Nanogap Electrodes Research Articles

Single-Molecule Bioelectronic Sensors with AI-Aided Data Analysis: Convergence and Challenges.

Single-molecule bioelectronic sensing, a groundbreaking domain in biological research, has revolutionized our understanding of molecules by revealing deep insights into fundamental biological processes. The advent of emergent technologies, such as nanogapped electrodes and nanopores, has greatly enhanced this field, providing exceptional sensitivity, resolution, and integration capabilities. However, challenges persist, such as complex data sets with high noise levels and stochastic molecular dynamics. Artificial intelligence (AI) has stepped in to address these issues with its powerful data processing capabilities. AI algorithms effectively extract meaningful features, detect subtle changes, improve signal-to-noise ratios, and uncover hidden patterns in massive data. This review explores the synergy between AI and single-molecule bioelectronic sensing, focusing on how AI enhances signal processing and data analysis to boost accuracy and reliability. We also discuss current limitations and future directions for integrating AI, highlighting its potential to advance biological research and technological innovation.

Control and Regulation of Au Hillocks Growth by the Electrical Field and their Metastable Dynamics in Ambient Atmosphere

Abstract With the rapid development of electronic engineering and nanotechnology, the electrical field-induced surface migration plays an increasingly important role in the fields of materials science. By comparing the changes in the surface migration behavior of gold nanogap electrodes under different electric field parameters, we reveal the kinetic processes and influencing factors of electric field-induced surface migration. Under the condition of only 1 pA current limit, under the continuous electric field, the hillcok only appears in the anode and gradually evolve into multiple peaks when rises to some extent. By establishing a finite element model of the nanogap, we find the hillock grows under the field strength gradient. Then hillock growth is biregulated by applying a positive or negative voltage to the drain end of the gap device. Located in the normal temperature atmosphere, the morphology will degenerate, and this feature is opposite to the hillock generated by electromigration.

Missing-cell defects in QCA wires: The ground and excited electronic states perspectives

Quantum Cellular Automata (QCA) technology offers promising prospects for designing molecular electronic circuits that operate at high frequencies and with ultra-low power consumption. QCA wires serve as crucial conduits for digital data transmission between logic gates. A series of QCA cells arranged sequentially forms these wires, with data written or read using paired nanogap electrodes. In this study, employing a simplified full-basis quantum mechanical model, we investigate the impact of single and double missing cells on the response function and output voltage of wires implemented within the two-dot QCA architecture. The electronic coupling between the quantum dots within each QCA cell stands out as a critical structural parameter influencing both the nonlinearity of the response function and the level of output voltage. Ground state analyses of wires affected by missing-cell defects suggest that employing QCA cells with weak electronic coupling could potentially enhance fault tolerance. However, examination of excited states reveals that reducing electronic coupling may compromise the thermal robustness of such defective QCA wires.

Swift and precise detection of unlabeled pathogens using a nanogap electrode impedimetric sensor facilitated by electrokinetics

For the protection of human health and environment, there is a growing demand for high-performance, user-friendly biosensors for the prompt detection of pathogenic bacteria in samples containing various substances. We present a nanogap electrode-based purely electrical impedimetric sensor that utilizes the dielectrophoresis (DEP) mechanism. Our nanogap sensor can directly and sensitively detect pathogens present at concentrations as low as 1–10 cells/assay in buffers and drinking milk without the need for separation, purification, or specific ligand binding. This is achieved by minimizing the electrical double-layer effect and electrode polarization in nanogap impedance sensors, reducing signal loss. In addition, even at low DEP voltages, nanogap sensors can quickly establish strong DEP forces between the nanogap electrodes to control the spatial concentration of pathogens around the electrodes. This activates and stabilizes inter-electrode signal transmission along the nanogap-aligned pathogens, increasing sensitivity and reducing errors during repeated measurements. The DEP-enabled nanogap impedance sensor developed in this study is valuable for a variety of pathogen detection and monitoring systems including point-of-care testing (POCT) as it can detect pathogens in diverse samples containing multiple substances quickly and with high sensitivity, is compatible with complex solutions such as food and beverages, and provides highly reproducible results without the need for separate binding and separation processes.

Pure Water Splitting Driven by Overlapping Electric Double Layers.

In pursuit of a sustainable future powered by renewable energy, hydrogen production through water splitting should achieve high energy efficiency with economical materials. Here, we present a nanofluidic electrolyzer that leverages overlapping cathode and anode electric double layers (EDLs) to drive the splitting of pure water. Convective flow is introduced between the nanogap electrodes to suppress the crossover of generated gases. The strong electric field within the overlapping EDLs enhances ion migration and facilitates the dissociation of water molecules. Acidic and basic environments, which are created in situ at the cathode and anode, respectively, enable the use of nonprecious metal catalysts. All these merits allow the reactor to exhibit a current density of 2.8 A·cm-2 at 1.7 V with a nickel anode. This paves the way toward a new type of water electrolyzer that needs no membrane, no supporting electrolyte, and no precious metal catalysts.

Negative Differential Resistance in Single‐Molecule Junctions Based on Heteroepitaxial Spherical Au/Pt Nanogap Electrodes

AbstractSingle‐molecule junctions exploit the internal structure of molecular orbitals to construct a new class of functional quantum devices. The demonstration of negative differential resistance (NDR) in single‐molecule junctions is direct evidence of quantum mechanical tunneling through a molecular orbital. Here, a pronounced NDR effect is reported with a peak‐to‐valley ratio of 30.1 on a single‐molecule junction of π‐conjugated quinoidal‐fused oligosilole derivatives, Si2 × 2, embedded between the unique electroless gold‐plated heteroepitaxial spherical Au/Pt nanogap electrodes. This NDR feature persists in a consecutive endurance test of 180 current traces. the thermally stable NDR effects in the Si2 × 2 single‐molecule junctions between 9 and 300 K are demonstrated. The density functional theory calculations under electric fields indicate that the NDR effect can be ascribed to the bias‐dependent resonant tunneling transport via the polarized HOMO, which has asymmetrically changed electrode coupling with increased bias voltages. The results confirm a promising electrical platform for constructing functional quantum devices at the single‐molecule level.

Regulation of quantum spin conversions in a single molecular radical.

Free radicals, generally formed through the cleavage of covalent electron-pair bonds, play an important role in diverse fields ranging from synthetic chemistry to spintronics and nonlinear optics. However, the characterization and regulation of the radical state at a single-molecule level face formidable challenges. Here we present the detection and sophisticated tuning of the open-shell character of individual diradicals with a donor-acceptor structure via a sensitive single-molecule electrical approach. The radical is sandwiched between nanogapped graphene electrodes via covalent amide bonds to construct stable graphene-molecule-graphene single-molecule junctions. We measure the electrical conductance as a function of temperature and track the evolution of the closed-shell and open-shell electronic structures in real time, the open-shell triplet state being stabilized with increasing temperature. Furthermore, we tune the spin states by external stimuli, such as electrical and magnetic fields, and extract thermodynamic and kinetic parameters of the transition between closed-shell and open-shell states. Our findings provide insights into the evolution of single-molecule radicals under external stimuli, which may proof instrumental for the development of functional quantum spin-based molecular devices.

Activationless Electron Transfer of Redox-DNA in Electrochemical Nanogaps.

Our recent discovery of decreased reorganization energy in electrode-tethered redox-DNA systems prompts inquiries into the origin of this phenomenon and suggests its potential use to lower the activation energy of electrochemical reactions. Here, we show that the confinement of the DNA chain in a nanogap amplifies this effect to an extent to which it nearly abolishes the intrinsic activation energy of electron transfer. Employing electrochemical atomic force microscopy (AFM-SECM), we create sub-10 nm nanogaps between a planar electrode surface bearing end-anchored ferrocenylated DNA chains and an incoming microelectrode tip. The redox cycling of the DNA's ferrocenyl (Fc) moiety between the surface and the tip generates a measurable current at the scale of ∼10 molecules. Our experimental findings are rigorously interpreted through theoretical modeling and original molecular dynamics simulations (Q-Biol code). Several intriguing findings emerge from our investigation: (i) The electron transport resulting from DNA dynamics is many times faster than predicted by simple diffusion considerations. (ii) The current in the nanogap is solely governed by the electron transfer rate at the electrodes. (iii) This rate rapidly saturates as overpotentials applied to the nanogap electrodes increase, implying near-complete suppression of the reorganization energy for the oxidation/reduction of the Fc heads within confined DNA. Furthermore, evidence is presented that this may constitute a general, previously unforeseen, behavior of redox polymer chains in electrochemical nanogaps.

Resonant tunneling in a colloidal CdS semiconductor quantum-dot single-electron transistor based on heteroepitaxial-spherical Au/Pt nanogap electrodes.

Semiconductor quantum dots (QDs) have unique discrete energy levels determined by the particle size and material. Therefore, they have potential applications as novel optical and electronic devices. Among those, colloidal group II-VI semiconductor quantum dots stand out for their facile synthesis and band gaps aligned with the visible light spectrum. However, the electrical characterization studies of an individual quantum dot necessitate the size of nanogap electrodes being equal to the size of the quantum dot, which has conventionally been evaluated using techniques such as scanning tunneling microscopy (STM) and nanogaps fabricated by electromigration. The complexity of device fabrication has restricted research in this area. Here, we present a pioneering approach for the electrical characterization of single-QD: heteroepitaxial-spherical (HS) Au/Pt nanogap electrodes. We fabricated transistors through chemisorption, an anchoring colloidal CdS QD (3.8 nm) between the HS-Au/Pt nanogap electrodes (gap separation: 4.5 nm). The resulting device functions as a quantum-dot single-electron transistor (QD-SET), showing resonant tunneling-an inherent characteristic of the QD. A steep current increase was observed at a negative voltage, apart from the theoretical single-electron tunneling current by Coulomb blockade phenomena, which agreed with the theoretical resonant tunneling current through a discrete energy level of the QD. This underscores the promise of HS-Au/Pt nanogap electrodes in realizing single-QD devices, offering a pathway toward unlocking their full potential.

Investigation of vacuum measurement by nano‐gap device

AbstractAdvances in microfabrication technology have enabled electron beam lithography (EB lithography) systems to produce microfabrication on the order of 10 of nanometers. Using this technology, we have fabricated nanogap electrodes that can generate large electric fields at low voltages. The gap between the tips of the fabricated electrodes is 100 nm, and the curvature of each tip is 50 nm. The device was confirmed to work as an electronic vacuum gauge, the device successfully measured vacuum from 10−3 to 1 Pa at the electrode voltage of 3 V.

Bottom Contact 100nm Channel-Length α-In2 Se3 In-Plane Ferroelectric Memory.

Owing to the emerging trend of non-volatile memory and data-centric computing, the demand for more functional materials and efficient device architecture at the nanoscale is becoming stringent. To date, 2D ferroelectrics are cultivated as channel materials in field-effect transistors for their retentive and switchable dipoles and flexibility to be compacted into diverse structures and integration for intensive production. This study demonstrates the in-plane (IP) ferroelectric memory effect of a 100nm channel-length 2D ferroelectric semiconductor α-In2 Se3 stamped onto nanogap electrodes on Si/SiO2 under a lateral electric field. As α-In2 Se3 forms the bottom contact of the nanogap electrodes, a large memory window of 13V at drain voltage between ±6.5V and the on/off ratio reaching 103 can be explained by controlled IP polarization. Furthermore, the memory effect is modulated by the bottom gate voltage of the Si substrate due to the intercorrelation between IP and out-of-plane (OOP) polarization. The non-volatile memory characteristics including stable retention lasting 17 h, and endurance over 1200 cycles suggest a wide range of memory applications utilizing the lateral bottom contact structure.

Direct biomolecule discrimination in mixed samples using nanogap-based single-molecule electrical measurement

In single-molecule measurements, metal nanogap electrodes directly measure the current of a single molecule. This technique has been actively investigated as a new detection method for a variety of samples. Machine learning has been applied to analyze signals derived from single molecules to improve the identification accuracy. However, conventional identification methods have drawbacks, such as the requirement of data to be measured for each target molecule and the electronic structure variation of the nanogap electrode. In this study, we report a technique for identifying molecules based on single-molecule measurement data measured only in mixed sample solutions. Compared with conventional methods that require training classifiers on measurement data from individual samples, our proposed method successfully predicts the mixing ratio from the measurement data in mixed solutions. This demonstrates the possibility of identifying single molecules using only data from mixed solutions, without prior training. This method is anticipated to be particularly useful for the analysis of biological samples in which chemical separation methods are not applicable, thereby increasing the potential for single-molecule measurements to be widely adopted as an analytical technique.

Electromechanical Switching of a C60 Chain in a Nanogap

Electromechanical switching in fullerene C60 nanochains, introduced in the device as a C60 pyrrolidine tris-acid (CPTA) film, was realized in nanogap electrodes with ∼20 nm separation. Unlike microscale C60 channels, a conductive C60 chain spontaneously formed in the nanogap without electron beam irradiation. The initial current flow was likely due to electron hopping through the CPTA molecules. A higher voltage generated a nonlinear current and caused a rapid current step to drastically generate a large current flow. A further high current generated a sudden current reduction recognized as the negative differential resistance, suggesting a resistance state change from a low state to a high state. At the high-resistance state, a step-like current increase changed the nanochain conduction to the low-resistance state. The high- to low-resistance state switching was reproducible, and a sequential input voltage executed a binary resistance switching operation at room temperature. From the switching voltage and current values, the switching energy for the C60 chain in the nanogap was estimated to be approximately several milliwatts, most probably caused by the polymerization and depolymerization of the conductive C60 chain.

Nanoscale Channel Gate-Tunable Diodes Obtained by Asymmetric Contact and Adhesion Lithography on Fluoropolymers.

Adhesion lithography offers to fabrication of coplanar asymmetric nanogap electrodes with a low-cost and facile process. In this study, a gate-tunable diode with coplanar asymmetric nanogap is fabricated using adhesion lithography. A fluoropolymer material is introduced to the adhesion lithography process to ensure a manufacturing patterning process yield as high as 96.7%. The asymmetric electrodes formed a built-in potential, leading to rectifying behavior. The coplanar electrode structure allowed the use of a gate electrode in vertical contact with the channel, resulting in gate-tunable diode characteristics. The nanoscale channel induced a high current density (3.38×10-7 A∙cm-1 ), providing a high rectification ratio (1.67×105 A∙A-1 ). This rectifier diode is confirmed to operate with pulsed input signals and suggests the gate-tunability of nanogap diodes.

Graphene-molecule-graphene single-molecule junctions to detect electronic reactions at the molecular scale.

The ability to measure the behavior of a single molecule during a reaction implies the detection of inherent dynamic and static disordered states, which may not be represented when measuring ensemble averages. Here, we describe the building of devices with graphene-molecule-graphene single-molecule junctions integrated into an electrical circuit. These devices are simple to build and are stable, showing tolerance to mechanical changes, solution environment and voltage stimulation. The design of a conductive channel based on a single molecule enables single-molecule detection and is sensitive to variations in physical properties and chemical structures of the detected molecules. The on-chip setup of single-molecule junctions further offers complementary metal-oxide-semiconductor (CMOS) compatibility, enabling logic functions in circuit elements, as well as deciphering of reaction intermediates. We detail the experimental procedure to prepare graphene transistor arrays as a basis for single-molecule junctions and the preparation of nanogapped carboxyl-terminal graphene electrodes by using electron-beam lithography and oxygen plasma etching. We describe the basic design of a molecular bridge with desired functions and terminals to form covalent bonds with electrode arrays, via a chemical reaction, to construct stably integrated single-molecule devices with a yield of 30-50% per chip. The immobilization of the single molecules is then characterized by using inelastic electron tunneling spectra, single-molecule imaging and fluorescent spectra. The whole protocol can be implemented within 2 weeks and requires users trained in using ultra-clean laboratory facilities and the aforementioned instrumentation.

Molecular Electronics: Creating and Bridging Molecular Junctions and Promoting Its Commercialization.

Molecular electronics is driven by the dream of expanding Moore's law to the molecular level for next-generation electronics through incorporating individual or ensemble molecules into electronic circuits. For nearly 50 years, numerous efforts have been made to explore the intrinsic properties of molecules and develop diverse fascinating molecular electronic devices with the desired functionalities. The flourishing of molecular electronics is inseparable from the development of various elegant methodologies for creating nanogap electrodes and bridging the nanogap with molecules. This review first focuses on the techniques for making lateral and vertical nanogap electrodes by breaking, narrowing, and fixed modes, and highlights their capabilities, applications, merits, and shortcomings. After summarizing the approaches of growing single molecules or molecular layers on the electrodes, the methods of constructing a complete molecular circuit are comprehensively grouped into three categories: 1) directly bridging one-molecule-electrode component with another electrode, 2) physically bridging two-molecule-electrode components, and 3) chemically bridging two-molecule-electrode components. Finally, the current state of molecular circuit integration and commercialization is discussed and perspectives are provided, hoping to encourage the community to accelerate the realization of fully scalable molecular electronics for a new era of integrated microsystems and applications.

A Tunable Single‐Molecule Light‐Emitting Diode with Single‐Photon Precision (Adv. Mater. 16/2023)

Single-Molecule Light-Emitting Diodes In article number 2209750, Zitong Liu, Xuefeng Guo, and co-workers integrate a functional electroluminescent molecular bridge into nanogapped graphene electrodes to build a high-performance single-molecule light-emitting diode (SM-LED) with unprecedented levels of stability and reproducibility. Precise tunability of its emission efficiency, color purity, emitted photon number, and energy is achieved upon application of external electric fields, rational molecular engineering, and Förster resonance energy transfer, affording a new practical single-photon emitter, a milestone in developing the next generation of commercial display devices, and for quantum computation and communication.

A Tunable Single-Molecule Light-Emitting Diode with Single-Photon Precision.

A robust single-molecule light-emitting diode (SM-LED) with high color purity, linear polarization, and efficiency tunability is prepared by covalently integrating one fluorescent molecule into nanogapped graphene electrodes. Furthermore, single-molecule Förster resonance energy transfer from the electroluminescent center to different accepters is achieved through rational molecular engineering, enabling construction of a multicolor SM-LED. All these characterizations are accomplished in the photoelectrical integration system with high temporal/spatial/energy resolution, demonstrating the capability of the single-photon emission of SM-LEDs. The success in developing high-performance SM-LEDs inspires the development of the next generation of commercial display devices and promises a single-photon emitter for use in quantum computation and quantum communication.

Integrated Glass Microfluidics with Electrochemical Nanogap Electrodes.

We present a framework for the fabrication of chip-based electrochemical nanogap sensors integrated with microfluidics. Instead of polydimethylsiloxane (PDMS), SU-8 aided adhesive bonding of silicon and glass wafers is used to implement parallel flow control. The fabrication process permits wafer-scale production with high throughput and reproducibility. Additionally, the monolithic structures allow simple electrical and fluidic connections, alleviating the need for specialized equipment. We demonstrate the utility of these flow-incorporated nanogap sensors by performing redox cycling measurements under laminar flow conditions.

High On/Off Ratio Carbon Quantum Dot–Chitosan Biomemristors with Coplanar Nanogap Electrodes

High On/Off Ratio Carbon Quantum Dot–Chitosan Biomemristors with Coplanar Nanogap Electrodes