Fluorinated phthalocyanines as molecular semiconductor thin films

Abstract

Thin films of perfluorinated phthalocyanines F16Pc show promise as molecular semiconductors in organic field effect transistors. A review is provided of growth studies and electrical characterization of presently discussed materials. Using this state‐of‐the‐art as a starting point the synthesis and position of energy levels of partly fluorinated Zn(II) phthalocyanines is described. Growth characteristics of vapour‐deposited thin films on inorganic and organic dielectrics are studied. Possibilities to use fluorinated phthalocyanines in technical applications of OFET are discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Copper-phthalocyanine based metal–organic interfaces: The effect of fluorination, the substrate, and its symmetry

“…37 Previous work reported the disappearance of the Au(111) herringbone reconstruction under the F 16 CuPc monolayers. 26 However, higher quality STM measurements have now proven the opposite, revealing the substrate reconstruction under the organic overlayer with an fcc/hcp periodicity measured along the [1][2][3][4][5][6][7][8][9][10] direction of 65 ± 3 Å, thus virtually unchanged with respect to the pristine Au(111). While this could be interpreted as the result of very weak molecule-substrate interactions, 31 the reported disappearance of the Au(111) surface state upon F 16 CuPc adsorption, as measured by valence band photoelectron spectroscopy, 26 still supports the picture of a significant interaction.…”

“…31,38 CuPc on Au(111) leads to the growth of crystalline layers characterized by a square unit cell of dimensions a = 13.9 ± 0.7 Å, and it hardly affects the underlying Au(111) surface reconstruction. 30,39 The unit cell vectors are directed along the high symmetry and [1][2][3][4][5][6][7][8][9][10] directions (Fig. 4).…”

“…1). 7,8 As a consequence, perfluorinated copperphthalocyanine (F 16 CuPc, Fig. 1) presents a preferred acceptor behavior and has shown remarkable performance in devices as n-type semiconductor.…”

Practical Applications of Phthalocyanines – from Dyes and Pigments to Materials for Optical, Electronic and Photo-electronic Devices

“…Therefore it is better to employ metal acetates such as zinc(II) acetate. For purer products milder reaction conditions are necessary: reactions of phthalonitiles in high boiling alcoholes in the presence of Li alcoholates or in the presence of 1,8-diazabicyclo[5.4.0] undec-7-en (DBU) and then addition of metal acetates; 5 to 10 min batch reaction of 3 with metal acetates in a microwave oven (several publications exist, and only few references from the authors work are given [3,4] [5] The yields of Pcs are often >70%. It should be mentioned that the formation of CuPc from 3 with Cu is highly exothermic with an enthalpy of AH = -830 kJ mol -1 (driving force is formation of a new aromatic system!).…”

“…[1,2] The reaction is carried out in the melt or in a solvent at 120 to 220 °C. [3] If, for example, CuCl 2 is used in the reaction with 3, two electrons are needed to get the dianionic ligand which are available through the oxidation of 2Cl -to Cl 2 . A disadvantage may be here that Cl 2 acts as electrophile in an aromatic substitution causing partially chlorinated products.…”