Two commonly observed charge transport mechanisms in single-molecule junctions are coherent tunneling and incoherent hopping. It has been generally believed that tunneling processes yield temperature-independent conductance behavior and hopping processes exhibit increasing conductance with increasing temperature. However, it has recently been proposed that tunneling can also yield temperature-dependent transport due to the thermal broadening of the Fermi energy of the contacts. In this work, we examine a series of rigid, planar furan oligomers that are free from a rotational internal degree of freedom to examine the temperature dependence of tunneling transport directly over a wide temperature range (78-300 K). Our results demonstrate conductance transition from a temperature-independent regime to a temperature-dependent regime. By examining various hopping and tunneling models and the correlation between the temperature dependence of conductance and molecular orbital energy offset from the Fermi level, we conclude thermally assisted tunneling is the dominant cause for the onset of temperature-dependent conductance in these systems.
Furans , Nanotechnology , Temperature
In this paper, the contact configuration of single molecular junction is controlled through side group, which is explored by electrochemical jump-to-contact STM break junction. The conductance values of 2-methoxy-1,3-benzenedicarboxylic acid (2-M-1,3-BDC) is around 10-3.65 G0, which is different from that of 5-methoxy-1,3-benzenedicarboxylic acid (5-M-1,3-BDC) with 10-3.20 G0. Interestingly, the conductance value of 2-M-1,3-BDC is the same as that of 1,3-benzenedicarboxaldehyde (1,3-BDCA), while single molecular junctions of 5-M-1,3-BDC and 1,3-benzenedicarboxylic acid (1,3-BDC) give out similar conductance value. Since 1,3-BDCA binds to the Cu electrode through one oxygen atom, the dominated contact configuration for 1,3-BDC is through two oxygen atoms. The different conductance values between 2-M-1,3-BDC and 5-M-1,3-BDC can be attributed to the different contact configurations caused by the position of the side group. The current work provides a feasible way to control the contact configuration between the anchoring group and the electrode, which may be useful in designing future molecular electronics.
The ability to control over the quantum interference (QI) effect in single molecular junctions is attractive in the application of molecular electronics. Herein we report that the QI effect of meta-benzene based molecule with dihydrobenzo[ b]thiophene as the anchoring group ( meta-BT) can be controlled by manipulating the electrode potential of the junctions in electrolyte while the redox state of the molecule does not change. More than 2 orders of magnitude conductance change is observed for meta-BT ranging from <10-6.0 to 10-3.3 G0 with varying the electrode potential, while the upper value is even larger than the conductance of para-BT ( para-benzene based molecule with anchoring group of dihydrobenzo[ b]thiophene). This phenomenon is attributed to the shifting of energy level alignment between the molecule and electrodes under electrode potential control. Calculation is carried out to predict the transmission function of single molecular junction and the work function of Au surface in the presence of the molecule, and good agreement is found between theory and experiments, both showing sharp-valley featured destructive QI effect for the meta-BT. The present work demonstrates that the QI effect can be tuned through electrochemical gating without change of molecular redox states, which provides a feasible way toward realization of effective molecular switches.
One key issue for the development of molecular electronic devices is to understand the electron transport of single-molecule junctions. In this work, we explore the electron transport of iodine-terminated alkane single molecular junctions using the scanning tunneling microscope-based break junction approach. The result shows that the conductance decreases exponentially with the increase of molecular length with a decay constant ßN = 0.5 per -CH2 (or 4 nm-1). Importantly, the tunneling decay of those molecular junctions is much lower than that of alkane molecules with thiol, amine, and carboxylic acid as the anchoring groups and even comparable to that of the conjugated oligophenyl molecules. The low tunneling decay is attributed to the small barrier height between iodine-terminated alkane molecule and Au, which is well supported by DFT calculations. The work suggests that the tunneling decay can be effectively tuned by the anchoring group, which may guide the manufacturing of molecular wires.
The single molecular conductance of amino acids was measured by a scanning tunneling microscope (STM) break junction. Conductance measurement of alanine gives out two conductance values at 10-1.85 G0 (1095 nS) and 10-3.7 G0 (15.5 nS), while similar conductance values are also observed for aspartic acid and glutamic acid, which have one more carboxylic acid group compared with alanine. This may show that the backbone of NH2-C-COOH is the primary means of electron transport in the molecular junction of aspartic acid and glutamic acid. However, NH2-C-COOH is not the primary means of electron transport in the methionine junction, which may be caused by the strong interaction of the Au-SMe (methyl sulfide) bond for the methionine junction. The current work reveals the important role of the anchoring group in the electron transport in different amino acids junctions.
Electron Transport , Carboxylic Acids , Nanotechnology
We have measured the alkane and benzene-based molecules with aldehyde and carboxylic acid as anchoring groups by using the electrochemical jump-to-contact scanning tunneling microscopy break junction (ECSTM-BJ) approach. The results show that molecule with benzene backbone has better peak shape and intensity than those with alkane backbone. Typically, high junction formation probability for same anchoring group (aldehyde and carboxylic acid) with benzene backbone is found, which contributes to the stronger attractive interaction between Cu and molecules with benzene backbone. The present work shows the import role of backbone in junction, which can guide the design molecule to form effective junction for studying molecular electronics.
