Morphology and energy transfer study between conjugated polymers thin films: experimental and theoretical approaches.

In this paper, the effect of a silafluorene derivative copolymer, the poly[2,7-(9,9-dioctyl-dibenzosilole)-alt-4,7-bis(thiophene-2-yl)benzo-2,1,3-thiadiazole] (PSiF-DBT) sensitized by a simpler homopolymer, the poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) were investigated in a bilayer and ternary blend configuration. The energy transfer between the polymers prior to electron transfer to the acceptors can be an efficient alternative to photocurrent improvement in photovoltaic devices. The interactions between the two donor polymer films were evaluated optically and morphologically with several experimental techniques and correlated to the photovoltaic performance. Improved photon to charge conversion was observed in the blend films at different device geometries-considering bilayer devices with fullerene and inverted flexible devices blade coated in air conditions with a non-fullerene small molecule acceptor. Resonant Auger spectroscopy using the core-hole clock method was employed to evaluate the ultrafast charge delocalization times of conjugated polymers in the low-femtosecond regime. Density functional theory and time-dependent DFT methods were used to help understand some experimental observations. The results show that the homopolymer can improve the absorption spectra and the nonradiative-energy transfer from MDMO-PPV to PSiF-DBT and act as a photosensitizer in the copolymer units. In addition, the PSiF-DBT blended with MDMO-PPV exhibits a more organized structure than the neat material resulting in better absorption stability of films kept under continuous illumination.

Universal deformation pathways and flexural hardening of nanoscale 2D-material standing folds.

In the present work, we use atomic force microscopy nanomanipulation of 2D-material standing folds to investigate their mechanical deformation. Using graphene, h-BN and talc nanoscale wrinkles as testbeds, universal force-strain pathways are clearly uncovered and well-accounted for by an analytical model. Such universality further enables the investigation of each fold bending stiffness κ as a function of its characteristic height h 0. We observe a more than tenfold increase of κ as h 0 increases in the 10-100 nm range, with power-law behaviors of κ versus h 0 with exponents larger than unity for the three materials. This implies anomalous scaling of the mechanical responses of nano-objects made from these materials.

Dynamic negative compressibility of few-layer graphene, h-BN, and MoS2.

We report a novel mechanical response of few-layer graphene, h-BN, and MoS(2) to the simultaneous compression and shear by an atomic force microscope (AFM) tip. The response is characterized by the vertical expansion of these two-dimensional (2D) layered materials upon compression. Such effect is proportional to the applied load, leading to vertical strain values (opposite to the applied force) of up to 150%. The effect is null in the absence of shear, increases with tip velocity, and is anisotropic. It also has similar magnitudes in these solid lubricant materials (few-layer graphene, h-BN, and MoS(2)), but it is absent in single-layer graphene and in few-layer mica and Bi(2)Se(3). We propose a physical mechanism for the effect where the combined compressive and shear stresses from the tip induce dynamical wrinkling on the upper material layers, leading to the observed flake thickening. The new effect (and, therefore, the proposed wrinkling) is reversible in the three materials where it is observed.