Structural, optical and crystal field analyses of undoped and Mn2+-doped ZnS nanoparticles synthesized via reverse micelle route

Zinc sulfide, both as a bulk material and in nanocrystalline form, is a valuable luminescent material with important applications. Doped ZnS nanoparticles of around 5 nm are the material of choice for optoelectronic applications running in the UV region owing to their significant quantum size effect. This paper concerns detailed structural, spectroscopic and crystal field studies of ZnS nanoparticles, both pure and doped with Mn2+ ions, successfully synthesized at room temperature using a simple reverse micelle technique in the Triton X-100/cyclohexane medium. The resulting ZnS sphalerite phase small-size nanoparticles (3–5 nm) have a much larger energy band gap (∼4.7 eV) than that reported for the bulk ZnS (3.6 eV), thus confirming a pronounced quantum confinement effect. The electron paramagnetic resonance data provided evidence for the existence of two distinct environments for Mn2+ ions: the interior (core) and near the surface of the nanoparticles. The presence of an Mn2+-characteristic orange emission centered at 600 nm confirmed that our samples were properly doped with Mn2+ ions, as the 4T1→6A1 radiation transition could arise only on the basis of Mn2+ ions incorporated into the ZnS nanoparticles. To the best of our knowledge, our finding include the longest decay time component for the orange emission ever observed, timed at about 3.3 ms. The experimental excitation spectra were analyzed and the transitions assigned using the exchange charge model of theory of crystal field, which allowed to calculate the energy level scheme of the Mn2+ ions. The results presented in this paper provide us with detailed information about the ZnS sphalerite nanocrystals studied and can be readily applied to other similar systems. -- Highlights: • 3–5 nm ZnS and ZnS:Mn2+ NPs synthesized at RT via reverse micelle synthesis. • Pronounced Quantum Confinement effect: Eg (NPs)=4.7 eV>Eg (bulk)=3.6 eV. • Estimated distribution of the Mn2+ ions throughout the ZnS nanoparticles. • We report on the longest lifetime component for Mn2+ orange emission of 3.3 ms. • Detailed CF analysis of the Mn2+ energy levels is presented