Novel Hole‐Transport Material for Efficient Polymer Light‐Emitting Diodes by Photoreaction

Summary: The photo‐crosslinking of carbazole dendrimers was analyzed by UV and IR spectroscopic methods. Photoirradiation results in the formation of a film that is insoluble in toluene and benzene. Time‐of‐flight mass spectrometry studies revealed that the photoirradiation lead to an oligomerization of the dendrimer through crosslinking. The resulting insoluble dendrimer film could be applied as a hole‐transport layer in efficient polymer electroluminescence devices (PLEDs).

Luminance‐voltage characteristics for PLEDs wherein PEDOT:PSS and CbzG3 complex with SnCl₂ were employed as the hole transport layer (ITO/HTL/EML/Ca/Ag).     

Polymerization of Aniline by Auric Acid: Formation of Gold Decorated Polyaniline Nanoballs

Summary: We report a new method for the preparation of polyaniline nanoballs by using HAuCl₄ as an oxidizing agent. During the reaction, aniline is oxidized and forms polyaniline whilst the hydrogen tetrachloroaurate is reduced and forms gold nanoparticles. These gold nanoparticles are found to decorate the nanoballs.

The resultant precipitate and corresponding TEM image of the gold‐nanoparticle covered polyaniline nanoball.     

Laser Single Pulse Initiated RAFT Polymerization for Assessing Chain‐Length Dependent Radical Termination Kinetics

Summary: A novel method combining RAFT polymerization with pulsed‐laser initiation for determining chain‐length dependent termination rate coefficients, k_t, is presented. Degenerative chain‐transfer in RAFT enables single‐pulse pulsed‐laser polymerization (SP‐PLP) traces to be measured on systems with a narrow radical distribution that remains essentially unchanged during the experiment. SP‐PLP‐RAFT experiments at different polymerization times allow for determining k_t as a function of chain length via classical kinetics assuming chain‐length independent k_t.

Single‐pulse pulsed‐laser polymerization trace for BMPT‐mediated RAFT polymerization of butyl acrylate.     

A First Approach to White Organic Electroluminescence Device from a Single Rod‐Coil Poly[thiophene‐block‐(N‐vinylcarbazole)] Diblock Copolymer

A rod‐coil block copolymer consisting of poly(3‐hexylthiophene) (P3HT) and poly(N‐vinylcarbazole) (PVK) ( P3HT‐ b ‐PVK ) in a single molecular architecture is prepared as the first example for WOLEDs. By obtaining the phase separated domains in thin film of the resulting block copolymer, it is possible to suppress energy transfer from PVK as wide bandgap units to P3HT as low bandgap blocks, yielding dual emissions for white electroluminescence with CIE coordination of (0.34, 0.33).

     

Fabrication of Au/Titania Composite Nanodot Arrays from Au‐Loaded Block Copolymer Micellar Films

Summary: A simple route to an ordered array of metal/semiconductor oxide composite nanodots is presented. Micellar monolayer films of polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) loaded with HAuCl₄ in the P2VP nanodomains are used as templates. TiO₂ is generated selectively within the polar P2VP domains of PS‐b‐P2VP/HAuCl₄ films by chemical vapor deposition of TiCl₄. Subsequent removal of the organic matrix by oxygen plasma or UV light leads to an array of Au/TiO₂ composite nanoparticles on the substrate surface.

Schematic illustration of the process to fabricate an array of Au/titania composite nanodots.     

Gold Nanoparticles Functionalized by a Dextran‐Based pH‐ and Temperature‐Sensitive Polymer

A dextran‐based dual‐sensitive polymer is employed to endow gold nanoparticles with stability and pH‐ and temperature‐sensitivity. The dual‐sensitive polymer is prepared by RAFT polymerization of N‐isopropylacrylamide from trithiocarbonate groups linked to dextran and succinoylation of dextran after polymerization. The functionalized nanoparticles show excellent stability under various conditions and can be stored in powder‐form. UV and DLS measurements confirm that the temperature‐induced optical changes and aggregation behaviors of the particles are strongly dependent on pH.

     

Small‐Angle Scattering From Branched Polymers

The single‐polymer form factor is determined for branched polymers using a scaling argument in order to recover the low‐Q Porod exponent characteristic of the overall structure. The high‐Q Porod exponent characterizes the local branching structure. An alternative approach based on a high‐Q expansion contains information about functionality, branch length and branch content. The specific case of a starburst dendrimer for which the form factor is known is discussed. The model predictions are compared to small‐angle neutron scattering data from a dilute solution of dendrimer in D₂O.

     

Enhancement of Photostability in Blue‐Light‐Emitting Polymers Doped with Gold Nanoparticles

A dramatic increase in the photostability of a blue‐light‐emitting polymer, poly(9,9‐dioctylfluorene), was achieved by the addition of 5–10 nm gold nanoparticles. The optical absorption band of the gold nanoparticles was tuned to resonate the triplet exciton ground state bandgap energy of the polymer. Photo‐oxidation rate of poly(9,9‐dioctylfluorene) was effectively reduced by doping the polymer with very small amounts (≈10⁻⁶–10⁻⁵ volume fraction) of the gold nanoparticles.

Retarded photo‐oxidation in PDOF nanocomposite films with various doped gold nanoparticles.     

Opto‐Mechanical Effect in Photoactive Nematic Side‐Chain Liquid‐Crystalline Elastomers

The mechanical behaviour of monodomain nematic side‐chain liquid‐crystalline elastomers containing azoderivatives as pendant groups or crosslinkers has been studied under UV irradiation and in the darkness at different temperatures. From the evaluation of the opto‐mechanical experiments, the mechanical efficiency, kinetic rates, activation energies and the isomerization mechanism of the azocompounds in the liquid‐crystalline matrix could be determined, as well as the effect of the chemical constitution of the azobenzene derivatives and their role in the elastomeric network.

     

Self‐Assembled Single‐Crystal Polyaniline Microplates and Their Anisotropic Electrical Transport Property

Self‐assembly of two‐dimensional (2D) structures from functional molecules is of great scientific importance. Herein, using a typical linear conducting polymer, polyaniline as building blocks, 2D single crystalline microplates are successively produced. The structure of 2D microplates is clearly defined by selected area electron diffraction, X‐ray diffraction, and Raman spectroscopy. Owing to the anisotropic arrangement of linear conjugated PANI molecules, the microplate shows a typical anisotropic electrical transport property.

     

Elasticity of Single Poly(amido amine) Dendrimers

An atomic force microscope in the compression mode was used to probe the nanomechanical response of single dendrimeric molecules, as well as dendrimer aggregates adsorbed on silicon surface. The force‐compression behaviour of individual, generation 5 poly(amido amine) (PAMAM) dendrimers was described by a Hertzian model for the deformation of elastic bodies. The modulus values obtained ranged between 700 MPa (single dendrimers) and 150 MPa (dendrimer aggregates).

     

Facile One‐Pot Synthesis of a Polyvinylpyrrolidone‐Based Self‐Crosslinked Fluorescent Film

A polyvinylpyrrolidone (PVP)‐based fluorescent film with stable optical properties is successfully prepared in one pot without any additive. The reaction mechanism of ring‐opening and self‐crosslinking of linear PVP is proposed and demonstrated. The morphologies and the nanostructures of the fluorescent film as well as the unmodified film are investigated. The dye is incorporated into the film networks via covalent linkages, thus leading to the highly stable optical properties. The facile and effective synthesis approach opens a new way for the design of other multi‐functional composite materials based on linear PVP.

     

Biotin α‐End‐Functionalized Gradient Glycopolymers Synthesized by RAFT Copolymerization

Biotinylated gradient glycopolymers have been synthesized via RAFT copolymerization of an acrylamide derivative of galactose with N‐acryloylmorpholine in the presence of a biotin CTA. The polymerization was controlled with a linear increase in molecular weights up to 80% conversion. Copolymer chains have a gradient microstructure with an increasing proportion of galactose units towards the ω chain end. The presence of the biotin ligand at the α end of the chains was confirmed by ¹H NMR and MALDI‐ToF MS. This strategy based on the use of a biotin‐CTA instead of a post‐polymerization labelling of the chains resulted in a high percentage of α‐functionalized chains (92–95%). Such α‐end‐functionalized glycopolymer chains may interact with streptavidin‐modified surfaces.

     

Low‐Band Gap Polyplatinaynes with Electron‐Accepting Silole Units

Summary: The synthesis and thermal, redox and photoluminescence properties of a soluble donor‐acceptor polyplatinayne with the electron‐accepting silole ring and its model compound are described. The polymer has an optical band gap of 2.10 eV which is much lower than that of thienyl‐ or silyl‐bridged congeners. The incorporation of electron‐accepting silole unit in the metallopolymer main chain creates a new π‐conjugated system that features unique donor‐acceptor characteristics.

     

Structure‐Transport Relationship of Dendritic Core‐Shell Nanocarriers for Polar Dyes

TriPEGylated functionalized dendritic poly(ethylene imines) were synthesized and their transportation properties for rose Bengal (up to 50 guests per dendrimer) were evaluated. A critical aggregation concentration was observed, demonstrating the formation of aggregates among the dendrimers. The structure‐activity relationships show that their encapsulation capacities were dependent linearly on the density of the PEG shell, either as PEG length or degree of functionality, which confirmed that the PEG chains play a predominant role in the encapsulation process. It further gives some insights that the guest molecules appeared to be predominantly located in the PEG shell rather than in the core.

     

Significant Improvement of the Processability of Ladder‐Type Polymers by Using Aqueous Colloidal Dispersions

Summary: It has been shown that stable aqueous dispersions of nanoparticles of the rigid‐rod ladder‐type polymer poly(benzo‐bisimidazobenzo‐phenanthroline) (BBL) can be prepared in order to facilitate BBL processing. The obtained dispersions have a controllable particle size in the range between 50 and 150 nm and, consequently, the deposition of layers by spin‐coating or drop‐casting is realized. The resultant films exhibit a particulate structure and their morphology has been characterized by means of SEM and AFM. Upon investigation of the BBL dispersions in organic field‐effect transistors an ambipolar charge carrier transport has been observed, which presumably is related to the presence of mobile ions.

SEM image of a drop‐cast film of the BBL nanoparticles.     

Thermoswitchable Electronic Properties of a Gold Nanoparticle/Hydrogel Composite

Summary: A well‐dispersed gold nanoparticle/poly(N‐isopropylacrylamide) (PNIPAm) hydrogel nanocomposite with thermoswitchable electrical properties is prepared by the copolymerization of functional Au nanoparticles with N‐isopropylacrylamide. It is found that the electrical conductivity of the nanocomposite changes by two orders of magnitude at moderate temperature (T_tran) upon temperature stimuli. The change of electrical properties is reversible during a heating and cooling cycle.

Schematic illustration of the mechanism of the thermo‐switchable electronic properties of the Au nanoparticle/PNIPAm composite.     

Synthesis and Characterization of a Novel Calix[4]arene‐Based Periodic Mesoporous Organosilica

Summary: A new calix[4]arene‐based periodic mesoporous organosilica has been synthesized using tetraethoxysilane (TEOS) and a calix[4]arene‐based silane monomer as the precursors and cetyltrimethylammonium bromide (CTAB) surfactant as the structure‐directing template, and is shown to be capable of visual detection and entrapment of NO₂.

Synthesis of the novel mesoporous organosilica material containing covalently bound tetra‐O‐alkylated calix[4]arene hosts.     

Ink‐Jet Printing of Metallic Nanoparticles and Microemulsions

Summary: Two types of ink‐jet inks are presented: ink containing an aqueous dispersion of silver nanoparticles and an oil‐in‐water microemulsion‐based ink. The metallic ink contains nanoparticles of silver, which are formed in the presence of an ionic polymeric stabilizer. Sintering of the printed image obtained with the use of such silver‐based inks at temperatures as low as 300 °C results in formation of patterns possessing noticeable conductivity. The microemulsion inks are based on a thermodynamically stable microemulsion, in which the dispersed oil phase is a volatile solvent containing a water‐insoluble colorant. After contact of the jetted ink droplets with a substrate, nanodroplets of the microemulsion are converted into nanoparticles of the solubilized colorant. In some cases, it was found that the evaporation of microemulsion ink droplets leads to formation of rings composed of ordered nanoparticles.

Scheme of ink‐jet printing of an oil‐in‐water microemulsion followed by conversion of the nanodroplets into nanoparticles, caused by quick evaporation of the solvent within the microemulsion droplets. Therefore, the ink behaves as a dye‐based ink prior to printing, but after printing it behaves like a pigment‐based ink.