2D Amino-Functionalized Black Phosphorus: A New Approach to Improve Hydrogen Gas Detection Performance.

In recent years, hydrogen has gained attention as a potential solution to replace fossil fuels, thus reducing greenhouse gas emissions. The development of ever improving hydrogen sensors is a topic that is constantly under study due to concerns about the inherent risk of leaks of this gas and potential explosions. In this work, a new, long-term, stable phosphorene-based sensor was developed for hydrogen detection. A simple functionalization of phosphorene using urea was employed to synthesize an air-stable material, subsequently used to prepare films for gas sensing applications, via the drop casting method. The material was deeply characterized by different techniques (scanning electron microscopy, X-ray diffraction, X-ray photoelectron, and Raman spectroscopy), and the stability of the material in a noninert atmosphere was evaluated. The phosphorene-based sensor exhibited high sensitivity (up to 700 ppm) and selectivity toward hydrogen at room temperature, as well as long-term stability over five months under ambient conditions. To gain further insight into the gas sensing mechanism over the surface, we employed a dedicated apparatus, namely operando diffuse reflectance infrared Fourier transform, by exposing the chemoresistive sensor to hydrogen gas under dry air conditions.

In vitro gastrointestinal gas monitoring with carbon nanotube sensors.

In vitro simulators of the human gastrointestinal (GI) tract are remarkable technological platforms for studying the impact of food on the gut microbiota, enabling continuous and real-time monitoring of key biomarkers. However, comprehensive real-time monitoring of gaseous biomarkers in these systems is required with a cost-effective approach, which has been challenging to perform experimentally to date. In this work, we demonstrate the integration and in-line use of carbon nanotube (CNT)-based chemiresitive gas sensors coated with a thin polydimethylsiloxane (PDMS) membrane for the continuous monitoring of gases within the Simulator of the Human Microbial Ecosystem (SHIME). The findings demonstrate the ability of the gas sensor to continuously monitor the different phases of gas production in this harsh, anaerobic, highly humid, and acidic environment for a long exposure time (16 h) without saturation. This establishes our sensor platform as an effective tool for real-time monitoring of gaseous biomarkers in in vitro systems like SHIME.

Nano Hotplate Fabrication for Metal Oxide-Based Gas Sensors by Combining Electron Beam and Focused Ion Beam Lithography.

Metal oxide semiconductor (MOS) gas sensors are widely used for gas detection. Typically, the hotplate element is the key component in MOS gas sensors which provide a proper and tunable operation temperature. However, the low power efficiency of the standard hotplates greatly limits the portable application of MOS gas sensors. The miniaturization of the hotplate geometry is one of the most effective methods used to reduce its power consumption. In this work, a new method is presented, combining electron beam lithography (EBL) and focused ion beam (FIB) technologies to obtain low power consumption. EBL is used to define the low-resolution section of the electrode, and FIB technology is utilized to pattern the high-resolution part. Different Au++ ion fluences in FIBs are tested in different milling strategies. The resulting devices are characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and secondary ion mass spectrometry (SIMS). Furthermore, the electrical resistance of the hotplate is measured at different voltages, and the operational temperature is calculated based on the Pt temperature coefficient of resistance value. In addition, the thermal heater and electrical stability is studied at different temperatures for 110 h. Finally, the implementation of the fabricated hotplate in ZnO gas sensors is investigated using ethanol at 250 °C.

Fabrication of a Highly NO2-Sensitive Gas Sensor Based on a Defective ZnO Nanofilm and Using Electron Beam Lithography.

Hazardous substances produced by anthropic activities threaten human health and the green environment. Gas sensors, especially those based on metal oxides, are widely used to monitor toxic gases with low cost and efficient performance. In this study, electron beam lithography with two-step exposure was used to minimize the geometries of the gas sensor hotplate to a submicron size in order to reduce the power consumption, reaching 100 °C with 0.09 W. The sensing capabilities of the ZnO nanofilm against NO2 were optimized by introducing an enrichment of oxygen vacancies through N2 calcination at 650 °C. The presence of oxygen vacancies was proven using EDX and XPS. It was found that oxygen vacancies did not significantly change the crystallographic structure of ZnO, but they significantly improved the electrical conductivity and sensing behaviors of ZnO film toward 5 ppm of dry air.

Elucidating the Ambient Stability and Gas Sensing Mechanism of Nickel-Decorated Phosphorene for NO2 Detection: A First-Principles Study.

In the field of layered two-dimensional functional materials, black phosphorus has attracted considerable attention in many applications due to its outstanding electrical properties. It has experimentally shown superior chemical sensing performance for the room temperature detection of NO2, highlighting high sensitivity at a ppb level. Unfortunately, pristine black phosphorus demonstrated an unstable functionality due to the fast degradation of the material when exposed to the ambient atmosphere. In the present work, a deepened investigation by density functional theory was carried out to study how nickel decoration of phosphorene can improve the stability of the material. Further, an insight into the sensing mechanism of nickel-loaded phosphorene toward NO2 was given and compared to pristine phosphorene. This first-principles study proved that, by introducing nickel adatoms, the band gap of the material decreases and the positions of the conduction band minimum and the valence band maximum move toward each other, resulting in a drop in the conduction band minimum under the redox potential of O2/O2 -, which may result in a more stable material. Studying the adsorption of O2 molecules on pristine phosphorene, we also proved that all oxygen molecules coming from the surrounding atmosphere react with phosphorus atoms in the layer, resulting in the oxidation of the material forming oxidized phosphorus species (PO x ). Instead, by introducing nickel adatoms, part of the oxygen from the surrounding atmosphere reacts with nickel atoms, resulting in a decrease of the oxidation rate of the material and in subsequent long-term stability of the device. Finally, possible reaction paths for the detection of NO2 are given by charge transfer analyses, occurring at the surface during the adsorption of oxygen molecules and the interaction with the target gas.

Air Stable Nickel-Decorated Black Phosphorus and Its Room-Temperature Chemiresistive Gas Sensor Capabilities.

In the rapidly emerging field of layered two-dimensional functional materials, black phosphorus, the P-counterpart of graphene, is a potential candidate for various applications, e.g., nanoscale optoelectronics, rechargeable ion batteries, electrocatalysts, thermoelectrics, solar cells, and sensors. Black phosphorus has shown superior chemical sensing performance; in particular, it is selective for the detection of NO2, an environmental toxic gas, for which black phosphorus has highlighted high sensitivity at a ppb level. In this work, by applying a multiscale characterization approach, we demonstrated a stability and functionality improvement of nickel-decorated black phosphorus films for gas sensing prepared by a simple, reproducible, and affordable deposition technique. Furthermore, we studied the electrical behavior of these films once implemented as functional layers in gas sensors by exposing them to different gaseous compounds and under different relative humidity conditions. Finally, the influence on sensing performance of nickel nanoparticle dimensions and concentration correlated to the decoration technique and film thickness was investigated.

Optimization of a Low-Power Chemoresistive Gas Sensor: Predictive Thermal Modelling and Mechanical Failure Analysis.

The substrate plays a key role in chemoresistive gas sensors. It acts as mechanical support for the sensing material, hosts the heating element and, also, aids the sensing material in signal transduction. In recent years, a significant improvement in the substrate production process has been achieved, thanks to the advances in micro- and nanofabrication for micro-electro-mechanical system (MEMS) technologies. In addition, the use of innovative materials and smaller low-power consumption silicon microheaters led to the development of high-performance gas sensors. Various heater layouts were investigated to optimize the temperature distribution on the membrane, and a suspended membrane configuration was exploited to avoid heat loss by conduction through the silicon bulk. However, there is a lack of comprehensive studies focused on predictive models for the optimization of the thermal and mechanical properties of a microheater. In this work, three microheater layouts in three membrane sizes were developed using the microfabrication process. The performance of these devices was evaluated to predict their thermal and mechanical behaviors by using both experimental and theoretical approaches. Finally, a statistical method was employed to cross-correlate the thermal predictive model and the mechanical failure analysis, aiming at microheater design optimization for gas-sensing applications.

Nanostructured SmFeO3 Gas Sensors: Investigation of the Gas Sensing Performance Reproducibility for Colorectal Cancer Screening.

Among the various chemoresistive gas sensing properties studied so far, the sensing response reproducibility, i.e., the capability to reproduce a device with the same sensing performance, has been poorly investigated. However, the reproducibility of the gas sensing performance is of fundamental importance for the employment of these devices in on-field applications, and to demonstrate the reliability of the process development. This sensor property became crucial for the preparation of medical diagnostic tools, in which the use of specific chemoresistive gas sensors along with a dedicated algorithm can be used for screening diseases. In this work, the reproducibility of SmFeO3 perovskite-based gas sensors has been investigated. A set of four SmFeO3 devices, obtained from the same screen-printing deposition, have been tested in laboratory with both controlled concentrations of CO and biological fecal samples. The fecal samples tested were employed in the clinical validation protocol of a prototype for non-invasive colorectal cancer prescreening. Sensors showed a high reproducibility degree, with an error lower than 2% of the response value for the test with CO and lower than 6% for fecal samples. Finally, the reproducibility of the SmFeO3 sensor response and recovery times for fecal samples was also evaluated.

Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors.

This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature.