Timothy Fulghum

Hybrid Gold‐Nanoparticle‐Cored Conjugated Thiophene Dendrimers: Synthesis, Characterization, and Energy‐Transfer Studies

A series of hybrid Au-nanoparticle-dendrimer materials: nanoparticle-cored thiophene dendrimers (NCTDs) were synthesized, characterized, and investigated for their energy-transfer properties. These hybrid nanoparticles were obtained by the simultaneous and in situ reduction of gold(III) chloride and self-assembly of the thiol-containing thiophene dendritic ligands. The dendron ligands were radially attached to the gold nanoparticles and were analyzed by TEM, UV/Vis, (1)H NMR, and FTIR spectroscopies. The solution fluorescence of the attached thiophene dendrons are quenched progressively. Both alkyl-chain length and dendron size have significant influence on the energy-transfer efficiency, as well as on core sizes and size distribution of the Au nanoparticles. In spite of the phenomenons dependence on nanoparticle size, the energy transfer generally follows the 1/d(2) distance dependence. Single NCTD nanoparticles were also adsorbed on highly ordered pyrolytic graphite (HOPG) and uniform aggregates were observed on mica flat substrates.

Intercalative Poly(carbazole) Precursor Electropolymerization within Hybrid Nanostructured Titanium Oxide Ultrathin Films

A protocol for nanostructuring and electropolymerization of a hybrid semiconductor polycarbazole-titanium oxide ultrathin film is described. Ultrathin (<100 nm) films based on polycarbazole precursor polyelectrolytes and titanium oxide (TiOx) have been fabricated by combining the layer-by-layer (LbL) and surface sol-gel layering techniques. Film growth was followed and confirmed through UV-vis spectroscopy, ellipsometry and quartz crystal microbalance with dissipation (QCM-D). Subsequent anodic electrochemical oxidation of the carbazole pendant units afforded a conjugated polymer network (CPN) film within intercalating TiOx layers of cross-linked and π-conjugated carbazole units. Cyclic voltammetry (CV), UV-vis, and fluorescence spectroscopy measurements confirmed this process. The LbL-driven polyelectrolyte deposition process resulted in a quantified electrochemical response, proportional to the number of layers, while the TiOx acted as a dielectric spacer limiting electron transfer kinetics and attenuating energy transfer in fluorescence. Electro-optical properties were compared with other polycarbazole thin film materials with respect to bandgap energy (Eg). The straightforward protocol in film nanostructuring and barrier/dielectric properties of the inorganic oxide slab (denoted here as, TiOx) should enable applications in organic light-emitting diodes (OLEDs), dielectric mirrors, planar waveguides, and photovoltaic devices for these hybrid ultrathin films.