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 Cu2S 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 Cu2S samples studied, the early time-transient profiles feature a pulse-width-limited (<150 fs) 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 CuxS 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.

A new synthetic method has been developed for preparing silver sulfide, Ag 2 S, nanoparticles capped with cysteine or glutathione. The average particle diameter has been determined to be around 9 nm using transmission electron microscopy. The ground-state electronic absorption spectra of the Ag 2 S nanoparticles show a continuous increase in absorption cross section toward shorter wavelengths starting from the red (600-800 nm). Ultrafast dynamics of photoinduced electrons in these nanoparticles have been measured using femtosecond transient absorption/bleach spectroscopy. In most cases studied, the early time transient profiles feature a pulse-width limited (<150 fs) rise followed by a fast decay (750 fs) and a slower rise (4.5 ps). The signal has contribution from both transient absorption and transient bleach. On longer time scales, three (Cys-1, Cys-2, and GSH-2) of the four samples studied show a recovery with 4.5 ps time constant that goes above the baseline and then decays gradually toward the baseline with a time constant of >1 ns. One sample (GSH-1) shows a bleach recovery that gradually approaches the baseline with a similar time constant (>1 ns) following the fast 4.5 ps rise. An interesting power dependence was observed for all the samples: the transient absorption contribution becomes more dominant over bleach with increasing excitation intensity. A simple four-state kinetic model developed to account for the main features of the dynamics suggests that initial photoexcitation populates the conduction band and depletes the valence band within the laser pulse (<150 fs). The conduction band electrons are first trapped in shallow trap states with a time constant of 500 fs and then further trapped into deep traps with a constant of 4 ps. The deep trapped electrons finally recombine with the hole with a time constant of >1 ns. This model suggests that the difference in dynamics observed between the different samples is due to different absorption cross sections of deep trap states. The observed excitation intensity dependence of the dynamics is attributed to shallow trap state saturation at high intensities.

Direct measurements of the dynamics of photoinduced electrons in AgI, AgI/Ag2S, and AgBr/Ag2S semiconductor colloidal nanoparticles have been performed using femtosecond pump–probe laser spectroscopy. In AgI the transient absorption signal features a laser pulsewidth limited rise followed by a double exponential decay with time constants of 2.5 ps and &gt;0.5 ns. The decay dynamics were found to be independent of pump power, indicating that the decays are not second order kinetic processes. The dynamics were also independent of the probe wavelengths, suggesting that the absorption spectrum of the photogenerated electrons is fully developed within ∼150 fs. The fast 2.5 ps decay is attributed to trapping and nonradiative electron–hole recombination mediated by a high density of trap states while the slow decay is attributed to reaction of deep trapped electrons with silver ions to form Ag atoms. For core/shell structured cocolloids of AgI/Ag2S, similar decay dynamics were observed. The only interesting difference is that the fast decay becomes faster with increasing concentration of Ag2S. This is due to direct excitation of Ag2S, which has a faster initial decay (800 fs) than in AgI. This is supported by the results of AgBr/Ag2S for which the same 800 fs decay was observed while no signal was observed for AgBr colloids alone, indicating clearly that the signal is from Ag2S. These findings on the early time dynamics of photo-induced excitons in AgI, AgI/Ag2S, and AgBr/Ag2S are important in better understanding the photographic process involving silver halides.