In this thesis, we present the development and characterization of novel approaches to carrier-selective passivating contacts for crystalline silicon (c-Si) solar cells. In our first approach, we benefit from a wide-bandgap material, namely mixed-phase silicon oxide (SiOx). High hydrogen dilution during the plasma-enhanced chemical vapor deposition of a SiOx layer leads to the growth of vertically oriented silicon filaments embedded in a silicon oxide matrix. The resulting mixed-phase material combines transparency and vertical conduction through the layer. We propose a layered contact structure starting with an ultra-thin chemically grown SiOx (~1.2 nm) at the c-Si wafer surface, followed by a phosphorus-doped bilayer of the mixed-phase SiOx, finishing with a nanocrystalline silicon layer that ensures contact with the metallization. With such a stack, an electron-selective passivating contact with a saturation current density J0 of 5.3 fA/cm2 is achieved on n-type wafers with hydrogenation, whereas on p-type wafers the contact reached 5.8 fA/cm2 even without hydrogenation. The contact is analyzed in detail with respect to its structure and its change upon thermal treatment. Two different growth regions are detected: one with the vertically oriented silicon inclusions and a second one in which the silicon phases have more lateral growth. Crystallization and atomic redistribution are analyzed during in-situ annealing in an electron microscope, leading to a better understanding of the change in distribution of phosphorus and oxygen as well as the nucleation sites. The influence of the annealing temperatures and dwell times as well as the initial doping concentration on the resulting in-diffused region and the passivation quality is reported. We use simulations to relate the influence of these parameters on passivation to the different recombination mechanisms. From the analyzed phosphorus doping profiles, an interesting observation is reported. The chemical oxide varies in thickness and density depending on the wafer polarity as well as the base resistivity. Proof-of-concept cells including this novel structure demonstrate the suitability for electron-selective passivating contacts at the device level with conversion efficiencies of 19.0% on planar wafers and 20.1% on textured wafers. Promisingly high short-circuit current densities (Jsc) of 35 mA/cm2 (40 mA/cm2) on planar (textured) with low parasitic absorption indicate its potential as a front contact in next-generation solar cells. Additionally, the beneficial feature of the smooth refractive index change within the layers that leads to a low reflectance over a broad wavelength range, similar to a built-in anti-reflection coating, is presented. A second approach to reach highly transparent electron-selective passivating contacts is demonstrated by the use of a plasma process based on the precursor gases phosphine (PH3), silicon tetrafluoride (SiF4), hydrogen (H2), and argon (Ar). The beneficial effect of fluorine in terms of passivation without the need for additional hydrogenation processes is shown, reaching implied open-circuit voltages of 730 mV on planar surfaces and 707 mV on textured surfaces. These layers are implemented in first proof-of-concept working devices with efficiencies of 19.5% on single-side-textured wafers and Jsc values of up to 40 mA/cm2.