From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo(p-phenylene ethynylene)s

The charge transport mechanism of oligo(p-phenylene ethynylene)s with lengths ranging from 0.98 to 5.11 nm was investigated using modified scanning tunneling microscopy break junction and conducting probe atomic force microscopy methods. The methods were based on observing the length dependence of molecular resistance at single molecule level and the current-voltage characteristics in a wide length distribution. An intrinsic transition from tunneling to hopping charge transport mechanism was observed near 2.75 nm. A new transitional zone was observed in the long length molecular wires compared to short ones. This was not a simple transition between direct tunneling and field emission, which may provide new insights into transport mechanism investigations. Theoretical calculations provided an essential explanation for these phenomena in terms of molecular electronic structures.

Polymerization of 1,3-butadiene with VO(P-204)(2) and VO(P-507)(2) activated by alkylaluminum

The oxovanadium phosphonates (VO(P-204)(2) and VO(P-507)(2)) activated by various alkylaluminums (AlR3, R = Et, i-Bu, n-Oct; HAIR(2), R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P-204)(2) and VO(P-507)(2) showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl3, V(acac)(3)). Among the examined catalysts, the VO(P-204)(2)/Al(Oct)(3) system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M-n of 3.76 x 10(4) g/mol, and M-w/M-n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 degrees C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 degrees C (polymer yield > 33%); the M-n value and M-w/M-n, ratio were independent of polymerization temperature in the range of 40-70 degrees C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (> 65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.

n-channel, ambipolar, and p-channel organic heterojunction transistors fabricated with various film morphologies

The relationship between the performance characteristics of organic field-effect transistors (OFETs) with 2,5-bis(4-biphenylyl)-bithiophene/copper hexadecafluorophthalocyanine (BP2T/F16CuPc) heterojunctions and the thickness of the BP2T bottom layer is investigated. Three operating modes (n-channel, ambipolar, and p-channel) are obtained by varying the thickness of the organic semiconductor layer. The changes in operating mode are attributable to the morphology of the film and the hetero-junction effect, which also leads to an evolution of the field-effect mobility with increasing film thickness. In BP2T/F16CuPc heterojunctions the mobile charge carriers accumulate at both sides of the heterojunction interface, with an accumulation layer thickness of ca. 10 nm. High field-effect mobility values can be achieved in continuous and flat films that exhibit the heterojunction effect.