A new homologous series of semi-conducting liquid crystals based on phenyl-anthracene: synthesis and effect of the alkyloxy terminal chain on charge transport and photoconductive properties.

π-Conjugated systems are the key to the charge transport properties of organic semiconductors. Four multifunctional mesogenic materials were designed and synthesised from 2-amino anthracene and para-hydroxybenzaldehyde. Each material contains a central, rigid phenyl-anthracene core and one flexible alkyloxy chain with different lengths based on the concept of combining liquid crystal (LC) materials featuring facile processability, highly ordered alignment, and effective charge transport. (E)-N-(Anthracen-2-yl)-1-(4-(alkyloxy)phenyl) methanimine (n-OPIA) with n = 8, 10, 12, and 16 was chemically characterized by nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Their thermal behaviours were performed by means of differential scanning calorimetry and polarised optical microscopy and showed differences in mesomorphic behaviours with respect to the alkyloxy chain length. Concerning their frontier molecular energy levels, they were studied by optical spectroscopy and cyclic voltammetry and compared to values obtained via ab initio density-functional theory (DFT) calculations. LC field-effect transistors (LC-FETs) using a solvent vapour enhanced drop casting based n-OPIA material showed efficient electrical parameters and interesting photoconductive properties, indicating their potential applications in multifunctional integrated devices. As the alkyloxy chain length of the n-OPIA compounds increased, the hole mobility, on/off current ratio, and responsivity decreased. The 8-OPIA homologue exhibits a mobility one order of magnitude larger than the previously studied homologue, namely 10-OPIA.

Novel organic semiconductors based on 2-amino-anthracene: Synthesis, charge transport and photo-conductive properties.

Anthracene is considered to be a popular choice as a building block for organic semiconductors. The present work is dedicated to the synthesis and characterization of a novel semiconductor (10-OPIA) possessing mesogenic properties, which allows better control over charge transport in the bulk of a material. A novel anthracene-based molecule is characterized for its potential applications: frontier molecular energy levels are studied by optical spectroscopy and cyclic voltammetry and compared to values obtained via ab initio calculations. Thermophysical and mesogenic properties are investigated by optical microscopy and differential scanning calorimetry. Charge transport properties are characterized by means of an OFET device. It is found that this material can be easily aligned and exhibits a field effect hole mobility of 5.22 × 10-5 cm2 V-1 s-1 and an ON/OFF ratio of 104 in the device prepared by drop casting. Finally, the photoconductive properties of this novel material are addressed in order to investigate its potential applications for organic phototransistors: it exhibits a large photoconductive gain of >100 and a photo-responsivity of >1 A W-1.

Molecular p-doping in organic liquid crystalline semiconductors: influence of the charge transfer complex on the properties of mesophase and bulk charge transport.

We explore the molecular nature of doping in organic semiconductors (OSCs) by employing a liquid crystalline organic semiconductor based on phenyl naphthalene as a model. The mesophase nature of composites that include a charge transfer complex (CTC) between the OSC (8-PNP-O12) and an electron acceptor (F4TCNQ) has been investigated by means of differential scanning calorimetry, polarized optical microscopy and X-ray scattering. Optical and vibrational spectroscopies allow us to explore the characteristics and the amount of charge transfer in the CTC and expose some properties that appear only in the complexed state. We have found this system to exhibit partial charge transfer, which manifests itself in all the phase states of the host 8-PNP-O12, as well as in solution. Due to the lowering of molecular symmetry as a result of the charge transfer, one of the previously IR-only vibrational bands of the nitrile group is found to be now active in the Raman spectrum. We have also made an attempt to further investigate the influence of dopant introduction on the bulk hole mobility of 8-PNP-O12. It is found that the presence of the CTC promotes the hole transport in the Smectic B mesophase, however it seems to have a somewhat negative influence in the less ordered smectic A mesophase. This work aims to establish the link between the inevitable change of molecular geometry that occurs on charge transfer with the results obtained by spectroscopic techniques and electronic charge carrier mobility measurements.

Ionic transport in nematic liquid crystals and alignment layer effects on electrode polarization.

The physical properties of a liquid crystal-ionic liquid system were investigated. Low-frequency dielectric spectroscopy for 4-cyano-4'-pentylbiphenyl (5CB) doped with 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF 4) for the nematic and isotropic phase of host substances was performed. We obtained electrical conductivity values in the range from 298.2 K to 313.2 K and the conductivity anisotropy was confirmed. Further study of the relaxation process for bmim + allowed us to extract the relaxation frequencies and amplitudes from experimental data and confirm the temperature scaling; the thickness of the interfacial layers was estimated for the homogeneous and homeotropic alignments of the prepared composite. An attempt to unfold the ion contribution on the charge transport was made in order to better understand the electrode polarization process. In this work, the influence of the alignment layer and phase state on the interfacial layer formation in liquid crystal media will be explained better.