Suxiang Deng

Nanostructured ultrathin films of alternating sexithiophenes and electropolymerizable polycarbazole precursor layers investigated by electrochemical surface plasmon resonance (EC-SPR) spectroscopy.

Nanostructured ultrathin films of linear and dendrimeric cationic sexithiophenes, 6TNL and 6TND, respectively, alternated with anionic polycarbazole precursor, poly(2-( N-carbazolyl) ethyl methacrylate- co-methacrylic acid) or PCEMMA32, were successfully fabricated using the layer-by-layer self-assembly deposition technique. The two electro-optically active oligomers exhibited distinct optical properties and aggregation behavior in solution and films as studied by UV-vis and fluorescence spectroscopy. The stepwise increase of the 6TNL/PCEMMA32 and 6TND/PCEMMA32 layers was confirmed by UV-vis spectroscopy and in situ surface plasmon resonance (SPR) spectroscopy. The intralayer electrochemical polymerization and cross-linking behavior of the carbazole functionalized PCEMMA32 layers were then investigated using cyclic voltammetry (CV) and electrochemical surface plasmon resonance (EC-SPR) spectroscopy. The increase in current with each cycle confirmed intralayer cross-linking followed by the doping-dedoping process within these films. The two types of films differed with respect to dielectric constant and thickness changes before and after electropolymerization, indicating the influence of the oligothiophene layers. This demonstrated for the first time the preparation of highly ordered organic semiconductors alternated with in situ electropolymerizable layers in ultrathin films.

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.

Dual aggregation behavior of porphyrin-cored thiophene dendrimers.

Two porphyrin-cored thiophene dendrimers T(3T)P and T(7T)P have been successfully synthesized and characterized by UV-vis and fluorescence measurements. The self-assembly of these two water-insoluble free base porphyrins to form both intrinsic H- and J-aggregates has been reported for the first time. This intrinsic behavior is in contrast to the use of surfactants, dyes, and metal ions to induce aggregation behavior on most porphyrin systems. This work emphasizes the importance of controlling the size, solvent, and extent of conjugation of polythiophene dendron groups in porphyrin systems. These materials may yet be applied to polythiophene or porphyrin blend system in energy conversion devices with the light-harvesting properties of the polythiophene dendrons.

Conjugated Polymer Network Ultrathin Films on Metal Interfaces using the Precursor Polymer Approach: Design, Synthesis and In-situ Characterization

We have reported recently a novel method for cross-linking conjugated polymers involving a “precursor polymer” route, where the electrochemical method can be used to prepare ultrathin films on conducting metal and metal oxide surfaces. In this paper, we present the design, synthesis, protocol, and recent results in the application of these thin film materials. An emphasis will be given on how these films are characterized in-situ by a combined surface plasmon spectroscopy (SPS) and electrochemical approach. As a methodology, the concept can be extended to new methods of electrodeposition, patterning, and grafting of conjugated polymers on electrochemically addressable metal surfaces. Compared to spin-cast or electropolymerized monomer films, they are very robust both thermally and mechanically. Other applications of these films to sensors, dielectric materials, non-lithographic patterning, etc. are currently being investigated.

The Precursor Polymer Approach to Electrodeposition and Patterning of Conjugated Polymer Ultrathin Films

In this paper, we report strategies for electrodepositing and patterning ultrathin films of conjugated polymers on flat electrode surfaces using the precursor polymer approach. This involves a rational synthesis design of the precursor polymer followed by careful electrodeposition and characterization of ultrathin films on conducting substrates. This has resulted in the preparation of smooth, high optical quality films, which should be important for applications involving flat electrode surfaces in devices. Characterization was made using surface sensitive spectroscopic and microscopic techniques. Copolymerization with monomers, polymer backbone design, and grafting on modified surfaces are key points in this strategy. Novel methods of in-situ characterization techniques have also been developed combing electrochemistry and surface plasmon resonance techniques.