Nanogap Electrodes Research Articles

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Optical Trapping of a Single Molecule of Length Sub-1 nm in Solution

Highly-sensitive single-step sensing of levodopa by swellable microneedle-mounted nanogap sensors

Microneedle (MN) sensing of biomarkers in interstitial fluid (ISF) can overcome the challenges of self-diagnosis of diseases by a patient, such as blood sampling, handling, and measurement analysis. However, the MN sensing technologies still suffer from poor measurement accuracy due to the small amount of target molecules present in ISF, and require multiple steps of ISF extraction, ISF isolation from MN, and measurement with additional equipment. Here, we present a swellable MN-mounted nanogap sensor that can be inserted into the skin tissue, absorb ISF rapidly, and measure biomarkers in situ by amplifying the measurement signals by redox cycling in nanogap electrodes. We demonstrate that the MN-nanogap sensor measures levodopa (LDA), medication for Parkinson disease, down to 100 nM in an aqueous solution, and 1 μM in both the skin-mimicked gelatin phantom and porcine skin.

Electrically induced light emission via nanoscale vacuum discharge in nanogap electrodes without luminescent molecules

Understanding the mechanisms of electrically induced light emission in nanoscale junctions is crucial in molecular-scale optoelectronics. In this study, we investigated the light emission from nanogap electrodes with an insulating and nonluminescent material (polystyrene). Electrically induced light emission was observed over a wide wavelength range of 400–600 nm. The threshold voltages for the light emission ranged from 3 to 15 V, depending on the device, indicating that the electric field induced at the nanogap, rather than the applied potential, is the driving force for the light emission. The intensity of the light emission varies exponentially with the current with an exponent higher than 1.6, and the light emission is driven by a thermally activated current. These characteristics are inconsistent with the mechanisms reported for solid-state nanogap devices. We conclude that light emission in the nanogap electrodes is attributed to nanoscale vacuum discharge with metal plasma. The light emission from this mechanism can conflict with the other mechanisms ever reported since it occurs at such low voltages. The results also suggest intrinsic instability in molecular-scale electronic devices based on nanogap electrodes because the vacuum discharge is accompanied by the plasticization of the electrode.

Multiple connected artificial synapses based on electromigrated Au nanogaps

Building an artificial synaptic device with multiple presynaptic inputs will be a significant step toward realization of sophisticated brain-inspired platforms for neuromorphic computing. However, an artificial synapse that can mimic functions of multiple synapses in a single device has not yet been well developed with existing electronic devices. Here, we experimentally implement the functions of multiple synapses in a single artificial synaptic device consisting of multiple connected nanogap electrodes. The “activation” technique, which is based on electromigration of metal atoms induced by a field emission current, was applied to the device to emulate the synaptic functions. We show that the device, upon application of activation, exhibits conductance changes in response to stimulation voltage, similar to the memory states of biological synapses. Several important synaptic responses—notably, short-term plasticity and long-term plasticity—were successfully demonstrated in multiple connected Au-nanogaps. For further application, a simple network was implemented using multi-input devices based on a two-terminal Au nanogap array, exhibiting the ability to classify the digital input vector pattern. These demonstrations pave the way for brain-inspired computing applications such as associative memory, pattern classification, and image recognition.

A Single-Molecule Memristor based on an Electric-Field-Driven Dynamical Structure Reconfiguration.

A robust single-molecule memristor is prepared by covalently integrating one phenol molecule with multiple binding sites into nanogapped graphene electrodes. Multilevel resistance switching is realized by the electric-field-manipulated reconfiguration of the acyl moiety on the phenol center, that is, the Fries rearrangement. In situ measurements of the reaction trajectories with an initial single substrate and an intermediate break through the limitation of macroscopic experiments, therefore unveiling both intramolecular and intermolecular mechanistic pathways (a long-term controversy) as well as comprehensive dynamic information. Based on this advance, high-performance single-molecule memristors in both the solution and solid states are achieved successively, providing a new understanding of memristive systems and neural network computing.

Amplifying Quantum Tunneling Current Sensitivity through Labeling Nucleotides Using Graphene Nanogap Electrodes

Amplifying Quantum Tunneling Current Sensitivity through Labeling Nucleotides Using Graphene Nanogap Electrodes

Nanogap Electrode-Enabled Versatile Electrokinetic Manipulation of Nanometric Species in Fluids.

Noninvasive manipulation of nanoscopic species in liquids has attracted considerable attention due to its potential applications in diverse fields. Many sophisticated methodologies have been developed to control and study nanoscopic entities, but the low-power, cost-effective, and versatile manipulation of nanometer-sized objects in liquids remains challenging. Here, we present a dielectrophoretic (DEP) manipulation technique based on nanogap electrodes, with which the on-demand capturing, enriching, and sorting of nano-objects in microfluidic systems can be achieved. The dielectrophoretic control unit consists of a pair of swelling-induced nanogap electrodes crossing a microchannel, generating a steep electric field gradient and thus strong DEP force for the effective manipulation of nano-objects microfluidics. The trapping, enriching, and sorting of nanoparticles and DNAs were performed with this device to demonstrate its potential applications in micro/nanofluidics, which opens an alternative avenue for the non-invasive manipulation and characterization of nanoparticles such as DNA, proteins, and viruses.

Straightforward fabrication of sub-10 nm nanogap electrode pairs by electron beam lithography

The consistent motivation to observe molecular electronics and quantum effects drives the need for the tunable and robust fabrication of nanogap devices. Electron beam lithography (EBL) offers high fidelity fabrication to construct arrayed nanogaps, and methods have been developed to achieve sub-10 nm channel widths. However, many of these approaches involve multiple lithography steps or specialized techniques that limit throughput and universality. This work describes a simple, single EBL step, continuous dose, and direct feature write method of fabricating electrode pairs with nanogap spacing from 5 to 40 nm. This straightforward technique relies on precise electron beam focusing coupled with cold lithography for developing. Overall, this protocol enables efficient production of electrode nanogaps to facilitate the study of nanoscale materials and effects.

Radiofrequency Schottky Diodes Based on p-Doped Copper(I) Thiocyanate (CuSCN).

Schottky diodes based on inexpensive materials that can be processed using simple manufacturing methods are of particular importance for the next generation of flexible electronics. Although a number of high-frequency n-type diodes and rectifiers have been demonstrated, the progress with p-type diodes is lagging behind, mainly due to the intrinsically low conductivities of existing p-type semiconducting materials that are compatible with low-temperature, flexible, substrate-friendly processes. Herein, we report on CuSCN Schottky diodes, where the semiconductor is processed from solution, featuring coplanar Al–Au nanogap electrodes (<15 nm), patterned via adhesion lithography. The abundant CuSCN material is doped with the molecular p-type dopant fluorofullerene C60F48 to improve the diode’s operating characteristics. Rectifier circuits fabricated with the doped CuSCN/C60F48 diodes exhibit a 30-fold increase in the cutoff frequency as compared to pristine CuSCN diodes (from 140 kHz to 4 MHz), while they are able to deliver output voltages of >100 mV for a VIN = ±5 V at the commercially relevant frequency of 13.56 MHz. The enhanced diode and circuit performance is attributed to the improved charge transport across CuSCN induced by C60F48. The ensuing diode technology can be used in flexible complementary circuits targeting low-energy-budget applications for the emerging internet of things device ecosystem.

Dual-gated single-molecule field-effect transistors beyond Moore\u2019s law

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.

14GHz Schottky Diodes Using a p-Doped Organic Polymer.

The low carrier mobility of organic semiconductors and the high parasitic resistance and capacitance often encountered in conventional organic Schottky diodes hinder their deployment in emerging radio frequency (RF) electronics. Here, these limitations are overcome by combining self-aligned asymmetric nanogap electrodes (≈25nm) produced by adhesion lithography, with a high mobility organic semiconductor, and RF Schottky diodes able to operate in the 5G frequency spectrum are demonstrated. C16 IDT-BT is used, as the high hole mobility polymer, and the impact of p-doping on the diode performance is studied. Pristine C16 IDT-BT-based diodes exhibit maximum intrinsic and extrinsic cutoff frequencies (fC ) of >100and 6GHz, respectively. This extraordinary performance is attributed to the planar nature of the nanogap channel and the diode's small junction capacitance (<2pF). Doping of C16 IDT-BT with the molecular p-dopant C60 F48 improves the diode's performance further by reducing the series resistance resulting to intrinsic and extrinsic fC of >100and ≈14GHz respectively, while the DC output voltage of an RF rectifier circuit increases by a tenfold. Ourwork highlights the importance of the planar nanogap architecture and paves the way for the use of organic Schottky diodes in large-area RF electronics of the future.

Time-Evolved SERS Signatures of DEP-Trapped Aβ and Zn2+Aβ Peptides Revealed by a Sub-10 nm Electrode Nanogap.

Alzheimer's disease (AD) has become highly relevant in aging societies, yet the fundamental molecular basis for AD is still poorly understood. New tools to study the undergoing structural conformation changes of amyloid beta (Aβ) peptides, the pathogenic hallmark of AD, could play a crucial role in the understanding of the underlying mechanisms of misfolding and cytotoxicity of this peptide. It has been recently reported that Zn2+ interacts with Aβ and changes its aggregation pathway away from less harmful fibrillar forms to more toxic species. Here, we present a versatile platform based on a set of sub-10 nm nanogap electrodes for the manipulation and sensing of biomolecules in the physiological condition at a low copy number, where molecules are trapped via dielectrophoresis (DEP) across the nanogap, which also serves as a surface-enhanced Raman spectroscopy hotspot. In this study, we demonstrate that our electrode nanogap platform can be used to study the structural difference between Aβ40 and ZnAβ40 peptides at different aggregation stages in the physiologically relevant concentration and in solution phase. The Raman spectroscopic signatures of the DEP-captured neuropeptides prove the device to be attractive as a label-free bioanalytical tool.

A Tutorial on Electrochemical Impedance Spectroscopy and Nanogap Electrodes for Biosensing Applications

Electrochemical Impedance Spectroscopy (EIS) is a powerful measurement technique used by scientists and engineers to characterize and understand the interfacial behavior of liquid-solid interfaces. Such investigations are important in numerous applications and fields of research, including electrochemical synthesis and deposition of materials, such as metals and conducting polymers, corrosion protection analysis, investigation of molecule-surface interactions, and research on batteries and fuel cells. In recent years, advances in nanotechnology have led to a rise in the use of EIS in chemical and bio-sensing. Areas such as molecular diagnostics and healthcare can greatly benefit from this novel technology, which includes low-cost, rapid response measurements that can be done by non-experts at the point of care. For new entrants, the depth of knowledge and breadth of EIS and its many applications can be rather daunting. This article therefore serves as a tutorial on basic EIS theory, whilst highlighting new applications in advanced bio-sensing. The tutorial begins with a theoretical overview, including electrical AC impedance, formation and structure of electrical double layers at liquid solid-interfaces and equivalent circuit models used to represent interfacial phenomena. This is followed by an introduction to bio-sensing and a review of recent research highlights on resistive and capacitive biosensors based on nanogap electrodes, especially those having novel applications from DNA detection to nanoparticle capturing. Lastly, the article highlights a recent new breakthrough on how the combination of nanogap electrodes with label-free methods, such as aptamer functionalized surfaces, can make capacitive sensors with extremely high sensitivity and specificity.

Towards single electron transistor-based photon detection with microplasma-enabled graphene quantum dots

Single-electron transistors (SETs) represent a new generation of electronic devices with high charge sensitivity, high switching speed, and low power consumption. Here a simple and controlled fabrication of graphene quantum dot (GQD)-based SETs for photon detectors has been demonstrated. The plasma-synthesized GQDs exhibit stable photoluminescence and are successfully used as the Coulomb islands between heteroepitaxial spherical-gold/platinum (HS-Au/Pt) nanogap electrodes. The as-fabricated GQD-SETs enable photon detection with 410 nm excitation owing to the ability of GQDs to generate photoluminescence emission.

Investigation of Molecular Bridging Using Atom Migration in Nanogap Electrodes

Investigation of Molecular Bridging Using Atom Migration in Nanogap Electrodes

Unveiling the full reaction path of the Suzuki-Miyaura cross-coupling in a single-molecule junction.

Conventional analytic techniques that measure ensemble averages and static disorder provide essential knowledge of the reaction mechanisms of organic and organometallic reactions. However, single-molecule junctions enable the in situ, label-free and non-destructive sensing of molecular reaction processes at the single-event level with an excellent temporal resolution. Here we deciphered the mechanism of Pd-catalysed Suzuki-Miyaura coupling by means of a high-resolution single-molecule platform. Through molecular engineering, we covalently integrated a single molecule Pd catalyst into nanogapped graphene point electrodes. We detected sequential electrical signals that originated from oxidative addition/ligand exchange, pretransmetallation, transmetallation and reductive elimination in a periodic pattern. Our analysis shows that the transmetallation is the rate-determining step of the catalytic cycle and clarifies the controversial transmetallation mechanism. Furthermore, we determined the kinetic and thermodynamic constants of each elementary step and the overall catalytic timescale of this Suzuki-Miyaura coupling. Our work establishes the single-molecule platform as a detection technology for catalytic organochemistry that can monitor transition-metal-catalysed reactions in real time.

Recent advances in techniques for fabrication and characterization of nanogap biosensors: A review.

Nanogap biosensors have fascinated researchers due to their excellent electrical properties. Nanogap biosensors comprise three arrays of electrodes that form nanometer-size gaps. The sensing gaps have become the major building blocks of several sensing applications, including bio- and chemosensors. One of the advantages of nanogap biosensors is that they can be fabricated in nanoscale size for various downstream applications. Several studies have been conducted on nanogap biosensors, and nanogap biosensors exhibit potential material properties. The possibilities of combining these unique properties with a nanoscale-gapped device and electrical detection systems allow excellent and potential prospects in biomolecular detection. However, their fabrication is challenging as the gap is becoming smaller. It includes high-cost, low-yield, and surface phenomena to move a step closer to the routine fabrications. This review summarizes different feasible techniques in the fabrication of nanogap electrodes, such as preparation by self-assembly with both conventional and nonconventional approaches. This review also presents a comprehensive analysis of the fabrication, potential applications, history, and the current status of nanogap biosensors with a special focus on nanogap-mediated bio- and chemical sonsors.

In-situ control of on-chip angstrom gaps, atomic switches, and molecular junctions by light irradiation

Pairs of electrodes with nanometer gap, termed as nano-gapped electrodes, are fundamental building blocks for the fabrication of nanometer-sized devices and are essential for the examination of molecular properties and extreme nano-optics. Although modern fabrication techniques make it feasible to fabricate nanometer gaps, it is still a formidable challenge to fabricate adjustable gaps arrays with angstrom precision. Here, we demonstrate that in-situ adjustable nanogaps (arrays) with sub-angstrom precision can be fabricated via laser irradiation on the substrate which supports the electrode pairs. We further demonstrate that atomic-level metal contacts can be switched and the direction of the switching can be selectively controlled by the laser irradiation position. By varying the laser power gradually, the nanogap’s size can be continuously changed, providing a reliable break junction technique to address the properties of single-molecule junctions. The small spatial focus size of the laser beam makes it feasible to realize addressable on-chip molecular junction arrays.

Nano-gap planar metal electrodes: fabrication and I-V characteristics

The nanowires/bars and nano-gap electrodes are vital components for emerging electronics and have wide ranging applications in flat-panel displays, sensors, sub-100 nm transistor circuits, and miniaturized computers/devices. Focused ion beam (FIB) has emerged as a powerful and unique tool for nanofabrication. The research work described here is concerned with (a) the FIB fabrication of planar metallic (copper and gold) nanostructures, (b) their current-voltage (I–V) measurements in situ, and (c) a viable method for extracting the realistic values of emission parameters. The planar electrodes with gap of 80-100 nm are realized by FIB milling of thin metal films. The difficulties faced in objective interpretation of their I-V data (based on known mechanisms) are highlighted. For determining the parameters (namely, effective emission area α eff, apparent work function ф, and the field enhancement factor β), Fowler-Nordheim [ln(I/V2) versus 1/V] plots showing a minimum with straight line of negative slope can be used. The striking findings demonstrated are (i) occurrence of emission from a tiny region (<1 nm2) vis-à-vis physical area (400 μm × 200 nm), (ii) significant lowering of barrier height, and (iii) enhancement of local field due to protrusions present. Typical values of α eff, ϕ, and β deduced are 52.3 Å2, 1.62 eV, and 39.3, respectively for copper planar electrodes (gap ∼100 nm); the corresponding data for the case of gold (gap ∼80 nm) are 29.1 Å2, 1.97 eV, and 12.1, respectively. Moreover, β lowering observed with bias is accompanied by increase in the emission area due to progressive smoothening of protrusions at the cathode surface. The electrodes are found rough/rocky at the nanoscale with protrusions and varying separations at places. These features make the electron emissive region small and pointed with an enhanced local electric field and effectively of a lower barrier height. The current discrepancy in the Child-Langmuir’s space charge regime is attributed to the emission occurring from a restricted area only. These findings are important for futuristic nano-devices like thermo-tunnelling refrigerator, energy harvester, etc.

20-nm-Nanogap oxygen gas sensor with solution-processed cerium oxide

Pt-based nanogap electrodes with a gap separation of 20 nm were prepared by electron-beam lithography (EBL). These electrodes were employed to fabricate nanogap gas sensors by combining solution-processed cerium oxide (ceria, CeO2) as the sensing material. Two types (bottom- and top-contact) of nanogap gas sensors were prepared by alternating the EBL and the solution process. Oxygen gas responses were investigated as functions of the gap separation, ceria film thicknesses, and operating temperatures. The sensor response strongly depended on the gap separation and the nanostructure of the cerium oxide film. In the cases of the small gap separation below 35 nm, the nanogap gas sensor exhibits a fast response time of 10 s at a relatively low operating temperature of 573 K; this response time is approximately three orders of magnitude shorter than that exhibited by a microgap sensor under the same measurement conditions. The nanogap gas sensor could also be in use at 1 atm. The improved sensor performance is attributed to the extremely small gap separation of the nanogap electrodes; the reduced gap separation facilitates electron hopping conduction in the ceria film. The proposed approach for fabricating robust and ultrafine nanogap electrodes together with a facile coating method for forming the sensing layer opens up possibilities to develop various nanogap gas sensors with a fast response time.