Richard A. Loomis

Origin of High Photoluminescence Efficiencies in CdSe Quantum Belts

CdSe quantum belts (QBs) having lengths of 0.5-1.5 microm and thicknesses of 1.5-2.0 nm exhibit high photoluminescence (PL) efficiencies of approximately 30%. Epifluorescence studies establish the PL spectra to be uniform along single QBs, and nearly the same from QB to QB. Photogenerated excitons are shown to be effectively delocalized over the entire QBs by position-selective excitation. Decoration of the QBs with gold nanoparticles indicates a low density of surface-trap sites, located primarily on the thin belt edges. The high PL efficiencies and effective exciton delocalization are attributed to the minimization of defective {1100} edge surface area or edge-top/bottom (face) line junctions in QBs relative to quantum wires having roughly isotropic cross sections, for which very low PL quantum efficiencies have been reported. The results suggest that trap sites can be minimized in pseudo-one-dimensional nanocrystals, such that the facile transport of energy and charge along their long axes becomes possible.

Isolation of the Magic-Size CdSe Nanoclusters [(CdSe)13(n-octylamine)13] and [(CdSe)13(oleylamine)13]†

The preparation, isolation, stoichiometric characterization, and dissolution of purified (CdSe)13 nanoclusters are described. We[1] and others[2] recently reported that (CdSe)13 nanoclusters were intermediates in the synthesis of CdSe quantum belts (nanoribbons). We now demonstrate that a lamellar intermediate phase[1] collected from the quantum-belt synthesis is [(CdSe)13(n-octylamine)13], the smallest, discrete, magic-size nanocluster of CdSe that has been observed.[3] Kinetic data show that free, soluble [(CdSe)13(oleylamine)13] nanoclusters are released from the insoluble [(CdSe)13(n-octylamine)13] upon ligand exchange.

The Magic-Size Nanocluster (CdSe)34 as a Low-Temperature Nucleant for Cadmium Selenide Nanocrystals; Room-Temperature Growth of Crystalline Quantum Platelets

Reaction of Cd(OAc)2·2H2O and selenourea in primary-amine/secondary-amine cosolvent mixtures affords crystalline CdSe quantum platelets at room temperature. Their crystallinity is established by X-ray diffraction analysis (XRD), high-resolution transmission electron microscopy (TEM), and their sharp extinction and photoluminescence spectra. Reaction monitoring establishes the magic-size nanocluster (CdSe)34 to be a key intermediate in the growth process, which converts to CdSe quantum platelets by first-order kinetics with no induction period. The results are interpreted to indicate that the critical crystal-nucleus size for CdSe under these conditions is in the range of (CdSe)34 to (CdSe)68. The nanocluster is obtained in isolated form as [(CdSe)34(n-octylamine)16(di-n-pentylamine)2], which is proposed to function as crystal nuclei that may be stored in a bottle.

Influence of the Nanoscale Kirkendall Effect on the Morphology of Copper Indium Disulfide Nanoplatelets Synthesized by Ion Exchange

CuInS2 nanocrystals are prepared by ion exchange with template Cu2-xS nanoplatelets and InX3 [X = chloride, iodide, acetate (OAc), or acetylacetonate (acac)]. The morphologies of the resultant nanocrystals depend on the InX3 precursor and the reaction temperature. Exchange with InCl3 at 150 °C produces CuInS2 nanoplatelets having central holes and thickness variations, whereas the exchange at 200 °C produces intact CuInS2 nanoplatelets in which the initial morphology is preserved. Exchange with InI3 at 150 °C produces CuInS2 nanoplatelets in which the central hollowing is more extreme, whereas exchange with In(OAc)3 or In(acac)3 at 150 °C produces intact CuInS2 nanoplatelets. The results establish that the ion exchange occurs through the thin nanoplatelet edge facets. The hollowing and hole formation are due to a nanoscale Kirkendall Effect operating in the reaction-limited regime for displacement of X(-) at the edges, to allow insertion of In(3+) into the template nanoplatelets.

Photofragmentation of ammonia at 193.3 nm: Bimodal rotational distributions and vibrational excitation of NH2(Ã)

Time-resolved Fourier transform infrared emission spectroscopy is used to measure the nascent rovibrational distribution of low-lying electronically excited NH2(A 2A1) produced in the 193.3 nm photolysis of room-temperature and jet-cooled ammonia. Emission is observed predominantly from NH2(A) states with rotational motion about the a-axis and without bending excitation, υ2′=0. A bimodal N′=Ka′ rotational state population distribution is observed with up to Ka′=7 in υ2′=0 and with maxima at Ka′=5 and Ka′=1. We suggest that the bimodal rotational distribution may result from the competition between planar and bent geometries during dissociation. Weaker emission from NH2(A) with bending excitation, υ2′=1 and 2, is detected; the υ2′=1, N′=Ka′ rotational state population distribution spans from Ka′=0 to the energetic limit of Ka′=4. The vibrational energy partitioning for the formation of NH2(A,υ2′=0):NH2(A,υ2′=1) is 3:1 and 2:1 in the room-temperature and jet-cooled conditions, respectively. An upper limit o...

Excitation Energy Dependence of the Photoluminescence Quantum Yields of Core and Core/Shell Quantum Dots.

The photoluminescence (PL) intensity of semiconductor quantum dots (QDs) is routinely monitored to track the chemical and physical properties within a sample or device incorporating the QDs. A dependence of the PL quantum yields (QYs) on the excitation energy could lead to erroneous conclusions but is commonly not considered. We summarize previous evidence and present results from two methodologies that confirm the possibility of a dependence of the PL QYs on the excitation energy. The data presented indicate that PL QYs of CdSe and CdSe/ZnS QDs suspended in toluene are highest for excitation just above the band gap, Eg, of each. The PL QYs decrease with increasing excitation energies up to 1 eV above Eg. The PL intensity decay profiles recorded for these samples at varying emission and excitation energies indicate that the changes in the PL QYs result from the nonradiative relaxation pathways sampled as the charge carriers relax down to the band edge.

Characterization of dynamical product-state distributions by spectral extended cross-correlation: Vibrational dynamics in the photofragmentation of NH2D and ND2H

The spectral cross-correlation method [Jacobson et al., J. Chem. Phys. 107, 8349 (1997)], developed for the identification and extraction of spectroscopic patterns, is extended to the analysis of product-state dynamical data from photofragmentation. Fragment product state vibrational distributions for the photodissociation of ammonia and deuterated ammonia species are extracted. Since chemical isolation of the mixed isotopic parent molecules is prohibited, the photodissociation dynamics of all four parent species (NH3, NH2D, ND2H and ND3) are studied simultaneously at 193.3 nm. The electronic emission spectra from the NH2(A 2A1), ND2(A 2A1), and NHD(A 2A1) fragments are recorded by time-resolved Fourier transform infrared spectroscopy. Spectral signatures for the photodissociation products from each parent species are extracted by the cross-correlation method. The formalism is derived to extend the spectral cross-correlation method to dynamical reactive product state information. The application of the cr...

A laser photolysis/time-resolved Fourier transform infrared emission study of OH(X 2Π,v) produced in the reaction of alkyl radicals with O(3P)

The emission spectra of vibrationally excited hydroxyl radical products formed in the reactions of alkyl radicals with O(3P) atoms are detected using a laser photolysis/time-resolved Fourier transform infrared spectroscopy technique. For the reaction between oxygen atoms and ethyl, the radicals are produced simultaneously by the 193 nm photolysis of the precursors SO2 and diethyl ketone, respectively. The observed initial OH(v) product vibrational state distribution for the C2H5+O(3P) reaction is 0.18±0.03, 0.23±0.04, 0.29±0.05, 0.23±0.07, and 0.07±0.04 for v=1 to 5, respectively. The population inversion is best explained by a direct abstraction mechanism for this radical–radical reaction. Vibrationally excited hydroxyl radicals are also observed in the O+ethyl, O+n-propyl, and O+i-propyl reactions when using alkyl iodides as precursors of the alkyl radicals, although quantitative detail is not obtained due to competing reaction processes.

Bright Core–Shell Semiconductor Quantum Wires

Colloidal CdTe quantum wires are reported having ensemble photoluminescence efficiencies as high as 25% under low excitation-power densities. High photoluminescence efficiencies are achieved by formation of a monolayer CdS shell on the CdTe quantum wires. Like other semiconductor nanowires, the CdTe quantum wires may contain frequent wurtzite-zinc-blende structural alternations along their lengths. The present results demonstrate that the optical properties, emission-peak shape and photoluminescence efficiencies, are independent of the presence or absence of such structural alternations.

Fourier transform infrared emission study of the mechanism and dynamics of HOI formed in the reaction of alkyl iodides with O(3P)

Vibrationally excited hypoiodous acid (HOI) is observed as a product in the reaction of alkyl iodides with O(3P). Fourier transform infrared emission techniques are used to detect the excited ν1, OH, stretch of the HOI product, to determine the mechanism of HOI production, and to measure the vibrational product state distributions. The HOI product is formed by O atom reaction with two-carbon and larger straight or branched chain alkyl iodides and cyclic alkyl iodides, e.g., C2H5I, n-C3H7I, i-C3H7I, (CH3)3CI, n-C6H13I, and c-C6H11I, but not with CH3I. Experiments with selectively deuterated ethyl iodides provide direct evidence that HOI is formed in a beta-elimination mechanism involving a five-membered ring transition state. The O atom attacks the iodine and then abstracts a hydrogen from the beta carbon during the lifetime of the complex. Time-resolved experiments allow the extraction of nascent vibrational state distributions for the ν1 stretch of HOI (v=1:v=2:v=3) using different alkyl iodides and assu...