Abstract

The concept of using single molecules as key building blocks for logic gates, diodes and transistors to perform basic functions of digital electronic devices at the molecular scale has been explored over the past decades. However, in addition to mimicking the basic functions of current silicon devices, molecules often possess unique properties that have no parallel in conventional materials and promise new hybrid devices with novel functions that cannot be achieved with equivalent solid-state devices. The most appealing example is the molecular switch. Over the past decade, molecular switches on surfaces have been intensely investigated. A variety of external stimuli such as light, electric field, temperature, tunneling electrons and even chemical stimulus have been used to activate these molecular switches between bistable or even multiple states by manipulating molecular conformations, dipole orientations, spin states, charge states and even chemical bond formation. The switching event can occur either on surfaces or in break junctions. The aim of this review is to highlight recent advances in molecular switches triggered by various external stimuli, as investigated by low-temperature scanning tunneling microscopy (LT-STM) and the break junction technique. We begin by presenting the molecular switches triggered by various external stimuli that do not provide single molecule selectivity, referred to as non-selective switching. Special focus is then given to selective single molecule switching realized using the LT-STM tip on surfaces. Single molecule switches operated by different mechanisms are reviewed and discussed. Finally, molecular switches embedded in self-assembled monolayers (SAMs) and single molecule junctions are addressed.

Highlights

  • In addition to switches formed on surfaces investigated by STM, single molecule switches have been intensively investigated using single molecule junctions,[187] for example, scanning probe microscopy (SPM) based break junctions,[9,11,12,21,188,189,190,191,192] mechanically controlled break junction (MCBJs)[5,22,193,194,195,196,197,198,199,200,201] and electromigration break junctions (EBJs).[23,156,202,203,204,205,206,207,208,209]

  • We review recent progress of various molecular switches on surfaces and in single molecule junctions

  • Different external stimuli can be used to induce switching, and the molecular switches can be operated by different mechanisms according to their intrinsic properties

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Summary

Introduction of molecular switches on surfaces

Molecules often possess unique properties that have no parallel in conventional materials, such as monodispersity, self-assembly ability, intrinsic quantum mechanical behavior, functionality and the ease of replacing functional groups, flexible and low cost solution synthesis, etc. Self-assembly represents a promising bottom up approach to integrate these molecules into circuits on surfaces.[99] Single molecular switches can be chemically connected to one or two external electrodes by the break junction techniques, such as STM-based break junctions, MCBJs and EBJs. Single molecular diode or single molecule field-effect transistor behavior can be realized in the break junction configurations. Single molecule switches developed using break junction techniques are demonstrated

Non selective switching triggered by various external stimuli
Light induced switching
Electric field induced switching
Temperature induced switching
Tunneling electron induced switching
Chemical stimulus induced switching
Selective single molecule manipulation studied by STM
Conformation switching
Dipole switching
Spin switching
Charge switching
Bonding switching
Conductance switching
Single molecule switches developed using single molecule junctions
Molecular isomerization
Field effect transistors
Diodes
Findings
Conclusions and outlook
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