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Tire and Road Wear Particles (TRWP) are non-exhaust particulate matter generated by road transport means during the mechanical abrasion of tires, brakes and roads. TRWP accumulate on the roadsides and are transported into the aquatic ecosystem during stormwater runoffs. Due to their size (sub-millimetric) and rubber content (elastomers), TRWP are considered microplastics (MPs). While the amount of the MPs polluting the water ecosystem with sizes from ~ 5 μm to more than 100 μm is known, the fraction of smaller particles is unknown due to the technological gap in the detection and analysis of < 5 μm MPs. Here we show that Raman Tweezers, a combination of optical tweezers and Raman spectroscopy, can be used to trap and chemically analyze individual TWRPs in a liquid environment, down to the sub-micrometric scale. Using tire particles mechanically grinded from aged car tires in water solutions, we show that it is possible to optically trap individual sub-micron particles, in a so-called 2D trapping configuration, and acquire their Raman spectrum in few tens of seconds. The analysis is then extended to samples collected from a brake test platform, where we highlight the presence of sub-micrometric agglomerates of rubber and brake debris, thanks to the presence of additional spectral features other than carbon. Our results show the potential of Raman Tweezers in environmental pollution analysis and highlight the formation of nanosized TRWP during wear.

We report on the use of Raman Tweezers, a combination of Optical Tweezers and Raman Spectroscopy, for the detection and chemical identification of nanometric particles of plastics and car tires fragments dispersed in water, at the single particle level.

Optical printing of metal-nanoparticle-protein complexes in microfluidic chips is of particular interest in view of the potential applications in biomolecular sensing by surface-enhanced Raman spectroscopy (SERS). SERS-active aggregates are formed when the radiation pressure pushes the particle-protein complexes on an inert surface, enabling the ultrasensitive detection of proteins down to pM concentration in short times. However, the role of plasmonic resonances in the aggregation process is still not fully clear. Here, we study the aggregation velocity as a function of excitation wavelength and power. We use a model system consisting of complexes formed of gold nanorods featuring two distinct localized plasmon resonances bound with bovine serum albumin. We show that the aggregation speed is remarkably accelerated by 300 or 30% with respect to the off-resonant case if the nanorods are excited at the long-axis or minor-axis resonance, respectively. Power-dependent experiments evidence a threshold below which no aggregation occurs, followed by a regime with a linear increase in the aggregation speed. At powers exceeding 10 mW, we observe turbulence, bubbling, and a remarkable 1 order of magnitude increase in the aggregation speed. Results in the linear regime are interpreted in terms of a plasmon-enhanced optical force that scales as the extinction cross section and determines the sticking probability of the nanorods. Thermoplasmonic effects are invoked to describe the results at the highest power. Finally, we introduce a method for the fabrication of functional SERS substrates on demand in a microfluidic platform that can serve as the detection part in microfluidic bioassays or lab-on-a-chip devices.

Radiation pressure is used to push gold nanorods on multilayer graphene and create hybrid active surfaces for surface-enhanced Raman spectroscopy (SERS) in liquid. As a proof of concept, ultrasensitive detection of bovine serum albumin is shown and the aggregation kinetics is studied as a function of the irradiation time. We compare the results on graphene with experiments on glass and gold surfaces. Optical aggregation on graphene occurs on time scales of 20 min, ca. 3.5 times slower than on glass. No stable aggregation is obtained on gold. We attribute the differences to the destabilization effect of the standing wave produced on the metallic substrates, due to their higher reflectivity, and to the reduced thermophoretic effects, related to the higher heat dissipation. Despite the slowdown of the aggregation kinetics, the usage of graphene as substrate offers manifold benefits: an almost negligible fluorescence background when using near-infrared light (785 nm), the absence of thermal absorption as well as the possibility to easily functionalize the surface to enhance the affinity with the analytes. Our results enlarge the spectrum of materials that can be used for optical aggregation and SERS detection of biomolecules, highlighting the importance of controlling the physical properties of the surfaces. Graphic abstract: [Figure not available: see fulltext.]

The preparation and characterization of a hybrid composite, based on carbon cloth (CC) matrix functionalized with two-dimensional (2D) MoS2 flakes and MoO3, and its use for developing an electrochemical sensor for the determination of riboflavin (RF) is here reported. The 2D-MoS2-MoO3CC composite was prepared by depositing 2D-MoS2 nanosheets, obtained by liquid phase exfoliation (LPE), on the surface of a carbon cloth fiber network, previously functionalized with a layer of molybdenum oxide (α-MoO3) by radio-frequency magnetron reactive sputtering technique. The 2D-MoS2-MoO3CC composite was characterized by scanning electron microscopy and energy dispersive X-ray analysis (SEM-EDX), and Raman spectroscopy. An electrochemical sensor has been then fabricated by fixing a slice of the 2D-MoS2-MoO3CC composite on the working electrode of a screen-printed carbon electrode (SPCE). The 2D-MoS2-MoO3-CC/SPCE sensor display good electrochemical characteristics which have been exploited, for the first time, in the electroanalytical determination of riboflavin (RF). The sensitivity to RF, equal to 0.67 µA mM−1 in the linear range from 2 to 40 µM, and a limit of detection (LOD) of 1.5 µM at S/N = 3, demonstrate the promising characteristics of the proposed 2D-MoS2-MoO3-CC/SPCE electrochemical sensor for the determination of riboflavin.

We demonstrate a simple enzyme-free electrochemical sensor for tyrosine (Tyr) detection, based on the enhanced catalytical activity of two-dimensional molybdenum disulphide nanosheets (2D-MoS2), prepared by liquid phase exfoliation and deposited on commercial screen-printed carbon and gold electrodes (SPE). We first evaluate the electrochemical performances of the sensor by cyclic voltammetry (CV) in phosphate buffer solutions (PBS; pH = 7) as a function of the chemical nature and microscale texture of the working electrode, as well as the operating potential window. Results show that the modified-carbon (2D-MoS2-SPCE) and gold (2D-MoS2-SPAuE) electrodes display various anodic and cathodic peaks, whose potential and intensity depend on the potential window, electrode nature and 2D-MoS2 loading. 2D-MoS2 SPE electrodes are finally tested for voltammetric and amperometric detection of tyrosine. We show that 2D-MoS2-SPCE provide the best results, reaching a maximum sensitivity of 1580 μA mM−1 cm−2 and a limit of detection (LOD) of 0.5 μM computed at a S/N = 3. The proposed method shows satisfactory results also for the detection of tyrosine in a real food integrator sample. To our best knowledge, this is the first report demonstrating the use of 2D-MoS2 for the electrochemical determination of tyrosine.

Two-dimensional (2D) layered transition-metal dichalcogenides (2DMX(2)) are materials with unique optoelectronic properties, high surface-to-volume ratio, and high carrier mobility. The combination of noble metal nanoparticles (MNPs) with 2DMX(2) opens new avenues in conceiving more efficient plasmonic sensors, allowing one to optimize both electromagnetic and chemical signal enhancement. Photoinduced enhanced Raman spectroscopy (PIERS) exploits the electron migration from semiconductors to MNPs, upon UV light irradiation, to further boost the chemical enhancement in the surface-enhanced Raman scattering (SERS) of molecules deposited on hybrid 2DMX(2)-MNP nanostructures. Here, we propose a new PIERS sensor architecture based on tungsten disulfide (WS2) nanosheets produced by liquid-phase exfoliation (LPE) and functionalized with citrate-stabilized Au MPNs. Electron injection from WS2 to AuNPs is observed when the Au@WS2 is exposed to ultraviolet light, yielding an increase of the charge carriers' density approximate to 1.8%. The PIERS sensor performances are tested by detecting 4-mercaptobenzoic acid at a concentration of 10 mu M. The overall PIERS signal enhancement is similar to 10(6), whereas the photoactivation of WS2 yields a signal improvement of factor 4 with respect to SERS from Au@WS2 before UV irradiation. Our sensor is of low cost, easy to fabricate, and has the potential to detect biomolecules and chemical molecules at trace levels.

In recent years, considerable effort has been devoted to the synthesis and characterization of two-dimensional materials. Liquid phase exfoliation (LPE) represents a simple, large-scale method to exfoliate layered materials down to mono- and few-layer flakes. In this context, the contactless trapping, characterization, and manipulation of individual nanosheets hold perspectives for increased accuracy in flake metrology and the assembly of novel functional materials. Here, we use optical forces for high-resolution structural characterization and precise mechanical positioning of nanosheets of hexagonal boron nitride, molybdenum disulfide, and tungsten disulfide obtained by LPE. Weakly optically absorbing nanosheets of boron nitride are trapped in optical tweezers. The analysis of the thermal fluctuations allows a direct measurement of optical forces and the mean flake size in a liquid environment. Measured optical trapping constants are compared with T-matrix light scattering calculations to show a quadratic size scaling for small size, as expected for a bidimensional system. In contrast, strongly absorbing nanosheets of molybdenum disulfide and tungsten disulfide are not stably trapped due to the dominance of radiation pressure over the optical trapping force. Thus, optical forces are used to pattern a substrate by selectively depositing nanosheets in short times (minutes) and without any preparation of the surface. This study will be useful for improving ink-jet printing and for a better engineering of optoelectronic devices based on two-dimensional materials.

Our understanding of the fate and distribution of micro- and nano- plastics in the marine environment is limited by the intrinsic difficulties of the techniques currently used for the detection, quantification, and chemical identification of small particles in liquid (light scattering, vibrational spectroscopies, and optical and electron microscopies). Here we introduce Raman Tweezers (RTs), namely optical tweezers combined with Raman spectroscopy, as an analytical tool for the study of micro- and nanoplastics in seawater. We show optical trapping and chemical identification of sub-20 mu m plastics, down to the 50 nm range. Analysis at the single particle level allows us to unambiguously discriminate plastics from organic matter and mineral sediments, overcoming the capacities of standard Raman spectroscopy in liquid, intrinsically limited to ensemble measurements. Being a microscopy technique, RTs also permits one to assess the size and shapes of particles (beads, fragments, and fibers), with spatial resolution only limited by diffraction. Applications are shown on both model particles and naturally aged environmental samples, made of common plastic pollutants, including polyethylene, polypropylene, nylon, and polystyrene, also in the presence of a thin ecocorona. Coupled to suitable extraction and concentration protocols, RTs have the potential to strongly impact future research on micro and nanoplastics environmental pollution, and enable the understanding of the fragmentation processes on a multiscale level of aged polymers.

Silicon nanowires are held and manipulated in controlled optical traps based on counter-propagating beams focused by low numerical aperture lenses. The double-beam configuration compensates light scattering forces enabling an in-depth investigation of the rich dynamics of trapped nanowires that are prone to both optical and hydrodynamic interactions. Several polarization configurations are used, allowing the observation of optical binding with different stable structure as well as the transfer of spin and orbital momentum of light to the trapped silicon nanowires. Accurate modeling based on Brownian dynamics simulations with appropriate optical and hydrodynamic coupling confirms that this rich scenario is crucially dependent on the non-spherical shape of the nanowires. Such an increased level of optical control of multiparticle structure and dynamics open perspectives for nanofluidics and multi-component light-driven nanomachines.

Cylindrical vector beams are used to improve back scattering detection in photonic force microscopy measurements near a dielectric surface. We compare back focal plane interferometry signals acquired on a quadrant photodiode when optical trapping a latex microparticle with gaussian, radial, and azimuthal beams. We find a consistent reduction of the interference pattern generated by the superposition of light backscattered by the trapped particle and backreflected by the dielectric surface. We contrast experimental findings with a model based on light scattering theory in the T - matrix formalism. (C) 2020 Elsevier Ltd. All rights reserved.

Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) were prepared by liquid-phase exfoliation and used to modify screen-printed carbon electrodes (SPCE), in order to develop an electrochemical sensor for the simultaneous determination of dopamine (DA) and tyrosine (Tyr) in presence of uric acid (UA). To demonstrate the layered morphology, the synthesized molybdenum disulphide nanostructures, have been characterized by Raman and SEM in both liquid dispersion and after deposition on SPCE. The performances of the 2D-MoS2-SPCE electrode have been tested and optimized in terms of sensitivity, reaching high sensitivity values of 1044 μA mM−1 cm−2 for DA and 321 μA mM−1 cm−2 for Tyr, selectivity against UA and high stability. The simultaneous detection of these biomolecules is the first study so far reported with the use of 2D-MoS2-based sensors. The promising characteristics of the developed electrodes suggest 2D-MoS2 as a versatile, low cost and easy to produce material for the next generation of electrochemical sensors of a variety of important biomolecules.

Optical forces are used to aggregate plasmonic nanoparticles and create SERS-active hot spots in liquid. When biomolecules are added to the nanoparticles, high sensitivity SERS detection can be accomplished. Here, we pursue studies on Bovine Serum Albumin (BSA) detection, investigating the BSA-nanorod aggregations in a range from 100 mu M to 50 nM by combining light scattering, plasmon resonance and SERS, and correlating the SERS signal with the concentration. Experimental data are fitted with a simple model describing the optical aggregation process. We show that BSA-nanorod complexes can be optically printed on non-functionalized glass surfaces, designing custom patterns stable with time. Furthermore, we demonstrate that this methodology can be used to detect catalase and hemoglobin, two Raman resonant biomolecules, at concentrations of 10 nM and 1 pM, respectively, i.e., well beyond the limit of detection of BSA. Finally, we show that nanorods functionalized with specific aptamers can be used to capture and detect Ochratoxin A, a fungal toxin found in food commodities and wine. This experiment represents the first step towards the addition of molecular specificity to this novel biosensor strategy.

Optical tweezers, tools based on strongly focused light, enable optical trapping, manipulation, and characterisation of a wide range of microscopic and nanoscopic materials. In the limiting cases of spherical particles either much smaller or much larger than the trapping wavelength, the force in optical tweezers separates into a conservative gradient force, which is proportional to the light intensity gradient and responsible for trapping, and a non-conservative scattering force, which is proportional to the light intensity and is generally detrimental for trapping, but fundamental for optical manipulation and laser cooling. For non-spherical particles or at intermediate (meso)scales, the situation is more complex and this traditional identification of gradient and scattering force is more elusive. Moreover, shape and composition can have dramatic consequences for optically trapped particle dynamics. Here, after an introduction to the theory and practice of optical forces with a focus on the role of shape and composition, we give an overview of some recent applications to biology, nanotechnology, spectroscopy, stochastic thermodynamics, critical Casimir forces, and active matter.

We study the rotational dynamics of solid chiral and birefringent microparticles induced by elliptically polarized laser light in optical tweezers. We find that both reflection of left circularly polarized light and residual linear retardance affect the particle dynamics. The degree of ellipticity of laser light needed to induce rotations is found. The experimental results are compared with analytical calculations of the transfer of angular moment from elliptically polarized light to chiral birefringent particles.

Strategies for in-liquid molecular detection via Surface Enhanced Raman Scattering (SERS) are currently based on chemically-driven aggregation or optical trapping of metal nanoparticles in presence of the target molecules. Such strategies allow the formation of SERS-active clusters that efficiently embed the molecule at the “hot spots” of the nanoparticles and enhance its Raman scattering by orders of magnitude. Here we report on a novel scheme that exploits the radiation pressure to locally push gold nanorods and induce their aggregation in buffered solutions of biomolecules, achieving biomolecular SERS detection at almost neutral pH. The sensor is applied to detect non-resonant amino acids and proteins, namely Phenylalanine (Phe), Bovine Serum Albumin (BSA) and Lysozyme (Lys), reaching detection limits in the μg/mL range. Being a chemical free and contactless technique, our methodology is easy to implement, fast to operate, needs small sample volumes and has potential for integration in microfluidic circuits for biomarkers detection.

Optical forces are used to push and aggregate gold nanorods onto several substrates creating surface-enhanced Raman scattering (SERS) active hot spots for Raman-based identification of proteins. By monitoring the increase of the protein SERS signal, we observe different aggregation times for different curvatures of the substrates. The slower aggregation dynamics on curved surfaces is justified by a simple geometrical model. In particular, this technique is used to decorate three-dimensional microstructures and to quickly realize hybrid micro/nanosensors for highly sensitive detection of biological material directly in a liquid environment. (C) 2018 Optical Society of America

Due to its exceptional physical properties, synthetic diamond is an ideal material for the realization of UV and X-ray detectors to be used for the characterization of laser-generated plasmas. Diamond detectors are able to operate at high temperatures and in the presence of high fluxes of ionizing radiation, where traditional silicon-based detectors usually fail. In this paper, we report on Raman and electro-optical characterization of a structure consisting of intrinsic diamond/boron-doped diamond homoepitaxially grown by chemical vapor deposition onto a commercial high pressure high temperature Ib-type diamond substrate using a 1% CH4/H2 gas mixture. A metal–insulator–semiconductor (MIS) diode was obtained by thermally evaporating an aluminum contact on the growth surface of the intrinsic layer. The detection capability of this device operating in transverse configuration was measured in the deep UV spectral range. The device sensitivity has been estimated at different biasing voltages and at two wavele...

The crucial role of precursor gas (PG) and of catalyst support (CS) in the growth of multi-walled C nanotubes (MWCNTs) by iron-catalysed chemical vapour deposition (CVD) is evidenced. This is accomplished by comparing structural and morphological properties of MWCNTs synthesised by the use of different PGs (ethane and isobutane) and CSs (silica and alumina). The results of analyses, carried out on catalysts and C deposits by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS), thermo-gravimetry (TG) and X-ray diffraction (XRD), demonstrate that Al2O3-supported catalysts are more efficient than SiO2-supported ones in decomposing hydrocarbons. The use of i-C4H10 as PG allows reducing Fe-encapsulation and improving yield (YC) and selectivity, so as the large-scale production (YC > 900 wt.%) of high-quality nanotubes can be operated even at moderate reaction temperature (600 °C) after proper calibration of Fe-load (29 wt.%) and catalyst reduction temperature (500 °C).

In this paper, porous silicon (PS) layers of different porosity and thickness have been investigated by Raman spectroscopy. The estimation of built-in strain in PS is reported. Moreover, wetting phenomena in PS layers have been also investigated. The results prove a reversible blue shift of Raman spectra of wetted PS layers with respect to unperturbed layers. We ascribe the shift to a compressive stress due to the increased lattice mismatch between the PS layer and the bulk silicon substrate in wetting conditions. Copyright © 2008 John Wiley & Sons, Ltd.

This work shows that a set of quality indicators (QI), able to reliably monitor the basic characteristics of carbon nanotubes (CNT) grown by of Fe-catalysed chemical vapour deposition (CVD), can be derived from Raman spectroscopy (RS) measurements. Multi-walled nanotubes, prepared at 750 °C in C2H6+H2 mixture over 20%Fe/SiO2 catalyst, are demonstratively considered. By quantitatively analysing the spectra measured in the 100-3100 cm−1 range, information is obtained on level of defectiveness and degree of smoothness of C deposits, as well as, on relative amount of Fe-nanoparticles incorporated. The effect of the growth atmosphere composition on the quality of synthesis products is investigated. Indications provided by RS are confirmed by the results of scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analyses. Raman QI agreeably correlate with the average growth rate of the carbonaceous species.

Optical trapping of silver nanoplatelets obtained with a simple room temperature chemical synthesis technique is reported. Trap spring constants are measured for platelets with different diameters to investigate the size-scaling behaviour. Experimental data are compared with models of optical forces based on the dipole approximation and on electromagnetic scattering within a T-matrix framework. Finally, we discuss applications of these nanoplatelets for surface-enhanced Raman spectroscopy.

Optical trapping of hybrid core–shell gold–polymer particles is studied. Optical forces are measured for different gold core size and polymer shell thickness, revealing how a polymer shell increases the trapping efficiency with respect to the bare gold nanoparticles. Data are in agreement with calculations of optical trapping based on electromagnetic scattering theory in the T-matrix approach. The scaling behaviour of optical forces with respect to the ratio between polymer layer thickness and the whole particle radius is found and discussed.

Polycrystalline (pCVD) and single crystal (scCVD) diamond films grown from Chemical Vapour Deposition (CVD), if sufficiently pure at Raman analysis, are very good materials for beam or flux monitors inside accelerators or nuclear reactors. This is because they are very hard to damage in high radiation fields and very resistant to high temperatures. Films of pCVD diamond are, however, not so good as spectroscopy detectors due to inhomogeneities induced by their growth in grains with the consequent presence of grain boundaries which worsen their energy resolution. The latter can be significantly improved by growing scCVD diamond films onto HPHT synthetic diamond substrates. We have shown that it is possible to measure the density of defects inside diamond specimens using as probes suitable penetrating nuclear radiations. With the preliminary results reported here we'll show that, bombarding CVD diamond films grown at Roma 'Tor Vergata' with energetic protons and 4 He, Li-6 and C-12 ions produced in the accelerators of Catania laboratories, the pulse height defects are higher than those in silicon detectors and likewise well described by a power law in the deposited energy. Furthermore, we'll show that pulse heights for the same particles seem to depend on the duration of the measurement, thus exhibiting a sort of depolarization of the insulator when exposed to the electric voltage which makes it a particle detector. (c) 2006 Elsevier B.V. All rights reserved.

The performance of detectors based on CVD diamond films strongly depends on the material quality, which, in turn, is extremely sensitive to even slight variations of the deposition conditions. In this work, a careful Raman and photoluminescence (PL) study has been carried out on diamond films grown on Si substrates by microwave plasma CVD under nominally identical deposition conditions, but exhibiting, quite surprisingly, different detection sensitivity. Micro-PL measurements performed on the growth surface and on the cross-section of the samples have shown higher incorporation of Si impurities in films having lower detection performance. Optical microscopy on the nucleation side of such films has evidenced a lower nucleation density, leading to diamond grains of greater size, but also to higher incorporation of Si atoms. Thus, a greater grain size does not necessarily guarantee a higher film quality, if the nucleation density is low. On the basis of these results, the nucleation density is identified as the 'hidden' variable in the growth process of our CVD diamond films, determining, ultimately, their detection sensitivity.

The mid-range structure of glasses of the glass-forming system xNb(2)O(5)-(60 - x)P(2)O(5)-40Na(2)O, with x varying from 0 to 40, has been investigated by Raman spectroscopy and electro-optical Kerr measurements. It was found that the mid-range inhomogeneities in the glasses under study vary with x and their compositions and structures dramatically differ from the gross glass composition. It is shown that inhomogeneities with the 8NaNbO(3) + (Nb(2)O(5)·P(2)O(5)) composition are responsible for the electro-optical sensitivity of the glasses. The electro-optical structural elements of the inhomogeneities of this type are assumed to be fragments of the quasicubic lattice of crystalline NaNbO(3) demonstrating a rather high electro-optic Kerr coefficient. The obtained results are discussed in terms of the concepts of constant stoichiometric groupings and crystal motifs.

The tetraanionic water soluble meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) can be easily embedded into Nafion®, obtaining membranes which exhibit interesting optical properties strongly dependent both on the aggregation extent and on the organic solvent used for the re-cast procedure.

Raman amplification was demonstrated in the early 1970s, but the invention of erbium-doped fiber amplifiers (EDFA) overshadowed the interest in it. Today, Raman scattering has again become a competitive approach for optical amplification because it is only restricted by the pump wavelength and Raman active modes of the gain medium. Puresilica and germanium-doped silica fibres, currently utilized as Raman gain media in telecommunications, have quite low Raman gain coefficients and a limited usable spectral bandwidth of approx. 5 THz. Therefore, the investigation of materials possessing both large Raman gain coefficients and broader spectral bandwidth than fused silica is becoming necessary to satisfy the increasing telecommunications demands.

In this paper, niobium-phosphate glasses doped with rare earths (Er and Sm) are investigated by Raman scattering. The goal of Raman characterization is twofold: (a) to perform a fine structural characterization of the synthesized glasses and (b) to measure the Raman gain coefficient of the samples and to compare it with fused silica. The results reveal the presence of NbO6 octahedra and Nb–O–P–Nb–O mixed chains. A broadening of bandwidth and a significant enhancement (∼24 times) in gain coefficient G with respect to conventional silica glasses are also demonstrated.

In this work, the characteristics of the edge emission of a homoepitaxial diamond sample grown by chemical vapor deposition (CVD) are reported. Photoluminescence has been excited at 220 nm by using a tunable optical parametric oscillator laser, giving ∼5 ns wide laser pulses. The temperature of the sample has been decreased from room temperature down to 30 K. Free exciton emission and its phonon replicas have been observed at all the temperatures explored. Excitonic lifetime shows a nonmonotonic dependence on the sample temperature. Luminescence at low temperatures from electron-hole drops at approximately 5.18 eV has been observed for the first time in CVD diamond.

Catalytic activity of iron based catalysts in the production of multi-walled carbon nanotubes (MWCNTs) has been investigated. The effect of the carbon source (ethane or isobutane), catalyst support (Al2O3 or SiO2), iron loading, catalyst reduction temperature and reaction temperature on yield and quality of carbon products has been examined. The structural and morphological properties of catalyst and carbon products obtained have been analyzed by means of scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS), thermogravimetric analysis (TGA) and X-ray powder diffraction (XRD). The iron-based catalysts supported on alumina seem to be efficient systems for the production of carbon nanotubes from chemical vapor deposition (CVD) of isobutane with very interesting yields. The opportune calibration of reaction parameters, such as iron loading and reaction temperature, can in fact drive the synthesis toward the formation of high quality CNTs.

Multi-walled carbon nanotubes (MWCNTs) are prepared by chemical vapor deposition (CVD) in C2H6 + H2 mixture over 20%Fe/SiO2 catalysts. The effects, in terms of yield and selectivity of the growth process, of the changes in composition (H2 at 0–75%) and flow-rate (100–150 sccm) of gas-mixture, catalyst reduction-temperature (400 °C and 650 °C), temperature (750–850 °C) and duration (0.5−6 h) of the synthesis-reaction are investigated. Although yield to C deposits improves by increasing gas flow-rate, temperature or duration of the synthesis-reaction, and by diminishing H2 volume fraction in growth atmosphere, it never exceeds 90% due to the heavy catalyst encapsulation. Moreover, the results of morphological and structural analyses show that a loss of selectivity towards nanotubes and a deterioration of CNT crystalline quality generally accompany the yield enhancement. This suggests the unsuitability of the ethane decomposition over silica-supported Fe-catalysts to the large-scale production of CNTs. Nevertheless, the nanotubes attained might be profitably used in all applications exploiting the magnetic properties originating from the encapsulated iron. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

In this work, a Raman and photoluminescence (PL) study of synthetic diamond films grown by hot filament chemical vapor deposition (CVD) on WC-Co is presented. The changes in the Raman spectrum induced by the different pretreatments of the substrate and/or different growth parameters of the films are discussed. In particular, the spectra of the films grown at 740 degrees C substrate temperature, 36 mbar pressure and 1.7% methane content in the CH4-H-2 gas mixture and after different substrate pretreatments show all the features commonly observed in nanocrystalline diamond films, overlapped with a large PL background. A significant level of compressive stress is qualitatively deduced by the shift of the diamond Raman peaks. The different pretreatments of the substrates seem to have no influence on the quality of the diamond films. On the contrary, in samples grown at 700 degrees C substrate temperature, 10 mbar pressure and 1% methane content in the CH4-H-2 gas mixture, the contribution of the non-diamond carbon phases to the Raman spectrum substantially decreases, even though the diamond Raman peak remains shifted and broad. Impurities in the films have been identified by means of low-temperature PL measurements. Wand Si-related optical centers have been clearly observed, together with a band at approximately 1.967 eV probably connected to a nitrogen-related defect center. Copyright (C) 2008 John Wiley & Sons, Ltd.

The action of molecular interaction between a fluid and an adsorbent results in adsorption and wetting phenomena. However, the adsorbent is also submitted to the action of the molecular forces. In order to provide a large adsorption capacity, adsorbents with a large specific surface area are preferable. For this reason, for the study of adsorption phenomena, porous silicon is a material of great interest. Wetting phenomena in porous silicon layers are experimentally investigated by Raman scattering. The experimental results prove a reversible blue-shift of Raman spectra of wetted porous silicon layers with isopropanol or ethanol with respect to unperturbed layers. We ascribe the shift to a compressive stress due to the increased lattice mismatch between the porous silicon layer and the bulk silicon substrate in wetting conditions. The use of two liquids having quite similar density and surface tension resulted, as expected, in quite comparable blue shift of the peak. This effect may be conveniently used in sensing applications of liquids on porous silicon layers.

The results of the quantitative Raman analysis, performed on multi-walled carbon nanotubes produced by iron-catalysed chemical vapour deposition, are utilised for deriving a scaling law for the growth parameters. A semi-empirical approach, already successfully applied to different materials and growth techniques, is utilised and demonstration is given that the reaction outcome, in terms of yield to C deposits and crystalline perfection of nanotubes attained, analytically depends on the growth parameters through a single dimensionless combination of them. Copyright © 2007 John Wiley & Sons, Ltd.

In this work, it is shown that some Raman-active modes may be detected, below 500cm−1, in the spectrum of nanotubes synthesized by iron catalyzed chemical vapor deposition. By comparatively discussing results of Raman, high-resolution transmission electron microscopy, and thermogravimetric analyses, demonstration is given that these spectral features originate from scattering by nanoparticles of iron catalyst encapsulated within the tubes under nonstationary growth regime. Their intensity progressively weakens with increasing carbon supply rate until bands disappear as stationary conditions are reached.

The infrared (IR) absorption dependence on visible light illumination has been measured in doped and undoped hydrogenated amorphous silicon carbide (a-Si1−xCx:H) films grown by plasma enhanced chemical vapour deposition. The measurements were made by a highly sensitive technique which exploits properly designed a-Si1−xCx:H/ZnO test waveguides for lengthening the interaction region between the IR and visible (VIS) radiations in the material. Experimental data show that boron doping strongly enhances the VIS light induced variation of the IR absorption, whereas the increase in carbon content has a quenching effect on the phenomenon. The a-SiC:H films have been also characterized by photoluminescence measurements. The spectra are dominated by a photoluminescence band, ranging between 1.4 eV and 1.9 eV. This band is enhanced by the increase in carbon content, while is strongly quenched with increasing B-doping level. On the basis of these results, a correlation is found between the measurements of optical absorption, photo-induced absorption and photoluminescence. The type and the density of defects induced in the films by the different growth conditions have been recognized as the origin of the different behaviors observed.

The photoresponse of high quality single crystal diamond films homoepitaxially grown by Chemical Vapor Deposition (CVD) onto low cost diamond substrates has been studied. The time evolution electrical response to the excitation by 5 ns laser pulses at 215 nm closely reproduces the laser pulse shape. The single crystal diamond response is therefore much faster than the laser pulse duration. The output signal is also very stable and reproducible, without significant priming or memory effects. Single crystal diamond films can therefore be grown by CVD having enough high quality to be used as photodetectors. However, a minor slow component shows up in the charge-integrated sample response. A systematic speed up of this slow component when increasing the detector temperature from − 25 °C to + 50 °C demonstrates its thermally activated origin. The slow component is therefore attributed to detrapping effects from shallow trapping centres. A model of the charge transport mechanism in the presence of trapping–detrapping centres can be developed and the results can be compared to the experimental ones. The activation energy of the shallow defects is accordingly determined as E a = 0.4 eV.

Recently, great effort has been devoted to the deposition of homoepitaxial diamond for electronic applications. Its single-crystal nature avoids the problems due to grain boundaries in polycrystalline diamond films, although the quality of such materials may still be very high. However, the optimisation of the deposition process of single-crystal diamond has not yet been achieved. In fact, the surface morphology of homoepitaxial diamond seems to be very sensitive to the quality of the diamond substrate and to even slight variations in the deposition parameters (composition of the gas mixture, microwave power, substrate temperature). Moreover, the growth of flat samples needs very low growth rates, which are not practical for technological exploitation of the material. Thus, a deposition process at relatively high growth rates needs to be developed. In this view, characterisation studies of the material deposited play a key role, because they may give precious hints for the optimisation of a fast growth process of electronic-grade homoepitaxial diamond. In this work, we report on the characterisation of single-crystal diamond grown on diamond substrates of different origin. The samples have been deposited by means of microwave plasma-enhanced chemical vapour deposition (MWPECVD) with a CH 4 -H 2 gas mixture at different methane concentrations and at approximately 560°C substrate temperature. The growth rates range between approximately 1 μ/h and 4.5 μ/h. Optical and scanning electron microscopy have been used to study the surface morphology of the samples. A Raman investigation has been carried out to study the crystalline quality and the spatial homogeneity of the material, by means of accurate measurements of position and width of the diamond Raman peak at different points in the samples. Photoluminescence (PL) has been used to investigate both the phase purity and the distribution of possible impurities in the deposited material. The results indicate that homoepitaxial CVD diamond samples having very high crystalline quality (full width of the diamond Raman peak ~ 1.75 cm -1 ) and no impurity-related defect centers can be obtained in the adopted deposition conditions

A single-crystal homoepitaxial CVD diamond film, grown on a Ib-type diamond substrate, was analysed using optical and electro-optical measurements. The type and the distribution of its crystalline defects are discussed in connection with its photoconductive response to deep UV light. A similar device based on a high quality polycrystalline CVD diamond was also analysed using the same techniques in order to compare the results. Raman spectroscopy and photoluminescence (PL) have been used to assess the crystalline quality and to study the distribution of defects in the films, respectively. The results of the electro-optical measurements show that the single crystal diamond has very high responsivity and signal-to-noise ratio. Hence, the role of defects on the detection performance is discussed.

A systematic Raman analysis has been carried out on diamond films prepared by microwave plasma enhanced chemical vapour deposition, using a CH 4 –CO 2 gas mixture at methane concentrations varying between 47 and 52%, at 750 and 850°C substrate temperatures, in order to assess the influence of the growth conditions on the film crystalline quality, as measured by the linewidth of the diamond peak. The trends observed by changing substrate temperature and CH 4 concentration are understood on the basis of the results of a complementary film characterisation by means of micro-Raman spectroscopy, scanning electron microscopy and X-ray diffraction, aimed at investigating the local stress distribution, the surface morphology and the preferential orientation, respectively. The existence of a strong correlation is evidenced between the texturing achieved by varying the gas-mixture composition and the lineshape of the diamond peak in the micro-Raman spectra. The competition between different growth sectors within the film promotes the occurrence of large anisotropic stresses that split and inhomogeneously broaden the diamond peak. As a result, quite large macro-Raman diamond peaks are correspondingly detected, suggesting the possible unreliability of linewidth as defect density indicator in the presence of large anisotropic stresses. Finally, a quantitative estimation of the stress level in the investigated films is preliminarily presented.

High quality synthetic diamonds were grown on single-crystal silicon by microwave plasma enhanced chemical vapour deposition (CVD). A careful optimisation of both the experimental setup and the growth parameters was necessary before that the achievement of the best results was made possible. The films were deposited using a CH4-H2 gas mixture at methane concentrations variable in the range 0.6-2.2%, while the substrate temperature was fixed at 750 °C. Raman spectroscopy and photoluminescence (PL) were utilised to monitor the quality of the deposited films and to study the spatial distribution of defects, respectively. Micro-Raman analysis shows that linewidths of the diamond peak lower than 2.4 cm-1 can be easily measured at the growth surface, indicating that the crystalline quality of individual grains is comparable to that of the best natural diamonds. The excellent phase purity of the diamond microcrystals at the growth surface is witnessed by the complete absence of any non-diamond carbon feature and by a very weak luminescence background in the 1.6-2.4 eV spectral range. A worsening of the quality of the diamond particles is found moving from the growth surface towards the film-substrate interface. A photoluminescence feature at about 1.68 eV, commonly associated to Si impurities, is distinctly observed as the exciting laser beam is focused close to the interface. A progressive degradation of the global quality of the films is found with increasing methane concentration in the gas mixture, as witnessed by an increased PL background in the films grown at higher methane concentrations.

We use laser beams with radial and azimuthal polarization to optically trap carbon nanotubes. We measure force constants and trap parameters as a function of power showing improved axial trapping efficiency with respect to linearly polarized beams. The analysis of the thermal fluctuations highlights a significant change in the optical trapping potential when using cylindrical vector beams. This enables the use of polarization states to shape optical traps according to the particle geometry, as well as paving the way to nanoprobe-based photonic force microscopy with increased performance compared to a standard linearly polarized configuration. (C) 2012 Optical Society of America

Silicon nanoparticles obtained by ball-milling of a 50% porosity silicon layer have been optically trapped when dispersed in a water–surfactant environment. We measured the optical force constants using linearly and radially polarized trapping beams finding a reshaping of the optical potential and an enhanced axial spring constant for the latter. These measurements open perspectives for the control and handling of silicon nanoparticles as labeling agents in biological analysis and fluorescence imaging techniques. (Some figures may appear in colour only in the online journal)

In this paper, the optical dispersion properties and the Raman gain of sodium phosphate glasses containing niobium oxide at increasing concentrations have been systematically investigated, with the aim of establishing a potential enhancement of the Raman gain and its bandwidth with respect to silica. A broadening of the bandwidth and a higher peak Raman gain (approximately 17 times) than in silica glass have been observed at high niobium oxide molar content. Our findings point out that sodium-niobium-phosphate glasses could be utilized for the realization of Raman amplifiers.

Optical forces are used to position and aggregate nanoparticles for different applications. In particular, plasmonic enhanced optical forces are exploited to direct gold nanorods surrounded by biomolecules to create hot-spots on demand in a liquid buffered environment. This enables protein detection at the 10 nM level. Furthermore, optical forces on liquid phase exfoliated layered materials (hBN, MoS2, WS2) are studied and used to push and aggregate nanostructures in specific patterns.