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The novel synthesis route has been developed for hierarchically structured; nanorods and nanosheets of Sb4O5Cl2 from a single precursor, with dimension range between 57–90 nm. X-ray powder diffraction analysis confirmed the monoclinic crystal symmetry in P21/c(14)with structure type Sb4O5Cl2 for both forms; the nanorods and nanosheets. Rietveld refinements and crystallite size investigations of the powder patterns revealed significant enhancement in intensity with subtle variation in the lattice parameters and crystallite size decrease in case of nanosheets in comparison to the nanorods assembly. Through scanning electron microscopy, a composition commensurate to Sb4O5Cl2 at% with averaged dimensions; dia.∼90 nm, l ∼ 2 μm for nanorods and dia.∼50–150 nm for nanosheets got corroborated. Owing to the quantum confinement a band gap widening was observed while moving from bulk to nano regime, i.e. 3.25, 3.31 and 3.34 eV, for bulk, nanosheets, and nanorods, respectively. In the case of nanosheets, the highest value of dielectric constant was observed, i.e. 87, as compared to nanorods and the bulk, i.e. 40 and 35.5, respectively. The nanosheets also showed the highest value of dielectric and tangent loss with an increase in frequency due to the least crystallite size of these nanonetworks. Nanosheets depicted the higher AC conductivity at low frequency due to the alignment of the charges but its value decreases at the higher frequency due to lack of time for charge reorientation. The hopping phenomenon was observed in all three cases with the most prominent one in bulk case at higher frequencies.
In this work, two novel donor/acceptor (D/A) complexes, namely, diindenoperylene (DIP)/1,3,4,5,7,8-hexafluoro-tetracyanonaphthoquinodimethane (F6TCNNQ) and alpha-sexithiophene (6T)/F6TCNNQ, are studied. The D/A complexes segregate in form of π−π stacked D/A cocrystals and can be observed by X-ray scattering. The different conformational degrees of freedom of the donor molecules, respectively, seem to affect the thin-film crystalline texture and composition of the D/A mixtures significantly. In equimolar mixtures, for DIP/F6TCNNQ, the crystallites are mostly uniaxially oriented and homogeneous, whereas for 6T/F6TCNNQ, a mostly 3D (isotropic) orientation of the crystallites and coexistence of domains of pristine compounds and D/A complex, respectively, are observed. Using optical absorption spectroscopy, we observe for each of the two mixed systems a set of new, strong transitions located in the near-IR range below the gap of the pristine compounds: such transitions are related to charge-transfer (CT) interactions between donor and acceptor. The optical anisotropy of domains of the D/A complexes with associated new electronic states is studied by ellipsometry. We infer that the
CT-related transition dipole moment is perpendicular to the respective π-conjugated planes in the D/A complex.