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Meni Wanunu

Publications and source records attributed to Meni Wanunu.

4 recordsLinked to original sources

Assembly of coordination nanostructures via ligand derivatization of oxide surfaces.

A scheme is presented for the construction of coordination nanostructures on oxide surfaces (glass, Si/SiO2, quartz), based on application of epoxy-terminated monolayers as anchors for covalent grafting of ligands. Two ligands bearing amine groups were reacted with epoxysilane monolayers on oxide surfaces, providing ligand-terminated substrates. The ligands employed were (i) a pyridine moiety, used for subsequent binding of cobalt tetraphenylporphine (CoTPP), and (ii) deferoxamine (DFX), which contains hydroxamic acid moieties, used for subsequent construction of various Zr4+-based coordination layers. The results suggest that a dense ligand layer was obtained in both cases, allowing the formation of coordination overlayers on the oxide surfaces. The growth of coordinated layers was similar to analogous overlayers assembled on Au substrates, indicating that high ligand coverage is achieved by the epoxy-amine surface reaction. Epoxy-based functionalization of oxide substrates is a mild and efficient method for preparing high-quality coordination overlayers. Moreover, the method makes use of commercially available silane and amine reactants, providing the basis for wide application.

Journal Article↗

Branched coordination multilayers on gold.

A C3-symmetric tridentate hexahydroxamate ligand molecule was specially synthesized and used for coordination self-assembly of branched multilayers on Au surfaces precoated with a self-assembled monolayer (SAM) of ligand anchors. Layer-by-layer (LbL) growth of multilayers via metal-organic coordination using Zr4+ ions proceeds with high regularity, adding one molecular layer in each step, as shown by ellipsometry, wettability, UV-vis spectroscopy, and atomic force microscopy (AFM). The branched multilayer films display improved stiffness, as well as a unique defect self-repair capability, attributed to cross-linking in the layers and lateral expansion over defects during multilayer growth. Transmetalation, i.e., exposure of Zr4+-based assemblies to Hf4+ ions, was used to evaluate the cross-linking. Conductive atomic force microscopy (AFM) was used to probe the electrical properties of the multilayers, revealing excellent dielectric behavior. The special properties of the branched layers were emphasized by comparison with analogous multilayers prepared similarly using linear (tetrahydroxamate) ligand molecules. The process of defect annihilation by bridging over defective areas, attributed to lateral expansion via the excess bishydroxamate groups, was demonstrated by introduction of artificial defects in the anchor monolayer, followed by assembly of two layers of either the linear or the branched molecule. Analysis of selective binding of Au nanoparticles (NPs) to unblocked defects emphasized the superior repair mechanism in the branched layers with respect to the linear ones.

Journal Article↗

Coordination-based gold nanoparticle layers.

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.

Gold↗

Widely-applicable gold substrate for the study of ultrathin overlayers.

Ultrathin films on gold substrates have been the subject of enormous scientific and technological interest. Comprehensive study of such systems requires concomitant application of a variety of complementary characterization techniques. The reliability of the result is frequently hampered by the fact that different characterization methods impose different requirements on the Au substrate, resulting in the need to use different types of Au substrates for different measurements, possibly influencing the overlayer structure. This results in an average, rather than exact, structure determination. Here, we show that 15-nm-thick Au films evaporated at 0.5 A/sec on silanized glass and annealed are semi-transparent, electrically conducting, and morphologically well-defined, showing a smooth, [111] textured surface. Such Au films provide a high-quality, widely applicable and relatively inexpensive platform for ultrathin overlayers, enabling characterization by a wide spectrum of experimental methods, applied to the same substrate. The exceptional qualities and analytical capabilities of such substrates are demonstrated with several different systems: (i) Cu underpotential deposition (upd); (ii) alkanethiol self-assembly; (iii) formation of Au nanoparticle layers; (iv) binding of the chromophore protoporphyrin IX (PPIX) to a monolayer of 11-mercaptoundecanoic acid (MUA). In the latter case it is shown that the use of Cu(2+) ions for binding between the carboxylate groups of PPIX and MUA promotes better organization of the porphyrin layer.

Glass↗