Diamond is considered as a very promising material for the development of devices for radiation detection. Unlike other conventional photoconductive detectors diamond-based devices should provide high discrimination between UV and visible radiation. In this work we present the electro-optical properties of devices based on randomly oriented diamond films, synthesized in a microwave plasma enhanced chemical vapor deposition reactor. A comparative study on devices with coplanar interdigitated Cr/Au electrodes (with different interelectrode pitches) made of films grown simultaneously on intrinsic and p-doped silicon (100) substrates has been performed. The chemical-structural, morphological, electrical and optical properties of ROD films have been studied. In particular, the optical response has been measured in air using a Xe flash lamp coupled with an optical quartz fiber and a properly tailored front-end electronics based on a charge sensitive amplifier. Experimental results gave indications on how the device performances are dependent on the two types of employed substrates. (C) 2011 Elsevier B.V. All rights reserved.

Laser Induced Breakdown Spectroscopy (LIBS) is an appealing technique to study laser-induced plasmas (LIPs), both from the basic diagnostics point of view and for analytical applications. LIPs are complex dynamic systems, expanding at supersonic velocities and undergoing a transition between different plasma regimes. If the Local Thermodynamic Equilibrium (LTE) condition is valid for such plasmas, several analytical methods can be employed and fast quantitative analyses can be performed on a variety of samples. In the present paper, a discussion about LTE is carried out and an innovative application to the analysis of the alexandrite gemstone is presented. In addition, a study about the influence of plasma parameters on the performance of LTE-based methods is reported for bronze and brass targets.

In Laser Induced Plasma Spectroscopy (LIPS) or Laser Induced Breakdown Spectroscopy (LIBS) the relation between recombining electrons and optical emission intensity has been studied in hydrogen and different metals targets. The role played by the electron impact excitation cross section on the temporal trend of emission lines has addressed and a methodology for the evaluation of the excitation cross sections by optical emission spectroscopy has been tested on several species including H I, Fe I, Ni I, Co I and Ti II. In connection with the theory drawn in this paper, the results show a good agreement with respect to theoretical ones. These results allow the direct linking of the emission intensity to the electronic excitation binary collision. The latter does not depend on experimental conditions and can be applied for elemental analysis. The use of estimated cross sections forms the basis for a different calibration free approach. LIBS elemental analysis on iron meteorites (to be considered as ternary alloys) and on a set of copper based alloys demonstrates the promising use of this analytical approach.

Laser-Induced Breakdown Spectroscopy (LIBS) is a fast and reliable technique suitable for the simultaneous qualitative and quantitative analysis of major and trace elements in samples of various nature and origin. In last decades, the use of metal accumulator plants, in combination with compost, has become a cheap and sustainable alternative technique to lower soil contamination by toxic heavy metals. In the present work, the LIBS technique has been applied to measure the concentrations of selected elements, including Al, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Pb, Sr, and Zn, in two composts of different origin and nature and four accumulator plant species (Atriplex halimus, Brassica alba, Brassica napus, and Eruca vesicaria). The plant samples were analyzed either as bulk plant material or as specific organs (i.e., shoots and roots). The concentrations measured by LIBS were assessed by the complementary Induced Coupled Plasma - Optical Emission Spectroscopy (ICP-OES) technique. The significant correlation found between the data obtained by the two techniques (R = 0.732-0.999) supports the feasibility of LIBS for fast screening of major, trace and toxic elements in plant and compost samples. In conclusion, the LIBS technique shows promising for further applications in soil remediation as well as in agriculture.

An ultrashort (100 fs) Ti:Sapphire pulsed laser has been employed in order to produce nanostructures by pulsed ablation of a graphite target in water. Different (10-100-1000 Hz) repetition rates have been used, and the features of material produced have been investigated by surface enhanced Raman spectroscopy (SEAS) and scanning electron microscopy (SEM). SERS spectra show that a broad asymmetric band associated with diamond-like carbon (DLC) is observed when repetition rates of 10 or 100 Hz are used. On the contrary, ablated species produced with 1 kHz pulses present a narrow peak at 1333 cm(-1), the typical mode of diamond, which is, however, embedded in a DLC band centered at 1540 cm(-1). SEM images show the presence of dispersed octahedral-shaped structures having a size from 1 to 5 mu m, in the case of 10 or 100 Hz repetition rates, and agglomerates of particles having a dimension below 300 nm, when 1 kHz pulses are used.

Although the first nanoseconds to microseconds rule the resulting process yield of laser ablation in liquid, a comprehensive view involving combination of time-resolved measurement techniques is still lacking. In this paper, fundamental aspects of laser ablation of metals underwater during the production of nanoparticles are discussed. Three fast diagnostic methods have been applied simultaneously. These are Optical Emission Spectroscopy for the plasma characterization, fast shadowgraph for plasma and cavitation bubble dynamics and laser scattering for the mechanisms of delivery of the produced materials in the liquid. Moreover, in order to validate the discussion, the effect on cavitation dynamics of the ablation of bulk and wire-shaped targets has been investigated together with the relative nanoparticles production yield. Unusal arrow-bow ejection phenomena between cavitation bubble and wire results in suppressed material back-deposition, causing efficient ejection of ablated matter into the liquid. The presented nanosecond and microsecond-resolved analysis allows estimating timescale and role of the basic mechanisms involved in laser ablation in liquids as well as the thermodynamic characteristics of the processes.

Photodetectors based on polycrystalline diamond (PCD) films are of great interest to many researchers for the attractive electronic, mechanical, optical and thermal properties. PCD films are grown using the Microwave Plasma Enhanced Chemical Vapor Deposition (MWPECVD) method. First, we characterized films by means of structural and morphological analysis (Raman spectroscopy and scanning electron microscopy), then we evaporated a pattern of coplanar interdigitated Cr/Au contacts with an inter-electrode spacing of 100 mu m in order to perform the electrical characterization. We carried out measurements of dark current and impedance spectroscopy to investigate the film properties and conduction mechanisms of films and the effects of post-growth treatments. Finally we developed a charge sensing pre-amplifier to read-out the signal produced by UV photons in the detector. (C) 2009 Elsevier B.V. All rights reserved.

Photodetectors based on polycrystalline diamond (PCD) films are of great interest to many researchers for the attractive electronic, mechanical, optical and thermal properties. PCD films are grown using the Microwave Plasma Enhanced Chemical Vapor Deposition (MWPECVD) method. First, we characterized films by means of structural and morphological analysis (Raman spectroscopy and scanning electron microscopy), then we evaporated a pattern of coplanar interdigitated Cr/Au contacts with an inter-electrode spacing of 100 mu m in order to perform the electrical characterization. We carried out measurements of dark current and impedance spectroscopy to investigate the film properties and conduction mechanisms of films and the effects of post-growth treatments. Finally we developed a charge sensing pre-amplifier to read-out the signal produced by UV photons in the detector. (C) 2009 Elsevier B.V. All rights reserved.

Photodetectors based on polycrystalline diamond (PCD) films are of great interest to many researchers for the attractive electronic, mechanical, optical and thermal properties. PCD films are grown using the Microwave Plasma Enhanced Chemical Vapor Deposition (MWPECVD) method. First, we characterized films by means of structural and morphological analysis (Raman spectroscopy and scanning electron microscopy), then we evaporated a pattern of coplanar interdigitated Cr/Au contacts with an inter-electrode spacing of 100 mu m in order to perform the electrical characterization. We carried out measurements of dark current and impedance spectroscopy to investigate the film properties and conduction mechanisms of films and the effects of post-growth treatments. Finally we developed a charge sensing pre-amplifier to read-out the signal produced by UV photons in the detector. (C) 2009 Elsevier B.V. All rights reserved.

In this paper the most important features of Laser Induced Plasma (LIP) evolution were analyzed from the fundamental point of view, in order to point out the effects of background environment on the plasma emission spectra. In particular, the main differences between air and vacuum Laser- Induced Breakdown (LIBS) are discussed, as well as those arising in high-pressure gases and in liquid environment. As can be expected, the dynamics of the plasma is strongly dependent on the environment where the plasma itself expands, which can be exploited for several different applications, ranging from chemical analysis and process diagnostics to materials science. The effect of other experimental conditions, such as the state of aggregation of the irradiated target, and the effect of laser pulse duration are also briefly reviewed.

A zero-dimensional collisional-radiative (CR) model, coupled self-consistently with the electron Boltzmann equation, has been applied to the description of a metallic-laser induced plasma at experimental conditions typical of LIBS experiment. To take in account expansion effects, the experimental temperature and total number density as function of time have been used as input data. Plasma composition and the simultaneous time evolution of both heavy particle level distributions and the electron energy distribution function have been calculated by taking into account the most relevant collisional and radiative processes. This approach estimates the hierarchy of the elementary processes during the expansion and possible deviations from LTE conditions. The comparison of the experimental and theoretical results shows a good agreement, but at the same time new questions arise on the analysis of spectroscopic results and on the assumption generally made in LIBS.

In the present work, laser ablation of a graphite target submerged in pure water was tested as a methodology for the production of carbon-based nanoparticles. The effect of varying the external pressure imposed to the liquid was investigated for the first time, in the range from 1 to 146 atm. Single or double laser pulses were used to ablate the target and the produced nanoparticles were characterized by atomic force microscopy (AFM) and by Raman spectroscopy. A spectroscopic study of the laser induced plasma features was carried out with a Ti target and interpreted in terms of laser-induced cavitation phenomena. Tubular nanoparticles of 25 nm average diameter were obtained only by single pulse (SP) ablation of graphite, while particles formed with the double pulse (DP) technique mainly consisted of graphite particulates. At 1 atm, these tubular nanoparticles were few and mixed with diamondlike carbon, while at 146 atm they were produced in a larger amount, suggesting that the high density effect induced by pressure plays a key role for their generation.

A fast procedure for chemical analysis of different meteorites is presented, based on LIBS (Laser Induced Breakdown Spectroscopy). The technique is applied to several test cases (Dhofar 019, Dhofar 461, Sahara 98222, Toluca, Sikhote Alin and Campo del Cielo) and can be useful for rapid meteorite identification providing geologists with specific chemical information for meteorite classification. Concentration profiles of Fe, Ni and Co are simultaneously detected across the Widmanstätten structure of the iron meteorite Toluca with a view to determining cooling rates. The LIBS analysis of meteorites is also used as a laboratory test for analogous studies on the respective parent bodies (Mars, asteroids) in space exploration missions where one clear advantage of the proposed technique is that no direct contact with the sample is required.

This paper presents an evaluation of Laser Induced Breakdown Spectroscopy (LIBS) as a technique for gathering data relevant to Solar System geophysics. Two test cases were demonstrated: elemental analysis of chondrules in a chondrite meteorite, and space- resolved analysis of the interface between kamacite and taenite crystals in an octahedrite iron meteorite. In particular most major and minor elements (Fe, Mg, Si, Ti, Al, Cr, Mn, Ca, Fe, Ni, Co) in Sahara 98222 (chondrite) and its chondrules, as well as the profile of Ni content in Toluca (iron meteorite), were determined with the Calibration Free (CF) method. A special attention was devoted to exploring the possibilities offered by variants of the basic technique, such as the use of Fe I Boltzmann distribution as an intensity calibration method of the spectroscopic system, and the use of spatially resolved analysis.

Analytical applications of Laser Induced Breakdown Spectroscopy (LIBS), namely optical emission spectroscopy of laser-induced plasmas, have been constantly growing thanks to its intrinsic conceptual simplicity and versatility. Qualitative and quantitative analysis can be performed by LIBS both by drawing calibration lines and by using calibration-free methods and some of its features, so as fast multi-elemental response, micro-destructiveness, instrumentation portability, have rendered it particularly suitable for analytical applications in the field of environmental science, space exploration and cultural heritage. This review reports and discusses LIBS achievements in these areas and results obtained for soils and aqueous samples, meteorites and terrestrial samples simulating extraterrestrial planets, and cultural heritage samples, including buildings and objects of various kinds.

A modified version of the calibration-free (CF) method was applied to the analysis of a set of archaeological brooches made of various copper-based alloys and coming from the archaeological site of Egnatia (Apulia, Southern Italy). The developed methodology consists in determining the plasma temperature by reversing the set of equations employed in the usual CF algorithm, and it is thus referred to as "inverse method". The plasma temperature is determined for one certified standard, by using its known elemental composition as an input data, and then applied to the set of unknown samples to evaluate their composition in a CF mode. The feasibility of such an approach is demonstrated by comparing the results obtained with classical LIBS (drawing calibration lines with a series of matrix-matched certified standards) and with independent measurements performed with a conventional technique (LA-ICP-MS).

The excitation temperature of Laser Induced Plasmas (LIPs) of copper-based alloys was determined with an alternative approach, which reverses the procedure of calibration-free methods for quantitative analysis through Laser Induced Breakdown Spectroscopy (LIBS). The inverse method here proposed is based on the Local Thermodynamic Equilibrium (LTE) equations, which were applied to simulate the elemental composition of certified samples at different temperatures, assuming that the actual plasma temperature was the one providing the best agreement with certified data. This procedure was validated for a set of bronze and brass standard samples and in different experimental conditions, by changing laser pulse width (7 ns and 250 fs) and laser wavelength (1064 nm, 532 nm and 355 nm). The temperature determined with the inverse method was then employed to determine the elemental composition of archeological findings of different copper-based alloys from Southern Italy sites (from VII century B.C. to VII A.D.), in order to test its validity for the analysis of actual unknown samples. The obtained weight percentages showed a good correlation with those obtained with the calibration line method, which provided a further confirmation of the assumptions made.

In the Laser-Induced Breakdown Spectroscopy (LIBS) technique, the existence of Local Thermodynamic Equilibrium (LTE) is the essential requisite for meaningful application of theoretical Boltzmann–Maxwell and Saha–Eggert expressions that relate fundamental plasma parameters and concentration of analyte species. The most popular criterion reported in the literature dealing with plasma diagnostics, and usually invoked as a proof of the existence of LTE in the plasma, is the McWhirter criterion [R.W.P. McWhirter, in: Eds. R.H. Huddlestone, S.L. Leonard, Plasma Diagnostic Techniques, Academic Press, New York, 1965, pp. 201–264]. However, as pointed out in several papers, this criterion is known to be a necessary but not a sufficient condition to insure LTE. The considerations reported here are meant to briefly review the theoretical analysis underlying the concept of thermodynamic equilibrium and the derivation of the McWhirter criterion, and to critically discuss its application to a transient and non-homogeneous plasma, like that created by a laser pulse on solid targets. Specific examples are given of theoretical expressions involving relaxation times and diffusion coefficients, as well as a discussion of different experimental approaches involving space and timeresolved measurements that could be used to complement a positive result of the calculation of the minimum electron number density required for LTE using the McWhirter formula. It is argued that these approaches will allow a more complete assessment of the existence of LTE and therefore permit a better quantitative result. It is suggested that the mere use of the McWhirter criterion to assess the existence of LTE in laser-induced plasmas should be discontinued.

Laser Induced Breakdown Spectroscopy (LIBS) is a fast and multi-elemental analytical technique particularly suitable for the qualitative and quantitative analysis of heavy metals in solid samples, including environmental ones. Although LIBS is often recognised in the literature as a well-established analytical technique, results about quantitative analysis of elements in chemically complex matrices such as soils are quite contrasting. In this work, soil samples of various origins have been analyzed by LIBS and data compared to those obtained by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The emission intensities of one selected line for each of the five analytes (i.e., Cr, Cu, Pb, V, and Zn) were normalized to the background signal, and plotted as a function of the concentration values previously determined by ICP-OES. Data showed a good linearity for all calibration lines drawn, and the correlation between ICP-OES and LIBS was confirmed by the satisfactory agreement obtained between the corresponding values. Consequently, LIBS method can be used at least for metal monitoring in soils. In this respect, a simple method for the estimation of the soil pollution degree by heavy metals, based on the determination of an anthropogenic index, was proposed and determined for Cr and Zn.

Gem-quality alexandrite, hiddenite and kunzite, elbaite and topaz minerals were characterized through a multi-methodological investigation based on EMPA-WDS, LA-ICP-MS, and laser-induced breakdown spectroscopy (LIBS). With respect to the others, the latter technique enables a simultaneous multi-elemental composition without any sample preparation and the detection of light elements, such as Li, Be and B. The criteria for the choice of minerals were: (a) the presence of chromophore elements in minor contents and/or as traces; (b) the presence of light lithophile elements (Li, Be and B); (c) different crystal chemistry complexity. The results show that LIBS can be employed in mineralogical studies for the identification and characterization of minerals, and as a fast screening method to determine the chemical composition, including the chromophore and light lithophile elements.

In this paper the use of metallic nanoparticles (NPs) for improving Laser Induced Breakdown Spectroscopy (LIBS) is discussed. In the case of conductors an emission signal enhancement up to 1-2 orders of magnitude was easily obtained depositing NPs on the sample surface by drying a micro-drop of colloidal solution. The basic mechanisms of Nanoparticles Enhanced LIBS (NELIBS) were studied and the main causes of the huge enhancement were found to be related to the effect of NPs on the laser ablation process, in terms of a faster and more efficient production of seed electrons with respect to conventional LIBS. The characteristics of NELIBS-produced plasma were investigated by fast emission spectroscopy and spectral resolved image, and in spite of similar plasma parameters , the NELIBS plasma was found to have larger emission volume and longer persistence than the LIBS one. On the other hand a methodology for determination of NPs concentration and size was pointed out when the NPs are deposited on insulators, proving the feasibility of LIBS as a fast detection tool for a preliminary characterization of NPs.

In this paper an increase of 1-2 orders of magnitude in Laser Induced Breakdown Spectroscopy (LIBS) signals was obtained by depositing silver nanoparticles on metal samples. Nanoparticle-Enhanced LIBS (NELIBS) proved a robust and flexible tool for the chemical analysis of metals because the sample emission signal did not appear very affected by the size and concentration of deposited nanoparticles (NPs), respectively within a range of 10 nm of diameter and one order of magnitude of concentration. On the other hand, preliminary NELIBS tests on insulators and semiconductors did not show any significant enhancement with respect to conventional LIBS. In this paper we present a detailed investigation of the fundamental features of the NELIBS spectra, in addition to some examples of analytical applications to the quantitative analysis of metal alloys.

In this work, different theories for the determination of the electron density in Laser-Induced Breakdown Spectroscopy (LIBS) utilizing the emission lines belonging to the hydrogen Balmer series have been investigated. The plasmas were generated by a Nd:Yag laser (1064 nm) pulsed irradiation of pure hydrogen gas at a pressure of 2 · 104 Pa. Hα, Ηβ, Ηγ, Ηδ, and Hε Balmer lines were recorded at different delay times after the laser pulse. The plasma electron density was evaluated through the measurement of the Stark broadenings and the experimental results were compared with the predictions of three theories (the Standard Theory as developed by Kepple and Griem, the Advanced Generalized Theory by Oks et al., and the method discussed by Gigosos et al.) that are commonly employed for plasma diagnostics and that describe LIBS plasmas at different levels of approximations. A simple formula for pure hydrogen plasma in thermal equilibrium was also proposed to infer plasma electron density using the Hα line. The results obtained showed that at high hydrogen concentration, the Hα line is affected by considerable self-absorption. In this case, it is preferable to use the Hβ line for a reliable calculation of the electron density. © 2013 Elsevier B.V. All rights reserved.

Using wires of defined diameters instead of a planar target for pulsed laser ablation in liquid results in significant increase of ablation efficiency and nanoparticle productivity up to a factor of 15. We identified several competitive phenomena based on thermal conductivity, reflectivity and cavitation bubble shape that affect the ablation efficiency when the geometry of the target is changed. On the basis of the obtained results, this work represents an intriguing starting point for further developments related to the up-scaling of pulsed laser ablation in liquid environments at the industrial level.

This paper focuses on the interpretation of the origin of the continuum radiation in Laser Induced Plasma (LIP) emission spectra, a subject that has received little consideration in the literature when compared to the analysis of the line emission spectrum. The understanding of the spectral peculiarities observed immediately after the laser pulse, when the continuum radiation prevails on discrete emission lines, can be extremely important to retrieve the initial conditions of LIP and to correlate the produced plasma to the ablation mechanism. In this work, in addition to a qualitative interpretation of the LIP continuum in the initial stage of expansion, a methodology is proposed for a better measurement of the atomic temperature in the expansion stage of the LIP. Such methodology is based on the analysis of the combined Boltzmann and Planck plots. The results obtained stress once again the importance of considering non equilibrium effects in the initial stage of LIP expansion.