Charge transport through alkane monolayers on gold is measured as a function of molecule length in a controlled ambient using a metal/molecule/nanoparticle bridge structure and compared for both thiol and amine molecular end groups. The current through molecules with an amine/gold junction is observed to be more than a factor of 10 larger than that measured in similar molecules with thiol/gold linkages. Conducting probe atomic force microscopy is also used to characterize the same monolayer systems, and the results are quantitatively consistent with those found in the nanoparticle bridge geometry. Scaling of the current with contact area is used to estimate that approximately 100 molecules are probed in the nanoparticle bridge geometry. For both molecular end groups, the room-temperature conductivity at low bias as a function of molecule length shows a reasonable fit to models of coherent nonresonant charge tunneling. The different conductivity is ascribed to differences in charge transfer and wave function mixing at the metal/molecule contact, including possible effects of amine group oxidation and molecular conformation. For the amine/Au contact, the nitrogen lone pair interaction with the gold results in a hybrid wave function directed along the molecule bond axis, whereas the thiol/Au contact leads to a more localized wave function.
Electrical conductance through conjugated biphenyl and saturated alkane molecules on gold electrodes is characterized using a molecule/nanoparticle/molecule electrical test-bed assembly, and comparisons are made between molecules containing isocyanide (-NC) and thiol (-S) terminal groups bound to the gold. Current versus voltage analysis is consistent with charge tunneling through all systems studied. For molecules containing biphenyl, diphenyl acetylene, and alkane bridges, those containing an isocyanide terminal group show an order of magnitude increase in conductance as compared to those containing a thiol terminal group. Various theoretical predictions of the effect of isocyanide terminal groups on charge transfer through conjugated molecular systems are discussed and related to the results observed for charge transfer through conjugated and saturated molecules. The similar trends in charge transport observed for the different metal/linker interfaces suggest that the metal/linker contact plays an important role in interface electronic structure, even when the molecules are expected to have very different electron delocalization across the backbone.
Nanoparticle/molecule/nanoparticle dimer assemblies have been successfully trapped by dielectrophoresis across nanogap electrodes, enabling temperature dependent charge transport measurements through an oligomeric phenylene ethynylene molecule, and transition from direct tunnelling to Fowler-Nordheim tunnelling is observed at approximately 1.5 V. Samples formed by dielectrophoresis show better contact stability than those formed by receding meniscus. The junction shows stable operation over several weeks in a vacuum, but current increases with time upon exposure to air, possibly due to the adsorbed water molecules near the molecule/gold nanoparticle contacts.
Phosphorescent and thermally activated delayed fluorescence (TADF) blue organic light-emitting diodes (OLEDs) have been developed to overcome the low efficiency of fluorescent OLEDs. However, device instability, originating from triplet excitons and polarons, limits blue OLED applications. Here, we develop a phosphor-sensitized TADF emission system with TADF emitters to achieve high efficiency and long operational lifetime. Peripheral carbazole moieties are introduced in conventional multi-resonance–type emitters containing one boron atom. The triplet exciton density of the TADF emitter is reduced by facilitating reverse intersystem crossing, and the Förster resonant energy transfer rate from phosphor sensitizer is enhanced by high absorption coefficient of the emitters. The emitter exhibited an operational lifetime of 72.9 hours with Commission Internationale de L’Eclairage chromaticity coordinate
y
= 0.165, which was 6.6 times longer than those of devices using conventional TADF emitters.
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