Germanium quantum dots: Optical properties and synthesis

Three different size distributions of Ge quantum dots (>~200, 110, and 60 Å) have been synthesized via the ultrasonic mediated reduction of mixtures of chlorogermanes and organochlorogermanes (or organochlorosilanes) by a colloidal sodium/potassium alloy in heptane, followed by annealing in a sealed pressure vessel at 270 °C. The quantum dots are characterized by transmission electron microscopy, x-ray powder diffraction, x-ray photoemission, infrared spectroscopy, and Raman spectroscopy. Colloidal suspensions of these quantum dots were prepared and their extinction spectra are measured with ultraviolet/visible (UV/Vis) and near infrared (IR) spectroscopy, in the regime from 0.6 to 5 eV. The optical spectra are correlated with a Mie theory extinction calculation utilizing bulk optical constants. This leads to an assignment of three optical features to the E(1), E(0'), and E(2) direct band gap transitions. The E(0') transitions exhibit a strong size dependence. The near IR spectra of the largest dots is dominated by E(0) direct gap absorptions. For the smallest dots the near IR spectrum is dominated by the Gamma25-->L indirect transitions

Resilient Pathways to Atomic Attachment of Quantum Dot Dimers and Artificial Solids from Faceted CdSe Quantum Dot Building Blocks.

The goal of this work is to identify favored pathways for preparation of defect-resilient attached wurtzite CdX (X = S, Se, Te) nanocrystals. We seek guidelines for oriented attachment of faceted nanocrystals that are most likely to yield pairs of nanocrystals with either few or no electronic defects or electronic defects that are in and of themselves desirable and stable. Using a combination of in situ high-resolution transmission electron microscopy (HRTEM) and electronic structure calculations, we evaluate the relative merits of atomic attachment of wurtzite CdSe nanocrystals on the {11̅00} or {112̅0} family of facets. Pairwise attachment on either facet can lead to perfect interfaces, provided the nanocrystal facets are perfectly flat and the angles between the nanocrystals can adjust during the assembly. Considering defective attachment, we observe for {11̅00} facet attachment that only one type of edge dislocation forms, creating deep hole traps. For {112̅0} facet attachment, we observe that four distinct types of extended defects form, some of which lead to deep hole traps whereas others only to shallow hole traps. HRTEM movies of the dislocation dynamics show that dislocations at {11̅00} interfaces can be removed, albeit slowly. Whereas only some extended defects at {112̅0} interfaces could be removed, others were trapped at the interface. Based on these insights, we identify the most resilient pathways to atomic attachment of pairs of wurtzite CdX nanocrystals and consider how these insights can translate to the creation of electronically useful materials from quantum dots with other crystal structures

Photoluminescence of tetrahedral quantum-dot quantum wells

Taking into account the tetrahedral shape of a quantum dot quantum well (QDQW) when describing excitonic states, phonon modes and the exciton-phonon interaction in the structure, we obtain within a non-adiabatic approach a quantitative interpretation of the photoluminescence spectrum of a single CdS/HgS/CdS QDQW. We find that the exciton ground state in a tetrahedral QDQW is bright, in contrast to the dark ground state for a spherical QDQW. The position of the phonon peaks in the photoluminescence spectrum is attributed to interface optical phonons. We also show that the experimental value of the Huang-Rhys parameter can be obtained only within the nonadiabatic theory of phonon-assisted transitions.Comment: 4 pages, 4 figures, E-mail addresses: [email protected], [email protected], [email protected], [email protected], to be published in Phys. Rev. Letter

Detection of topological transitions by transport through molecules and nanodevices

We analyze the phase transitions of an interacting electronic system weakly coupled to free-electron leads by considering its zero-bias conductance. This is expressed in terms of two effective impurity models for the cases with and without spin degeneracy. We demonstrate using the half-filled ionic Hubbard ring that the weight of the first conductance peak as a function of external flux or of the difference in gate voltages between even and odd sites allows one to identify the topological charge transition between a correlated insulator and a band insulator.Comment: 4 pages, 5 figures, to appear in Phys. Rev. Let

Lead halide perovskite nanowires stabilized by block copolymers for Langmuir-Blodgett assembly

The rapid development of solar cells based on lead halide perovskites (LHPs) has prompted very active research activities in other closely-related fields. Colloidal nanostructures of such materials display superior optoelectronic properties. Especially, one-dimensional (1D) LHPs nanowires show anisotropic optical properties when they are highly oriented. However, the ionic nature makes them very sensitive to external environment, limiting their large scale practical applications. Here, we introduce an amphiphilic block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-P4VP), to chemically modify the surface of colloidal CsPbBr3 nanowires. The resulting core-shell nanowires show enhanced photoluminescent emission and good colloidal stability against water. Taking advantage of the stability enhancement, we further applied a modified Langmuir-Blodgett technique to assemble monolayers of highly aligned nanowires, and studied their anisotropic optical properties. [Figure not available: see fulltext.]

Chemical patterning for the highly specific and programmed assembly of nanostructures

We have developed a new chemical patterning technique based on standard lithography-based processes to assemble nanostructures on surfaces with extraordinarily high selectivity. This patterning process is used to create patterns of aminosilane molecular layers surrounded by highly inert poly (ethylene glycol) (PEG) molecules. While the aminosilane regions facilitate nanostructure assembly, the PEG coating prevents adsorption of molecules and nanostructures, thereby priming the semiconductor substrate for the highly localized and programmed assembly of nanostructures. We demonstrate the power and versatility of this manufacturing process by building multilayered structures of gold nanoparticles attached to molecules of DNA onto the aminosilane patterns, with zero nanocrystal adsorption onto the surrounding PEG regions. The highly specific surface chemistry developed here can be used in conjunction with standard microfabrication and emerging nanofabrication technology to seamlessly integrate various nanostructures with semiconductor electronics

Photothermal heterodyne imaging of individual nonfluorescent nanoclusters and nanocrystals

We introduce a new, highly sensitive, and simple heterodyne optical method for imaging individual nonfluorescent nanoclusters and nanocrystals. A 2 order of magnitude improvement of the signal is achieved compared to previous methods. This allows for the unprecedented detection of individual small absorptive objects such as metallic clusters (of 67 atoms) or nonluminescent semiconductor nanocrystals. The measured signals are in agreement with a calculation based on the scattering field theory from a photothermal-induced modulated index of refraction profile around the nanoparticle

Faraday Rotation Spectroscopy of Quantum-Dot Quantum Wells

Time-resolved Faraday rotation studies of CdS/CdSe/CdS quantum-dot quantum wells have recently shown that the Faraday rotation angle exhibits several well-defined resonances as a function of probe energy close to the absorption edge. Here, we calculate the Faraday rotation angle from the eigenstates of the quantum-dot quantum well obtained with k.p theory. We show that the large number of narrow resonances with comparable spectral weight observed in experiment is not reproduced by the level scheme of a quantum-dot quantum well with perfect spherical symmetry. A simple model for broken spherical symmetry yields results in better qualitative agreement with experiment.Comment: 9 pages, 4 figure

Real time imaging of two-dimensional iron oxide spherulite nanostructure formation

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. A growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth. [Figure not available: see fulltext.]