Space and time characterization of laser-induced plasmas for applications in chemical analysis and thin film deposition

Après des décennies de développement, l'ablation laser est devenue une technique importante pour un grand nombre d'applications telles que le dépôt de couches minces, la synthèse de nanoparticules, le micro-usinage, l’analyse chimique, etc. Des études expérimentales ainsi que théoriques ont été menées pour comprendre les mécanismes physiques fondamentaux mis en jeu pendant l'ablation et pour déterminer l’effet de la longueur d'onde, de la durée d'impulsion, de la nature de gaz ambiant et du matériau de la cible. La présente thèse décrit et examine l'importance relative des mécanismes physiques qui influencent les caractéristiques des plasmas d’aluminium induits par laser. Le cadre général de cette recherche forme une étude approfondie de l'interaction entre la dynamique de la plume-plasma et l’atmosphère gazeuse dans laquelle elle se développe. Ceci a été réalisé par imagerie résolue temporellement et spatialement de la plume du plasma en termes d'intensité spectrale, de densité électronique et de température d'excitation dans différentes atmosphères de gaz inertes tel que l’Ar et l’He et réactifs tel que le N2 et ce à des pressions s’étendant de 10‾7 Torr (vide) jusqu’à 760 Torr (pression atmosphérique). Nos résultats montrent que l'intensité d'émission de plasma dépend généralement de la nature de gaz et qu’elle est fortement affectée par sa pression. En outre, pour un délai temporel donné par rapport à l'impulsion laser, la densité électronique ainsi que la température augmentent avec la pression de gaz, ce qui peut être attribué au confinement inertiel du plasma. De plus, on observe que la densité électronique est maximale à proximité de la surface de la cible où le laser est focalisé et qu’elle diminue en s’éloignant (axialement et radialement) de cette position. Malgré la variation axiale importante de la température le long du plasma, on trouve que sa variation radiale est négligeable. La densité électronique et la température ont été trouvées maximales lorsque le gaz est de l’argon et minimales pour l’hélium, tandis que les valeurs sont intermédiaires dans le cas de l’azote. Ceci tient surtout aux propriétés physiques et chimiques du gaz telles que la masse des espèces, leur énergie d'excitation et d'ionisation, la conductivité thermique et la réactivité chimique. L'expansion de la plume du plasma a été étudiée par imagerie résolue spatio-temporellement. Les résultats montrent que la nature de gaz n’affecte pas la dynamique de la plume pour des pressions inférieures à 20 Torr et pour un délai temporel inférieur à 200 ns. Cependant, pour des pressions supérieures à 20 Torr, l'effet de la nature du gaz devient important et la plume la plus courte est obtenue lorsque la masse des espèces du gaz est élevée et lorsque sa conductivité thermique est relativement faible. Ces résultats sont confirmés par la mesure de temps de vol de l’ion Al+ émettant à 281,6 nm. D’autre part, on trouve que la vitesse de propagation des ions d’aluminium est bien définie juste après l’ablation et près de la surface de la cible. Toutefois, pour un délai temporel important, les ions, en traversant la plume, se thermalisent grâce aux collisions avec les espèces du plasma et du gaz.

Ablation laser femtoseconde de verres métalliques de Cu_x Zr_(1−x) : une étude par dynamique moléculaire

L’ablation laser de verres métalliques de CuxZr1−x (x = 0.33, 0.50 et 0.67) et d’un alliage métallique cristallin de CuZr2 dans la structure C11b a été étudiée par dynamique moléculaire (DM) combinée à un modèle à deux températures (TTM). Le seuil d’ablation (Fth) a été déterminé pour chacun des 4 échantillons et s'est avéré plus bas pour les échantillons plus riches en Cu étant donné que la cohésion du Cu est plus faible que celle du Zr dans tous les échantillons. Pour x=0.33, Fth est plus bas pour le cristal que pour l’amorphe car le couplage électron-phonon est plus faible dans ce dernier, ce qui implique que l’énergie est transférée plus lentement du système électronique vers le système ionique pour le a-CuZr2 que le c-CuZr2. La vitesse de l’onde de pression créée par l’impact du laser croît avec la fluence dans l’échantillon cristallin, contrairement aux échantillons amorphes dans lesquels sa vitesse moyenne est relativement constante avec la fluence. Ceci est expliqué par le fait que le module de cisaillement croît avec la pression pour le cristal, ce qui n’est pas le cas pour les verres métalliques étudiés. Finalement, la zone affectée par la chaleur (HAZ) a été étudiée via la profondeur de fusion et les déformations plastiques. La plus faible température de fusion des échantillons amorphes implique que la profondeur de fusion est plus importante dans ceux-ci que dans l’échantillon cristallin. Dans les verres métalliques, les déformations plastiques ont été identifiées sous forme de zones de transformation par cisaillement (STZ) qui diffusent et fusionnent à plus haute fluence. Aucune déformation plastique importante n’a été identifiée dans le c-CuZr2 mis à part de légères déformations près du front de fusion causées par les contraintes résiduelles. Ce travail a ainsi permis d’améliorer notre compréhension de l’ablation laser sur les verres métalliques et de l’étendue des dommages qu’elle peut entraîner.

Characterization and Imaging Diagnostics of Laser Induced Plasma from Solid Targets

Laser induced plasma (LIP) emissions from some metal oxide targets were studied with corresponding metal targets of pure quality as a reference. Atomic emissions in the visible region were used in the spectroscopic procedures of LIP characterization. The studies were meant to throw light into LIP dynamics and they provided many experimental results which improved the general awareness of plasma state.When target materials were photo-ablated with an energetically suitable laser pulse, they developed electric charges in them.An electrical signal which was delivered from the target served as an alternative probe signal for the diagnostics of LIP and to track different charged states in the plasma. The signal showed a double peak distribution with positive polarity and a modified time of flight with various voltage levels of a given polarity.The expansion dynamics of LIP in magnetic field were also investigated by monitoring the voltage transients generated at the target.

Prompt electron emission and collisional ionization of ambient gas during pulsed laser ablation of silver

A silver target kept under partial vacuum conditions was irradiated with focused nanosecond pulses at 1:06 mm from a Nd:YAG laser. The electron emission monitored with a Langmuir probe shows a clear twin-peak distribution. The first peak which is very sharp has only a small delay and it indicates prompt electron emission with energy as much as 60 5 eV. Also the prompt electron emission shows a temporal profile with a width that is same as that for the laser pulse whereas the second peak is broader, covers several microseconds, and represents the low-energy electrons (2 0:5 eV) associated with the laser-induced silver plasma as revealed by time-of-flight measurements. It has been found that prompt electrons ejected from the target collisionally excite and ionize ambient gas molecules. Clearly resolved rotational structure is observed in the emission spectra of ambient nitrogen molecules. Combined with time-resolved spectroscopy, the prompt electrons can be used as excitation sources for various collisional excitation–relaxation experiments. The electron density corresponding to the first peak is estimated to be of the order of 1017 cm?--3 and it is found that the density increases as a function of distance away from the target. Dependence of probe current on laser intensity shows plasma shielding at high laser intensities.

Twin peak distribution of electron emission profile and impact ionization of ambient molecules during laser ablation of silver target

Laser-induced plasma generated from a silver target under partial vacuum conditions using the fundamental output of nanosecond duration from a pulsed Nd:yttrium aluminum garnet laser is studied using a Langmuir probe. The time of flight measurements show a clear twin peak distribution in the temporal profile of electron emission. The first peak has almost the same duration as the laser pulse while the second lasts for several microseconds. The prompt electrons are energetic enough ('60 eV) to ionize the ambient gas molecules or atoms. The use of prompt electron pulses as sources for electron impact excitation is demonstrated by taking nitrogen, carbon dioxide, and argon as ambient gases.

Time evolution of the electron density and temperature in laser-produced plasmas from YBa2Cu3O7

Laser radiation at 1.06 µm from a pulsed Nd:YAG laser was focused onto a multielement YBa2Cu3O7 target in vacuum and the plasma thus generated was studied using time-resolved spectroscopic techniques. Line broadening of the Ba I emission line at 553.5 nm was monitored as a function of time elapsed after the incidence of a laser pulse on the target. Measured line profiles of barium species were used to infer the electron density and temperature, and the time evolution of these important plasma parameters has been worked out.

Time resolved study of CN band emission from plasma generated by laser irradiation of graphite

Time and space resolved studies of emission from CN molecules have been carried out in the plasma produced from graphite target by 1.06 urn pulses from a Q-switched Nd:YAG laser. Depending on the laser pulse energy, time of observation and position of the sampled volume of the plasma, the features of the emission spectrum are found to change drastically. The vibrational temperature and population distribution in the different vibrational levels have been studied as functions of distance, time, laser energy and ambient gas pressure. Evidence for nonlinear effects of the plasma medium such as self focusing which exhibits threshold-like behaviour are also obtained. Temperature and electron density of the plasma have been evaluated using the relative line intensities of successive ionization stages of carbon atom. These electron density measurements are verified by using Stark broadening method.

Electron density and temperature measurements in a laser produced carbon plasma

Plasma generated by fundamental radiation from a Nd:YAG laser focused onto a graphite target is studied spectroscopically. Measured line profiles of several ionic species were used to infer electron temperature and density at several sections located in front of the target surface. Line intensities of successive ionization states of carbon were used for electron temperature calculations. Stark broadened profiles of singly ionized species have been utilized for electron density measurements. Electron density as well as electron temperature were studied as functions of laser irradiance and time elapsed after the incidence of laser pulse. The validity of the assumption of local thermodynamic equilibrium is discussed in light of the results obtained.

Investigations on nanosecond laser produced plasma in air from the multi-component material YBa2Cu3O7

The laser produced plasma from the multi-component target YBa2CU3O7 was analyzed using Michelson interferometry and time resolved emission spectroscopy. The interaction of 10 ns pulses of 1.06 mum radiation from a Q-switched Nd:YAG laser at laser power densities ranging from 0.55 GW cm-2 to 1.5 GW cm-2 has been studied. Time resolved spectral measurements of the plasma evolution show distinct features at different points in its temporal history. For a time duration of less than 55 ns after the laser pulse (for a typical laser power density of 0.8 GW cm-2, the emission spectrum is dominated by black-body radiation. During cooling after 55 ns the spectral emission consists mainly of neutral and ionic species. Line averaged electron densities were deduced from interferometric line intensity measurements at various laser power densities. Plasma electron densities are of the order of 1017 cm-3 and the plasma temperature at the core region is about 1 eV. The measurement of plasma emission line intensities of various ions inside the plasma gave evidence of multiphoton ionization of the elements constituting the target at low laser power densities. At higher laser power densities the ionization mechanism is collision dominated. For elements such as nitrogen present outside the target, ionization is due to collisions only.

Spatial and time resolved analysis of CN bands in the laser induced plasma from graphite

Analysis of the emission bands of the CN molecules in the plasma generated from a graphite target irradiated with 1-06/~m radiation pulses from a Q-switched Nd:YAG laser has been done. Depending on the position of the sampled volume of the plasma plume, the intensity distribution in the emission spectra is found to change drastically. The vibrational temperature and population distribution in the different vibrational levels have been studied as function of distance from the target for different time delays with respect to the incidence of the laser pulse. The translational temperature calculated from time of flight is found to be higher than the observed vibrational temperature for CN molecules and the reason for this is explained.

Anomalous profile of a self-reversed resonance line from Ba+ in a laser produced plasma from YBa2Cu307

A laser produced plasma from the multielement solid target YBa2Cu3O7 is generated using 1.06 μm, 9 ns pulses from a Q-switched Nd:YAG laser in air at atmospheric pressure. A time resolved analysis of the profile of the 4554.03 Å resonance line emission from Ba II at various laser power densities has been carried out. It has been found that the line has a profile which is strongly self-reversed. It is also observed that at laser power densities equal to or exceeding 1.6×1011 W cm−2, a third peak begins to develop at the centre of the self-reversed profile and this has been interpreted as due to the anisotropic resonance scattering (fluorescence). The number densities of singly ionized barium ions evaluated from the width of the resonance line as a function of time delay with respect to the beginning of the laser pulse give typical values of the order of 1019 cm−3. The higher ion concentrations existing at smaller time delays are seen to decrease rapidly. The Ba II ions in the ground state resonantly absorb the radiation and this absorption is maximum around 120 ns after the laser pulse.

Femtosecond spectroscopy of molecular autoionization and fragmentation

Femtosecond laser pulses are applied to the study of the dynamics and the pathways of multiphoton-induced ionization, autoionization, and fragmentation of Na_2 in molecular-beam experiments. In particular, we report on first results obtained studying electronic autoionization (leading to Na_2{^+} + {e ^-}) and autoionization-induced fragmentation (leading to Na{^+} + Na + {e ^-}) of a bound doubly excited molecular state. The final continuum states are analyzed by photoelectron spectroscopy and by measuring the mass and the released kinetic energy of the corresponding ionic fragments with a time-of-flight arrangement.

Time-resolved studies of neutral and ionized Na_n clusters with femtosecond light pulses

The real-time dynamics of Na_n (n=3-21) cluster multiphoton ionization and fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Three dimensional wave packet motions in the trimer Na_3 ground state X and excited state B have been observed. We report the first study of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na_n^*) with femtosecond laser pulses. The observation of four absorption resonances for the cluster Na_8 with different energy widths and different decay patterns is more difficult to interpret by surface plasmon like resonances than by molecular structure and dynamics. Timeresolved fragmentation of cluster ions Na_n^+ indicates that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

Femtosecond dynamics of molecular and cluster ionization and fragmentation

The real-time dynamics of molecular (Na_2 . Na_3) and cluster Na_n (n=4-2l) multiphoton ionization and -fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Wave packet motion in the dimer Na_2 reveals two independent multiphoton ionization processes while the higher dimensional motion in the trimer Na_3 reflects the chaotic vibrational motion in this floppy system. The first studies of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na^*_n) ) with femtosecond laser pulses give a striking illustration of the transition from "molecule-like" excitations to "surfaceplasma"-like resonances for increasing cluster sizes. Time-resolved fragmentation of cluster ions Na_n^* indicate that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

High laser field effects in multiphoton ionization of Na_2

Femtosecond pump/probe multiphoton ionization experiments on Na_2 molecules are performed. The dependence of the total Na^+_2 ion signal on the delay time and the intensity of the femtosecond laser pulses is studied in detail. It is observed that molecular vibrational wavepacket motion in different electronic states dominates the time dependence of the ion signal. For higher laser intensities the relative contributions from the A ^1 \summe^+_u and the 2 ^1 \produkt__g states change dramatically, indicating the increasing importance of a two-electron versus a one-electron process. For even stronger fields (10 ^12 W/ cm²) a vibrational wavepacket in the electronic ground state X ^1 \summe^+_g is formed and its dynamics is also observed in the transient Na^+_2 signal. Time-dependent quantum calculations are presented. The theoretical results agree well with the experiment.