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We report a novel Mn-Co-Ni-O (MCN) nanocomposite in which the p-type semiconductivity of Mn-Co-Ni-O can be manipulated by addition of graphene. With an increase of graphene content, the semiconductivity of the nanocomposite can be tuned from p-type through electrically neutral to n-type. The very low effective mass of electrons in graphene facilitates electron tunneling into the MCN, neutralizing holes in the MCN nanoparticles. XPS analysis shows that the multivalent manganese ions in the MCN nanoparticles are chemically reduced by the graphene electrons to lower-valent states. Unlike traditional semiconductor devices, electrons are excited from the filled graphite band into the empty band at the Dirac points from where they move freely in the graphene and tunnel into the MCN. The new composite film demonstrates inherent flexibility, high mobility, short carrier lifetime, and high carrier concentration. This work is useful not only in manufacturing flexible transistors, FETs, and thermosensitive and thermoelectric devices with unique properties but also in providing a new method for future development of 2D-based semiconductors.

Flexible Diodes/Transistors Based on Tunable p-n-Type Semiconductivity in Graphene/Mn-Co-Ni-O Nanocomposites