Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s

The absorption and emission spectra of most luminescent, pi-conjugated, organic molecules are the mirror image of each other. In some cases, however, this symmetry is severely broken. In the present work, the asymmetry between the absorption and fluorescence spectra in molecular systems consisting of para-linked phenyl rings is studied. The vibronic structure of the emission and absorption bands is calculated from ab-initio quantum chemical methods and a subsequent, rigorous Franck-Condon treatment. Good agreement with experiment is achieved. A clear relation can be established between the strongly anharmonic double-well potential for the phenylene ring librations around the long molecular axis and the observed deviation from the mirror image symmetry. Consequences for related compounds and temperature dependent optical measurements are also discussed.Comment: 12 pages, 13 Figure

Probing Crystallinity and Grain Structure of 2D Materials and 2D-Like Van der Waals Heterostructures by Low-Voltage Electron Diffraction

4D scanning transmission electron microscopy (4D-STEM) is a powerful method for characterizing electron-transparent samples with down to sub-Ångstrom spatial resolution. 4D-STEM can reveal local crystallinity, orientation, grain size, strain, and many more sample properties by rastering a convergent electron beam over a sample area and acquiring a transmission diffraction pattern (DP) at each scan position. These patterns are rich in information about the atomic structure of the probed volume, making this technique a potent tool to characterize even inhomogeneous samples. 4D-STEM can also be used in scanning electron microscopes (SEMs) by placing an electron-sensitive camera below the sample. 4D-STEM-in-SEMs is ideally suited to characterize 2D materials and 2D-like van der Waals heterostructures (vdWH) due to their inherent thickness of a few nanometers. The lower accelerating voltage of SEMs leads to strong scattering even from monolayers. The large field of view and down to sub-nm spatial resolution of SEMs are ideal to map properties of the different constituents of 2D-like vdWH by probing their combined sample volume. A unique 4D-STEM-in-SEM system is applied to reveal the single crystallinity of MoS2 exfoliated with gold-mediation as well as the crystal orientation and coverage of both components of a C60/MoS2 vdWH are determined

Deep blue polymer light emitting diodes based on easy to synthesize, non-aggregating polypyrene

Thorough analyses of the photo- and devicephysics of poly-7-tert-butyl-1,3-pyrenylene (PPyr) by the means of absorption and photoluminescence emission, time resolved photoluminescence and photoinduced absorption spectroscopy as well as organic light emitting devices (OLEDs) are presented in this contribution. Thereby we find that this novel class of polymers shows deep blue light emission as required for OLEDs and does not exhibit excimer or aggregate emission when processed from solvents with low polarity. Moreover the decay dynamics of the compound is found to be comparable to that of well blue emitting conjugated polymers such as polyfluorene. OLEDs built in an improved device assembly show stable bright blue emission for the PPyr homopolymer and further a considerable efficiency enhancement can be demonstrated using a triphenylamine(TPA)/pyrene copolymer. (C) 2011 Optical Society of Americ

Emission properties of pristine and oxidatively degraded polyfluorene type polymers

We present a detailed and comprehensive picture of the photophysics including device applications within the polyfluorene family of conjugated polymers. First, the photophysics of pristine polyfluorenes in solution and film is outlined, including a discussion of the so-called β-phase, which is characterised by a more planar ground state configuration. Particular attention is also dedicated to the occurence of low energy emission bands, which often deteriorate the initially blue emission of polyfluorenes, especially in electroluminescent devices. Although the origin of these emission features has been the object of a controversial discussion, strong evidence for our current ascription to emissive on-chain fluorenone defects is given also in contrast to previous assignments to aggregates, excimers, or exciplexes. According to the current attribution fluorenone-containing polyfluorenes can be described as a guest host system. Following this picture the photoexcitation dynamics from the fs to the ms regime is outlined. Finally, polymer light emitting diodes (PLEDs) based on polyfluorene-type emitters are discussed, especially related to their degradation mechanisms and possible remedies provided by chemistry to reduce the oxidative degradation of polyfluorene-based PLEDs. © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim