Electrical properties and luminescence of CuInSe2

We have studied the electrical properties and luminescence spectra of melt-grown CuInSe₂ single crystals and the doping of the crystals with intrinsic defects and extrinsic impurities. The preparation and the properties of p-n junctions are also discussed. We find that the low temperature photoluminescence spectra of crystals as-grown or annealed between 400 and 700 C are characteristic of the conductivity type. At 77 K, p-type crystals emit in a band peaked at 1.00 eV (type A spectrum) whereas the emission of n-type crystals peaks at 0.93 eV (type B spectrum). Type A and type B spectra can be interchanged by alternate anneals in minimum or maximum Se pressure. Type B emission dominates the electroluminescence spectrum of p-n junctions. These features are explained by the appearing and disappearing of a donor level as a consequence of annealing in vacuum or in Se atmosphere. We find that Zn and Cd act as donors. Crystals doped with these impurities have electron concentrations above 10¹⁸ cm⁻³. Zn-dopped samples exhibit a very broad recombination band below the bandgap in photoluminescence both at 77 and 300 K.