Ultralow-Power Single-Sensor-Based E-Nose System Powered by Duty Cycling and Deep Learning for Real-Time Gas Identification.

This study presents a novel, ultralow-power single-sensor-based electronic nose (e-nose) system for real-time gas identification, distinguishing itself from conventional sensor-array-based e-nose systems, whose power consumption and cost increase with the number of sensors. Our system employs a single metal oxide semiconductor (MOS) sensor built on a suspended 1D nanoheater, driven by duty cycling─characterized by repeated pulsed power inputs. The sensor's ultrafast thermal response, enabled by its small size, effectively decouples the effects of temperature and surface charge exchange on the MOS nanomaterial's conductivity. This provides distinct sensing signals that alternate between responses coupled with and decoupled from the thermally enhanced conductivity, all within a single time domain during duty cycling. The magnitude and ratio of these dual responses vary depending on the gas type and concentration, facilitating the early stage gas identification of five gas types within 30 s via a convolutional neural network (classification accuracy = 93.9%, concentration regression error = 19.8%). Additionally, the duty-cycling mode significantly reduces power consumption by up to 90%, lowering it to 160 µW to heat the sensor to 250 °C. Manufactured using only wafer-level batch microfabrication processes, this innovative e-nose system promises the facile implementation of battery-driven, long-term, and cost-effective IoT monitoring systems.

Batch Nanofabrication of Suspended Single 1D Nanoheaters for Ultralow-Power Metal Oxide Semiconductor-Based Gas Sensors.

The demand for power-efficient micro-and nanodevices is increasing rapidly. In this regard, electrothermal nanowire-based heaters are promising solutions for the ultralow-power devices required in IoT applications. Herein, a method is demonstrated for producing a 1D nanoheater by selectively coating a suspended pyrolyzed carbon nanowire backbone with a thin Au resistive heater layer and utilizing it in a portable gas sensor system. This sophisticated nanostructure is developed without complex nanofabrication and nanoscale alignment processes, owing to the suspended architecture and built-in shadow mask. The suspended carbon nanowires, which are batch-fabricated using carbon-microelectromechanical systems technology, maintain their structural and functional integrity in subsequent nanopatterning processes because of their excellent mechanical robustness. The developed nanoheater is used in gas sensors via user-designable localization of the metal oxide semiconductor nanomaterials onto the central region of the nanoheater at the desired temperature. This allows the sensing site to be uniformly heated, enabling reliable and sensitive gas detection. The 1D nanoheater embedded gas sensor can be heated immediately to 250 °C at a remarkably low power of 1.6 mW, surpassing the performance of state-of-the-art microheater-based gas sensors. The presented technology offers facile 1D nanoheater production and promising pathways for applications in various electrothermal devices.

Development of a Novel Gas-Sensing Platform Based on a Network of Metal Oxide Nanowire Junctions Formed on a Suspended Carbon Nanomesh Backbone.

Junction networks made of longitudinally connected metal oxide nanowires (MOx NWs) have been widely utilized in resistive-type gas sensors because the potential barrier at the NW junctions leads to improved gas sensing performances. However, conventional MOx-NW-based gas sensors exhibit limited gas access to the sensing sites and reduced utilization of the entire NW surfaces because the NW networks are grown on the substrate. This study presents a novel gas sensor platform facilitating the formation of ZnO NW junction networks in a suspended architecture by growing ZnO NWs radially on a suspended carbon mesh backbone consisting of sub-micrometer-sized wires. NW networks were densely formed in the lateral and longitudinal directions of the ZnO NWs, forming additional longitudinally connected junctions in the voids of the carbon mesh. Therefore, target gases could efficiently access the sensing sites, including the junctions and the entire surface of the ZnO NWs. Thus, the present sensor, based on a suspended network of longitudinally connected NW junctions, exhibited enhanced gas response, sensitivity, and lower limit of detection compared to sensors consisting of only laterally connected NWs. In addition, complete sensor structures consisting of a suspended carbon mesh backbone and ZnO NWs could be prepared using only batch fabrication processes such as carbon microelectromechanical systems and hydrothermal synthesis, allowing cost-effective sensor fabrication.

Hierarchical Porous Carbon Electrodes with Sponge-Like Edge Structures for the Sensitive Electrochemical Detection of Heavy Metals.

This article presents the development of a highly sensitive electrochemical heavy metal sensor based on hierarchical porous carbon electrodes with sponge-like edge structures. Micrometer-scale hierarchical nanoporous carbon electrodes were fabricated at a wafer-scale using cost-effective batch microfabrication technologies, including the carbon microelectromechanical systems technology and oxygen plasma etching. The sponge-like hierarchical porous structure and sub-micrometer edges of the nanoporous carbon electrodes facilitate fast electron transfer rate and large active sites, leading to the efficient formation of dense heavy metal alloy particles of small sizes during the preconcentration step. This enhanced the peak current response during the square wave anodic stripping voltammetry, enabling the detection of Cd(II) and Pb(II) at concentrations as low as 0.41 and 0.7 µg L-1, respectively, with high sensitivity per unit sensing area (Cd: 109.45 nA µg-1 L mm-2, Pb: 100.37 nA µg-1 L mm-2).

Mixed-scale poly(methyl methacrylate) channel network-based single-particle manipulation via diffusiophoresis.

Despite the unique advantages of nanochannels imparted by their small size, their utility is limited by the lack of affordable and versatile fabrication methods. Moreover, nanochannel-incorporated fluidic devices require micro-sized conduit integration for efficient access of liquid samples. In this study, a simple and cost-effective fabrication method for mixed-scale channel networks via hot-embossing of poly(methyl methacrylate) (PMMA) using a carbon stamp is demonstrated. Due to its high rigidity, PMMA ensures collapse-free channel fabrication. The carbon stamp is fabricated using only batch microfabrication and has a convex architecture that allows the fabrication of a complex channel network via a single imprinting process. In addition, the microchannels are connected to nanochannels via three-dimensional (3D) microfunnels that serve as single-particle-entrapment chambers, ensuring smooth transport of samples into the nanochannels. Owing to the 3D geometry of the microfunnels and the small size of the nanochannels, a solute gradient can be generated locally at the microfunnel. This local solute gradient enables the entrapment of microparticles at the microfunnels via diffusiophoresis, which can manipulate the particle motion in a controllable manner, without any external equipment or additional electrode integration into the channels. To the best of our knowledge, this is the first report of diffusiophoresis-based single-particle entrapment.

An electrochemical immunosensor based on a 3D carbon system consisting of a suspended mesh and substrate-bound interdigitated array nanoelectrodes for sensitive cardiac biomarker detection.

We developed an electrochemical redox cycling-based immunosensor using a 3D carbon system consisting of a suspended mesh and substrate-bound interdigitated array (IDA) nanoelectrodes. The carbon structures were fabricated using a simple, cost-effective, and reproducible microfabrication technology known as carbon microelectromechanical systems (C-MEMS). We demonstrated that the 3D sub-micrometer-sized mesh architecture and selective modification of the suspended mesh facilitated the efficient production of large quantities of electrochemical redox species. The electrochemically active surfaces and small size of IDA nanoelectrodes with a 1:1 aspect ratio exhibited high signal amplification resulting from efficient redox cycling of electrochemical species (PAP/PQI) by a factor of ~25. The proposed selective surface modification scheme facilitated efficient redox cycling and exhibited a linear detection range of 0.001-100 ng/mL for cardiac myoglobin (cMyo). The specific detection of cMyo was also achieved in the presence of other interfering species. Moreover, the proposed 3D carbon system-based immunosensor successfully detected as low as ~0.4 pg/mL cMyo in phosphate-buffered saline and human serum.

Development of a Sensitive Electrochemical Enzymatic Reaction-Based Cholesterol Biosensor Using Nano-Sized Carbon Interdigitated Electrodes Decorated with Gold Nanoparticles.

We developed a versatile and highly sensitive biosensor platform. The platform is based on electrochemical-enzymatic redox cycling induced by selective enzyme immobilization on nano-sized carbon interdigitated electrodes (IDEs) decorated with gold nanoparticles (AuNPs). Without resorting to sophisticated nanofabrication technologies, we used batch wafer-level carbon microelectromechanical systems (C-MEMS) processes to fabricate 3D carbon IDEs reproducibly, simply, and cost effectively. In addition, AuNPs were selectively electrodeposited on specific carbon nanoelectrodes; the high surface-to-volume ratio and fast electron transfer ability of AuNPs enhanced the electrochemical signal across these carbon IDEs. Gold nanoparticle characteristics such as size and morphology were reproducibly controlled by modulating the step-potential and time period in the electrodeposition processes. To detect cholesterol selectively using AuNP/carbon IDEs, cholesterol oxidase (ChOx) was selectively immobilized via the electrochemical reduction of the diazonium cation. The sensitivity of the AuNP/carbon IDE-based biosensor was ensured by efficient amplification of the redox mediators, ferricyanide and ferrocyanide, between selectively immobilized enzyme sites and both of the combs of AuNP/carbon IDEs. The presented AuNP/carbon IDE-based cholesterol biosensor exhibited a wide sensing range (0.005-10 mM) and high sensitivity (~993.91 µA mM-1 cm-2; limit of detection (LOD) ~1.28 µM). In addition, the proposed cholesterol biosensor was found to be highly selective for the cholesterol detection.

Unconventional micro-/nanofabrication technologies for hybrid-scale lab-on-a-chip.

Micro-/nanofabrication-based lab-on-a-chip (LOC) technologies have recently been substantially advanced and have become widely used in various inter-/multidisciplinary research fields, including biological, (bio-)chemical, and biomedical fields. However, such hybrid-scale LOC devices are typically fabricated using microfabrication and nanofabrication processes in series, resulting in increased cost and time and low throughput issues. In this review, after briefly introducing the conventional micro-/nanofabrication technologies, we focus on unconventional micro-/nanofabrication technologies that allow us to produce either in situ micro-/nanoscale structures or master molds for additional replication processes to easily and conveniently create novel LOC devices with micro- or nanofluidic channel networks. In particular, microfabrication methods based on crack-assisted photolithography and carbon-microelectromechanical systems (C-MEMS) are described in detail because of their superior features from the viewpoint of the throughput, batch fabrication process, and mixed-scale channels/structures. In parallel with previously reported articles on conventional micro-/nanofabrication technologies, our review of unconventional micro-/nanofabrication technologies will provide a useful and practical fabrication guideline for future hybrid-scale LOC devices.

Mixed-scale channel networks including Kingfisher-beak-shaped 3D microfunnels for efficient single particle entrapment.

Reproducible research results for nanofluidics and their applications require viable fabrication technologies to produce nanochannels integrated with microchannels that can guide fluid flow and analytes into/out of the nanochannels. We present the simple fabrication of mixed-scale polydimethylsiloxane (PDMS) channel networks consisting of nanochannels and microchannels via a single molding process using a monolithic mixed-scale carbon mold. The monolithic carbon mold is fabricated by pyrolyzing a polymer mold patterned by photolithography. During pyrolysis, the polymer mold shrinks by ∼90%, which enables nanosized carbon molds to be produced without a complex nanofabrication process. Because of the good adhesion between the polymer mold and the Si substrate, non-uniform volume reduction occurs during pyrolysis resulting in the formation of curved carbon mold side walls. These curved side walls and the relatively low surface energy of the mold provide efficient demolding of the PDMS channel networks. In addition, the trigonal prismatic shape of the polymer is converted into to a Kingfisher-beak-shaped carbon structure due to the non-uniform volume reduction. The transformation of this mold architecture produces a PDMS Kingfisher-beak-shaped 3D microfunnel that connects the microchannel and the nanochannel smoothly. The smooth reduction in the cross-sectional area of the 3D microfunnels enables efficient single microparticle trapping at the nanochannel entrance; this is beneficial for studies of cell transfection.

Glucose sensor based on redox-cycling between selectively modified and unmodified combs of carbon interdigitated array nanoelectrodes.

We present a novel electrochemical glucose sensor employing an interdigitated array (IDA) of 1:1 aspect ratio carbon nanoelectrodes for the electrochemical-enzymatic redox cycling of redox species (ferricyanide/ferrocyanide) between glucose oxidase (GOx) and the two comb-shaped nanoelectrodes of the IDA. The carbon nanoelectrodes were fabricated using a simple, cost-effective, reproducible microfabrication technology known as the carbon-microelectromechanical-systems (C-MEMS) process. One comb (comb 1) of the IDA was selectively modified with GOx via the electrochemical reduction of an aryl diazonium salt, while the other comb (comb 2) remained unmodified; this facilitates electrochemically more active surface of comb 2, resulting in sensitive glucose detection. Ferricyanide is reduced to ferrocyanide by the GOx in the presence of glucose, and ferrocyanide diffuses to both combs of the IDA where it is oxidized. The limited electrochemical current collection at the surface-modified comb 1 is counterbalanced by the efficient redox cycling between the enzyme sites at comb 1 and the bare carbon surface of comb 2. Reducing the electrode-to-electrode gap between the two combs (gap = 1.9 µm) increases the diffusion flux of redox species at comb 2 hence, enhanced the sensitivity and limit of detection of the glucose sensor by ∼2.3 and ∼295 times, respectively at comb 2 compared to comb 1. The developed IDA-based glucose sensor demonstrated good amperometric response to glucose, affording two linear ranges from 0.001 to 1 mM and from 1 to 10 mM, with limits of detection of 0.4 and 61 µM and sensitivities of 823.2 and 70.0 µA mM(-1) cm(-2), respectively.

Simultaneous imaging of the topography and electrochemical activity of a 2D carbon nanotube network using a dual functional L-shaped nanoprobe.

The application of nanomaterials for biosensors and fuel cells is becoming more common, but it requires an understanding of the relationship between the structure and electrochemical characteristics of the materials at the nanoscale. Herein, we report the development of scanning electrochemical microscopy-atomic force microscopy (SECM-AFM) nanoprobes for collecting spatially resolved data regarding the electrochemical activity of nanomaterials such as carbon nanotube (CNT) networks. The fabrication of the nanoprobe begins with the integration of a CNT-bundle wire into a conventional AFM probe followed by the deposition of an insulating layer and cutting of the probe end. In addition, a protrusive insulating tip is integrated at the end of the insulated CNT-bundle wire to maintain a constant distance between the nanoelectrode and the substrate; this yields an L-shaped nanoprobe. The resulting nanoprobes produced well-fitted maps of faradaic current data with less than 300 nm spatial resolution and topographical images of CNT networks owing to the small effective distance (of the order of tens of nanometers) between the electrode and the substrate. Electrochemical imaging using the L-shaped nanoprobe revealed that the electrochemical activity of the CNT network is not homogeneous and provided further understanding of the relationship between the topography and electrochemical characteristics of CNT networks.

Surface charge, electroosmotic flow and DNA extension in chemically modified thermoplastic nanoslits and nanochannels.

Thermoplastics have become attractive alternatives to glass/quartz for microfluidics, but the realization of thermoplastic nanofluidic devices has been slow in spite of the rather simple fabrication techniques that can be used to produce these devices. This slow transition has in part been attributed to insufficient understanding of surface charge effects on the transport properties of single molecules through thermoplastic nanochannels. We report the surface modification of thermoplastic nanochannels and an assessment of the associated surface charge density, zeta potential and electroosmotic flow (EOF). Mixed-scale fluidic networks were fabricated in poly(methylmethacrylate), PMMA. Oxygen plasma was used to generate surface-confined carboxylic acids with devices assembled using low temperature fusion bonding. Amination of the carboxylated surfaces using ethylenediamine (EDA) was accomplished via EDC coupling. XPS and ATR-FTIR revealed the presence of carboxyl and amine groups on the appropriately prepared surfaces. A modified conductance equation for nanochannels was developed to determine their surface conductance and was found to be in good agreement with our experimental results. The measured surface charge density and zeta potential of these devices were lower than glass nanofluidic devices and dependent on the surface modification adopted, as well as the size of the channel. This property, coupled to an apparent increase in fluid viscosity due to nanoconfinement, contributed to the suppression of the EOF in PMMA nanofluidic devices by an order of magnitude compared to the micro-scale devices. Carboxylated PMMA nanochannels were efficient for the transport and elongation of λ-DNA while these same DNA molecules were unable to translocate through aminated nanochannels.

Monolithic carbon structures including suspended single nanowires and nanomeshes as a sensor platform.

With the development of nanomaterial-based nanodevices, it became inevitable to develop cost-effective and simple nanofabrication technologies enabling the formation of nanomaterial assembly in a controllable manner. Herein, we present suspended monolithic carbon single nanowires and nanomeshes bridging two bulk carbon posts, fabricated in a designed manner using two successive UV exposure steps and a single pyrolysis step. The pyrolysis step is accompanied with a significant volume reduction, resulting in the shrinkage of micro-sized photoresist structures into nanoscale carbon structures. Even with the significant elongation of the suspended carbon nanowire induced by the volume reduction of the bulk carbon posts, the resultant tensional stress along the nanowire is not significant but grows along the wire thickness; this tensional stress gradient and the bent supports of the bridge-like carbon nanowire enhance structural robustness and alleviate the stiction problem that suspended nanostructures frequently experience. The feasibility of the suspended carbon nanostructures as a sensor platform was demonstrated by testing its electrochemical behavior, conductivity-temperature relationship, and hydrogen gas sensing capability.

The effect of channel height and electrode aspect ratio on redox cycling at carbon interdigitated array nanoelectrodes confined in a microchannel.

Redox cycling is a commonly used electrochemical sensing scheme for enhancing faradaic current signals. This effect can be improved by either optimizing electrode geometries or restricting electrochemical reactions within a limited volume. Here, we demonstrate a simple batch fabrication of 1 : 1 aspect ratio carbon interdigitated array nanoelectrodes integrated in a polydimethylsiloxane microchannel that enables current amplification by up to 1116 times. We also examine the factors that influence the effect of redox cycling, including the electrode aspect ratio and channel height, by using experiments and simulations.

Current application of micro/nano-interfaces to stimulate and analyze cellular responses.

Microfabrication technologies have a high potential for novel approaches to access living cells at a cellular or even at a molecular level. In the course of reviewing and discussing the current application of microinterface systems including nanointerfaces to stimulate and analyze cellular responses with subcellular resolution, this article focuses on interfaces based on microfluidics, nanoparticles, and scanning electrochemical microscopy (SECM). Micro/nanointerface systems provide a novel, attractive means for cell study because they are capable of regulating and monitoring cellular signals simultaneously and repeatedly, leading us to an enhanced understanding and interpretation of cellular responses. Therefore, it is hoped that the integrated micro/nanointerfaces presented in this review will contribute to future developments of cell biology and facilitate advanced biomedical applications.

Ac dielectrophoresis of tin oxide nanobelts suspended in ethanol: manipulation and visualization.

This article presents results of detailed and direct real-time observations of the wide variety of SnO(2) nanobelt motions induced by ac dielectrophoresis (DEP) in an innovative microfluidic setup. High ac electric fields were generated on a gold microelectrode (approximately 20 microm electrode gap) array, patterned on a glass substrate and covered by a approximately 10 microm tall polydimethylsiloxane (PDMS) microchannel. Ethanol suspended SnO(2) nanobelts were introduced into the microchannel, and the DEP experiments were performed. Negative DEP (repulsion) of the nanobelts was observed in the low-frequency range (<100 kHz) of the applied electric field, which caused rigid body motion as well as deformation of the nanobelts. The negative DEP effect observed in ethanol is unusual and contrary to what is predicted by the Clausius-Mossotti factor (using bulk SnO(2) conductivity and permittivity values) of the dipole approximation theory. In the high-frequency range (approximately 1-10 MHz), positive DEP (attraction) of the nanobelts was observed. Pearl chain formation involving short nanobelts and particles was also observed in the two DEP regimes.

Frequency dependence of the electrochemical activity contrast in AC-scanning electrochemical microscopy and atomic force microscopy-AC-scanning electrochemical microscopy imaging.

Alternating current mode scanning electrochemical microscopy (AC-SECM) enables local detection of electrochemical surface activity without any redox mediator present in solution. Z-approach curves toward the substrate result in a negative feedback curve of the ac signal for insulating samples. On conducting samples, however, the shape of the feedback curve was found to be dependent on the ac perturbation frequency. Approach curves over a wide range of frequencies were performed, and the results were applied to interpret laterally resolved frequency-dependent measurements obtained with combined atomic force microscopy-AC-SECM (AFM-AC-SECM). For the first time, this frequency dependence of the signal was utilized to fine-tune the electrochemical contrast in lateral imaging in AC-SECM. An array of gold microelectrodes embedded in silicon nitride displaying significant changes in electrochemical activity as well as in topography was investigated using a bifunctional AFM-SECM tip with an integrated recessed ring microelectrode. Due to the unique geometrical conditions the electrochemical contrast between the conducting gold spots and the insulating SixNy is reversed, crosses zero, and inverts as a function of the applied ac frequency.

Batch fabrication of atomic force microscopy probes with recessed integrated ring microelectrodes at a wafer level.

A batch fabrication process at the wafer-level integrating ring microelectrodes into atomic force microscopy (AFM) tips is presented. The fabrication process results in bifunctional scanning probes combining atomic force microscopy with scanning electrochemical microscopy (AFM-SECM) with a ring microelectrode integrated at a defined distance above the apex of the AFM tip. Silicon carbide is used as AFM tip material, resulting in reduced mechanical tip wear for extended usage. The presented approach for the probe fabrication is based on batch processing using standard microfabrication techniques, which provides bifunctional scanning probes at a wafer scale and at low cost. Additional benefits of batch fabrication include the high processing reproducibility, uniformity, and tuning of the physical properties of the cantilever for optimized AFM dynamic mode operation. The performance of batch-fabricated bifunctional probes was demonstrated by simultaneous imaging micropatterned platinum structures at a silicon dioxide substrate in intermittent (dynamic) and contact mode, respectively, and feedback mode SECM. In both, intermittent and contact mode, the bifunctional probes provided reliable correlated electrochemical and topographical data. In addition, simulations of the diffusion-limited steady-state currents at the integrated electrode using finite element methods were performed for characterizing the developed probes.