Selenium nanoparticles with diameters of 100-400 nm are prepared via hydrazine-driven reduction of selenious acid. The as-prepared amorphous, red selenium (a-Se) particles were neither a stable phase nor were they colloidally stable. Due to phase transition to crystalline (trigonal), grey selenium (t-Se) at or even below room temperature, the particles merged rapidly and recrystallized as micronsized crystal needles. As a consequence, such Se particles were not suited for layer deposition and as a precursor to manufacture thin-film CIS (copper indium selenide/CuInSe2) solar cells. To overcome this restriction, Se@CuSe core@shell particles are presented here. For these Se@CuSe core@shell nanoparticles, the phase transition a-Se -> t-Se is shifted to temperatures higher than 100 degrees C. Moreover, a spherical shape of the particles is retained even after phase transition. Composition and structure of the Se@CuSe core@shell nanostructure are evidenced by electron microscopy (SEM/STEM), DLS, XRD, FT-IR and line-scan EDXS. As a conceptual study, the newly formed Se@CuSe core@shell nanostructures with CuSe acting as a protecting layer to increase the phase-transition temperature and to improve the colloidal stability were used as a selenium precursor for manufacturing of thin-film CIS solar cells and already lead to conversion efficiencies up to 3%. (C) 2013 Elsevier Inc. All rights reserved.