Synthesis and characterization of CuxS nanoparticles. Nature of the infrared band and charge-carrier dynamics

CuxS (x = 1,2) nanoparticles have been synthesized utilizing different capping molecules including polyethyleneglycol (PEG), polyvinylpyrrolidone (PVP), casein hydrolysate-enzymatic (CAS), and bovine serum albumin (BSA). The ground-state electronic absorption spectra of the CuxS nanoparticles show three distinct types of CuxS formed: a green type assigned as crystalline CuS, and two brown types assigned as crystalline CuxS and amorphous Cu2S. The brown types exhibit a steady increase in absorption toward shorter wavelengths starting at around 650 nm, while the green type shows the same steady increase in absorption, but with an additional absorption band in the infrared (IR). The IR band is attributed to an electron-acceptor state lying within the bandgap. ESR measurements of free Cu(II) ions in solution for all samples show the presence of Cu(II) in the brown amorphous samples, but not in the green or brown crystalline samples. Ultrafast dynamics of photoinduced electrons have been measured for all samples using femtosecond-transient absorption/bleach spectroscopy. In all brown CuS samples studied, the early time-transient profiles feature a pulse-width-limited (<150 ps) rise followed by a fast decay (1.1 ps) and a slow decay (>80 ps). These decay dynamics were found to be independent of pump power and stabilizing agent. The fast 1.1 ps decay is attributed to charge carrier trapping, while the long decay may be due to either recombination or deep trapping of the charge carriers. The green Cu2S samples studied showed interesting power-dependent behavior. At low excitation intensities, the green CuxS samples showed a transient bleach signal, while at high intensities, a transient absorption signal has been observed. The increased transient absorption over bleach at high intensities is attributed to trap-state saturation. A kinetic model has been developed to account for the main features of the electronic relaxation dynamics.