Etudes in situ par GISAXS de la croissance de nanoparticules

I started research using synchrotron radiation (at LURE-Orsay and SRS-Daresbury) during my PhD-Thesis, between 1985 and 1988, mostly using X-Ray Absorption Fine Structure (XAS-EXAFS) and Diffuse Scattering, to investigate the structural properties of alloys, in parallel with laboratory physical metallurgy studies2. I next spent one and a half year as a postdoc at Bell-Labs, where I learnt the bases of Grazing Incidence X-Rays Scattering/Diffraction (GIXS/GIXD), both at NSLS (Brokhaven)3,4 and PEP (Stanford)5. I was employed at the CEA in 1990 to develop synchrotron radiations studies of surfaces and thin films. Between 1990 and 1992, I first built a beamline (in collaboration) and a surface diffractometer6 at LURE, on the supraconducting wiggler, in which I performed first surface diffraction (SRXD) experiments. At that time, I choose to investigate the atomic structure of metal-oxide surfaces by SXRD7,8, as well as the in situ growth of metal on oxide by GIXS and GIXD9, performing also the first in situ Grazing Incidence Small Angle X-Ray Scattering (GISAXS) measurements with a punctual detector. Then I have been quickly involved in the development of the French Interface CRF/BM32 beamline at the ESRF, where I co-developed (with Robert Baudoing-Savois) a new surface diffractometer10, associated with a large UHV chamber equipped with Molecular Beam Epitaxy (MBE). This instrument went in operation in 1996. I continued the study of oxide surfaces11 and metal-oxide interfaces12-15, there and on different ESRF beamlines, combining SXRD, GIXS, GIXD and 0D-GISAXS. This was a fast developing and very gratifying period, which was partly summarized in 1998 in a review paper13. In 1999, I developed a complete instrument on the ID32 ESRF beamline to perform GISAXS using a 2-dimensional detector, in UHV, in situ during growth, without any window before the sample, the UHV chamber being directly hooked to the sychrotron ring16,17. This yielded GISAXS measurements of exceptional quality which opened a new area of diverse studies, during which I progressively shifted from metal on oxide growth to the organized growth of metal dots on different patterned substrates1,16,18-23. Around 2001, I developed in situ GISAXS, combined with SXRD/GIXS/GIXD, on the MBE X-ray chamber of the BM32 beamline. Between 2000 and 2005, both instruments have been intensively exploited to investigate growing metal on oxides and (nanostructured) metal surfaces, together with first studies of germanium growth on nanostructured Si surfaces. I had the chance to collaborate with Remi Lazzari, a postdoc, Frederic Leroy, a PhD-student, and Christine Revenant, forming a team who developed the quantitative analysis of our GISAXS data, trying to go beyond simple analyses, and to understand in detail the diffuse scattering in GISAXS16,18,19,21,24. In parallel, thanks to the venue in our laboratory of specialists of anomalous scattering (Vincent Favre-Nicolin, Hubert Renevier, Johann Coraux), we developed the technique of Multiple Anomalous GISAXS (MAD-GISAXS)22. During all these years, we performed GISAXS measurements during growth, probing the morphology, in parallel with scattering measurements (SXRD, GIXS, GIXD), sometimes 2 anomalous, to probe the structure and composition of growing islands. Because covering all these results would be too wide a field , I have chosen in the first part of this manuscript to concentrate on the GISAXS part of our studies, corresponding to about 6 years of work, between 1999 and 2005. This work also led to the writing of an invited review25. Since then, my research has evolved toward in situ studies with all these x-ray techniques, of the growth of semiconductor islands (Ge on Si) and semiconductor surface structure26, with a very recent extension of our MBE system to perform Chemical beam Epitaxy (CBE or UHV-CVD, Chemical Beam Epitaxy) in parallel with MBE. One of the objective of this combined MBE/CVD system is to allow for in situ structural investigations of growing semiconductor nanowires, which we already started by studying the fusion/solidification processes of AuSi eutectic catalysers27. This last work is the object of a very brief perspective chapter at the end of this manuscript. During all my research work, I have tried to develop and use synchrotron radiation scattering techniques to get the most accurate structural or morphological information during growth, with the goal of going beyond technical studies, to try to understand the basic mechanisms of the processes involved, such as the 3D growth of metal on oxide, or the intermixing between the Si substrate and the Ge deposit. I hope that this permanent concern is also revealed in this manuscript