In2 O3 , an n-type semiconducting transparent transition metal oxide, possesses a surface electron accumulation layer (SEAL) resulting from downward surface band bending due to the presence of ubiquitous oxygen vacancies. Upon annealing In2 O3 in ultrahigh vacuum or in the presence of oxygen, the SEAL can be enhanced or depleted, as governed by the resulting density of oxygen vacancies at the surface. In this work, an alternative route to tune the SEAL by adsorption of strong molecular electron donors (specifically here ruthenium pentamethylcyclopentadienyl mesitylene dimer, [RuCp*mes]2 ) and acceptors (here 2,2'-(1,3,4,5,7,8-hexafluoro-2,6-naphthalene-diylidene)bis-propanedinitrile, F6 TCNNQ) is demonstrated. Starting from an electron-depleted In2 O3 surface after annealing in oxygen, the deposition of [RuCp*mes]2 restores the accumulation layer as a result of electron transfer from the donor molecules to In2 O3 , as evidenced by the observation of (partially) filled conduction sub-bands near the Fermi level via angle-resolved photoemission spectroscopy, indicating the formation of a 2D electron gas due to the SEAL. In contrast, when F6 TCNNQ is deposited on a surface annealed without oxygen, the electron accumulation layer vanishes and an upward band bending is generated at the In2 O3 surface due to electron depletion by the acceptor molecules. Hence, further opportunities to expand the application of In2 O3 in electronic devices are revealed.
Keywords: 2D electron gas; In 2O 3; charge transfer; photoemission spectroscopy.
© 2023 The Authors. Small published by Wiley-VCH GmbH.