Comparison of single-layer and bilayer InAs/GaAs quantum dots with a higher InAs coverage

Epitaxially grown self-assembled InAs quantum dots (QDs) have found applications in optoelectronics. Efforts are being made to obtain efficient quantum-dot lasers operating at longer telecommunication wavelengths, specifically 1.3 μm and 1.55 μm. This requires narrow emission linewidth from the quantum dots at these wavelengths. In InAs/GaAs single layer quantum dot (SQD) structure, higher InAs monolayer coverage for the QDs gives rise to larger dots emitting at longer wavelengths but results in inhomogeneous dot-size distribution. The bilayer quantum dot (BQD) can be used as an alternative to SQDs, which can emit at longer wavelengths (1.229 μm at 8 K) with significantly narrow linewidth (∼16.7 meV). Here, we compare the properties of single layer and bilayer quantum dots grown with higher InAs monolayer coverage. In the BQD structure, only the top QD layer is covered with increased (3.2 ML) InAs monolayer coverage. The emission line width of our BQD sample is found to be insensitive towards post growth treatments.     

A novel approach to increase emission wavelength of InAs/GaAs quantum dots by using a quaternary capping layer

In this paper, we present a new approach to obtain large size dots in an MBE grown InAs/GaAs multilayer quantum dot system. This is achieved by adding an InAlGaAs quaternary capping layer in addition to a high growth temperature (590°C) GaAs capping layer with the view to tune the emission wavelength of these QDs towards the 1.3 μm/0.95 eV region important for communication devices. Strain driven migration of In atoms from InAlGaAs alloy to the InAs QDs effectively increases the size of QDs. Microscopic investigations were carried out to study the dot size and morphology in the different layers of the grown samples. Methods to reduce structural defects like threading dislocations in multilayer quantum dot samples are also studied.     

A comprehensive study of the effect of <Emphasis Type="Italic">in situ</Emphasis> annealing at high growth temperature on the morphological and optical properties of self-assembled InAs/GaAs QDs

We investigate the effect of in situ annealing during growth pause on the morphological and optical properties of self-assembled InAs/GaAs quantum dots (QDs). The islands were grown at different growth rates and having different monolayer coverage. The results were explained on the basis of atomic force microscopy (AFM) and photo-luminescence (PL) measurements. The studies show the occurrence of ripening-like phenomenon, observed in strained semiconductor system. Agglomeration of the self-assembled QDs takes place during dot pause leading to an equilibrium size distribution. The PL properties of the QDs are affected by the Indium desorption from the surface of the QDs during dot pause annealing at high growth temperature (520°C) subsiding the effect of the narrowing of the dot size distribution with growth pause. The samples having high monolayer coverage (3.4 ML) and grown at a slower growth rate (0.032 ML s⁻¹) manifested two different QD families. Among the islands the smaller are coherent defect-free in nature, whereas the larger dots are plastically relaxed and hence optically inactive. Indium desorption from the island surface during the in situ annealing and inhomogeneous morphology as the dots agglomerate during the growth pause, also affects the PL emission from these dot assemblies.     

Photoinduced electron transfer across a molecular wall: coumarin dyes as donors and methyl viologen and TiO2 as acceptors

Coumarins C-153, C-480, and C-1 formed 1:2 (guest:host) complexes with a water-soluble cavitand having eight carboxylic acid groups (OA) in aqueous borate buffer solution. The complexes were photoexcited in the presence of electron acceptors (methyl viologen, MV(2+), or TiO(2)) to probe the possibility of electron transfer between a donor and an acceptor physically separated by a molecular wall. In solution at basic pH, the dication MV(2+) was associated to the exterior of the complex C-153@OA(2), as suggested by diffusion constants (~1.2 × 10(-6) cm(2)/s) determined by DOSY NMR. The fluorescence of C-153@OA(2) was quenched in the presence of increasing amounts of MV(2+) and Stern-Volmer plots of I(o)/I and τ(o)/τ vs [MV(2+)] indicated that the quenching was static. As per FT-IR-ATR spectra, the capsule C-153@OA(2) was bound to TiO(2) nanoparticle films. Selective excitation (λ(exc) = 420) of the above bound complex resulted in fluorescence quenching. When adsorbed on insulating ZrO(2) nanoparticle films, excitation of the complex resulted in a broad fluorescence spectrum centered at 500 nm and consistent with C-153 being within the lipophilic capsule interior. Consistent with the above results, colloidal TiO(2) quenched the emission while colloidal ZrO(2) did not.     

Dehydration of the nanoporous coordination framework ErIII[CoIII(CN)6].4(H2O): single crystal to single crystal transformation and negative thermal expansion in ErIII[CoIII(CN)6

Desorption of bound and unbound water molecules from the nanoporous coordination framework ErIII[CoIII(CN)6].4(H2O) to form the apohost, ErIII[CoIII(CN)6], proceeds via a single crystal to single crystal transformation in which the Er(III) cations change from 8- to 6-coordinate; dehydration results in a striking change in the thermal expansion properties.     

Gold nanostructures from cube-shaped crystalline intermediates

Conventional bottom-up approaches for building nanostructures rely on the ability to synthesize nanoparticles of different shapes and sizes in a controlled manner that are then assembled to produce useful structures. Here, we present an alternate approach for producing nanostructures based on the formation of a crystalline intermediate in which the metal ion can be reduced in a controlled manner. Partial reduction of HAuCl4 by a long-chain amine results in the formation of a cube-shaped crystalline intermediate in which Au is present in a +1 oxidation state. By control of the nucleation of the metal in the intermediate, a variety of nanostructures can be synthesized. Here, we present results on the formation of superlattices, hollow cubes, nanotubes, and extended hollow structures starting from the intermediate. Direct evidence for the formation of metal within the intermediate by in situ electron-beam-induced reduction in the transmission electron microscope is presented.     

Eye‐Catching Dual‐Fluorescent Dynamic Metal–Organic Framework Senses Traces of Water: Experimental Findings and Theoretical Correlation

A guest‐dependent dynamic fivefold interpenetrated 3D porous metal–organic framework (MOF) of Zn^II ions has been synthesized that exhibits selective carbon dioxide adsorption. Furthermore, the MOF shows excellent luminescence behavior, which is supported by a systematic study on the guest‐responsive multicolor emission of a suspension of the MOF. The dual‐emission behavior arises from the excited‐state intramolecular proton transfer (ESIPT), and the compound also shows remarkable potential to detect traces of water in various organic solvents. The experimental observations were also painstakingly authenticated by using time‐dependent density‐functional‐theory (DFT) calculations.     

1‐Alkyl‐2‐{(O‐Thioalkyl)Phenylazo}Imidazole Complexes of PbII and Their Photochromic Property

Pb^II complexes of 1‐alkyl‐2‐{(o‐thioalkyl)phenylazo}imidazole (SRaaiNR'), [Pb(SRaaiNR')₂X₂] were characterized by spectroscopic studies. The single‐crystal X‐ray structure of [Pb(SEtaaiNEt)₂Cl₂] (SEtaaiNEt = 1‐ethyl‐2‐{(o‐thioalkyl)phenylazo}imidazole) proved imidazolyl‐N and –SEt coordination forming unusual puckered eight member chelate rings. UV light irradiation of the complexes in DMF solution shows E‐to‐Z (E and Z refer to trans and cis‐configuration about –N=N–, respectively) photoisomerization of the coordinated azoimidazole. The rate of isomerization follows the sequence: [Pb(SRaaiNR')₂Cl₂] < [Pb(SRaaiNR')₂Br₂] < [Pb(SRaaiNR')₂I₂]. Quantum yields (φ_E→Z) and the activation energy (E_a) of the isomerization of the complexes are lower than observed for the free ligand. This can be explained by considering the molecular assembly and the thus observed increase in mass and rotor volume of the complexes. DFT and TDDFT calculations of optimized geometry could explained the spectral properties and photochromic activity.     

DAIB/TEMPO mediated synthesis of anomeric lactones from anomeric hydroxides

Anomeric sugar lactones are important intermediates for the synthesis of C-glycosides, carbasugars and iminosugars. Herein we present a facile synthesis of anomeric sugar lactones via the DAIB/TEMPO oxidation of anomeric hydroxides. The reactions are very efficient providing the lactones in 2–4 h in almost quantitative yields. The reaction conditions tolerate several common protecting groups used in carbohydrate synthesis. The advantages of the present methodology over previously reported non-metal based methods have also been demonstrated through head to head comparisons. Finally, we have applied the reaction for the sequential conversion of anomeric thioglycosides to the lactones through sequential reactions with NBS followed by the oxidation with DAIB/TEMPO.     

Investigation of gas transport and other physical properties in relation to the bromination degree of polymers of intrinsic microporosity

In this work, the synthesis of novel polymers of intrinsic microporosity (PIMs) with different degrees of bromine substitution by a free-radical substitution reaction was performed. The synthesized polymers were thoroughly characterized and their bromination degree was verified via nuclear magnetic resonance. The brominated PIMs were investigated by infrared spectroscopy, X-ray diffraction, and density measurements and correlated with their gas transport properties. It was found that with an increase in the bromination degree, the synthesized PIMs exhibited a significant increase in polymer chain packing density which led to reduced fractional free volume and consequent decrease in gas diffusion and permeability coefficients. The change in permeability coefficients caused an improvement in the CO₂/N₂, CO₂/CH₄, and O₂/N₂ ideal permeability selectivities. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2752–2761