Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiOx matrix, Si:SiO2, were studied. The structures were obtained by reactive ion beam sputter deposition of SiOx (x~0.6) thin films at 450 °C and subsequent crystallization using conventional oven as well as millisecond line focus laser annealing. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven annealing resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72 % within the Si volume, almost single-domain Si structures with 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: Conventional oven tempering proceeds via solid state, millisecond laser application via liquid phase crystallization of Si. The 5 orders of magnitude larger diffusion constant in the liquid phase is responsible for the three times larger Si nanostructure diameter. In conclusion, laser annealing offers not only significantly shorter process times but moreover a superior structural order of nano-Si compared to conventional heating.

L’objectif de ce travail de thèse est l’élaboration du silicium polycristallin en phase liquide, sur substrat de verre borosilicate, en utilisant l’irradiation par laser continu de forte puissance d’un film de silicium amorphe. Des simulations numériques modélisant l’interaction laser-silicium amorphe ont été effectuées grâce à un modèle que nous avons développé sur l’outil COMSOL. Nous avons ainsi pu suivre l’évolution des transferts thermiques dans les différentes structures Si/verre irradiées par laser et ainsi pu évaluer l’impact des paramètres expérimentaux tels que la vitesse de balayage, la puissance du laser, la température du substrat sur les seuils de transition de phase du Si amorphe (fusion, cristallisation, évaporation). Ces résultats de simulation ont été confrontés à des données réelles obtenues en réalisant différentes expériences d’irradiation de films Si amorphe. Les résultats de cette comparaison ont été largement discutés. Dans une deuxième partie, nous avons étudié les propriétés structurales et morphologiques de films Si polycristallin obtenus par l’irradiation laser de films Si amorphe. En particulier, nous avons mis en évidence les effets de la présence d’impuretés tels que l’hydrogène ou l’argon présent dans les couches Si amorphe préalablement au traitement laser. Nous avons également montré que la croissance des cristaux silicium s’opère par épitaxie à partir d’un effet de gradient thermique latéral et longitudinal, produit respectivement par le profil énergétique du faisceau laser et la diffusion thermique par conduction, et par convection thermique dans la direction de balayage. L’optimisation des conditions opératoires nous a permis de réaliser des films Si polycristallin à larges grains, jusqu’à plusieurs centaines de µm de long sur plusieurs dizaines de µm de large. Ces structures sont très intéressantes pour des applications en électronique et en photovoltaïque. / The objective of this thesis is the elaboration of polycrystalline silicon, on borosilicate glass substrate, by a Continuous Wave laser annealing of amorphous silicon operating in the liquid phase regime. Numerical simulations of the laser-amorphous silicon interaction have been carried out using COMSOL tool. We were able to monitor the evolution of the heat transfer in the different laser irradiated Si/glass structures. Thus, we have evaluated the effects of experimental parameters such as the scan speed, the laser power, the substrate temperature on the phase transition thresholds (melting, crystallization, evaporation). The modeling data were compared to the experimental data obtained on laser irradiated amorphous Si films, and the results were thoroughly discussed. In a second part, we have investigated the structural and morphological properties of polysilicon films prepared by CW laser irradiation of different amorphous silicon. We have shown that the presence of impurities such as hydrogen or argon in the amorphous silicon affects strongly the quality of the formed polysilicon film. We also found that the Si crystal growth occurs epitaxially from lateral and longitudinal thermal gradient produced respectively by the laser beam profile and thermal conduction, and by thermal convection in the scanning direction. The optimization of the experimental procedure led to the formation of polysilicon films with large grains up to several hundred microns long and tens microns in width. Such materials are of great interest to electronic and photovoltaic devices.

Silizium basierende Technologie bestimmt den technologischen Fortschritt in der Welt und ist weiterhin ein Material für die weitere Entwicklung von Schlüsseltechnologien. Die Änderung der Silizium-Materialeigenschaft der optischen und elektronische Bandlücke durch die Reduktion der Materialdimension auf die Nanometerskala ist dabei von besonders großem Interesse. Die meisten Silizium-Nanomaterialien bestehen aus Punkt-, Kugel- oder Drahtformen. Ein relativ neues Materialsystem sind dreidimensionale, durchdringende, Nano-Komposit Netzwerke aus Silizium in einer Siliziumdioxid Matrix. Die vorliegende Arbeit untersucht die Entstehung von dreidimensionalen Silizium-Nanokomposit-Netzwerken durch Abscheidung eines siliziumreichen Siliziumoxids(SiOx, mit x<2) und anschlieÿender thermischen Behandlung. Hierbei wurden die reaktive Ionenstrahl-Sputterabscheidung (IBSD), sowie das reaktive Magnetronsputtern (RMS) verglichen. Auch wurden die Unterschiede zwischen klassischer Ofen und Millisekunden-Linienlaser Behandlung untersucht. Abgeschiedene und thermisch behandelte Dünnschichten wurden hinsichtlich der integralen Zusammensetzung, Homogenität, Morphologie und Struktur mittels Rutherford-Rückstreuspektroskopie, Ramanspektroskopie, Röntgenbeugung, spektroskopische Ellipsometrie, Photospektrometrie und (Energie gefilterter) Transmissionselektronenmikroskopie untersucht. Abhängig von der Abscheidemethode und des thermischen Ausheilprozesses wurden unterschiedliche Strukturgrößen und Kristallisationsgrade erzeugt. Insbesondere wurde gezeigt, dass während der 13 ms langen Laserbearbeitung (Ofen: 90 min) wesentlich größere Strukturen (laser:~50 nm; oven:~10 nm) mit einer deutlich höheren Kristallinität (laser:~92-99%; oven:~35-80%) entstehen. Darüber hinaus erhält sich die abscheidebedingte Morphologie nach der Ofenbehandlung, verschwindet jedoch nach der Laserprozessierung. Erklärt wurde dies mit einem Prozess über die flüssige Phase während der Laserbearbeitung, im Gegensatz zu einem Festphasenprozess bei der Ofenbehandlung. Abschließend wurde gezeigt, dass absichtlich eingebrachte vertikale und horizontale Schwankungen der Zusammensetzung genutzt werden können, um definierte Silizium Nanonetzwerke mit einer dreidimensionalen quadratischen Netzstruktur herzustellen.:1 Introduction 2 Fundamentals 2.1 The silicon - silicon oxide system 2.1.1 The Si-O phase diagram 2.1.2 Chemical reaction consideration 2.2 Phase separation of binary systems 2.2.1 Phase separation regimes 2.2.2 Diffusion in solids 2.3 Different types of silicon nanostructures 2.3.1 0D - Silicon nanoparticles 2.3.2 1D - Silicon nanowires 2.3.3 3D - Silicon nanonetworks 3 Experimental methods 3.1 SiOx thin film deposition 3.1.1 SiOx thin films by ion beam sputter deposition 3.1.2 SiOx thin films by reactive magnetron sputter deposition 3.1.3 Comparison of ion beam and magnetron sputter deposition 3.2 Thermal processing of as-deposited SiOx thin films 3.2.1 Oven treatment 3.2.2 Laser treatment 3.3 Thin-film characterization 3.3.1 Rutherford backscattering 3.3.2 Spectroscopic ellipsometry and photospectrometry 3.3.3 Raman spectroscopy 3.3.4 X-ray diffraction 3.3.5 Transmission electron microscopy 4 Results 4.1 Accessible SiOx compositions as a function of deposition and annealing method 4.2 Structure and properties of ion beam sputter deposited SiOx thin films before and after thermal processing 4.2.1 Phase- and microstructure of SiO0:6 thin films deposited by ion beam sputter deposition at 450°C 4.2.2 Phase- and microstructure of SiO0.6 thin films deposited by ion beam sputter deposition at room temperature 4.3 Structure and properties of reactive magnetron sputter deposited SiOx thin films before and after thermal processing 4.4 Multilayer SiOx films for the generation of defined squared mesh structures 5 Discussion 5.1 Compositional homogeneity of SiO0:6 thin films before and after thermal treatment 5.2 Phase structure of as-deposited SiOx thin films 5.3 Influence of the thermal treatment on the structural properties of percolated Si:SiO2 nanostructures 5.3.1 Observed structural properties 5.3.2 Origin of different structure sizes - liquid vs. solid state crystallization 5.4 Influence of the deposition temperature during ion beam sputtering on the structural properties of percolated Si:SiO2 nanostructures before and after thermal processing 5.5 Influence of the deposition method on the structural properties of percolated Si:SiO2 nanostructures 5.6 Formation of interface layers and electrical characterization 6 Summary and outlook 6.1 Summary 6.2 Outlook A EFTEM imaging / Silicon-based technology determines the technological progress in the world significantly and is still a material of choice for further development of key technologies. In particular the reduction of silicon structure sizes to a nanometer scale are of great interest. Most silicon nano structures are based on spherical, dot-like or cylindrical, wire-like geometries. A relatively new material system are three dimensional percolated nanocomposite networks of silicon within a silica matrix. To form any of these nano structures fast, room temperature processes are desired which also offer the possibility of structure modification by different process management. The present work studies the formation of three-dimensional silicon nanocomposite networks by the deposition of a silicon rich silicon oxide (SiO x , with x < 2) and subsequent thermal treatment. Thereby, reactive ion beam sputter deposition (IBSD) as well as reactive magnetron sputtering (RMS) was compared. As well, the differences between a conventional oven and a millisecond line-focused diode laser were studied. As-deposited and thermally treated thin films were characterized with regard to the overall mean composition, homogeneity, morphology and structure by Rutherford backscattering, Raman spectroscopy, X-ray diffraction, spectroscopic ellipsometry, photospectrometry as well as cross-sectional and energy-filtered transmission electron microscopy. Depending on the deposition method as well as the thermal treatment process different structure sizes and degrees of crystallization were achieved. Most notably it was found, that during 13 ms laser processing (oven: min. 90 min), much bigger structures (laser: ≈ 50 nm; oven: ≈ 10 nm) with a notably higher degree of crystallization (laser: ≈ 92-99%; oven: ≈ 35-80%) evolve. Moreover, the structure morphology after deposition is preserved during oven treatment but diminishes following laser processing. This was explained by a process via the liquid phase for laser processing in contrast to a solid state process during oven treatment. Finally it was shown, that intentional introduced vertical and horizontal composition fluctuations can be used to form well-defined silicon nano-networks with a three dimensional square mesh structure.:1 Introduction 2 Fundamentals 2.1 The silicon - silicon oxide system 2.1.1 The Si-O phase diagram 2.1.2 Chemical reaction consideration 2.2 Phase separation of binary systems 2.2.1 Phase separation regimes 2.2.2 Diffusion in solids 2.3 Different types of silicon nanostructures 2.3.1 0D - Silicon nanoparticles 2.3.2 1D - Silicon nanowires 2.3.3 3D - Silicon nanonetworks 3 Experimental methods 3.1 SiOx thin film deposition 3.1.1 SiOx thin films by ion beam sputter deposition 3.1.2 SiOx thin films by reactive magnetron sputter deposition 3.1.3 Comparison of ion beam and magnetron sputter deposition 3.2 Thermal processing of as-deposited SiOx thin films 3.2.1 Oven treatment 3.2.2 Laser treatment 3.3 Thin-film characterization 3.3.1 Rutherford backscattering 3.3.2 Spectroscopic ellipsometry and photospectrometry 3.3.3 Raman spectroscopy 3.3.4 X-ray diffraction 3.3.5 Transmission electron microscopy 4 Results 4.1 Accessible SiOx compositions as a function of deposition and annealing method 4.2 Structure and properties of ion beam sputter deposited SiOx thin films before and after thermal processing 4.2.1 Phase- and microstructure of SiO0:6 thin films deposited by ion beam sputter deposition at 450°C 4.2.2 Phase- and microstructure of SiO0.6 thin films deposited by ion beam sputter deposition at room temperature 4.3 Structure and properties of reactive magnetron sputter deposited SiOx thin films before and after thermal processing 4.4 Multilayer SiOx films for the generation of defined squared mesh structures 5 Discussion 5.1 Compositional homogeneity of SiO0:6 thin films before and after thermal treatment 5.2 Phase structure of as-deposited SiOx thin films 5.3 Influence of the thermal treatment on the structural properties of percolated Si:SiO2 nanostructures 5.3.1 Observed structural properties 5.3.2 Origin of different structure sizes - liquid vs. solid state crystallization 5.4 Influence of the deposition temperature during ion beam sputtering on the structural properties of percolated Si:SiO2 nanostructures before and after thermal processing 5.5 Influence of the deposition method on the structural properties of percolated Si:SiO2 nanostructures 5.6 Formation of interface layers and electrical characterization 6 Summary and outlook 6.1 Summary 6.2 Outlook A EFTEM imaging