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This topical review focuses on the recently active debate on the bandalignment between two polymorphs of TiO$_2$, rutile and anatase. A summary isgiven to the popular methods for measurement and calculation of band alignmentbetween materials. We point out, through examination of recently experimentaland theoretical reports, that the outstanding discrepancy in the band alignmentbetween two TiO$_2$ phases is attributed to factors that influence bandalignment rather than needs a definite answer of which band alignment is right.According to an important factor, the presence of an interface, a newclassification of band alignment is proposed as the coupled and intrinsic bandalignments. This classification indeed reveals that the rutile/anataseinterface can qualitatively change the type of their band alignment. However,further systematic information of the interface and other factors thatinfluence band alignment will be needed to understand changes in energy bandsof materials better. The results obtained from discussion of the band alignmentbetween rutile and anatase may also work for the band alignment between othersemiconductors.

Challenges in Band Alignment between Semiconducting Materials: A Case of Rutile and Anatase TiO$_2$