Dynamic Nuclear Polarization (DNP) is an indispensable technique in NMR that significantly enhances its inherently low sensitivity by transferring the higher polarization of electron spins to nuclear spins. Traditionally, most DNP experiments rely on exogenous paramagnetic agents, such as organic radicals, which are dissolved in a glass-forming solvent and introduced into the sample before the DNP-NMR experiment. In contrast, endogenous DNP NMR utilizes intrinsic paramagnetic species to enhance nuclear spin polarization, offering a non-invasive and efficient approach to enhance the NMR signals. Ideally, these intrinsic species act as structural probes without altering the host structure or impacting its properties. Our research focuses on using endogenous DNP approach to investigate the structure-property relationships in organic semiconductors and thin films. Thin films play a critical role in advancing nanotechnology and materials science, offering unique properties and transformative applications in electronics, energy storage, and catalysis. Despite the challenges due to small sample volumes, DNP NMR provides a powerful approach to understand the self-assembly behavior of thin films. This technique is particularly effective for investigating interfaces, functional groups, and catalytic sites, making it an important tool for thin-film analysis. The idea is to attach a sulfur containing radical into Au / Pt which is coated on silicon. Our approach is to understand the self-assemble feature on the surface and study about the correlation of enhancement against distance. This is achieved by increasing the thickness of Au coating on the silicon. The initial progress in characterizing the radical is going well, which includes collecting sweep profile and measurement of relaxation parameters.