Realizing the next-generation electronic devices with added features, i.e., flexibility, smaller dimension, higher density (transistors per unit area), lightweight, and low-power consumption, would require extensive work to optimize the processing conditions that would yield high-quality Si wires (microwire/nanowire) with optimum device performance at an affordable price. The standard photolithography process used to pattern the catalyst seed layer for the vapor-liquid-solid (VLS) growth of Si wires provides highly ordered, epitaxial Si wires. However, this process is not scalable owing to the high cost involved; hence there is a need to explore alternate routes to grow Si wires using cost-effective strategies. To this end, we employed a cost-effective lithography-free de-wetting technique to fabricate the seed layer for the growth of highly ordered Si microwires (Si MWs). There are several reports on VLS growth of Si wires that study the growth kinetics and effect of growth parameters like gas flow rate and growth temperature on Si wire growth rate. However, a quantitative and qualitative analysis of the impact of various growth parameters on Si wire size and quality is still lacking. Herein, we report the quantitative analysis of the effect of different growth parameters on Si MW growth rate and size (length and diameter) using the lithography-free growth technique and the influence of growth parameters on Si MW quality and device performance. An exponential dependence of MW growth rate is observed, similar to that in thin-film growth rate, and is reported for the first time for a wire configuration. This has important implications in device fabrication as the optoelectronic properties in one-dimensional (1D) structures are strongly affected by size and growth conditions. The electrical transport properties of as-grown Si MW have been extracted via two-probe and three-probe measurements. The FET characterization of as-grown intrinsic Si MW demonstrated p-type behavior. The temperature-dependent I-V measurement on as-grown and passivated Si MW has been done to determine the impact of trap states on the Si MW properties. Lastly, we demonstrate the fabrication of Si MW Near-infrared (NIR) photodetector via a solution-processable route with optimum photoresponse at a low applied bias of 0.1 V and incident power density of 1.24x10-4 W/cm2 with a responsivity of 3.05 A/W, Ton/Toff of 0.308 s / 0.363 s, external quantum efficiency (EQE) of 421%. This study will enable a clear understanding of the impact of the various growth parameters on Si MW quality and allow us to utilize that knowledge to fabricate Si MW device with improved performance. Overall, the motivation for this dissertation is to develop a comprehensive understanding of the Si MW growth environment on its transport properties for optoelectronic device applications.