Amit Sitt

Highly Emissive Nano Rod-in-Rod Heterostructures with Strong Linear Polarization

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.

Multiexciton Engineering in Seeded Core/Shell Nanorods: Transfer from Type-I to Quasi-type-II Regimes

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.

Effect of Nanoparticle Dimensionality on Fluorescence Resonance Energy Transfer in Nanoparticle–Dye Conjugated Systems

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.

Polarization Properties of Semiconductor Nanorod Heterostructures: From Single Particles to the Ensemble.

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 nanorods 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.

Nanoscale Near-Field Imaging of Excitons in Single Heterostructured Nanorods

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.

Single-particle studies of band alignment effects on electron transfer dynamics from semiconductor hetero-nanostructures to single-walled carbon nanotubes.

We utilize single-molecule spectroscopy combined with time-correlated single-photon counting to probe the electron transfer (ET) rates from various types of semiconductor hetero-nanocrystals, having either type-I or type-II band alignment, to single-walled carbon nanotubes. A significantly larger ET rate was observed for type-II ZnSe/CdS dot-in-rod nanostructures as compared to type-I spherical CdSe/ZnS core/shell quantum dots and to CdSe/CdS dot-in-rod structures. Furthermore, such rapid ET dynamics can compete with both Auger and radiative recombination processes, with significance for effective photovoltaic operation.

Autonomic Molecular Transport by Polymer Films Containing Programmed Chemical Potential Gradients

Materials which induce molecular motion without external input offer unique opportunities for spatial manipulation of molecules. Here, we present the use of polyacrylamide hydrogel films containing built-in chemical gradients (enthalpic gradients) to direct molecular transport. Using a cationic tertiary amine gradient, anionic molecules were directionally transported up to several millimeters. A 40-fold concentration of anionic molecules dosed in aerosol form on a substrate to a small region at the center of a radially symmetric cationic gradient was observed. The separation of mixtures of charged dye molecules was demonstrated using a boronic acid-to-cationic gradient where one molecule was attracted to the boronic acid end of the gradient, and the other to the cationic end of the gradient. Theoretical and computational analysis provides a quantitative description of such anisotropic molecular transport, and reveals that the gradient-imposed drift velocity is in the range of hundreds of nanometers per second, comparable to the transport velocities of biomolecular motors. This general concept of enthalpy gradient-directed molecular transport should enable the autonomous processing of a diversity of chemical species.

Colloidal self-assembly: Superparticles get complex

The assembly of hundreds of thousands of semiconductor nanorods into nearly spherical or needle-like colloidal superparticles made of highly ordered supercrystalline domains can be explained by simple thermodynamic and kinetic principles.

Microscale Rockets and Picoliter Containers Engineered from Electrospun Polymeric Microtubes

Chemically functional core/shell microtubes made of biodegradable polymers are fabricated using coaxial electrospinning. The luminal walls are chemically functionalized, allowing for regioselective chemical binding or adsorption inside the microtube. Attaching catalytic nanoparticles or enzymes to the luminal walls converts the microtubes into bubble-propelled microrockets. Upon exposure to ultrasound, the microtubes undergo shape shifting, transforming them into picoliter-scale containers.

Directed Transport by Surface Chemical Potential Gradients for Enhancing Analyte Collection in Nanoscale Sensors

Nanoscale detectors hold great promise for single molecule detection and the analysis of small volumes of dilute samples. However, the probability of an analyte reaching the nanosensor in a dilute solution is extremely low due to the sensors small size. Here, we examine the use of a chemical potential gradient along a surface to accelerate analyte capture by nanoscale sensors. Utilizing a simple model for transport induced by surface binding energy gradients, we study the effect of the gradient on the efficiency of collecting nanoparticles and single and double stranded DNA. The results indicate that chemical potential gradients along a surface can lead to an acceleration of analyte capture by several orders of magnitude compared to direct collection from the solution. The improvement in collection is limited to a relatively narrow window of gradient slopes, and its extent strongly depends on the size of the gradient patch. Our model allows the optimization of gradient layouts and sheds light on the fundamental characteristics of chemical potential gradient induced transport.