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The relaxation dynamics of photoexcited CdSe nanoparticles (NPs) were studied with femtosecond pump−probe spectroscopy in the spectral range from 450 nm to 5 μm. Thus, the intraband relaxation of the electron and the hole were monitored with femtosecond time resolution. The transition from delocalized electronic to localized defect states and the slower relaxation through the trapping sites (trap hopping mechanism) were followed by time-resolved emission on time scales from picoseconds to milliseconds in the spectral range from the visible into the mid-infrared. The spectral dynamics in the visible, near-infrared (NIR), and infrared (IR) range give a mechanistic picture about the relaxation pathway of the excited charge carriers in CdSe NPs. In addition, by using electron and hole quenchers to the photoexcited nanoparticles, we could assign the observed dynamics to the electron or the hole. In the visible range, bleach features (negative signals in the differential transient absorption measurements) were observed at early delay times with time components of 2 ps, 30 ps, and a long-lived component of ~200 ps. Based on the quenching experiments, the bleach could be assigned to contributions from the electron and the hole. In the NIR and IR spectral range, the transient signal for short delay times (<1 ns) were positive (transient absorption). A decay time of 1.2 ps was found for the transient absorption observed in the NIR. With the carrier removal technique, it could be shown that the NIR signal is mainly due to hole transitions. The IR signal with lifetimes of 2 ps, 30 ps, and a long component of ~200 ps compares directly to the decay times observed in the visible spectral range. It therefore is also composed of contributions from electron and hole. Photoluminescence is observed in the visible range at 570 nm (near band edge recombination), in the NIR at 1000 nm (deep-trap emission), and in the IR region at 4.8 μm (deeper-trap emission) with lifetimes of 43 ns, 250 ns, and 1 μs, respectively. The lifetimes of the emission increased for longer monitoring wavelengths, suggesting that for the investigated sample, the carriers relax from the band edge into shallow traps and from there continue stepwise relaxation into lower energy sites (trap hopping mechanism).

Addition of butylamine to a solution of colloidal CdSe nanoparticles (NPs) caused a decrease in fluorescence intensity, with no effect on the picosecond bleach recovery of the exciton formation or on the luminescence dynamics. The relative fluorescence quantum yield was found to decrease with increasing butylamine concentration and to level off at high concentrations, but the fluorescence lifetimes were not influenced. The nonlinear concentration dependence of the fluorescence quantum yield did not follow the Stern−Volmer equation. This is in agreement with the observation that the CdSe luminescence lifetime was not affected by the addition of butylamine. A mechanism is proposed in which the emission observed in CdSe is assumed to result from the combination of surface-trapped electrons and holes. n-Butylamine occupies hole sites, thus blocking the recombination process, which results in decreasing the density of luminescent centers. These results will be discussed in terms of the nature of the binding sites of the amine on the nanoparticle surface.

Gold nanorods have been found to change their shape after excitation with intense pulsed laser irradiation. The final irradiation products strongly depend on the energy of the laser pulse as well as on its width. We performed a series of measurements in which the excitation power was varied over the range of the output power of an amplified femtosecond laser system producing pulses of 100 fs duration and a nanosecond optical parametric oscillator (OPO) laser system having a pulse width of 7 ns. The shape transformations of the gold nanorods are followed by two techniques:  (1) visible absorption spectroscopy by monitoring the changes in the plasmon absorption bands characteristic for gold nanoparticles; (2) transmission electron microscopy (TEM) in order to analyze the final shape and size distribution. While at high laser fluences (~1 J cm^-2) the gold nanoparticles fragment, a melting of the nanorods into spherical nanoparticles (nanodots) is observed when the laser energy is lowered. Upon decreasing the energy of the excitation pulse, only partial melting of the nanorods takes place. Shorter but wider nanorods are observed in the final distribution as well as a higher abundance of particles having odd shapes (bent, twisted, φ-shaped, etc.). The threshold for complete melting of the nanorods with femtosecond laser pulses is about 0.01 J cm^-2. Comparing the results obtained using the two different types of excitation sources (femtosecond vs nanosecond laser), it is found that the energy threshold for a complete melting of the nanorods into nanodots is about 2 orders of magnitude higher when using nanosecond laser pulses than with femtosecond laser pulses. This is explained in terms of the successful competitive cooling process of the nanorods when the nanosecond laser pulses are used. For nanosecond pulse excitation, the absorption of the nanorods decreases during the laser pulse because of the bleaching of the longitudinal plasmon band. In addition, the cooling of the lattice occurring on the 100 ps time scale can effectively compete with the rate of absorption in the case of the nanosecond pulse excitation but not for the femtosecond pulse excitation. When the excitation source is a femtosecond laser pulse, the involved processes (absorption of the photons by the electrons (100 fs), heat transfer between the hot electrons and the lattice (<10 ps), melting (30 ps), and heat loss to the surrounding solvent (>100 ps) are clearly separated in time.

The power dependence of the transient absorption spectrum of CdSe nanoparticle colloids with size distribution of 4.0 ± 0.4 nm diameter is studied with femtosecond pump−probe techniques. At the lowest pump laser power, the absorption bleaching (negative spectrum) characteristic of the exciton spectrum is observed with maxima at 560 and 480 nm. As the pump laser power increases, two new transient absorptions at 510 and 590 nm with unresolved fast rise (<100 fs) and long decay times (≫150 ps) are observed. The energy of each of the positive absorption is red shifted from that of the bleach bands by ~120 meV. The origin of this shift is discussed in terms of the effect of the internal electric field of the many electron−hole pairs formed within the quantum dot at the high pump intensity, absorption from a metastable excited state or the formation of biexcitons.

The formation and decay of the optical hole (bleach) for 4 nm CdSe nanoparticles (NPs) with adsorbed electron acceptors (1,4-benzoquinone and 1,2-naphthoquinone) and the rise and decay of the reduced electron acceptors formed after interfacial electron transfer from the CdSe NPs were investigated by femtosecond laser spectroscopy. The ultrashort (200−400 fs) rise times of the bleach at the band-gap energy of the CdSe NP as well as of the acceptor radical anion are found to increase with increasing the excitation energy. This suggests that the electron transfer from the CdSe NP to the quinone electron acceptor occurs after thermalization of the excited hot electrons. The decay times of the transient absorption for the electron acceptor radical anions are found to be comparable to that of the CdSe NP bleach recovery time (3 ps). This suggests that the surface quinones shuttle the electron from the conduction band to the valence band of the excited NP. We contrast this behavior with the excited-state dynamics of the recently investigated CdS−MV²⁺ system in which the electron acceptor does not shuttle the accepted electron back to the hole in CdS.