M. Donarelli

Exfoliated black phosphorus gas sensing properties at room temperature

Room temperature gas sensing properties of chemically exfoliated black phosphorus (BP) to oxidizing (NO2, CO2) and reducing (NH3, H2, CO) gases in a dry air carrier have been reported. To study the gas sensing properties of BP, chemically exfoliated BP flakes have been drop casted on Si3N4 substrates provided with Pt comb-type interdigitated electrodes in N2 atmosphere. Scanning electron microscopy and x-ray photoelectron spectroscopy characterizations show respectively the occurrence of a mixed structure, composed of BP coarse aggregates dispersed on BP exfoliated few layer flakes bridging the electrodes, and a clear 2p doublet belonging to BP, which excludes the occurrence of surface oxidation. Room temperature electrical tests in dry air show a p-type response of multilayer BP with measured detection limits of 20 ppb and 10 ppm to NO2 and NH3 respectively. No response to CO and CO2 has been detected, while a slight but steady sensitivity to H2 has been recorded. The reported results confirm, on an experimental basis, what was previously theoretically predicted, demonstrating the promising sensing properties of exfoliated BP.

Metal-induced self-assembly of peroxiredoxin as a tool for sorting ultrasmall gold nanoparticles into one-dimensional clusters†

Nanomanipulation of matter to create responsive, ordered materials still remains extremely challenging. Supramolecular chemistry has inspired new strategies by which such nanomaterials can be synthesized step by step by exploiting the self-recognition properties of molecules. In this work, the ring-shaped architecture of the 2-Cys peroxiredoxin I protein from Schistosoma mansoni, engineered to have metal ion-binding sites, is used as a template to build up 1D nanoscopic structures through metal-induced self-assembly. Chromatographic and microscopic analyses demonstrate the ability of the protein rings to stack directionally upon interaction with divalent metal ions and form well-defined nanotubes by exploiting the intrinsic recognition properties of the ring surfaces. Taking advantage of such behavior, the rings are then used to capture colloidal Ni(2+)-functionalized ultrasmall gold nanoparticles and arrange them into 1D arrays through stacking into peapod-like complexes. Finally, as the formation of such nano-peapods strictly depends on nanoparticle dimensions, the peroxiredoxin template is used as a colloidal cut-off device to sort by size the encapsulated nanoparticles. These results open up possibilities in developing Prx-based methods to synthesize new advanced functional materials.

The electronic structure of gas phase croconic acid compared to the condensed phase: More insight into the hydrogen bond interaction

The electronic structure of croconic acid in the gas phase has been investigated by means of core level and valence band photoemission spectroscopy and compared with hybrid Heyd-Scuseria-Ernzerhof density functional theory calculations. The results have been compared with the corresponding ones of the condensed phase. In the gas phase, due to the absence of hydrogen bond intermolecular interactions, the O 1 s core level spectrum shows a shift of binding energy between the hydroxyl (O-H) and the carbonyl group (C=O) of 2.1 eV, which is larger than the condensed phase value of 1.6 eV. Interestingly, such a shift decreases exponentially with the increase of the O-H distance calculated from theory. The significant differences between the gas and condensed phase valence band spectra highlight the important role played by the hydrogen bonding in shaping the electronic structure of the condensed phase.

Graphene oxide for gas detection under standard humidity conditions

Graphene oxide (GO) synthesis is the easiest way to functionalize graphene, preserving the high graphene surface to volume ratio. Therefore, GO is a promising candidate for gas sensing applications. In this paper, an easy-to-fabricate and high sensitivity GO-based gas sensor is proposed. The device is fabricated by drop-casting a solution of GO flakes dispersed in water on a prepatterned Si3N4 substrate with 30 μm spaced Pt electrodes. The sensing material has been studied using scanning electron microscopy and x-ray photoelectron spectroscopy. The large lateral dimensions of the flakes (tens of microns) allow single GO flake to bridge adjacent electrodes. The high quality of the synthesized flakes results in the gas sensor high sensitivity to and low detection limit (20 ppb) of NO2. The gas sensor response to NO2 has been studied in various relative humidity environments and it is demonstrated not to be affected by the presence of water vapor. Finally, the gas sensor responses to acetone, toluene, ethanol, and ammonia are reported.

Magnetic gas sensing exploiting the magneto-optical Kerr effect on ZnO nanorods/Co layer system

A new system based on a Co film covered by ZnO nanorods (NRs) has been fabricated with sputtering technique. Its stability and magneto-optical properties are suitable for magnetic gas sensing applications. The tests have been performed at room temperature exploiting a magneto-optical Kerr effect magnetometer using H2 and CO as target gases. The reaction process is affected by a thin interface constituted by Co-doped ZnO. The surface of ZnO NRs and the interface are the sensing elements of the sensor, while Co acts as a magnetic transducer. The sensor is sensitive, stable and fast as concern both the response and the recovery time. The used system for gas detection can be easily reduced in size allowing the development of a low-cost and portable sensor.

Transfer of CVD-grown graphene for room temperature gas sensors

An easy transfer procedure to obtain graphene-based gas sensing devices operating at room temperature (RT) is presented. Starting from chemical vapor deposition-grown graphene on copper foil, we obtained single layer graphene which could be transferred onto arbitrary substrates. In particular, we placed single layer graphene on top of a SiO2/Si substrate with pre-patterned Pt electrodes to realize a chemiresistor gas sensor able to operate at RT. The responses to ammonia (10, 20, 30 ppm) and nitrogen dioxide (1, 2, 3 ppm) are shown at different values of relative humidity, in dark and under 254 nm UV light. In order to check the sensor selectivity, gas response has also been tested towards hydrogen, ethanol, acetone and carbon oxide. Finally, a model based on linear dispersion relation characteristic of graphene, which take into account humidity and UV light effects, has been proposed.

Non-Plasmonic SERS with Silicon: Is It Really Safe? New Insights into the Optothermal Properties of Core/Shell Microbeads

Silicon is one of the most interesting candidates for plasmon-free surface-enhaced Raman scattering (SERS), because of its high-refractive index and thermal stability. However, here we demonstrate that the alleged thermal stability of silicon nanoshells irradiated by conventional Raman laser cannot be taken for granted. We investigated the opto-thermal behavior of SiO2/Si core/shell microbeads (Si-rex) irradiated with three common Raman laser sources (λ = 532, 633, 785 nm) under real working conditions. We obtained an experimental proof of the critical role played by bead size and aggregation in heat and light management, demonstrating that, in the case of strong opto-thermal coupling, the temperature can exceed that of the melting points of both core and shell components. In addition, we also show that weakly coupled beads can be utilized as stable substrates for plasmon-free SERS experiments.

Unravelling the role of the central metal ion in the electronic structure of tris(8-hydroxyquinoline) metal chelates: photoemission spectroscopy and hybrid functional calculations.

The electronic structures of tris(8-hydroxyquinolinato)-erbium(III) (ErQ(3)) and tris(8-hydroxyquinolinato)-aluminum(III) (AlQ(3)) have been studied by means of core level and valence band photoemission spectroscopy with the theoretical support of hybrid Heyd-Scuseria-Ernzerhof density functional theory, to investigate the role played by the central metal atom. A lower binding energy (0.2 eV and 0.3 eV, respectively) of the O 1s and N 1s core levels has been observed for ErQ(3) with respect to AlQ(3). Differences in the valence band spectra, mainly related to the first two peaks next to the highest occupied molecular orbital (HOMO), have been ascribed to an energetic shift (to 0.4 eV lower energies for ErQ(3)) of the σ molecular orbital between the oxygen atoms and the central metal atom. A lower (by 0.5 eV) ionization energy has been measured for the ErQ(3). The interpretation of these results is based on a reduced interaction between the central metal atom and the ligands in ErQ(3), with increased electronic charge around the ligands, due to the higher ionic radius and the lower electronegativity of Er with respect to Al.

Fabrication of single-nanowire sensing devices by electron beam lithography

In this paper, we report on the feasibility of single nanowire devices fabrication by electron beam lithography. SnO2 and ZnO nanowires bundles have been synthesized by vapor-liquid-solid technique, dispersed in isopropanol and then deposited on SiO2/Si substrates. Once the nanowire has been selected, the electrodes have been patterned on the photoresist by the electron beam. Finally, after Pt sputtering and subsequent lift-off, we have obtained samples with SnO2 or ZnO nanowire and Pt electrodes deposited on it. The electrical characteristics of the devices have been preliminary investigated by DC measurements and impedance spectroscopy. The SnO2 single nanowire devices show a good sensitivity to relative humidity. The ZnO single nanowire device shows three orders of magnitude increase of the current when exposed to UV light and a fast recovery of the baseline in air when the UV light is switched off.

2D Materials for Gas Sensing Applications: A Review on Graphene Oxide, MoS2, WS2 and Phosphorene

After the synthesis of graphene, in the first year of this century, a wide research field on two-dimensional materials opens. 2D materials are characterized by an intrinsic high surface to volume ratio, due to their heights of few atoms, and, differently from graphene, which is a semimetal with zero or near zero bandgap, they usually have a semiconductive nature. These two characteristics make them promising candidate for a new generation of gas sensing devices. Graphene oxide, being an intermediate product of graphene fabrication, has been the first graphene-like material studied and used to detect target gases, followed by MoS2, in the first years of 2010s. Along with MoS2, which is now experiencing a new birth, after its use as a lubricant, other sulfides and selenides (like WS2, WSe2, MoSe2, etc.) have been used for the fabrication of nanoelectronic devices and for gas sensing applications. All these materials show a bandgap, tunable with the number of layers. On the other hand, 2D materials constituted by one atomic species have been synthetized, like phosphorene (one layer of black phosphorous), germanene (one atom thick layer of germanium) and silicone (one atom thick layer of silicon). In this paper, a comprehensive review of 2D materials-based gas sensor is reported, mainly focused on the recent developments of graphene oxide, exfoliated MoS2 and WS2 and phosphorene, for gas detection applications. We will report on their use as sensitive materials for conductometric, capacitive and optical gas sensors, the state of the art and future perspectives.