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.

Insights into the Sensing Mechanism of a Metal-Oxide Solid Solution via Operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy.

Recently, the influence of Nb addition in the oxide solid solution of Sn and Ti was investigated with regard to the morphological, structural and electrical properties for the production of chemoresistive gas sensors. (Sn,Ti,Nb)xO2-based sensors showed promising features for ethanol monitoring in commercial or industrial settings characterized by frequent variation in relative humidity. Indeed, the three-metal solid solution highlighted a higher response level vs. ethanol than the most widely used SnO2 and a remarkably low effect of relative humidity on the film resistance. Nevertheless, lack of knowledge still persists on the mechanisms of gas reaction occurring at the surface of these nanostructures. In this work, operando Diffuse Reflectance Infrared Fourier Transform spectroscopy was used on SnO2- and on (Sn,Ti,Nb)xO2-based sensors to combine the investigations on the transduction function, i.e., the read-out of the device activity, with the investigations on the receptor function, i.e., compositional characterization of the active sensing element in real time and under operating conditions. The sensors performance was explained by probing the interaction of H2O and ethanol molecules with the material surface sites. This information is fundamental for fine-tuning of material characteristics for any specific gas sensing applications.

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.

New Approach for the Detection of Sub-ppm Limonene: An Investigation through Chemoresistive Metal-Oxide Semiconductors.

R-(+)-limonene, one of the major constituents of citrus oils, is a monoterpene that is widely used as a fragrance additive in cosmetics, foods, and industrial solvents. Nowadays, its detection mainly relies on bulky and expensive analytical methods and only a few research works proved its revelation through affordable and portable sensors, such as electrochemical and quartz crystal microbalance sensors. In response to the demand for effective miniaturized sensing devices to be integrated into Internet of Things systems, this study represents a pioneering investigation of chemoresistive gas sensor capabilities addressed to R-(+)-limonene detection. An array of seven metal-oxide sensors was exploited to perform a complete electrical characterization of the target analyte. The experimental evidence allowed us to identify the WO3-based sensor as the most promising candidate for R-(+)-limonene detection. The material was highly sensitive already at sub-ppm concentrations (response of 2.5 at 100 ppb), consistent with applicative parameters, and it resulted in selective vs. different gases at a lower operating temperature (200 °C) than the other sensors tested. Furthermore, it exhibited a humidity-independent behavior under real-life conditions (relative humidity > 20%). Finally, the WO3 sensor also demonstrated a remarkable cross-selectivity, thus enabling its exploitation in cutting-edge applications.

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.

Design of a Metal-Oxide Solid Solution for Sub-ppm H2 Detection.

Hydrogen is largely adopted in industrial processes and is one of the leading options for storing renewable energy. Due to its high explosivity, detection of H2 has become essential for safety in industries, storage, and transportation. This work aims to design a sensing film for high-sensitivity H2 detection. Chemoresistive gas sensors have extensively been studied for H2 monitoring due to their good sensitivity and low cost. However, further research and development are still needed for a reliable H2 detection at sub-ppm concentrations. Metal-oxide solid solutions represent a valuable approach for tuning the sensing properties by modifying their composition, morphology, and structure. The work started from a solid solution of Sn and Ti oxides, which is known to exhibit high sensitivity toward H2. Such a solid solution was empowered by the addition of Nb, which─according to earlier studies on titania films─was expected to inhibit grain growth at high temperatures, to reduce the film resistance and to impact the sensor selectivity and sensitivity. Powders were synthesized through the sol-gel technique by keeping the Sn-Ti ratio constant at the optimal value for H2 detection with different Nb concentrations (1.5-5 atom %). Such solid solutions were thermally treated at 650 and 850 °C. The sensor based on the solid solution calcined at 650 °C and with the lowest content of Nb exhibited an extremely high sensitivity toward H2, paving the way for H2 ppb detection. For comparison, the response to 50 ppm of H2 was increased 6 times vs SnO2 and twice that of (Sn,Ti)xO2.

Investigation on Sensing Performance of Highly Doped Sb/SnO2.

Tin dioxide (SnO2) is the most-used semiconductor for gas sensing applications. However, lack of selectivity and humidity influence limit its potential usage. Antimony (Sb) doped SnO2 showed unique electrical and chemical properties, since the introduction of Sb ions leads to the creation of a new shallow band level and of oxygen vacancies acting as donors in SnO2. Although low-doped SnO2:Sb demonstrated an improvement of the sensing performance compared to pure SnO2, there is a lack of investigation on this material. To fill this gap, we focused this work on the study of gas sensing properties of highly doped SnO2:Sb. Morphology, crystal structure and elemental composition were characterized, highlighting that Sb doping hinders SnO2 grain growth and decreases crystallinity slightly, while lattice parameters expand after the introduction of Sb ions into the SnO2 crystal. XRF and EDS confirmed the high purity of the SnO2:Sb powders, and XPS highlighted a higher Sb concentration compared to XRF and EDS results, due to a partial Sb segregation on superficial layers of Sb/SnO2. Then, the samples were exposed to different gases, highlighting a high selectivity to NO2 with a good sensitivity and a limited influence of humidity. Lastly, an interpretation of the sensing mechanism vs. NO2 was proposed.

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.

First-Principles Study of Electronic Conductivity, Structural and Electronic Properties of Oxygen-Vacancy-Defected SnO2.

The use of computer simulations has become almost essential for prediction and interpretation of device's performance. In gas sensing field, the simulation of specific conditions, which determine the physical-chemical properties of widely used metal oxide semiconductors, can be used to investigate the performance of gas sensors based on these kinds of materials. The aim of this work was to evaluate the physical-chemical properties of tin dioxide employed for environmental and health gas sensing application and to investigate the influence of oxygen vacancies on its properties by means of density functional theory. Two samples, having different concentration of oxygen vacancies, were deeply studied in terms of their structural, electronic and electrical properties. It was proved the influence of oxygen vacancies on lattice parameter. By increasing oxygen vacancies concentration, the increased number of impurity states took these closer to the conduction band minimum, which can lead to an easier adsorption process of oxygen species and their availability to be exchanges with the molecules of the target gases. In this way a reduction of the operating temperature can be observed, thus reducing the power consumption of devices, while keeping the catalytic performance of the material.

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.

Strengthening of Wood-Like Materials via Densification and Nanoparticle Intercalation.

Recently, several chemical and physical treatments were developed to improve different properties of wood. Such treatments are applicable to many types of cellulose-based materials. Densification leads the group in terms of mechanical results and comprises a chemical treatment followed by a thermo-compression stage. First, chemicals selectively etch the matrix of lignin and hemicellulose. Then, thermo-compression increases the packing density of cellulose microfibrils boosting mechanical performance. In this paper, in comparison with the state-of-the-art for wood treatments we introduce an additional nano-reinforcemeent on densified giant reed to further improve the mechanical performance. The modified nanocomposite materials are stiffer, stronger, tougher and show higher fire resistance. After the addition of nanoparticles, no relevant structural modification is induced as they are located in the gaps between cellulose microfibrils. Their peculiar positioning could increase the interfacial adhesion energy and improve the stress transfer between cellulose microfibrils. The presented process stands as a viable solution to introduce nanoparticles as new functionalities into cellulose-based natural materials.

Nanostructured Chemoresistive Sensors for Oncological Screening and Tumor Markers Tracking: Single Sensor Approach Applications on Human Blood and Cell Samples.

Preventive screening does not only allow to preemptively intervene on pathologies before they can harm the host; but also to reduce the costs of the intervention itself; boosting the efficiency of the NHS (National Health System) by saving resources for other purposes. To improve technology advancements in this field; user-friendly yet low-cost devices are required; and various applications for gas sensors have been tested and proved reliable in past studies. In this work; cell cultures and blood samples have been studied; using nanostructured chemoresistive sensors; to both verify if this technology can reliably detect tumor markers; and if correlations between responses from tumor line metabolites and the screening outcomes on human specimens could be observed. The results showed how sensors responded differently to the emanations from healthy and mutant (for cells) or tumor affected (for blood) samples, and how those results were consistent between them, since the tumoral specimens had higher responses compared to the ones of their healthy counterparts. Even though the patterns in the responses require a bigger population to be defined properly; it appeared that the different macro-groups between the same kind of samples are distinguishable from some of the sensors chosen in the study; giving promising outcomes for further research.

Crystalline Microporous Organosilicates with Reversed Functionalities of Organic and Inorganic Components for Room-Temperature Gas Sensing.

A deepened investigation on an innovative organic-inorganic hybrid material, referred to as ECS-14 (where ECS = Eni carbon silicates), revealed the possibility to use them as gas sensors. Indeed, among ECS phases, the crystalline state and the hexagonal microplateletlike morphology characteristic of ECS-14 seemed favorable properties to obtain continuous and uniform films. ECS-14 phase was used as functional material in screen-printable compositions and was thus deposited by drop coating for morphological, structural, thermal, and electrical characterizations. Possible operation at room temperature was investigated as technological progress, offering intrinsic safety in sensors working in harsh or industrial environments and avoiding high power consumption of most common sensors based on metal oxide semiconductors. Electrical characterization of the sensors based on ECS-14 versus concentrations of gaseous analytes gave significant results at room temperature in the presence of humidity, thereby demonstrating fundamental properties for a good quality sensor (speed, reversibility, and selectivity) that make them competitive with respect to systems currently in use. Remarkably, we observed functionality reversal of the organic and inorganic components; that is, in contrast to other hybrids, for ECS-14 the functional site has been ascribed to the inorganic phase while the organic component provided structural stability to the material. The sensing mechanism for humidity was also investigated.

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.

Chemoresistive gas sensors for the detection of colorectal cancer biomarkers.

Numerous medical studies show that tumor growth is accompanied by protein changes that may lead to the peroxidation of the cell membrane with consequent emission of volatile organic compounds (VOCs) by breath or intestinal gases that should be seen as biomarkers for colorectal cancer (CRC). The analysis of VOCs represents a non-invasive and potentially inexpensive preliminary screening technique. An array of chemoresistive gas sensors based on screen-printed metal oxide semiconducting films has been selected to discriminate gases of oncological interest, e.g., 1-iodononane and benzene, widely assumed to be biomarkers of colorectal cancer, from those of interference in the gut, such as methane and nitric oxide.

Self-standing quasi-mosaic crystals for focusing hard X-rays.

A quasi mosaic bent crystal for high-resolution diffraction of X and γ rays has been realized. A net curvature was imprinted to the crystal thanks to a series of superficial grooves to keep the curvature without external devices. The crystal highlights very high diffraction efficiency due to quasi mosaic curvature. Quasi mosaic crystals of this kind are proposed for the realization of a high-resolution focusing Laue lens for hard X-rays.

High-efficiency deflection of high-energy protons through axial channeling in a bent crystal.

Beam deflection due to axial channeling in a silicon crystal bent along the 111 axis was observed with 400 GeV/c protons at the CERN Super Proton Synchrotron. The condition for doughnut scattering of protons by the atomic strings of the crystal was attained. Such a condition allowed one to observe a beam deflection of 50 murad with about 30% efficiency. The contribution of hyperchanneled states of protons to the observed beam deflection was less than 2% according to simulation results.

Apparatus to study crystal channeling and volume reflection phenomena at the SPS H8 beamline.

A high performance apparatus has been designed and built by the H8-RD22 collaboration for the study of channeling and volume reflection phenomena in the interaction of 400 GeV/c protons with bent silicon crystals, during the 2006 data taking in the external beamline H8 of the CERN SPS. High-quality silicon short crystals were bent by either anticlastic or quasimosaic effects. Alignment with the highly parallel (8 murad divergence) proton beam was guaranteed through a submicroradian goniometric system equipped with both rotational and translational stages. Particle tracking was possible by a series of silicon microstrip detectors with high-resolution and a parallel plate gas chamber, triggered by various scintillating detectors located along the beamline. Experimental observation of volume reflection with 400 GeV/c protons proved true with a deflection angle of (10.4+/-0.5) murad with respect to the unperturbed beam, with a silicon crystal whose (111) planes were parallel to the beam.

High-efficiency volume reflection of an ultrarelativistic proton beam with a bent silicon crystal.

The volume reflection phenomenon was detected while investigating 400 GeV proton interactions with bent silicon crystals in the external beam H8 of the CERN Super Proton Synchrotron. Such a process was observed for a wide interval of crystal orientations relative to the beam axis, and its efficiency exceeds 95%, thereby surpassing any previously observed value. These observations suggest new perspectives for the manipulation of high-energy beams, e.g., for collimation and extraction in new-generation hadron colliders, such as the CERN Large Hadron Collider.