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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.

Faradaic junction and isoenergetic charge transfer mechanism on semiconductor/semiconductor interfaces