Two alternative chemical etchings (aqueous solution of bromine and bromine methanol solution) have been here tested to replace the KCN etching step in Cu-rich CuInSe2 based solar cells fabrication process. This new oxidative etch aims also at smoothing and thinning the as-grown films. This directly affects the interface between the absorber and the CdS buffer, interface which causes problems for Cu-rich solar cells. We present here the effect of these two alternative etchings on both the absorber surface and the solar cells parameters: whereas the bromine methanol etching destroys the solar cell, the aqueous solution of bromine leads to an improvement of the device through reduced interface and tunneling enhanced recombination.

The linear polarisation of luminescence light allows conclusions on the symmetry of defects in semiconductors with non-cubic symmetry, like chalcopyrites, for which three shallow acceptors have been identified by photoluminescence. The polarisation dependent photoluminescence allows to determine the symmetry of the defects relative to the c-axis of the crystal. A simple geometrical model implies that chalcogen sites show a predominant direction perpendicular to the c-axis, while metal sites show a predominant direction parallel to the c-axis. Since all three shallow acceptors show polarization parallel to the c-axis, it can be concluded that they are situated on a metal site

Unlike other photoactive layers (e.g. Si) polycrystalline chalcopyrite layers achieve higher efficiency than monocrystalline ones. Although grain boundaries may play an important role for this phenomenon, there is currently no commonly accepted model for the electronic structure of grain boundaries. First experimental results on CuGaSe2 absorbers indicated a small neutral barrier for majority carriers (20-40meV) at sigma 3 grain boundaries, which is the predominant grain boundary in polycrystalline chalcopyrite absorbers [1]. These results are in discrepancy with theory, which predicts a 10 times higher barrier; we suspect that the copper excess might reduce the barrier height.

Here we present a study using Hall-effect and Kelvin Probe Force Microscopy (KPFM) measurements to investigate the composition dependence of the barrier height of epitaxially grown CuGaSe2 layers containing a sigma 3 grain boundary as a function of the Cu/Ga ratio. First results show that the barrier height is independent of the copper content. In addition, we present initial results on sigma 9 grain boundaries which are observed to occur in high efficiency absorbers.

The objective of this work is to increase the open circuit voltage of CuGaSe2(CGS)-based solar cells without decreasing their efficiency. For that, the interface between the p-type CGS absorber and the n-type CdS/ZnO window layer is compared using three different recipes for the growth of the buffer layer. Results show the importance of the adaptation of the CdS buffer layer to the CuGaSe2 absorber film. A maximum open circuit voltage of 922 mV is achieved for the devices when using 60ºC as the chemical bath temperature and a low thiourea concentration. Drive-level capacitance profiling, external quantum efficiency and temperature dependent current-voltage measurements reveal a better quality of the CdS/CuGaSe2 interface for this buffer layer deposition conditions. Factors such as the larger depletion region width and the lower doping level, reducing the tunnelling component, are pointed out as responsible of the higher Voc.

In this work we investigate bias - induced metastability in CIGS solar cells. Long - term capacitance transients have been measured for two baseline CIGS devices with different efficiencies and a CGS cell in order to analyze carrier trapping processes. Based on the results we discuss hole emission process which leads to metastable increase of net acceptor density and also hole capture related to its relaxation. Time constants and activation energies for hole emission and capture have been obtained. Apart of carrier trapping processes we have also distinguished an interface-related change of capacitance. Our results indicate processes involving thermal lattice relaxation. We explain them in light of properties of (VSe+VCu) divacancy, defect with negative correlation energy, which can exist in both donor and acceptor configuration.

For preparation of ZnO/CdS/Cu(In,Ga)Se2 solar cells, physical vapor deposition (PVD) was employed to deposit CdS buffer layers in ultrahigh vacuum on Se-decapped absorber surfaces, thus realizing an all ‘dry' fabrication process of the device. An 14.1% total area and 14.5% active area efficient ZnO/CdS/Cu(In,Ga)Se2 solar cell under AM1.5 conditions was achieved after annealing the as-prepared solar cells in air. Kelvin probe force microscopy (KPFM) measurements were carried out in-situ to monitor the initial growth of the CdS buffer layer on the absorber, as well as its electronic properties, in particular, the work function. It was observed that the PVD-CdS growth is initially inhibited at the absorber grain boundaries. Quantum efficiency measurements allowed us to suppose that during the initial growth stage a passivation of the grain boundaries occurs. The latter explains the higher short-circuit currents of the cells with PVD-CdS compared to their references with CdS grown by chemical bath deposition (CBD). The beneficial effect of the annealing seems to originate from a formation of a region with higher band gap than that of the absorber bulk and inverted conductivity type at the absorber surface, close to the CdS/Cu(In,Ga)Se2 interface, leading to a dramatic change in the electronic transport properties and finally, to a significant enhancement of the open-circuit voltage. Annealing of the ZnO/PVD-CdS/Cu(In,Ga)Se2 solar cells provides formation of PVDCdS/ Cu(In,Ga)Se2 interface with properties similar to that of reference samples with CBD-CdS.

Chalcopyrites are doped by intrinsic defects, therefore their doping behavior depends on their composition. The doping and transport properties of epitaxial CuGaSe2 layers prepared under varying Cu excess have been investigated by temperature dependent Hall effect and conductivity measurements. Two acceptors, 134 meV and 80 meV deep, and a high degree of compensation, increasing with decreasing Cu excess, are found. The temperature dependence of the mobility indicates scattering with phonons, demonstrating high quality material. Defect scattering dominates at lower temperatures for CuGaSe2 grown under moderate Cu excess. CuGaSe2 grown under little or no Cu excess shows transport in a defect band at lower temperatures.

Photocurrents in phthalocyanine ohmic samples and in phthalocyanine/perylene solar cells are shown. In principle current spectra follow the absorption spectra of the materials. Deviations from this behaviour can be accounted for by filtering effects. The influence of intensity, bias light and applied voltage is discussed.