Three-dimensional confinement in the conduction band structure of InP

Includes bibliographical references.Strong quantum confinement in InP is observed to significantly reduce the separation between the direct and indirect conduction band states. The effects of three-dimensional confinement are investigated by tailoring the initial separation between conduction band states using quantum dots (QDs) of different sizes and hydrostatic pressure. Analyses of the QD emission spectra show that the X1c states are lowest in energy at pressures of ~6 GPa, much lower than in the bulk. The transition to the X1c states can be explained by either a sequence of Γ-L and L-X crossings, or by the crossover between strongly coupled Γ and X states.The work at CSU was supported by the National Science Foundation, and that at NREL by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences Division

Sub-picosecond injection of electrons from excited [Ru(2,2′-bipy-4,4′-dicarboxy)₂(SCN)₂] into TiO₂ using transient mid-infrared spectroscopy

We have used femtosecond pump-probe spectroscopy to time resolve the injection of electrons into nanocrystalline TiO2 film electodes under ambient conditions following photoexcitation of the adsorbed dye, [Ru(4,4’-dicarboxy-2,2’-bipyridine)2(NCS)2] (N3). Pumping at one of the metal-to-ligand charge transfer adsorption peaks and probing the absorption of electrons injected into the TiO2 conduction band at 1.52 µm and in the range of 4.1 to 7.0 µm, we have directly observed the arrival of the injected electrons. Our measurements indicate an instrument-limited ~50-fs upper limit on the electron injection time under ambient conditions in air. We have compared the infrared transient absorption for noninjecting (blank) systems consisting of N3 in ethanol and N3 adsorbed to films of nanocrystalline Al2O3 and ZrO2, and found no indication of electron injection at probe wavelengths in the mid-IR (4.1 to 7.0 µm). At 1.52 µm interferences exist in the observed transient adsorption signal for the blanks

Self-Assembly of Linear Arrays of Semiconductor Nanoparticles on Carbon Single-Walled Nanotubes †

Ligand-stabilized nanocrystals (NCs) were strongly bound to the nanotube surfaces by simple van der Waals forces. Linear arrays of CdSe and InP quantum dots were formed by self-assembly using the grooves in bundles of carbon single-walled nanotubes (SWNTs) as a one-dimensional template. A simple geometrical model explains the ordering in terms of the anisotropic properties of the nanotube surface. CdSe quantum rods were also observed to self-organize onto SWNTs with their long axis parallel to the nanotube axis. This approach offers a route to the formation of ordered NC/SWNT architectures that avoids problems associated with surface derivatization. Both semiconductor quantum dots (QDs) 1 and carbon singlewalled nanotubes (SWNTs) 2 possess interesting and potentially useful optical and electronic properties due to their nanoscale structures. In the case of QDs, quantum confinement in three dimensions produces a size-dependent modification of the electronic band structure, resulting in the formation of discrete electronic states. QDs exhibit unique behaviors such as efficient photoluminescence and photon up-conversion, slowed relaxation and cooling of hot carriers, enhanced lasing, and carrier multiplication via impact ionization. 3 SWNTs, however, consist of sp 2 -hybridized carbon atoms that form the walls of nanometer-wide, seamless cylinders. Past efforts to attach semiconductor nanocrystals (NCs) to nanotubes have focused on forming chemical attachments between the two different nanostructures. In this approach, defects in the nanotube lattice, i.e., any site where the sp 2 -bonded carbon network is broken, are used as sites for chemical bond formation. Such defects are typically present after acid-based purification methods or may be specifically introduced by chemical derivatization. In this paper, we report the formation of organized, onedimensional (1-D) arrays of semiconductor QDs by van der Waals (vdW) adsorption onto SWNTs. Two representative II-VI and the III-V semiconductor NCs, CdSe and InP, respectively, demonstrated linear ordering when adsorbed from nonaqueous colloidal solutions onto high-purity, low-defectdensity SWNTs. The tendency to form linear arrays was greatest when tube-tube alignment was relatively good within bundles and when the QDs were relatively large. The edge-to-edge (ee) separation distance between QDs in the 1-D arrays was ∼18 Å for both the InP and the CdSe QDs, indicating that QD-QD separation is governed by the thickness of the ligand shells, as is the case in two-and three-dimensional QD arrays