Evaporated organic films of tetrathiafulvalene and related materials

Abstract

This thesis describes the design, construction and application of a novel vacuum system for the preparation of thin films of organic charge-transfer compounds. The method of thermal evaporation was used for four materials: tetrathiafulvalene (TTF) and three of its derivatives, dimethyltetrathiafiilvalene (DiMe-TTF), trimethyltetrathiafiilvalene (TriMe-TTF) and bis(ethylenedithio)tetrathiafiilvalene (BEDT-TTF). The resulting thin layers were characterised using optical and electron microscopy, infrared/visible spectroscopy and dc conductivity measurements down to 77K.Thin films of tetrathiafulvalene, after doping with iodine, exhibited a maximum value of dc, in-plane room temperature conductivity σ of 8.0+2.4 S cm(^-1). Semiconducting behaviour was exhibited over the range 77-300 K with AE = 0.09+0.02 eV. The effect of the deposition rate on fihn morphology is reported. TTF iodide layers were also prepared by co- evaporating the two components. These films exhibited a maximum conductivity of 2.9+0.4 S cm(^-1) at room temperature. Again, semiconducting behaviour was noted over the range 77- 300 K with AE = 0.2+0.02 eV. A comparison of the optical, structural and electrical properties of the two types of films is made. DiMe-TTF and TriMe-TTF thin films were also successfully prepared. Doping with iodine resulted in in-plane, dc room temperature conductivities of 10(^-6) and 10(^-7) S cm(^-1), respectively. These values, together with data from optical spectroscopy, suggested that both salts were in the full charge-transfer state. (BEDT-TTF) iodide thin films were deposited by evaporating the organic compound and subsequent doping. Doped films possessed a dc, in-plane room temperature conductivity of 10(^-3) S cm(^-1).Annealing these layers at 60ºC resulted in an increase in conductivity with a final value of 1.6 S cm(^-1). Semiconducting behaviour over the range 77-300 K was exhibited by the annealed films (ΔE = 0.028 eV).Finally, thin film transistors, incorporating TTF and BEDT-TTF doped layers, were fabricated and their electrical characteristics measured.