Mechanism and Characterization of Electron Transport Through Metal/Molecule/Metal Junctions†

doi:10.7503/cjcu20140941

Abstract

Abstract:

Although molecular electronics emerged several decades ago, it is still concerning about fundamental issues so far. Metal/molecule/metal junction is a conceptually basic unit in molecular electronics. The mechanism of electron transport through metal/molecule/metal junction has attracted great interest. In general, the mechanisms for electron transport through metal/molecule/metal junctions can be divided into two categories: coherent transport and non-coherent transport according to the phase change of tunneling electrons. In this review, the electron transport mechanism is illustrated briefly by employing energy diagrams. More-over, several extensively measured approaches for studying metal/molecule/metal junctions, including I-V characteristic curve, I-t trace and conductance histogram, transition voltage spectroscopy, shot noise, inelastic electron tunneling spectroscopy, and thermoelectricity are introduced through referring to some recent publications including our works.

Key words: Molecular electronics, Metal/molecule/metal junction, Electron transport, Self-assembly, Single molecule conductance

CLC Number:

O641

TrendMD:

YANG Yang, LIU Junyang, YAN Runwen, WU Deyin, TIAN Zhongqun. Mechanism and Characterization of Electron Transport Through Metal/Molecule/Metal Junctions^†[J]. Chem. J. Chinese Universities, 2015, 36(1): 9.

Figures/Tables 13

Fig.1 Typical representation of metal/molecule/ metal junction A 4,4'-bipyridine molecule is covalently bound to Au electrodes pair.

Fig.2 Energy diagram for a D-B-A protocol molecular junction Ef: Fermi enegy. ϕ: barrier height.

Fig.3 Energy diagram showing the hopping mechanism in a D-B-A protocol molecular junction

Fig.4 Relationship between most probable electron transport mechanisms for metal/molecule/metal junction[35,40]

Table 1 Relationship between transporting current and experimental condition for metal/molecule/metal junction under different electron transport mechanisms[35,40]*

Mechanism	Temperature	Length	Voltage
Superexchange	None	I∝exp(-βd)	I∝V
Fowler-Nordheim Tunneling	None	I∝exp(-βd)	ln(I/V²)∝1/V
Steady state hopping	ln(I/V)∝1/T	I∝d^-1	I∝V
Non-directional hopping	ln(I/V)∝1/T	I∝d^-2	I∝V

Fig.5 Typical I-V characteristic and conductance-voltage(G-V) curves for Au/BDT/Au single molecules junction[27]

Fig.6 Energy diagrams of a metal/molecule/metal junction under Vbias=0(A) and Vbias≠0(B), respectively

Fig.7 Schematic description of STM-break junction method for fabricating metal/molecule/metal junction(A), (C) and(E) give the measured conductance curves, while (B), (D) and (F) illustrate the corresponding conductance histograms. Herein (E) and (F) are the data obtained without probe molecule[30].

Table 2 Comparison of conductance values of Au/BDT/Au by employing different approaches

Approach	Normalized value/G₀	Ref.	Approach	Normalized value/G₀	Ref.
I-V curve	5.86× 10^-4	[27]	Conductance histogram	1.0×10^-2	[67]
I-V curve	1.43×10^-3	[64]	Conductance histogram	4.0×10^-3	[68]
I-V curve	4.96×10^-5	[65]	Conductance histogram	1.0×10^-2	[69]
Conductance histogram	1.1×10^-2	[66]	Conductance histogram	1.0×10^-2	[18]

Fig.8 Measured Fowler-Nordheim plot corresponding to the I-V curve(the inset) of an Au/anthracenethiol/Au molecular junction The dashed curve indicates the transition from direct to Fowler-Nordheim tunneling[70].

Fig.9 Measured shot noise as a function of current for Pt/D2/Pt molecular junction(filled circle) The molecular junction conductance for this set of shot noise data is 1.010 G0. The shot noise can be described quite well with theory assuming {τi}= {0.995, 0.015}. Nevertheless, if {τi} is slightly changed to {0.985, 0.025}, the fitted curve cannot describe the shot noise at all[89].

Fig.10 Schematic presentation of inelastic electron tunneling spectroscopy(IETS)

Fig.11 Measured thermoelectric voltage for Au/1,4-bezenedithiol/Au junction and clean Au/Au junction as there is a temperature differential(ΔT = 20 K)(A), response of molecule thermoelectric voltage for Au/1,4-bezenedithiol/Au junction as ΔT changed(C), theoretically predicted transmission function for Au/1,4-bezenedithiol/Au junction by employing nonequilibrium Green’s function formalism combined with extended Hückel theory(B) and theoretically predicted Seebeck coefficient for Au/1,4-bezenedithiol/Au junction[124](D)

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