In the search for highly transparent and non-toxic alternative front layers replacing state-of-the-art CdS in Cu(In,Ga)Se₂ thin-film solar cells, alternatives rarely exceed reference devices in terms of efficiency. Full-area ultra-thin aluminium oxide tunnelling layers do not require any contact patterning and thus overcome the main drawback of insulating passivation layers. Even a few monolayers of aluminium oxide can be deposited in a controlled manner by atomic layer deposition, they show excellent interface passivation properties, low absorption, and suitable current transport characteristics on test devices. Depositing a ZnO-based transparent front contact, however, results in extremely poor solar cell performance. The issue is not necessarily a low quality of the alternative front layer, but rather the intricate relation between front layer processing and electronic bulk properties in the absorber layer. We identify three challenges critical for the development of novel front passivation approaches: (i) both Cd and Zn impurities beneficially reduce the high native net dopant concentration in the space charge region, (ii) sputter deposition of ZnO damages the passivation layer resulting in increased interface recombination, (iii) thermal treatments of devices with ZnO layer result in substantial Zn diffusion, which can penetrate the full absorber thickness already at moderate temperatures.

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Copper-indium-gallium-diselenide (CIGS) thin-film solar cells suffer from high recombination losses at the back contact and parasitic absorption in the front-contact layers. Dielectric passivation layers overcome these limitations and enable an efficient control over interface recombination, which becomes increasingly relevant as thin-film solar cells increase in efficiency and become thinner to reduce the consumption of precious resources. We present the optoelectronic and chemical interface properties of oxide-based passivation layers deposited by atomic layer deposition on CIGS. A suitable postdeposition annealing removes detrimental interface defects and leads to restructuring and oxidation of the CIGS surface. The optoelectronic interface properties are very similar for different passivation approaches, demonstrating that an efficient suppression of interface states is possible independent of the metal used in the passivating oxide. If aluminum oxide (Al2O3) is used as the passivation layer we confirm an additional field-effect passivation due to interface charges, resulting in an efficient interface passivation superior to that of a state-of-the-art cadmium-sulfide (CdS) buffer layer. Based on this chemical interface model we present a full-area rear-interface passivation layer without any contact patterning, resulting in a 1% absolute efficiency gain compared to a standard molybdenum back contact.