Efficient
tuning of the polarity of photoactive nanomaterials is
of great importance in improving the performance of photoelectrochemical
(PEC) sensing platforms. Herein, polarity of the Ag2S/AgInS2 heterojunction is converted by radical-induced positive feedback
polydopamine (PDA) adhesion, which is further employed to develop
a signal-switchable PEC biosensor. In the nanocomposites, Ag2S and AgInS2 achieve electron–hole separation,
exhibiting a strong anodic PEC response. Under the irradiation of
light, the Ag2S/AgInS2 heterojunction is able
to produce superoxide radical and hydroxyl radical intermediate species,
leading to the polymerization of dopamine (DA) and the subsequent
adhesion of PDA onto the Ag2S/AgInS2 heterojunction
(Ag2S/AgInS2@PDA). By constructing a new electron-transfer
pathway with PDA, the polarity of the Ag2S/AgInS2 heterojunction is converted, and the PEC response changes from anodic
to cathodic photocurrents. In addition, since the photoreduction activity
of PDA is stronger than that of the Ag2S/AgInS2 heterojunction, more superoxide radical can be produced by Ag2S/AgInS2@PDA once PDA is generated, thereby promoting
the generation of PDA. Consequently, a positive feedback mechanism
is established to enhance the polarity conversion of the Ag2S/AgInS2 heterojunction and amplify the responding to
DA. As a result, the bioanalytical method is capable of sensitively
quantifying DA in 10 orders of magnitude with an ultralow limit of
detection. Moreover, the applicability of this biosensor in real samples
is identified by measuring DA in fetal bovine serum and compared with
a commercial ELISA method. Overall, this work offers an alternative
perspective for adjusting photogenerated carriers of nanomaterials
and designing high-performance PEC biosensors.