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Stress and Microstructural Evolution During the Growth of Transition Metal Oxide Thin Films by PVDNarayanachari, K V L V January 2015 (has links) (PDF)
System on Chip (SoC) and System in Package (SiP) are two electronic technologies that involve integrating multiple functionalities onto a single platform. When the platform is a single wafer, as in SOC, it requires the ability to deposit various materials that enable the different functions on to an underlying substrate that can host the electronic circuitry. Transition metal oxides which have a wide range of properties are ideal candidates for the functional material. Si wafer on which micro-electronics technology is widely commercialized is the ideal host platform.
Integrating oxides with Si, generally in the form of thin films as required by microelectronics technology, is however a challenge. It starts with the fact that the properties of crystalline oxides to be exploited in performing various functions are direction dependent. Thus, thin films of these oxides need to be deposited on Si in certain crystallographic orientations. Even if a suitably oriented Si wafer surface were available, it does not always provide for epitaxial growth a critical requirement for controlling the crystalline orientation of thin films. This is because Si surface is covered by an amorphous oxide of Si (SiOx). Thus, during growth of the functional oxide, an ambience in which the Si itself will not oxidize needs to be provided. In addition, during thin film growth on either Si or SiOx surface stresses are generated from various sources. Stress and its relaxation are also associated with the formation and evolution of defects. Both, stress and defects need to be managed in order to harness their beneficial effects and prevent detrimental ones.
Given the requirement of SoC technology and the problem associated, the research work reported in this thesis was hence concerned with the precise controlling the stress and microstructure in oxide thin films deposited on Si substrates. In order to do so a versatile, ultra high vacuum (UHV) thin film with a base pressure of 10-9 Torr was designed and built as part of this study. The chamber is capable of depositing films by both sputtering (RF & DC) and pulsed laser ablation (PLD). The system has been designed to include an optical curvature measurement tool that enabled real-time stress measurement during growth.
Doped zirconia, ZrO2, was chosen as the first oxide to be deposited, as it is among the few oxides that is more stable than SiOx. It is hence used as a buffer layer. It is shown in this thesis that a change in the growth rate at nucleation can lead to (100) or (111) textured films. These two are among the most commonly preferred orientation. Following nucleation a change in growth rate does not affect orientation but affects stress. Thus, independent selection of texture and stress is demonstrated in YSZ thin films on Si. A quantitative model based on the adatom motion on the growth surface and the anisotropic growth rates of the two orientations is used to explain these observations. This study was then subsequent extended to the growth on platinized Si another commonly used Si platform..
A knowledge of the stress and microstructure tailoring in cubic zirconia on Si was then extended to look at the effect of stress on electrical properties of zirconia on germanium for high-k dielectric applications. Ge channels are expected to play a key role in next generation n-MOS technology. Development of high-k dielectrics for channel control is hence essential.
Interesting stress and property relations were analyzed in ZrO2/Ge. Stress and texture in pulsed laser deposited (PLD) oxides on silicon and SrTiO3 were studied. It is shown in this thesis that stress tuning is critical to achieve the highest possible dielectric constant. The effect of stress on dielectric constant is due to two reasons. The first one is an indirect effect involving the effect of stress on phase stability. The second one is the direct effect involving interatomic distance. By stress control an equivalent oxide thickness (EOT) of 0.8 nm was achieved in sputter deposited ZrO2/Ge films at 5 nm thickness. This is among the best reported till date.
Finally, the effect of growth parameters and deposition geometry on the microstructural and stress evolution during deposition of SrTiO3 on Si and BaTiO3 on SrTiO3 by pulsed laser deposition is the same chamber is described.
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Spatially resolved optical measurements on supported metal particles and oxide surfaces with the STMBenia, Hadj Mohamed 08 December 2008 (has links)
In der vorliegenden Arbeit wurde mit Hilfe eines Photon-STM die Korrelation zwischen optischen Eigenschaften und der lokalen Morphologie an zwei unterschiedlichen Systemen untersucht. Hierfür wurden zum einem oxidgetragene Ensemble von Silber-Partikeln präpariert, wobei sowohl die Partikelform (Kuppel- und Scheibenform) als auch die deponierte Partikeldichte variiert werden konnte. Neben der Präparation solcher Partikel auf Al10O13/NiAl, konnten sphärische Silber-Kolloide geordnet, als auch ungeordnet auf HOPG aufgebracht und untersucht werden. Dabei zeigte sich, dass das Verhältnis von Höhen zu Breiten nicht nur einen signifikanten Einfluss auf die Mie-Resonanz des einzelnen Partikels hat, sondern auch die elektromagnetische Kopplung der Partikel in einem Ensemble stark kontrolliert. Die energetische Lage der Mie-Resonanz zeigt im Fall der kuppelförmigen Ag-Partikel eine starke Abhängigkeit vom Intepartikel-Abstand, was sich in einer Verschiebung zu höheren Energien für eine steigende Partikeldichte äußert. Eine solche Abhängigkeit konnte bei den Ensembles der scheibenförmigen Partikel nicht beobachtet werden. Des weiteren zeigte sich, dass, verglichen mit den ungeordneten Ensembles, die selbstorganisierte langreichweitige Ordnung der Silber-Kolloide auf HOPG nur einen schwachen Einfluss auf die energetische Position der Mie Resonanz hat.Das zweite hier untersuchte System sind dünne MgO Filme unterschiedlicher Dicken auf einem Mo(001) Substrat. Diese zeigen ein reichhaltiges Wachstumsverhalten, welches durch eine Differenz in den Gitterkonstanten von 5.3% begründet ist und erst ab etwa 25 ML zu einem flachen und defektarmen Film führt. Die so induzierte Spannung relaxiert bis zu einer Dicke von etwa 7 ML in einer periodischen Überstruktur die aus abwechselnd flachen und verkippten Ebenen an der MgO-Mo Grenzschicht hervorgeht. Für MgO Filme mit einer Dicke von etwa 12 ML werden dann Schraubenversetzungen, ausgedehnte verkippte Ebenen und Stufenkanten mit einer Orientierung entlang der Richtung beobachtet. Die optische Charakterisierung durch Feldemission von Elektronen aus der STM-Spitze in den MgO-Film wird dominiert von zwei Emissionsmaxima bei Energien von 3.1 eV und 4.4 eV. Die kontrollierte Nukleation von Gold Partikeln und die Erzeugung von Farbzentren im MgO Film erlaubten eine Zuordnung dieser Emissionen zu strahlenden Zerfällen von Exitonen an Ecken, Kinken bzw. Stufen des Magnesiumoxids. Solche Emissionsprozesse konnten allerdings nur unter Einstellungen beobachtet werden, bei denen ein gleichzeitiges Rastern der Oberfläche unmöglich ist. Bei moderaten Einstellungen war auch eine ortsaufgelösten Spektroskopie möglich, wobei dann neue Emissionsmechanismen beobachtet wurden. Dabei sind zwei Prozesse wesentlich; zum einen die Ausbildung von sog. Spitzen-induzierten Plasmonen im Bereich zwischen Spitze und dem Mo-Substrat, zum anderen strahlende Elektronenübergänge zwischen sog. Feldemissionsresonanzen, die sich im Spitze/MgO-Film System ausbilden. / In this thesis, the correlation between the optical properties and the local morphology of supported silver nanoparticle ensembles and MgO thin films deposited on Mo(001) systems is explored by means of Photon-STM. In the first section, dome and disk shaped Ag nanoparticle ensembles with increasing density on an alumina film on NiAl(110) were analyzed as well as ordered and disordered ensembles of Ag nanocolloids on HOPG. The aspect ratio of the Ag nanoparticles was found to have a significant influence not only on the Mie plasmon resonance of a single particle, but also on the electromagnetic coupling within the nanoparticle ensembles. The Mie resonance in the ensemble of dome shaped Ag nanoparticles shows a strong dependence on the interparticle distance, where it shifts to higher energies with increasing particle density, due to destructive interference effects. In the disk-like Ag ensembles, however, the plasmon energy is independent of particle-particle separation. The long-range lateral ordering of size-selected Ag nanocolloids is found to induce a high dipole-dipole coupling within the ensemble. This is mainly reflected by the enhancement of the spectral intensity of the in-plane Mie mode, due to constructive coupling. However, ensembles with either well-ordered or disordered arrangements reveal no important difference in their optical properties, reflecting the weak influence of the long-range order in the particle ensemble. Thin MgO films with different thicknesses were grown on a Mo(001) surface. The stress resulting from the 5.3% lattice mismatch between the MgO(001) and the Mo(001) lattice parameters is found to control the surface morphology of the MgO film until thicknesses of around 25ML at which flat and defect-poor films are obtained. The relaxation of the stress induces a periodic network in the first 7ML of the MgO film, consisting of alternated flat and tilted mosaics. The presence of screw dislocations, steps oriented along the MgO directions, and tilted planes is observed when the MgO films are approximately 12ML thick. In addition, an increase of the MgO work function around these new surface features is revealed from STM spectroscopy. The photon emission induced by field-emitted electron injection from the STM tip into the MgO films is dominated by two emission bands located at 3.1eV and 4.4eV. To check the origin of these bands, further experiments, namely, nucleation of Au particles and creation of F-centers on the MgO surface, have been performed. The nucleation of Au particles at the low coordinated sites is found to quench the MgO optical signal, while the creation or annihilation of F-centers does not alter the MgO emission bands. The 3.1eV and the 4.4eV bands are therefore assigned to the radiative decay of MgO excitons at corner and kink sites, and step sites, respectively. Besides, spatially resolved optical measurements in the tunneling mode of the STM revealed different light emission mechanisms. These radiative processes are mainly related to tip-induced plasmons that form between the tip and the Mo support and to electron transitions between field-emission-resonance states in the STM tip-MgO film junction. The signal from exciton decays at corners and kinks of the MgO surface is however only observed at excitation conditions where the spatial resolution is already strongly reduced.
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