Dynamically blocking leakage current in molecular tunneling junctions.

Molecular tunneling junctions based on self-assembled monolayers (SAMs) have demonstrated rectifying characteristics at the nanoscale that can hardly be achieved using traditional approaches. However, defects in SAMs result in high leakage when applying bias. The poor performance of molecular diodes compared to silicon or thin-film devices limits their further development. In this study, we show that incorporating "mixed backbones" with flexible-rigid structures into molecular junctions can dynamically block tunneling currents, which is difficult to realize using non-molecular technology. Our idea is achieved by the interaction between interfacial dipole moments and electric field, triggering structured packing in SAMs. Efficient blocking of leakage by more than an order of magnitude leads to a significant enhancement of the rectification ratio to the initial value. The rearrangement of supramolecular structures has also been verified through electrochemistry and electroluminescence measurements. Moreover, the enhanced rectification is extended to various challenging environments, including endurance measurements, bending of electrodes, and rough electrodes, thus demonstrating the feasibility of the dynamic behavior of molecules for practical electronic applications.

Fabrication of multi-functional molecular tunnelling junctions by click chemistry.

Continuous advancement in molecular electronics demands increasing functionality and diversity of integrated molecular junctions; however, single-functional molecular junctions fail to meet these requirements. In this article, we propose the use of a widely applicable and efficient click reaction on the surface to modify self-assembled monolayers (SAMs) to achieve multifunctional molecular tunnelling junctions, current rectification and memristance, on a single chip. This approach has allowed us to meet the growing demand for versatility and functionality in molecular electronic devices.

Extreme long-lifetime self-assembled monolayer for air-stable molecular junctions.

The molecular electronic devices based on self-assembled monolayer (SAM) on metal surfaces demonstrate novel electronic functions for device minimization yet are unable to realize in practical applications, due to their instability against oxidation of the sulfur-metal bond. This paper describes an alternative to the thiolate anchoring group to form stable SAMs on gold by selenides anchoring group. Because of the formation of strong selenium-gold bonds, these stable SAMs allow us to incorporate them in molecular tunnel junctions to yield extremely stable junctions for over 200 days. A detailed structural characterization supported by spectroscopy and first-principles modeling shows that the oxidation process is much slower with the selenium-gold bond than the sulfur-gold bond, and the selenium-gold bond is strong enough to avoid bond breaking even when it is eventually oxidized. This proof of concept demonstrates that the extraordinarily stable SAMs derived from selenides are useful for long-lived molecular electronic devices and can possibly become important in many air-stable applications involving SAMs.

High performance mechano-optoelectronic molecular switch.

Highly-efficient molecular photoswitching occurs ex-situ but not to-date inside electronic devices due to quenching of excited states by background interactions. Here we achieve fully reversible in-situ mechano-optoelectronic switching in self-assembled monolayers (SAMs) of tetraphenylethylene molecules by bending their supporting electrodes to maximize aggregation-induced emission (AIE). We obtain stable, reversible switching across >1600 on/off cycles with large on/off ratio of (3.8 ± 0.1) × 103 and 140 ± 10 ms switching time which is 10-100× faster than other approaches. Multimodal characterization shows mechanically-controlled emission with UV-light enhancing the Coulomb interaction between the electrons and holes resulting in giant enhancement of molecular conductance. The best mechano-optoelectronic switching occurs in the most concave architecture that reduces ambient single-molecule conformational entropy creating artificially-tightened supramolecular assemblies. The performance can be further improved to achieve ultra-high switching ratio on the order of 105 using tetraphenylethylene derivatives with more AIE-active sites. Our results promise new applications from optimized interplay between mechanical force and optics in soft electronics.

Supramolecular Memristor Based on Bistable [2]Catenanes: Toward High-Density and Non-Volatile Memory Devices.

The ever-increasing demand for data storage and neuromorphic computing calls for innovative, high-density solutions, such as resistive random-access memory (RRAM). However, the integration of resistive switching and rectification at the nanoscale remains a formidable challenge. In this study, we introduce a bistable [2]catenane-based supramolecular junction that simultaneously functions as a resistive switch and a diode. All supramolecular junctions are highly stable and reproducible over thousands of resistive switching cycles, because the nano-confinement of two mechanically interlocked rings can stabilize the radical states of pyridinium moieties under ambient conditions. The successful realization of supramolecular junctions in functionality with a thickness of approximately 2 nm presents a promising avenue for the development of molecule-scale based RRAM for a better solution to high density and energy efficiency.

Fine-Tuning the Molecular Design for High-Performance Molecular Diodes Based on Pyridyl Isomers.

Better control of molecule-electrode coupling (Γ) to minimize leakage current is an effective method to optimize the functionality of molecular diodes. Herein we embedded 5 isomers of phenypyridyl derivatives, each with an N atom placed at a different position, in two electrodes to fine-tune Γ between self-assembled monolayers (SAMs) and the top electrode of EGaIn (eutectic Ga-In terminating in Ga2 O3 ). Combined with electrical tunnelling results, characterizations of electronic structures, single-level model fittings, and DFT calculations, we found that the values of Γ of SAMs formed by these isomers could be regulated by nearly 10 times, thereby contributing to the leakage current changing over about two orders of magnitude and switching the isomers from resistors to diodes with a rectification ratio (r+ =|J(+1.5 V)/J(-1.5 V)|) exceeding 200. We demonstrated that the N atom placement can be chemically engineered to tune the resistive and rectifying properties of the molecular junctions, making it possible to convert molecular resistors into rectifiers. Our study provides fundamental insights into the role of isomerism in molecular electronics and offers a new avenue for designing functional molecular devices.

Ionogel-Electrode for the Study of Protein Tunnel Junctions under Physiologically Relevant Conditions.

The study of charge transport through proteins is essential for understanding complicated electrochemical processes in biological activities while the reasons for the coexistence of tunneling and hopping phenomena in protein junctions still remain unclear. In this work, a flexible and conductive ionogel electrode is synthesized and is used as a top contact to form highly reproducible protein junctions. The junctions of proteins, including human serum albumin, cytochrome C and hemoglobin, show temperature-independent electron tunneling characteristics when the junctions are in solid states while with a different mechanism of temperature-dependent electron hopping when junctions are hydrated under physiologically relevant conditions. It is demonstrated that the solvent reorganization energy plays an important role in the electron-hopping process and experimentally shown that it requires ≈100 meV for electron hopping through one heme group inside a hydrated protein molecule connected between two electrodes.

Direct synthesis of the organic and Ge free Al containing BOG zeolite (ITQ-47) and its application for transformation of biomass derived molecules.

Aluminosilicate boggsite (Si/Al-BOG) has been hydrothermally synthesized without adding organic structure-directing agents (OSDAs) in the synthesis gel using the borosilicogermanium ITQ-47 (Si/B-ITQ-47) zeolite as seeds. The introduction of the costly and environmentally less benign phosphazene organic structure-directing agent is not required to grow the zeolite. Physicochemical characterization experiments show that Si/Al-BOG has good crystallinity, high surface area, tetrahedral Al3+ species, and acid sites. In order to test the catalytic performance of the zeolite, the synthesis of l,l-lactide from l-lactic acid was performed. Si/Al-BOG exhibits 88.2% conversion of l-lactic acid and 83.8% l,l-lactide selectivity, which are better than those of other zeolites studied up to now.

Correction: Direct synthesis of the organic and Ge free Al containing BOG zeolite (ITQ-47) and its application for transformation of biomass derived molecules.

[This corrects the article DOI: 10.1039/D0SC04044D.].