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Zeljko Tomović

Publications and source records attributed to Zeljko Tomović.

6 recordsLinked to original sources

High anisotropy of the field-effect transistor mobility in magnetically aligned discotic liquid-crystalline semiconductors.

A magnetic field has been utilized for producing highly oriented films of a substituted hexabenzocoronene (HBC). Optical microscopy studies revealed large area HBC monodomains that covered the entire film, while wide-angle X-ray measurements showed that the HBC molecules are aligned with their planes along the applied field. On the basis of this method, solution-processed field-effect transistors (FET) have been constructed with charge carrier mobilities of up to 10(-3) cm2/V.s, which are significantly enhanced with respect to the unaligned material. Exceptionally high mobility anisotropies of 25-75 for current flow parallel and perpendicular to the alignment direction have been measured as a function of the channel length. Atomic force microscopy performed on the FET structures reveals fibril superstructures that are oriented perpendicularly to the magnetic field direction, consisting of molecular columns with a slippage angle of 40 degrees between the molecules. For channel lengths larger than 2.5 mum, the fibrils are smaller than the electrode spacing, which adversely affects the device performance.

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Influence of molecular order on the local work function of nanographene architectures: a Kelvin-probe force microscopy study.

We report a Kelvin-probe force microscopy (KPFM) investigation on the structural and electronic properties of different submicron-scale supramolecular architectures of a synthetic nanographene, including extended layers, percolated networks and broken patterns grown from solutions at surfaces. This study made it possible to determine the local work function (WF) of the different pi-conjugated nanostructures adsorbed on mica with a resolution below 10 nm and 0.05 eV. It revealed that the WF strongly depends on the local molecular order at the surface, in particular on the delocalization of electrons in the pi-states, on the molecular orientation at surfaces, on the molecular packing density, on the presence of defects in the film and on the different conformations of the aliphatic peripheral chains that might cover the conjugated core. These results were confirmed by comparing the KPFM-estimated local WF of layers supported on mica, where the molecules are preferentially packed edge-on on the substrate, with the ultraviolet photoelectron spectroscopy microscopically measured WF of layers adsorbed on graphite, where the molecules should tend to assemble face-on at the surface. It appears that local WF studies are of paramount importance for understanding the electronic properties of active organic nanostructures, being therefore fundamental for the building of high-performance organic electronic devices, including field-effect transistors, light-emitting diodes and solar cells.

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From branched hydrocarbon propellers to C3-symmetric graphite disks.

Branched hydrocarbon propellers (9 and 12) were prepared by stepwise palladium-catalyzed Hagihara-Sonogashira coupling reactions and Diels-Alder cycloadditions and submitted to oxidative cyclodehydrogenation by FeCl3 to afford two new giant graphite disks 2 and 3 with 3-fold symmetry in high yield. One of the precursors, the polyphenylene dendrimer 9 containing 150 carbon atoms, was crystallographically characterized. The poorly soluble graphite disks were characterized by isotope-resolved MALDI-TOF mass spectroscopy, and their electronic and vibrational properties were investigated by solid-state UV-vis and Raman spectroscopy. The effect of molecular size and geometry on their properties was discussed. The molecule 2 represents the largest, 3-fold-symmetric all-benzenoid graphite disk, and the five-membered rings in molecule 3 open the opportunity to synthesize large bowl-shaped PAHs.

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Graphitic molecules with partial "zig/zag" periphery.

A new synthetic protocol that affords novel hexa-peri-hexabenzocoronene (HBC) derivatives with partial "zig/zag" periphery and dramatically different electronic properties has been developed, which represents an important step toward understanding structure-property relationships of graphitic materials. The scope of this methodology was broadened by application to a much larger polycyclic aromatic hydrocarbon (PAH) with a more extended "zig/zag" character.

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The optical and charge transport properties of discotic materials with large aromatic hydrocarbon cores.

The optical absorption and charge transport properties of a series of discotic molecules consisting of peripherally alkyl-substituted polycyclic aromatic cores have been investigated for core sizes, n, of 24, 42, 60, 78, 96, and 132 carbon atoms. In dilute solution, the wavelength maximum of the first absorption band increases linearly with n according to lambda(max) = 280 + 2n and the spectral features become increasingly broadened. The two smallest core compounds display a slight red-shift and increased spectral broadening in spin-coated films. For derivatives with n = 24, 42, 60, and 96, the one-dimensional, intracolumnar charge mobility, Sigma mu(1D), was determined using the pulse-radiolysis time-resolved microwave conductivity technique. For the compounds which were crystalline solids at room temperature, Sigma mu(1D) lay within the range 0.4-1.0 cm(2)/Vs. In the discotic mesophases at ca. 100 degrees C, Sigma mu(1D) was somewhat lower and varied from 0.08 to 0.38 cm(2)/Vs. The mobility values in both phases are considerably larger than the maximum values found previously for discotic triphenylene derivatives. However, the recently proposed trend toward increasing mobility with increasing core size is not substantiated by the results on the present series of increasingly large aromatic core compounds.

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