Structural phase transition in pentacene caused by molecular doping and its effect on charge carrier mobility

The structural properties and charge carrier mobility of pentacene doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) and 2,2-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) are studied by X-ray diffraction, scanning electron microscopy, field effect transistor measurements, and space charge limited currents (SCLC). We observe the presence of polycrystalline and amorphous domains within the doped pentacene film grown under co-deposition conditions. The appearance of the amorphous phase is induced by the molecular dopants F4-TCNQ and F6-TCNNQ. A strong drop of crystallite size is obtained at a doping concentration of around 7 and 4 wt.%, respectively. The loss of the polycrystalline structure is correlated to a strong decrease of the charge carrier mobility in pentacene in horizontal and vertical film structures. We discuss typical scenarios of charge transport for polycrystalline and amorphous thin films in order to explain the observed loss of mobility originated by the doping induced structural phase transition. In this way an optimum doping concentration for highest conductivity with acceptable mobility is determined which can help to improve the performance of organic solar cells and organic high-frequency rectification diodes.

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► We investigate structural and electronic properties of molecular doped pentacene.
► We employ two strong acceptor materials F4-TCNQ and F6-TCNNQ.
► We reveal a structural phase transition for doping ratios above 4 wt.%.
► The structural transition is correlated to a strong loss in charge carrier mobility.
► Different scenarios of charge carrier transport are discussed for explanation.