Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu     

Insulator-metal transition in a conservative system: An evidence for mobility coalescence in island silver films

Aging, which manifests itself as an irreversible increase in electrical resistance in island metal films is of considerable interest from both academic as well as applications point of view. Aging is attributed to various causes, oxidation of islands and mobility of islands followed by coalescence (mobility coalescence) being the main contenders. The effect of parameters like substrate temperature, substrate cleaning, residual gases in the vacuum chamber, ultrasonic vibration of the substrate, suggest that the mobility coalescence is responsible for the aging in island metal films. Electron microscopy studies show evidence for mobility of islands at high substrate temperatures. The comparison of aging data of island silver films deposited on glass substrates in ultra high vacuum and high vacuum suggests that the oxidation of islands, as being responsible for aging in these films, can be ruled out. Further, under certain conditions of deposition, island silver films exhibit a dramatic and drastic fall in electrical resistance, marking the insulator-metal transition. This interesting transition observed in a conservative system — after the stoppage of deposition of the film — is a clear evidence for mobility coalescence of islands even at room temperature. The sudden fall in resistance is preceded by fluctuations in resistance with time and the fluctuations are attributed to the making and breaking of the percolation path in the film.     

Atomic layer deposition of iridium(III) acetylacetonate on alumina, silica-alumina, and silica supports

The deposition of noble metal particles and films by atomic layer deposition (ALD) has recently gained interest in the fields of catalysis and microelectronics. However, there is little information on the mechanisms governing the reactions of noble metals with high surface area supports. In this work, iridium(III) acetylacetonate was deposited from gas phase onto alumina, silica-alumina, and silica supports to gain insight into the reaction mechanisms. According to elemental analysis and infrared spectroscopy, ligand exchange reaction between iridium acetylacetonate and surface OH groups took place on all substrate surfaces, but the iridium deposition on alumina and silica-alumina appeared to be hindered by sterical effects of the acetylacetonate ligands. Part of the iridium on silica was in metallic form. To reduce the content of iridium, reactive sites of the support surfaces were blocked with H-acetylacetonate (2,4-pentanedione). The blocking reduced the iridium content by more than 90% on alumina but by only 30-50% on silica-alumina. The attempted blocking had almost no effect on silica as expected. According to the results of this work, ALD can provide a feasible method for preparing iridium catalyst with reasonable iridium loadings.     

Growth of Indium Nanorods by Magnetron Sputtering

Indium nanorods are grown on silicon substrates by using magnetron-sputtering technique. Film morphologies and nanorod microstructure are investigated by using scanning electron microscopy, high-resolution transmission electron microscopy （HRTEM）, and x-ray diffraction. It is found that the mean diameter of the nanorods ranges from 30nm to 100nm and the height ranges from 30nm to 200nm. The HRTEM investigations show that the indium nanorods are single crystals and grow along the [100] axis. The nanorods grow from the facets near the surface undulation that is caused by compressive stress in the indium grains generated during grain coalescence process. For low melting point and high diffusivity metal, such as bismuth and indium, this spontaneous nanorod growth mechanism can be used to fabricate nanostructures.     

Growth of polymer–metal nanocomposites by pulsed laser deposition

Complex polymer–metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.     

Enhanced diamond nucleation on copper substrates by graphite seeding and CO2 laser irradiation

Diamond nucleation on copper (Cu) substrates was investigated by graphite seeding and CO₂ laser irradiation at initial stages of the combustion-flame deposition. A graphite aerosol spray was used to generate a thin layer of graphite powders (less than 1 μm) on Cu substrates. The graphite-seeded Cu substrates were then heated by a continuous CO₂ laser to about 750 °C within 1 min. It was found that diamond nucleation density after this treatment was more than three times as much as that on the virgin Cu substrates. As a consequence, diamond films up to 4 μm were obtained in 5 min. The enhancement of diamond nucleation on the graphite-seeded Cu substrates was attributed to the formation of defects and edges during the etching of the seeding graphite layers by the OH radicals in the flame. The defects and edges served as nucleation sites for diamond formation. The function of the CO₂ laser was to rapidly heat the deposition areas to create a favorable temperature for diamond nucleation and growth.     

TEM studies on the formation of nano crystallites of Si by metal induced crystallization

In the present investigations, we have grown the nano-crystallites of Si by metal induced crystallization process. Layers of two different metals (Al and Au) were deposited on either side of Si using thermal evaporation technique to study metal induced crystallization. Annealing of such samples was carried out in the hot stage of TEM. We have found that the crystallization of amorphous silicon starts at 150 °C through the formation of metal silicides. Formation of metal silicides was observed through selected area diffraction. Nearly complete formation of nano crystallites of Si throughout the sample was observed at 200 °C. High-resolution TEM studies confirm the formation of nano-crystallites of Si all along the film.     

On the problem of the consistency of the high-temperature precipitation model with the classical nucleation theory

The adequacy of the model of high-temperature precipitation in dislocation-free silicon single crystals to the classical theory of nucleation and growth of second-phase particles in solids has been considered. It has been shown that the introduction and consideration of thermal conditions of crystal growth in the initial equations of the classical nucleation theory make it possible to explain the precipitation processes occurring in the high-temperature range and thus extend the theoretical basis of the application of the classical nucleation theory. According to the model of high-temperature precipitation, the smallest critical radius of oxygen and carbon precipitates is observed in the vicinity of the crystallization front. Cooling of the crystal is accompanied by the growth and coalescence of precipitates. During heat treatments, the nucleation of precipitates starts at low temperatures, whereas the growth and coalescence of precipitates occur with an increase in the temperature. It has been assumed that the high-temperature precipitation of impurities can determine the overall kinetics of defect formation in other dislocation-free single crystals of semiconductors and metals.     

Substrate-step-induced effects on the growth of CaF2 on Si (111)

The growth of CaF₂ on vicinal Si (111) surfaces was studied by scanning tunneling microscopy (STM) and atomic force microscopy (AFM) for the temperature range from 300 to 750 °C. In the submonolayer range a transition from terrace to step nucleation is observed for increasing temperature. The first monolayer grows in the step-flow growth mode since second layer islands are not nucleated before completion of the wetting layer. For the subsequent growth of CaF₂ on the CaF interface layer, substrate-induced steps do not act as preferential nucleation sites, but rather as growth barriers. Thus CaF₂ films grow very inhomogeneously at high temperatures. At lower deposition temperatures, the film homogeneity increases due to the increased (homogeneous) nucleation rate on terraces. The lattice mismatch leads to (lateral) relaxation of thicker CaF₂ film close to substrate steps. In addition, CaF₂ self-decoration effects are caused by the relaxed regions close to the film steps at temperatures above 500 °C. Received: 7 August 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002     

Simulation of polycrystalline 3D film growth: An investigation of the evolution of grain size and texture in diamond films

An analytical method for simulating gas phase film growth has been developed and used to study the growth of diamond films during prolonged deposition, i.e. the film thickness is much larger than the lateral grain size. From a model system composed of 10⁴ grains, reliable results can be evaluated for the growth of diamond films by (111) and (001) deposition under different initial conditions and with varying growth parameters. It is demonstrated that the rate of structure evolution is sensitively influenced by the aspect ratio of diamond crystal. A near-linear proportionality between the average grain size and the thickness of films can be approximately yielded for a large film thickness which is about 10 times of the average distance of the nuclei. The proportionality constant varies for a statistical nucleation from 0.0056 to 0.43 by changing the aspect ratio. Furthermore, the orientational distribution is drastically narrowed down so that the probability of coalescence of grains with a slight orientational difference is considerably increased. Received: 28 September 2000 / Accepted: 19 February 2001 / Published online: 3 May 2001     

Effect of Incident Intensity on Films Growth in Pulsed Laser Deposition

Incident intensity, defined by the amount of particles deposited per pulse, is an important parameter in the film growth process of pulsed laser deposition （PLD）. Different from previous models, we investigate the irreversible and reversible growth processes by using a kinetic Monte Carlo method and find that island density and film morphology strongly depend on pulse intensity. At higher pulse intensities, lots of adatoms instantaneously diffuse on the substrate surface, and then nucleation easily occurs between the moving adatoms resulting in more smaller-size islands. In contrast, at the lower pulse intensities, nucleation event occurs preferentially between the single adatom and existing islands rather than forming new islands, and therefore the average island size becomes larger in this case. Additionally, our results show that substrate temperature plays an important role in film growth. In particular, it can determine the films shape and weaken the effect of pulse intensity on film growth at the lower temperatures by controlling the mobility rate of atoms. Our results can match the related theoretical and experimental results.     

Theoretical study of magnetic ordering and electronic properties of AgxAl1−x N compounds

Ferromagnetic ordering of silver impurities in the AlN semiconductor is predicted by plane-wave ultrasoft pseudopotential and spin-polarized calculations based on density functional theory (DFT). It was found that an Ag impurity atom led to a ferromagnetic ground state in Ag_0.0625Al_0.9375N, with a net magnetic moment of 1.95 μ_B per supercell. The nitrogen neighbors at the basal plane in the AgN₄ tetrahedron are found to be the main contributors to the magnetization. This magnetic behavior is different from the ones previously reported on transition metal (TM) based dilute magnetic semiconductor (DMS), where the magnetic moment of the TM atom impurity is higher than those of the anions bonded to it. The calculated electronic structure band reveals that the Ag-doped AlN is p-type ferromagnetic semiconductor with a spin-polarized impurity band in the AlN band gap. In addition, the calculated density of states reveals that the ferromagnetic ground state originates from the strong hybridization between 4d-Ag and 2p-N states. This study shows that 4d transition metals such as silver may also be considered as candidates for ferromagnetic dopants in semiconductors.     

Radiation defects induced by helium implantation in gold-based alloys investigated by positron annihilation spectroscopy

The formation of gas bubbles in metallic materials may result in drastic degradation of in-service properties. In order to investigate this effect in high density and medium-low melting temperature (T _M) alloys, positron annihilation spectroscopy measurements were performed on helium-implanted gold–silver solid solutions after isochronal annealing treatments. Three recovery stages are observed, attributed to the migration and elimination of defects not stabilized by helium atoms, helium bubble nucleation and bubble growth. Similarities with other metals are found for the recovery stages involving bubble nucleation and growth processes. Lifetime measurements indicate that He implantation leads to the formation of small and over-pressurized bubbles that generate internal stresses in the material. A comprehensive picture is drawn for possible mechanisms of helium bubble evolution. Two values of activation energy (0.26 and 0.53 eV) are determined below and above 0.7T _M, respectively, from the variation of the helium bubble radius during the bubble growth stage. The migration and coalescence mechanism, which accounts for these very low activation energies, controls the helium bubble growth.     

Use of chlorinated carbon and silicon precursors for epitaxial growth of 4H‐SiC at very high growth rates

A possibility to apply the advantages of chlorinated carbon precursors, which had been previously used in low‐temperature epitaxial growth of 4H‐SiC, to achieve very high growth rates at higher growth temperatures was investigated. Silicon tetrachloride was used as the silicon precursor to suppress gas‐phase homogeneous nucleation. The temperature increase from 1300 °C (which is the temperature of the previously reported low‐temperature halo‐carbon epitaxial growth) to 1600 °C enabled an increase of the precursor flow rates and consequently of the growth rate from 5 to more than 100 μm/h without morphology degradation. High quality of the epilayers was confirmed by low‐temperature photoluminescence spectroscopy and time‐resolved luminescence. No evidences of homogeneous nucleation were detected, however, liquid Si droplet formation on the epilayer surface seems to remain a bottleneck at very high growth rate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Epitaxial growth La0.67Ca0.33MnO3 thin film by radio frequency sputtering method

Perfect epitaxial growth of La_0.67Ca_0.33MnO₃ (LCMO) thin film has been achieved on (1 0 0) LaAlO₃ (LAO) single crystal substrate by radio frequency sputtering method. X-ray diffraction (XRD) and electron diffraction analysis indicates that La_0.67Ca_0.33MnO₃ film grows epitaxially on LaAlO₃ along [1 0 0] direction of the substrate. The resistivity variation with temperature of the film shows a sharp metal to semiconductor transition peak around 253 K, which is close to that of the target. The magnetoresistance (MR) also reveals high quality epitaxy film characteristic at low temperatures and near the metal to semiconductor transition temperature.     

Formation of periodic ring structures of relief and voids under laser vapor deposition of metallic films

The formation of periodic ring structures during laser-induced chemical vapor deposition of metals from metal carbonyl is observed experimentally and described by a theoretical model.     

Study on low-energy bombardment of Au (1 1 1) by noble metal atoms with molecular dynamics simulations

The low-energy bombardment of Au (1 1 1) surface by noble metal atoms is studied with molecular dynamics (MD) simulations. With the incident-energy dependence of adatom yields, sputtering yields, and vacancy yields for different projectiles, we find that the implantation of projectiles in shallow layers below surface can be distinguished by subplantation (in the first and second layers) and implantation (deeper than the third layer). The transition from subplantation to implantation occurs at the incident energy of about 45 eV for the low-energy bombardment of noble metal atoms on Au (1 1 1). The incident-energy dependence of defect yields is obviously different for the subplantation and implantation of projectiles. Based on our MD simulations, we discuss the influence of low-energy bombardment on film growth and the guide to the search for optimum deposition parameters.     

General regularities of interaction between halogens and surface of fcc metals

Main peculiarities of chemical interaction between halogens and fcc metals have been analyzed and results for chemical reaction on copper and silver surfaces as the most studied ones are discussed. General information about the structure of adsorbed layers on metal surfaces is presented. It has been shown that halogenation occurs in two stages. First, a monolayer of chemisorbed halogen atoms is formed, and then metal halide starts to grow, forming a continuous halide film on the surface. The chlorination of silver is indicated (on the basis of the spectroscopic data) as a unique case due to the possible chlorine dissolution into the substrate bulk. It has also been shown that the use of low-energy electron diffraction is usually ineffective for identification of incommensurate lattices at the stage of monolayer and halide film structure formation. To study incommensurate surface structures and halide nucleation processes on atomic scale, probe microscopy and methods for detecting local structure are necessary.     

Epitaxial growth of CeO2 on (100) InP using reactive r.f. magnetron sputtering

The epitaxial growth of CeO₂ thin films has been realized on (100) InP substrates using reactive r.f. magnetron sputtering. Oxide films were nucleated in the presence of molecular hydrogen (4% H₂/Ar sputtering gas) in order to reduce the native oxide formation on the InP surface, which interferes with CeO₂ epitaxy. A metal cerium target was used as the cation source, with water vapor serving as the oxidizing species. Epitaxial films were sputter-deposited at a substrate temperature of 550 °C in a H₂O vapor pressure of approximately 10^-3 Torr. Crystallinity of the oxide films was examined using θ–2θ X-ray diffraction, ω-rocking curves, and in-plane φ-scans. The best results were obtained when the initial nucleation layer was deposited with P(H₂O)<10^-5 Torr, followed by deposition at P(H₂O)=10^-3 Torr. The epitaxial growth of CeO₂ on InP could prove enabling in efforts to integrate functional oxides with InP-based optoelectronic and microwave technologies. Received: 20 February 20002 / Accepted: 21 February 2002 / Published online: 19 July 2002     

Laser-assisted activation of dielectrics for electroless metal plating

2 O₃, SiC, diamond, ZrO₂, etc. are presented. The activation of the dielectric surface can be achieved in a wide range of laser wavelengths and is stable in time. This activation allows selective deposition of various metals (Cu, Ni, Pt, Pd, etc.) with lateral dimensions of several μm. The model of the activation process is discussed. This deals with the modification of the band gap of the dielectric, which involves the appearance of a non-zero density of electronic states in the vicinity of the potential of electroless metal reduction. These electronic states can arise either from the formation of point defects in the ablated surface (for example, F centers in Al₂O₃, CeO₂, or ZrO₂) or from the band bending of the dielectric caused by residual mechanical stresses left in the material after laser ablation (SiC or diamond). The data on the activation of dielectrics by mechanical indentation are qualitatively consistent with the model. Received: 5 January 1998/Accepted: 7 January 1998