Working Group of Electronic Phenomena

Research Staff Papers Collaboration PhD
studies
Equipment

Head: Jiří Pfleger , Ph.D
(phone +420-2-22514610, e-mail pfleger @imc.cas.cz)

Research Activities

Research activities are focused on studies of photo- and electroactive polymers and their low-molecular-weight analogues. Physical phenomena, such as electrical conductivity, photoconductivity, photochromism, photorefractivity, electroluminescence, as well as injection, generation, recombination, and transport of charge carriers are investigated in dependence on the chemical structure of the materials. Both p - and s -conjugated polymers are studied. Understanding the processes associated with photon absorption and emission, like photoexcitation, excited state dynamics, photoinduced electron transfer, changes in molecular conformations, dissociation and recombination of ion-pairs allowed to determine basic principles of designing organic solar cells. The transport of free charge carriers and polarons are studied on polymer photoconductors and structures of organic FET transistors.

Electron structure and conformation of molecules were studied also theoretically by ab initio and semiempirical quantum chemical methods. Attention was paid to the formation of quasiparticle conformational defects (polarons, bipolarons and excitons) upon photoexcitation and charge injection. Photostabilization studies were focused on various polymer systems with photoactive impurities like transformation products of stabilizers or sensitizing dopands and/or photoactive built-in functional moieties. Details of photochemical and photophysical activity mechanisms for various classes of light stabilizers were elucidated to minimize depleting effects of the photoactive polymeric matrix. Experimental work was supported by theoretical studies and quantum chemical calculations of exciton-phonon coupling and vibrationally induced energy dissipation.

Recently, new methods of the synthesis of p -conjugated polymers such as the Stile coupling, were tested with positive results. Further, new types of polysilanes were synthesized and their electronic properties, mainly the influence of polar side groups on the charge carrier transport were studied. Light excitation induces several photophysical and photochemical changes on the surface of polymer films, e.g. Si-Si bond cleavage, formation of siloxane structures, formation of ion-pairs with long lifetime and of new local electron states, which were studied by means of the orientation of liquid-crystalline structures deposited on the polymer surface, thermostimulated luminescence and photoluminescence. Degradation fragments influence the visible photoluminescence. This effect was studied in detail on model poly[methyl(phenyl)silanediyl] (PMPSi), especially in connection with the metastability and reversibility of bond and electron structure. Photoluminescence in visible region was found to be also influenced by the dimensionality of Si skeletons. Two- and three-dimensional structures increased the photoluminescence in the spectral region of 480-600 nm, as it was shown on materials prepared by plasma polymerization. In this context a possibility of long-term stabilization of polymers sensitive to photodegradation (polymers with increased contents of chromophores) with light stabilizers from the group of phenolic UV absorbers was studied. In the light, excitation of polysilanes, photoinduced electron transfer from the main Si chain to p -conjugated side groups and the formation of positive polarons was detected. The conformation and electron structure of these polarons were studied by quantum chemical calculations. Experimentally, the photoinduced charge transfer was modelled using a double layer structure phthalocyanine - tetracyano-1,4-quinodimethane. Phthalocyanine was further used for the construction of FET transistors; possible use of the space-charge-limited-current method for the study of charge injection, which is important for the construction of electroluminescence diodes, was examined on phthalocyanine thin films. During the injection of a hole to the Pc molecule, a positive polaron was formed. It was found that on NiPc a singlet polaron was formed, whereas on CoPc a triplet polaron arose. The changes of IR spectra associated with the oxidation were found to be independent of the polaron multiplicity.

Institute of Macromolecular Chemistry AS CR, v.v.i.
Heyrovského nám. 2
CZ-162 06 Praha 6
Czech Republic
phone:+420 296 809 111
fax:+420 296 809 410

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