A detailed analysis of the radiative recombination processes in CuxGaySe2 epitaxial layers is presented aiming at an investigation of the intrinsic defect levels as a function of chemical composition. CuxGaySe2 is grown by metalorganic vapor phase epitaxy to allow a precise control of composition. Temperature and excitation intensity dependent photoluminescence is used to identify different recombination mechanisms and to determine the ionization energies of the defect levels involved. Defect-correlated optical transitions in Cu-rich epilayers are described in a recombination model consisting of two acceptor and one donor levels showing ionization energies of (60±10) meV, (100±10) meV, and (12±5) meV, respectively. The identification of a shallow compensating donor in CuxGaySe2 and the assignment of the 100 meV state to an acceptor are the most important new aspects in this model. Photoluminescence properties of layers showing Ga-rich compositions are discussed in a model of highly doped and highly compensated semiconductors—the model of fluctuating potentials.

Highly efficient Cu(In,Ga)(S,Se)2 thin film solar cells are fabricated using a scalable drop-on-demand inkjet printing approach from environmentally-friendly molecular ink.

The electronic structure of grain boundaries in polycrystalline Cu(In,Ga)Se2 thin films and their role on solar cell device efficiency is currently under intense investigation. A neutral barrier of about 0.5 eV has been suggested as the reason for the benign behavior of grain boundaries in chalcopyrites. Previous experimental investigations have in fact shown a neutral barrier but only a few 10 meV high, which cannot be expected to have a significant influence on the solar cell efficiency. Here we show that a full investigation of the electrical behavior of charged and neutral grain boundaries shows the existence of an additional narrow neutral barrier, several 100 meV high, which is tunneled through by the majority carriers but is sufficiently high to explain the benign behavior of the grain boundaries.

Excitonic line spectra from CuGaSe2 single crystals and epitaxial layers are investigated as a function of temperature. Near band edge luminescence from free and bound excitons is observed at 10 K. The identification of both, free exciton ground and first excited state allows to determine the free exciton binding energy, which is found to be (13±2) meV. The bound exciton line is attributed to the recombination of an exciton bound to a neutral acceptor (A0, X). The widely discussed phenomenon of an anomalous temperature dependence of the band gap energies in different chalcopyrite-type I-III-VI2 compounds is reconsidered for CuGaSe2 on the basis of temperature dependent photoluminescence studies. No anomalous behaviour of the band gap energy as a function of temperature is found in CuGaSe2.

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