Pyridylenevinylene based Cu2+-specific, injectable metallo(hydro) gel: thixotropy and nanoscale metal-organic particles

A Cu2+-selective metallo(hydro) gelation of a p-pyridyl ended oligophenylenevinylene system is reported over its respective meta- and ortho-regioisomers. The metallogel formed via the self-assembly of the nanoscale-metal-organic particles is injectable and also shows multi-stimuli responsiveness, including thixotropy.

Multicomponent Assembly of Fluorescent-Tag Functionalized Ligands in Metal-Organic Frameworks for Sensing Explosives

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by singlecrystal XRD. Single-crystal structures of the MOFs-12 and 13 showed the formation of three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron-rich MOFs were utilized for detection of ex- plosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6-trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6-trinitrotoluene (TNT).

Optical detection of submicromolar levels of nitro explosives by a submicron sized metal-organic phosphor material

Two isomorphous submicron sized metal-organic network compounds, Y-2(PDA)(3)(H2O)1]center dot 2H(2)O (PDA = 1,4-phenylenediacetate), 1 and Y1.8Tb0.2(PDA)(3)(H2O)1]center dot 2H(2)O, Tb@1 have been synthesized by employing solvent assisted liquid grinding followed by heating at 180 degrees C for 1' min and washing with water. Single crystal X-ray data of bulk 1 confirmed a three dimensional porous structure. The structure and morphology of 1 and Tb@1 were systematically characterized by PXRD, TGA, DSC, IR, SEM and EDX analysis. Dehydrated Tb@1 Tb@1'] shows a high intense visible green emission upon exposure to UV light. The green emission of Tb@1' was used for the detection of nitro explosives, such as 2,4,6-trinitrophenol (TNP), 1,3-dinitro benzene (DNB), 2,4-dinitro toluene (DNT), nitro benzene (NB), and 4-nitro toluene (NT) in acetonitrile. The results show that the emission intensity of dehydrated Tb@1' can be quenched by all the nitro analytes used in the present work. Remarkably, Tb@1' exhibited a high efficiency for TNP, DNB and DNT detection with K-SV K-SV = quenching constant based on linear Stern-Volmer plot] values of 70 920, 44 000 and 35 430 M-1, respectively, which are the highest values amongst known metal-organic materials. Using this material submicromolar level (equivalent to 0.18 ppm), a detection of nitro explosives has been achieved.

Metal-organic chemical vapor-deposited cobalt oxide films as negative electrodes for thin film Li-ion battery

In this study, thin films of cobalt oxide (Co3O4) have been grown by the metal-organic chemical vapor deposition (MOCVD) technique on stainless steel substrate at two preferred temperatures (450 degrees C and 500 degrees C), using cobalt acetylacetonate dihydrate as precursor. Spherical as well as columnar microstructures of Co3O4 have been observed under controlled growth conditions. Further investigations reveal these films are phase-pure, well crystallized and carbon-free. High-resolution TEM analysis confirms that each columnar structure is a continuous stack of minute crystals. Comparative study between these Co3O4 films grown at 450 degrees C and 500 degrees C has been carried out for their application as negative electrodes in Li-ion batteries. Our method of electrode fabrication leads to a coating of active material directly on current collector without any use of external additives. A high specific capacity of 1168 micro Ah cm(-2) mu m(-1) has been measured reproducibly for the film deposited at 500 degrees C with columnar morphology. Further, high rate capability is observed when cycled at different current densities. The Co3O4 electrode with columnar structure has a specific capacity 38% higher than the electrode with spherical microstructure (grown at 450 degrees C). Impedance measurements on the Co3O4 electrode grown at 500 degrees C also carried out to study the kinetics of the electrode process. (C) 2014 Published by Elsevier B.V.

Nanocomposite Made of an Oligo(p-phenylenevinylene)-Based Trihybrid Thixotropic Metallo(organo)gel Comprising Nanoscale Metal-Organic Particles, Carbon Nanohorns, and Silver Nanoparticles

A silver ion (Ag+)-triggered thixotropic metallo(organo)gel of p-pyridyl-appended oligo(p-phenylenevinylene) derivatives (OPVs) is reported for the first time. Solubilization of single-walled carbon nanohorns (SWCNHs) in solutions of the pure OPVs as well as in the metallogels mediated by pi-pi interactions has also been achieved. In situ fabrication of silver nanoparticles (AgNPs) in the SWCNH-doped dihybrid gel leads to the formation of a trihybrid metallogel. The mechanical strength of the metallogels could be increased step- wise in the order: freshly prepared gel metal organic particles (NMOPs), flowerlike aggregates of SWCNHs and AgNPs, and also their integration with each other. Detailed studies suggest lamellar organizations of the linear metal ligand complexes in the NMOPs, which upon association create a three-dimensional network that eventually immobilizes the solvent molecules.

Structural and optical properties of a-plane ZnO thin films synthesized on γ-LiAlO2 (302) substrates by low pressure metal-organic chemical vapor deposition

Nonpolar a-plane (1120) ZnO thin films have been fabricated on gamma-LiAlO2 (302) substrates via the low-pressure metal-organic chemical vapor deposition. An obvious intensity variation of the E-2 mode in the Raman spectra indicates that there exhibits in-plane optical anisotropy in the a-plane ZnO thin films. Highly-oriented uniform grains of rectangular shape can be seen from the atomic force microscopy images, which mean that the lateral growth rate of the thin films is also anisotropic. It is demonstrated experimentally that a buffer layer deposited at a low temperature (200 degrees C) can improve the structural and optical properties of the epilayer to a large extent. (c) 2007 Elsevier B.V. All rights reserved.

Characterization of m-plane ZnO thin film on gamma-LiAlO2 (100) substrate by metal-organic chemical vapor deposition

Non-polar (1 (1) over bar 00)m-plane ZnO thin film has been prepared on gamma-LiAlO2 (100)substrate via the low pressure metal organic chemical vapor deposition. Obvious intensity variation of the E-2 mode in the polarized Raman spectra and the absorption edge shift in the polarized optical transmission spectra indicate that the m-plane film exhibits optical anisotropy, which have applications in certain optical devices, such as the UV modulator and polarization-dependent beam switch. From the atomic force microscopy images, highly-oriented uniform-sized grains of rectangular shape were observed. (c) 2008 Elsevier B.V. All rights reserved.

Individual grain boundary properties and overall performance of metal-organic-deposition coated conductors

We have investigated single grain boundaries (GBs) isolated in coated conductors produced by Metal-Organic Deposition (MOD). When a magnetic field is swept in the film plane, an angle-dependent crossover from boundary to grain limited critical current density Jc is found. In the force-free orientation, even at fields as high as 8 T, the GBs still limit Jc. We deduce that this effect is a direct consequence of GB meandering. We have employed these single GB results to explain the dependence of Jc of polycrystalline tracks on their width: in-plane measurements become flatter as the tracks are narrowed down. This result is consistent with the stronger GB limitation at field configurations close to force-free found from the isolated boundaries. Our study shows that for certain geometries even at high fields the effect of GBs cannot be neglected.

Photoluminescence and lasing properties of InAs/GaAs quantum dots grown by metal-organic chemical vapour deposition

Photoluminescence (PL) and lasing properties of InAs/GaAs quantum dots (QDs) with direrent growth procedures prepared by metalorganic chemical vapour deposition are studied. PL measurements show that the low growth rate QD sample has a larger PL intensity and a narrower PL line width than the high growth rate sample. During rapid thermal annealing, however, the lowgrowth rate sample shows a greater blue shift of PL peak wave length. This is caused by the larger InAs layer thickness which results from the larger 2-3 dimensional transition critical layer thickness for the QDs in the low-growth-rate sample. A growth technique including growth interruption and in-situ annealing, named indium flush method, is used during the growth of GaAs cap layer, which can flatten the GaAs surface effectively. Though the method results in a blue shift of PL peak wavelength and a broadening of PL line width, it is essential for the fabrication of room temperature working QD lasers.

Characterization of ZnMgO hexagonal-nanotowers/films on m-plane sapphire synthesized by metal organic chemical vapour deposition

ZnMgO hexagonal-nanotowers/films grown on m-plane sapphire substrates were successfully synthesized using a vertical low-pressure metal organic chemical vapour deposition system. The structural and optical properties of the as-obtained products were characterized using various techniques. They were grown along the non-polar [1 0 (1) over bar 0] direction and possessed wurtzite structure. The ZnMgO hexagonal-nanotowers were about 200 nm in diameter at the bottom and 120 nm in length. Photoluminescence and Raman spectra show that the products have good crystal quality with few oxygen vacancies. With Mg incorporation, multiple-phonon scattering becomes weak and broad, and the intensities of all observed vibrational modes decrease. The ultraviolet near band edge emission shows a clear blueshift (as much as 100 meV) and broadening compared with that of pure ZnO products.

Photoluminescence properties of tensile-strained GaAsP/GaInP single quantum wells grown by metal organic chemical vapor deposition

Tensile-strained GaAsP/GaInP single quantum well (QW) laser diode (I-D) structures have been grown by low-pressure metal organic chemical vapor deposition (LP-MOCVD) and related photoluminescence (PL) properties have been investigated in detail. The samples have the same well thickness of 16 nm but different P compositions in a GaAsP QW. Two peaks in room temperature (RT) PL spectra are observed for samples with a composition larger than 0.10. Temperature and excitation-power-dependent PL spectra have been measured for a sample with it P composition of 0.15. It is found that the two peaks have a 35 meV energy separation independent of temperature and only the low-energy peak exists below 85 K. Additionally, both peak intensities exhibit a monotonous increase as excitation power increases. Analyses indicate that the two peaks arise from the intrinsic-exciton recombination mechanisms of electron-heavy hole (e-hh) and electron-light hole (e-hh). A theoretical calculation based oil model-solid theory, taking, into account the spin-orbit splitting energy, shows good agreement with our experimental results. The temperature dependence of PL intensity ratio is well explained using the spontaneous emission theory for e-hh and e-hh transitions. front which the ratio can be characterized mainly by the energy separation between the fill and Ill states.

A simple route of morphology control and structural and optical properties of ZnO grown by metal-organic chemical vapour deposition

Employing the metal-organic chemical vapour deposition (MOCVD) technique, we prepare ZnO samples with different morphologies from the film to nanorods through conveniently changing the bubbled diethylzinc flux (BDF) and the carrier gas flux of oxygen (OCGF). The scanning electron microscope images indicate that small BDF and OCGF induce two-dimensional growth while the large ones avail quasi-one-dimensional growth. X-ray diffraction (XRD) and Raman scattering analyses show that all of the morphology-dependent ZnO samples are of high crystal quality with a c-axis orientation. From the precise shifts of the 2 theta. locations of ZnO (002) face in the XRD patterns and the E-2(high) locations in the Raman spectra, we deduce that the compressive stress forms in the ZnO samples and is strengthened with the increasing BDF and OCGF. Photoluminescence spectroscopy results show all the samples have a sharp ultraviolet luminescent band without any defects-related emission. Upon the experiments a possible growth mechanism is proposed.