Currently, crystalline silicon (c-Si) wafer-based solar cells dominate the photovoltaic market (80-90%). In this thesis we concentrate on silicon heterojunction (SHJ) solar cells that--in contrast to diffused homojunction cells--rely on the application of amorphous silicon (a-Si:H) thin films. Unlike standard homojunction devices, which are typically limited by their highly recombination-active semiconductor-to-metal contacts, SHJ devices exhibit excellent surface passivation enabled by intrinsic and doped a-Si:H films. These a-Si:H layers, however, entail drawbacks for optical performance and carrier transport, two topics that will be addressed in this work. To this end we investigate non-traditional materials for SHJ devices, with the goal of replacing the a-Si:H or the transparent electrodes. These materials include microcrystalline silicon (uc-Si:H) and organic semiconductors for contact formation; amorphous silicon suboxides (a-SiOx:H) for surface passivation; and transparent electrodes applied by atomic layer deposition (ALD) as protective layers against subsequent processing steps. Along with the optical and electrical properties of these materials, we study the impact on device performance associated with their deposition. For this we test the devices under standard testing conditions (25 °C) and at elevated temperatures closer to those encountered in the field. For the investigations on uc-Si:H layers, we vary process parameters (including temperature, pressure, power, excitation frequency and hydrogen dilution) as well as pre-treatments, gas variations and nucleation layers. We assess the suitability of these approaches for SHJ solar cells and apply selected measures in devices. Thereby we demonstrate a gain in short-circuit current density in the range of 0.5-1 mA.cm-2 and good fill factor values of up to 79.2% using either n- and p-type uc-Si:H layers. Furthermore, with the goal of reducing optical losses, we test wide-bandgap a-SiOx:H layers for passivation. In terms of current gain without negative side effects on transport, we argue that these layers are best applied to the electron-collecting contact--put at the front of the device--as their application to the hole-collecting contact introduces a transport barrier for holes. This barrier deteriorates the device performance at 25 °C, but shows a beneficial effect on the temperature coefficient of the device, yielding coefficients as low as -0.1%/°C. In some cases--compared to standard devices--devices with a-SiOx:H layers exhibit superior performance at elevated temperatures, which can be of interest in warmer climates. In parallel to these main topic we also study aluminium-doped zinc oxide (ZnO:Al) layers deposited by ALD as a protective layer against sputter-induced damage and organic semiconductors as transparent electrodes for the hole-collecting contact. In both cases we observe a gain in terms of surface passivation, which indicates that these materials may be beneficial for the contact formation in future device structures. In addition to these material-related investigations, we unravel the temperature-dependence of each individual cell parameter and present a brief comparison of state-of-the-art technologies and their respective temperature dependence.