Direct Monitoring of Thickness and Refractive Index of Optical Thin Film Deposited on Fiber End-face

We propose a system for depositing thin films on waveguides which enables low-temperature deposition and precise control of the refractive index and film thickness. It is composed of a conventional ion-beam sputtering (IBS) system and a new system for directly monitoring film characteristics during deposition. We controlled refractive indices over a wide range from 1.52 to 1.97 by moving the sputtering targets (SiO₂ and Si₃N₄) in the IBS system. The refractive index or film thickness was in-situ monitored by observing the optical power reflected from the end-face of a monitoring fiber set in the deposition chamber. Antireflection coating films were successfully deposited on a fiber end-face and a laser diode chip facet with low reflectivity from 0.05 to 0.07%. This deposition system is attractive for constructing highly functional optical devices for future photonic networks.     

The power of in situ pulsed laser deposition synchrotron characterization for the detection of domain formation during growth of Ba0.5Sr0.5TiO3 on MgO

A highly sophisticated pulsed laser deposition (PLD) chamber has recently been installed at the NANO beamline at the synchrotron facility ANKA (Karlsruhe, Germany), which allows for comprehensive studies on the PLD growth process of dielectric, ferroelectric and ferromagnetic thin films in epitaxial oxide heterostructures or even multilayer systems by combining in situ reflective high‐energy diffraction with the in situ synchrotron high‐resolution X‐ray diffraction and surface diffraction methods. The modularity of the in situ PLD chamber offers the opportunity to explore the microstructure of the grown thin films as a function of the substrate temperature, gas pressure, laser fluence and target–substrate separation distance. Ba_0.5Sr_0.5TiO₃ grown on MgO represents the first system that is grown in this in situ PLD chamber and studied by in situ X‐ray reflectivity, in situ two‐dimensional reciprocal space mapping of symmetric X‐ray diffraction and acquisition of time‐resolved diffraction profiles during the ablation process. In situ PLD synchrotron investigation has revealed the occurrence of structural distortion as well as domain formation and misfit dislocation which all depend strongly on the film thickness. The microstructure transformation has been accurately detected with a time resolution of 1 s. The acquisition of two‐dimensional reciprocal space maps during the PLD growth has the advantage of simultaneously monitoring the changes of the crystalline structure as well as the formation of defects. The stability of the morphology during the PLD growth is demonstrated to be remarkably affected by the film thickness. A critical thickness for the domain formation in Ba_0.5Sr_0.5TiO₃ grown on MgO could be determined from the acquisition of time‐resolved diffraction profiles during the PLD growth. A splitting of the diffraction peak into two distinguishable peaks has revealed a morphology change due to modification of the internal strain during growth.     

Thin film solid oxide fuel cells

We have investigated the deposition of 91% ZrO₂ − 9% Y₂O₃ thin films by a variety of sputtering techniques for the application as electrolytes in thin film solid oxide fuel cells. The deposition by RF sputtering was accomplished by using an oxide target of the desired composition. The deposition rate in these initial tests was limited to 0.5 μm/hr and the morphology of the film was substantially modified by deposition rate and substrate temperature. Using DC magnetron sputtering we deposited metallic films from a metallic target with the desired chemical composition. We introduced oxygen into the sputtering chamber to reactively deposit the desired 91% ZrO₂ − 9% Y₂O₃ thin films; however, we encountered problems with target oxidation and growth rate reproducibility. We subsequently demonstrated that controlled oxidation of the metallic films could result in adhering, non porous yttria stabilized zirconia films. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Spray pyrolysis deposition of YSZ and YSZ-Pt composite films

In the present paper procedures are described for spray pyrolysis deposition of YSZ films (0.1-30 μm in thickness) with 8 or 15 mole % of YO_1.5 on different substrates. Aqueous or ethylene glycol solutions of Y-Zr-citrates were used as starting material and O₂ as carrier gas. The crystal structure and the morphology of the films were studied.The optimal deposition and post-deposition annealing conditions were defined, taking into account the desired film thickness and characteristics. Substrate temperatures of 250 °C during the deposition followed by heating for 10 min to 400 °C after every spraying and to 590 °C after every three sprayings with final annealing at 590 °C for 2 h in static air atmosphere were found to be suitable for the production of dense, uniform and cracks-free films.     

Surface characterization of TiO2 thin films obtained by high-energy reactive magnetron sputtering

This paper presents the results of surface characterization of TiO₂ thin films deposited on different substrates by the use of high-energy reactive magnetron sputtering. Structural investigations carried out by X-ray diffraction (XRD) and atomic force microscopy (AFM) have shown a strong influence of both the substrate type, and its placement in the deposition chamber (relative to the sputtering target), on the structural properties of the films. In all cases, there is evidence for pseudoepitaxial growth. XRD examination showed existence of TiO₂-rutile phase with preferred (1 1 0) orientation and AFM measurements revealed nanocrystalline structure directly after deposition. X-ray photoelectron spectroscopy analysis showed that the TiO₂ films have stoichiometric composition.     

Kinetic Monte Carlo simulation of thin film growth

A three-dimensional kinetic Monte Carlo technique has been developed for simulating growth of thin Cu films. The model involves incident atom attachment, diffusion of the atoms on the growing surface, and detachment of the atoms from the growing surface. The related effect by surface atom diffusion was taken into account. A great improvement was made on calculation of the activation energy for atom diffusion based on a reasonable assumtion of interaction potential between atoms. The surface roughness and the relative density of the films were simulated as the functions of growth substrate temperature and film thickness. The results showed that there exists an optimum growth temperatureT _opt at a given deposition rate. When the substrate temperature approaches toT _opt, the growing surface becomes smoothing and the relative density of the films increases. The surface roughness minimizes and the relative density saturates atT _opt. The surface roughness increases with an increment of substrate, temperature when the temperature is higher thanT _opt.T _opt is a function of the deposition rate and the influence of the deposition rate on the surface roughness depends on the substrate temperatures. The simulation results also showed that the relative density decreases with the increasing of the deposition rate and the average thickness of the film.     

A layer of reduced switchable polarisation in (Pb,La)TiO3 films leading to a thickness dependence of the ferroelectric parameters

Two sets of ferroelectric (Pb,La)TiO₃ thin films have been prepared by a diol-based sol-gel technique by varying the heating rate to the crystallisation temperature of 650°C. Films of increasing thickness were obtained by repeating the solution deposition from 1 to 5 times. The switchable polarisation was evaluated from hysteresis loops and from the integration of the switching current transients during pulse tests, and was found to significantly depend on film thickness. Measurements of the thickness dependence of the reciprocal capacitance and Rutherford backscattering spectrometry results indicate that a layer with different dielectric permittivity, and composition for one set of films, existed next to the bottom electrode. In the one set of films it originated because of interdiffusion between the film and the substrate, while in the other set, it was linked to the tensile stress at the film/substrate interface. These layers had a reduced switchable polarisation, which caused the observed dependence of their properties on thickness.     

Spray-pyrolysis deposition of LaMnO3 and La1−xCaxMnO3 thin films

Ethylene glycol solutions of La-Mn(II) and La-Ca-Mn(II) citric complexes has been used as a starting material for spray-pyrolysis deposition of LaMnO₃ and La_1−xCa_xMnO₃ thin films on β-quartz, fused quartz, Si(0 0 1) and SrTiO₃(1 0 0) substrates heated during the deposition at 380 °C. At suitable post-deposition heating conditions highly uniform films, 0.1-1 μm in thickness, with good crystal structure were obtained. Highly textured LaMnO₃ films are obtained on SrTiO₃(1 0 0) substrate. Interaction between the layer and Si-containing substrates is observed during the post-deposition heating in static air.     

X-ray pole-figure study of the epitaxial growth of C60 thin films on mica (001)

The growth of epitaxial C₆₀ thin films on mica(001) by thermal evaporation has been studied in detail by X-ray pole-figure measurements. The influence of the deposition rate, the substrate temperature and the film thickness on the in-plane epitaxial arrangements and the formation of twins has been investigated. It has been demonstrated that the C₆₀ growth is determined by two independent and equivalent C₆₀-crystal grain alignments (type-A and type-B). The nearly six-fold symmetry of the mica(001)-substrate surface offers the three-fold fcc-(111)-oriented C₆₀-crystal grains two equivalent crystal alignments. A high deposition rate of 0.5 Å/s is responsible for the formation of twins at a substrate temperature of 150°C, which diminishes by a higher substrate temperature of 200°C. By a decrease of the deposition rate down to 0.08 Å/s the twins vanish at a film thickness of 200 nm and at the substrate temperature of 150°C. Under the same sublimation conditions, in addition to the type-A and type-B crystal orientations, the growth of the thin C₆₀ films starts with a slight fibre texture which does not appear at a larger film thickness.     

Large area excimer laser induced deposition of titanium from titanium tetrachloride

Large area excimer laser induced deposition of titanium on fused silica from TiCl₄ is studied with an emphasis on process modeling. We show that several TiCl₄ monolayers can be adsorbed if the surface is adequately prepared and that the Ti thin film growth occurs through the photodecomposition of this adsorbed TiCl₄ layer. We propose two growth regimes. During an initiation phase, up to 3 nm in thickness, the adsorbed layer is photochemically decomposed giving a growth rate of 0.015 nm/pulse. In a second phase, the deposition rate increases to between 2 and 7 nm/pulse due to the laser heating of the preceding photochemically deposited titanium film. Between consecutive pulses, TiCl₄ molecules primarily from the adsorbed layer diffuse to the reaction zone leading to a new adsorbed layer ready to be transformed to solid titanium.     

Influence of deposition conditions on the structural characteristics of sublimated CdTe thin films

In this paper the results obtained by X-ray diffraction studies on the structural characteristics of CdTe thin films deposited onto glass substrates by close-spaced sublimation technique are presented. Using different experimental arrangements and appropriate settings for growth parameters, the films with different polycrystalline structures were prepared. The geometry and the volume of the deposition chamber influence the size of film crystallites and also their preferential orientation. The role of deposition parameters such as the substrate temperature, the incidence angle, the film thickness, and the heat treatment in determination of the structural properties of the films are also investigated. Received: 26 November 1999 / Accepted: 7 January 2000 / Published online: 5 April 2000     

Amorphous film thickness dependence for epitaxy of perovskite oxide films under excimer laser irradiation

We have studied the epitaxial growth of perovskite manganite LaMnO₃ (LMO) on SrTiO₃(1 0 0) in the excimer laser assisted metal organic deposition process. The LMO was preferentially grown from the substrate surface by the KrF laser irradiation. The study of amorphous LMO film thickness dependence on epitaxial growth under the excimer laser irradiation revealed that the photo-thermal heating effect strongly depended on the amorphous film thickness due to a low thermal conductivity of amorphous LMO: the ion-migration for chemical bond-forming at the reaction interface would be strongly enhanced in the amorphous LMO film with the large film thickness about 210 nm. On the other hand, the photo-chemical effect occurred efficiently for the amorphous film thickness in the range of 35-210 nm. These results indicate that the epitaxial growing rate was dominated by the photo-thermal heating after the photo-chemical activation at the growth interface.     

Design and development of an ultra-compact drum-shaped chamber for combinatorial pulsed laser deposition

We have designed a compact combinatorial pulsed laser deposition (PLD) chamber as a building block of a desktop laboratory for advanced materials research. Development of small-size systems for the growth and characterization of films would greatly help in interconnecting a variety of analytical tools for rapid screening of advanced materials. This PLD chamber has four special features: (1) a drum-shaped growth chamber, (2) a waterwheel-like combinatorial masking system, (3) a multi-target system having one feedthrough, and (4) a small reflection high-energy electron diffraction (RHEED) system. The performance of this system is demonstrated by the RHEED intensity oscillation during homoepitaxial growth of SrTiO₃ as well as by simultaneous fabrication of a ternary phase diagram of rare earth-doped Y₂O₃ phosphors.     

Towards the synthesis of MAX-phase functional coatings by pulsed laser deposition

Pulsed laser deposition with a Nd:YAG laser was used to grow thin films from a pre-synthesized Ti₃SiC₂ MAX-phase formulated ablation target on oxidized Si(1 0 0) and MgO(1 0 0) substrates. The depositions were carried out in a substrate temperature range from 300 to 900 K, and the pressure in the deposition chamber ranged from vacuum (10⁻⁵ Pa) to 0.05 Pa Argon background pressure. The properties of the films have been investigated by Rutherford backscattering spectrometry for film thickness and stoichiometric composition and X-ray diffraction for the crystallinity of the films. The silicon content of the films varied with the energy density of the laser beam. To suppress especially the silicon re-sputtering from the substrate, the energy of the incoming particles must be below a threshold of 20 eV. Therefore, the energy density of the laser beam must not be too high. At constant deposition energy density the film thickness depends strongly on the background pressure. The X-ray diffraction measurements show patterns that are typical of amorphous films, i.e. no Ti₃SiC₂ related reflections were found. Only a very weak TiC(2 0 0) reflection was seen, indicating the presence of a small amount of crystalline TiC.     

Fabrication of hollow thin films of yttria-stabilized zirconia by chemical vapor infiltration using NiO as oxygen source

Deposition of yttria-stabilized zirconia films on surface oxidized Ni wire substrate by chemical vapor infiltration (CVI) using ZrCl₄ and YCl₃ as metal sources and NiO as oxygen source were studied. The resultant films were cubic crystals of YSZ with a Y₂O₃ content of 1.0–3.7 mol%. The growth rate is larger than that obtained by conventional method of chemical vapor deposition (CVD), increased with the flow rate and decreased with diameter of NiO fiber. The growth rate above its thickness of 4 μm decreased with an increase in the oxidation temperature since the porosity of NiO wire might decrease with an increase in the oxidation temperature. Growth of YSZ films with the CVI method simultaneously involved CVD and electrochemical vapor deposition (EVD).     

Influence of the thickness on structural,magnetic and electrical properties of La0.7Ca0.3MnO3 thin film

We have studied the effect of thickness on the structural, magnetic and electrical properties of La_0.7Ca_0.3MnO₃ thin films prepared by pulsed laser deposition method using X-ray diffraction, electrical transport, magneto-transport and dc magnetization. X-ray diffraction pattern reflects that all films have c-axis epitaxial growth on LaAlO₃ substrate. The decrease in out-of-plane cell parameter specifies a progressive relaxation of in the plane compressive strain as the film thickness is increases. From the dc magnetization measurements, it is observed that ferromagnetic to paramagnetic transition temperature increases with increase in the film thickness. Magneto-resistance and temperature coefficient of resistance increases with film thickness and have maximum value near its metal to insulator transition temperature.     

First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al₂O₃ and TiO₂ by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V₂O₄, while those prepared by the latter had a V₂O₅ stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al₂O₃ are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al₂O₃ or with plasma on TiO₂ consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al₂O₃ depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.     

RHEED observation of BaTiO3 thin films grown by MBE

Ferroelectric BaTiO₃ thin films with a thickness of 10 monolayers (ML) were epitaxially grown on SrTiO₃(0 0 1) substrates by very slow deposition using molecular beam epitaxy (MBE). The investigations were carried out by two growth methods: (i) codeposition and (ii) alternate deposition of the metal elements in an oxygen atmosphere. In situ observation of reflection high-energy electron diffraction confirmed that an epitaxial cube-on-cube structure was prepared. After the deposition, X-ray diffraction measurements were carried out. The 10-ML-thick BaTiO₃ films were highly c-axis oriented single crystals with good film quality.     

Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Deposition and growth kinetics studies of thin zirconium dioxide films by UVILS-CVD

We report the deposition of thin zirconium dioxide films on Si(1 0 0) by a technique of ultraviolet-assisted injection liquid source chemical vapor deposition (UVILS-CVD) by using ultraviolet with 222 nm radiation. The alkoxide zirconium(IV) tert-butoxide (Zr[OC(CH₃)₃]₄) was used as precursor while nitrous oxide was driven into the reaction chamber as an oxidizing agent. The ZrO₂ films were deposited under various conditions and characterized by ellipsometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and scanning electron microscopy. The growth rate decreased with the increasing of substrate temperatures from 200 to 400 °C. Deposition rate of 20 nm/min was observed at a substrate temperature of 350 °C. There was a liner relation between the thicknesses of the films and deposition times. As a result the thicknesses can be accurately controlled by changing the number of drops of precursor introduced by the injection liquid source. The growth rate increased with the increasing concentrations of the precursor, nevertheless the trend stopped when the concentration exceeded 8.5%. The growth kinetics were also studied and the results were fit to a three-step kinetic model involving a photo chemical reaction, a reversible precursor absorption process and a following irreversible deposition reaction.