Single-molecule conductance measurements for 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) may offer unique insight into the bent-to-planar photocycle between the ground and excited states. Herein, we employ DPAC derivative DPAC-SMe as the molecular prototype to fabricate single-molecule junctions using the scanning tunneling microscope break junction technique and explore photoconductance dependence on the excited-state structural/electronic changes. We find up to ∼200% conductance enhancement of DPAC-SMe under continuous 340 nm light irradiation than that without irradiation, while photoconductance disappears in the case where structural evolution of the DPAC-SMe is halted through macrocyclization. The in situ conductance modulation as pulsed 340 nm light irradiation is monitored in the DPAC-SMe-based junctions alone, suggesting that the photoconductance of DPAC-SMe stems from photoinduced intramolecular planarization. Theoretical calculations reveal that the photoinduced structural evolution brings about a significant redistribution of the electron cloud density, which leads to the appearance of Fano resonance, resulting in enhanced conductance through the DPAC-SMe-fabricated junctions. This work provides evidence of bent-to-planar photocycle-induced conductance differences at the single-molecule level, offering a tailored approach for tuning the charge transport characteristics of organic photoelectronic devices.

Photoconductance from the Bent-to-Planar Photocycle between Ground and Excited States in Single-Molecule Junctions.

The concept of using single molecules as functional building blocks in electronic circuitry represents the ultimate device miniaturization and has garnered tremendous attention from physics, chemistry, and engineering. Recent advances in single-molecule junction techniques have enabled direct investigation of charge transport in a quasi-one-dimensional conduction channel composed of an individual molecule. One of the main research focuses over the past decade has been to understand the conductance switching effect of single molecules as it is essential for developing molecular-scale optoelectronics, computing, and sensing applications. In this perspective, we highlight the established physical and chemical mechanisms for single-molecule conductance switching behavior and examine the associated stimuli in single-molecule junction systems. Graphical abstract

Switching the conductance of a single molecule: Lessons from molecular junctions

Atomically precise graphene nanoribbons (GNRs) are increasingly attracting interest due to their largely modifiable electronic properties, which can be tailored by controlling their width and edge structure during chemical synthesis. In recent years, the exploitation of GNR properties for electronic devices has focused on GNR integration into field‐effect‐transistor (FET) geometries. However, such FET devices have limited electrostatic tunability due to the presence of a single gate. Here, on the device integration of 9‐atom wide armchair graphene nanoribbons (9‐AGNRs) into a multi‐gate FET geometry, consisting of an ultra‐narrow finger gate and two side gates is reported. High‐resolution electron‐beam lithography (EBL) is used for defining finger gates as narrow as 12 nm and combine them with graphene electrodes for contacting the GNRs. Low‐temperature transport spectroscopy measurements reveal quantum dot (QD) behavior with rich Coulomb diamond patterns, suggesting that the GNRs form QDs that are connected both in series and in parallel. Moreover, it is shown that the additional gates enable differential tuning of the QDs in the nanojunction, providing the first step toward multi‐gate control of GNR‐based multi‐dot systems.

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Tunable Quantum Dots from Atomically Precise Graphene Nanoribbons Using a Multi‐Gate Architecture

Single-molecule field-effect transistors (FETs) are promising to break the development bottleneck of device miniaturization, which is of great significance for realizing the development of more than Moore. However, the field-effect...

Dipole-improved gating of azulene-based single-molecule transistors

Food contamination by aflatoxins is an urgent global issue due to its high level of toxicity and the difficulties in limiting the diffusion. Unfortunately, current detection techniques, which mainly use biosensing, prevent the pervasive monitoring of aflatoxins throughout the agri-food chain. In this work, we investigate, through ab initio atomistic calculations, a pyrrole-based Molecular Field Effect Transistor (MolFET) as a single-molecule sensor for the amperometric detection of aflatoxins. In particular, we theoretically explain the gate-tuned current modulation from a chemical–physical perspective, and we support our insights through simulations. In addition, this work demonstrates that, for the case under consideration, the use of a suitable gate voltage permits a considerable enhancement in the sensor performance. The gating effect raises the current modulation due to aflatoxin from 100% to more than 103÷104%. In particular, the current is diminished by two orders of magnitude from the μA range to the nA range due to the presence of aflatoxin B1. Our work motivates future research efforts in miniaturized FET electrical detection for future pervasive electrical measurement of aflatoxins.

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Design of Pyrrole-Based Gate-Controlled Molecular Junctions Optimized for Single-Molecule Aflatoxin B1 Detection

As conventional silicon-based transistors are fast approaching the physical limit, it is essential to seek alternative candidates, which should be compatible with or even replace microelectronics in the future. Here, we report a robust solid-state single-molecule field-effect transistor architecture using graphene source/drain electrodes and a metal back-gate electrode. The transistor is constructed by a single dinuclear ruthenium-diarylethene (Ru-DAE) complex, acting as the conducting channel, connecting covalently with nanogapped graphene electrodes, providing field-effect behaviors with a maximum on/off ratio exceeding three orders of magnitude. Use of ultrathin high-k metal oxides as the dielectric layers is key in successfully achieving such a high performance. Additionally, Ru-DAE preserves its intrinsic photoisomerisation property, which enables a reversible photoswitching function. Both experimental and theoretical results demonstrate these distinct dual-gated behaviors consistently at the single-molecule level, which helps to develop the different technology for creation of practical ultraminiaturised functional electrical circuits beyond Moore's law. 

/pdf/dual-gated-single-molecule-field-effect-transistors-beyond-1h6qcavb.pdf

Dual-gated single-molecule field-effect transistors beyond Moore’s law

Single-molecule junctions (SMJs) offer a novel strategy for miniaturization of electronic devices. In this work, we realize a graphene-porphyrin-graphene SMJ driven by electric field and proton transfer in two configurations. In the transistor configuration with ionic liquid gating, an unprecedented field-effect performance is achieved with a maximum on/off ratio of ~4800 and a gate efficiency as high as ~179 mV/decade in consistence with the theoretical prediction. In the other configuration, controllable proton transfer, tautomerization switching, is directly observed with bias dependence. Room temperature proton transfer leads to a two-state conductance switching, and more precise tautomerization is detected, showing a four-state conductance switching at high bias voltages and low temperatures. Such an SMJ in two configurations provides new insights into not only building multifunctional molecular nanocircuits toward real applications but also deciphering the intrinsic properties of matters at the molecular scale.

Single-molecule field effect and conductance switching driven by electric field and proton transfer

In aromatic systems with large π-conjugated structures, armchair and zigzag configurations can affect each material's electronic properties, determining their performance and generating certain quantum effects. Here, we explore the intrinsic effect of armchair and zigzag pathways on charge transport through single hexabenzocoronene molecules. Theoretical calculations and systematic experimental results from static carbon-based single-molecule junctions and dynamic scanning tunneling microscope break junctions show that charge carriers are preferentially transported along the hexabenzocoronene armchair pathway, and thus, the corresponding current through this pathway is approximately one order of magnitude higher than that through the zigzag pathway. In addition, the molecule with the zigzag pathway has a smaller energy gap. In combination with its lower off-state conductance, it shows a better field-effect performance because of its higher on-off ratio in electrical measurements. This study on charge transport pathways offers a useful perspective for understanding the electronic properties of π-conjugated systems and realizing high-performance molecular nanocircuits toward practical applications.

https://www.science.org/doi/pdf/10.1126/sciadv.adg4346?download=true

Zhuang Yan

Papers

Dual-gated single-molecule field-effect transistors beyond Moore’s law

Single-molecule field effect and conductance switching driven by electric field and proton transfer

Distinct armchair and zigzag charge transport through single polycyclic aromatics.