Self-Assembly-Directed Exciton Diffusion in Solution-Processable Metalloporphyrin Thin Films

The study of excited-state energy diffusion has had an important impact in the development and optimization of organic electronics. For instance, optimizing excited-state energy migration in the photoactive layer in an organic solar cell device has been shown to yield efficient solar energy conversion. Despite the crucial role that energy migration plays in molecular electronic device physics, there is still a great deal to be explored to establish how molecular orientation impacts energy diffusion mechanisms. In this work, we have synthesized a new library of solution-processable, Zn (alkoxycarbonyl)phenylporphyrins containing butyl (ZnTCB4PP), hexyl (ZnTCH4PP), 2-ethylhexyl (ZnTCEH4PP), and octyl (ZnTCO4PP) alkoxycarbonyl groups. We establish that, by varying the length of the peripheral alkyl chains on the metalloporphyrin macrocycle, preferential orientation and molecular self-assembly is observed in solution-processed thin films. The resultant arrangement of molecules consequently affects the electronic and photophysical characteristics of the metalloporphyrin thin films. The various molecular arrangements in the porphyrin thin films and their resultant impact were determined using UV-Vis absorption spectroscopy, steady-state and time-resolved fluorescence emission lifetimes, and X-ray diffraction in thin films. The films were doped with C60 quencher molecules and the change in fluorescence was measured to derive a relative quenching efficiency. Using emission decay, relative quenching efficiency, and dopant volume fraction as input, insights on exciton diffusion coefficient and exciton diffusion lengths were obtained from a Monte Carlo simulation. The octyl derivative (ZnTCO4PP) showed the strongest relative fluorescence quenching and, therefore, the highest exciton diffusion coefficient (5.29 × 10−3 cm2 s−1) and longest exciton diffusion length (~81 nm). The octyl derivative also showed the strongest out-of-plane stacking among the metalloporphyrins studied. This work demonstrates how molecular self-assembly can be used to modulate and direct exciton diffusion in solution-processable metalloporphyrin thin films engineered for optoelectronic and photonic applications.

Bound of diffusion constants from pole-skipping points: spontaneous symmetry breaking and magnetic field

We investigate the properties of pole-skipping of the sound channel in which the translational symmetry is broken explicitly or spontaneously. For this purpose, we analyze, in detail, not only the holographic axion model, but also the magnetically charged black holes with two methods: the near-horizon analysis and quasi-normal mode computations. We find that the pole-skipping points are related with the chaotic properties, Lyapunov exponent (λL) and butterfly velocity (vB), independently of the symmetry breaking patterns. We show that the diffusion constant (D) is bounded by $$ D\ge {v}_B^2/{\lambda}_L $$ D ≥ v B 2 / λ L , where D is the energy diffusion (crystal diffusion) bound for explicit (spontaneous) symmetry breaking. We confirm that the lower bound is obtained by the pole-skipping analysis in the low temperature limit.

Physico-Chemical Properties of a Hybrid Biomaterial (PVA/Chitosan) Reinforced with Conductive Fillers

In this study, a novel hybrid material based on Polyvinyl Alcohol-Chitosan (PVA-Chi) was made, reinforced with conductive fillers such as the polypyrrole (PPy), Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT: PSS), carbon black (CB), and multi-wall carbon nanotube (MWCNT). In order to observe the mechanical and electrical responses of this composite material, for obtaining composite materials, and to characterize them for the development of applications in engineering, FTIR analysis made clear the different functional groups present in the matrix and the fillers used. Using quaternary mixtures (4 fillers) increased the contact angle, which increased hydrophobicity of the biocomposite. The Nyquist diagram of the analyzed samples showed a decrease in resistance and energy diffusion; the latter because of transferring electrons caused by the conductive polymers CB and the MWCNT. In the mechanical tension tests, Young’s modulus values of 18.386 MPa were obtained, in contrast with the material matrix of PVA-Chi, which showed values of 11.628 MPa. Morphological analysis by SEM showed the materials got were homogeneous. The materials got showed higher electrical conductivity in the OH’s presence and NH2 groups, which could have possible applications in biopolymer electrodes.