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The amplification of Raman signals of the heteroaromatic cation 1-(N-methylpyrid-4-yl)-2-(N-methylpyrrol-2-yl)ethylene (PEP+)) bound to Au nanorods (NRs) was investigated at different excitation wavelengths to study the effect of the laser resonance with the absorption band of the PEP+ moiety and with the two plasmon oscillation modes of the NR. Two different PEP+ derivatives, differing in the length of the alkyl chain bearing the anchoring group, were used as target molecules. Raman spectra obtained exciting at 514 or at 785 nm (i.e., exciting the transverse or the longitudinal plasmon band) present a higher intensity than that at 488 nm suggesting a higher Raman amplification when the laser excitation wavelength is resonant with one of the two plasmon modes. Moreover, considering results of Discrete Dipole Approximation (DDA) calculations of the local field generated at the NR surface when either the transverse or the longitudinal plasmon modes are excited, we deduced that the resonance condition of the 514-nm laser excitation with the absorption band of the dye strongly contributes to the amplification of the Raman signal. © 2014 The Author(s).

The widespread application of quantum dots greatly profits from their broad absorption band. However, the variable nature of excitations within these bands is expected to result in undesired excitation energy dependence of steady state emission properties. We demonstrate the different role played by hot and cold carrier trapping in determining fluorescence quantum yields. Our analysis relates the energetic parameters with the available knowledge on the dynamics of charge trapping. It turns out that detrapping processes play a pivotal role in determining steady state emission properties. We studied excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1-xS (x = 0, 0.5, and 1) quantum dots to identify best performing heterostructures in terms of shell thickness and composition. Our rationalization of the observed behavior is focused on the modulation of trapping and detrapping rates. The combination of experimental results and PLQY kinetics modeling reveals the need to consider hot-carrier trapping, supporting recent dynamics observations. This work provides a deeper insight into the trapping process in quantum dots, relating its energetics and dynamics.

Exciton interactions and dynamics are the most important factors determining the exceptional photophysical properties of semiconductor quantum dots (QDs). In particular, best performances have been obtained for ingeniously engineered core/shell QDs. We have studied two factors entering in the exciton decay dynamics with adverse effects for the luminescence efficiency: exciton trapping at surface and interface traps, and non-radiative Auger recombination in QDs carrying either net charges or multiple excitons. In this work, we present a detailed study into the optical absorption, fluorescence dynamics and quantum yield, as well as ultrafast transient absorption properties of CdSe/CdS, CdSe/Cd0.5Zn0.5S, and CdSe/ZnS QDs as a function of shell thickness. It turns out that de-trapping processes play a pivotal role in determining steady state emission properties. By studying the excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1-xS (x = 0, 0.5, 1) QDs, we demonstrate the different role played by hot and cold carrier trapping rates in determining fluorescence quantum yields. Finally, the use of global analysis allows us untangling the complex ultrafast transient absorption signals. Smoothing of interface potential, together with effective surface passivation, appear to be crucial factors in slowing down both Auger-based and exciton trapping recombination processes.

Two dimers of a heteroaromatic quadrupolar (acceptor-donor-acceptor) chromophore have been synthesized with different interchromophoric distances. Optical spectra of dimers in solution show a red shift of the linear absorption band upon decreasing the interchromophore distance, while fluorescence and two-photon absorption spectra are only marginally affected by the interactions. A bottom up approach is adopted to describe the spectra: via a detailed spectroscopic analysis of the monomeric species in solution, we define an essential-state model for the isolated chromophore and use this information to set up a model for the dimers also accounting for interchromophore electrostatic interactions. To discriminate between static screening governed by the static dielectric constant and dynamical screening at optical frequencies, we first solve the problem in the mean-field approximation and then define the excitonic Hamiltonian on the resulting best excitonic basis. Along this line, the evolution of spectral properties with the interchromophore distance is properly rationalized.

Semiconductor nanocrystals are rapidly spreading into the display and lighting markets. Compared with liquid crystal and organic LED displays, nanocrystalline quantum dots (QDs) provide highly saturated colors, wide color gamut, resolution, rapid response time, optical efficiency, durability and low cost. This remarkable progress has been made possible by the rapid advances in the synthesis of colloidal QDs and by the progress in understanding the intriguing new physics exhibited by these nanoparticles. In this review, we provide support to the idea that suitably engineered core/graded-shell QDs exhibit exceptionally favorable optical properties, photoluminescence and optical gain, while keeping the synthesis facile and producing QDs well suited for light emitting applications. Solid-state laser emitters can greatly profit from QDs as efficient gain materials. Progress towards fabricating low threshold, solution processed DFB lasers that are optically pumped using one- and two-photon absorption is reviewed. In the field of display technologies, the exploitation of the exceptional photoluminescence properties of QDs for LCD backlighting has already advanced to commercial levels. The next big challenge is to develop the electroluminescence properties of QD to a similar state. We present an overview of QLED devices and of the great perspectives for next generation display and lighting technologies.

The outstanding optical properties of Semiconductor Quantum Dots (QDs) have attracted much interest for over two decades. The development of synthetic methods for the production of core-shell QDs has opened the way to attaining almost ideal emitting properties. Their implementation in opto-electronic devices, such as light emitting diodes (LEDs) and lasers, requires a full understanding of the fine details of their photophysics. The exciton dynamics of core and coreshell QDs was extensively studied by means of pump and probe (P and P) and transient photoluminescence (TRPL) spectroscopies. Nevertheless, the wealth of possible exciton and multi-exciton decay mechanisms, operating on comparable time-scales, results in complex signals. In this work, the exciton dynamics of a complete CdSe/Cd1-xZnxS series is investigated, with a focus on exciton trapping processes. Insights into the energy distribution of exciton traps are unveiled by wavelength resolve QY measurements. Multicolor P and P measurements give a deeper insight into the dynamics of exciton trapping and Auger recombinations. An inversion method is proposed as a powerful tool for separating different contribution in complex P and P transients. The outcomes of this work clarify the role of core/shell interfaces and surfaces in modulating the optical properties and suggest possible routes for their improvement.

The linear and nonlinear optical properties of the heteroaromatic push-pull-push two-photon absorbing dye N-methyl-2,5-bis[1-(N-methylpyrid-4-yl) ethen-2-yl]-pyrrole ditriflate (PEPEP) are reported. The determination of the two-photon absorption (TPA) cross-section spectrum has been performed with different techniques: femtosecond TPA-white light continuum probe experiments, two-photon-induced fluorescence, and open aperture Z-scan measurements using both nanosecond and femtosecond laser pulses. The measured TPA cross sections and their wavelength dispersion show a marked dependence on the parameters of the laser pulses and on the measurement technique employed. These properties are discussed in terms of the different microscopic mechanisms that can contribute to the multiphoton absorption processes, with different weight depending on the measurement conditions and on the photophysical parameters of the dye. © 2008 American Chemical Society.

An original and convenient three steps (swelling-poling-deswelling) process of poling a cross-linked polymer/NLO-phore composite to produce a stable second harmonic generation is described, using as a model system a cross-linked poly-amido amine network carrying covalently attached a modified Disperse Red One, a well known NLO-phore. This procedure is expected to be of wide applicability to produce composite polymeric materials with a rather stable second harmonic generation and of particular interest for NLO-phores sensitive to temperature. © 2007 Elsevier B.V. All rights reserved.

The shell thickness and composition of CdSe-CdxZn1-xS core-shell quantum dots (QDs) are defining parameters for the efficiency of such materials as light emitters. In this work we present a detailed study into the optical absorption and fluorescence properties of CdSe-CdS, CdSe-Cd0.5Zn0.5S, and CdSe-ZnS QDs as a function of shell thickness. Moreover, the single-exciton recombination dynamics of these systems are analyzed by means of a time-correlated single-photon counting technique and directly related to the specific core-shell interfaces of the various QDs studied using a phenomenological kinetic model. The findings from this model highlight the strong role of the core-shell interface on both steady state photoluminescence and exciton recombination dynamics in these systems.

Semiconductor quantum dots possess attractive optical properties useful in the photonic field. Thanks to the evolution of core-shell colloidal synthesis, quantum dots exhibit almost ideal emitting properties. Their employment in optoelectronic devices is encouraged by their size-tunable emission as well as by their high absorption cross-section and high photoluminescence quantum yield. In this work, starting from the archetypal CdSe based system, the influence of shell thickness and composition on exciton dynamics in CdSe/CdxZn1-xScore-shell QDs is investigated. By means of steadystate and transient optical spectroscopy, single-and multi-exciton recombination processes are characterized and correlated with different shell materials. The present study clarifies why graded CdSe-CdS-Cd0.5Zn0.5-ZnS core-shell represents the best performing heterostructure for optical gain applications, since such quantum dots combine the high radiative rates of CdS with the superior confinement potential of ZnS in a single dot.