Charge transport in a zinc–porphyrin single-molecule junction (original) (raw)
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Charge Transport in a Zn-Porphyrin single molecule junction
2011
We have investigated charge transport in ZnTPPdT-Pyr molecular junctions using the lithographic MCBJ technique at room temperature and cryogenic temperature (6K). We combined low-bias statistical measurements with spectroscopy of the molecular levels using I(V) characteristics. This combination allows us to characterize the transport in a molecular junction in detail. This complex molecule can form different junction configurations, which is observed in trace histograms and in current-voltage (I(V)) measurements. Both methods show that multiple stable single-molecule junction configurations can be obtained by modulating the inter-electrode distance. In addition we demonstrate that different ZnTPPdT-Pyr junction configurations can lead to completely different spectroscopic features with the same conductance values. We show that statistical low-bias conductance measurements should be interpreted with care, and that the combination with I(V) spectroscopy represents an essential tool for a more detailed characterization of the charge transport in a single molecule.
2011
Porphyrin molecules can form stable single molecule junctions without anchoring groups. Adding thiol end groups and pyridine axial groups yields more stable junctions with an increased spread in low-bias conductance. This is a result of different bridging geometries during breaking, the stability of which is demonstrated in time-dependent conductance measurements. This is in strong contrast with rod like molecules which show one preferential binding geometry.
Charge injection and transport in tetra-phenyl-porphyrin
Synthetic Metals, 2003
The analysis of charge injection and transport in 5,10,15,20-tetra-phenyl-phorphyrin (H 2-TPP) has been analysed by I(V, T) measurements in the 50-350 K range. Different metals have been used to study the influence of the metal/organic interface on the transport properties. Organic films have been deposited by spray coating and organic molecular beam deposition (OMBD). The observed results show ohmic transport at each temperature for thin films deposited by both the techniques. Two injection mechanisms have been evidenced: thermionic emission over a barrier independent of the metal contact for T > 250 K and tunnel effect at the lower temperatures. On the other hand, a different behaviour has been evidenced on thick films deposited by spray coating. Here, the dark current as a function of the applied voltage increases linearly at the low electric fields independent of the metal contact and shows the same temperature dependence observed for thinner films. At high voltage a non-linear field dependent transport mechanism has been seen. Moreover, the tunnelling contribution to the current increases with the metal work function. The observed trends have been analysed on the basis of injection limited transport in organic amorphous semiconductors. The resistance of interface states and deposition induced defects are considered to discuss the applicability of the Anderson principle for band alignment and justify the observed results.
Electronic transport through tape-porphyrin molecular bridges
Thin Solid Films, 2004
We investigated theoretically how molecular conjugation affects current-voltage (I-V) curves through three types of oligoporphyrin molecules, i.e., the tape-porphyrin, the butadiyne-linked porphyrin, and the edge-fused porphyrin molecules. Among these, the tapeporphyrin molecule is found to be the most conductive due to its extremely small HOMO-LUMO energy gap. Furthermore, the I-V curves through this type of molecule are found to depend considerably on atomic sites to which electrodes are connected. In particular, as long as the applied bias is weak, the current is found to flow strongest when both electrodes are connected to the atomic sites referred to as meso sites. This feature is caused by the fact that the HOMO relevant to resonant tunneling has a higher charge density on the meso sites. These findings indicate that designing not only molecules but also contact structures is highly significant for realizing a desirable function in single molecular devices.
Long-range electron tunnelling in oligo-porphyrin molecular wires
Nature nanotechnology, 2011
Short chains of porphyrin molecules can mediate electron transport over distances as long as 5-10 nm with low attenuation. This means that porphyrin-based molecular wires could be useful in nanoelectronic and photovoltaic devices, but the mechanisms responsible for charge transport in single oligo-porphyrin wires have not yet been established. Here, based on electrical measurements of single-molecule junctions, we show that the conductance of the oligo-porphyrin wires has a strong dependence on temperature, and a weak dependence on the length of the wire. Although it is widely accepted that such behaviour is a signature of a thermally assisted incoherent (hopping) mechanism, density functional theory calculations and an accompanying analytical model strongly suggest that the observed temperature and length dependence is consistent with phase-coherent tunnelling through the whole molecular junction.
SI- Physical Chemistry Chemical Physics, 2016
In contrast with conventional single-molecule junctions, in which the current flows parallel to the long axis or plane of a molecule, we investigate the transport properties of M(II)-5,15-diphenylporphyrin (M-DPP) single-molecule junctions (M=Co, Ni, Cu, or Zn divalent metal ions), in which the current flows perpendicular to the plane of the porphyrin. Novel STM-based conductance measurements combined with quantum transport calculations demonstrate that current-perpendicular-to-the-plane (CPP) junctions have three-orders-of-magnitude higher electrical conductances than their current-in-plane (CIP) counterparts, ranging from 2.10−2 G0 for Ni-DPP up to 8.10−2 G0 for Zn-DPP. The metal ion in the center of the DPP skeletons is strongly coordinated with the nitrogens of the pyridyl coated electrodes, with a binding energy that is sensitive to the choice of metal ion. We find that the binding energies of Zn-DPP and Co-DPP are significantly higher than those of Ni-DPP and Cu-DPP. Therefore when combined with its higher conductance, we identify Zn-DPP as the favoured candidate for high-conductance CPP single-molecule devices.
Conductive-probe measurements with nanodots of free-base and metallated porphyrins
Journal of Colloid and Interface Science, 2017
The conductive properties of nanodots of model porphyrins were investigated using conductive-probe atomic force microscopy (CP-AFM). Porphyrins provide excellent models for preparing surface structures that can potentially be used as building blocks for devices. The conjugated, planar structure of porphyrins offers opportunities for tailoring the electronic properties. Two model porphyrins were selected for studies, 5,10,15,20tetraphenyl-21H,23H-porphine cobalt(II) (TPC) and its metal-free analog 5,10,15,20tetraphenyl-21H,23H-porphine (TPP). Nanodots of TPP and TPC were prepared within a dodecanethiol resist on gold using particle lithography. The nanopatterned surfaces exhibit millions of reproducible test structures of porphyrin nanodots. The porphyrin nanodots have slight differences in dimensions at the nanoscale, to enable size-dependent measurements of conductive properties. The size of the nanodots corresponds to ~ 5-7 layers of porphyrin. The conductivity along the vertical direction of the nanodots was measured by applying a bias voltage between the gold surface and a metal-coated AFM cantilever. The TPP nanodots exhibited semi-conductive profiles while the TPC nanodots exhibited profiles that are typical of a conductive film or molecular wire. The engineered nanostructures of porphyrins provide an effective platform for investigation and measurement of conductive properties.