High performance Pt-anchored MoS2based chemiresistive ascorbic acid sensor.

Ascorbic acid (AA), known as vitamin C, is a vital bioactive compound that plays a crucial role in several metabolic processes, including the synthesis of collagen and neurotransmitters, the removal of harmful free radicals, and the uptake of iron by cells in the human intestines. As a result, there is an absolute need for a highly selective, sensitive, and economically viable sensing platform for AA detection. Herein, we demonstrate a Pt-decorated MoS2for efficient detection of an AA biosensor. MoS2hollow rectangular structures were synthesized using an easy and inexpensive chemical vapor deposition approach to meet the increasing need for a reliable detection platform. The synthesized MoS2hollow rectangular structures are characterized through field effect scanning electron microscopy (FESEM), energy-dispersive spectroscopy elemental mapping, Raman spectroscopy, and x-ray photoelectron spectroscopy. We fabricate a chemiresistive biosensor based on Pt-decorated MoS2that measures AA with great precision and high sensitivity. The experiments were designed to evaluate the response of the Pt-decorated MoS2biosensor in the presence and absence of AA, and selectivity was evaluated for a variety of biomolecules, and it was observed to be very selective towards AA. The Pt-MoS2device had a higher response of 125% against 1 mM concentration of AA biomolecules, when compared to that of all other devices and 2.2 times higher than that of the pristine MoS2device. The outcomes of this study demonstrate the efficacy of Pt-decorated MoS2as a promising material for AA detection. This research contributes to the ongoing efforts to enhance our capabilities in monitoring and detecting AA, fostering advancements in environmental, biomedical, and industrial applications.

Quasicrystal Nanosheet/α-Fe2O3 Heterostructure-Based Low Power NO2 Sensors: Experimental and DFT Studies.

Industrial emissions, environmental monitoring, and medical fields have put forward huge demands for high-performance and low power consumption sensors. Two-dimensional quasicrystal (2D QC) nanosheets of metallic multicomponent Al70Co10Fe5Ni10Cu5 have emerged as a promising material for gas sensors due to their excellent catalytic and electronic properties. Herein, we demonstrate highly sensitive and selective NO2 sensors developed by low-cost and scalable fabrication techniques using 2D QC nanosheets and α-Fe2O3 nanoparticles. The sensitivity (ΔR/R%) of the optimal amount of 2D QC nanosheet-loaded α-Fe2O3 sensor was 32%, which is significantly larger about 3.5 times than bare α-Fe2O3 sensors for 1 ppm of NO2 at 150 °C operating temperature. The sensors exhibited p-type conduction, and resistance was reduced when exposed to NO2, an oxidizing gas. The enhanced sensing characteristics are a result of the formation of nanoheterojunctions between 2D QC and α-Fe2O3, which improved the charge transport and provided a large sensing signal. In addition, the heterojunction sensor demonstrated excellent NO2 selectivity over other oxidizing and reducing gases. Furthermore, density functional theory calculation examines the adsorption energy and charge transfer between NO2 molecules on the α-Fe2O3(110) and QC/α-Fe2O3(110) heterostructure surfaces, which coincides well with the experimental results.

Photocatalytic degradation of methylene blue at nanostructured ZnO thin films.

The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l-1MB solution, 540 minUV irradiation), the rate constantkof MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10-9(mol·l-1·min-1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB.

Flower-like ZnO Nanostructures Local Surface Morphology and Chemistry.

This work presents the results of comparative studies using complementary methods, such as scanning electron microscopy (SEM), X-ray photoemission spectroscopy (XPS), and thermal desorption spectroscopy (TDS) to investigate the local surface morphology and chemistry of flower-like ZnO nanostructures synthesized by the thermal oxidation technique on native Si/SiO2 substrates. SEM studies showed that our flower-like ZnO nanostructures contained mostly isolated and irregular morphological low-dimensional forms, seen as rolled-up floss flowers, together with local, elongated, complex stalks similar to Liatris flowers, which contained joined short flosses in the form of nanodendrites. Beyond this, XPS studies showed that these nanostructures exhibited a slight surface nonstoichiometry, mostly related to the existence of oxygen-deficient regions, combined with strong undesired C surface contamination. In addition, the TDS studies showed that these undesired surface contaminations (including mainly C species and hydroxyl groups) are only slightly removed from the surface of our flower-like ZnO nanostructures, causing an expected modification of their nonstoichiometry. All of these effects are of great importance when using our flower-like ZnO nanostructures in gas sensor devices for detecting oxidizing gases because surface contamination leads to an undesired barrier for toxic gas adsorption, and it can additionally be responsible for the uncontrolled sensor aging effect.

Covalent Immobilization of Organic Photosensitizers on the Glass Surface: Toward the Formation of the Light-Activated Antimicrobial Nanocoating.

Two highly efficient commercial organic photosensitizers-azure A (AA) and 5-(4-aminophenyl)-10,15,20-(triphenyl)porphyrin (APTPP)-were covalently attached to the glass surface to form a photoactive monolayer. The proposed straightforward strategy consists of three steps, i.e., the initial chemical grafting of 3-aminopropyltriethoxysilane (APTES) followed by two chemical postmodification steps. The chemical structure of the resulting mixed monolayer (MIX_TC_APTES@glass) was widely characterized by X-ray photoelectron (XPS) and Raman spectroscopies, while its photoactive properties were investigated in situ by UV-Vis spectroscopy with α-terpinene as a chemical trap. It was shown that both photosensitizers retain their activity toward light-activated generation of reactive oxygen species (ROS) after immobilization on the glassy surface and that the resulting nanolayer shows high stability. Thanks to the complementarity of the spectral properties of AA and APTPP, the effectiveness of the ROS photogeneration under broadband illumination can be optimized. The reported light-activated nanocoating demonstrated promising antimicrobial activity toward Escherichia coli (E. coli), by reducing the number of adhered bacteria compared to the unmodified glass surface.

Correlation between Microstructure and Chemical Composition of Zinc Oxide Gas Sensor Layers and Their Gas-Sensitive Properties in Chlorine Atmosphere.

In this article, we present results concerning the impact of structural and chemical properties of zinc oxide in various morphological forms and its gas-sensitive properties, tested in an atmosphere containing a very aggressive gas such as chlorine. The aim of this research was to understand the mechanism of chlorine detection using a resistive gas sensor with an active layer made of zinc oxide with a different structure and morphology. Two types of ZnO sensor layers obtained by two different technological methods were used in sensor construction. Their morphology, crystal structure, specific surface area, porosity, surface chemistry and structural defects were characterized, and then compared with gas-sensitive properties in a chlorine-containing atmosphere. To achieve this goal, scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL) methods were used. The sensing properties of obtained active layers were tested by the temperature stimulated conductance method (TSC). We have noticed that their response in a chlorine atmosphere is not determined by the size of the specific surface or porosity. The obtained results showed that the structural defects of ZnO crystals play the most important role in chlorine detection. We demonstrated that Cl2 adsorption is a concurrent process to oxygen adsorption. Both of them occur on the same active species (oxygen vacancies). Their concentration is higher on the side planes of the zinc oxide crystal than the others. Additionally, ZnO sublimation process plays an important role in the chlorine detection mechanism.

Novel insight on the local surface properties of ZnO nanowires.

Novel insight on the local surface properties of ZnO nanowires (NW) deposited by the evaporation-condensation method on Ag-covered Si substrates is proposed, based on the results of comparative studies by using the scanning electron microscopy (SEM), x-ray photoemission spectroscopy (XPS) and thermal desorption spectroscopy (TDS) methods, respectively. SEM studies showed that ZnO nanowires (nanoribbons) are mostly isolated and irregular, having the average length µm and the average at the level of tens nm, respectively. Our XPS studies confirmed their evident surface non-stoichiometry, combined with strong C surface contaminations, which was related to the existence of oxygen-deficient regions. Additionally, TDS studies showed that undesired surface contaminations (including C species and hydroxyl groups) on the surface of ZnO NWs can be removed almost completely, leading to an increase of the final non-stoichiometry. Both effects are of great importance when using ZnO NWs for the detection of oxidizing gases, because the undesired C contaminations (including C-OH species) play the role of undesired barriers for the gas adsorption, especially at the low working temperature, additionally affecting the uncontrolled sensor ageing effect.

Rheotaxially Grown and Vacuum Oxidized SnOx Nanolayers for NO2 Sensing Characteristics at Ppb Level and Room Temperature.

* Correspondence: Barbara [...].

Studies of NO2 Gas-Sensing Characteristics of a Novel Room-Temperature Surface-Photovoltage Gas Sensor Device.

In this work the characteristics of a novel type of room temperature NO2 gas sensor device based on the surface photovoltage effect are described. It was shown that for our SPV gas sensor device, using porous sputtered ZnO nanostructured thin films as the active gas sensing electrode material, the basic gas sensor characteristics in a toxic NO2 gas atmosphere are strongly dependent on the target NO2 gas flow rate. Moreover, it was also confirmed that our SPV gas sensor device is able to detect the lowest NO2 relative concentration at the level of 125 ppb, with respect to the commonly assumed signal-to-noise (S/N) ratio, as for the commercial devices.

Surface Properties of SnO2 Nanowires Deposited on Si Substrate Covered by Au Catalyst Studies by XPS, TDS and SEM.

The surface chemistry and the morphology of SnO2 nanowires of average length and diameter of several µm and around 100 nm, respectively, deposited by vapor phase deposition (VPD) method on Au-covered Si substrate, were studied before and after subsequent air exposure. For this purpose, surface-sensitive methods, including X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and the scanning electron microscopy (SEM), were applied. The studies presented within this paper allowed to determine their surface non-stoichiometry combined with the presence of carbon contaminations, in a good correlation with their surface morphology. The relative concentrations of the main components [O]/[Sn]; [C]/[Sn]; [Au]/[Sn], together with the O⁻Sn; O⁻Si bonds, were analyzed. The results of TDS remained in a good agreement with the observations from XPS. Moreover, conclusions obtained for SnO2 nanowires deposited with the use of Au catalyst were compared to the previous obtained for Ag-assisted tin dioxide nanowires. The information obtained within these studies is of a great importance for the potential application of SnO2 nanowires in the field of novel chemical nanosensor devices, since the results can provide an interpretation of how aging effects influence gas sensor dynamic characteristics.

A Novel Type Room Temperature Surface Photovoltage Gas Sensor Device.

In this paper a novel type of a highly sensitive gas sensor device based on the surface photovoltage effect is described. It is based on the Kelvin probe approach. Porous ZnO nanostructured thin films deposited by the direct current (DC) reactive magnetron sputtering method are used as the active gas sensing electrode material. Crucially, the obtained gas sensing material exhibited a nanocoral surface morphology and surface Zn to O non-stoichiometry with respect to its bulk mass. Among other responses, the demonstrated SPV gas sensor device exhibits a high response to an NO2 concentration as low as 1 ppm, with a signal to noise ratio of about 50 and a fast response time of several seconds under room temperature conditions.

Oxide-organic heterostructures: a case study of charge transfer disturbance at a SnO2-copper phthalocyanine buried interface.

Reduced tin dioxide/copper phthalocyanine (SnOx/CuPc) heterojunctions recently gained much attention in hybrid electronics due to their defect structure, allowing tuning of the electronic properties at the interface towards particular needs. In this work, we focus on the creation and analysis of the interface between the oxide and organic layer. The inorganic/organic heterojunction was created by depositing CuPc on SnOx layers prepared with the rheotaxial growth and vacuum oxidation (RGVO) method. Exploiting surface sensitive photoelectron spectroscopy techniques, angle dependent X-ray and UV photoelectron spectroscopy (ADXPS and UPS, respectively), supported by semi-empirical simulations, the role of carbon from adventitious organic adsorbates directly at the SnOx/CuPc interface was investigated. The adventitious organic adsorbates were blocking electronic interactions between the environment and surface, hence pinning energy levels. A significant interface dipole of 0.4 eV was detected, compensating for the difference in work functions of the materials in contact, however, without full alignment of the energy levels. From the ADXPS and UPS results, a detailed diagram of the interfacial electronic structure was constructed, giving insight into how to tailor SnOx/CuPc heterojunctions towards specific applications. On the one hand, parasitic surface contamination could be utilized in technology for passivation-like processes. On the other hand, if one needs to keep the oxide's surficial interactions fully accessible, like in the case of stacked electronic systems or gas sensor applications, carbon contamination must be carefully avoided at each processing step.

Surface Properties of Nanostructured, Porous ZnO Thin Films Prepared by Direct Current Reactive Magnetron Sputtering.

In this paper, the results of detailed X-ray photoelectron spectroscopy (XPS) studies combined with atomic force microscopy (AFM) investigation concerning the local surface chemistry and morphology of nanostructured ZnO thin films are presented. They have been deposited by direct current (DC) reactive magnetron sputtering under variable absolute Ar/O2 flows (in sccm): 3:0.3; 8:0.8; 10:1; 15:1.5; 20:2, and 30:3, respectively. The XPS studies allowed us to obtain the information on: (1) the relative concentrations of main elements related to their surface nonstoichiometry; (2) the existence of undesired C surface contaminations; and (3) the various forms of surface bondings. It was found that only for the nanostructured ZnO thin films, deposited under extremely different conditions, i.e., for Ar/O2 flow ratio equal to 3:0.3 and 30:3 (in sccm), respectively, an evident and the most pronounced difference had been observed. The same was for the case of AFM experiments. What is crucial, our experiments allowed us to find the correlation mainly between the lowest level of C contaminations and the local surface morphology of nanostructured ZnO thin films obtained at the highest Ar/O2 ratio (30:3), for which the densely packaged (agglomerated) nanograins were observed, yielding a smaller surface area for undesired C adsorption. The obtained information can help in understanding the reason of still rather poor gas sensor characteristics of ZnO based nanostructures including the undesired ageing effect, being of a serious barrier for their potential application in the development of novel gas sensor devices.

Pure and Highly Nb-Doped Titanium Dioxide Nanotubular Arrays: Characterization of Local Surface Properties.

This paper presents the results of studies of the local surface properties of pure and highly Nb-doped (12 wt %) TiO2 nanotubes (TNT) using the X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) methods, respectively. XPS analysis showed that the pure TNT exhibit an evident over-stoichiometry combined with high level of undesired C contaminations, which was confirmed by the relative concentration of specific elements O, Ti and C (with respect to all the surface atoms) equal to 0.46, 018 and 0.36, respectively. In turn, for the highly Nb-doped (12 wt %) TNT, a slightly different surface chemistry was observed because the relative concentration of specific elements O and Ti and, with respect to all the surface atoms, is slightly lower, that is, 0.42 and 0.12, respectively; this is directly related to the fact that Nb atoms appeared having the relative concentration at the level of 0.09, whereas the undesired C contaminations reached the same level (0.36), as is the case of pure TNT. In addition, SEM analysis confirms that there are evident free spaces between the specific slops containing several TNT, what was additionally confirmed by the contribution of specific surface bonding coming from the SiO2/Si substrate. The obtained information allowed us a new insight on the potential origin of aging effect at the surface of TNT in atmosphere being the undesired limitation for their potential application as the chemical resistive type sensors or in any other fields of their application related to their surface activity.

Impact of air exposure and annealing on the chemical and electronic properties of the surface of SnO2 nanolayers deposited by rheotaxial growth and vacuum oxidation.

In this paper the SnO2 nanolayers were deposited by rheotaxial growth and vacuum oxidation (RGVO) and analyzed for the susceptibility to ambient-air exposure and the subsequent recovery under vacuum conditions. Particularly the surface chemistry of the layers, stoichiometry and level of carbon contamination, was scrutinized by X-ray photoelectron spectroscopy (XPS). The layers were tested i) pristine, ii) after air exposure and iii) after UHV annealing to validate perspective recovery procedures of the sensing layers. XPS results showed that the pristine RGVO SnO2 nanolayers are of high purity with a ratio [O]/[Sn] = 1.62 and almost no carbon contamination. After air exposure the relative [O]/[Sn] concentration increased to 1.80 while maintaining a relatively low level of carbon contaminants. Subsequent UHV annealing led to a relative [O]/[Sn] concentration comparable to the pristine samples. The oxidation resulted in a variation of the distance between the valence band edge and the Fermi level energy. This was attributed to oxygen diffusion through the porous SnO2 surface as measured by atomic force microscopy.

XPS, TDS, and AFM studies of surface chemistry and morphology of Ag-covered L-CVD SnO2 nanolayers.

This is well known that the selectivity and sensitivity of tin dioxide (SnO2) thin film sensors for the detection of low concentration of volatile sulfides such as H2S in air can be improved by small amount of Ag additives. In this paper we present the results of comparative X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS), and atomic force microscopy (AFM) studies of the surface chemistry and morphology of SnO2 nanolayers obtained by laser-enhanced chemical vapor deposition (L-CVD) additionally covered with 1 monolayer (ML) of Ag. For as deposited SnO2 nanolayers, a mixture of tin oxide (SnO) and tin dioxide (SnO2) with the [C]/[Sn] ratio of approximately 1.3 was observed. After dry air exposure, the [O]/[Sn] ratio slightly increased to approximately 1.55. Moreover, an evident increasing of C contamination was observed with [C]/[Sn] ratio of approximately 3.5. After TDS experiment, the [O]/[Sn] ratio goes back to 1.3, whereas C contamination evidently decreases (by factor of 3). Simultaneously, the Ag concentration after air exposure and TDS experiment subsequently decreased (finally by factor of approximately 2), which was caused by the diffusion of Ag atoms into the subsurface layers related to the grain-type surface morphology of Ag-covered L-CVD SnO2 nanolayers, as confirmed by XPS ion depth profiling studies. The variation of surface chemistry of the Ag-covered L-CVD SnO2 after air exposure observed by XPS was in a good correlation with the desorption of residual gases from these nanolayers observed in TDS experiments.

Surface chemistry of SnO2 nanowires on Ag-catalyst-covered Si substrate studied using XPS and TDS methods.

In this paper we investigate the surface chemistry, including surface contaminations, of SnO2 nanowires deposited on Ag-covered Si substrate by vapor phase deposition (VPD), thanks to x-ray photoelectron spectroscopy (XPS) in combination with thermal desorption spectroscopy (TDS). Air-exposed SnO2 nanowires are slightly non-stoichiometric, and a huge amount of C contaminations is observed at their surface. After the thermal physical desorption (TPD) process, SnO2 nanowires become almost stoichiometric without any surface C contaminations. This is probably related to the fact that C contaminations, as well as residual gases from air, are weakly bounded to the crystalline SnO2 nanowires and can be easily removed from their surface. The obtained results gave us insight on the interpretation of the aging effect of SnO2 nanowires that is of great importance for their potential application in the development of novel chemical nanosensor devices.