Silicon structures incorporating contact points between depleted layers with opposing n–p and p–n potential barriers demonstrate unique photoelectronic properties arising from the interplay of their counteracting currents. When electromagnetic radiation with longitudinal absorption successively passes through the active regions of near-surface and back p–n junctions, it produces a compensated photocurrent exhibiting unconventional spectral characteristics that enable novel functionalities. This work extends previous research by examining how structural and technological parameters govern photoelectronic processes, specifically clarifying the conditions for spectral photocurrent sign reversal and the mechanisms of internal amplification through potential barrier interactions. The sign inversion results from asymmetric potential barriers, while current amplification occurs when barriers are balanced, with enhancement factors derived from experimental photocurrent values assuming 100% absorption efficiency. The amplification mechanism involves substantial electron injection from the forward-bias p–n junction into the p-base, facilitated by barrier height reduction from both applied voltage and space charge compensation by photogenerated carriers. The near-surface barrier’s height advantage establishes a characteristic voltage range where progressive barrier equalization induces spectral photocurrent inversion. Mutual compensation of currents in oppositely directed potential barriers creates extremely low dark currents. These findings provide critical insights for developing tunable silicon photodetectors with injection spectral response and enhanced sensitivity.