InAs nanocrystals field‐effect transistors with an ON/OFF ratio of 10⁵ are reported. By tailoring the interface regions in the active layer step‐by‐step, the evolution of the ON/OFF ratio can be followed from approximately 5 all the way to around 10⁵. The formation of a semiconducting solid from colloidal nanocrystals is achieved through targeted design of the nanocrystal–nanocrystal interaction. The manipulation characteristics of the nanocrystal interfaces include the matrix surrounding the inorganic core, the interparticle distance, and the order of nanocrystals in the 3D array. Through careful analysis of device characteristics following each treatment, the effect of each on the physical properties of the films are able to be verified. The enhanced performance is related to interparticle spacing, reduction in sub‐gap states, and better electronic order (lower σ parameter). Films with enhanced charge transport qualities retain their quantum‐confined characteristics throughout the procedure, thus making them useful for optoelectronic applications.

We report wiring of individual colloidal nanorods (NRs), 30−60 nm long by 3.5−5 nm diameter. Strong electrical coupling is achieved by electron beam induced deposition (EBID) of metallic lines targeting NR tips with nanometric precision. At T = 4 K many devices exhibit smooth I(V) curves with no sharp onset features, which remarkably fit a Fowler−Nordheim tunneling model. All devices exhibit an anomalous exponential temperature dependence of the form I ∼ exp(T/T₀). This irregular behavior cannot be explained by any hopping or activation model and is interpreted by accounting for the lowering of the NR conduction band due to lattice dilation and phonon coupling.

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 precursor’s 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.

Organic‐inorganic sol‐gel composite incorporating highly emitting CdSe/ZnS quantum dots and CdSe/CdS/ZnS quantum rods is reported. Optical gain measurements conducted on a quantum rod/sol‐gel composite film show stable room temperature amplified spontaneous emission under ambient conditions.

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.

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.

The ability to tailor the properties of semiconductor nanocrystals through creating core/shell heterostructures is the cornerstone for their diverse application in nanotechnology. The band-offsets between the heterostructure components are determining parameters for their optoelectronic properties, dictating for example the degree of charge-carrier separation and localization. So far, however, no method was reported for direct measurement of these factors in colloidal nanocrystals and only indirect information could be derived from optical measurements. Here we demonstrate that scanning tunneling spectroscopy along with theoretical modeling can be used to determine band-offsets in such nanostructures. Applying this approach to CdSe/CdS quantum-dot/nanorod core/shell nanocrystals portrays its type I band structure where both the hole and electron ground state are localized in the CdSe core, in contrast to previous reports which predicted electron delocalization. The generality of the approach is further demonstrated in ZnSe/CdS nanocrystals where their type II band alignment, leading to electron−hole separation, is manifested.

A hybrid Pt‐CdSe nanoparticle system is prepared in aqueous media, displaying rod or nanonet structures depending on the pH. The new hybrids display morphology‐dependent photocatalytic activity under visible light irradiation. Separation between photo‐generated charge carriers occurs at the metal/semiconductor interface (see figure), allowing redox reactions to take place at the nanoparticle surface.

The use of inorganic charge transport layers has enabled the fabrication of bright, environmentally stable LEDs that are based on electrically pumped colloidal solutions of quantum dots.

A radiationless transition process of long-range, resonance interconversion of electronic-to-vibrational energy transfer (EVET) is discovered between the band-gap excitation of nanocrystal quantum dots to matrix vibrational overtone modes using fluorescence lifetime measurements. A theoretical analysis based on long-range dipole-dipole nonadiabatic couplings, being distinct from the traditional adiabatic or "static-coupling" pictures, is given and is in qualitative agreement with experiments. EVET should be considered in matrix choices for near-infrared optoelectronic applications of nanocrystals.

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.

Apertureless near-field scanning optical microscopy, along with time-resolving capabilities, is used to produce optical imaging and spectroscopy measurements of single-semiconductor nanocrystals, in correlation with the AFM topography scan. The strongly distance-dependent energy transfer between the excited particle and silicon or metallic-coated AFM tips provides a contrast mechanism for subdiffraction-limited optical imaging. Fluorescence lifetime optical images show excellent contrast, sharpness, sensitivity, and resolution equivalent to that of the AFM topography images (sub 20 nm) and significantly improved over fluorescence intensity images. The sharper resolution of lifetime images is consistent with model predictions of energy transfer between an emitting dipole and a dielectric surface. Lifetime images also enable resolving multiple emitters located in the excitation spot. The comprehensive time and distance dependent data is used to study the imaging mechanism and the properties of silicon tips and platinum-coated tips as energy acceptors and quenchers. The findings provide a basis for use of lifetime imaging, in conjunction with apertureless near field microscopy, for simultaneous high-resolution topography and optical imaging.

A coarse-grained lattice gas model is developed to study the drying-mediated self-assembly of nanoparticles on diblock copolymer substrates. The model describes the nanoparticles, the solvent and the diblock copolymer on length scales that are typical to the solvent bulk correlation length. Monte Carlo simulation techniques are used to delineate the various mechanisms of this out-of-equilibrium hierarchical self-assembly. Several different assembly scenarios corresponding to different selectivity of the nanoparticles/liquid/substrate are discussed. The role of surface tension, evaporation rate, diffusion rate, nanoparticle coverage, and diblock copolymer periodicity is explored. Optimal conditions to form a stripe phase of nanoparticles along with predictions of novel 3D structures resulting from high nanoparticle and solvent selectivity are described.

We studied the electronic level structure of assemblies of InAs quantum dots and CdSe nanorods cross-linked by 1,4-phenylenediamine molecules using scanning tunneling spectroscopy. We found that the bandgap in these arrays is reduced with respect to the corresponding ligand-capped nanocrystal arrays. In addition, a pronounced sub-gap spectral structure commonly appeared which can be attributed to unpassivated nanocrystal surface states or associated with linker-molecule-related levels. The exchange of the ligands by the linker molecules also affected the structural array properties. Most significantly, clusters of close-packed standing CdSe nanorods were formed.

A study was to demonstrate a seeded growth approach that provides shape-controlled bimetallic nanocrystals, generating new ways for selecting new nanoscale building blocks. It was demonstrated that semiconductor and oxide nanowires were grown, using metal seeding approach that acted as catalysts. Gold rod growth in solution was also carried out by seeding with small gold particles, while semiconductor rods were grown using semiconductor nanoparticles as seeds. The new approach also used faceted metal nanocrystals as nucleation centers for the overgrowth of a secondary metal. It was also observed that the ability of the new approach to synthesize binary-metal nanoparticles has significant implications for diverse applications in memory devices, electrical contacts, biological applications, and catalysis.

We studied the optical gain characteristics of CdSe/ZnS core/shell colloidal quantum rods, investigated their temperature dependence, and compared the gain properties with quantum dots (QD). The gain was measured systematically for close-packed films of rods and dots under quasi-CW nanosecond optical pumping, using the variable stripe length method measuring the amplified spontaneous emission (ASE). Tunable ASE can be achieved by changing the rod diameter. Optical gain factors of up to 350 cm^-1 at a temperature range of 10−120 K were measured for quantum rods. Above 120 K, the gain decreased sharply, but by increasing the pump power, ASE was easily achieved also at room temperature. The temperature dependence was assigned to the Auger heating process and phonon assisted thermal relaxation. QD of similar diameters as the rods showed much smaller gain values (∼50 cm^-1) and a sharp decrease in gain at lowered temperatures (∼50 K), and ASE could not be detected at room temperature even at high pump powers. The significantly improved gain values in quantum rods as compared with dots were attributed to the slower Auger relaxation rates, the higher absorption cross-section, and the reduced self-absorption due to the larger Stokes shift. The temperature dependence of the threshold power for the quantum rods, used to characterize the thermal insensitivity of the system, showed two distinct temperature regions. In the low-temperature region, a very high T₀ value of 3500 K was measured, as predicted for a low-dimensional quantum confined system.

The spectroscopy and dynamics of multiple excitations on colloidal type-II CdTe∕CdSe core-shell quantum dots (QDs) are explored via quasi-cw multiexciton spectroscopy. The charge separation induced by the band offset redshifts the exciton emission and increases the radiative lifetime. In addition, we observe a significant modification of multiexciton properties compared with core-only or type-I QDs. In particular, the Auger recombination lifetimes are significantly increased, up to a nanosecond time scale. While in type-I QDs the Auger lifetime scales with the volume, we find for type-II QDs a scaling law that introduces a linear dependence also on the radiative lifetime. We observe a blueshift of the biexciton emission and extract biexciton repulsion of up to 30meV in type-II QDs. This is assigned to the dominance of the Coulomb repulsion as the positive and negative charges become spatially separated, which overwhelms the correlation binding term. Higher electronic excited states can remain type I even when the lowest transition is already type II, resulting in a different size dependence of the triexciton emission. Finally, we discuss the possibilities of “multiexciton band gap engineering” using colloidal type-II QDs.

The invention comprises a composite material comprising a host material in which are incorporated semiconductor nanocrystals. The host material is light-transmissive and/or light-emissive and is electrical charge-transporting thus permitting electrical charge transport to the core of the nanocrystals. The semiconductor nanocrystals emit and/or absorb light in the near infrared spectral range. The nanocrystals cause the composite material to emit/absorb energy in the near infrared (NIR) spectral range, and/or to have a modified dielectric constant, compared to the host material. The invention further comprises electro-optical devices composed of this composite material and a method of producing them. Specifically described are light emitting diodes that emit light in the NIR and photodetectors that absorb light in the same region.

A blue solid-state laser material based on 4,4′4′ dibenzyl carbamido stilbene-2,2′2′ disulfonic acid incorporated into solgel zirconia and inorganic–organic hybrid matrices is presented. The absorption maxima of the dye in various matrices are around 339–361 nm, and the broad fluorescence peaks are at 411–413 nm. Optical gain measurements using the variable stripe method show amplified spontaneous emission peaking at 437 nm.