The effect of flux angle, substrate temperature and deposition rate on obliquely deposited germanium (Ge) films has been investigated. By carrying out deposition with the vapor flux inclined at 87° to the substrate normal at substrate temperatures of 250°C or 300°C, it may be possible to obtain isolated Ge nanowires. The Ge nanowires are crystalline as shown by Raman Spectroscopy. / Singapore-MIT Alliance (SMA)

With the aim to gain a deeper understanding of the role of the angle of incidence in physical vapor deposition, experimental, and computer-based studies were conducted. Electron beam evaporation and ion beam sputtering were used as deposition methods. The materials germanium, silicon, and molybdenum were deposited at different incidence angle, different temperatures and varied residual gas atmospheres. Established models could not be used to adequately explain the obtained relations between morphological parameters, as the tilt angle, with the incidence angle. To investigate the interplay of self-shadowing and competitive growth, an on-lattice simulation was developed. Care was taken to avoid any artificial anisotropy. Comparison with an, additionally developed, off-lattice simulation was used to verify this. Based on the made observations, an analytical model was deduced that combines the material properties and the deposition conditions into a single parameter. The predictions of this model were verified for the experimental observations, the results of the computer simulations, and on literature data. In the last part of the thesis, methods are shown that facilitate to modify the properties of the obliquely deposited thin films to fit requirements of various applications. This includes in situ doping of silicon nanostructures, creation of core-shell structures, as well as biochemical surface functionalization of silver nanostructures. On the example of the latter, various bio-sensing applications are presented.:1 MOTIVATION 7 2 BASIC CONCEPTS 9 2.1 Physical vapor deposition (PVD) 9 2.2 Deposition at oblique angles 14 2.3 Controlling the thin film morphology 16 3 EXPERIMENTAL METHODS 19 3.1 Sample preparation 19 3.2 Characterization techniques 32 4 EXPERIMENTAL RESULTS 37 4.1 Columnar structure and evolutionary selection 37 4.2 Tilt angles and density 42 4.3 Fan angles 45 4.4 Relevance of beam divergence 47 4.5 Summary 50 5 SIMULATION 53 5.1 Introduction 53 5.2 Off-lattice approach 54 5.3 On-lattice approach 59 5.4 Further applications of the on-lattice simulation 64 5.5 Other aspects 72 5.6 Summary 76 6 OBLIQUE ANGLE DEPOSITION MODEL 77 6.1 Semi-Empirical models 77 6.2 Tanto’s fan model 78 6.3 Development of the Competition Model 80 6.4 Verification of the model 84 6.5 Summary 89 7 FILM OPTIMIZATION FOR APPLICATIONS 91 7.1 Boron doped Si nanostructures 91 7.2 Surface functionalization for biosensors 95 7.3 Core-shell structures by pulsed electrodeposition 101 7.4 Summary 105 8 SUMMARY 107 9 BIBLIOGRAPHY 109 10 LIST OF ABBREVIATIONS 121 11 ACKNOWLEDGEMENTS 123 APPENDIX 125 PUBLICATION LIST 131 SELBSTSTÄNDIGKEITSERKLÄRUNG 133 / Mit dem Ziel ein besseres Verständnis des Einflusses des Einfallswinkels in der physikalischen Gasphasenabscheidung zu erreichen, wurden experimentell realisierte und am Computer simulierte Dünnschichten untersucht. Als Abscheidetechniken kamen sowohl Elektronenstrahl-Verdampfen als auch Ionenstrahl-Zerstäubung zum Einsatz. Es wurden die Materialien Germanium, Silicium und Molybdän verwendet, die bei verschiedenen Einfallswinkeln, verschiedenen Substrattemperaturen und variiertem Restgas abgeschieden wurden. Die beobachteten Zusammenhänge, von bspw. kolumnarer Verkippung und Einfallswinkel, konnten nicht mit den etablierten Modellen in Einklang gebracht werden. Um das genaue Zusammenspiel von Abschattung und Konkurrenz-Wachstum zu verstehen, wurde eine „on-lattice“ Computersimulation entwickelt, mit dem besonderen Augenmerk auf die Vermeidung von gitterbasierten Anisotropien. Dies wurde durch Vergleich mit einer, ebenfalls entwickelten, „off-lattice“ Simulation sichergestellt. Ausgehend von den beobachteten Effekten konnte ein analytisches Modell entwickelt werden, welches die Materialeigenschaften und Abscheidebedingungen in einen einzigen Parameter vereint. Die Vorhersagen des Modells wurden an den hergestellten Schichten, den Computersimulationen und an Literaturdaten verifiziert. Abschließend werden Methoden aufgezeigt, die schräg abgeschiedenen nanostrukturierten Schichten verschiedenen Anwendungen anzupassen. Dies umfasst die in situ Dotierung von Siliciumnanostrukturen, die Erzeugung von Kern-Schale-Strukturen, sowie die biochemische Oberflächenfunktionalisierung von Silbernanostrukturen. Am Beispiel der letztgenannten werden verschiedene Anwendungen in der Biosensorik detaillierter vorgestellt.:1 MOTIVATION 7 2 BASIC CONCEPTS 9 2.1 Physical vapor deposition (PVD) 9 2.2 Deposition at oblique angles 14 2.3 Controlling the thin film morphology 16 3 EXPERIMENTAL METHODS 19 3.1 Sample preparation 19 3.2 Characterization techniques 32 4 EXPERIMENTAL RESULTS 37 4.1 Columnar structure and evolutionary selection 37 4.2 Tilt angles and density 42 4.3 Fan angles 45 4.4 Relevance of beam divergence 47 4.5 Summary 50 5 SIMULATION 53 5.1 Introduction 53 5.2 Off-lattice approach 54 5.3 On-lattice approach 59 5.4 Further applications of the on-lattice simulation 64 5.5 Other aspects 72 5.6 Summary 76 6 OBLIQUE ANGLE DEPOSITION MODEL 77 6.1 Semi-Empirical models 77 6.2 Tanto’s fan model 78 6.3 Development of the Competition Model 80 6.4 Verification of the model 84 6.5 Summary 89 7 FILM OPTIMIZATION FOR APPLICATIONS 91 7.1 Boron doped Si nanostructures 91 7.2 Surface functionalization for biosensors 95 7.3 Core-shell structures by pulsed electrodeposition 101 7.4 Summary 105 8 SUMMARY 107 9 BIBLIOGRAPHY 109 10 LIST OF ABBREVIATIONS 121 11 ACKNOWLEDGEMENTS 123 APPENDIX 125 PUBLICATION LIST 131 SELBSTSTÄNDIGKEITSERKLÄRUNG 133

The objectives of the work presented were to 1) fabricate reproducible nanorod array SERS substrates, 2) detection of bacteria using nanorod substrates, 3) detection of DNA hybridization using nanorod substrates and 4) critically evaluate the sensing method. Important findings from this work are as follows. A novel method for batch fabrication of substrates for surface enhanced Raman scattering (SERS) has been developed using a modified platen machined to fit in a commercial electron beam evaporator. The use of this holder enables simultaneous deposition of silver nanorod (AgNR) arrays onto six microscope slide substrates utilizing glancing angle deposition. In addition to multiple substrate fabrication, patterning of the AgNR substrates with 36 wells allows for physical isolation of low volume samples. The well-to-well, slide-to-slide, and batch-to-batch variability in both physical characteristics and SERS response of substrates prepared via this method was nominal. A critical issue in the continued development of AgNR substrates is their stability over time, and the potential impact on the SERS response. The thermal stability of the arrays was investigated and changes in surface morphology were evaluated using scanning electron microscopy and x-ray diffraction and correlated with changes in SERS enhancement. The findings suggest that the shelf-life of AgNR arrays is limited by migration of silver on the surface. Continued characterization of the AgNR arrays was carried out using fluorescent polystyrene microspheres of two different sizes. Theory suggests that enhancement between nanorods would be significantly greater than at the tops due to contributing electromagnetic fields from each nanostructure. In contrast to the theory, SERS response of microspheres confined to the tops of the AgNR array was significantly greater than that for beads located within the array. The location of the microspheres was established using optical fluorescence and scanning electron microscopy. The application of SERS to characterizing pathogens such as bacteria and viruses is an active area of investigation. AgNR array-based SERS substrates have enabled detection of pathogens present in biofluids. Specifically, several publications have focused on determining the spectral bands characteristic of bacteria from different species and cell lines. Studies were carried out on three strains of bacteria as well as the medium in which the bacteria were grown. The spectra of the bacteria and medium were surprisingly similar, so additional spectra were acquired for commonly used bacterial growth media. In many instances, these spectra were similar to published spectra purportedly characteristic of specific bacterial species. In addition to bacterial samples, nucleic acid hybridization assays were investigated. Oligonucleotide pairs specifically designed to detect respiratory syncytial virus (RSV) in nasal fluids were prepared and evaluated. SERS spectra acquired on oligos, alone or in combination, contain the known spectral signatures of the nucleosides that comprise the oligo. However, spectra acquired on an oligo with a 5'- or 3' thiol were distinctly different from that acquired on the identical oligo without a thiol pendant group suggesting some control over the orientation of the oligo on the nanorod surface. The signal enhancement in SERS depends markedly upon the location of the probe relative to the substrate surface. By systematic placement of nucleotide markers along the oligo chain, the point at which the nucleotide disappears from the spectrum was identified. The overall findings for AgNR SERS substrates suggest that the applicability of SERS for detecting nucleic acid hybridization is limited. The strong distance dependence coupled with the lack of substrate stability at temperatures required for annealing oligos during hybridization suggest that AgNRs are not the platform to use for hybridization assays.

Depuis une dizaine d'années, on observe un développement de l'électronique embarquée intégrée à la plupart des objets que nous utilisons au quotidien. Il s'agit maintenant de les interconnecter en créant des réseaux embarqués connectés tels que les réseaux de capteurs autonomes sans fils. La miniaturisation des composants permet d'envisager une autonomie énergétique de ces réseaux composés de capteurs, récupérateurs d'énergie et de micro-batteries. Cependant la faible durée de vie des batteries et leur puissance limitée sont problématiques pour de telles applications. Les micro-supercondensateurs représentent une alternative pertinente pour la gestion de l'énergie dans les systèmes embarqués, notamment grâce à leur durée de vie très élevée. L'objectif de cette thèse concerne l'optimisation des performances de ces dispositifs en termes de densité de puissance et d'énergie. La capacité du supercondensateur étant proportionnelle à la surface électrochimiquement active des électrodes, nous nous sommes donc intéressés à la structuration de collecteurs de courant en or pour optimiser les performances des micro-supercondensateurs à base d'oxyde de ruthénium. Nous avons sélectionné deux principales techniques pour fabriquer une structure tridimensionnelle de l'or. Dans un premier temps, le dépôt physique d'or par évaporation à angle oblique (OAD) nous a permis de réaliser un substrat colonnaire suivi d'un dépôt d'oxyde de ruthénium. Dans un deuxième temps, nous avons mis en place un dépôt électrochimique d'or avec un modèle dynamique à bulles d'hydrogène. Cette technique permet la fabrication d'une structure d'or en trois dimensions par le biais d'un dépôt d'or réalisé simultanément avec une évolution d'hydrogène. L'électrodéposition de l'oxyde de ruthénium sur cette structure poreuse a montré une très bonne compatibilité notamment en terme d'homogénéité du dépôt, une forte capacité à faible vitesse de balayage (> 3 F/cm2) et une bonne cyclabilité. Pour tester les performances de ces électrodes, nous avons réalisé un dispositif complet en configuration empilée présentant de bonnes caractéristiques. Cette technologie de fabrication a pu par ailleurs être transférée à la micro-échelle pour des dispositifs planaires à l'aide de procédés de photolithographie sur électrodes interdigitées. / The increasing importance of portable and wearable electronics as well as embedded wireless sensor networks has made energy autonomy a critical issue. Micro-energy autonomy solutions based on the combination of energy harvesting and storage may play a decisive role. However, the short lifetime of micro-batteries is problematic. Micro-supercapacitors are a promising solution in terms of energy storage for embedded systems on the account of their important lifetime. In this work we have focused on the optimization of the performances of micro-supercapacitors in terms of energy and power density. As the capacitance is directly related to the accessible surface area of the electrodes, we have investigated the structuration of the current collectors in order to improve the performances of ruthenium oxide-based micro-supercapacitors. Two mains technics have been studied to obtain three dimensional structures. In a first phase, the oblique angle physical vapor deposition (OAD) has been investigated to fabricate a columnar gold structure, subsequently covered by an electrochemical ruthenium oxide. In a second phase, a highly porous gold architecture has been studied using electrodeposition via a hydrogen bubbles dynamic template. The ruthenium oxide electrodeposited on the resulting mesoporous gold structure shows good compatibility, in terms of homogeneous deposition, with a significant capacitance at slow rate (> 3F.cm-2) and an important cyclability. As proof of concept, a device has been designed in a stack configuration with good performances. Moreover, the technology finalized for electrodes fabrication has been transferred to the micro-scale on planar interdigitated devices using a suitable photolithography process.

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Les traitements antireflets (AR) sont très largement utilisés pour améliorer la transmission de systèmes optiques composés de hublots, lentilles, de lames séparatrices,… Dans cette thèse les gammes spectrales visées sont le visible étendu [400-1800nm] et le moyen infrarouge [3,7-4,8µm]. La méthode de nanostructuration par dépôts de films minces utilisant des techniques PVD en incidence oblique (Oblique Angle Deposition) a été choisie car elle permet d’envisager des AR hautes performances sur une large gamme de longueur d’onde, via un procédé industrialisable. L’introduction de porosité via le contrôle des angles de dépôt est utilisée pour nanostructurer l’architecture de chaque couche et de l’empilement ; méthode permettant de modifier et d’optimiser les propriétés optiques des couches constituantes en vue d’un design complet optimal. Une cartographie des indices effectifs accessibles par OAD a été dégagée concernant les trois matériaux déposés (TiO2, SiO2 et Ge). Mais les propriétés optiques de ces couches nanostructurées diffèrent largement de celles des couches denses du fait de la présence d’anisotropie, de gradient d’indice, de diffusion et d’absorption. A partir de caractérisations microstructurales, chimiques et optiques poussées (AFM, MEB, MET, tomographie FIB, tomographie MET, EDX, EELS, spectrophotométrie et ellipsométrie généralisée) un modèle optique analytique plus complexe et couplé à des analyses par éléments finis (FDTD) est présenté. L’ensemble du travail a permis d’élaborer par OAD de simples antireflet bicouches démontrant déjà de hauts niveaux de transmission, supérieurs aux traitements AR existants (interférentiel) ou en développement (Moth-eyes). / Anti-reflective (AR) coatings are widely used to improve the transmission of optical systems composed of window, lenses, separating filters,... In this thesis, the spectral ranges targeted are the extended visible [400-1800nm] and the mid infrared [3.7-4.8µm]. Thin film deposition nanostructuring method using oblique angle deposition (oblique angle deposition) PVD technique was chosen because it allows high performance AR to be considered over a wide wavelength range, by an industrial process. The introduction of porosity with the control of deposition angle is used to nanostructure the architecture of each layer and stack; a method for modifying and optimizing the optical properties of the constituent layers for optimal complete design. A mapping of the effective indices accessible by OAD has been identified for the three materials deposited (TiO2, SiO2 and Ge). However optical properties of these nanostructured layers differ greatly from those of dense layers due to the presence of anisotropy, index gradient, diffusion and absorption. Based on advanced microstructural, chemical and optical characterizations (AFM, SEM, TEM, FIB tomography, TEM tomography, EDX, EELS, spectrophotometry and generalized ellipsometry) a more complex analytical optical model coupled with finite element analyses (FDTD) is presented. All the work has enabled OAD to develop simple two-layer anti-reflective coatings that already demonstrate high levels of transmission, superior to existing (interferential) or work in progress (Moth-eyes) AR treatments.