• Journal of the Korean Chemical Society
• /
• v.59 no.1
• /
• pp.18-21
• /
• 2015

We use a scanning tunneling microscope based break-junction technique to measure the conductance of a 4,4'-dimethoxybiphenyl molecular junction formed with Ag and Au electrodes. We observe the formation of a clear molecular junction with Ag electrodes that result from stable Ag-oxygen bonding structures. However we have no molecular bonding formation when using Au electrodes, resulting in a tunneling current between the top and bottom metal electrodes. We also see a clear peak in the conductance histogram of the Ag-oxygen molecular junctions, but no significant molecular features are seen with Au electrodes. Our work should open a new path to the conductance measurements of single-molecule junctions with oxygen linkers.

• Journal of the Korean Chemical Society
• /
• v.58 no.6
• /
• pp.513-516
• /
• 2014

We measure the conductance of a 4,4'-diaminobiphenyl formed with Ni electrodes using a scanning tunneling microscope-based break-junction technique. For comparison, we use Au or Ag electrodes to form a metal-molecular junction. For molecules that conduct through the highest occupied molecular orbital, junctions formed with Ni show similar conductance as Au and are more conductive than those formed with Ag, consistent with the higher work function for Ni or Au. Furthermore, we observe that the measured molecular junction length that is formed with the Ni or Au electrodes was shorter than that formed with the Ag electrodes. These observations are attributed to a larger gap distance of the Ni or Au electrodes compared to that of the Ag electrodes after the metal contact ruptures. Since our work allows us to measure the conductance of a molecule formed with various electrodes, it should be relevant to molecular electronics with versatile materials.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2014.02a
• /
• pp.184.2-184.2
• /
• 2014

Recent advances in the synthesis and characterization of nanoscale objects provided us with the atomistic understanding of charge transport through single molecular junctions. The representative examples are the mechanically controlled break junction technique and STM or conducting AFM junction techniques. Theoretical studies have been reported on the dependence of electronic charge transport on the geometry of molecule-electrode contacts, the critical element toward the realization of molecular electronics. In this report, we will clarify the puzzling discrepancies between theoretical predictions and experiments.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.654-654
• /
• 2013

One of the most important yet unresolved problems in molecular electronics is the controversy over the number and nature of multiple conductance peaks in single-molecule junctions. Currently, there are three competing explanations of this observation: (1) manifestation of different molecule-electrode contact geometries, (2) formation of gauche defects within the molecular core, (3) involvement of different electrode surface orientations [1]. However, the exact origin of multiple conductance peaks is not yet fully understood, which indicates our incomplete understanding of the scientifically as well as techno-logically important organic-metal contacts. To theoretically resolve this problem, we previously applied a multiscale computational approach that combines force fields molecular dynamics (FF MD), density functional theory (DFT), and matrix Green's function (MGF) calculations [2] to a thermally fluctuating haxanedithiol (C6DT) molecule stretched between flat Au(111) electrodes, but could observe only a single conductance peak [3]. In this presentation, using DFT geometry optimizations and MGF calculations, we consider molecular junctions with more realistic molecule-metal contact conformations and Au(111) electrode surface directions. We also conduct DFT-based molecular dynamics for the highly stretched junction models to confirm our conclusion. We conclude that the S-Au coordination number should be the more dominant factor than the electrode surface orientation.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2014.02a
• /
• pp.415.1-415.1
• /
• 2014

Carrying out first-principles calculations, we study N-doped capped carbon nanotube (CNT) electrodes applied to DNA sequencing. While we obtain for the face-on nucleobase junction configurations a conventional conductance ordering where the largest signal results from guanine according to its high highest occupied molecular orbital (HOMO) level, we extract for the edge-on counterparts a distinct conductance ordering where the low-HOMO thymine provides the largest signal. The edge-on mode is shown to operate based on a novel molecular sensing mechanism that reflects the chemical connectivity between N-doped CNT caps that can act both as electron donors and electron acceptors and DNA functional groups that include the hyperconjugated thymine methyl group[1].

• Journal of the Korean Chemical Society
• /
• v.59 no.2
• /
• pp.132-135
• /
• 2015

Bonding force and stiffness in amine-linked single-molecule junctions for Ag electrodes were measured using a home-built conducting atomic force microscope under ambient conditions at room temperature. For comparison, Au electrodes were used to measure the rupture force and stiffness of the molecular junctions. The traces of the force along with the conductance showed a characteristic saw-tooth pattern owing to the breaking of the metal atomic contacts or the metal-molecule- metal junctions. We found the rupture force and stiffness for Ag are smaller than those for Au electrodes. Furthermore, we observed that the force required to break the amine-Ag bond in the conjugated molecule, 1,4-benzenediamine, is smaller than in 1,4-butanediamine which is fully saturated. These results consist with the previous theoretical calculations for the binding energies of the nitrogen bonded to Ag or Au atoms.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.02a
• /
• pp.27-27
• /
• 2011

For the design of real applicable molecular devices, current-voltage properties through molecular nanostructures such as metal-molecule-metal junctions (molecular junctions) have been studied extensively. In thiolate monolayers on the gold electrode, the chemical bonding of sulfur to gold and the van der Waals interactions between the alkyl chains of neighboring molecules are important factors in the formation of well-defined monolayers and in the control of the electron transport rate. Charge transport through the molecular junctions depends significantly on the energy levels of molecules relative to the Fermi levels of the contacts and the electronic structure of the molecule. It is important to understand the interfacial electron transport in accordance with the increased film thickness of alkyl chains that are known as an insulating layer, but are required for molecular device fabrication. Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Electrochemical voltammetry and current-voltage (I-V) characteristics are measured to elucidate electron transport processes in the bistable conducting states of single molecular junctions of a molecular switch, Ru(II) terpyridine complexes. (1) On the basis of the Ru-centered electrochemical reaction data, the electron transport rate increases in the mixed self-assembled monolayer (SAM) of Ru(II) terpyridine complexes, indicating strong electronic coupling between the redox center and the substrate, along the molecules. (2) In a low-conducting state before switch-on, I-V characteristics are fitted to a direct tunneling model, and the estimated tunneling decay constant across the Ru(II) terpyridine complex is found to be smaller than that of alkanethiol. (3) The threshold voltages for the switch-on from low- to high-conducting states are identical, corresponding to the electron affinity of the molecules. (4) A high-conducting state after switch-on remains in the reverse voltage sweep, and a linear relationship of the current to the voltage is obtained. These results reveal electron transport paths via the redox centers of the Ru(II) terpyridine complexes, a molecular switch.

• Journal of the Korean Vacuum Society
• /
• v.10 no.3
• /
• pp.350-355
• /
• 2001

We have investigated characteristics of ZnSe epilayer grown by molecular beam epitaxy(MBE) on semi-insulating(SI) GaAs by using surface photovoltage(SPV). The measurements of SPV were performed with illumination intensity and modulation frequency. The bandgap energy of ZnSe epilayer was determined from derivative surface photovoltage (DSPV). The five states were observed at room temperature(RT), and those states relate to the impurity and defect formed hetero-interface of ZnSe and GaAs during the sample growth. The observed states represented as a tendency of typical extrinsic transition on the increasing illumination intensity. The 1s and 2s signals related to the excitonic absorption were not observed at RT, but those were presented with the splitted of two peaks in the SPV at 80 K. From the modulation frequency dependence, we obtained the junction conductance and capacitance of the sample.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.645-645
• /
• 2013

Applying a first-principles computational approach combining density-functional theory and matrix Green's function calculations, we have studied the effects [2+2] cycloaddition olligormerization of fullerene $C_{60}$ chains on their junction charge transport properties. Analyzing first the microscopic mechanism of the switching realized in recent scanning tunneling microscope (STM) experiments, we found that, in agreement with experimental conclusions, the device characteristics are not significantly affected by the changes in electronic structure of $C_{60}$ chains. It is further predicted that the switching characteristics will sensitively depend on the STM tip metal species and the associated energy level bending direction in the $C_{60}-STM$ tip vacuum gap. Considering infinite $C_{60}$ chains, however, we confirm that unbound $C_{60}$ chains with strong orbital hybridizations and band formation should in principle induce a much higher conductance state. We demonstrate that a nanoelectromechanical approach in which the $C_{60}-STM$ tip distance is maintained at short distances can achieve a metal-independent and drastically improved switching performance based on the intrinsically better electronic connectivity in the bound $C_{60}$ chains.