C. The diffusivity from 300° C to 550° C is: D[m²s^–1]=3×10^–18 exp[–30/(RT)] in B ₀ layers and D[m²s^–1]=1.4×10^–16 exp[–48/(RT)] in B ₊ TiN layers. The activation-energy values determined indicate a grain boundary diffusion mechanism. The difference between the diffusion values is determined implicitly by the microstructure of the layers. Thus, the porous B ₀ layers contain a considerable amount of oxygen absorbed in the intercolumnar voids and distributed throughout the film thickness. As found by AES depth profiling, this oxygen supply allows the formation of Al₂O₃ during annealing the latter preventing the subsequent diffusion of the aluminium atoms.     

Exchange processes in interlayer diffusion – kinks, corners and the growth mode

Interlayer diffusion, i.e. mass transport between different terraces, is known to be an essential process for obtaining layer-by-layer growth, avoiding formation of three-dimensional (3D) islands when growing thin films. We present experimental results for the growth of cobalt on Pt (111), which demonstrate the importance of kinks and corners for interlayer diffusion. We show that Co grows two-dimensionally as long as strain caused by the Pt-Co interface keeps the step edges rough, with a high kink density, and then transforms to 3D growth with straight steps. The results for growth with adsorbed carbon monoxide show that CO acts as a surfactant, causing two-dimensional growth unless heterogeneous nucleation occurs. Again, this process is related to roughening of the steps, being a new mechanism for the action of a surfactant. A scanning tunneling microscopy study at the atomic scale confirms the fact that step descent happens only at kinks and (concave) corners, and in conjunction with simulations allows us to identify some of the relevant atomic-exchange processes. We finally argue that the dependence of the growth mode on the step morphology, together with straightening of the steps by step–step interaction, can lead to an instability of the growth mode. Received: 27 March 2000 / Accepted: 4 September 2000 / Published online: 7 March 2001     

Self-organization in a chromium thin film under laser irradiation

Self-organization of chromium on glass was observed during laser ablation of the metal film with partially overlapping laser pulses. The beam of a nanosecond pulse laser tightly focused to a line was applied to the back-side ablation of the chromium thin film on a glass substrate. While the line ablated with a single laser pulse had sharp edges on both sides with ridges of the melted metal, the use of partially overlapping pulses formed a complicated structure made of the metal remaining from the ridges. Regular structures of ripples were developed in a certain range of laser fluence and pulse overlap. The ripple period could be controlled from 2.5 to 4 μm by variation of the processing parameters. Various experimental techniques were applied to test the structures, and different models of the ripple formation in the thin metal film were considered. The initial quasi-periodical formation started because of dewetting of thin liquid metal films on the glass substrate after its melting. Similar to the evaporation of liquid films, the small perturbation in the ridge thickness was able to induce instability in evaporation of the thin melted metal film. Freezing of the nonequilibrium state between laser pulses was one of the stabilizing factors in self-organization of the metal.     

Dynamics and stability of nanostructures on metal surfaces

Ultrathin metal films consisting of two-dimensional clusters are typically unstable: the cluster ensemble has the tendency to reduce its total free energy via Ostwald ripening or dynamic coalescence of mobile clusters. In this paper we give an overview of recent model experiments addressing these coarsening mechanisms. The experiments have been performed using STM on ensembles consisting of adatom or vacancy clusters with typical diameters in the nanometer range on fcc(111)-metal surfaces. Agreement with and deviations from conventional theories are discussed. Received: 29 March 1999 / Accepted: 17 August 1999 / Published online: 30 September 1999     

Surface modification of a WTi thin film on Si substrate by nanosecond laser pulses

Interaction of a nanosecond transversely excited atmospheric (TEA) CO₂ laser, operating at 10.6 μm, with tungsten-titanium thin film (190 nm) deposited on silicon of n-type (1 0 0) orientation, was studied. Multi-pulse irradiation was performed in air atmosphere with laser energy densities in the range 24-49 J/cm². The energy absorbed from the laser beam was mainly converted to thermal energy, which generated a series of effects. The following morphological changes were observed: (i) partial ablation/exfoliation of the WTi thin film, (ii) partial modification of the silicon substrate with formation of polygonal grains, (iii) appearance of hydrodynamic features including nano-globules. Torch-like plumes started appearing in front of the target after several laser pulses.