NiO alloyed with aluminum, Ni1-x Al x O, is analyzed in terms of its stoichiometry, electronic and transport properties, as well as interfacial band alignment with Si to evaluate its potential use as a hole transport layer (HTL) in p-i-n type solar cells. The analysis is based on component material and slab structural simulations, as well as simulated and measured angle-resolved valence-band photoemission spectroscopy (PES) data, in order to reveal the best suitable stoichiometry. It is concluded that the ionization energy from the highest occupied states tends to increase with Al content as the simulated work function grows from 4.1 eV for pure NiO to 4.7 eV for heavily alloyed Al0.50Ni0.50O. The electronic structure as a function of the interface design between crystalline silicon and the transport layer is used to assess the band lineup and its correlation with the discontinuity of the affinities. The affinity rule is tested by evaluating the workfunctions of the component layers and justified best for a particular Ni-enriched interface design. Technology Computer-Aided Design (TCAD) device simulations show, that the band offset between oxide and crystalline silicon remains within the range of values to sustain a staggering alignment - a condition suitable for effective charge separation, similar to a situation in a tunneling diode. The self-energy of the hole carriers is estimated by contrasting simulated and measured photoemission data, which in the case of non-annealed Al-rich samples is shown to be an order of magnitude higher due to the disorder effects. The work functions derived from the measured PES data for the epitaxially grown oxide films with nearly identical alloy stoichiometry correlate well with the simulated values. The findings suggest that the optimal HTL is formed by starting with a pure Ni layer, followed by a graded doping Al x Ni1-x O, with x high at contact/oxide interface and low at the oxide/semiconductor.
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