Nous avons développé de nouveaux concepts de fabrication de matériaux nanostructurés en couche mince basés sur le dépôt par ablation laser alterné d'un métal (Ag) et d'un diélectrique (Al2O3). Cette technique permet d'atteindre un contrôle optimal sur les paramètres morphologiques des nanostructures qui déterminent la réponse optique des couches minces. Nous avons produit des nanosphères, des nanolentilles et des nanocolonnes, auto-organisées et orientées, encapsulées dans une matrice d'alumine amorphe. Leur réponse optique a été étudiée en fonction de leur morphologie et comparée à des simulations théoriques. En parallèle à cette étude, la réponse vibrationnelle des nanostructures a été analysée par spectrométrie Raman basse fréquence. Finalement, des nanostructures contenant des couches alternées de nanoparticules de Co et d'Ag séparées par une distance de quelques nanomètres ont aussi été fabriquées. Il a été montré que l'interaction entre le plasmon de surface et les modes sphéroïdaux de vibration des nanoparticules active le signal Raman.

Pulsed laser deposition has been used to grow Pb(Zr₀.₅₂Ti₀.₄₈)O₃ (PZT)/LaNiO₃ (LNO) heterostructures with restricted crystallographic orientations on bare Si(001) and SiO₂-coated Si(001) substrates, using TiN buffer layers. The effect of background gas pressure on orientation of the thin films was investigated in detail. XRD analyses showed that under optimized conditions, (001)-oriented PZT/LNO/TiN heterostructures could be grown on either Si(001) or SiO₂/Si substrates. The (001)-textured PZT films had remnant polarizations as high as 23µC/cm², and also had a low coercive field. Up to 10¹⁰ switching cycles have been achieved in these PZT films. / Singapore-MIT Alliance (SMA)

Ph.D. / Electrical Engineering / Nanometer-scale devices have attracted great attention as the ultimate evolution of silicon integrated circuit technology. However, fabrication of nanometer-scale silicon based devices has met great difficulty because it places severe constraints on process technology. This is especially true for SiGe/Si heterostructures because they are particularly sensitive to strain relaxation and/or process induced defects. Recently developed Pulsed Laser Induced Epitaxy (PLIE) offers a promising approach for the fabrication of nanometer- scale SiGe/Si devices. It possesses the advantage of ultra-short time, low thermal budget and full compatibility with current silicon technology. The selective nature of the process allows epitaxial growth of high quality, localized SiGe layers in silicon. In this thesis, a process to fabricate SiGe nanowires in silicon using PLIE is described. In particular, Ge nanowires with a cross-section of ~6 x 60 nm² are first formed using a lift-off process on the silicon substrate with e-beam lithography, followed by a thin low-temperature oxide deposition. Defect-free SiGe nanowires with a cross-section of ~25 x 95 nm² are then produced by impinging the laser beam on the sample. We thus demonstrate PLIE is a suitable fabrication technique for SiGe/Si nanostructures. Fabrication of Ge nanowires is also studied using Focused Ion Beam (FIB) micromachining techniques. Based on the SiGe nanowire process, we propose two advanced device structures, a quantum wire MOSFET and a lateral SiGe Heterojunction Bipolar Transistor (HBT). MEDICI simulation of the lateral SiGe HBT demonstrates high performance of the device. In order to characterize the SiGe nanowires using cross-sectional transmission electron microscopy, an advanced versatile focused ion beam assisted sample preparation technique using a multi-layer stack scheme for localized surface structures is developed and described in this thesis.

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Advancements in the semiconductor industry require new materials with improved performance. With the introduction of copper as the interconnect material for integrated circuits, efficient diffusion barriers are required to prevent the diffusion of copper into silicon, which is primarily through grain boundaries. This dissertation reports the processing of high quality stoichiometric thin films of TiN, TaN and HfN, and studies their Cu diffusion barrier properties. Epitaxial metastable cubic TaN (B1-NaCl) thin films were grown on Si(001) using an ultra-thin TiN (B1-NaCl) seed layer which was as thin as 1 nm. The TiN/TaN stacks were deposited by Pulsed Laser Deposition (PLD), with the TiN thickness systematically reduced from 15 to 1 nm. Microstructural studies included X-ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution TEM (HRTEM). Preliminary Cu diffusion experiments showed that the TiN seed layer thickness had little or no obvious effect on the overall microstructure and the diffusion barrier properties of the TaN/TiN stacks. Epitaxial and highly textured cubic HfN (B1-NaCl) thin films (~100 nm) were deposited on MgO(001) and Si(001) using PLD. Low resistivities (~40 mu omega-cm) were measured with a four point probe (FPP). Microstructural characterizations included XRD, TEM, and HRTEM. Preliminary Cu diffusion tests demonstrated good diffusion barrier properties, suggesting that HfN is a promising candidate for Cu diffusion barriers. Cubic HfN (B1-NaCl) thin films were grown epitaxially on Si(001) substrates by using a TiN (B1-NaCl) buffer layer as thin as ~10 nm. The HfN/TiN stacks were deposited by PLD with an overall thickness less than 60 nm. Detailed microstructural characterizations included XRD, TEM, and HRTEM. The electrical resistivity measured by FPP was as low as 70 mu omega-cm. Preliminary copper diffusion tests showed good diffusion barrier properties with a diffusion depth of 2~3 nm after vacuum annealing at 500 degrees C for 30 minutes. Additional samples with Cu deposited on top of the cubic HfN/TiN/Si(001) were vacuum annealed at 500 degrees C, 600 degrees C and 650 degrees C for 30 minutes. The diffusivity of copper in the epitaxial stack was investigated using HRTEM. The measured diffusion depths, 2 Dt , were 3, 4 and 5 nm at 500 degrees C, 600 degrees C and 650 degrees C respectively. Finally, the diffusivity of Cu into epitaxial HfN was determined to be D=D0 exp(-Q/kT)cm2s-1 with D0=2.3x10-14cm2s-1 and Q=0.52eV.

Diamond and diamond-like carbon films, with their exceptionally good mechanical, chemical, and optical properties, are the best materials as protective hard coatings for electronic devices and cutting tools. The biocompatibility of these materials makes it suitable for bone implants. The wide range applications of these films are hindered because of the high compressive stresses developed during the deposition. Use of carbide and nitride interfacial layers has emerged as one of the methods to reduce the compressive stresses.The present research focuses on the study of different materials as the interfacial layers for diamond and tetrahedral amorphous carbon films. For tetrahedral amorphous carbon AlN, Ta, TiN, TiC, TaN and W were investigated as the interlayer materials. The interlayer was deposited at different substrate temperatures to study the temperature induced changes in the residual stress. The tetrahedral amorphous carbon with TiN interlayer deposited at 300°C and 600°C exhibited a maximum reduction in the stress.TiN and TiC were deposited as interlayer for the diamond films on Ti-6Al-4V alloy. TiC has improved the adhesion of diamond with the substrate and exhibited less compressive stresses compared to TiN.

Silver, gold, and copper metallic nanoparticle films have been utilized in various MEMS devices due to not only their electrical but also their optical properties. The focus of this research is to study the detection at room temperature of carbon monoxide (CO) and hydrogen (H2) via Surface Plasmon Resonance (SPR) phenomenon of silver-embedded Yttrium Stabilized Zirconium (Ag-YSZ) nanocomposite film, gold (Au) nanoparticle film, and an alloy film of silver-copper (Ag-Cu) , grown by the Pulsed Laser Deposition (PLD). To determine the appropriate film materials for quick and accurate CO and H2 detection at room temperature with the PLD technique, the growth process was done repeatedly. Optical tools such as X-Ray Diffraction, Alpha Step 200 Profilometer, Atomic Force Microscopy, and Scanning Electron Microscopy were used to characterize thin films. The gas sensing performance was studied by monitoring the SPR band peak behavior via UV/vis spectrophotometer when the films were exposed to CO and H2 and estimating the percent change in wavelength. The metallic nanoparticle films were tested for concentration of CO (100 to 1000 ppm) and H2 (1 to 10%). Silver based sensors were tested for the cross-selectivity of the gases. Overall the sensors have a detection limit of 100 ppm for CO and show a noticeable signal for H2 in the concentration range as low as 1%. The metallic films show stable sensing over a one-hour period at room temperature. The SPR change by UV/vis spectrophotometer shows a significant shift of 623 nm wavelength between 100 ppm CO gas and dry air at room temperature for the alloy films of Ag-Cu with a wider curve as compared to silver and gold films upon their exposure to CO and H2 indicating an improvement in accuracy and quick response. The results indicate that in research of CO and H2 detection at room temperature, optical gas sensors rather than metal oxide sensors are believed to be effective due to not only the absence of chemical involvement in the process but also the sensitivity improvement and accuracy, much needed characteristics of sensors when dealing with such hazardous gases.

In the past decade, there has been an increased interest in magnetostrictive materials for micro actuators and sensors. Of particular importance are the Fe₂R intermetallics, where R = Tb, Dy. In this study, films of Tb[subscript 0.3]Dy[subscript 0.7]Fe[subscript 1.92] were prepared by three laser processing techniques (pulsed laser deposition, flat plate ablation and laser ablation of microparticles) to explore the effect of processing parameters on particle size, crystallinity and magnetic properties. The laser used in the experiments was a KrF laser with a 12 ns pulse width. Pulsed laser deposition of an alloyed target in vacuum produces dense amorphous films with the similar composition to the target, low coercivity (46 Oe) and good magnetostriction ([lambda][subcript two horizontal lines] = 305 ppm at 2300 Oe). Flat plate ablation and laser ablation of microparticles produced amorphous nanoparticles at 1 atm. The particles were subsequently jet deposited onto substrates to form thick films. Nanoparticle films produced by flat plate ablation resulted in oxidized and segregated particles due to extended, non-uniform plume expansion, laser target modification, and open porosity. Laser ablation of microparticles produced thick films with M[subscript s] = 13.8 emu/g. Two types of annealing treatments were performed to close porosity and increase Youngs modulus. Annealing of LAM films at temperatures up to 700°C in-situ and 950°C in a reducing atmosphere did not result in coarsening of the particles or crystallization of the Laves phase due to the core-shell structure of nanoparticles (rare earth oxide shell, Fe rich core) brought about by oxidation-induced segregation.

The growth of thin-film metal nitride materials from elemental metal targets by plasma-assisted pulsed laser deposition (PLD) has been explored and analysed. A new UHV PLD growth system has been installed and assembled and its system elements were calibrated. A series of GaN thin films have been grown to calibrate the system. In-situ RHEED indicated that the films were single crystal and that growth proceeded in a three-dimensional fashion. SEM images showed heavy particulation of film surfaces that was not in evidence for later refractory metal nitride films. This may be connected to the fact that Ga targets were liquid while refractory metals were solid. Most GaN films were not continuous due to insufficient laser fluence. Continuous films did not exhibit photoluminescence. HfN films have been grown by PLD for the first time. Films grown have been shown to have high reflectivity in the visible region and low resistivity. These factors, along with their crystal structure, make them suitable candidates to be used as back-contacts in GaN LEDs and could also serve as buffer layers to enable the integration of GaN and Si technologies. Growth factors affecting the films’ final properties have been investigated. Nitrogen pressure, within the operating range of the plasma source, has been shown to have little effect on HfN films. Substrate temperature has been demonstrated to have more influence on the films’ properties, with 500 °C being established as optimum. ZrN films have also been grown by PLD. Early results indicated that they exhibit reflectivities 50 % ± 5 % lower than those of HfN. However, further growth and characterisation would be required in order to establish this as a fundamental property of ZrN as nitride targets were mostly used in ZrN production. Single-crystal epitaxial GdN and SmN films have been produced by PLD. This represents an improvement in the existing quality of GdN films reported in the literature, which are mostly polycrystalline. In the case of SmN, these are the first epitaxial films of this material to be grown. Film quality has been monitored in-situ by RHEED which has allowed growth to be tailored to produce ever-higher crystal quality. Post-growth analyses by collaborators was also of assistance in improving film growth. Substrate temperatures and nitrogen plasma parameters have been adjusted to find optimum values for each. In addition, laser fluence has been altered to minimise the presence of metal particulates in the films, which interfere with magnetic measurements carried out in analyses. Capping layers of Cr, YSZ or AlN have been deposited on the GdN and SmN prior to removal from vacuum to prevent their degradation upon exposure to atmospheric water vapour. The caps have been steadily improved over the course of this work, extending the lifetime of the nitride films in ambient. However, they remain volatile and this may persist since water vapour can enter the film at the edge regardless of capping quality. Optical transmission has shown an onset of absorption at 1.3 eV for GdN and 1.0 eV for SmN.

This thesis deals with the synthesis and characterization of Ge-Te-Sb (GST) thin films. The films were deposited using a Pulsed Laser Deposition (PLD) method and mainly characterized with XRD, SEM, AFM and TEM. For amorphous and polycrystalline films, un-etched Si(100) was used. The amorphous films showed a similar crystallization behavior as films deposited with sputtering and evaporation techniques. When depositing GST on un-etched Si(100) substrates at elevated substrate temperatures (130-240°C), polycrystalline but highly textured films were obtained. The preferred growth orientation was either GST(111) or GST(0001) depending on if the films were cubic or hexagonal. Epitaxial films were prepared on crystalline substrates. On KCl(100), a mixed growth of hexagonal GST(0001) and cubic GST(100) was observed. The hexagonal phase dominates at low temperatures whereas the cubic phase dominates at high temperatures. The cubic phase is accompanied with a presumed GST(221) orientation when the film thickness exceeds ~70 nm. Epitaxial films were obtained with deposition rates as high as 250 nm/min. On BaF2(111), only (0001) oriented epitaxial hexagonal GST films are found, independent of substrate temperature, frequency or deposition background pressure. At high substrate temperatures there is a loss of Ge and Te which shifts the crystalline phase from Ge2Sb2Te5 towards GeSb2Te4. GST films deposited at room temperature on BaF2(111) were in an amorphous state, but after exposure to an annealing treatment they crystallize in an epitaxial cubic structure. Film deposition on pre-cleaned and buffered ammonium fluoride etched Si(111) show growth of epitaxial hexagonal GST, similar to that of the deposition on BaF2(111). When the Si-substrates were heated directly to the deposition temperature films of high crystal-line quality were obtained. An additional heat treatment of the Si-substrates prior to deposition deteriorated the crystal quality severely. The gained results show that PLD can be used as a method in order to obtain high quality epitaxial Ge-Sb-Te films from a compound target and using high deposition rates.