Multiple excitations in core/shell CdSe/CdS-seeded nanorods of different core diameters are studied by quasi-cw multiexciton spectroscopy and envelope function theoretical calculations. For core diameters below 2.8 nm, a transfer from binding to repulsive behavior is detected for the biexciton, accompanied by significant reduction of the triexciton oscillator strength. These characteristics indicate a transition of the electronic excited states from type-I localization in the core to a quasi-type-II delocalization along the entire rod as the core diameter decreases, in agreement with theoretical calculations.

We report the synthesis of CdSe/CdS rod in rod core/shell heterostructures. These rods, synthesized using a seeded-growth approach, show narrow distributions of rod diameters and lengths and exhibit high emission quantum efficiencies and highly polarized emission. The degree of polarization is controlled by the inner core rod dimensions, and it is equal or up to 1.5 times higher than the polarization of equivalent sphere in rod systems. Using the method of photoselection we measure the polarization anisotropy at different excitation wavelengths and study the interplay between electronic contribution and dielectric effects in determining the absorption and emission polarization.

Semiconductor heterostructured seeded nanorods exhibit intense polarized emission, and the degree of polarization is determined by their morphology and dimensions. Combined optical and atomic force microscopy were utilized to directly correlate the emission polarization and the orientation of single seeded nanorods. For both the CdSe/CdS sphere-in-rod (S@R) and rod-in-rod (R@R), the emission was found to be polarized along the nanorod's main axis. Statistical analysis for hundreds of single nanorods shows higher degree of polarization, p, for R@R (p = 0.83), in comparison to S@R (p = 0.75). These results are in good agreement with the values inferred by ensemble photoselection anisotropy measurements in solution, establishing its validity for nanorod samples. On this basis, photoselection photoluminescence excitation anisotropy measurements were carried out providing unique information concerning the symmetry of higher excitonic transitions and allowing for a better distinction between the dielectric and the quantum-mechanical contributions to polarization in nanorods.

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Colloidal nanocrystal synthesis provides a powerful approach for creating unique nanostructures of relevance for applications. Here, we report that wurtzite ZnSe nanorod couples connected by twinning structures can be synthesized by means of a self-limited assembly process. Unlike for individual nanorods, the band-edge states calculated for the nanorod couples are predominantly confined to the short edges of the structure and this leads to low photoluminescence polarization anisotropy, as confirmed by single-particle fluorescence. Through a cation-exchange approach, the composition of nanorod couples can be readily expanded to additional materials, such as CdSe and PbSe. We anticipate that this family of nanorod-couple structures with distinct compositions and controlled properties will constitute an ideal system for the investigation of electronic coupling effects between individual nanorod components on the nanoscale, with relevance to applications in optics, photocatalysis and optoelectronic devices.

Fluorescence resonance energy transfer (FRET) involving a semiconductor nanoparticle (NP) acting as a donor, attached to multiple acceptors, is becoming a common tool for sensing, biolabeling, and energy transfer applications. Such nanosystems, with dimensions that are in the range of FRET interactions, exhibit unique characteristics that are related to the shape and dimensionality of the particles and to the spatial distribution of the acceptors. Understanding the effect of these parameters is of high importance for describing the FRET process in such systems and for utilizing them for different applications. In order to demonstrate these dimensionality effects, the FRET between CdSe/CdS core/shell NPs with different geometries and dimensionalities and Atto 590 dye molecules acting as multiple acceptors covalently linked to the NP surface is examined. Steady-state emission and temporal decay measurements were performed on the NPs, ranging from spherical to rod-like shaped systems, as a function of acceptor concentration. Changes in the NP geometry, and consequently in the distributions of acceptors, lead to distinctively different FRET behaviors. The results are analyzed using a modified restricted geometries model, which captures the dimensionality of the acceptor distribution and allows extracting the concentration of dye molecules on the surface of the NP for both spherical and elongated NPs. The results obtained from the model are in good agreement with the experimental results. The approach may be useful for following the spatial dynamics of self-assembly and for a wide variety of sensing applications.

We investigated systematically the temperature dependence of the spectral properties such as the band gap, bandwidth and fluorescence intensity of CdSe/CdS dot-in-rod nanocrystals. These asymmetry nanoparticles were synthesized by seeded growth techniques with band alignment of the type-I and quasi type-II with initial core sizes of 3.3 and 2.3 nm, respectively. With increasing temperature the band gap decreases and bandwidth increases, largely due to exciton-phonon scattering. Anomalous variations of the band gap and bandwidth were observed at 200-240 K, and the variations are attributed to the anisotropic strain in the CdSe/CdS interface due to temperature dependent lattice mismatch. The integrated intensity of fluorescence shows two variation regimes. In the low temperature regime, the intensity remained roughly constant due to the temperature dependent carrier mobility and trapping by the defect states in the CdS shell. However, in the higher temperature regime, the intensity decreased quickly due to thermal/phonon assisted escape from the CdSe dot. The barrier depths are estimated to be about 557 and 285 meV for type-I and quasi type-II samples, respectively.

The mixed 0D-1D dimensionality of heterostructured semiconductor nanorods, resulting from the dot-in-rod architecture, raises intriguing questions concerning the location and confinement of the exciton and the origin of the fluorescence in such structures. Using apertureless near-field distance-dependent lifetime imaging together with AFM topography, we directly map the emission and determine its location with high precision along different types of nanorods. We find that the fluorescence is emanating from a sub-20 nm region, correlated to the seed location, clearly indicating exciton localization.