Akihide Arima

Thermoelectricity in atom-sized junctions at room temperatures

Atomic and molecular junctions are an emerging class of thermoelectric materials that exploit quantum confinement effects to obtain an enhanced figure of merit. An important feature in such nanoscale systems is that the electron and heat transport become highly sensitive to the atomic configurations. Here we report the characterization of geometry-sensitive thermoelectricity in atom-sized junctions at room temperatures. We measured the electrical conductance and thermoelectric power of gold nanocontacts simultaneously down to the single atom size. We found junction conductance dependent thermoelectric voltage oscillations with period 2e2/h. We also observed quantum suppression of thermovoltage fluctuations in fully-transparent contacts. These quantum confinement effects appeared only statistically due to the geometry-sensitive nature of thermoelectricity in the atom-sized junctions. The present method can be applied to various nanomaterials including single-molecules or nanoparticles and thus may be used as a useful platform for developing low-dimensional thermoelectric building blocks.

Particle Trajectory-Dependent Ionic Current Blockade in Low-Aspect-Ratio Pores

Resistive pulse sensing with nanopores having a low thickness-to-diameter aspect-ratio structure is expected to enable high-spatial-resolution analysis of nanoscale objects in a liquid. Here we investigated the sensing capability of low-aspect-ratio pore sensors by monitoring the ionic current blockades during translocation of polymeric nanobeads. We detected numerous small current spikes due to partial occlusion of the pore orifice by particles diffusing therein reflecting the expansive electrical sensing zone of the low-aspect-ratio pores. We also found wide variations in the ion current line-shapes in the particle capture stage suggesting random incident angle of the particles drawn into the pore. In sharp contrast, the ionic profiles were highly reproducible in the post-translocation regime by virtue of the spatial confinement in the pore that effectively constricts the stochastic capture dynamics into a well-defined ballistic motion. These results, together with multiphysics simulations, indicate that the resistive pulse height is highly dependent on the nanoscopic single-particle trajectories involved in ultrathin pore sensors. The present finding indicates the importance of regulating the translocation pathways of analytes in low-aspect-ratio pores for improving the discriminability toward single-bioparticle tomography in liquid.

High thermopower of mechanically stretched single-molecule junctions

Metal-molecule-metal junction is a promising candidate for thermoelectric applications that utilizes quantum confinement effects in the chemically defined zero-dimensional atomic structure to achieve enhanced dimensionless figure of merit ZT. A key issue in this new class of thermoelectric nanomaterials is to clarify the sensitivity of thermoelectricity on the molecular junction configurations. Here we report simultaneous measurements of the thermoelectric voltage and conductance on Au-1,4-benzenedithiol (BDT)-Au junctions mechanically-stretched in-situ at sub-nanoscale. We obtained the average single-molecule conductance and thermopower of 0.01 G0 and 15 μV/K, respectively, suggesting charge transport through the highest occupied molecular orbital. Meanwhile, we found the single-molecule thermoelectric transport properties extremely-sensitive to the BDT bridge configurations, whereby manifesting the importance to design the electrode-molecule contact motifs for optimizing the thermoelectric performance of molecular junctions.

Fabrications of insulator-protected nanometer-sized electrode gaps

We developed SiO2-coated mechanically controllable break junctions for accurate tunneling current measurements in an ionic solution. By breaking the junction, we created dielectric-protected Au nanoprobes with nanometer separation. We demonstrated that the insulator protection was capable to suppress the ionic contribution to the charge transport through the electrode gap, thereby enabled reliable characterizations of liquid-mediated exponential decay of the tunneling conductance in an electrolyte solution. From this, we found distinct roles of charge points such as molecular dipoles and ion species on the tunneling decay constant, which was attributed to local structures of molecules and ions in the confined space between the sensing electrodes. The device described here would provide improved biomolecular sensing capability of tunneling current sensors.

Tailoring particle translocation via dielectrophoresis in pore channels

Understanding and controlling electrophoretic motions of nanoscopic objects in fluidic channels are a central challenge in developing nanopore technology for molecular analyses. Although progress has been made in slowing the translocation velocity to meet the requirement for electrical detections of analytes via picoampere current measurements, there exists no method useful for regulating particle flows in the transverse directions. Here, we report the use of dielectrophoresis to manipulate the single-particle passage through a solid-state pore. We created a trap field by applying AC voltage between electrodes embedded in a low-aspect-ratio micropore. We demonstrated a traffic control of particles to go through center or near side surface via the voltage frequency. We also found enhanced capture efficiency along with faster escaping speed of particles by virtue of the AC-mediated electroosmosis. This method is compatible with nanopore sensing and would be widely applied for reducing off-axis effects to achieve single-molecule identification.

Identification of Individual Bacterial Cells through the Intermolecular Interactions with Peptide-Functionalized Solid-State Pores

Bioinspired pore sensing for selective detection of flagellated bacteria was investigated. The Au micropore wall surface was modified with a synthetic peptide designed from toll-like receptor 5 (TLR5) to mimic the pathogen-recognition capability. We found that intermolecular interactions between the TLR5-derived recognition peptides and flagella induce ligand-specific perturbations in the translocation dynamics of Escherichia coli, which facilitated the discrimination between the wild-type and flagellin-deletion mutant (ΔfliC) by the resistive pulse patterns thereby demonstrating the sensing of bacteria at a single-cell level. These results provide a novel concept of utilizing weak intermolecular interactions as a recognition probes for single-cell microbial identification.

Discrimination of equi-sized nanoparticles by surface charge state using low-aspect-ratio pore sensors

In the field of nanopore sensing, it is difficult to distinguish particles of similar sizes by the ionic current signatures. In contrast, here, we demonstrated discrimination of equi-sized polystyrene (PS) particles by utilizing a low thickness-to-diameter aspect-ratio nanopore. We found distinct changes of the ionic current through the pore associated with translocation of PS particles modified with different functional groups. Comparing results about different size of nanopore can lead to discrimination of their surface charge densities. This discrimination technique may be useful in the development of low-aspect-ratio nanopore sensors for bioanalysis.

Temporal Response of Ionic Current Blockade in Solid-State Nanopores

Signal delay is a crucial factor in resistive pulse analyses using low-thickness-to-diameter aspect-ratio pores that aim to detect fine features in the ionic current blockade during the fast translocation of individual analytes to attain single-molecule tomography. Here we report on evaluations of the ionic current response to dynamic motions of nanoparticles in ultrathin solid-state nanopores. We systematically investigated the effects of pore resistance and membrane capacitance on resistive pulse waveforms under different salt concentration conditions and device configurations. The results revealed substantial modifications in the resistive pulse waveforms due to a slow charging/discharging processes at the water-touching thin dielectrics in the solid-state nanopore chips. We also provide a device design to improve the temporal resolution without compromising the spatial sensitivity. The present findings offer a breakthrough toward nanoporescopy to measure the nanoscopic shape of single-bioparticles and -molecules in electrolyte solution.

Discriminating single-bacterial shape using low-aspect-ratio pores

Conventional concepts of resistive pulse analysis is to discriminate particles in liquid by the difference in their size through comparing the amount of ionic current blockage. In sharp contrast, we herein report a proof-of-concept demonstration of the shape sensing capability of solid-state pore sensors by leveraging the synergy between nanopore technology and machine learning. We found ionic current spikes of similar patterns for two bacteria reflecting the closely resembled morphology and size in an ultra-low thickness-to-diameter aspect-ratio pore. We examined the feasibility of a machine learning strategy to pattern-analyse the sub-nanoampere corrugations in each ionic current waveform and identify characteristic electrical signatures signifying nanoscopic differences in the microbial shape, thereby demonstrating discrimination of single-bacterial cells with accuracy up to 90%. This data-analytics-driven microporescopy capability opens new applications of resistive pulse analyses for screening viruses and bacteria by their unique morphologies at a single-particle level.

Electrical trapping mechanism of single-microparticles in a pore sensor

Nanopore sensing via resistive pulse technique are utilized as a potent tool to characterize physical and chemical property of single –molecules and –particles. In this article, we studied the influence of particle trajectory to the ionic conductance through a pore. We performed the optical/electrical simultaneous sensing of electrophoretic capture dynamics of single-particles at a pore using a microchannel/nanopore system. We detected ionic current drops synchronous to a fluorescently dyed particle being electrophoretically drawn and become immobilized at a pore in the optical imaging. We also identified anomalous trapping events wherein particles were captured at nanoscale pin-holes formed unintentionally in a SiN membrane that gave rise to relatively small current drops. This method is expected to be a useful platform for testing novel nanopore sensor design wherein current behaves in unpredictable manner.