The sun provides us with a surplus of energy convertible to electricity using solar cells. This thesis focuses on solar cells based on chalcopyrite (CIGSe) as well as kesterite (CZTS(e)) absorber layers. These materials yield record efficiencies of 20.4 % and 11.1 %, respectively. Especially for CZTS(e), the absorber layers often do not consist of one single desired phase but can exhibit areas with deviating material properties, referred to as secondary phases. Furthermore, several material layers are required for a working solar cell, each exhibiting interfaces. Even though secondary phases and interfaces represent a very small fraction of the solar cell they can have a profound influence on the over-all electrical solar cell characteristics. As such, it is crucial to understand how secondary phases and interfaces influence the local electrical characteristics. Characterising secondary phases and interfaces is challenging due to their small sample volume and relatively small differences in composition amongst others. This is where electronmicroscopy, especially transmission electron microscopy, offers valuable insight to material properties on the microscopic scale. The main challenge is, however, to link these material properties to the corresponding electrical characteristics of a solar cell. This thesis uses electron beam induced current imaging and introduces a new method for JV characterisation of solar cells on the micron scale. Combining microscopic structural and electrical characterisation techniques allowed identifying and characterising local defects found in the absorber layer of CIGS solar cells after thermal treatment. Furthermore, CZTSe solar cells in this thesis exhibited a low photo-current density which is traced to the formation of a current blocking ZnSe secondary phase at the front contact interface. The electron microscopy work has contributed to an understanding of the chemical stability of CZTS and has shown the need for an optimised back contact interface in order to avoid chemical decomposition reactions and formation of detrimental secondary phases. With this additional knowledge, a comprehensive picture of the material properties from the macroscopic down to the microscopic level can be attained throughout all required material layers.

A deeper understanding of Cu(In,Ga)Se2 (CIGS) solar cells is important for the further improvement of these devices. This thesis is focused on the use of electrical modelling as a tool for pursuing this aim. Finished devices and individual layers are characterized and the acquired data are used as input in the simulations. Band gap gradients are accounted for when modelling the devices. The thesis is divided into two main parts. One part that treats the influence of cadmium free buffer layers, mainly atomic layer deposited (Zn,Mg)O, on devices and another part in which the result of CIGS absorber layer modifications is studied. Recombination analysis indicates that interface recombination is limitting the open circuit voltage (Voc) in cells with ZnO buffer layers. This recombination path becomes less important when magnesium is introduced into the ZnO giving a positive conduction band offset (CBO) towards the CIGS absorber layer. Light induced persistent photoconductivity (PPC) is demonstrated in (Zn,Mg)O thin films. Device modelling shows that the measured PPC, coupled with a high density of acceptors in the buffer-absorber interface region, can explain light induced metastable efficiency improvement in CIGS solar cells with (Zn,Mg)O buffer layers. It is shown that a thin indium rich layer closest to the buffer does not give any significant impact on the performance of devices dominated by recombination in the CIGS layer. In our cells with CdS buffer the diffusion length in the CIGS layer is the main limitting factor. A thinner CIGS layer improves Voc by reducing recombination. However, for thin enough absorber layers Voc deteriorates due to recombination at the back contact. Interface recombination is a problem in thin devices with Zn(O,S) buffer layers. This recombination path is overshadowed in cells of standard thickness by recombination in the CIGS bulk. Thin cells with Zn(O,S) buffer layers have a higher efficiency than CdS cells with the same absorber thickness.