ZrN Back-Contact Reflectors and Ga Gradients in Cu(In,Ga)Se2 Solar Cells

Abstract: Solar cells constitute the most direct way of converting solar energy to electricity, and thin-film solar-cell technologies have lately been growing in importance, allowing the fabrication of less expensive modules that nonetheless have good power-conversion efficiencies. This thesis focuses on solar cells based on Cu(In,Ga)Se2, which is the thin-film technology that has shown the highest conversion efficiency to date, reaching 20.3 % on the laboratory scale. Solar modules still have some way to go to become entirely competitive with existing energy technologies, and there are two possible paths to this goal: Firstly, reducing their manufacturing costs, for instance by minimizing the material usage per module and/or by increasing the throughput of a given factory; and secondly, increasing the power output per module in other words, the module efficiency. The subject matters of this thesis are related to those two approaches.The first issue investigated is the possibility for reducing the thickness of the Cu(In,Ga)Se2 layer and compensating for lost absorption by using a ZrN back reflector. ZrN layers are fabricated by reactive sputtering and I present a method for tuning the sputtering parameters so as to obtain a back reflector with good optical, electrical and mechanical properties. The reflector layer cannot be used directly in CIGS devices, but relatively good devices can be achieved with a precursor providing a homogeneous supply of Na, the addition of a very thin sacrificial Mo layer that allows the formation of a film of MoSe2 passivating the back contact, and optionally a Ga gradient that further keeps electrons away from the back contact.The second field of study concerns the three-stage CIGS coevaporation process, which is widely used in research labs around the world and has yielded small-area cells with highest efficiencies, but has not yet made it to large scale production. My focus lies on the development and the effect of gradients in the [Ga]/[In+Ga] ratio. On the one hand, I investigate 'intrinsic' gradients (ones that form autonomously during the evaporation), and present a formation model based on the differing diffusivity of Ga and In atoms in CIGS and on the development along the quasi-binary tie line between (In,Ga)2Se3 and Cu2Se. On the other hand, I determine how the process should be designed in order to preserve 'extrinsic' gradients due to interdiffusion. Lastly, I examine the electrical effects of Ga-enhancement at the back and at the front of the absorber and of In-enhancement at the front. Over a wide range, In-rich top layers prove to have no or a weakly beneficial effect, while Ga-rich top regions pose a high risk to have a devastating effect on device performance.