Metal/semiconductor structures, particularly Schottky diodes, play a crucial role in semiconductor identification and the production of electronic devices, like solar cells, photodetectors, photodiodes, and field-effect transistors (FETs). These structures are of great interest due to their ability to modify electrical and optical properties, responding to external factors such as illumination and temperature. However, despite extensive research in this field, there has been limited exploration of silicon-based metal/semiconductor structures incorporating PANI:Borophene interfacial materials. In this study, we prepared PANI:Borophene/p-Si and PANI:Borophene/n-Si structures and examined their photodiode properties using various measurements. The unoccupied trap levels (m) obtained 0.44 and 0.33 for Al/PANI:Borophene/p-Si and Au/PANI:Borophene/n-Si device, respectively. Our investigation revealed that both structures exhibited rectification behavior, with linear characteristics in the forward bias region, and deviations attributed to series resistance effects at higher voltages. Moreover, the presence of borophene in the interfacial layer led to improvements in the devices’ electrical properties. Finally, the PANI:Borophene/Si Schottky diodes was tested for salt detection and the Al/PANI:Borophene/p-Si diode has the characteristics of salt (NaCl) concentration detection sensor and it successfully detected salt concentration changes with respect to current flow.