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CuInSe 2 single crystals have been studied employing photoluminescence (PL), optical reflection (OR), optical absorption (OA) and wavelength derivative reflection (WDR) techniques at temperatures from 4.2 to 300 K. Exciton-related peaks were observed in the near-band-edge region of the PL spectra: several narrow lines, with full width at half maximum (FWHM) of about 0.3 meV, and two wider peaks (FWHM about 0.7 meV) at 1.0414 (A) and 1.0449 eV (B). The A and B peaks were also observed in the OR and OA spectra and identified as A and B free excitonic states. The narrow lines were attributed to bound exciton recombination on intrinsic defects. A third exciton resonance (C) was observed in the WDR spectra at 1.2779 eV. The crystal-field and spin-orbit splittings were derived to be 5.3 and 234.7 meV, respectively.

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