Energy band alignment theory has been widely used to understand interface charge transfer in semiconductor/semiconductor heterojunctions for solar conversion or storage, such as quantum-dot sensitized solar cells, perovskite solar cells and photo(electro)catalysis. However, abnormally high open-circuit voltage and charge separation efficiency in these applications cannot be explained by the classic theory. Here, we demonstrate a Faradaic junction theory with isoenergetic charge transfer at semiconductor/semiconductor interface. Such Faradaic junction involves coupled electron and ion transfer, which is substantively different from the classic band alignment theory only involving electron transfer. The Faradaic junction theory can be used to explain these abnormal results in previous studies. Moreover, the characteristic of zero energy loss of charge transfer in a Faradaic junction also can provide a possibility to design a solar conversion device with a large open-circuit voltage beyond the Shockley-Queisser limit by the band alignment theory.

Interface charge transfer plays a key role in the performance of semiconductors for different kinds of solar energy utilization, such as photocatalysis, photoelectrocatalysis, photochromism and photo-induced superhydrophilicity. In previous studies, different mechanisms have been used to understand interface charge transfer process. However, the charge transfer mechanism at solid/liquid interface remains a controversial topic. Here, taking TiO2 as a model, we find and prove a new characteristic of photo-induced bipolarity of the surface layer (reduction faradaic layer and oxidation faradaic layer) on a semiconductor by experiments for the first time. Different from energy level positions in classic surface states transfer mechanism, the potential window of a surface faradaic layer locates out of the forbidden band. Moreover, we find that the reduction faradaic layer and oxidation faradaic layer serve as electron and hole transfer mediators in photocatalysis, while the bipolarity or mono-polarity of the surface layer on a semiconductor depends on the applied potential in photoelectrocatalysis. The new characteristic of bipolarity can also offer new insights on charge transfer process at semiconductor/liquid interface for solar energy utilization.

Two-electrode solar rechargeable device is one of the promising technologies to address the problem of solar energy storage in large scale. However, the mechanism of dark output voltage remains unclear and the low volumetric energy density also limits its practical applications. Herein, we report that a Si/CoOx/KBi(aq)/MnOx Faradaic junction device exhibits a photovoltage memory effect, that is, the dark output voltage can precisely record the value of the photovoltage in the device. To investigate the mechanism of the effect, we develop an open circuit potential method to real-time monitor the photo charge and dark discharge processes in the Faradaic junction device. This effect leads to minimized interface energy loss in the Faradaic junction device, which achieves much higher performances than the devices without the effect. Moreover, we realize a portable device with a record value of the dark volumetric energy density (∼1.89 mJ cm−3) among all reported two-electrode solar rechargeable devices. These results offer guidance to improve the performance of a solar rechargeable device and design other photoelectric devices for new applications.