Laser-Induced Breakdown Spectroscopy

Index

PART I

BASIC PHYSICS AND INSTRUMENTATION

Chapter 1 Fundamentals of Laser Induced Breakdown Spectroscopy

Chapter 2 Atomic Emission Spectroscopy

Chapter 3 Laser Ablation

Chapter 4 Physics of Plasma in Laser-Induced Breakdown Spectroscopy

Chapter 5 Instrumentation for Laser-Induced Breakdown Spectroscopy

Chapter 1

Fundamentals of Laser Induced Breakdown Spectroscopy

S.N. Thakura and J.P. Singhb

aLaser and Spectroscopy Laboratory, Department of Physics, Banaras Hindu University, Varanasi-221005, INDIA

bInstitute for Clean Energy Technology, Mississippi State University Mississippi State, U.S.A

1.

INTRODUCTION

The devastating power of the laser was demonstrated soon after its invention when a focused laser beam produced a bright flash in air similar to the spark produced by lightening discharge between two clouds [1]. Another spectacular effect involved the production of luminous clouds of vaporized material blasted from a metallic surface and often accompanied by a shower of sparks when the laser was focused on a metal surface [2,3]. These laser effects have found many technological applications in the fields of metalworking, plasma production, and semiconductors. When a pulsed laser beam of high intensity is focused, it generates plasma from the material. This phenomenon has opened up applications in many fields of science from thin film deposition to elemental analysis of samples. The possibility of using a high-power, short-duration laser pulse to produce a high temperature, high-density plasma was pointed out by Basov and Krokhin [4] as a means of filling a fusion device by vaporizing a small amount of material. Laser ablation of solids into background gases is now a proven method of cluster-assembly [5,6]. In this method, a solid target is vaporized by a powerful laser pulse to form partially ionized plasma that contains atoms and small molecules. Not much is known about the formation and transport of particles in laser ablation plumes. In recent years there has been notable interest both in an increased understanding of laser induced plasmas (LIP) and in the development of their applications. Emission spectroscopy is used for elemental analysis of targets from which the luminous plasma is generated and it can also be applied to determine the temperature, electron density and atom density in the LIP [7].

The history of laser spark spectroscopy runs parallel to the development of highpower lasers, starting with the early use of a ruby laser for producing sparks in gases [8]. In subsequent years the spectral analysis of LIP became an area of study that has significantly matured at present. The current developments of this technique for chemical analysis can be traced to the work of Radziemski and Cremers [9] and their co-workers at Los Alamos National Laboratory in the 1980s. It was this research group that first coined the acronym LIBS for laser induced breakdown spectroscopy. During the last two decades, LIBS has undergone a dramatic transformation in terms of hardware, software and application areas. It has become a powerful sensor technology for both laboratory and field use. In order to obtain a reliable quantitative elemental analysis of a sample using LIBS, one needs to control several parameters that can strongly affect the measurements. Some of these parameters are the laser wavelength, its irradiance, the morphology of the sample surface, the amount of ablated and vaporized sample, and the ability of the resulting plasma to absorb the optical energy. If these and related parameters are properly optimized, the spectral line intensities will be proportional to the elemental concentration. In the following sections we briefly describe the basic components and the underlying physical processes that are essential to appreciate the range of applications and power of LIBS.

2. LASERS FOR LIBS

The main properties of laser light which distinguish it from conventional light sources are the intensity, directionality, monochromaticity, and coherence. In addition the laser may operate to emit radiation continuously or it may generate radiation in short pulses. Some lasers can generate radiation with the above mentioned properties and that is tunable over a wide range of wavelengths. Generally pulsed lasers are used in the production of plasmas and also in laser induced breakdown spectroscopy (LIBS). We consider only those properties of lasers relevant to plasma production in gaseous, liquid and solid samples so that the role of various types of laser systems used in LIBS experiments is clearly understood in the later chapters of this book. It is possible to generate short-duration laser pulses with wavelengths ranging from the infrared to the ultraviolet, with powers of the order of millions of watts. Several billions to trillions of watts and more have been obtained in a pulse from more sophisticated lasers. Such high-power pulses of laser radiation can vaporize metallic and refractory surfaces in a fraction of a second. It is to be noted that not only the peak power of the laser, but also the ability to deliver the energy to a specific location is of great importance. For LIBS, the power per unit area that can be delivered to the target is more important than the absolute value of the laser power. The power per unit area in the laser beam is termed irradiance and is also called flux or flux density. Conventional light sources with kilowatts powers cannot be focused as well as laser radiation and therefore are not capable of producing effects that lasers can.

The next property of laser radiation that is of interest is the directionality of the beam. Laser radiation is confined to a narrow cone of angles which is of the order of a few tenths of a milliradian for gas lasers to a few milliradians for solid state lasers. Because of the narrow divergence angle of laser radiation, it is easy to collect all the radiation with a simple lens. The narrow beam angle also allows focusing of the laser light to a small spot. Therefore the directionality of the beam is an important factor in the ability of lasers to deliver high irradiance to a target. Coherence of the laser is also related to the narrowness of the beam divergence angle and it is indirectly related to the ability of the laser to produce high irradiance. However, coherence is not of primary concern in LIBS. Provided that a certain number of watts per square centimeter are delivered to a surface, the effect will be much the same whether the radiation is coherent or not. The monochromaticity of the laser as such plays very little role as far as plasma production is concerned because it is the power per unit area on the target that matters irrespective of the fact whether the radiation is monochromatic or covers a broad band. In special cases, one may require highly monochromatic laser radiation to probe the plasma using resonance excitation of atomic species. The frequency spread of gas lasers is of the order of one part in 10¹⁰ or even better and for solid lasers, it is of the order of several megahertz. In specifying the frequency spread, we have taken the width of a single cavity mode of the laser, although most lasers operate in more than one cavity mode so that the total frequency spread may cover the entire line width of the laser transition. The frequency spread of each of the cavity modes is much narrower than the line width of the laser transition and the former is used to characterize the frequency stability of the laser.

2.1. Mode Properties of Lasers

The optical cavity of a laser is determined by the configuration of the two end mirrors. The stationary patterns of the electromagnetic waves formed in the cavity are called modes. For a cavity formed by two confocal spherical mirrors separated by a distance L, the frequency ν of a mode (mnq) is given by

(1)

where c is the velocity of light, q is a large integer, and m and n are small integers. The axial modes correspond to m = n = 0 and involve a standing wave pattern with an integral number q of half wavelengths with q λ/2 = L, between the two mirrors with a node at each mirror. The separation between frequencies of two consecutive axial modes (c/2L) is of the order of gigahertz for typical solid state lasers. The transverse modes of the laser are designated by TEMmn. They affect the focusing properties of the laser beam. The smallest focal spots and highest irradiance is obtained with beams containing the lowest transverse modes with the smallest pair of values m, n. The higher transverse modes have radial intensity distributions which are less and less concentrated along the resonator axis with increasing values of m or n. These modes are also known as off-axis modes and their diffraction losses are much higher than that of the fundamental modes TEM00q. Some of the patterns for transverse modes are shown in Fig. 1.

Fig. 1 Transverse modes showing off-axis intensity distribution in selected higher modes.

The presence of higher transverse modes (large m, n) increases the divergence angle and affects the focusing of the laser beam. If there is no control over the mode properties, the modes present in the laser pulse can change from one shot to the next and different pulses from a high power laser would be focused differently. High brightness is essential for delivering high irradiance. The brightness of a source is the power emitted per unit area per unit solid angle. As laser power increases, the number of transverse modes increases with little increase in brightness. The technology to produce high irradiance in a laser beam thus involves decreasing beam divergence as much as increasing power.

2.2. Spatial Intensity Distribution and Focusing of Laser Beam

In order to determine the irradiance produced by a laser, it is necessary to know the spot size to which the beam can be focused. It is impossible to focus the beam to a geometrical point and the minimum spot size is dependent on diffraction. Since optical systems are not perfect, the actual spot size is larger than the limit set by diffraction. Maximum irradiance is obtained with minimum focal area of the laser spot.

The spatial distribution of the output of a continuous gas laser follows the mode patterns shown in Fig. 1 and for the lowest transverse mode, the intensity distribution is given by

(2)

where w is called the Gaussian radius of the TEM00 mode. The output of a high-power solid state laser has a complicated spatial intensity distribution and does not exhibit the recognizable mode patterns shown in Fig. 1. The output is a superposition of many modes along with distortions caused by inhomogeneities of the crystal. This irregular spatial distribution leads to problems in focusing the laser beam to the minimum size. A schematic spatial profile of a solid laser is shown in Fig. 2.

Fig. 2 Schematic contour of irradiance in unfocused high power ruby laser.

The spatial profile of the laser beam can change during the course of the laser pulse [10]. Many methods have been employed for improvement of the mode properties of high power solid state lasers. One is shown in Fig. 3 where an aperture was introduced at the focus of a lens system contained within the laser cavity. This arrangement can reduce the off-axis mode content significantly, because the high order modes have large diffraction losses at the aperture. The output from a ruby laser can be made more spatially uniform than that shown in Fig. 2 and can have a divergence angle close to the diffraction limit [11].

Fig. 3 Schematic diagram of laser cavity with an aperture to remove higher order transverse modes.

The number of axial modes in a laser output can be reduced with an optical cavity in which one mirror is made up of a number of uncoated interferometric flats. Laser oscillation occurs at those wavelengths which are simultaneously modes of the total cavity and of the individual interferometers formed by each pair of flat parallel surfaces. Since the gain of the laser is nonlinear, the output power is funneled into a single or a few axial modes. In an optical cavity, introduction of a dye mode-selector has been used to produce a single TEM00 axial mode output from a ruby laser [12].

The design and fabrication of a single mode laser oscillator followed by amplifiers has led to diffraction-limited lasers of high brightness [14]. An important concept in the context of lasers is the distinction between near and far field spatial patterns. In the near field, the intensity pattern is the same as at the output mirror of the laser and it follows the mode patterns shown in Fig. 1. If ‘a’ is the aperture diameter of the output mirror and the laser beam is approximated by a Gaussian beam, then the near field pattern persists for a distance of the order of a²/λ where λ is the wavelength of laser light. However for larger distances from the output mirror, the well defined mode pattern in the near field would be washed out by diffraction effects; the spreading angle is of the order of λ/a. Gaussian beams have the same phase across the entire wave front, and they are capable of being focused to the minimum possible size [13].

Ruby lasers with an ordinary optical cavity can be focused with a simple lens to produce spots with diameters of the order of 300 microns whereas those with an apertured optical cavity have focal spot sizes of the order of a few microns.

A focal area of 10−3cm² is typical for a ruby laser focused with a simple lens and the following peak power and irradiance can be obtained by different types of ruby lasers:

2.3. Time Behavior of Laser Pulses

Solid state lasers, such as ruby lasers, Nd: glass and Nd: YAG lasers that produce high powers are generally pulsed with widely different pulse durations and with different methods of pulsing. If the laser is pumped by a flashlamp, pulse widths in the range of 100 to 1000 microseconds are typical. In many cases, the laser emission is not uniform, but consists of many microsecond duration spikes called relaxation oscillations whose amplitudes and spacing are not uniform. The presence of these spikes in the laser pulse causes heating and cooling of the target surface and is not suitable for producing a uniform plasma plume.

Laser pulse durations in the range of 10 to 1000 nanoseconds can be produced by Q-switching techniques, where laser operation is suppressed and population inversion in the solid rod increases greatly over the normal threshold condition [14]. If the Q-switching component in the laser cavity is changed to a transparent condition, the laser rod, now in a highly inverted state, gets coupled to the two mirrors of the cavity and the stored energy is emitted in a pulse of much higher power and much shorter duration than without Q-switching.

It is possible to produce laser pulses of picoseconds duration by the phenomenon of mode locking. If there are N resonant axial modes of the cavity simultaneously present in the linewidth of the lasing transition, then these can be coupled by using a Q-switching dye with nonlinear transparency. This coupling of modes leads to a locking of the phases of different axial modes. In the time domain, a single ultrashort pulse circulates in the cavity with a time period equal to the round trip transit time (2L/c). The laser output is in the form of identical pulses whose spacing is equal to 2L/c. The width τ of each pulse is approximately the inverse of the frequency spread of the laser output. Thus, for N axial modes in the lasing transition linewidth, the pulse duration is given by

(3)

Femtosecond laser pulses are produced by the technique of colliding pulse mode locking (CPM) which utilizes the collision of two counter-propagating pulse trains in a thin saturable dye jet. The interaction of the counter-propagating pulses creates a transient grating of the population of dye molecules, which synchronizes, stabilizes and shortens the pulse. The operation of femtosecond pulses is very sensitive to mirror coatings. The short duration and high electric field intensities encountered in amplifying femtosecond pulses introduce new problems in amplifier design. Improvement in amplification techniques has permitted generation of femtosecond laser pulses of gigawatt intensities [15].

2.4. Measurement of Laser Power and Energy

In order to study the physics of laser induced plasmas, reliable measurements of laser beam power, beam energy, beam divergence angle, and spatial intensity distribution of the beam cross-section are needed.

The most common detectors used in the measurement of laser power are referred to as square law detectors because they respond to the square of the electric field. Photomultiplier tubes (PMTs) and single stage vacuum photoemissive detectors are sensitive in the ultraviolet (UV), visible, and near infrared, whereas photoconductive detectors are used for lasers emitting at wavelengths longer than one micron. For pulsed lasers, the phototube output is displayed on a fast oscilloscope to determine the pulse shape. The response speed of the photodetector must be fast and circuitry must be carefully designed to preserve the pulse shape. Intense laser output tends to saturate the output of the detectors, so absorbing filters are used to keep the detector in the linear portion of their operating range and to make them blind to background radiation.

Another widely used detector is the semiconductor photodiode which is a photovoltaic device. Laser radiation incident on the detector produces a voltage across the p-n junction even in the absence of an external bias. When light falls on a back-biased diode, the reverse current increases sharply. Room temperature devices are used in the visible region and up to 3.6 microns whereas liquid nitrogen-cooled devices operate up to 5.7 microns.

The total energy in a laser pulse is measured by calorimetric methods using blackbody absorbers of low thermal mass in contact with thermocouples or other temperature measuring devices. In one common form, the absorber is a small hollow cone of carbon such that radiation entering the base of the cone cannot be reflected out of the cone. Thermistor beads, forming an element of a balanced bridge circuit, are placed intimately in contact with the cone. As the cone is heated by a pulse of energy, the resistance of the thermistors changes, resulting in an imbalance of the bridge and a voltage pulse which decays as the cone cools to ambient temperature. The magnitude of the voltage pulse gives a measure of the energy in the laser pulse.

2.5. Varieties of Lasers

A laser is not one single device, but there are a wide variety of different lasers with many different characteristics. Each type has its own properties of wavelength and operating parameters. Even within one type, there are many varieties of construction. Now several thousands laser lines are known which span a whole spectral range from extreme ultraviolet to the far-infrared region. Developments in LIBS have taken place by using the laser wavelengths provided by existing technology. In 1962 a ruby laser at 694 nm was used by Breach and Cross [16], but its pulse-to-pulse stability was very poor and LIBS was not considered to be a very reliable technique for spectrochemical analysis. The next phase of LIBS development was marked by the sophisticated pulsed-laser technology of the 1980s which led to very reliable Nd: YAG lasers in the near-IR, visible, and UV regions and to excimer lasers in the UV region. At present many more laser wavelengths have become available to study their effects on LIBS measurements [17–19]. Lasers commonly employed in LIBS are listed in Table 1 along with properties associated with these lasers. These are representative values, not necessarily the highest or the best ever achieved.

Table 1. Characteristic properties of some lasers for LIBS[ 20 ]

3.

LASER INDUCED PLASMAS

To produce a spark in air or a gas requires laser intensities of the order of 10¹¹ W cm−2. Sparks are caused by the breakdown of the gas due to the electric field associated with the light wave. Breakdown thresholds are of the order of 10⁶ to 10⁷ V cm−1. The spark is accompanied by production of charged particles, absorption of laser light, and re-radiation of light from the spark. If the temperature of the plasma at the position of the gas breakdown becomes high enough, X-ray emission is also observed, in addition of visible and UV radiation. This phenomenon was termed laser induced breakdown in analogy with the electrical breakdown of gases [21]. The breakdown results from strong ionization and absorption by gases that are usually transparent to light. The breakdown is marked by a threshold irradiance below which virtually no effects are observed. The onset of the breakdown is a sudden, dramatic phenomenon occurring at an easily determined threshold. Its spatial as well as temporal profiles make interesting study [22].

The breakdown in the focal volume of the lens in which the peak laser irradiance occurs can be understood as occurring in two steps. First, the production of the initial ionization and the subsequent cascade by which the ionization grows resulting in the breakdown. Multiphoton ionization, where simultaneous absorption of many quanta by an atom produces an ion-electron pair, is considered to be a plausible mechanism for the initial ionization. An alternative possibility is multiphoton excitation of an atom to an excited state with many other excited states between it and the free electron continuum. Single photon absorption processes may rapidly ionize the atom from this excited level. A free electron in the focal volume absorbs photons and gains enough energy to ionize additional atoms by collisions. In each such ionization process, the colliding electron is replaced by two electrons with lower energy in the free electron continuum. These in turn absorb photons so that an avalanche or cascade of ionization will occur. The absorption of a photon by an electron may be visualized in two equivalent ways. (1) It can be considered as an inverse Bremsstrahlung process in which a single light quantum is absorbed by an electron in the field of an atom or ion. (2) Secondly it can be considered as analogous to microwave-generated breakdown, in which the electron oscillates in the electric field of the incident radiation.

3.1. Laser Induced Breakdown in Gases

One of the most striking observations is the extinction of laser light by a plasma plume produced by breakdown in gases. When the laser irradiance is less than the threshold, no significant attenuation is observed, but with laser irradiance exceeding the threshold, the absorption is so strong that it is often used as a critical test of whether breakdown has actually occurred. Fig. 4 shows the shape of the original laser pulse and the pulse transmitted through the plasma when breakdown occurs. It is evident that early in the transmitted profile, there is little attenuation, but at later times, after breakdown occurs, the plasma becomes very opaque. The abrupt shutoff of the transmitted light occurs simultaneously with initiation of the spark. When light transmission is studied for a series of laser pulses with increasing energy, breakdown occurs earlier in the pulse as laser irradiance increases. The time to breakdown as a function of intensity depends on the focal area [23]. For a small focal volume, higher laser intensity is required to produce breakdown within the same time.

Fig. 4 Schematic temporal profile of laser pulse in the absence and in presence of gas breakdown showing attenuation of laser beam.

Although the laser induced blue-white spark appears spatially uniform to the naked eye, it is indeed elongated along the direction of the incoming laser beam. For laser powers of the order of 100 MW, the spark may be 1 cm long and a few millimeters in diameter. A schematic shape of the spark is shown in Fig. 5 where its expansion back toward the laser essentially fills the converging cone of laser radiation. The growth of the spark in the direction opposite to the light flux has led to the model of a radiation-supported detonation wave. A detonation wave is a shock wave which is fed by release of energy behind the shock wavefront. In this case the energy is supplied by the absorption of the incoming laser beam. This is analogous to the detonation of reacting gases, with the reaction energy of the gases replaced by the absorbed laser energy. A shock wave propagates from the focal region into the undisturbed gas and absorption of energy from the laser beam drives the shock wave, causing it to spread. The motion of the luminous front has been measured as a function of time and two time regions have been identified. The plasma front has been found to move faster before the end of the laser pulse but its expansion is slowed down after the end of the pulse. This is schematically shown in Fig. 6.

Fig. 5 Schematic shape of laser-produced spark in air. The intense core is indicated by the white contour. Arrows indicate the propagation of the focused laser beam.

Fig. 6 Relative displacement of expanding luminous front as a function of time.

Spectroscopic investigations of laser induced spark in air show that its emission consists of spectral lines of N and O atoms as well as a strong continuum [24]. It has been found that in the early part of the development of the spark, the continuum is the dominant component of emission in addition to broad lines of ions and neutral atoms. When the spark has expanded and cooled, less broadened lines from neutral atoms are observed.

3.2. Plasma Production from Solid Targets

When a high-power laser beam strikes a solid surface, it produces a plasma plume due to rapid melting and/or vaporization of the sample surface. The vaporization of a tungsten surface by a Nd:glass laser pulse was found to be accompanied by a shower of sparks characteristic of molten material expelled along with vaporization, whereas a plume of glowing material was emitted by a pulse from a ruby laser beam on a carbon target [25]. The plasma is produced by vaporization of the opaque target surface and subsequent absorption of laser light in this vaporized material. The phenomena observed in this interaction are in many ways similar to the phenomena accompanying gas breakdown, but the initial density of the material is much lower in the latter case. Plasma production studies are carried out at laser irradiances of the order of 10⁹ W/cm² or greater which produce a denser, more absorbing blow-off material. There is a great difference in the behavior of surfaces struck by laser pulses with millisecond duration as compared to those with pulse durations in the nanosecond region. The short pulses of very high power do not produce much vaporization, but instead remove only a small amount of material from the surface, whereas longer, low-power pulses produce deep, narrow holes in the target. For laser pulses of picosecond (ps) and femtosecond (fs) duration there is no reheating of the plasma due to absorption of laser radiation as in the case of nanosecond (ns) laser pulses (see Fig. 4). Thus the volume of plasma produced in the cases of ps and fs laser pulses is much smaller than in the case of ns laser pulses. The plasma plume produced by ns laser pulses gets elongated towards the incident laser beam as a result of reheating as shown in Fig. 5.

The interaction of the laser with a target surface is considerably modified by the presence of material emitted from the surface by ns pulsed high power laser irradiation [26]. It exerts a high pressure on the surface and changes the vaporization characteristics of the surface. Since the laser flux density is very high, the ejected material can be heated further by absorption of incoming laser radiation. It becomes thermally ionized and opaque to the incident radiation. The absorbing plasma prevents light from reaching the target surface, which is effectively cut off from the incoming radiation for a large fraction of the laser pulse. At the end of the laser pulse, the blow off material becomes so hot that it begins to radiate thermally and some of this radiation may reach the surface, causing further vaporization. The temporal evolution of the depth vaporized by the high-power laser pulse is schematically shown in Fig. 7.

Fig. 7 Schematic representation of depth vaporized in a metal target as function of time showing effect of shielding by the blow-off material.

The processes involved in vaporization by a ns laser can be understood in terms of a simple model [27]. It takes into account the pressure produced by a small amount of the blow-off material early in the laser pulse. This recoil pressure raises the boiling point of the target above its usual vaporization temperature. If the increase in vaporization temperature is sufficiently high, the surface will be prevented from vaporizing further and the material will continue to heat to a high temperature (above the normal vaporization temperature) as more and more laser light from the pulse is absorbed by the target surface. Eventually, the target surface will reach the critical point and at that point vaporization can occur. This model has been used to estimate the maximum depth at which the critical temperature is exceeded. At depths greater than this, removal of the material which is heated above the critical point will continue to exert a sufficiently high pressure so that no vaporization will occur. The heat will eventually be conducted into the interior of the target. This model does not take into account the shielding of the target surface from the incoming laser light as the blow-off material becomes hot, ionized and