Effect of Aluminum Nanostructured Electrode on the Properties of Bulk Heterojunction Based Heterostructures for Electronics.

The properties of organic heterostructures with mixed layers made of arylenevinylene-based polymer donor and non-fullerene perylene diimide acceptor, deposited using Matrix Assisted Pulsed Laser Evaporation on flat Al and nano-patterned Al electrodes, were investigated. The Al layer electrode deposited on the 2D array of cylindrical nanostructures with a periodicity of 1.1 µm, developed in a polymeric layer using UV-Nanoimprint Lithography, is characterized by an inflorescence-like morphology. The effect of the nanostructuring on the optical and electrical properties was studied by comparison with those of the heterostructures based on a mixed layer with fullerene derivative acceptor. The low roughness of the mixed layer deposited on flat Al was associated with high reflectance. The nano-patterning, which was preserved in the mixed layer, determining the light trapping by multiple scattering, correlated with the high roughness and led to lower reflectance. A decrease was also revealed in photoluminescence emission both at UV and Vis excitation of the mixed layer, with the non-fullerene acceptor deposited on nano-patterned Al. An injector contact behavior was highlighted for all Al/mixed layer/ITO heterostructures by I-V characteristics in dark. The current increased, independently of acceptor (fullerene or non-fullerene), in the heterostructures with nano-patterned Al electrodes for shorter conjugation length polymer donors.

Multi-Functional Materials Based on Cu-Doped TiO2 Ceramic Fibers with Enhanced Pseudocapacitive Performances and Their Dielectric Characteristics.

In this work, pure TiO2 and Cu (0.5, 1, 2%)-doped TiO2 composites prepared by electrospinning technique followed by calcination at 900 °C, and having high pseudocapacitive and dielectric characteristics were reported. These nanocomposites were characterized by scanning electron microscopy, X-ray diffraction, and dynamic water sorption vapor measurements. The structural characterization of these nanostructures highlighted good crystallinity including only the rutile phase. The electrochemical characteristics were investigated by cyclic voltammetry and galvanostatic charge-discharge measurements, which were performed in a KOH electrolyte solution. Among the Cu-doped TiO2 nanostructures that were prepared, the one containing 0.5% Cu exhibited superior electrochemical properties, including high specific gravimetric capacitance of 1183 F·g-1, specific capacitance of 664 F·g-1, energy density of 45.20 Wh·kg-1, high power density of 723.14 W·kg-1, and capacitance retention of about 94% after 100 cycles. The dielectric investigation shows good dielectric properties for all materials, where the dielectric constant and the dielectric loss decreased with the frequency increase. Thus, all the interconnected studies proved that these new materials show manifold ability and real applicative potential as pseudocapacitors and high-performance dielectrics. Future work and perspectives are anticipated for characterizing electrochemical and dielectric properties for materials including larger amounts of Cu dopant.

Arylenevinylene Oligomer-Based Heterostructures on Flexible AZO Electrodes.

We investigated the optical and electrical properties of flexible single and bi-layer organic heterostructures prepared by vacuum evaporation with a p-type layer of arylenevinylene oligomers, based on carbazole, 3,3' bis(N hexylcarbazole)vinylbenzene = L13, or triphenylamine, 1,4 bis [4 (N,N' diphenylamino)phenylvinyl] benzene = L78, and an n-type layer of 5,10,15,20-tetra(4-pyrydil)21H,23H-porphyne = TPyP. Transparent conductor films of Al-doped ZnO (AZO) with high transparency, >90% for wavelengths > 400 nm, and low resistivity, between 6.9 × 10-4 Ω·cm and 23 × 10-4 Ω·cm, were deposited by pulsed laser deposition on flexible substrates of polyethylene terephthalate (PET). The properties of the heterostructures based on oligomers and zinc phthalocyanine (ZnPc) were compared, emphasizing the effect of the surface morphology. The measurements revealed a good absorption in the visible range of the PET/AZO/arylenevinylene oligomer/TPyP heterostructures and a typical injection contact behavior with linear (ZnPc, L78) or non-linear (L13) J-V characteristics in the dark, at voltages < 0.4 V. The heterostructure PET/AZO/L78/TPyP/Al showed a current density of ~1 mA/cm2 at a voltage of 0.3 V. The correlation between the roughness exponent, evaluated from the height-height correlation function, grain shape, and electrical behavior was analyzed. Consequently, the oligomer based on triphenylamine could be a promising replacement of donor ZnPc in flexible electronic applications.

An electrochemical study of two self-dopable water-soluble aniline derivatives: electrochemical deposition of copolymers.

An electrochemical study of two water-soluble aniline derivatives, N-(3-sulfopropyl) aniline (AnPS) and N-(3-sulfopropyl) p-aminodiphenylamine (DAnPS), in aqueous acidic electrolytic solutions containing different kinds of doping anions (Cl (-), SO(4) (2-), and ClO(4) (-)) was carried out. At sufficiently high anodic potential, the sulfonated aniline derivatives undergo oxidation processes yielding cation-radical and dimer intermediates, but no polymer deposition was observed on the working electrode surface. Experimental results showed that both aniline derivatives are electroactive compounds exhibiting redox behaviour in the range of potential of -0.2 V-1.6 V. Due to the self-doping effect induced by sulfonic groups, AnPS and DAnPS compounds have good electroactivity even in neat water solution. By adding a small amount of aniline into electrolytic system, thin layers of copolymers were deposited on the working electrode surface. The copolymer layers formed on the electrodes show a highly orientational and positional order, confirmed by AFM and XRD spectroscopic techniques. During the anodic oxidation processes some distinct colour changes were observed.

Synthesis and optoelectronic characterization of some star-shaped oligomers with benzene and triphenylamine cores.

Six star-shaped oligomers containing triphenylamine (D1-D3) and benzene unit (D4-D6) as cores have been synthesized by Wittig condensation or Heck coupling reaction using aromatic aldehydes and triphenylphosphonium salts or aromatic halogenated compounds with vinyl triphenylamine. All oligomers have well-defined molecular structure and high purity. Characterization of the oligomers was made by FT-IR, (1)H-NMR spectroscopy, UV-Vis, and fluorescence spectroscopy. The electrochemical behavior was studied by cyclic voltammetry (CV). The cyclic voltammograms have revealed that oligomers undergo quasireversible or irreversible redox processes. The irreversible process is associated with electrochemical polymerization of oligomers by dimerization of unsubstituted triphenylamine groups. Thermal characterization was accomplished by TGA and DSC methods and evidenced that all oligomers were stable materials until 250°C and have formed stable molecular glasses after first heating scan.

Triphenylamine-based rhombimine macrocycles with solution interconvertable conformation.

Three imine macrocycles having rhomboidal shape were synthesized in good yields by [2+2] cyclocondensation reaction between equimolar quantities of (R,R)-1,2-diaminocyclohexane and 4,4'-bisformyl triphenylamine derivatives. The macrocycles structure was assigned by electrospray ionization mass spectrometry (ESI-MS), (1)H-NMR, and elemental analysis. UV, FTIR spectroscopy, and TG measurements were also used to characterize and prove the structure of these compounds. A conformational modification arising out of the rotation of triphenylamine group around the flexible cyclohexane-N bonds was observed in solution by (1)H-NMR and UV spectroscopy for all three macrocycles.