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Spatial properties of $pi-pi$ conjugated network in semicrystalline polymer thin films studied by intensity x-ray cross-correlation functions

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 Added by Ivan Vartaniants
 Publication date 2013
  fields Physics
and research's language is English




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We present results of x-ray study of spatial properties of $pi-pi$ conjugated networks in polymer thin films. We applied the x-ray cross-correlation analysis to x-ray scattering data from blends of poly(3-hexylthiophene) (P3HT) and gold nanoparticles. The Fourier spectra of the intensity cross-correlation functions for different films contain non-zero components of orders $n=2,4$ and $6$ measuring the degree of structural order in the system.

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A microscopic theory of the transport in a scanning tunnelling microscope (STM) set-up is introduced for pi-conjugated molecules on insulating films, based on the density matrix formalism. A key role is played in the theory by the energy dependent tunnelling rates which account for the coupling of the molecule to the tip and to the substrate. In particular, we analyze how the geometrical differences between the localized tip and extended substrate are encoded in the tunnelling rate and influence the transport characteristics. Finally, using benzene as an example of a planar, rotationally symmetric molecule, we calculate the STM current voltage characteristics and current maps and analyze them in terms of few relevant angular momentum channels.
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Electric fields are central to the operation of optoelectronic devices based on conjugated polymers since they drive the recombination of electrons and holes to excitons in organic light-emitting diodes but are also responsible for the dissociation of excitons in solar cells. One way to track the microscopic effect of electric fields on charge carriers formed under illumination of a polymer film is to exploit the fluorescence arising from delayed recombination of carrier pairs, a process which is fundamentally spin dependent. Such spin-dependent recombination can be probed directly in fluorescence, by optically detected magnetic resonance (ODMR). Depending on the relative orientation, an electric field may either dissociate or stabilize an electron-hole carrier pair. We find that the ODMR signal in a polymer film is quenched in an electric field, but that, at fields exceeding 1 MV/cm, this quenching saturates. This finding contrasts the complete ODMR suppression that was previously observed in polymeric photodiodes, indicating that exciton-charge interactions---analogous to Auger recombination in crystalline semiconductors---may constitute the dominant carrier-pair dissociation process in organic electronics.
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