Transparent conductive oxides (TCOs) are key functional materials in existing and future electro-optical devices in the fields of energy efficiency, energy generation and information technology. The main application of TCOs is as thin films transparent electrodes where a combination of maximum electrical conductivity and transmittance in the visible to nearinfrared spectral range is required. However, due to the interdependence of the optical properties and the free electron density and mobility, respectively, these requirements cannot be achieved simultaneously in degenerately doped wide band-gap oxide semiconductors. Therefore, a detailed understanding of the mechanisms governing the generation of free charge carriers by extrinsic doping and the charge transport in these materials is essential for further development of high performance TCOs and corresponding deposition methods. The present work is aimed at a comprehensive investigation of the electrical, optical and structural properties as well as the elemental composition of (Al,Ga) doped ZnO and Nb doped TiO2 thin films prepared by pulsed DC reactive magnetron sputtering. The evolution of the film properties is studied in dependence of various deposition parameters through a combination of characterization techniques including Hall-effect, spectroscopic ellipsometry, spectral photometry, X-ray diffraction, X-ray near edge absorption, Rutherford backscattering spectrometry and particle induced X-ray emission. This approach resulted in the development of an alternative process control method based on the material specific current-voltage pressure characteristics of the reactive magnetron discharge which allows to precisely control the oxygen deficiency of the sputter deposited films. Based on the experimental data, models have been established that describe the room temperature charge transport properties and the dielectric function of the obtained ZnO and TiO2 based transparent conductors. On the one hand, these findings allow the prediction of material specific electron mobility limits by identifying the dominating charge carrier scattering mechanisms. On the other hand, new insight is gained into the origin of the observed transition from highly conductive to electrically insulating ZnO layers upon the incorporation of increasing concentrations of Al at elevated growth temperatures. Moreover, the Al and Ga dopant activation in ZnO have been quantified systematically for a wide range of Al concentrations and deposition conditions. A direct comparison of the Ga and Al doping efficiency demonstrates that Ga is a more efficient electron donor in ZnO. Further, it has been shown that high free electron mobilities in polycrystalline and epitaxial Nb:TiO2 layers can be achieved by reactive magnetron sputtering of TiNb alloy targets. The suppression of rutile phase formation and the control of the Nb dopant activation by fine tuning the oxygen deficiency have been identified as crucial for the growth of high quality TiO2 based TCO layers.

L’intégration 3D séquentielle représente une alternative potentielle à la réduction des dimensions afin de gagner encore en densité d’une génération à la suivante. Le principal défi concerne la fabrication du transistor de l’étage supérieur avec un faible budget thermique; ceci afin d’éviter la dégradation du niveau inférieur. L’étape de fabrication la plus critique pour la réalisation du niveau supérieur est l’activation des dopants. Celle-ci est généralement effectuée par recuit à une température supérieure à 1000 °C. Dans ce contexte, cette thèse propose des solutions pour activer les dopants à des températures inférieures à 600 °C par la technique dite de recristallisation en phase solide. Les conditions de dopage ont été optimisées pour améliorer le niveau d’activation et le temps de recuit tout en réduisant la température d’activation jusqu’à 450°C. Les avancées obtenues ont été implémentées sur des dispositifs avancés FDSOI et TriGate générant des dispositifs avec des performances inférieures aux références fabriquées à hautes températures (supérieures à 1000 °C). En utilisant des simulations TCAD et en les comparant aux mesures électriques, nous avons montré que la région la plus critique en termes d’activation se trouve sous les espaceurs de la grille. Nous montrons alors qu’une intégration dite « extension first » est le meilleur compromis pour obtenir de bonnes performances sur des dispositifs fabriqués à faible température. En effet, l’implantation des dopants avant l’épitaxie qui vise à surélever les sources et drains compense l’absence de diffusion à basse température. Ces résultats ont par la suite été étendus pour des dispositifs TriGate et FinFETs sur isolants. Pour la première fois, l’intégration « extension first » a été démontrée pour des N et PFETs d’une technologie 14 nm FDSOI avec des résultats prometteurs en termes de performances. Les résultats obtenus montrent notamment qu’il est possible d’amorphiser partiellement un film très mince avant d’effectuer une recroissance épitaxiale sur une couche dopée. Finalement, une implantation ionique à relativement haute température (jusqu’à 500 °C) a été étudiée afin de doper les accès sans amorphiser totalement le film mince, ce qui est critique dans le cas des dispositifs FDSOI et FinFET. Nous montrons que les niveaux d’activation après implantation sont trop faibles pour obtenir des bonnes performances et que l’implantation ionique « chaude » est prometteuse à condition d’être utilisée avec un autre mécanisme d’activation comme le recuit laser. / 3D sequential integration is a promising candidate for the scaling sustainability for technological nodes beyond 14 nm. The main challenge is the development of a low temperature process for the top transistor level that enables to avoid the degradation of the bottom transistor level. The most critical process step for the top transistor level fabrication is the dopant activation that is usually performed at temperature higher than 1000 °C. In the frame of this Ph.D. work, different solutions for the dopant activation optimization at low temperature (below 600 °C) are proposed and integrated in FDSOI and TriGate devices. The technique chosen for the dopant activation at low temperature is the solid phase epitaxial regrowth. First, doping conditions have been optimized in terms of activation level and process time for low temperatures (down to 450 °C) anneals. The obtained conditions have been implemented in FDSOI and TriGate devices leading to degraded electrical results compared to the high temperature process of reference (above 1000 °C). By means of TCAD simulation and electrical measurements comparison, the critical region of the transistor in terms of activation appears to be below the offset spacer. The extension first integration scheme is then shown to be the best candidate to obtain high performance low temperature devices. Indeed, by performing the doping implantation before the raised source and drain epitaxial growth, the absence of diffusion at low temperature can be compensated. This conclusion can be extrapolated for TriGate and FinFET on insulator devices. Extension first integration scheme has been demonstrated for the first time on N and PFETs in 14 nm FDSOI technology showing promising results in terms of performance. This demonstration evidences that the two challenges of this integration i.e. the partial amorphization of very thin films and the epitaxy regrowth on implanted access are feasible. Finally, heated implantation has been investigated as a solution to dope thin access regions without full amorphization, which is particularly critical for FDSOI and FinFET devices. The as-implanted activation levels are shown to be too low to obtain high performance devices and the heated implantation appears a promising candidate for low temperature devices if used in combination with an alternative activation mechanism.

Transparent conductive oxides (TCOs) are key functional materials in existing and future electro-optical devices in the fields of energy efficiency, energy generation and information technology. The main application of TCOs is as thin films transparent electrodes where a combination of maximum electrical conductivity and transmittance in the visible to nearinfrared spectral range is required. However, due to the interdependence of the optical properties and the free electron density and mobility, respectively, these requirements cannot be achieved simultaneously in degenerately doped wide band-gap oxide semiconductors. Therefore, a detailed understanding of the mechanisms governing the generation of free charge carriers by extrinsic doping and the charge transport in these materials is essential for further development of high performance TCOs and corresponding deposition methods. The present work is aimed at a comprehensive investigation of the electrical, optical and structural properties as well as the elemental composition of (Al,Ga) doped ZnO and Nb doped TiO2 thin films prepared by pulsed DC reactive magnetron sputtering. The evolution of the film properties is studied in dependence of various deposition parameters through a combination of characterization techniques including Hall-effect, spectroscopic ellipsometry, spectral photometry, X-ray diffraction, X-ray near edge absorption, Rutherford backscattering spectrometry and particle induced X-ray emission. This approach resulted in the development of an alternative process control method based on the material specific current-voltage pressure characteristics of the reactive magnetron discharge which allows to precisely control the oxygen deficiency of the sputter deposited films. Based on the experimental data, models have been established that describe the room temperature charge transport properties and the dielectric function of the obtained ZnO and TiO2 based transparent conductors. On the one hand, these findings allow the prediction of material specific electron mobility limits by identifying the dominating charge carrier scattering mechanisms. On the other hand, new insight is gained into the origin of the observed transition from highly conductive to electrically insulating ZnO layers upon the incorporation of increasing concentrations of Al at elevated growth temperatures. Moreover, the Al and Ga dopant activation in ZnO have been quantified systematically for a wide range of Al concentrations and deposition conditions. A direct comparison of the Ga and Al doping efficiency demonstrates that Ga is a more efficient electron donor in ZnO. Further, it has been shown that high free electron mobilities in polycrystalline and epitaxial Nb:TiO2 layers can be achieved by reactive magnetron sputtering of TiNb alloy targets. The suppression of rutile phase formation and the control of the Nb dopant activation by fine tuning the oxygen deficiency have been identified as crucial for the growth of high quality TiO2 based TCO layers.

We present the development of a novel, UHV-compatible device fabrication strategy for the realisation of nano- and atomic-scale devices in silicon by harnessing the atomic-resolution capability of a scanning tunnelling microscope (STM). We develop etched registration markers in the silicon substrate in combination with a custom-designed STM/ molecular beam epitaxy system (MBE) to solve one of the key problems in STM device fabrication ??? connecting devices, fabricated in UHV, to the outside world. Using hydrogen-based STM lithography in combination with phosphine, as a dopant source, and silicon MBE, we then go on to fabricate several planar Si:P devices on one chip, including control devices that demonstrate the efficiency of each stage of the fabrication process. We demonstrate that we can perform four terminal magnetoconductance measurements at cryogenic temperatures after ex-situ alignment of metal contacts to the buried device. Using this process, we demonstrate the lateral confinement of P dopants in a delta-doped plane to a line of width 90nm; and observe the cross-over from 2D to 1D magnetotransport. These measurements enable us to extract the wire width which is in excellent agreement with STM images of the patterned wire. We then create STM-patterned Si:P wires with widths from 90nm to 8nm that show ohmic conduction and low resistivities of 1 to 20 micro Ohm-cm respectively ??? some of the highest conductivity wires reported in silicon. We study the dominant scattering mechanisms in the wires and find that temperature-dependent magnetoconductance can be described by a combination of both 1D weak localisation and 1D electron-electron interaction theories with a potential crossover to strong localisation at lower temperatures. We present results from STM-patterned tunnel junctions with gap sizes of 50nm and 17nm exhibiting clean, non-linear characteristics. We also present preliminary conductance results from a 70nm long and 90nm wide dot between source-drain leads which show evidence of Coulomb blockade behaviour. The thesis demonstrates the viability of using STM lithography to make devices in silicon down to atomic-scale dimensions. In particular, we show the enormous potential of this technology to directly correlate images of the doped regions with ex-situ electrical device characteristics.

We present the development of a novel, UHV-compatible device fabrication strategy for the realisation of nano- and atomic-scale devices in silicon by harnessing the atomic-resolution capability of a scanning tunnelling microscope (STM). We develop etched registration markers in the silicon substrate in combination with a custom-designed STM/ molecular beam epitaxy system (MBE) to solve one of the key problems in STM device fabrication ??? connecting devices, fabricated in UHV, to the outside world. Using hydrogen-based STM lithography in combination with phosphine, as a dopant source, and silicon MBE, we then go on to fabricate several planar Si:P devices on one chip, including control devices that demonstrate the efficiency of each stage of the fabrication process. We demonstrate that we can perform four terminal magnetoconductance measurements at cryogenic temperatures after ex-situ alignment of metal contacts to the buried device. Using this process, we demonstrate the lateral confinement of P dopants in a delta-doped plane to a line of width 90nm; and observe the cross-over from 2D to 1D magnetotransport. These measurements enable us to extract the wire width which is in excellent agreement with STM images of the patterned wire. We then create STM-patterned Si:P wires with widths from 90nm to 8nm that show ohmic conduction and low resistivities of 1 to 20 micro Ohm-cm respectively ??? some of the highest conductivity wires reported in silicon. We study the dominant scattering mechanisms in the wires and find that temperature-dependent magnetoconductance can be described by a combination of both 1D weak localisation and 1D electron-electron interaction theories with a potential crossover to strong localisation at lower temperatures. We present results from STM-patterned tunnel junctions with gap sizes of 50nm and 17nm exhibiting clean, non-linear characteristics. We also present preliminary conductance results from a 70nm long and 90nm wide dot between source-drain leads which show evidence of Coulomb blockade behaviour. The thesis demonstrates the viability of using STM lithography to make devices in silicon down to atomic-scale dimensions. In particular, we show the enormous potential of this technology to directly correlate images of the doped regions with ex-situ electrical device characteristics.