Atomic Layer Deposition of Al₂O₃ onto Sn-Doped In₂O₃: Absence of Self-Limited Adsorption during Initial Growth by Oxygen Diffusion from the Substrate and Band Offset Modification by Fermi Level Pinning in Al₂O₃

The growth of Al₂O₃ onto Sn-doped In₂O₃ (ITO) by atomic layer deposition (ALD) was studied in situ using X-ray photoelectron spectroscopy. Significant diffusion of oxygen from the substrate destroys the self-terminated monolayer adsorption of the metal precursor and results in a nominal initial growth per cycle of >1 nm. The observed mechanism precludes the preparation of monolayer thick Al₂O₃ films on ITO substrates by ALD. The energy band alignment at the ITO/Al₂O₃ interface is significantly different from that obtained when magnetron sputtering is used for the deposition of Al₂O₃ onto ITO [Gassenbauer et al., <i>Phys. Chem. Chem. Phys.</i> <b>2009</b>, <i>11</i>, 3049]. The difference is attributed to a pinning of the Fermi level in the ALD-Al₂O₃ layer close to midgap, which is attributed to the incorporation of hydrogen in the film during growth