Spatially-Modulated Silicon Interface Energetics via Hydrogen Plasma-Assisted Atomic Layer Deposition of Ultrathin Alumina

Atomic layer deposition (ALD) is a key technique for the continued scaling of semiconductor devices, which increasingly relies on reproducible and scalable processes for interface manipulation of 3D structured surfaces on the atomic scale. While ALD allows the synthesis of conformal films at low temperature with utmost control over the thickness, atomically-defined closed coatings and surface modifications are still extremely difficult to achieve because of three-dimensional growth during nucleation. Here, we present a route towards sub-nanometer thin and continuous aluminum oxide (AlOx) coatings on silicon (Si) substrates for the spatial control of the surface charge density and interface energetics. We use trimethylaluminum (TMA) in combination with remote hydrogen plasma instead of a gas-phase oxidant for the transformation of silicon oxide into alumina (AlOx). During the initial ALD cycles, TMA reacts with the surface oxide (SiO2) on silicon until there is a saturation of bindings sites, after which the oxygen from the underlying surface oxide is consumed, thereby transforming the silicon oxide into Si capped with AlOx. Depending on the number of ALD cycles, the SiO2 can be partially or fully transformed, which we exploit to create sub-nanometer thin and continuous AlOx layers deposited in selected regions defined by lithographic patterning. The resulting patterned surfaces are characterized by lateral AlOx/SiO2 interfaces possessing step heights as small as 0.3 nm and surface potential steps in excess of 0.4 V. In addition, the introduction of fixed negative charges of $9 \times 10^{12}$ cm$^{-2}$ enables modulation of the surface band bending, which is relevant to the field-effect passivation of Si and low-impedance charge transfer across contact interfaces.