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In order to study the impact of negative oxygen ion bombardment on the electronic transport properties of ZnO:Al films, a systematic magnetron sputtering study from ceramic targets with excitation frequencies from DC to 27 MHz, accompanied by strongly varying discharge voltages, has been performed. Higher plasma excitation frequencies significantly improve the transport properties of ZnO:Al films. The effect of the bombardment of the films by energetic particles (negative oxygen ions) can be explained by the dynamic equilibrium between the formation of acceptor-like oxygen interstitials compensating the extrinsic donors and the self-annealing of the interstitial defects at higher deposition temperatures.

The origin of the pronounced radial distributions of structural and electrical properties of magnetron sputtered ZnO:Al films has been investigated. The film properties were correlated with the radially resolved ion-distribution functions. While the positive ions exhibit low energies and a radial distribution with a maximum intensity opposite the center of the target, the negative ions can have energies up to several hundred eV, depending on the target potential, with a radial distribution with two maxima opposite the erosion tracks. The most prominent positive ion is that of the working gas (Ar+), while the highest flux of the negative ions is measured for negative oxygen O−. The radial distribution of the flux of the high-energetic negative ions can clearly be related to the radial variations of the structural (c-axis lattice parameter, crystallite size) and electronic (resistivity) properties for sputtering from the planar target, which points to the decisive role of the high-energetic negative oxygen ions for the film quality. The relation between the negative ion bombardment and the structural as well as electronic properties can be explained by a qualitative model recently developed by us. The same target has also been investigated in the eroded state. In this case, the limited acceptance angle of the mass spectrometer leads to a misinterpretation of the radial distribution of the flux of the high-energetic negative ions. This effect can be explained by a simulation, based on the assumption that the high-energetic negative ions are mainly accelerated in the cathode (target) sheath perpendicular to the uneven substrate surface.

The prospects of scaling current photovoltaic technologies to terawatt levels remain uncertain. All-oxide photovoltaics could open rapidly scalable manufacturing routes, if only oxide materials with suitable electronic and optical properties were developed. A potential candidate material is tin monoxide (SnO), which has exceptional doping and transport properties among oxides, but suffers from a low absorption coefficient due to its strongly indirect band gap. Here, we address this shortcoming of SnO by band-structure engineering through isovalent but heterostructural alloying with divalent cations (Mg, Ca, Sr, Zn). Using first-principles calculations, we show that suitable band gaps and optical properties close to that of direct semiconductors are achievable in such SnO based alloys. Due to the defect tolerant electronic structure of SnO, the dispersive band-structure features and comparatively small effective masses are preserved in the alloys. Initial Sn 1−x Zn x O thin films deposited by sputtering exhibit crystal structure and optical properties in accord with the theoretical predictions, which confirms the feasibility of the alloying approach. Thus, the implications of this work are important not only for terawatt scale photovoltaics, but also for other large-scale energy technologies where defect-tolerant semiconductors with high quality electronic properties are required.

An analytical description of the charge carrier transport, valid for non-degenerated and degenerated semiconductors, was developed, critically reviewed, and fitted to the temperature-dependent Hall mobility data of magnetron sputtered, degenerately doped ZnO:Al films. Our extended model for grain boundary scattering in semiconductors of arbitrary degeneracy is based on previous models from literature and suitable to describe the Hall mobility of the carriers as a function of the free carrier concentration and the temperature at the same time. It is mathematically simple enough for a fast fit procedure, which is not possible with most of the previous models. Applying a combined transport model consisting of ionized impurity scattering, phonon scattering, and grain boundary scattering in degenerate semiconductors, we were able to determine the trap density at the grain boundaries Nt ≈ 3 × 1013 to 5 × 1013 cm−2 and the deformation potential Eac in the range of 5 eV to 9 eV depending on the details of the transport model.