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  • Review Article
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Concepts in the design and engineering of single-molecule electronic devices

Nature Reviews Physics volume 1, pages 211–230 (2019)Cite this article

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Abstract

Over the past two decades, various techniques for fabricating nano-gapped electrodes have emerged, promoting rapid development in the field of single-molecule electronics, on both the experimental and theoretical sides. To investigate intrinsic quantum phenomena and achieve desired functionalities, it is important to fully understand the charge transport characteristics of single-molecule devices. In this Review, we present the principles that have been developed for fabricating reliable molecular junctions and tuning their intrinsic properties from an engineering perspective. Through holistic consideration of the device structure, we divide single-molecule junctions into three intercorrelated components: the electrode, the contact (spacer–linker) interface and the molecular backbone or functional centre. We systematically discuss the selection of the electrode material and the design of the molecular components from the point of view of the materials, the interface and molecular engineering. The influence of the properties of these elements on the molecule–electrode interface coupling and on the relative energy gap between the Fermi level of the electrode and the orbital energy levels of the molecule, which directly influence the charge transport behaviour of single-molecule devices, is also a focus of our analysis. On the basis of these considerations, we examine various functionalities demonstrated in molecular junctions through molecular design and engineering.

Key points

  • Single-molecule electronics has become a burgeoning subfield of nanoscience and has begun to develop beyond the basic description of carrier transport, expanding in different research directions.

  • A single-molecule junction can be divided into three intercorrelated components: the electrode, the contact interface and the molecular backbone or functional centre.

  • Both the mechanical stability and electronic coupling of the molecule–electrode interface increase with the binding energy of the electrode–anchoring moiety interaction. A compromise between these factors can be achieved by inserting suitable spacers between the molecular kernel and anchoring groups.

  • To select suitable electrode materials, chemical inertness to air, good processability, suitable work function and good compatibility with molecules should be taken into consideration.

  • The structures of molecular bridges can be tuned by the molecular length, the geometry of the main chains, the responsivity of the functional centres and the types of side groups, offering opportunities to probe intrinsic physical properties and realize various functionalities.

  • Challenges in the field of single-molecule electronics include improving device-to-device uniformity, stability, integration capability and accuracy of theoretical models.

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Fig. 1: Structure of single-molecule junctions.
Fig. 2: Strategies to control interface coupling.
Fig. 3: Single-molecule diodes.
Fig. 4: Typical spin-based switches.
Fig. 5: Switches based on destructive quantum interference.
Fig. 6: Use of substituents to tune the conductance in single-molecule junctions.
Fig. 7: Single-molecule dynamic detection of intermolecular reactions or interactions.
Fig. 8: Single-molecule dynamic detection of chemical reactions.

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Acknowledgements

The authors thank M. Schott and Y. Feng for giving feedback on the manuscript. The authors acknowledge primary financial support from the National Key R&D Program of China (2017YFA0204901; X.G.), the National Natural Science Foundation of China (21727806; X.G.), the Natural Science Foundation of Beijing (Z181100004418003; X.G.), Northwestern University (J.F.S. and M.A.R.), the Israel–US Binational Science Foundation (A.N.), the German Research Foundation (DFG TH 820/11–1; A.N.), the US National Science Foundation (grant no. CHE1665291; A.N.) and the University of Pennsylvania (A.N.).

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  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Na Xin, Jianxin Guan, Chenguang Zhou, Xinjiani Chen, Chunhui Gu, Yu Li & Xuefeng Guo

  2. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Mark A. Ratner & J. Fraser Stoddart

  3. Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA

    Abraham Nitzan

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Xin, N., Guan, J., Zhou, C. et al. Concepts in the design and engineering of single-molecule electronic devices. Nat Rev Phys 1, 211–230 (2019). https://doi.org/10.1038/s42254-019-0022-x

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