Nous avons réalisé des couches minces de Co sur un substrat semi-conducteur (Si(111)) par voix électrochimique, en mode potentiostatique et en mode galvanostatique, et étudié leurs propriétés topographiques (AFM, MEB) et magnétique (RMN, effet Kerr, SQUID), afin de relier ces propriétés aux modes de croissance et aux conditions de dépôt à priori identiques conduisent à des morphologies et donc des propriétés magnétiques très différentes. Nous avons développé une approche rigoureuse avec un contrôle systématique de la qualité du substrat de départ pour clarifier les modes de nucléation et de croissance en fonction du potentiel appliqué en chronoampérométrie. Une transition d’un mode de nucléation instantanée vers un mode de nucléation progressive en fonction du potentiel appliqué est mise en évidence. La modélisation à l’aide du modèle de Scharifker-Hills des modes de nucléation et de croissance est cohérente avec les images de topographie AFM. La croissance est tridimensionnelle du type Volmer-Weber et l’aimantation est orientée dans le plan. Par RMN et également X-Ray Photoemission Spectroscopy (XPS), nous montrons qu’une couche d’hydroxyde de cobalt magnétiquement morte se forme à l’interface avec le Si. En mode galvanostatique, des grains avec des facettes parfaitement cristallisés présentent des domaines magnétiques localisés dans la plupart des ilots. Nous avons également effectué une étude très critique des techniques de dépôt/arrachage employées dans la littérature montrant que celle-ci sont inadaptées aux substrats semi-conducteur, un dépôt subsistant sur la surface quel que soit la technique d’arrachage choisie. / We have deposited thin layers of Co on a semiconductor substrate Si(111), by electrochemical method, in potentiostatic and galvanostatic mode, and we have studied their topographic properties (AFM, MEB) and magnetic (RMN, effet Kerr, SQUID). Thanks to these different techniques, we could relate these properties to the growth modes and to the a priori identical deposition conditions, which lead to different morphologies and therefore different magnetic properties. We have developed a rigorous approach with a systematic control of the quality of the substrate in order to clarify the nucleation and growth modes as a function of the potential applied in chronoamperometry. A transition from an instantaneous nucleation mode to a progressive nucleation mode as a function of the applied potential is highlighted. Modeling with Scharifker-Hills model of nucleation and growth modes is consistent with AFM topography images. The growth is three-dimensional of a Volmer-Weber type and the magnetization is oriented in the plane. By NMR and also X-Ray Photoemission Spectroscopy (XPS), we could show that a layer of magnetically dead cobalt hydroxide layer forms at the interface with Si. In galvanostatic mode, grains with perfectly crystallized facets have magnetic domains located in most of the islands. We have also carried out a very critical study of the deposition / tearing techniques used in the literature showing that they are unsuitable for semiconductor substrates, a deposit remaining on the surface whatever the tearing technique chosen.

Iron filled carbon nanotubes (FeCNT) can be described as carbon nanotubes which contain an iron nanowire of several micrometers length and a diameter of approximately 10-100 nm. The carbon shells protect the iron core from oxidation and mechanical damage thus enabling a wide range of applications that require a long-term stability. The magnetic properties of the enclosed nanowire are in part determined by its small size and elongated shape. Magnetic force microscopy (MFM) measurements show that the iron wire exhibits a single domain behavior. Due to the large shape anisotropy it is magnetized along the long wire axis in the remanent state. Two magnetic monopoles of opposing polarity are located at the wire extremities. Depending on the structure and geometry of the individual nanowire, switching fields in the range of 100-400 mT can be found when the external field is applied along the FeCNT’s easy axis. Cantilever magnetometry shows that the switching can be attributed to a thermally assisted magnetization reversal mechanism with the nucleation and propagation of a domain wall. The defined magnetic properties of individual FeCNT combined with their mechanical strength make them ideal candidates for an application as high resolution high stability MFM probes. The fabrication of such probes can be achieved with the help of a micromanipulation setup in a scanning electron microscope. FeCNT MFM probes achieve a sub 25 nm lateral magnetic resolution. MFM measurements with FeCNT MFM probes in external fields show that the magnetization of these probes is exceptionally stable compared to conventional coated MFM probes. This greatly simplifies the data evaluation of such applied field MFM measurements. The emphasis of this work was put on the calibration of FeCNT probes to enable straightforward quantitative MFM measurements. The defined shape of the magnetically active iron nanowire allows an application of a point monopole description. Microscale parallel current carrying lines that produce a defined magnetic field are used as calibration structures to determine the effective magnetic moment of different MFM probes. The line geometry is varied in order to produce multiple magnetic field decay lengths and investigate the influence on the effective probe moment. The results show that while the effective magnetic monopole moment of a conventional MFM probe increases with an increasing sample stray field decay length, the effective moment of a FeCNT MFM probe remains constant. This enables a MFM probe calibration that stays valid for a large variety of magnetic samples. Furthermore, the fitted monopole moment of a FeCNT probe (in the order of 10E-9 Am) is consistent with the moment calculated from the nanowire geometry and the saturation magnetization of iron.

Zur Aufklärung der lokalen Magnetisierungs- und magnetischen Streufeldstruktur in ferromagnetischen und supraleitenden Materialien wurden magnetkraftmikroskopische (Magnetkraftmikroskopie-MFM) Untersuchungen durchgeführt und quantitativ ausgewertet. Für eine solch quantitative Auswertung muss der Einfluß der verwendeten MFM-Spitzen auf das MFM-Bild bestimmt und in geeigneter Weise subtrahiert werden. Hierzu wurden Spitzenkalibrierungsroutinen und ein Verfahren zur Entfaltung der gemessenen MFM-Daten implementiert, das auf der Wiener Dekonvolution basiert. Mit Hilfe dieser Prozedur können sowohl die räumliche Ausdehnung als auch die Größe der Streufelder direkt aus gemessenen MFM-Bildern bestimmt werden. Gezeigt wurde diese Anwendung für die Durchmesserbestimmung von Blasendomänen in einer (Co/Pd)-Multilage und für die Bestimmung der temperaturabhängigen magnetischen Eindringtiefe in einem supraleitendem BaFe2(As0.24P0.76)2 Einkristall. Desweiteren konnte durch die Kombination von mikromagnetischen Rechnungen und der quantitativen MFM-Datenanalyse die Existenz einer dreidimensionalen Vortex-Struktur am Ende von Co48Fe52-Nanodrähten nachgewiesen werden. Damit ist es gelungen die Tiefensensitivität der Magnetkraftmikroskopie erfolgreich in die Rekonstruktion der vermessenen Magnetisierungsstruktur einzubeziehen.

Zur Aufklärung der lokalen Magnetisierungs- und magnetischen Streufeldstruktur in ferromagnetischen und supraleitenden Materialien wurden magnetkraftmikroskopische (Magnetkraftmikroskopie-MFM) Untersuchungen durchgeführt und quantitativ ausgewertet. Für eine solch quantitative Auswertung muss der Einfluß der verwendeten MFM-Spitzen auf das MFM-Bild bestimmt und in geeigneter Weise subtrahiert werden. Hierzu wurden Spitzenkalibrierungsroutinen und ein Verfahren zur Entfaltung der gemessenen MFM-Daten implementiert, das auf der Wiener Dekonvolution basiert. Mit Hilfe dieser Prozedur können sowohl die räumliche Ausdehnung als auch die Größe der Streufelder direkt aus gemessenen MFM-Bildern bestimmt werden. Gezeigt wurde diese Anwendung für die Durchmesserbestimmung von Blasendomänen in einer (Co/Pd)-Multilage und für die Bestimmung der temperaturabhängigen magnetischen Eindringtiefe in einem supraleitendem BaFe2(As0.24P0.76)2 Einkristall. Desweiteren konnte durch die Kombination von mikromagnetischen Rechnungen und der quantitativen MFM-Datenanalyse die Existenz einer dreidimensionalen Vortex-Struktur am Ende von Co48Fe52-Nanodrähten nachgewiesen werden. Damit ist es gelungen die Tiefensensitivität der Magnetkraftmikroskopie erfolgreich in die Rekonstruktion der vermessenen Magnetisierungsstruktur einzubeziehen.:Introduction 6 1 Contrast formation in Magnetic Force Microscopy (MFM) 9 1.1 Type of interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.1.1 Relevant interaction forces . . . . . . . . . . . . . . . . . . . . . . . 9 1.1.2 Magnetic interaction mechanisms . . . . . . . . . . . . . . . . . . . 11 1.2 Basic magnetostatics of the tip-sample system . . . . . . . . . . . . . . . . 12 1.2.1 General magnetostatic expressions . . . . . . . . . . . . . . . . . . . 12 1.2.2 Description of the tip sample system . . . . . . . . . . . . . . . . . 14 1.2.3 Magnetostatics in Fourier space . . . . . . . . . . . . . . . . . . . . 15 2 Instrumentation 20 2.1 Scanning Force Microscopy (SFM) . . . . . . . . . . . . . . . . . . . . . . . 20 2.1.1 Measurement principle and operation modes . . . . . . . . . . . . . 20 2.1.2 Dynamic mode SFM . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.2 Lift mode MFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.3 Non-contact MFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 2.4 Vibrating Sample Magnetometry . . . . . . . . . . . . . . . . . . . . . . . 26 3 Quantitative Magnetic Force Microscopy 28 3.1 The challenge of MFM image inversion . . . . . . . . . . . . . . . . . . . . 28 3.1.1 Description of the problem and state of the art . . . . . . . . . . . 28 3.1.2 The point probe approximations . . . . . . . . . . . . . . . . . . . . 31 3.1.3 The transfer function approach . . . . . . . . . . . . . . . . . . . . 33 3.2 Tip calibration: Adapted Wiener deconvolution . . . . . . . . . . . . . . . 39 3.2.1 Details of the procedure . . . . . . . . . . . . . . . . . . . . . . . . 39 3.2.2 Evaluation of possible errors . . . . . . . . . . . . . . . . . . . . . . 44 3.3 Noise measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 3.4 MFM probes and their specific characteristics . . . . . . . . . . . . . . . . 49 3.5 Calibration samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 3.6 Detection of tip-sample modification . . . . . . . . . . . . . . . . . . . . . 55 4 Quantitative MFM with iron filled carbon nanotube sensors (Fe-CNT) 56 4.1 The monopole character of Fe-CNT sensors . . . . . . . . . . . . . . . . . . 57 4.1.1 Calibration within the point probe approximation . . . . . . . . . . 57 4.1.2 Calibration results and discussion . . . . . . . . . . . . . . . . . . . 59 4.1.3 Quantitative MFM on a [Co/Pt]/Co/Ru multilayer . . . . . . . . . 62 4.2 Inplane sensitive MFM with Fe-CNT sensors . . . . . . . . . . . . . . . . . 63 4.2.1 Bimodal MFM technique . . . . . . . . . . . . . . . . . . . . . . . . 63 4.2.2 Comparison between calculated and measured in-plane contrast . . 66 5 Quantification of magnetic nanoobjects in MFM measurements 70 5.1 Bubble domains in a [Co/Pd]80 multilayer . . . . . . . . . . . . . . . . . . 71 5.1.1 Micromagnetic model . . . . . . . . . . . . . . . . . . . . . . . . . . 72 5.1.2 MFM image simulation . . . . . . . . . . . . . . . . . . . . . . . . . 72 5.1.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . 74 5.2 Quantitative assessment of the magnetic penetration depth in superconductors 78 5.2.1 Comparison of methods . . . . . . . . . . . . . . . . . . . . . . . . 79 5.2.2 Experimental determination of the temperature dependent penetration depth in a BaFe2(As0:24P0:76)2 single crystal . . . . . . . . . . . 83 6 Magnetization studies of CoFe nanowire arrays on a local and global scale 87 6.1 Revisiting the estimation of demagnetizing fields in magnetic nanowire arrays 88 6.1.1 Available approaches . . . . . . . . . . . . . . . . . . . . . . . . . . 88 6.1.2 Calculation of demagnetizing fields in nanowire arrays . . . . . . . . 91 6.2 Micromagnetic Simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 6.3 Combination of demagnetizing field calculations and micromagnetic simulation100 6.4 Experimental details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102 6.5 Global hysteresis measurements of CoFe nanowire arrays with varying length 104 6.6 Local magnetic characterization of a CoFe nanowire array by quantitative MFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 6.6.1 Magnetic structure of individual nanowires . . . . . . . . . . . . . . 107 6.6.2 Magnetization reversal of the nanowire array . . . . . . . . . . . . . 110 6.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 Conclusions and Outlook 119 Bibliography 121 Acknowledgements 135

The majority of UK’s intermediate level radioactive waste is currently stored in 316L and 304L austenitic stainless steel containers in interim storage facilities for permanent disposal until a geological disposal facility has become available. The structural integrity of stainless steel canisters is required to persevere against environmental degradation for up to 500 years to assure a safe storage and disposal scheme. Hitherto existing severe localised corrosion observances on real waste storage containers after 10 years of exposure to an ambient atmosphere in an in-land warehouse in Culham at Oxfordshire, however, questioned the likelihood occurrence of stress corrosion cracking that may harm the canister’s functionality during long-term storage. The more corrosion resistant duplex stainless steel grade 2205, therefore, has been started to be manufactured as a replacement for the austenitic grades. Over decades, the threshold stress corrosion cracking temperature of austenitic stainless steels has been believed to be 50-60°C, but lab- and field-based research has shown that 304L and 316L may suffer from atmospheric stress corrosion cracking at ambient temperatures. Such an issue has not been reported to occur for the 2205 duplex steel, and its atmospheric stress corrosion cracking behaviour at low temperatures (40-50°C) has been sparsely studied which requires detailed investigations in this respect. Low temperature atmospheric stress corrosion cracking investigations on 2205 duplex stainless steel formed the framework of this PhD thesis with respect to the waste storage context. Long-term surface magnesium chloride deposition exposures at 50°C and 30% relative humidity for up to 15 months exhibited the occurrence of stress corrosion cracks, showing stress corrosion susceptibility of 2205 duplex stainless steel at 50°C.The amount of cold work increased the cracking susceptibility, with bending deformation being the most critical type of deformation mode among tensile and rolling type of cold work. The orientation of the microstructure deformation direction, i.e. whether the deformation occurred in transverse or rolling direction, played vital role in corrosion and cracking behaviour, as such that bending in transverse direction showed almost 3-times larger corrosion and stress corrosion cracking propensity. Welding simulation treatments by ageing processes at 750°C and 475°C exhibited substantial influences on the corrosion properties. It was shown that sensitisation ageing at 750°C can render the material enhanced susceptible to stress corrosion cracking at even low chloride deposition densities of ≤145 µm/cm². However, it could be shown that short-term heat treatments at 475°C can decrease corrosion and stress corrosion cracking susceptibility which may be used to improve the materials performance. Mechanistic understanding of stress corrosion cracking phenomena in light of a comprehensive microstructure characterisation was the main focus of this thesis.