Atomic layer deposition of zinc tin oxide buffer layers for Cu(In,Ga)Se2 solar cells

The aim of this thesis is to provide an in-depth investigation of zinc tin oxide, Zn1-xSnxOy or ZTO, grown by atomic layer deposition (ALD) as a buffer layer in Cu(In,Ga)Se2 (CIGS) solar cells. The thesis analyzes how changes in the ALD process influence the material properties of ZTO, and how these in turn affect the performance of CIGS solar cells. It is shown that ZTO grows uniformly and conformably on CIGS and that the interface between ZTO and CIGS is sharp with little or no interdiffusion between the layers. The band gap and conduction band energy level of ZTO are dependent both on the [Sn]/([Zn]+[Sn]) composition and on the deposition temperature. The influence by changes in composition is non-trivial, and the highest band gap and conduction band energy level are obtained at a [Sn]/([Zn]+[Sn]) composition of 0.2 at 120 °C. An increase in optical band gap is observed at decreasing deposition temperatures and is associated with quantum confinement effects caused by a decrease in crystallite size. The ability to change the conduction band energy level of ZTO enables the formation of suitable conduction band offsets between ZTO and CIGS with varying Ga-content. It is found that 15 nm thin ZTO buffer layers are sufficient to fabricate CIGS solar cells with conversion efficiencies up to 18.2 %. The JSC is in general 2 mA/cm2 higher, and the VOC 30 mV lower, for cells with the ZTO buffer layer as compared to cells with the traditional CdS buffer layer. In the end comparable efficiencies are obtained for the two different buffer layers. The gain in JSC for the ZTO buffer layer is associated with lower parasitic absorption in the UV-blue region of the solar spectrum and it is shown that the JSC can be increased further by making changes to the other layers in the traditional CdS/i-ZnO/ZnO:Al window layer structure. The ZTO is highly resistive, and it is found that the shunt preventing i-ZnO layer can be omitted, which further increases the JSC. Moreover, an additional increase in JSC is obtained by replacing the sputtered ZnO:Al front contact with In2O3 deposited by ALD. The large gain in JSC for the ZTO/In2O3 window layer stack compensates for the lower VOC related to the ZTO buffer layer, and it is demonstrated that the ZTO/In2O3 window layer structure yields 0.6 % (absolute) higher conversion efficiency than the CdS/i-ZnO/ZnO:Al window layer structure.