▎ 摘　　要

Herein, we report the novel nanostructural interfaces,of self assembled hierarchical ZnO. nanotubes/graphene (ZNT/G) with three different growing times of ZNTs on graphene substrates (namely, SH1, SH2, and SH3). Each sample was fabricated with interdigitated electrodes to form hydrogen sensors, and their hydrogen sensing properties, were comprehensively studied. The systematic investigation revealed that SH1 sensor exhibits an ultrahigh sensor response even at a low detection level of 10 ppm (14.3%) to 100 ppm (28.1%) compared to those of the SH2 and SH3 sensors. The SH1 sensor was also found to be well-retained with repeatability, reliability, and long-term stability of 90 days under hydrogenation/dehydrogenation processes. This outstanding enhancement in sensing properties of SH1 is attributed to the formation of a strong metalized region in the ZNT/G interface due to the inner/outer surfaces of ZNTs, establishing a multiple depletion layer. Furthermore, the respective band models of each nanostructure were also purposed to describe their heterostructure, which illustrates the hydrogen sensing properties. Moreover, the long-term stability can be ascribed by the heterostructured combination of ZNTs and graphene via a spillover effect. The salient features of this self-assembled nanostructure are its reliability, simple synthesis method, and long-term stability, which makes it a promising candidate for new generation hydrogen sensors and hydrogen storage materials.