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This study introduces a novel and simple way to suppress the self-absorption effect in laser-induced breakdown spectroscopy (LIBS) by utilizing a defocusing laser irradiation technique. For this purpose, a Nd:YAG laser with a wavelength of 1,064 nm and repetition rate of 10 Hz with energy in the range of 10 mJ-50 mJ was used. The laser irradiation was focused by using a 150-mm-focal-length plano-convex lens onto the sample surface under defocusing of approximately -6 mm. Potassium chloride (KCl) and sodium chloride (NaCl) pellet samples were used to demonstrate this achievement. When the defocus position is adjusted to -6 mm for KCl and NaCl samples, the self-reversal in the emission lines of K I 766.4 nm, K I 769.9 nm, Na I 588.9 nm, and Na I 589.5 nm vanish. Meanwhile, the FWHM values of K I 766.4 and K I 769.9 nm are 0.29 nm and 0.23 nm, respectively, during -6 mm defocus laser irradiation, as opposed to 1.24 nm and 0.86 nm under tight focus laser irradiation. Additionally, this work demonstrates that, when the laser energy is changed between 10 and 50 mJ, no self-reversal occurs in the emission lines when -6 mm defocus laser irradiation is applied. Finally, a linear calibration curve was generated using KCl at a high concentration ranging between K concentrations from 16.6% to 29%. It should be noted that, even at such high K concentrations, the calibration curve is still linear. This means that self-absorption is almost negligible. This simple change in defocus laser irradiation will undoubtedly contribute to the suppression of the self-absorption phenomenon, which disrupts LIBS analytical results.

This study is aimed at elucidating the physical processes responsible for the excellent spectral qualities in terms of full width at half-maximum (fwhm) and signal-to-noise (S/N) ratio shown in a special double pulse laser-induced spectroscopy. Apart from the use of atmospheric He ambient gas, the achievement is due to the first laser for generating He gas plasma and the subsequent use of the second laser pulse for target ablation, in opposite order of the two-laser operations in conventional double pulse LIBS. This setup allows adjustments of the many experimental parameters to yield the optimal condition resulting in 0.03 nm fwhm and around 1000× S/N ratio of Cu I 521.8 nm and far surpasses the spectral qualities obtained by other techniques. This is obtained by allowing the crucial separation of the target plasma from the He gas plasma and thereby enabling the He-assisted excitation (HAE) to play its full and unique role of nonthermal excitation, taking advantage of metastable excited He atoms in the He plasma and the Penning-like energy transfer process. This excellent performance is further verified by its successful application analysis of Cr in low alloy steel samples, with the presence of smooth linear calibration lines, signifying the absence of the self-absorption effect well-known in ordinary LIBS.

Self-absorption, which is known to severely disturb identification of the emission peak intensity in emission-based spectroscopy, was first studied using ordinary single pulse laser-induced breakdown spectroscopy (LIBS). It was found that severe self-absorption, with an evident self-reversal, occurs in the resonance emission lines of high concentration Na, K, and Al, and thus it is impossible to obtain the linear calibration curve required for quantitative analysis. To overcome this problem, we introduce a double pulse orthogonal technique in which the first laser is fired in a parallel orientation at a varied distance of 2–6 mm from the sample surface. It is well known that the strong shock wave generated by this laser irradiation temporarily creates a vacuum-like condition immediately in front of the sample surface. This action is followed by a second laser irradiation oriented perpendicular to the sample surface. The sample ablated by the second laser irradiation expands following the shockwave excitation process in the vacuum-like air atmosphere created by the first laser. The obtained spectra of the resonance emission lines of high concentration Na, K, and Al are free from the self-reversal and weakly affected by the self-absorption effect. A linear calibration curve that intercepts near zero point for K element over a wide concentration range is also demonstrated in this study. This simple modification is considered notably helpful in overcoming the self-absorption that occurs in ordinary single pulse atmospheric pressure LIBS.

We present in this report the results of experimental study on the spectrochemical analysis of powder samples using subtarget supported micro mesh (SSMM) sample holder in low pressure ambient gases. The study is substantiated by establishing the analyte excitation mechanism with the evidence of shock wave plasma generation and the high temperature induced subsequently required for the thermal excitation and emission of the ablated atoms. The application of SSMM sample holder using Cu subtarget and stainless steel micro mesh to a number of powder samples in low pressure ambient gases are shown to produce generally sharp emission lines with low background, without suffering from intensity reduction and matrix effect commonly found in the use of pelletized powder samples. The same excellent spectral quality is demonstrated by its application to the analysis of rice samples which is the major staple diets in a large number of countries. In particular the analysis of Zn in rice is shown to exhibit a linear calibration line with extrapolated zero intercept and a detection limit of

Preliminary optical spectroscopy studies have been carried out on betel nut samples using a new analytical tool, LIBS. The LIBS system consists of an neodymium -doped yttrium aluminium garnet (Nd YAG) laser as an excitation source, laser beam conditioning equipment, and an optical multichannel analyzer system (OMA system). Betel nut samples were collected from Aceh, Indonesia. The experiment was carried out under ambient air with a pressure of 760 Torr. It was found that strong luminous plasma could be generated directly from fresh betel nut samples, which resulted in strong emission spectrum. The emission spectrum obtained should have been dominated by host organic matter (C-H-O-N), but not as imagined because the organic host elements did not appear predominantly in the spectrum. Different treatments need to be carried out in further research so that the host organic matter appears. However, some salts, namely Mg, Fe, Na, Ca, Si, Al and K can be detected clearly. These initial investigations hold the promise of LIBS for spectral studies of betel nuts.

Cocoa seeds well known contains many antioxidant, thus it is really useful to human health. The elemental content of cocoa (Theobroma cacao L.) was examined using LIBS. The Cocoa seed was collected from Pidie Jaya Regency in the special autonomy region of Aceh, Indonesia. The examination was carried out is using LIBS using an Nd-YAG laser (Q-Smart 850 model, 1064 nm, 5.5 ns, 10 Hz). The laser energy was varied from 12 mJ to 70 mJ. The tested cocoa is dried first, mashed and shaped into pellets with a radius of 3 cm and a thickness of 0.5 cm. The laser beam was focused on the pellet surface under air surrounding gas. The surrounding gas pressure was also varied. The emission spectrum was acquired for various experimental conditions. It was found in the recorded emission spectrum that many inorganic elements can clearly be detected such as Al, Mg, Mn, Ca, K, P, Fe, Cu and also main organic elements such as H, C, N, and O. The emission spectrum is dominated by the organic elements of C, H, O and N. The emission spectrum features changes with energy and surrounding gas pressure. The plasma characteristics in term of temperature and electron number density was examined. This results shows that the minor and trace elements can detected be detected clearly along with main organic element in the cocoa seeds using the emerging analytical tool of LIBS.

A new approach to allow detection of Cl emission using atransversely excited atmosphere (TEA) carbon dioxide (CO2) laser-induced breakdown spectroscopy (LIBS), namely utilization of a metal sub-target, was introduced. The Cl sample was prepared from pure chemical powder in the form of a solutiondeposited on the metal sub-target. A zinc selenium lens was used to focus the CO2 laser beam (10.6Mm, 2.5 J, 10 Hz, 200 ns) onto the deposited sample under the surrounding gas of helium (pressure of 1 atm) for generated luminous plasma. An optical multichannel analyzer (OMA) system was used for collecting plasma and acquiring the emission spectrum. It was found that luminous plasma can be produced upon focusing the laser irradiation onto the deposited layer of the sample on the subtarget metal while leaving no ablation from the sub-target metal. Many ionic emission lines from Cl can be detected in the visible region.The ionic emission lines occur withfavorable spectrochemical features, namely strong emission intensity and low background level. Thus, this new approach is promising for conducting Cl analysis using a CO2 LIBS.

A study was conducted for identification of heavy metal pollution from biological sample as a potential proxy of environmental pollution due to industrial waste. The identification was conducted using the emerging analytical tool, namely laser induced breakdown spectroscopy (LIBS). The sample was collected from seawater near a cement plant in Aceh. Samples is a conch shell. The sample was dried in the open air and then prepared in the form of a pellet. The analysis was made by generating a plasma on the pellet sample using an Nd-YAG laser with a wavelength of 1,064 nm which is focused with a lens that has a focal length (f = 15 cm) by varying laser energy under low pressure of 3 Torr of air surrounding gas. Emission from the generated plasma was transmitted to the Maya2000 spectrometer optical detector using an optical fiber and then the emission spectrum of each element is displayed on the monitor. The results showed that the snail shell contained the salts and heavy metal elements K, Pb, Gd, Se, Mg, Rb, Fe, and Xe. Thus, it can be concluded that the heavy metal elements Pb and Fe can be detected LIBS technique from the biological sample.

Quick qualitative elemental analysis of agriculture soil has been made using a pulsed CO2 LIBS. The laser beam with different pulse energy was focused on agriculture soil sample under ambient of helium at atmospheric pressure (760 Torr) after the laser beam passes through a covering metal mesh. Emission spectra from the consequent plasma was recorded in wavelength range from 200 nm to 800 nm. It was found that by utilizing the mesh, intense plasma was generated immediately after the CO2 laser irradiation. It was seen that emission lines belong to salts, namely Ca, Mg, Na, K and metals such as Al, Si, Fe, Ti, Cr can certainly be identified. It was also found that the profile of the emission spectrum detected are basically relative similar to the standard soil, nevertheless the agriculture soil color is very different from the standard soil. Higher resolution and sensitivity optical multichannel analyzer (OMA) system is required to evaluate in greater detail the elemental composition of the soil samples.

Temperature of plasma generated by CO2 laser from soil sample prepared by the two different methods, namely metal mesh, and silicone grease methods, was examined. The plasma was produced by focusing the laser beam on the sample at 1 atmospheric pressure. The plasma characteristics namely temperature was estimated by the Boltzmann plot method. The detection was made in region of 300 nm-400 nm. In the case sample prepared using the metal mesh method, the estimated temperature was about 11605 K for the metal mesh no. 50 and 12440 K for mesh no. 40, respectively when helium was used as surrounding gas. When air was used as surrounding gas, plasma temperature was about 10315 K and 10990 K, respectively. In case the soil sample prepared by soil mixed with silicon grease (SMS) smeared on a surface of metal sub target, plasma temperature was about 8913 K and 9218 K for air and helium as a surrounding gas, respectively. It can be concluded that plasma temperature is not significantly different although the sample was prepared with different methods.

Detection of chlorine (Cl) using LIBS technique is greatly influenced by experimental conditions including the delay time of the detecting device. Time evolution of Cl emission in plasma produced on polyvinyl chloride (PVC) sample using CO2 laser with variation of delay time has been carried out. The plasma was produced at atmospheric pressure under different environment of helium and air, respectively. It was found that when using the pulse energy of 750 mJ under helium surrounding, strong emission line of Cl at 479.45 nm can be observed until 4 μs of delay time, while when using laser energy 2500 mJ strong Cl emission line can be observed until 7 μs. The higher signal to background ratio was observed at delay time of 1 μs. However, Cl emission line cannot be detected under air environment.

Chlorine (Cl) detection using laser induced breakdown spectroscopy (LIBS) techniques in geology and environment samples is still challenging since the experimental conditions greatly influence the analytical performance of LIBS. Cl emission in LIBS must be studied carefully to find the optimum condition to allow Cl detection. In the present study, Cl emission was studied from polyvinyl chloride (PVC) sample containing Cl as major element. A Transversely Excited Atmosphere (TEA) carbon dioxide (CO2) laser was used for inducing plasma from the sample. Cl emission was investigated by varying the experimental conditions, especially energy of the laser pulse. The emission spectrum from the consequent plasma was detected using an Optical Multichannel Analyzer (OMA) system. It was found that Cl emission lines only can be obtained when helium was used as the surrounding gas. The strongest emission line of Cl I 837.59 nm in the infrared region cannot be detected even under helium surrounding gas. Instead, many ionic emission lines of Cl in ultraviolet regions including the strong ionic lines (Cl II 479.45 nm, Cl II 481.00 nm, Cl II 481.94 nm and the weak lines (Cl II 476. 86 nm, Cl II 478.13 nm, Cl II 489.67 nm, Cl II 490.47 nm and Cl II 491.77 nm) can unequivocally be detected. It was also found that the intensity of Cl emission lines critically depends on the energy of the laser pulse, namely the emission intensity of Cl lines increases sharply with energy. In present work, the highest intensity of Cl emission lines was obtained when the energy of the laser pulse was about 2500 mJ, giving strong and clear Cl emission lines with low background and relatively high signal to background ratio of more than 3.

This report presents the results of laser-induced breakdown spectroscopy (LIBS) study on biological and food samples of high water content using a picosecond (ps) laser at low output energy of 10 mJ and low-pressure helium ambient gas at 2 kPa. Evidence of excellent emission spectra of various analyte elements with very low background is demonstrated for a variety of samples without the need of sample pretreatment. Specifically, limits of detection in the range of sub-ppm are obtained for hazardous Pb and B impurities in carrots and meatballs. This study also shows the inferior performance of LIBS using a nanosecond laser and atmospheric ambient air for a soft sample of high water content and thereby explains its less successful applications in previous attempts. The present result has instead demonstrated the feasibility and favorable results of employing LIBS with a ps laser and low-pressure helium ambient gas as a less costly and more practical alternative to inductively coupled plasma for regular high sensitive inspection of harmful food preservatives and environmental pollutants.

Temperature as one very important characteristics of a laser-induced plasma was estimated using many calcium emission spectral lines. This was possible due to the availability of a wide coverage and high resolution optical multichannel analyser (OMA) system allowing a simultaneous detection of many emission spectral lines from one element. The plasma emission was produced after focusing an Nd-YAG (neodymium-doped yttrium aluminium garnet) laser onto a river clamshell samples under air as surrounding gas at low and high pressures. The emission spectrum was acquired using the OMA system equipped with an echelle spectrograph system. The clamshell sample was collected from Panga River, Panga, Aceh Jaya, Aceh, Indonesia. The plasma temperature estimation was carried out by Boltzmann plot method. All calcium spectral lines either atomic and ionic emission were identified including resonant emission spectral lines in the recorded spectrum. Boltzmann distribution function firstly was plotted for all identified calcium spectral lines either atomic and ionic emission including their respective resonant emission spectral lines. In the further stage, the resonant emission lines then were excluded from the Boltzmann plot. As the results, the estimated temperature changes significantly with the number emission lines included and also with inclusion of the resonant spectral lines. The plasma temperature heavily influenced by inclusion the resonant emission lines. Thus, this work demonstrated clearly the influence of number emission lines used in Boltzmann plot to the plasma temperature estimation. The results also demonstrated explicitly the apparent effect of self-absorption of the resonant spectral line in estimation the plasma temperature.

A wide coverage spectral investigation on the muscle of river calm sample has been carried out using laser-induced breakdown spectroscopy for examining the overall profile of the emission spectra from the produced plasma. The basic apparatus of LIBS system used is a Nd-YAG laser and wide coverage optical multichannel analyzer (OMA) system. The river clam samples used is collected from Panga River in Aceh Jaya Regency, Aceh, Indonesia up streaming in a mountain of Gunong Ujeun, which is used as a location of the intensive traditional mining activity. Assuming that heavy metal accumulated in the clam muscle, LIBS experiments were carried out on the muscle of the calm. The sample used was fresh muscle sliced and attached to a copper plate. Plasma was generated by focusing the laser beam on the sample surface under air surrounding gas at 1 atmosphere. It is found that there are only major elements of host organic, namely C, H, O, N and the minor element of salts can be detected from fresh the clam sample when using a high pulse laser energy under air surrounding at high pressure of 1 atmosphere. There is no emission lines from any metal can be detected. Several experimental parameters were explored to study the panoramic dynamic of the emission spectra. It is found that the lower energy and the lower pressure is better for obtaining better emission spectra showing the possibility for determination of the analyte.

An experimental study has been performed to examine the physical characteristics of pharmaceutical products, such as tablet, by employing an emission plasma induced by Nd-YAG laser at a low pressure of Helium gas. The hardness of tablet is one of the parameters that examined during the production process for standard quality of pharmaceutical products. In the Laser-Induced Shock Wave Plasma Spectroscopy (LISPS), the shock wave has a significant role in inducing atomic excitation. It was known that, the speed of the shock wavefront depends on the hardness of the sample, and it correlates with the ionization rate of the ablated atoms. The hardness of the tablet is examined using the intensity ratio between the ion of Mg (II) 275.2 nm and the neutral of Mg (I) 285.2 nm emission lines detected from the laser-induced plasma. It was observed that the ratio changes with respect to the change in the tablet hardness, namely the ratio is higher for the hard tablet. Besides the ratio measurements, we also measured the depth profile of a tablet by focusing 60 shots of irradiation of laser light at a fixed position on the surface of the tablet. It was found that the depth profile varies differently with the hardness of the tablet. These experiment results show that the technique of LISPS can be applied to examine the quality of pharmaceutical products.

We report the experimental evidence of shock wave plasma generation by direct observation of the plasma propagation using 68 mJ 1064 nm Nd-doped yttrium aluminum garnet laser irradiation on a relatively soft organic sample in He ambient gas at 2 kPa. The density jump associated with the arrival of the plasma front at a certain position is detected by means of the highly sensitive interferometric technique, in conjunction with the observation of the first appearance of the plasma emission at the same position and time of the plasma front arrival. The result shows that the plasma front moves at the Sedov speed, which is typical of shock wave propagation, yielding an excellent emission spectrum for the harder sample. The shock front speed is further found to decrease in the case of a softer sample, resulting in lesser spectroscopic performance, as demonstrated by the emission spectra measured from mochi samples of different hardnesses. The result of this study is promising for paving the way to extending the laser-induced breakdown spectroscopy application to the much needed spectrochemical analysis of agricultural and food products.

An experimental study is conducted on the possibility and viability of performing hardness measurement of the various stone and chert samples in low pressure (600 Pa) CO2 ambient gas, a condition that is encountered in the Mars atmosphere. For this study, a nanosecond Nd-YAG laser is employed to generate plasma emission from the samples with different degrees of hardness. This technique is developed in light of the role of the shock wave in the generation of a laser-induced plasma. It was previously shown that the speed of the shock front depends on the hardness of the sample, and a positive relationship was found between the speed of the shock front and the ionization rate of the ablated atoms. Hence, the ratio of the intensity between the Mg II 279.5 nm and Mg I 285.2 nm emission lines detected from the laser-induced plasma can be used to estimate the hardness of a material. In fact, it is shown that the ratio changes linearly with respect to changes of sample hardness. The result has thus demonstrated ...

We have conducted an experimental study exploring the possible application of laser-induced breakdown spectroscopy (LIBS) for practical and highly sensitive detection of metal impurities in water. The spectrochemical measurements were carried out by means of a 355 nm Nd-YAG laser within N2 and He gas at atmospheric pressures as high as 2 kPa. The aqueous samples were prepared as thin films deposited on indium-tin oxide (ITO) glass by an electrolysis process. The resulting emission spectra suggest that concentrations at parts per billion levels may be achieved for a variety of metal impurities, and it is hence potentially feasible for rapid inspection of water quality in the semiconductor and pharmaceutical industries, as well as for cooling water inspection for possible leakage of radioactivity in nuclear power plants. In view of its relative simplicity, this LIBS equipment offers a practical and less costly alternative to the standard use of inductively coupled plasma-mass spectrometry (ICP-MS) for water samples, and its further potential for in situ and mobile applications.

We report in this paper the results of an experimental study on the spectral and dynamical characteristics of plasma emission induced by 1 mJ picoseconds (ps) Nd-YAG laser using spatially resolved imaging and time resolved measurement of the emission intensities of copper sample. This study has provided the experimental evidence concerning the dynamical characteristics of the excitation mechanisms in various stages of the plasma formation, which largely consolidate the basic scenarios of excitation processes commonly accepted so far. However, it is also clearly shown that the duration of the shock wave excitation process induced by ps laser pulses is much shorter than those observed in laser induced breakdown spectroscopy employing nanosecond laser at higher output energy. This allows the detection of atomic emission due exclusively to He assisted excitation in low pressure He plasma by proper gating of the detection time. Furthermore, the triplet excited state associated with He I 587.6 nm is shown to be the one most likely involved in the process responsible for the excellent spectral quality as evidenced by its application to spectrochemical analysis of a number of samples. The use of very low energy laser pulses also leads to minimal destructive effect marked by the resulted craters of merely about 10 μm diameter and only 10 nm deep. It is especially noteworthy that the excellent emission spectrum of deuterium detected from D-doped titanium sample is free of spectral interference from the undesirable ubiquitous water molecules without a precleaning procedure as applied previously and yielding an impressive detection limit of less than 10 μg/g. Finally, the result of this study also shows a promising application to depth profiling of impurity distribution in the sample investigated.

We report the results of experimental study on CN 388.3 nm and C I 247.8 nm emission characteristics using 40 mJ laser irradiation with He and N2 ambient gases. The results obtained with N2 ambient gas show undesirable interference effect between the native CN emission and the emission of CN molecules arising from the recombination of native C ablated from the sample with the N dissociated from the ambient gas. This problem is overcome by the use of He ambient gas at low pressure of 2 kPa, which also offers the additional advantages of cleaner and stronger emission lines. The result of applying this favorable experimental condition to emission spectrochemical measurement of milk sample having various protein concentrations is shown to yield a close to linear calibration curve with near zero extrapolated intercept. Additionally, a low detection limit of 5 μg/g is found in this experiment, making it potentially applicable for quantitative and sensitive CN analysis. The visibility of laser induced breakdown spectroscopy with low pressure He gas is also demonstrated by the result of its application to spectrochemical analysis of fossil samples. Furthermore, with the use of CO2 ambient gas at 600 Pa mimicking the Mars atmosphere, this technique also shows promising applications to exploration in Mars.

An experimental study was conducted on the spatial distributions of hydrogen emission intensities from low-pressure plasmas generated by laser ablation of zircaloy-4 and black stone targets in nitrogen and helium ambient gases. In addition to confirming the previously observed intensity enhancement effect in ambient helium gas, the hydrogen and helium emission intensities measured along the plasma expansion direction revealed remarkable extended spatial distributions featuring unexpected maxima near the far end of the plasma where the available shock-wave generated thermal excitation energy should have been significantly reduced. This “anomalous” feature necessarily implied the presence of an additional excitation process beside the well known shock-wave excitation process which is responsible for the plasma emission of heavy atoms in low-pressure ambient gas. Further analysis of the data led to a suggested physical mechanism explaining the possible contribution of a helium metastable excited state to the unusual phenomenon observed in this experiment.