Uri Banin

Colloidal Hybrid Nanostructures: A New Type of Functional Materials

One key goal of nanocrystal research is the development of experimental methods to selectively control the composition and shape of nanocrystals over a wide range of material combinations. The ability to selectively arrange nanosized domains of metallic, semiconducting, and magnetic materials into a single hybrid nanoparticle offers an intriguing route to engineer nanomaterials with multiple functionalities or the enhanced properties of one domain. In this Review, we focus on recent strategies used to create semiconductor-metal hybrid nanoparticles, present the emergent properties of these multicomponent materials, and discuss their potential applicability in different technologies.

Heavily Doped Semiconductor Nanocrystal Quantum Dots

Impurities can be added into semiconductor nanoparticles to control their electronic and optical properties. Doping of semiconductors by impurity atoms enabled their widespread technological application in microelectronics and optoelectronics. However, doping has proven elusive for strongly confined colloidal semiconductor nanocrystals because of the synthetic challenge of how to introduce single impurities, as well as a lack of fundamental understanding of this heavily doped limit under strong quantum confinement. We developed a method to dope semiconductor nanocrystals with metal impurities, enabling control of the band gap and Fermi energy. A combination of optical measurements, scanning tunneling spectroscopy, and theory revealed the emergence of a confined impurity band and band-tailing. Our method yields n- and p-doped semiconductor nanocrystals, which have potential applications in solar cells, thin-film transistors, and optoelectronic devices.

Visible Light-Induced Charge Retention and Photocatalysis with Hybrid CdSe−Au Nanodumbbells

Visible light photocatalysis is a promising route for harnessing of solar energy to perform useful chemical reactions and to convert light to chemical energy. Nanoscale photocatalytic systems used to date were based mostly on oxide semiconductors aided by metal deposition and were operational only under UV illumination. Additionally, the degree of control over particle size and shape was limited. We report visible light photocatalysis using highly controlled hybrid gold-tipped CdSe nanorods (nanodumbbells). Under visible light irradiation, charge separation takes place between the semiconductor and metal parts of the hybrid particles. The charge-separated state was then utilized for direct photoreduction of a model acceptor molecule, methylene blue, or alternatively, retained for later use to perform the reduction reaction in the dark.

Colloidal chemical synthesis and characterization of InAs nanocrystal quantum dots

InAs nanocrystal quantum dots have been prepared via colloidal chemical synthesis using the reaction of InCl3 and As[Si(CH3)3]3. Sizes ranging from 25 to 60 A in diameter are produced and isolated with size distributions of ±10%–15% in diameter. The nanocrystals are crystalline and generally spherical with surfaces passivated by trioctylphosphine giving them solubility in common organic solvents. The dots have been structurally characterized by transmission electron microscopy (TEM) and powder x‐ray diffraction (XRD) and the optical absorption and emission have been examined. Quantum confinement effects are evident with absorption onsets well to the blue of the bulk band gap and size dependent absorption and emission features. The emission is dominated by band edge luminescence. These quantum dots are particularly interesting as they provide an opportunity to make important comparisons with comparably sized InAs quantum dots synthesized by molecular beam epitaxy techniques.

Particle Size, Surface Coating, and PEGylation Influence the Biodistribution of Quantum Dots in Living Mice

This study evaluates the influence of particle size, PEGylation, and surface coating on the quantitative biodistribution of near-infrared-emitting quantum dots (QDs) in mice. Polymer- or peptide-coated 64Cu-labeled QDs 2 or 12 nm in diameter, with or without polyethylene glycol (PEG) of molecular weight 2000, are studied by serial micropositron emission tomography imaging and region-of-interest analysis, as well as transmission electron microscopy and inductively coupled plasma mass spectrometry. PEGylation and peptide coating slow QD uptake into the organs of the reticuloendothelial system (RES), liver and spleen, by a factor of 6-9 and 2-3, respectively. Small particles are in part renally excreted. Peptide-coated particles are cleared from liver faster than physical decay alone would suggest. Renal excretion of small QDs and slowing of RES clearance by PEGylation or peptide surface coating are encouraging steps toward the use of modified QDs for imaging living subjects.

Lasing from Semiconductor Quantum Rods in a Cylindrical Microcavity

For transient ellipsometry, the sample is placed between crossed polarizers at an angle of 54 between the sample normal and the laser beam. A laser diode at a wavelength k = 905 nm is employed and the residual birefringence of the sam- ple is compensated by a crystal compensator. The transmission through the el- lipsometry setup is measured in response to a step function of the electric field applied to the sample with a rise time of ~100 ls. The two-wave mixing is measured in a standard geometry (29) with the two beams having external angles of 30 and 60 to the sample normal and beam ra- tio 1:1. The laser source is a Kr ion laser at a wavelength of 647 nm. The time transients are measured by opening a shutter for both beams with a switching time of about 150 ls. After the measurements, the gratings are erased by a larg- er, non-Bragg matched erasing beam. In the beam fanning experiments, the same setup as in the two-wave mixing is used except only one beam is present. The angle of the beam to the sample normal is 60 and the applied electric field is inverted compared to two-wave mixing to enhance the fanning. Additionally, an aperture is placed in the beam path 50 cm behind the sample, which clips only 5 % of the unperturbed beam.

Quantum Dot Sensitized Solar Cells with Improved Efficiency Prepared Using Electrophoretic Deposition

Quantum dot sensitized solar cells (QDSSC) may benefit from the ability to tune the quantum dot optical properties and band gap through the manipulation of their size and composition. Moreover, the inorganic nanocrystals may provide increased stability compared to organic sensitizers. We report the facile fabrication of QDSSC by electrophoretic deposition of CdSe QDs onto conducting electrodes coated with mesoporous TiO(2). Unlike prior chemical linker-based methods, no pretreatment of the TiO(2) was needed, and deposition times as short as 2 h were sufficient for effective coating. Cross-sectional chemical analysis shows that the Cd content is nearly constant across the entire TiO(2) layer. The dependence of the deposition on size was studied and successfully applied to CdSe dots with diameters between 2.5 and 5.5 nm as well as larger CdSe quantum rods. The photovoltaic characteristics of the devices are greatly improved compared with those achieved for cells prepared with a linker approach, reaching efficiencies as high as 1.7%, under 1 sun illumination conditions, after treating the coated electrodes with ZnS. Notably, the absorbed photon to electron conversion efficiencies did not show a clear size-dependence indicating efficient electron injection even for the larger QD sizes. The electrophoretic deposition method can be easily expanded and applied for preparations of QDSSCs using diverse colloidal quantum dot and quantum rod materials for sensitization.

EVIDENCE FOR A THERMAL CONTRIBUTION TO EMISSION INTERMITTENCY IN SINGLE CDSE/CDS CORE/SHELL NANOCRYSTALS

The on–off intermittent behavior of emission from single CdSe/CdS core/shell nanocrystals was investigated as a function of temperature and excitation intensity. Off times were found to be independent of excitation power and the temperature dependence reveals substantial reduction in the number of on–off cycles prior to final particle darkening at low temperatures. On times are found to vary linearly with excitation intensity over a broad range and the turn off rate shows activated Arrhenius behavior down to T=50 K. These observations are consistent with a darkening mechanism that is a combination of Auger photoionization and thermal trapping of charge. The inhomogeneity of various possible trap sites is discussed. A thermally activated neutralization process is required for the particle to return to the on state. The influence of shell composition on intermittency is compared for CdS and ZnS [M. Nirmal et al., Nature 383, 802 (1996)].

Au Growth on Semiconductor Nanorods: Photoinduced versus Thermal Growth Mechanisms

Gold growth on CdS nanorods and on seeded CdSe/CdS nanorods with and without illumination at different temperatures was studied. Two competing mechanisms were identified: thermal and light-induced growth. The thermal mechanism leads to growth of small gold particles at defects along the rod body and can be suppressed at lower temperatures. This control is attributed to a phase transition of the alkyl chains of the surface amine ligands to a static phase at lower temperatures, blocking the Au precursors access to the nanorod surfaces. While a long-chain (C18) amine shows effective blocking at 293 K, a shorter chain (C12) amine shows the same result only at 273 K; however, in the case of a bulky trialkylamine, defect growth was observed even at 273 K. Light-induced growth leads to selective deposition of gold on one end of the rods. The tip was shown to grow on sulfur-rich facets of the nanorod, producing end-on and angled tip orientations. Growth under illumination with decreased temperature provides a highly selective synthesis of hybrid semiconductor nanorods with a single gold tip. Such anisotropic semiconductor-metal hybrids are of interest for self-assembly and photocatalysis and as building blocks in optoelectronic devices.

IMPULSIVE EXCITATION OF COHERENT VIBRATIONAL MOTION GROUND SURFACE DYNAMICS INDUCED BY INTENSE SHORT PULSES

A framework for understanding impulsively photoinduced vibrational coherent motion on the ground electronic surface is presented. In particular strong resonant excitation to a directly dissociative electronic surface is considered. Three distinct approaches are employed. A two surface Fourier wavepacket method explicitly including the field explores this process in isolated molecules. A coordinate dependent two‐level system is employed to develop a novel analytical approximation to the photoinduced quantum dynamics. The negligible computational requirements make it a powerful interactive tool for reconstructing the impulsive photoexcitation stage. Its analytical nature provides closed form expressions for the photoinduced changes in the material. Finally the full simulation of the process including the solvent effects is carried out by a numerical propagation of the density operator. In all three techniques the excitation field is treated to all orders, allowing an analysis of current experiments using st...