Interactive Effect of Hysteresis and Surface Chemistry on Gated Silicon Nanowire Gas Sensors

Gated silicon nanowire gas sensors have emerged as promising devices for chemical and biological sensing applications. Nevertheless, the performance of these devices is usually accompanied by a “hysteresis” phenomenon that limits their performance under real-world conditions. In this paper, we use a series of systematically changed trichlorosilane-based organic monolayers to study the interactive effect of hysteresis and surface chemistry on gated silicon nanowire gas sensors. The results show that the density of the exposed or unpassivated Si–OH groups (trap states) on the silicon nanowire surface play by far a crucial effect on the hysteresis characteristics of the gated silicon nanowire sensors, relative to the effect of hydrophobicity or molecular density of the organic monolayer. Based on these findings, we provide a tentative model-based understanding of (i) the relation between the adsorbed organic molecules, the hysteresis, and the related fundamental parameters of gated silicon nanowire characteristics and of (ii) the relation between the hysteresis drift and possible screening effect on gated silicon nanowire gas sensors upon exposure to different analytes at real-world conditions. The findings reported in this paper could be considered as a launching pad for extending the use of the gated silicon nanowire gas sensors for discriminations between polar and nonpolar analytes in complex, real-world gas mixtures

Sensors for Breath Testing: From Nanomaterials to Comprehensive Disease Detection

The analysis of volatile organic compounds in exhaled breath samples represents a new frontier in medical diagnostics because it is a noninvasive and potentially inexpensive way to detect illnesses. Clinical trials with spectrometry and spectroscopy techniques, the standard volatile-compound detection methods, have shown the potential for diagnosing illnesses including cancer, multiple sclerosis, Parkinson’s disease, tuberculosis, diabetes, and more via breath tests. Unfortunately, this approach requires expensive equipment and high levels of expertise to operate the necessary instruments, and the tests must be done quickly and use preconcentration techniques, all of which impede its adoption.Sensing matrices based on nanomaterials are likely to become a clinical and laboratory diagnostic tool because they are significantly smaller, easier-to-use, and less expensive than spectrometry or spectroscopy. An ideal nanomaterial-based sensor for breath testing should be sensitive at very low concentrations of volatile organic compounds, even in the presence of environmental or physiological confounding factors. It should also respond rapidly and proportionately to small changes in concentration and provide a consistent output that is specific to a given volatile organic compound. When not in contact with the volatile organic compounds, the sensor should quickly return to its baseline state or be simple and inexpensive enough to be disposable.Several reviews have focused on the methodological, biochemical, and clinical aspects of breath analysis in attempts to bring breath testing closer to practice for comprehensive disease detection. This Account pays particular attention to the technological gaps and confounding factors that impede nanomaterial-sensor-based breath testing, in the hope of directing future research and development efforts towards the best possible approaches to overcome these obstacles. We discuss breath testing as a complex process involving numerous steps, each of which has several possible technological alternatives with advantages and drawbacks that might affect the performance of the nanomaterial-based sensors in a breath-testing system. With this in mind, we discuss how to choose nanomaterial-based sensors, considering the profile of the targeted breath markers and the possible limitations of the approach, and how to design the surrounding breath-testing setup. We also discuss how to tailor the dynamic range and selectivity of the applied sensors to detect the disease-related volatile organic compounds of interest. Finally, we describe approaches to overcome other obstacles by improving the sensing elements and the supporting techniques such as preconcentration and dehumidification

Effect of Functional Groups on the Sensing Properties of Silicon Nanowires toward Volatile Compounds

Molecular layers attached to a silicon nanowire field effect transistor (SiNW FET) can serve as antennas for signal transduction of volatile organic compounds (VOCs). Nevertheless, the mutual relationship between the molecular layers and VOCs is still a puzzle. In the present paper, we explore the effect of the molecular layer’s end (functional) groups on the sensing properties of VOCs. Toward this end, SiNW FETs were modified with tailor-made molecular layers that have the same backbone but differ in their end groups. Changes in the threshold voltage (Δ<i>V</i>_th) and changes in the mobility (Δμ_h) were then recorded upon exposure to various VOCs. Model-based analysis indicates that the interaction between molecular layers and VOCs can be classified to three main scenarios: (a) dipole–dipole interaction between the molecular layer and the polar VOCs; (b) induced dipole–dipole interaction between the molecular layers and the nonpolar VOCs; and (c) molecular layer tilt as a result of VOCs diffusion. Based on these scenarios, it is likely that the electron-donating/withdrawing properties of the functional groups control the dipole moment orientation of the adsorbed VOCs and, as a result, determine the direction (or sign) of the ΔV_th. Additionally, it is likely the diffusion of VOCs into the molecular layer, determined by the type of functional groups, is the main reason for the Δμ_h responses. The reported findings are expected to provide an efficient way to design chemical sensors that are based on SiNW FETs to nonpolar VOCs, which do not exchange carriers with the molecular layers

Self-Healable Sensors Based Nanoparticles for Detecting Physiological Markers via Skin and Breath: Toward Disease Prevention via Wearable Devices

Flexible and wearable electronic sensors are useful for the early diagnosis and monitoring of an individual’s health state. Sampling of volatile organic compounds (VOCs) derived from human breath/skin or monitoring abrupt changes in heart-beat/breath rate should allow noninvasive monitoring of disease states at an early stage. Nevertheless, for many reported wearable sensing devices, interaction with the human body leads incidentally to unavoidable scratches and/or mechanical cuts and bring about malfunction of these devices. We now offer proof-of-concept of nanoparticle-based flexible sensor arrays with fascinating self-healing abilities. By integrating a self-healable polymer substrate with 5 kinds of functionalized gold nanoparticle films, a sensor array gives a fast self-healing (<3 h) and attractive healing efficiency in both the substrate and sensing films. The proposed platform was used in sensing pressure variation and 11 kinds of VOCs. The sensor array had satisfactory sensitivity, a low detection limit, and promising discrimination features in monitoring both of VOCs and pressure variation, even after full healing. These results presage a new type of smart sensing device, with a desirable performance in the possible detection and/or clinical application for a number of different purposes

Field Effect Transistors Based on Polycyclic Aromatic Hydrocarbons for the Detection and Classification of Volatile Organic Compounds

We show that polycyclic aromatic hydrocarbon (PAH) based field effect transistor (FET) arrays can serve as excellent chemical sensors for the detection of volatile organic compounds (VOCs) under confounding humidity conditions. Using these sensors, w/o complementary pattern recognition methods, we study the ability of PAH-FET(s) to: (i) discriminate between aromatic and non-aromatic VOCs; (ii) distinguish polar and non-polar non-aromatic compounds; and to (iii) identify specific VOCs within the subgroups (i.e., aromatic compounds, polar non-aromatic compounds, non-polar non-aromatic compounds). We further study the effect of water vapor on the sensor array’s discriminative ability and derive patterns that are stable when exposed to different constant values of background humidity. Patterns based on different independent electronic features from an array of PAH-FETs may bring us one step closer to creating a unique fingerprint for individual VOCs in real-world applications in atmospheres with varying levels of humidity

Utility of Resistance and Capacitance Response in Sensors Based on Monolayer-Capped Metal Nanoparticles

We investigate the utility of resistance and capacitance responses, as derived by impedance spectroscopy, in well-controlled and real-world applications of monolayer-capped metal nanoparticle (MCNP) sensors. Exposure of the MCNP films to well-controlled analytes showed stable sensing responses and low baseline drift of the pertinent capacitance signals, when compared with equivalent resistance signals. In contrast, exposure of the MCNP films to breath of chronic kidney disease patients under dialysis, as a representative example to real-world multicomponent mixtures, showed low baseline drift but relatively scattered signals when compared with the equivalent resistance response. We ascribe these discrepancies to the level and fluctuating concentration of water molecules in the real-world samples

In Situ and Real-Time Inspection of Nanoparticle Average Size in Flexible Printed Sensors

Nanoparticles play an integral part for the production of contacts and active sensing layers in the fast-developing printed electronic technology on flexible devices. Unfortunately, all currently available techniques for nanoparticle characterization are limited to ex situ and/or off-line processing. Here, we describe a new approach composed of two complementary parts for in situ and real-time estimation of the nanoparticles’ effective diameter on flexible substrates. The first part of the approach is based on measurements of electrical resistance of the device in response to strain, and correlation of the response with the nanoparticles’ diameter. The second part takes place only when measuring the electrical resistance is unfeasible. It is based on UV–vis absorption of the device and correlation of the absorption peak with the nanoparticle diameter based on previous calibration data from strain sensitivity. The new approach shows excellent estimations of the nanoparticle diameter (2.5–20 nm) on the substrate with the advantages of being online, in situ, and inexpensive. In addition, the estimated nanoparticle diameter is in excellent agreement with atomic force microscopy (AFM) measurements. These capabilities are expected to improve the process of “quality control” of the nanoscale-enabled flexible devices, which, until now, has been considered to be one of the most annoying issues that inhibits the commercialization of nanotechnology-based flexible products

Dynamic Nanoparticle-Based Flexible Sensors: Diagnosis of Ovarian Carcinoma from Exhaled Breath

Flexible sensors based on molecularly modified gold nanoparticles (GNPs) were integrated into a dynamic cross-reactive diagnostic sensing array. Each bending state of the GNP-based flexible sensor gives unique nanoparticle spatial organization, altering the interaction between GNP ligands and volatile organic compounds (VOCs), which increases the amount of data obtainable from each sensor. Individual dynamic flexible sensor could selectively detect parts per billion (ppb) level VOCs that are linked with ovarian cancers in exhaled breath and discriminate them from environmental VOCs that exist in exhaled breath samples, but do not relate to ovarian cancer <i>per se</i>. Strain-related response successfully discriminated between exhaled breath collected from control subjects and those with ovarian cancer, with data from a single sensor being sufficient to obtain 82% accuracy, irrespective of important confounding factors, such as tobacco consumption and comorbidities. The approach raises the hope of achieving an extremely simple, inexpensive, portable, and noninvasive diagnostic procedure for cancer and other diseases

Designing Thin Film-Capped Metallic Nanoparticles Configurations for Sensing Applications

Thin film-capped metallic nanoparticles (TFCMNPs) hold big promise for rapid, low-cost, and portable tracing of gas analytes. We show that sensing properties can be controlled by the configuration of the TFCMNPs. To this end, two methods were developed: layer by layer (LbL) and drop-by-drop, i.e., drop casting (DC). The TFCMNP prepared via LbL method was homogeneous and gradually increased in thickness, absorbance, and conductivity relative to TFCMNP prepared via DC method. However, our results indicate that the sensing of TFCMNP devices prepared via DC is significantly higher than that of equivalent LbL devices. These discrepancies can be explained as follows: LbL forms a high dense layer of TFCMNPs without vacancies, and a well-controlled deposition of NPs. The distance between the adjacent NPs is controlled by the capped ligands and the linker molecules making a rigid TFCMNP. Thus, exposing LbL devices to analyte induces a marginal change in the NP–NP distance. However, in DC devices, the analyte induces major change in the NP distances and permittivity due to their lack of connection, making the sensing much more pronounced. The DC and LbL methods used thiol and amine ligands-capped metallic nanoparticles to demonstrate the applicability of the methods to all types of ligands. Our results are of practical importance for integrating TFCMNPs in chemiresistive sensing platforms and for (bio) and chemical sensing applications

Facile Graphene Oxide Modification Method via Hydroxyl-yne Click Reaction for Ultrasensitive and Ultrawide Monitoring Pressure Sensors

Enhancing the durability and functionality of existing materials through sustainable pathways and appropriate structural design represents a time- and cost-effective strategy for the development of advanced wearable devices. Herein, a facile graphene oxide (GO) modification method via the hydroxyl-yne click reaction is present for the first time. By the click coupling between propiolate esters and hydroxyl groups on GO under mild conditions, various functional molecules are successfully grafted onto the GO. The modified GO is characterized by FTIR, XRD, TGA, XPS, and contact angle, proving significantly improved dispersibility in various solvents. Besides the high efficiency, high selectivity, and mild reaction conditions, this method is highly practical and accessible, avoiding the need for prefunctionalizations, metals, or toxic reagents. Subsequently, a rGO-PDMS sponge-based piezoresistive sensor developed by modified GO-P2 as the sensitive material exhibits impressive performance: high sensitivity (335 kPa–1, 0.8–150 kPa), wide linear range (>500 kPa), low detection limit (0.8 kPa), and long-lasting durability (>5000 cycles). Various practical applications have been demonstrated, including body joint movement recognition and real-time monitoring of subtle movements. These results prove the practicality of the methodology and make the rGO-PDMS sponge-based pressure sensor a real candidate for a wide array of wearable applications