Ultrasensitive Paper-Based Photoelectrochemical Sensing Platform Enabled by the Polar Charge Carriers-Created Electric Field.

Efficient separation of electron-hole pairs is vitally crucial to enhancing the analytical performance of paper-based photoelectrochemical (PEC) bioanalysis. Herein, a simple but effective strategy is developed to modulate the effective separation of photogenerated electrons and holes via introducing a polar charge carriers-created (PCC) electric field induced by a classical perovskite ferroelectric BaTiO (BTO). By inserting it between the n-type WO nanoflakes and p-type CuO (WO nanoflakes/BTO/CuO), the photoelectrode is endowed with a renewable PCC electric field, as a sustaining driving force, to guarantee the realization of directional separation of charge carrier (DSCC) strategy in PEC bioanalysis. The enduring PCC electric field can attract the electrons of CuO and holes of WO, respectively, thereby regulating the directional migration of charge carriers and achieving an enhanced PEC photocurrent for the ultrasensitive quantification based on the highly efficient separation of electron-hole pairs. Consequently, with respect to WO nanoflakes/CuO and WO nanoflakes photoelectrode, the polarized WO nanoflakes/BTO/CuO photoelectrode exhibits 1.7 and 10.9 times higher photocurrent density, respectively. Benefiting from this, the prominent photocurrent density is obtained which is extremely beneficial for enhancing the sensitivity of PEC bioanalysis. Ultimately, the ultrasensitive detection of model prostate specific antigen (PSA) is realized and presents a linear range of 0.1 pg/mL-50 ng/mL with the detection limitation of 0.036 pg/mL. This work provides the basis for understanding the role of the polarized electric field induced by ferroelectric in tuning the charge separation as well as insights on strategies for constructing high-performance paper-based PEC bioanalysis.