F. Antolini

Alcohol detection using carbon nanotubes acoustic and optical sensors

We demonstrate the integration of single-walled carbon nanotubes (SWCNTs) onto quartz crystal microbalance (QCM) and standard silica optical fiber (SOF) sensor for alcohol detection at room temperature. Different transducing mechanisms have been used in order to outline the sensing properties of this class of nanomaterials, in particular the attention has been focused on two key parameters in sensing applications: mass and refractive index changes due to gas absorption. Here, Langmuir–Blodgett (LB) films consisting of tangled bundles of SWCNTs without surfactant molecules have been successfully transferred onto QCM and SOF. Mass-sensitive 10MHz QCM SWCNTs sensor exhibited a resonant frequency decreasing upon tested alcohols exposure; also the normalized optoelectronic signal (λ=1310nm) of the refractive index-sensitive SOF SWCNTs sensor was found to decrease upon alcohols ambient. Highly sensitive, repeatable and reversible responses of the QCM and SOF SWCNTs sensors indicate that the detection, at room t...

Photophysical and structural characterisation of in situ formed quantum dots

Conjugated polymer-semiconductor quantum dot (QD) composites are attracting increasing attention due to the complementary properties of the two classes of materials. We report a convenient method for in situ formation of QDs, and explore the conditions required for light emission of nanocomposite blends. In particular we explore the properties of nanocomposites of the blue emitting polymer poly[9,9-bis(3,5-di-tert-butylphenyl)-9H-fluorene] together with cadmium sulphide (CdS) and cadmium selenide (CdSe) precursors. We show the formation of emissive quantum dots of CdSe from thermally decomposed precursor. The dots are formed inside the polymer matrix and have a photoluminescence quantum yield of 7.5%. Our results show the importance of appropriate energy level alignment, and are relevant to the application of organic-inorganic systems in optoelectronic devices.

Recognition of organic solvents molecules by simultaneous detection using SAW oscillator sensors and optical fiber devices coated by Langmuir-Blodgett cadmium arachidate films

Surface acoustic waves (SAW) 433 and 315 MHz, two-port resonator-based oscillators coated with a Langmuir-Blodgett (LB) thin layer of chemosensitive cadmium arachidate (CdA) provide highly sensitive chemical acoustic sensors for detection and monitoring of organic vapors, at room temperature. LB CdA film-coated silica optical fibers (SOF) have been successfully fabricated and studied for organic solvents molecules sensing applications. The sensing performance of both types of acoustic and optical transducers has been compared for detecting six molecular species. Simultaneous measurements of frequency changes (Deltaf) and optoelectronic signal changes (DeltaV) of the LB CdA film assembled onto SAW sensors and SOF devices have been realized for organic vapors recognition purposes. Six molecular species such as ethanol, methanol, isopropanol, ethylacetate, acetone, and toluene have been identified and recognized by a specific index (Deltaf/DeltaV), which can be considered a characteristic property of the chemosensitive material. The discrimination of the six molecular species examined also has been obtained by chemical patterns using a couple of specific index (Deltaf433/DeltaV;Deltaf315/DeltaV) measured by combining SAW 433 or 315 MHz oscillators and SOF sensing devices. Transient responses, calibration curves, intertransducer relationships, and chemical patterns are presented and discussed

Acoustic and optical sensors incorporating carbon nanotubes for detection of organic solvents

We investigate the sensing properties of single-walled carbon nanotube (SWCNTs) films used as nanostructured materials for chemical sensors onto three types of transducers using different principles of operation. These are surface acoustic waves (SAWs), quartz crystal microbalance (QCM) and standard silica optical fiber (SOF) for detection of organic solvents, at room temperature. The sensing probes have been configured as a 315- and 433-MHz SAW two-port resonator based oscillator, 10 MHz QCM resonator, and SOF light-reflectometry based system at a wavelength of 1310 nm. A nanocomposite film of SWCNTs embedded in a cadmium arachidate (CdA) matrix was deposited by an LB technique onto SAW sensors. An LB multilayer of SWCNTs-onto-CdA buffer material was also deposited onto QCM and SOF sensors. Our experiments demonstrate that carbon nanotube acoustic and optical sensors are highly sensitive to a wide range of polar and non-polar organic solvents up to a sub-ppm detection limit.

CdS and ZnS nanoparticles growth in different reaction media: synthesis and characterization

In this work we report on the growth of cadmium sulfide and zinc sulfide nanocrystals by thermolysis, starting from a metal thiolate in a (i) solventless way, (ii) by a novel route in tryoctilphosphine oxide (TOPO), and (iii) by direct synthesis in a polystyrene matrix. The x-ray diffraction (XRD) and transmission electron microscopy (TEM) show that the nanocrystals fabricated by the different methods are under optimized growth conditions single crystals of zincblende structure and of regular spherical shape. The average size was estimated to be between 2.0-3.0 nm with a size dispersion that depends on the synthesis route and is in the range between 10% and 20%. The XPS results indicate that for the nanoparticles obtained via solventless strategy the sulfur is present both as bonded to the metal atom and to the organic residue, while in the TOPO synthesized nanoparticles the sulfur signal has only one component associated to the metal-sulfide bond. The photoluminescence spectroscopy (PL) analysis of CdS crystals clearly evidences the typical emissions of nanosized zincblende CdS monocrystalline particles. Furthermore, the optical spectroscopy data indicate that the size distribution of the Cdsulfide - TOPO nanoparticles seems to be generally larger than that ones grown directly in polymer matrix. For all the CdS samples, the metal-sulfide nanocrystals exhibit a trap-related radiative transition at about 2eV that can be attributed to the hole-electron recombination at particle surface defect-center.

Formation of quantum dots from precursors in polymeric films by ps-laser

Quantum dots (QDs) of semiconductors are promising materials for light emission applications due to their size-tunable optoelectronic properties. We present results of direct quantum dot (QD) formation from precursors inside a polymer matrix using laser irradiation. The method is important because it provides a simple means of patterning nanocomposite material within selected regions of a polymer, as required for device design. Several combinations of polymer/precursors films were treated with a picosecond laser at wavelength of 266 nm in order to verify the formation of the QDs inside the polymeric matrix. Precursors for CdS and CdSe QDs were used in experiments. The structural studies of laser-irradiated samples carried out by means of transmission electron microscopy (TEM) showed the QD formation. The size of QDs and the clusters depended on the laser irradiation dose transferred to the film. The QDs were collected to clusters including 10-60 QDs of different size. The mean size of QDs was less than 10nm. The optical analysis carried out by means of UV-VIS and optical microscopy confirmed the formation of the QDs after laser processing. The time-resolved photoluminescence revealed the energy transfer from the organic host to QDs. However, the charge separation was present due to a certain energy level alignment. Modification of the polymer/precursor blends is still required to prevent imbalance of carrier injection to QDs. Photo-luminescent spectroscopy and fluorescence microscopy have revealed that even if the QDs are not emissive, in certain polymer/QDs combinations the PL emission of the polymer is restored after laser treatment.

Structure of Nanocomposite films of CdS nanoparticles in a polymer matrix

A thiolate precursor was dispersed in a polymer solution and a precursor/polymer film was obtained by casting. Thermal annealing of the precursor/polymer film leads to the formation of a nanocomposite of nanometer-sized CdS dispersed in the polymer (thermolytic process). Different polymers were used as matrix material; in particular we employed a cyclo-olefin copolymer for its good optical properties and extremely low water absorption. After annealing with a temperature between 230 and 250°C in vacuum (pressure of about 6×10 −3 mbar) the CdS nanoparticles are found to be crystalline with a diameter of about 2nm in size. The nanoparticle size can be increased up to 15nm by annealing at higher temperatures (300°C). The details of the structural properties of the nanocomposite films have been investigated by small and wide angle x-ray scattering (SAXS and WAXS, respectively). A simple dependence of the nanoparticle dimensions on the annealing temperature was found. Furthermore, SAXS measurements indicate that the separation between the nanoparticles compares with their diameter.

Vapor sensing properties of carbon nanotubes onto cadmium arachidate multilayer investigated by optical-fiber-based reflectometer sensor and acoustic sensors

We have investigated the sensing properties of the carbon nanotubes deposited onto a cadmium arachidate buffered multilayer by acoustic sensors -- SAW and QCM -- and a reflectometric sensor system based on optical fiber for purposes of chemical detection of volatile organic compound (VOCs), at room temperature. The carbon nanotubes have been deposited by the molecular engineering Langmuir-Blodgett (L-B) technique onto a buffer multilayer of cadmium arachidate prepared monolayer-by-monolayer using the L-B technique as well. The sensing multilayered material has been prepared both onto a standard silica optical fiber configured in a reflectometer sensor system and onto acoustic sensors -- SAW and QCM -- configured as oscillators. The acoustic sensors and the optical sensor have been exposed simultaneously, in the same test chamber, towards different VOCs such as ethanol, methanol, iso-propanol, acetone, ethylacetate, toluene with different vapor pressures for comparing the sensitivity of the coating onto the different kinds of acoustic and optical transducers. Moreover, for the same type of transducer, acoustic or optical, the effect of carbon nanotubes onto the gas sensitivity is remarkably higher in all investigated cases.