© 2020In the present study, initially, the new rhodanine-based Bis(Rh)-Ph and Bis(Rh)-TPE were synthesized by a green approach. Following synthesis, Al/Bis(Rh)-Ph/p-Si (D1) and Al/Bis(Rh)-TPE/p-Si (D2) heterojunctions were fabricated by using spin coating method and thermal evaporation technique. The electrical characterizations of fabricated D1 and D2 devices were investigated and compared with each other by using the reverse and forward bias C–V measurements at room temperature and I–V measurements at the three different temperatures and distinct illumination intensities. Additionally, the AFM images of D1 and D2 were examined for surface properties. The crucial parameters such as ideality factor (n), saturation current (I0) and barrier height (ΦB) of D1 and D2 devices were calculated as 2.72, 4.26 × 10−10A, 0.80eV and 1.85, 2.33 × 10−9A, 0.76eV, respectively. Rectifier rate (RR) for D2 device is ~5.3 times higher than D1. While the ideality factor increased with effect of exposure light, the barrier height decreased. In addition, DFT calculations supported the non-planar structures or propeller structures. The results supported that these devices could be used in optoelectronic applications, especially photodiodes and photo detectors.