Saturation degree in dopant monolayers as modulator of Al-doping of ZnO by the Atomic Layer Deposition-supercycle approach

•Diethylzinc dose reduction while doping drives structural and morphological changes.•Al content results almost invariant despite diethylzinc reduction in doping-cycles.•Optoelectronic behavior reveals electronic and defect contributions from Al-doping. Transparent conductive oxides are trending topic in science and technology due to counterintuitive properties: optical transparency and high electrical conductivity. ZnO is a promising example with optoelectronic properties enhanced by supervalent doping. Al-doped ZnO (AZO) has emerged as leading candidate to replace environmentally hazardous In-doped SnO2. However, an ongoing debate exists regarding whether Al-doping improves its optoelectronic properties by substitutional doping or by promoting active defects. Here, we focused on Al-doping of ZnO by atomic layer deposition (ALD) applying the supercycle approach, showing that, decreasing Zn precursor dosing during dopant cycles, the decreasing saturation degree of Zn-species monolayers leads to morphological and microstructural changes that negatively impact optoelectronic properties, whereas Al content remains invariant. Our results demonstrate that unsaturated surfaces after decreasing Zn precursor dosing play a crucial role in Al incorporation, suggesting that, to maximize the effect of doping, complete oxide substitution reactions rather than those of conventional ALD must control growth, while crystallinity must remain. These findings could impact strategy designing for optimization of optoelectronic properties of AZO films deposited by ALD by inclining the debate towards the hypothesis that electrical properties are determined by Al substitutional doping together with active defects formed due to substitutional doping itself.