Tesi sul tema "Laser ablation in liquid medium"

Les nanoparticules (NPs) de métaux nobles sont le siège d’un phénomène de résonance plasmon de surface résultant de l’oscillation collective de leurs électrons de conduction sous l’effet d’une onde électromagnétique. Dans le cas de NPs d’or et l’argent, la fréquence de résonance est située dans visible ce qui confère à ces NPs plasmoniques des propriétés optiques uniques. En particulier, la position et l’intensité de la bande de résonance plasmon peuvent varier en fonction de leur taille, leur forme (rapport d'aspect) et de l'indice du milieu hôte. Les possibilités d’applications nécessitent des échantillons purs et de distribution mono disperse. La synthèse des NPs par voie chimique permet de contrôler dans une certaine mesure la forme et la taille des NPs. Elle nécessite cependant l’utilisation d’agents stabilisants qui mènent à une contamination de surface par les résidus de synthèse. Pour limiter cet inconvénient, la technique physique d’ablation laser en milieu liquide est une alternative prometteuse qui souffre cependant d’un manque de contrôle de la forme et de la taille des NPs produites. La forme et la taille des NPs élaborées par ablation laser en milieu liquide (ALML) sont étroitement liées aux trois étapes essentielles du processus : Interaction cible/laser ; Transport de masse ; Interaction laser/NPs en suspension dans le liquide. Afin d’appréhender les mécanismes régissant chacune de ces étapes, il est nécessaire de les étudier séparément. Dans ce travail, nous nous sommes focalisés sur les mécanismes d’interaction entre le faisceau laser et les NPs en suspension dans le liquide. Suivant la densité d’énergie absorbée par les NPs en suspension, celles-ci subissent la fragmentation ou le remodelage. Par la suite nous avons étudié les mécanismes à l’origine du phénomène de la fragmentation. L’évolution de la distribution de forme des NPs lors de la fragmentation des NPs a été étudiée en développant une technique originale et quantitative de spectroscopie optique in-situ. De même, l’évolution de la fraction volumique des NPs au cours de leur élaboration par ALML par spectroscopie optique in-situ est obtenue et analysée. En parallèle aux travaux expérimentaux, nous avons développé des modèles théoriques pour la compréhension des mécanismes de formation des nanoparticules métalliques par ablation laser en un milieu liquide. Une autre étude approfondie sur la modélisation des propriétés optiques et thermiques de l'interaction Laser-Nanoparticules est discutée dans cette thèse. Un modèle thermique de Takami modifié nommé MTM (Modified Takami Model) a été également introduit. Son utilité importante a été démontrée pour l’interprétation des mécanismes de l’interaction laser-NPs
Noble metal nanoparticles (NPs) are the site of a surface plasmon resonance phenomenon resulting from the collective oscillation of their conduction electrons under the effect of an electromagnetic wave. In the case of gold and silver NPs, the resonant frequency is in the visible range, which gives these plasmonic NPs unique optical properties. In particular, the position and intensity of the plasmon resonance depend on their size, shape (aspect ratio) and the index of the host medium. The possible applications require pure samples and mono-dispersed distribution. The chemical synthesis of NPs allows the shape and size of NPs to be controlled. However, it requires the use of stabilizing agents, which lead to surface contamination by synthetic residues. To limit this disadvantage, the physical technique of laser ablation in a liquid medium is a promising alternative, which, however, suffers from a lack of control over the shape and size of the NPs produced. The shape and size of NPs produced by liquid laser ablation (ALML) are closely related to the three essential steps of the process: Target / laser interaction; Mass transport; Laser / NPs interaction suspended in the liquid. In order to understand the mechanisms governing each of these stages, it is necessary to study them separately. In this work, we focused on the mechanisms of interaction between the laser beam and the NPs suspended in the liquid. Depending on the energy density absorbed by the suspended NPs, they undergo fragmentation or remodeling. We then studied the mechanisms behind the phenomenon of fragmentation. The evolution of the shape distribution of NPs during NP fragmentation was studied by developing an original and quantitative technique of in-situ optical spectroscopy. And, the evolution of the volume fraction of NPs during their preparation by ALML by in-situ optical spectroscopy is obtained and analyzed. In parallel with the experimental work, we have developed theoretical models for understanding the mechanisms of formation of metallic nanoparticles by laser ablation in a liquid medium. A modest study on the modeling of optical and thermal properties of the Laser-Nanoparticle interaction is discussed in this thesis. A modified Takami thermal model named MTM was also presented. Its important utility has been demonstrated for mechanisms for the interpretation of the mechanisms of laser-NPs interaction

Particles in the nanometer size range have attracted increasing attention with the growing interest in nanoscience and nanotechnology. They hold potential as basic components for sub-wavelength optical devices, for surface-enhanced spectroscopy, for biological labelling and sensing, and for cancer therapy. For such applications, it is crucial to prepare metal nanoparticles with desired shape, and size distribution. In this context, Pulsed Laser Ablation in Liquids (PLAL) has become a key method for synthesis of nanoparticles with controlled geometry and size.

The picosecond Nd:YAG laser at wavelengths of 1064 nm was used to produced the silicon-based nanoparticles in de-ionized water. The main goal of our work presented here was enlight the role of thermal effects on the process of laser ablation of solid target in liquid. To accieve this goal the additional heating of the target surface by continuous laser was applied during the experiment. The shift of nanoparticles size distribution caused by applying of additional continuous laser was reported in this work. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/34927

Lorsqu'une impulsion laser est focalisée sur une cible solide immergée dans un liquide, de la matière est vaporisée. La nucléation et la croissance ont lieu dans le liquide et des nanoparticules sont ainsi synthétisées. La méthode est très polyvalente puisqu'une grande variété de matériaux peut être générée. De plus, les nanoparticules sont directement stabilisées dans le solvant. L'ajout d'agent complexant n'est pas nécessaire mais peut tout de même permettre de mieux contrôler la taille des nanoparticules. Cependant, de nombreux processus sont mis en jeu durant la synthèse et l'objectif de ce travail doctoral est de développer la compréhension de ces éléments. Dans la mesure où l'ablation laser déploie une multitude d'´échelle de temps, il a fallu employer différentes méthodes pour élucider ces mécanismes. Pour commencer, je définirai un état de l'art de l'utilisation de l'ablation laser en milieu liquide et nos résultats concernant la synthèse d'aluminium oxyde dopé chrome. Par la suite, je présenterai la spectroscopie des plasmas et les questions sous-jacentes à la notion d'´équilibre dans un plasma moléculaire. Ensuite, je décrirai notre approche atomistique de la nucléation basée sur les techniques de chimie quantique. Enfin, je montrerai l'apport de l'utilisation des méthodes d'ombrographie pour mieux comprendre la thermodynamique du système au temps plus long. Notre étude démontre que la bulle formée suite à l'ablation laser est constituée essentiellement de molécule du solvant dont la quantité n'évolue quasiment pas au cours du temps de vie de la bulle
When a pulsed-laser is focused into a solid target immersed in water, the material is evaporated. Nucleation and growth occur in the liquid and nanoparticles are synthesized. The method can be considered as versatile because one can try to synthesize any kinds of materials. Also, the nanoparticles are directly stabilized by the solvant so there is no need of complexing agents. The nanoparticles are described as ligand-free. However, various processes can occur during the synthesis and the aim of my work is to understand these different components. Since the laser ablation in liquid displays a wide range of timescales, we used numerous methods to address this problem. First, I will present the use of plasma spectroscopy and the questions it raises towards local thermodynamic equilibrium. Then, I will describe our microscopic approach of nucleation based on quantum chemistry techniques. Finally, I will illustrate the advantages of shadowgraphic measurements to reach an hydrodynamic understanding of the system

The exponential spread of high level technology in the last decade has been followed by an increasing request for new materials able to fulfill all required characteristics for the construction of smaller devices. In this view, nanostructures and in particular metal nanoparticles are gaining attention since their unique optical, electrical and antibacterial properties. Pulsed Laser Ablation in Liquid represents a consolidated route for the synthesis of pure surface metal nanoclusters but, till now, the low production yield of this technique has stopped every attempt in this direction. For these reasons, the development of new strategies to enhance the amount of ablated material represents an interesting field of research. In particular, it has been studied how the ablation of a metal wire in a water flow chamber can lead to an increase of the productivity with respect to bulk ablation and a strong dependence of efficiency on the wire thickness and laser parameters has been noted. A model to describe this behaviour has been proposed, with considerations about heat loss phenomena, reflectivity of the wire surface and cavitation bubble mechanism. Laser fabricated nanoparticles have been also used for the preparation of different nanocomposites in order to tune their properties. Spontaneous and induced aggregation phenomena of noble metal nanoparticles have been studied, with regard to their influence on the Surface Plasmon Resonance variations. It is also possible to combine single metal colloidal solution for obtaining mixed metal nanoparticles with unique features. For this reason, Au/Ni mixed systems have been produced by laser mixing in liquid environment and characterized by spectroscopic and morphological techniques. The mechanism of their formation has been explained on the base of the laser irradiation environment conditions.

Zinc oxide (ZnO) is a wide band-gap semiconductor material (Eg=3.37 eV) characterized by many promising properties which make it appealing for several technological applications. One of the most attractive features is its high exciton binding energy (60 meV) which allows the observation of the UV excitonic emission at room temperature and favors the excitation of defect-related emission bands in the visible spectral region. In recent years, there has been an increasing interest in ZnO nanostructures due to their variety of morphologies and availability of simple and low cost processing methods. Among the techniques currently available, pulsed laser ablation in liquid (PLAL) offers a simple and versatile route to synthesize nanoparticles (NPs) of extremely high purity. In this Thesis we have reported an experimental study on ZnO NPs produced by PLAL providing a complete characterization of their morphological, structural and optical properties, as well as a deep insight on the formation processes involved during the NPs synthesis. Our investigation is founded on the combined use of several experimental techniques including in situ optical absorption (OA) and photoluminescence (PL), and ex situ force microscopy (AFM), high resolution TEM (HRTEM), Raman and time resolved. Microscopic analysis has evidenced that ns PLAL of zinc target in water produces ZnO nanocrystals with an average size of tens of nm having a wurtzite structure. Their UV-Vis absorption curve exhibits the typical edge of wurtzite ZnO and time resolved PL spectra show the corresponding excitonic PL peaked at 3.32 eV with a single exponential lifetime of 800 ps. ZnO NPs display a further PL peaking at 2.2 eV related to defects, which decays following a power law consistent with a recombination mechanisms where trapped electrons tunnel to recombination centers. Thermal annealing in O2 and in a He atmosphere produces a reduction of the A1(LO) Raman mode at 565 cm-1 associated with oxygen vacancies, accompanied by a decrease of defect-related emission at 2.2 eV. Based on our experimental results the emission at 2.2 eV is proposed to originate from a photo-generated hole in the valence band recombining with an electron deeply trapped in a singly ionized oxygen vacancy. In situ analysis has clarified the oxidation process of the ablated Zn, which occurs out of the plume region, due to the reaction of Zn NPs with water molecules. OA spectra exhibit a peak at 5 eV coming from surface plasmonic resonance (SPR) of Zn NPs and the typical absorption edge of the wurtzite ZnO, thus revealing transient Zn/ZnO core-shell NPs, which are fully oxidized only several hundreds of seconds after the end of PLAL. Defect-related PL arises with afurther delay time (100 s) indicating that the earliest oxidation of Zn essentially produces defect-free ZnO. We have also investigated the effects of laser parameters and of the solvent on the oxidation kinetics. The intensity ofthe SPR peak at 5 eV evidences that the Zn/ZnO ratio at the end of PLAL decreases on decreasing the laser repetition rates. Moreover, the oxidation rate of Zn NPs decreases on varying the mixture of water andethanol from 0 to 100%. These findings can be explained considering that initially produced Zn NPs are oxidized in two phases. An earliest and superficial oxidation, and a later and slower oxidation which is sensitive to the repetition rate, and it is completed only after the end of ablation thus leading to the disappearance of the metal species. Overall, our findings enrich the knowledge on the PL origin and dynamics of ZnO NPs useful in view of their use in new applications which exploit the enhancement of surface to volume ratio favoring the formation of luminescent defects as well as increase the material reactivity with the surrounding environment.

De nombreux domaines, tels que le biomédical, la micro-fluidique ou l'optique quantique, sont demandeurs de nanoparticules présentant des propriétés optiques spécifiques. L'ablation laser en liquide, PLAL (Pulsed Laser Ablation induced in Liquid) est une méthode de synthèse permettant d'élaborer rapidement des nanoparticules dans une large gamme de matériaux, et donc de tester la conservation ou la modification des propriétés optiques originales identifiées dans certains matériaux lorsque l'on passe aux tailles nanométriques (scintillation, thermoluminescence, photo-stimulation, haut rendement de luminescence...). Dans ce travail de thèse la synthèse, la caractérisation optique et structurale de nanoparticules dopées a été développé. Différents types de matériaux ont été testés dont l'oxyde de gadolinium dopé, l'yttrium aluminium garnet (YAG), l'alumine etc. Cela a permis de montrer la faisabilité et la potentialité de cette technique d'élaboration sur différents matériaux. Par ailleurs un outil de diagnostic du plasma par spectroscopie optique résolue en temps a été mis en place afin de comprendre les processus des croissances des particules formées.

The vectorial nature (polarization) of light plays a significant role in light-matter interaction that leads to a variety of optical devices. The polarization property of light has been exploited in imaging, metrology, data storage, optical communication and also extended to biological studies. Most of the past studies fully explored and dealt with the conventional polarization state of light that has spatially symmetric electrical field geometry such as linear and circular polarization. Recently, researchers have been attracted to light whose electric field vector varies in space, the so-called optical vector vortex beam (VVB). Such light is expected to further enhance and improve the efficiency of optical systems. For instance, a radially polarized light under focusing condition is capable of a tighter focus more than the general optical beams with a uniform polarization structure, which improves the resolution of the imaging system [1]. Interaction of ultrafast laser pulses with matter leads to numerous applications in material processing and biology for imaging and generation of microfluidic systems. A femtosecond pulse, with very high intensities of (10^{12} - 10^{13} W/cm^2), has the potential to trigger a phenomenon of optical breakdown at the surface and therefore induce permanent material modification. With such high intensities and taking into account the fact that most materials possess large bandgap, the interaction is completely nonlinear in nature, and the target material can be modified locally upon the surface and even further in bulk. The phenomenon of optical breakdown can be further investigated by studying the nonlinear absorption. Properties like very short pulse duration and the high irradiance of ultrashort laser pulse lead to more precise results during the laser ablation process over the long pulsed laser. The duration of femtosecond laser pulse provides a high resolution for material processing because of the significant low heat-affected zone (HAZ) beyond the desired interaction spot generated upon irradiating the material. Under certain condition, the interaction of intense ultrashort light pulses with the material gives rise to the generation of periodic surface structures with a sub-micron periodicity, i.e., much smaller than the laser wavelength. The self-oriented periodic surface structures generated by irradiating the material with multiple femtosecond laser pulses results in improving the functionality of the material's surface such as controlling wettability, improving thin film adhesion, and minimizing friction losses in automobile engines, consequently, influences positively on many implementations. In this work, we introduced a new method to study complex polarization states of light by imprinting them on a solid surface in the form of periodic nano-structures. Micro/Nanostructuring of diamond by ultrafast pulses is of extreme importance because of its potential applications in photonics and other related fields. We investigated periodic surface structures usually known as laser-induced periodic surface structures (LIPSS) formed by Gaussian beam as well as with structured light carrying orbital angular momentum (OAM), generated by a birefringent optical device called a q-plate (QP). We generated conventional nano-structures on diamond surface using linearly and circularly polarized Gaussian lights at different number of pulses and variable pulse energies. In addition, imprinting the complex polarization state of different orders of optical vector vortex beams on a solid surface was fulfilled in the form of periodic structures oriented parallel to the local electric field of optical light. We also produced a variety of unconventional surface structures by superimposing a Gaussian beam with a vector vortex beam or by superposition of different order vector vortex beams. This thesis is divided into five chapters, giving a brief description about laser-matter interaction, underlying the unique characterization of femtosecond laser over the longer pulse laser and mechanisms of material ablation under the irradiation of fs laser pulse. This chapter also presents some earlier studies reported in formation of (LIPSS) fabricated on diamond with Gaussian. The second chapter explains the properties of twisted light possessing orbital angular momentum in its wavefront, a few techniques used for OAM generation including a full explanation of the q-plate from the fabrication to the function of the q-plate, and the tool utilized to represent the polarization state of light (SoP), a Poincar'e sphere. Finally, the experimental details and results are discussed in the third and fourth chapters, respectively, following with a conclusion chapter that briefly summarizes the thesis and some potential application of our findings.

L’étude de matériaux thermoélectriques nanocomposites et nanostructurés est en plein essor suite à l’intérêt de multiplier le nombre d’interfaces et de diminuer la taille des objets pour améliorer les performances. Nous avons mis au point une nouvelle méthode de préparation de nanopoudres thermoélectriques de type n (Bi0.95Sb0.05)2(Te0.95Se0.05)3 et de type p (Bi0.2Sb0.8)2Te3, à partir de la fracturation laser en milieu aqueux de poudres de taille micrométrique. La cellule de préparation développée permet d’obtenir par jour environ 200 mg de poudres nanométriques cristallisés présentant la structure cristallographique des poudres initiales et dont la taille moyenne est comprise entre 7 et 12 nm. Les mécanismes mis en jeu dans l’obtention des nanoparticules ont été abordés. Ils dépendent fortement de la densité d’énergie du faisceau laser. Les nanopoudres ont ensuite été mélangées mécaniquement aux poudres micrométriques de même nature et ont été compactées à froid. Les propriétés thermoélectriques (résistivité électrique, pouvoir thermoélectrique, conductivité thermique) des nanocomposites ont été évaluées à température ambiante. Les premiers résultats montrent que même si le pouvoir thermoélectrique est maintenu dans les matériaux nanostructurés et nanocomposites et que la conductivité thermique totale peut, de manière tout à fait exceptionnelle, être diminuée d’un facteur deux, la résistivité électrique obtenue est jusqu’alors trop élevée pour conduire à de bonnes performances en terme de facteur de mérite adimensionnel, par rapport à un matériau massif conventionnel de même composition
The study of thermoelectric nanostructured and nanocomposite materials is expanding because of the interest to multiply the number of interfaces and to decrease the size of the objects in order to improve the thermoelectric performance. We developed a new method to prepare thermoelectric n type (Bi0.95Sb0.05)2(Te0.95Se0.05)3 and p type (Bi0.2Sb0.8)2Te3 nanopowders, from the laser fracture in a liquid medium of powders of micrometric size. The developed cell preparation makes it possible to obtain per day approximately 200 mg of crystallized nanometric powders having the crystallographic structure of the initial powders and whose mean size lies between 7 and 12 nm. The mechanisms concerned in obtaining the nanoparticules were approached. They strongly depend on the density of energy of the laser beam. The nanopowders then were mechanically mixed with the micrometric powders of comparable nature and were cold pressed. The thermoelectric properties (electrical resistivity, thermoelectric power, thermal conductivity) of the nanocomposites were evaluated at room temperature. The first results show that even if the thermoelectric power is maintained in nanostructured and nanocomposite materials and that the total thermal conductivity can, in a completely exceptional way, being decreased by a factor two, the electrical resistivity obtained is hitherto too high to lead to high values of the dimensionless thermoelectric figure of merit, with regard to conventional bulk materials of same composition

Les nanoparticules métalliques (NPs) présentent des propriétés optiques (PO) uniques provenant de l’oscillation collective de leurs électrons. Cet effet se traduit par l'émergence d'une bande plasmon dont les caractéristiques peuvent être modulées par la taille, la forme, la nature des NPs et le milieu hôte. Il existe de nombreuses méthodes pour la préparation de ces NPs, l'une d'entre elles est l'ablation laser en milieu liquide (ALML). Cette technique offre certains avantages comme la simplicité, l’adaptabilité et des NPs dépourvues de contamination. Ses principaux inconvénients sont la productivité et le contrôle de la taille et de la forme des NPs. Ce travail est consacré à l'élaboration de NPs d’Ag par l’ALML et à l'étude théorique de leurs PO. Nous donnons dans ce manuscrit, les résultats de l'optimisation des paramètres d'élaboration conduisant à l'obtention de distributions en NPs reproductibles et contrôlées. Les PO de ces NPs sont mesurées et comparées à des modèles physiques spécifiques basés sur la théorie des milieux effectifs (EMT). L'EMT, telle que le modèle de Maxwell-Garnett, permet de décrire les PO de NPs monodisperses. Cependant, les voies de préparation classiques conduisent inévitablement vers des NPs montrant une distribution de forme et de taille qui induit des changements drastiques sur leurs PO. Le modèle SDEMT est proposée pour le calcul de la fonction diélectrique effective et du coefficient d'absorption de solutions colloïdales de NPs métalliques. Contrairement à Maxwell-Garnett, ce modèle donne une meilleure description des spectres d'absorption et d’ellipsométrie mesurés sur des échantillons contenant des NPs d’Ag et d’Au
Metal nanoparticles (NPs) exhibit unique optical properties (OP) coming from the collective oscillations of their electrons. This effect is translated by the emergence of a band of plasmon, the characteristics which can be modulated by the size, the shape and the nature of the NPs as well as by the environment of the host. There are many methods for the preparation of NPs, and one of them is the pulsed-laser ablation in liquid (PLAL). This technique offers some advantages such as simplicity, versatility and surface NP without contamination (reducing agent residues and/or stabilizers). Its main drawbacks are the lacks of productivity and control of the NP size and shape. This work is devoted to elaboration of Ag NPs by PLAL and theoretical investigation of their OP. We give here the results about the optimization of elaboration parameters leading to obtaining reproducible and controlled distributions of Ag NPs. The OP of these NPs are measured and compared to specific physical models based on the effective medium theory (EMT). Classical EMT such as Maxwell Garnett approximation allows describing the OP of monodisperse NPs. However, conventional preparation routes unavoidably conduct to NPs showing a shape and a size distribution which induces drastic changes in the OP. A SDEMT model which considers the shape dispersion is proposed for the calculation of the effective dielectric function and absorption coefficient of colloidal solution of metal NPs in water. Contrary to the conventional theory, this model gives a better description of the measured absorption and ellispometry spectra of sample containing Ag and Au NPs

Thesis (Ph.D.)--Kent State University, 2009.
Title from PDF t.p. (viewed April 1, 2010). Advisor: Brett Ellman. Keywords: Laser; Charge generation; Charge transport; Mobility; Trapping; Space charge; Hopping; Tunneling; Lattice vibration; Exciton; Polaron; HUMO; LUMO; Action Spectrum; Quantum efficiency; Crystal Growth; Liquid crystal; Disordered medium. Includes bibliographical references.

The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.

The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.

Two types of core/shell nanoparticles (CS-NPs) generation based on laser ablation are developed in this study, namely, double pulse laser ablation and laser ablation in colloidal solutions. In addition to the study of the generation mechanism of CS-NPs in each scheme, the optical properties of designed CS-NPs are determined with UV-VIS-NIR spectroscopy and EM field simulation. In the first scheme, which is double pulse laser ablation, two laser beams are fired in a sequence on two adjacent targets with different material. We have successfully demonstrated the generation of Sn/Glass, Zn/Glass, Zn/Si, Ge/Si, and Cu/Zn CS-NPs. Key factors affecting the generation of CS-NPs are (1) surface tensions of the constructing materials affecting the associated Gibbs free energy of CS-NPs, (2) physical properties of selected background gases (i.e., He and Ar), (3) delay time between two laser pulses, and (4) the amount of laser energy. The second scheme examined for the generation of CS-NPs is through laser ablation of solid targets in colloidal solutions. Compared to the double pulse laser ablation, this second approach provides better control of the size and shape of the resulting CS-NPs. Two colloidal solutions, namely, Au and SiO2 colloidal solution are applied in the second scheme. Key factors affecting the formation of CS-NPs with the second scheme and are (a) the adhesion energy between the shell and the core material, (b) the diameter of the core and (c) the laser ablation time and the laser energy. Red shift of absorption peaks are measured in both SiO2/Au and SiO2/Ag colloids compared with pure nanoparticles (NPs). The amount of red-shift is very sensitive to the shell thickness of the CS-NPs. The same red shift is reproduced with the corresponding full wave analysis. The observed red shift can be attributed to the additional surface plasmon resonance at the interface of metal/dielectric of the CS-NPs compared with pure nanoparticles. Through adjusting the material and size combination, the absorption peak of the CS-NPs can be tuned in a limit range around the intrinsic absorption peak of the metal of the CS-NPs. The freedom of adjusting the absorption peak makes CS-NPs is favorable in bio and optical applications.

A new laser ablation mechanism of liquid water based on recent insights into its hydrogen bond dynamics has been studied and several applications of the ablation demonstrated. The mechanism, termed as Impulsive Heat Deposition through Vibrational Excitations (IHDVE), is based on the ability of the hydrogen bond network of water to rapidly thermalize vibrational O-H stretch excitations on a time scale of several picoseconds even for excitation intensities that are large enough to bring excited volumes far into the supercritical region. In this way, by using vibrationally resonant picosecond infrared laser pulses with sufficient energy, it is possible to drive ultrafast phase transitions in the excited water volume leading to a rapid and efficient ablation process of water and water rich targets with minimum perturbation of solute molecules of interest. The physics behind the IHDVE ablation process is outlined and the benefits of the IHDVE ablation are demonstrated for two important applications of tissue cutting and mass spectrometry of biomolecules. Finally, the development of two high power infrared laser systems suitable for the practical implementation of IHDVE is presented.

碩士
國立成功大學
機械工程學系
104
Global energy usage and production are inefficient. Triboelectric nanogenerator (TENG) is a promising technique to efficiently reuse the energy. Herein, we discuss cost efficient and feasible fabrication process for the enhancement of triboelectric effect in materials. The CO2 laser of 10.16 µm wavelength is one of the cost-effective, rapid and reliable polymer material processing methods. This photo-thermal process for material subtraction causes some defects like debris, cracks, and bulges near the laser-ablated area. We propose a novel concept in advanced laser processing for the fabrication of microstructure. Liquid-assisted laser processing (LALP) considered an idle method for the fabrication of polymer-based microstructure, reduces the defects relatively to the air assisted laser processing and benefits in a result of obtaining organised debris and size controlled bulges. The manipulation of the Laser Parameters, the Power, the Scanning speed, Points per inch, and nozzle air flow pressure over the different laser ablation techniques, liquid and Air, the organisation of Distribution of particles to sub-micrometre size possible. For the controlled parameters of laser ablation at a Power of 1.5 W, scanning speed of 57 mm/s, PPI of 1000 and nozzle air flow pressure of 1.42 psi the particles are found to be maximum. The Observed voltage and current in the TENG performance confirm the effect.

博士
國立中山大學
材料與光電科學學系研究所
100
This research deals with the synthesis and characterization (transmission electron microscopy and optical spectroscopy) of composite nanocondensates produced by pulse laser ablation (PLA) on Zn, Zn-Cu and Cu-Au targets in liquid or vacuum. First, wurtzite-type (W)-ZnO and