M.C. Marco de Lucas

Correlation Between the Electrical Properties and the Morphology of Low‐Pressure MOCVD Titanium Oxynitride Thin Films Grown at Various Temperatures

Titanium oxynitride (TiN x O y ) thin films were deposited by low-pressure metal-organic CVD (LP-MOCVD) on (100) silicon, sapphire, and polycrystalline alumina substrates. Titanium isopropoxide (TIP) and ammonia were used as precursors. The influence of the growth temperature, ranking from 450°C to 750°C, was investigated by scanning electron microscopy (SEM), and electrical DC measurements. Rutherford back-scattering (RBS) measurements were used to determine the N/O ratio in the films. The surface observations of the deposited films showed two morphological transitions. The resistivity decreased with the growth temperature, while the nitrogen content increased. Moreover, for the highest deposition temperatures, the temperature dependence of the resistivity revealed a transition from a semiconducting to a metallic behavior. Finally, these electrical properties were correlated with the two morphological transitions.

In-situ small-angle x-ray scattering study of nanoparticles in the plasma plume induced by pulsed laser irradiation of metallic targets

Small angle x-ray scattering was used to probe in-situ the formation of nanoparticles in the plasma plume generated by pulsed laser irradiation of a titanium metal surface under atmospheric conditions. The size and morphology of the nanoparticles were characterized as function of laser irradiance. Two families of nanoparticles were identified with sizes on the order of 10 and 70 nm, respectively. These results were confirmed by ex-situ transmission electron microscopy experiments.

Thermal effects on the growth by metal organic chemical vapour deposition of TiO2 thin films on (100) GaAs substrates

Abstract TiO 2 thin films were deposited on (100) GaAs substrates by LP-MOCVD with deposition temperatures ( T d ) ranking from 450 to 750 °C. The structure of these layers was studied by X-ray diffraction (XRD) and Raman spectroscopy. The growth of the TiO 2 anatase phase was observed for T d T d >600 °C. Finally, X-ray photoelectron spectrometry (XPS) and secondary ion mass spectroscopy (SIMS) experiments showed the presence of small quantities of Ga and As through the whole film thickness, slightly increasing at the surface of the layers. This result was related to the SEM observations and explained by considering the growth conditions.

MOCVD growth of TiO2 thin films on single crystal GaAs substrates

Abstract TiO 2 thin films have been grown on (100)GaAs and (111)GaAs substrates by low-pressure metal organic chemical vapour deposition (LP-MOCVD). Titanium(IV) isopropoxide, Ti{OCH(CH 3 ) 2 } 4 , was used as a precursor and TiO 2 films were obtained without an additional oxygen flux. Scanning electron microscopy (SEM) experiments have shown a well ordered rod-like crystallisation in the films grown on (100)GaAs. This ordered crystallisation was favoured by a high deposition temperature ( T d =700°C). By contrast, no distinct order was observed in the films grown on (111)GaAs substrates. X-ray diffraction patterns revealed a mainly rutile structure for the TiO 2 films deposited on (100)GaAs at 700°C. XPS results confirmed the TiO 2 stoichiometry of the surface of the films and revealed the presence of C, Ga and As as impurities.

Simple model for the vibrations of embedded elastically cubic nanocrystals

Laboratoire de Physico-Chimie des Mat´eriaux Luminescents, Universit´e de Lyon,Universit´e Claude Bernard Lyon 1, UMR 5620 CNRS, 69622 Villeurbanne, FranceThe purpose of this work is to calculate the vibrational modes of an elastically anisotropic sphereembedded in an isotropic matrix. This has important application to understanding the spectra oflow-frequency Raman scattering from nanoparticles embedded in a glass matrix. First some lowfrequency vibrational modes of a free cubically elastic sphere are found to be nearly independent ofone combination of elastic constants. This is then exploited to obtain an isotropic approximationfor these modes which enables to take into account the surrounding isotropic matrix. This methodis then used to quantatively explain recent spectra of gold and copper nanocrystals in glasses.

Influence of laser–target interaction regime on composition and properties of surface layers grown by laser treatment of Ti plates

Surface laser treatment of commercially pure titanium plates was performed in air using two different Nd : YAG sources delivering pulses of 5 and 35 ns. The laser fluence conditions were set to obtain with each source either yellow or blue surface layers. Nuclear reaction analysis (NRA) was used to quantify the amount of light elements in the formed layers. Titanium oxinitrides, containing different amounts of oxygen and nitrogen, were mainly found, except in the case of long pulses and high laser fluence, which led to the growth of titanium dioxide. The structure of the layers was studied by x-ray diffraction and Raman spectroscopy. In addition, reflectance spectra showed the transition from a metal-like behaviour to an insulating TiO2-like behaviour as a function of the treatment conditions.Modelling of the laser–target interaction on the basis of the Semak model was performed to understand the different compositions and properties of the layers. Numerical calculations showed that vaporization dominates in the case of short pulses, whereas a liquid-ablation regime is achieved in the case of 35 ns long pulses.

Coexistence of several structural phases in MOCVD TiO2 layers: evolution from nanometre to micrometre thick films

The morphology and the structure of TiO2 films, grown on Si (1 0 0) substrates by metal organic chemical vapour deposition (MOCVD) was investigated in 5–500 nm thick films. It was shown that the TiO2 layer is mainly amorphous at the first stages of deposition. The growth of nanocrystallites begins inside the amorphous TiO2 layer, and it continues at the expense of the amorphous phase until the crystallized grains occupy the whole layer. Then, the film growth continues with a columnar structure. The coexistence of anatase and rutile phases was evidenced from the beginning of the growth by high resolution transmission electron microscopy and grazing incidence x-ray diffraction. However, the anatase growth overcomes that of rutile, leading to an inhomogeneous phase distribution as a function of the film thickness.

Structural characterization of TiNxOy/TiO2 single crystalline and nanometric multilayers grown by LP-MOCVD on (110)TiO2

TiO2/TiNxOy superlattices were grown by Low Pressure-Metal-Organic Vapor Phase Epitaxy (LP-MOVPE) technique at deposition temperatures ranking from 650 to 750°C. The growth was performed on top of TiO2(110) rutile substrates. Intense peaks observed in the X-rays rocking curves and θ-2θ diffraction patterns show the presence of crystalline epilayers. The TiNxOy layers were grown in a (200) cubic structure on the (110) quadratic TiO2 epilayer structure. Transmission electron microscopy confirmed the XRD results and showed the formation of periodic and well structured epilayers.

Structural and in depth characterization of newly designed conducting/insulating TiNxOy/TiO2 multilayers obtained by one step LP-MOCVD growth

Abstract TiNxOy/TiO2 multilayers have been grown by LP-MOCVD using titanium isopropoxide (TIP) precursor during the whole growth, but with an ammonia flow interrupted for the TiO2 layers. The one step growth process used to grow these structures allowed to stack the conducting and insulating layers without any growth breakdown. SIMS and TEM analyses showed the presence of an alternated insulating/conducting layers structure. Moreover, electrical measurements allowed to measure the dielectric part of insulating TiO2 stacked in these structures, whose permittivity was found to be about 80 for a MOS structure. Thus, such multilayers may lead to very promising applications in the microelectronics field.

Optical Properties of Sputtered Silver Granular Films

In this research we study optical absorption and morphology of silver films prepared with a sputtering method. Silver granular films are obtained on a glass substrate for films with thickness smaller than about 60 Å. Superficial silver clusters of around 100 nm in diameter are clearly seen in the atomic force micrographs. The absorption of these samples are characterized by plasmon excitation in the 450-650 nm spectral range, which differs from the known excitation of silver nanoparticles fabricated by different techniques. The optical absorption of silver granular films depend on sputtering conditions like substrate temperature or deposition rate and correlates with the surface morphology.