Ultrafast photoinduced charge separation in metal-semiconductor nanohybrids.

Hybrid nano-objects formed by two or more disparate materials are among the most promising and versatile nanosystems. A key parameter in their properties is interaction between their components. In this context we have investigated ultrafast charge separation in semiconductor-metal nanohybrids using a model system of gold-tipped CdS nanorods in a matchstick architecture. Experiments are performed using an optical time-resolved pump-probe technique, exciting either the semiconductor or the metal component of the particles, and probing the light-induced change of their optical response. Electron-hole pairs photoexcited in the semiconductor part of the nanohybrids are shown to undergo rapid charge separation with the electron transferred to the metal part on a sub-20 fs time scale. This ultrafast gold charging leads to a transient red-shift and broadening of the metal surface plasmon resonance, in agreement with results for free clusters but in contrast to observation for static charging of gold nanoparticles in liquid environments. Quantitative comparison with a theoretical model is in excellent agreement with the experimental results, confirming photoexcitation of one electron-hole pair per nanohybrid followed by ultrafast charge separation. The results also point to the utilization of such metal-semiconductor nanohybrids in light-harvesting applications and in photocatalysis.

Absorption properties of metal-semiconductor hybrid nanoparticles.

The optical response of hybrid metal-semiconductor nanoparticles exhibits different behaviors due to the proximity between the disparate materials. For some hybrid systems, such as CdS-Au matchstick-shaped hybrids, the particles essentially retain the optical properties of their original components, with minor changes. Other systems, such as CdSe-Au dumbbell-shaped nanoparticles, exhibit significant change in the optical properties due to strong coupling between the two materials. Here, we study the absorption of these hybrids by comparing experimental results with simulations using the discrete dipole approximation method (DDA) employing dielectric functions of the bare components as inputs. For CdS-Au nanoparticles, the DDA simulation provides insights on the gold tip shape and its interface with the semiconductor, information that is difficult to acquire by experimental means alone. Furthermore, the qualitative agreement between DDA simulations and experimental data for CdS-Au implies that most effects influencing the absorption of this hybrid system are well described by local dielectric functions obtained separately for bare gold and CdS nanoparticles. For dumbbell shaped CdSe-Au, we find a shortcoming of the electrodynamic model, as it does not predict the "washing out" of the optical features of the semiconductor and the metal observed experimentally. The difference between experiment and theory is ascribed to strong interaction of the metal and semiconductor excitations, which spectrally overlap in the CdSe case. The present study exemplifies the employment of theoretical approaches used to describe the optical properties of semiconductors and metal nanoparticles, to achieve better understanding of the behavior of metal-semiconductor hybrid nanoparticles.

Synergistic effects on second harmonic generation of hybrid CdSe-Au nanoparticles.

Hybrid semiconductor-metal nanoparticles exhibit a combination of properties from the disparate components or even, more interestingly, synergetic properties which arise from the coupling between the two materials. In this work, we study the second harmonic generation (SHG) in CdSe-Au hybrid nanoparticles in comparison with their components, using the Hyper-Rayleigh scattering (HRS) method. Possible contribution of symmetry effects was studied by comparing symmetric two-sided gold-tipped CdSe nanodumbbells with asymmetric one-sided quantum dot-Au (QD-Au) hybrids. A simplistic view of a symmetry effect is disproved in this case by the experimental data, which shows an unexpected reduction in the SHG response in both cases, compared to the respective mixtures of Au and CdSe nanoparticles. For CdSe-Au hybrids with a long semiconductor rod segment, we find that the SHG response corresponds to a sum of the contributions from the semiconductor and the metal components. However, for QD-Au and smaller dumbbells, the SHG response is smaller than expected from a simple sum of the contribution from both components. This reduction is assigned to the effects related to the CdSe-Au interfacial region within these hybrids. A first plausible contribution to the reduction is the dephasing induced by the gold, leading to diminished SHG from the CdSe component. This reduced response of the semiconductor component is accompanied by reduced SHG from the gold component which is assigned to a partial change of the surface of the gold once an interface with CdSe is formed. These observations regarding the SHG response manifest the unique properties that arise from the combination of a semiconductor and a metal within one hybrid nanoparticle.

Size dependence of molar absorption coefficients of CdSe semiconductor quantum rods.

Fundamental properties: The molar absorption coefficients of CdSe quantum rods are determined experimentally as a function of their dimensions (see figure). Far above the band gap a simple dependence on volume is seen. The behavior at the band gap manifests a concentration of oscillator strength with decreased diameter in agreement with strong quantum confinement behavior.

Cobalt growth on the tips of CdSe nanorods.

Best of both worlds: Reduction of an organometallic Co precursor on preformed CdSe nanorods yields two distinct semiconducting-magnetic heterostructures (see picture). The selective growth of Co on the tips of CdSe first gives nanosphere-nanorod dimers, which evolve into nanorod-nanorod structures. In the hybrid objects the magnetic properties of Co remain intact, while the luminescence properties of CdSe are affected but not completely quenched.

Electric field induced switching of the fluorescence of single semiconductor quantum rods.

The exceptional fluorescence properties of single CdSe quantum rods (QRs) arising from internal and external electric fields are studied. Reversible external field induced switching of the emission in single QRs is reported for the first time. This effect was correlated with local field induced emission intensity reduction and newly observed darkening mechanism. Bimodal spectral jumps under a zero field were also observed and assigned to charged exciton emission, a phenomenon that was likewise directly controlled through an external field. These phenomena point to the use of single QRs as spectrally tunable charge sensitive fluorophores with polarized emission in fluorescence tagging and optical switching applications.