Tuning the type of charge carriers in N-heterocyclic carbene-based molecular junctions through electrodes

doi:10.1088/1674-1056/aba277

Abstract

Designing tunable molecular devices with different charge carriers in single-molecule junctions is crucial to the next-generation electronic technology. Recently, it has been demonstrated that the type of charge carriers depends on and can be tuned by controlling the molecular length and the number of interfacial covalent bonds. In this study, we show that the type of charge carriers can also be tuned by controlling the material and shape of electrodes. N-heterocyclic carbenes (NHCs) have attracted attention because of their ability to form strong, substitutional inert bonds in a variety of metals. Also, NHCs are more stable than the widely used thiol group. Therefore, we use electrodes to tune the type of charge carriers in a series of NHCs with different side groups. The ab initio calculations based on non-equilibrium Green’s formalism combined with density functional theory show that the dominant charge carrier switches from electrons to holes when gold electrodes are changed into platinum ones. The nature of the charge carriers can be identified by variations in the transport spectra at the Fermi level (E_F), which are caused by the side groups. The projections of transport spectra onto the central molecules further validate our inferences. In addition, the transmission coefficient at E_F is found to be dependent on the atomic interface structure. In particular, for the NHC without methyl or ethyl side groups, connecting a protruding atom on the electrode surface significantly enhances the transportability of both electrode materials. Overall, this study presents an effective approach to modifying transport properties, which has potential applications in designing functional molecular devices based on NHCs.

Keywords: molecular electronics charge carriers side groups non-equilibrium Green’s function

Received: 25 May 2020
Revised: 21 June 2020
Accepted manuscript online: 03 July 2020

Fund: the National Natural Science Foundation of China (Grants Nos. 11874242 and 21933002) and the Shandong Provincial Natural Science Foundation, China (Grant No. ZR2019PA022).

Corresponding Authors: ^†Corresponding author. E-mail: wangminglang@sdnu.edu.cn

Cite this article:

Ming-Lang Wang(王明郎) and Chuan-Kui Wang(王传奎) Tuning the type of charge carriers in N-heterocyclic carbene-based molecular junctions through electrodes 2020 Chin. Phys. B 29 113101

Fig. 1.

(a) Molecular structure of NHC with substitutional side group R, which includes H, methyl, and ethyl groups. (b) Schematic diagram of molecular transport junction, with central molecular backbone being NHC molecule that is attached to atop position (down panel) and adatom position (up panel) on Au (111) surface.

Fig. 2.

Frontier molecular orbitals of isolated NHC molecule with side group H (right), and variation in energy levels when side group is changed from H to methyl and ethyl (left).

Fig. 3.

Equilibrium transmission spectra at different contact positions on Au electrode surface: (a) atop position, (b) adatom position, with insets showing amplified transmission coefficient at E_F, and blue, red, and pink curves indicating H, methyl, and ethyl side groups at R position of NHC molecule, respectively.

Fig. 4.

Transmission spectra projected onto frontier molecular orbitals of NHC molecule, which are located at atop position on Au electrode surface with (a) H, (b) methyl, and (c) ethyl side groups.

Fig. 5.

Equilibrium transmission spectra at different contact positions on Pt electrode surface: (a) atop position and (b) adatom position. Inset in panel (a) shows amplified transmission coefficient at E_F. Blue and pink curves refer to H and ethyl side groups at the R position of the NHC molecule, respectively.

Fig. 6.

Transmission spectra projected onto frontier molecular orbitals of NHC molecule, which is located at atop position on Pt electrode surface with (a) H and (b) ethyl (b) side groups.

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Tuning the type of charge carriers in N-heterocyclic carbene-based molecular junctions through electrodes

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