Role of humidity on indium and tin migration in organic photovoltaic devices

The stability of a common interface used in organic photovoltaic cells, between the transparent electrode of Indium Tin Oxide (ITO) and a buffer layer of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is strongly influenced by the presence of humidity during processing, leading to significant migration of indium and tin species into the PEDOT:PSS layer. The interface was studied using neutral impact collision ion scattering spectroscopy (NICISS) and X-ray photoelectron spectroscopy (XPS), to determine migration of indium and tin into the polymer layer. It was found that the migration starts almost instantly after spin coating of the aqueous PEDOT:PSS solution and it reaches a saturation level within twenty four hours. The indium and tin were found always uniformly distributed over the sampling depth of almost one-third of the thickness of the PEDOT:PSS layer. Exposure to humidity following annealing resulted in the highest concentration (1.8 × 10(-3) mol cm(-3)) of indium or tin species, corresponding to about one indium or tin moiety per 4.7 monomer units in the PEDOT:PSS. The maximum bulk concentration of indium is about two orders of magnitude higher after exposure to humid conditions compared to vacuum dried conditions. XPS measurements confirm the presence of both indium and tin in the PEDOT:PSS and the formation of salts with the metal ions as cations.     

Solvent‐Dependent Truxene‐Based Nanostructures

Three truxene derivatives functionalized with alkyl chains, either attached directly or distanced by linking phenyl or ethynyl groups, self‐assemble in solution and induce the gelation of different solvents in spite of not being endowed with groups able to establish strong directional interactions. A ¹H NMR study points to face‐to‐face alternating π‐stacked motifs at the origin of nucleation. Solvents play an important role in modulating the aggregation of these derivatives giving rise to fibrous or spherical superstructures. Analysis of the influence of different solvents on the morphology of the aggregates provides a better understanding of the various stages of the hierarchical self‐assembly. The way in which alkyl chains are attached to the central core also strongly affects the self‐assembling properties and gelation ability of this series. Phenyl spacers present the highest association constants in solution and give rise to gelation in a broader range of solvents. This behavior has been rationalized by means of ¹H NMR spectroscopy, X‐ray powder diffraction, SEM, and photophysical measurements. Interestingly, it was found that these compounds in the gel state exhibit unusual emission properties most likely arising from the formation of excimers, which evidences that π–π interactions also occur in the excited state.     

Microwave-assisted synthesis of naphthalenemonoimides and N-desymmetrized naphthalenediimides

Naphthalenemonoimides and N-desymmetrized naphthalenediimides were synthesized using a stepwise microwave-assisted protocol. The steric and electronic properties of aliphatic amines determined the outcome of the reactions, while in the amino acid series their ability to solubilize the naphthalene dianhydride starting material was crucial. Molecular modeling was used to rationalize the observed selectivity.     

Zeta functions that hear the shape of a Riemann surface

To a compact hyperbolic Riemann surface, we associate a finitely summable spectral triple whose underlying topological space is the limit set of a corresponding Schottky group, and whose “Riemannian” aspect (Hilbert space and Dirac operator) encode the boundary action through its Patterson–Sullivan measure. We prove that the ergodic rigidity theorem for this boundary action implies that the zeta functions of the spectral triple suffice to characterize the (anti-)complex isomorphism class of the corresponding Riemann surface. Thus, you can hear the complex analytic shape of a Riemann surface, by listening to a suitable spectral triple.     

A practical approach to the living polymerization of functionalized monomers: application to block copolymers and 3‐dimensional macromolecular architectures

The tolerance of living free radical procedures to reactive functional groups, coupled with their ability to prepare well‐defined random and block copolymers is demonstrated by the use of novel α‐hydrogen alkoxyamine derivatives instead of the traditional TEMPO‐based systems. This refinement in the nitroxide structure overcomes many limitations typically associated with TEMPO and has permitted a dramatic increase in the range of monomers, which can be polymerized under controlled conditions. The ability to prepare well‐defined multi‐arm star polymers from a variety of alkoxyamine terminated vinyl and non‐vinyl linear polymers are major benefits when compared to traditional living procedures, such as anionic polymerizations.