In this thesis, we investigate the irradiation of silicon, in a background gas of near atmospheric pressure, with intense femtosecond laser pulses at energy densities exceeding the threshold for ablation (the macroscopic removal of material). We study the resulting structure and properties of the material ejected in the ablation plume as well as the laser irradiated surface itself. The material collected from the ablation plume is a mixture of single crystal silicon nanoparticles and a highly porous network of amorphous silicon. The crystalline nanoparticles form by nucleation and growth; the amorphous material has smaller features and forms at a higher cooling rate than the crystalline particles. The size distribution of the crystalline particles suggests that particle formation after ablation is fundamentally different in a background gas than in vacuum. We also observe interesting structures of coagulated particles such as straight lines and bridges. The laser irradiated surface exhibits enhanced visible and infrared absorption of light when laser ablation is performed in the presence of certain elements–-either in the background gas or in a film on the silicon surface. To determine the origin of this enhanced absorption, we perform a comprehensive annealing study of silicon samples irradiated in the presence of three different elements (sulfur, selenium and tellurium). Our results support that the enhanced infrared absorption is caused by a high concentration of dopants dissolved in the lattice. Thermal annealing reduces the infrared absorptance of each doped sample at the same rate that dopants diffuse from within the polycrystalline grains in the laser irradiated surface layer to the grain boundaries. Lastly, we measure the photovoltaic properties of the laser irradiated silicon as a function of several parameters: annealing temperature, laser fluence, background gas, surface morphology and chemical etching. We explore the concept of using thin silicon films as the irradiation substrate and successfully enhance the visible and infrared absorption of films < 2 micrometers thick. Our results suggest that the incorporation of a femtosecond laser modified region into a thin film silicon device could greatly enhance its photovoltaic efficiency.