Papers by Author: Christophe Girardeaux

Abstract: Generation of ultra-thin oxide layers (in the nanometer range) is currently a technological lock for numerous applications such as microelectronics, spintronics or even molecular electronics. A precise study of the stages of growth of Mg is essential before studying the growth of the oxide. In this work we report and discuss an experimental study of the very first stages of Mg growth onto Si(100) by Scanning Tunneling Microscopy-Spectroscopy (STM-STS), Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED). First, we have shown that an amorphous underlayer is formed onto the silicon substrate for Mg deposits of 0.25 monolayers (ML). This underlayer is attributed to a Mg₂Si silicide formed at RT during Mg deposition. Then, using an original growth method based on alternate cycles of magnesium monolayer adsorption and room temperature (RT) oxidation, we did grow ultra-thin magnesium oxide films onto Si(100). Our study revealed that the ultra-thin Mg₂Si layer at the MgO/Si(100) interface acts as a diffusion barrier and prevents oxidation of the highly-reactive silicon during magnesium oxide growth.

Abstract: In this paper, we report investigations concerning the fabrication of a diluted Ge (Mn) solution using solid state Mn diffusion, and Mn/Ge reactive diffusion for spintronic applications. The study of Mn diffusion shows that the quasi-totality of the incorporated Mn atoms occupies Ge substitutional sites and probably exhibits two negative elementary charges. The solubility limit of Mn in Ge is comprised between 0.7 and 0.9 % (T  600 °C). We show that substitutional Mn atoms are not ferromagnetic in Ge and consequently that Ge (Mn) diluted magnetic semiconductor can not be produced. Beside the ferromagnetic signal from Mn₅Ge₃, ferromagnetic signals detected in the samples could be always attributed to surface or bulk Mn-Ge clusters. Furthermore, we show that the CMOS Salicide process is potentially applicable to Mn₅Ge₃ nanolayer fabrication on Ge for spintronic applications. During Mn (thin-film)/Ge reaction, Mn₅Ge₃ is the first phase to form, being thermally stable up to 310 °C and exhibiting ferromagnetic properties up to T_C ~ 300 K.

Abstract: Silicide growth via reaction between a metallic film and a Si substrate has been well documented. In general, atomic transport kinetic during the growth of silicides is considered to be the same as during equilibrium diffusion, despite the reaction and its possible injection of point-defects in the two phases on each side of the interface. To date, the main studies aiming to investigate atomic transport during silicide growth used immobile markers in order to determine which element diffuses the fastest during growth and in which proportion. The quantitative measurements of effective diffusion coefficients during growth was also performed using Deal-and-Groove-type of models, however, these effective coefficients are in general not in agreement with the interdiffusion coefficients calculated using the equilibrium diffusion coefficients measured during diffusion experiments. In general, atomic transport kinetic measurements during growth and without growth are performed using different types of samples for experimental reasons. In this paper, we discuss the possible use of ultrahigh vacuum in situ Auger electron spectroscopy in order to measure the effective diffusion coefficient during growth, as well as the equilibrium self-diffusion coefficients, in the same samples, in the same experimental conditions. The first results on the Pd-Si system show that atomic transport during Pd₂Si growth is several orders of magnitude faster than at equilibrium without interfacial reaction.

Abstract: An alternative solution for producing logic devices in microelectronics is spintronics (SPIN TRansport electrONICS). It relies on the fact that in a magnetic layer, the electrical current can be spin polarized. To fabricate such components, a material whose electronic properties depend on its magnetic state is needed. The Mn-Ge system presents a lot of phases with different magnetic properties, which can be used for spintronics. The most interesting phase among the Mn-Ge system is Mn₅Ge₃ because of its stability at high temperatures, its Curie temperature which is close to room temperature and its ability of injecting spin-polarized electrons into semiconductors. In this paper, we have combined Reflection High-Energy Electron Diffraction (RHEED) and X-ray Diffraction (XRD), to study the sequence of formation of Mn_xGe_y phases during reactive diffusion of both a 50 nm and a 210 nm thick Mn films deposited by Molecular-Beam Epitaxy (MBE) on Ge (111).

Abstract: The use of nanometric size materials as embedded clusters, nanometric films, nanocrystalline layers and nanostructures is steadily increasing in industrial processes aiming to produce materials and devices. This is especially true in today Si-based microelectronics with transistors made of a multitude of different thin film materials (B-, As-, and P-doped Si, NiSi (Pt), poly-Si, W, TiO_x, LaO, SiO₂, Al, H_fO₂), and exhibiting a characteristic lateral size of 32-22 nm. Size reduction leads to an increasing role of surfaces and interfaces, as well as stress and nanoscale effects upon important phenomena driving fabrication processes, such as atomic diffusion, phase nucleation, phase growth, and coarsening. Consequently, nanotechnology related to Material Science requires an investigation at the nanometric (or atomic) scale of elementary physical phenomena that are well-known at the microscopic scale. This paper is focused on nanosize effects upon diffusion in Si and Si reactive diffusion. We present recent results showing that the kinetic of lattice diffusion is enhanced in semiconductor nanometric (nano) grains, while grain boundary (GB) diffusion is not changed in nanoGBs. It is also shown that diffusion in triple-junction (TJ) is several orders of magnitude faster than GB diffusion, and that its effect cannot be neglected in nanocrystalline (nc) layers made of 40 nm-wide grains. Experimental results concerning Si sub-nanometric film reaction on Ni (111) substrate are also presented and compared to theoretical results giving new prospects concerning nanosize effects on reactive diffusion at the atomic scale.

Abstract: In recent years, spintronics whose principle is based on controlling the spin of electrons in semiconductor layers is presented as a complementary or even an alternative solution for production of logic devices in microelectronics. It relies on the fact that electric current in a magnetic layer can be spin polarized. Manufacture of such components is based on the use of materials or heterostructures whose electronic properties depend on their magnetic state. The magnetic Mn-Ge system is interesting because of its possible development at high Curie temperature and its integration on Si substrate. Among all of the Mn-Ge phase compounds of the diagram, Mn₅Ge₃ seems the most interesting one for spintronics applications: it is a stable and ferromagnetic phase at room temperature. In this paper, we present first results of the study, by Reflection High Energy Electron Diffraction (RHEED), X-ray diffraction (XRD) and Atomic Force Microscopy (AFM), of the sequence of formation of the Mn_xGe_y phases in the case of reaction of a nanometric-thick Mn film (200nm) deposited by MBE on Ge (111).

Abstract: Silicide sequential phase formation during tens-of-nanometer-thick metallic film reaction on Si substrate has been extensively studied. Nevertheless, the reasons of sequential phase formation are still under debate, and have been poorly studied at the atomic scale. Using atomistic kinetic Monte Carlo simulations, we show that considering a binary fcc non-regular solid solution, without diffusion asymmetries, the diffusive reaction of a sub-nanometer-thick film (~5 atomic monolayers) on a semi-infinite substrate leads to the sequential formation of all the phases present in the binary phase diagram, starting with the film atom richest phase. These predictions are supported by experimental observations: the dissolution of a 4 monolayer-thick Si film on a Ni(111) substrate, during in-situ ultra high vacuum Auger electron spectroscopy, shows delays and kinetic changes in the dissolution process that may correspond to the sequential formation of the Ni-Si compounds, i.e. NiSi₂, NiSi, Ni₃Si₂, Ni₂Si, Ni₃₁Si₁₂ and Ni₃Si.

Abstract: Diffusion controlled processes play a crucial role in the degradation of technical materials. At low temperatures the most significant of them is the diffusion along grain boundaries. In thin film geometry one of the best methods for determining the grain boundary (GB) diffusion coefficient of an impurity element is the Hwang-Balluffi method, in which a surface sensitive technique is used to follow the surface accumulation kinetics. Results of grain boundary diffusion measurements, carried out in our laboratory by this method in three different materials systems (Ag/Pd, Ag/Cu and Au/Ni) are reviewed. In case of Ag diffusion along Pd GBs the surface accumulation was followed by AES method. The data points can be well fitted by an Arrhenius function with an activation energy Q=0.99eV

Abstract: We present an experimental study by Auger electron spectroscopy (AES) and low energy electron diffraction (LEED) of the dissolution of about one monolayer of silicon previously deposited at room temperature on Cu (001). The isochronal dissolution has been recorded in the temperature range [50-320°C] (annealing rate 1.5°C/min). The plateau observed in the kinetics dissolution for temperatures between 95°C and 240°C, reveals the formation of an intermetallic two dimensional superficial phase thermally stable in this range of temperature. On the plateau, LEED patterns show the formation of a (5x3) superstructure. Above 255°C, we observe a very fast dissolution of the surface alloy characteristic of a first-order surface transition. Isothermal dissolutions kinetics have been recorded above and under the surface transition temperature (250°C and 270°C). From these measurements, we have evaluated bulk diffusion coefficients of Si in Cu assuming a local equilibrium. The diffusion coefficients measured within this hypothesis at 250°C and 270°C are respectively higher and lower than those extrapolated from high temperature measurements for Ge in Cu.

Abstract: Depending on the thermodynamic, structural and diffusion properties of the system, a thin deposit dissolves into a substrate by different mechanisms. In this communication these different behaviours, investigated by surface analytical techniques (AES, XPS, STM, UPS, etc) [ - ], are reviewed. The experiments were also supported by computer simulations. The obtained results are compared and it is summarized how different parameters influence the dissolution of a thin film in a substrate. Furthermore, it is show that i) the volume dissolution kinetics is different on the atomic-/nano-scale than on the microscopic scale due to the diffusion asymmetry ii) the volume and GB diffusion in one measurement can be separated and iii) pure (C-kinetic) GB diffusivities can be determined from thin film kinetics measurements performed under adequate conditions.