Quantization in nanoparticles induced by magnetic and gravitational fields

A thesis presented in fulfillment of the degree of Doctor of Philosophy in Mechanical Engineering

Sid Senadheera

Abstract
Quantization in nanoparticles induced by magnetic and gravitational fields
Author: Sid D. Senadheera

Nanoparticles(NP) have attracted intensive interest in the nanotechnology applications due to their huge potential in medicine and new engineering materials. Several methods have been developed to generate nanoparticles in mass scale, among which laser ablation is desired because of simplicity in configuration and short process time. Recently, femtosecond laser ablation has been investigated for nanoparticle generation and it was observed that the nanoparticle structure generated by femtosecond laser ablation presents unique characteristics, compared to nanoparticles that are generated with conventional long pulse lasers. According to the current state of understanding in the work done in femtosecond laser ablation hydrodynamics, there is no clear agreement between the theoretical
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models and experimental results obtained from the production of nanoparticles and nanofibers. This thesis also gives an experimental approach to analyze the

theoretical derivations of the Raizer-Zeldovich theory (RZ theory) and look at the critical points where drastic changes or increments in the nucleation rate in the plume takes place. RZ theory is the most appropriate theory applicable to an expanding plume created by a femtosecond laser. In the experimental results a proof of the critical time limit deduced using the RZ theory to produce nanofibers is equal to the time span taken to form nanofibers. To keep the nanofibers forming, energy from the femtosecond laser has to be given to the sample at continuous intervals. A repetition frequency is calculated using this time interval and compared with the formation of nanofibers at different repetition frequencies. For the theory to agree with experimental results, the nanofiber formation repetition frequency has to be close to the repetition frequency predicted by the RZ theory. A sharp increase of vapor condensation occurs when there is an agreement of RZ theory and experimental results.

Table of Contents
Abstract 1 Table of Contents 4-5 List of Figures 6 List of Tables 7 Acknowledgements 8

Chapter 1.
1.1 Introduction and Overview 1.1.1 Nanoparticles in Science and Engineering 1.1.2 Advantages of research in Semiconducting NPs 1.2 NP production by Laser Ablation 1.2.1 Femtosecond Laser 1.2.2 Experimental setup 1.3 A preliminary analysis of a rapidly expanding plume 1.3.1 The evolution of the plume with time

Chapter 2.
2.1 Review of lasermatter interaction 2.2 INTRODUCTION 2.2.1 Femtosecond laser micromachining 2.2.2 Brief history 2.3 Femtosecond laser pulse ablation

Chapter 3.
3.1 Material removal processes and expansion 3.2 Photo-mechanical processes: Spallation 3.2.1 Phase explosion 3.2.2 Fragmentation of a highly strained supercritical fluid

Chapter 4.
4.1 Laser ablation process 4.2 The plume expansion and nucleation 4.2.1 A Classical theoretical analysis of nanoparticle aggregates Chapter 5. First experimental peer reviewed proof of RZ theory 50 years after it was derived by Raizer and Zeldovich. 5.1 Raizer-Zeldovich theory of hydrodynamics (RZ theory) 5.2 Predictions for nucleation and shock expansion 5.2.1 Experimental proof of RZ theory

Chapter 6.
6.1 Physical properties of nanoparticle aggregates 6.2 Size variation due to different repetition rates of the laser 6.3 Size variation due to changing pulse pulse widths 6.1.1 After nucleation has taken place 6.1.2 Quantum mechanical analogy of particle sizes and Energy.

Chapter 7.
7.1 Nanoparticle production in Magnetic fields 7.2 Behavior of nanoparticles under the influence of Magnetic fields. 7.2.1 Lorentz force on nanoparticles 7.3 Using magnetic properties of nanoparticle aggregates to change their physical attributes. Summary and Conclusions 105 APPENDIX [A] References 108
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I'm smart enough to know that I'm dumb.

Richard Feynman

Chapter 1.
1.1 Introduction and Overview
The emphasis of this thesis has been on semiconductors such as Silicon and Carbon nanoparticles created by laser ablation. Silicon has been widely recognized as the most important material of the 20th century. It is the second most abundant element in the Earths crust, making up 25.7% of it by mass. The term nanoparticles refer to particles that have one or more dimensions on the order of nanometers (10-9 meters). Attention has recently been given to the nanoscale region as a new and exciting area of material science with numerous applications. Much research has been done to describe particles of this size. This task has proven challenging in that the nanometer size particles behave differently from their bulk-size counterparts. As the size of the particles decreases, the physical properties of the materials change dramatically. This arises from the fact that the size is now similar to physical quantities such as grain size, magnetic domain size, elastic or inelastic scattering length of conduction electrons, wavelength of

excitations such as phonons or magnons, De Broglie wavelength of the electron or the phase-coherence length in a semiconductor, etc.
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The desire to fabricate materials with novel or improved properties, which has been driven by material science and technology, is currently giving the most significant contributions to nanoscale research. Such improved properties include strength, electrical and thermal conductivity, optical response, elasticity, or wear resistance. Research is also evolving toward materials that are designed to perform more complex and efficient tasks. Examples include nano-materials that bring about a higher rate of decomposition of pollutants and improved conversion of light into electric current or more efficient energy storage. For these and more complex tasks to be realized, novel materials have to be based on several components whose spatial organization is engineered at the molecular level. In electronics, the design and the assembly of functional materials and devices based on nanoscale building blocks can be seen as the natural, inevitable evolution of the trend toward miniaturization. The microelectronics industry, for instance, is fabricating integrated circuits and storage media whose basic units are approaching the size of few tens of nanometers. Memory devices sensitive to the presence or absence of a single electron have the possibility to drastically improve device characteristics in terms of high density, low power usage, fast write/erase processes, and a long retention time. For computers, smaller means higher computational power at lower cost and with greater portability. However, this race toward higher performance is
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driving current silicon-based electronics to the limits of its capability. Fortunately, the advent of new methods for the controlled production of nano-scale materials has provided new tools that can be adapted. New terms such as nanotubes, nanowires and quantum dots are now common jargon used throughout scientific publications. These objects are among the smallest man-made units that display physical and chemical properties which make them promising candidates as fundamental building blocks for novel transistors, diodes and integrated circuits. The advantages envisioned here are higher device versatility, faster switching speed, lower power dissipation, and the possibility of packing many more transistors on a single chip. Substantial efforts have focused on investigating nanoscale forms of silicon, both for the purpose of further miniaturizing the current microelectronic devices and in the hope of unveiling new properties that often arise at the nanoscale. The trend in semiconductor device fabrication to miniaturize the size of microchips and their subcomponents with the idea that with smaller dimensions will come devices that will operate at faster speeds than preceding generations.

1.1.1 Nanoparticles in Science and Engineering

Nanoparticles have attracted intensive interest in the nanotechnology applications due to their huge potential in medicine and new engineering materials. Several
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methods have been developed to generate nanoparticles in mass scale, among which laser ablation is desired because of simplicity in configuration and short process time. Recently, femtosecond laser ablation has been investigated for nanoparticle generation and it was observed that the nanoparticle structure generated by femtosecond laser ablation presents unique characteristics, compared to nanoparticles that are generated with conventional long pulse lasers.

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Figure 1. Examples of NPs and their size related phenomena

Nanoparticle Technology Handbook By Masuo Hosokawa, Published by Elsevier, (2007) ISBN 044453122X, 9780444531223

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1.1.2 Advantages of research in NPs

Manufactured products are made from rearranged atoms. [ ] The

properties of those products depend on how those atoms are arranged. If we rearrange the atoms in coal, we get diamonds. If we rearrange the atoms in sand (and add a pinch of impurities) we get computer chips. If we rearrange the atoms in dirt, water and air we get grass. Since we first made stone tools and flint knives we have been arranging atoms in great thundering statistical herds by casting, milling, grinding, chipping and the like. Weve gotten better at it: we can make more things at lower cost and greater precision than ever before. But at the molecular scale were still making great ungainly heaps and untidy piles of atoms. Nanotechnology is about rearranging atoms whichever way we want. Thats changing. In special cases we can already arrange atoms and molecules exactly as we want. Theoretical analyses make it clear we can do a lot more. Eventually, we should be able to arrange and rearrange atoms and molecules much as we might arrange LEGO blocks. In not too many decades we should have a manufacturing technology able to: * Build products with almost every atom in the right place. * Do so inexpensively. * Make most arrangements of atoms consistent with physical law.
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Often called nanotechnology, molecular nanotechnology or molecular manufacturing, it will let us make most products lighter, stronger, smarter, cheaper, cleaner and more precise. The technology allows us to work on a macroscopic scale. The advantages of nanotechnology One of the basic principles of nanotechnology is positional control. At the macroscopic scale, the idea that we can hold parts in our hands and assemble them by properly positioning them with respect to each other goes back to prehistory: we celebrate ourselves as the tool using species. Our wisdom and our knowledge would have done us scant good without an opposable thumb: wed still be shivering in the bushes, unable to start a fire. At the molecular scale, the idea of holding and positioning molecules is new and almost shocking. However, as long ago as 1959 Richard Feynman, the Nobel prize winning physicist, said that nothing in the laws of physics prevented us from arranging atoms the way we want: it is something, in principle, that can be done; but in practice, it has not been done because we are too big. What would it mean if we could inexpensively make things with every atom in the right place?

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Products could be much lighter, stronger, and more precise. * we could continue the revolution in computer hardware right down to molecular gates and wires something that todays lithographic methods (used to make computer chips) could never hope to do. * We could inexpensively make very strong and very light materials: shatter proof diamond in precisely the shapes we want, by the ton, and over fifty times lighter than steel of the same strength. * We could make a Cadillac that weighed fifty kilograms, or a full-sized sofa you could pick up with one hand. * We could make surgical instruments of such precision and deftness that they could operate on the cells and even molecules from which we are made, something well beyond todays medical technology. The list goes on almost any manufactured product could be improved, often by orders of magnitude. What will we be able to make? Nanotechnology should let us make almost every manufactured product faster, lighter, stronger, smarter, safer and cleaner. We can already see many of the possibilities as these few examples illustrate. New products that solve new problems in new ways are more difficult to foresee, yet their impact is likely to

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be even greater. Could Edison have foreseen the computer, or Newton the communications satellite? (a). Improved transportation Lighter materials will make air and space travel more economical. * Today, most airplanes are made from metal despite the fact that diamond has a strength-to-weight ratio over 50 times that of aerospace aluminum. Diamond is expensive, we cant make it in the shapes we want, and it shatters. Nanotechnology will let us inexpensively make shatterproof diamond (with a structure that might resemble diamond fibers) in exactly the shapes we want. This would let us make a Boeing 747 whose unloaded weight was 50 times lighter but just as strong. * Today, travel in space is very expensive and reserved for an elite few. Nanotechnology will dramatically reduce the costs and increase the capabilities of space ships and space flight.2 The strength-to-weight ratio and the cost of components are absolutely critical to the performance and economy of space ships: with nanotechnology, both of these parameters will be improved3 Beyond inexpensively providing remarkably light and strong materials for space ships, nanotechnology will also provide extremely powerful computers with which to guide both those ships and a wide range of other activities in space.
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(b). Atom computers (quantum computers) Computers of the future will use atoms instead of chips for memory. * Today, computer chips are made using lithography literally, stone writing. If the computer hardware revolution is to continue at its current pace, in a decade or so well have to move beyond lithography to some new post lithographic manufacturing technology. Ultimately, each logic element will be made from just a few atoms. * Designs for computer gates with less than 1,000 atoms have already been proposed but each atom in such a small device has to be in exactly the right place. To economically build and interconnect trillions upon trillions of such small and precise devices in a complex three dimensional pattern well need a manufacturing technology well beyond todays lithography: well need nanotechnology. * With it, we should be able to build mass storage devices that can store more than a hundred billion billion bytes in a volume the size of a sugar cube; RAM that can store a mere billion billion bytes in such a volume; and massively parallel computers of the same size that can deliver a billion billion instructions per second.

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(c). Military applications Weaponry can incorporate computer power but is this prudent? * Today, smart weapons are fairly big we have the smart bomb but not the smart bullet. In the future, even weapons as small as a single bullet could pack more computer power than the largest supercomputer in existence today, allowing them to perform real time image analysis of their surroundings and communicate with weapons tracking systems to acquire and navigate to targets with greater precision and control. * Well also be able to build weapons both inexpensively and much more rapidly, at the same time taking full advantage of the remarkable materials properties of diamond. Rapid and inexpensive manufacture of great quantities of stronger more precise weapons guided by massively increased computational power will alter the way we fight wars. Changes of this magnitude could destabilize existing power structures in unpredictable ways. Military applications of nanotechnology raise a number of concerns that prudence suggests we begin to investigate before, rather than after, we develop this new technology.

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(d). Solar energy Solar energy can replace other resources. * Nanotechnology will cut costs both of the solar cells and the equipment needed to deploy them, making solar power economical. In this application we need not make new or technically superior solar cells: making inexpensively what we already know how to make expensively would move solar power into the mainstream.

(e). Medical uses Medicine can heal at the molecular or cellular level. * It is not modern medicine that does the healing, but the cells themselves: we are but onlookers. If we had surgical tools that were molecular both in their size and precision, we could develop a medical technology that for the first time would let us directly heal the injuries at the molecular and cellular level that are the root causes of disease and ill health. With the precision of drugs combined with the intelligent guidance of the surgeons scalpel, we can expect a quantum leap in our medical capabilities.

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How long? The single most frequently asked question about nanotechnology is: How long? How long before it will let us make molecular computers? How long before inexpensive solar cells let us use clean solar power instead of oil, coal, and nuclear fuel? How long before we can explore space at a reasonable cost? The scientifically correct answer is: I dont know. From relays to vacuum tubes to transistors to integrated circuits to Very Large Scale Integrated circuits (VLSI) we have seen steady declines in the size and cost of logic elements and steady increases in their performance.

Conclusion: Nanotechnology is prediced to be developed by 2020 but much depends on our commitment to its research. * Extrapolation of these trends suggests we will have to develop molecular manufacturing in the 2010 to 2020 time frame if we are to keep the computer hardware revolution on schedule. * Of course, extrapolating past trends is a philosophically debatable method of technology forecasting. While no fundamental law of nature prevents us from developing nanotechnology on this schedule (or even faster), there is equally no law that says this schedule will not slip.

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* Much worse, though, is that such trends imply that there is some ordained schedule that nanotechnology will appear regardless of what we do or dont do. Nothing could be further from the truth. How long it takes to develop this technology depends very much on what we do. If we pursue it systematically, it will happen sooner. If we ignore it, or simply hope that someone will stumble over it, it will take much longer. And by using theoretical, computational and experimental approaches together, we can reach the goal more quickly and reliably than by using any single approach alone. While some advances are made through serendipitous accidents or a flash of insight, others require more work. It seems unlikely that a scientist would forget to turn off the Bunsen burner in his lab one afternoon and return to find hed accidentally made a Space Shuttle. Like the first human landing on the moon, the Manhattan project, or the development of the modern computer, the development of molecular manufacturing will require the coordinated efforts of many people for many years. How long will it take? A lot depends on when we start.

1997, Ralph C. Merkle. Abridged version of an article first published in the Feb/Mar issue of MIT Technology Review. 2000,

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1.2 NP production by Laser Ablation

Figure 3. An image of Laser Ablation plume.

When the irradiance (power per unit area) exceeds a particular threshold value depending on the material, evaporation takes place, leading to the subsequent formation of aerosols. Figure 3, schematically shows the ablation depth as a function of time (dotted line) for comparable experimental conditions after. The figure also shows qualitatively the time dependence of the absorbed laser power. In the first nanosecond, the reflectivity for smooth metal surfaces is high, and only a fraction of the laser power is absorbed. This small amount is sufficient to heat the surface, which increases absorption, causing the material to evaporate.

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The vapor is ionized and superheated in the focus of the laser beam to form a plasma with strong absorption bands that shield the target. At about 20 ns the ablation begins anew, because of increased reradiation from the plasma. When the laser pulse ends ablation comes to a halt. A schematic diagram of two regimes of the process is shown in Figure 3 for (a) the initial stage of laser ablation and (b) about 10 ns after the plasma plume has developed. For a given irradiance by a pulsed laser, the gas temperature generated by the plasma is similar for a variety of materials and the amount of ablated material is also similar. Hence the time-temperature history of the gases is probably similar for the various ablated materials because of the similar parameters. With these assumptions, it is possible to explain some ablated properties as discussed in the following sections.

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Figure ?. Schematic diagram of ablation depth for a single laser pulse. Within the first nanosecond, high reflectivity delays vapor production. After 8 ns the vapor shields the target from the laser beam and ablation is slow. At 23 ns the hot plasma heats the surface of the metal and evaporates more material. The energy efficiency is defined as the fraction of the pulse energy that is converted into evaporation of the material. The efficiency is calculated by dividing the enthalpy of evaporation for the amount of material removed by the energy supplied by the laser. For the materials studied by Ullmann et al. the energy absorbed for evaporation (evaporation energy) is about 0.15% of the laser

energy. The highest efficiency, nearly 5%, was observed for carbon, probably because of the high absorptivity of the carbon in the laser frequency range. The second highest efficiency, 1.5%, was observed for silica.
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The metal targets have high reflectivities, resulting in low efficiencies of 0.10.3%. The highest efficiencies of absorption that have been reported for metals were about 15% (Ullmann, 2002). These efficiencies were achieved using a continuous laser in the infrared spectrum. Light with short wavelength experiences high reflectivity at metallic surfaces dependent on material even though the absorption generally improves for shorter laser wavelength. The short pulses are absorbed less because of the high initial reflectivity for every pulse. Ullmann, Marca; Friedlander, Sheldon K.b; Schmidt-Ott "Nanoparticle Formation by Laser Ablation" Journal of Nanoparticle Research Vol: 4, Issue: 6, pp. 499-509 (December 2002)

1.2.1 The Femtosecond Laser

IMPULSE is an all-diode-pumped, direct-diode-pumped Yb-doped fiber oscillator/amplifier system capable of producing variable pulse energies up to 10 microjoules at repetition rates between 200 kHz ; and 25 MHz (20 Watts average power output at 2 MHz.) This is more than an order-of-magnitude higher than has traditionally been available in a one-box ultrashort pulse laser design.

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IMPULSE is based on a revolutionary new concept in mode-locked oscillator/amplifier technology. The use of a Yb-doped fiber-oscillator/fiberamplifier design combines the low noise performance associated with solid state operation with the high spatial mode quality of fiber lasers.

1.2.2 Experimental setup

The experimental setup and the basic concept are shown schematically in Figure ?. We used a femtosecond laser capable of producing variable pulse widths and pulse frequency as described in section 1.2.1. The laser source is an all-diode-pumped, direct-diode pumped Yb-doped fiber oscillator/amplifier system capable of producing variable pulse energies up to 10 mJ at a pulse frequency between 200 kHz and 25 MHz. Average power varies between 0-20W. Arrays of microvias
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were drilled into a graphite target and a blank silicon wafer with laser beam at various pulse frequencies. The samples were then characterized using scanning electrical microscopy (SEM). Large amounts of fibrous nanostructures were observed surrounding the microvias, as shown in Figures [?-?].

Figure ? : Setup for producing femtosecond laser ablation sample.

Figure [ ] 26

Reference: Clark MXR-Lasers Website : http://www.cmxr.com/scientific/impulse.htm

1.3 A preliminary analysis of a rapidly expanding plume

The first theoretical analysis of condensation dynamics in a rapidly expanding vapor was performed by Yu P Raizer in 1960 [ ]. He considered the selfconsistent problem of vapor condensation during expansion, as applied to the problem of cosmic dust in star formation regions. A constituent of the analysis is the classical theory of nucleation, which was developed in Refs [161 - 164]. This theory of dynamic condensation of expanding vapor will be referred to as the Zeldovich & Raizer (RZ) theory and will be analyzed in detail in Chapter 4. This theory is outlined theoretically in reference[?? ].

Figure [??]

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An advantage of the RZ theory is that, it is a clear manifestation of the physics of the process, and it also accounts correctly for the characteristic scale dimension of the resultant clusters. I have used the RZ theory as a good underlying model for the condensation. The hydrodynamic expansion of the plume is separated into two distinctive regimes : (1) Shortly after the laser pulse, when the internal energy is high enough to dominate the expansion process, it is described by free flight expansion. During this early period the ambient atmosphere does not influence the dynamics. (2) The later expansion, when the shock wave has fully developed can be described as a strong explosion. The following period, described by shock wave expansion is dominated by coalescing of previously condensed particles. It is this correlation of free flight and shock wave expansion with nucleation, condensation and coalescence, respectively, which makes the problem analytically possible.

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Chapter 2
2.1 Review of lasermatter interaction in Semiconductors and laser ablation. In this chapter, an introductory review in the fundamental interaction processes between light and matter is given. Starting with the optical properties of a material in a non-excited state, absorption, heating, melting, cooling, solidification, structural relaxation processes and their dynamics will be briefly described. At the end of the chapter an outline will be given about the research that has culminated to some outcomes at the Ryerson University. A more detailed approach will be taken in Chapter 6. The mathematical treatment of light-matter interaction can be done either by a classical or a quantum approach. In the following, I mostly restrict myself to the classical description except on a few occasions where I have shown that the quantum mechanical corollary describes certain features of nanoparticles similarly well or better. In addition, one of the main goals of this thesis is to elucidate some of the fundamental aspects regarding the laser-matter interaction and evolvement of the ablated matter through different stages until the solidification stage.

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2.2 INTRODUCTION Femtosecond, sub-picosecond pulsed laser ablation technique is currently attracting a great deal of attention both for fundamental physics and for technological applications. The first investigations on the interaction of femtosecond (fs) laser pulses with solid targets were mainly devoted to the study of the modifications of irradiated samples. These studies are still establishing fs laser ablation as the state-of-art technique for optimal control of material removal (or ablation) due to its peculiarity to process virtually any material with high precision and minimal collateral damage. In a number of applications (micromachining, metal processing, surgical operation, and so on) advantages over nanosecond (ns) and picoseconds (ps) laser pulses have been already demonstrated by other researchers. In my research with creating nanoparticle aggregates, an added advantage of working with femtosecond lasers is the cooling halftime during the condensation phase. It is few orders less than in the picosecond or the nanosecond cases.

A key benefit of femtosecond laser pulses lies in its ability to deposit energy into a material in a very short time period. The time period is so short that thermal diffusion can take longer. Following linear or multiphoton absorption of the laser energy, electron temperatures can be quickly raised up to many thousands of
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degrees of Kelvin. With the subsequent energy transfer from the electron subsystem to the atomic lattice, material removal, ablation and plasma formation occur[2]. At laser pulse durations shorter than the typical electron to lattice relaxation times (about some ps - please see APPENDIX [A]) the lattice energy transport in femtosecond laser is separated into two stages: 1) laser energy absorption by electrons during the pulse irradiation and 2) absorbed energy redistribution in bulk materials leading to material removal mostly occurring after the pulse duration. Both these cases are shown in Figure [ ] On the contrary, for ns laser pulses ablation occurs from both the melted and the vapour phases, leading also to emission of particulate and liquid micro-droplets. It will be shown later in this thesis that similar results occur when femtosecond lasers with low repetition rates are used. Moreover, the long lasting material emission and the longer pulse length lead to laser-vapor interaction, limiting the control on the properties of the ablated particles. For ultrashort pulses, on the other hand, the ablation wave actually precedes the thermal relaxation wave and ablation occurs with minimal collateral damage to the target. In spite of its enormous potentiality, there has been little work on the characterization of laser produced plasma and plume evolution as well as research in analyzing the resulting nanoparticles.
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The experimental investigations revealed the presence in the ultrashort ablated laser has produced, nanoparticle aggregates with mean radii of about 50-450 nm. In the supporting research work, nanoparticles produced by laser ablation technique is currently produced by means of a femtosecond laser system. By letting a plume to expand in ambient air : the collisions between the ablated atoms and the buffer gas give rise to vapour condensation and then, to cluster formation, after a super-heating and a super-cooling process. During femtosecond laser ablation, under suitable experimental conditions (low repetition rates), production of micrometric particles as liquid droplets coming from the melted target material has been frequently observed. Characterization of nanoparticles were done by the Scanning Electron Microscopy (SEM). The limited sizes and the quite narrow size distributions of nanoparticles found for each investigated material and experimental condition confirm how the lasermatter interaction is dependent on experimental parameters. On the other hand, a Monte Carlo approach was developed to simulate the spatial distribution of energy inside the bulk material as a consequence of both linear absorption and electron thermal diffusion mechanisms, Figure[ ]. The calculated spatial distributions were then used to predict the subsequent relaxation, through adiabatic thermodynamic pathways, of specific areas of the target during plume expansion. Finally, it clearly
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turns out that a deep characterization of the plume properties and dynamics is of great present interest both to demonstrate the main properties of all the ejected particles (ions, atoms and nanoparticles) and to shed light on their formation mechanisms, as widely reported in the next chapters.

2.2.1 Femtosecond laser micromachining Femtosecond laser micromachining is a process by which pulses from a femtosecond laser are used to induce micrometer-sized structures on the surface or in the bulk of solid materials. The study of the interaction of femtosecond pulses with absorptive materials and transparent materials has become a very prolific research area. Ablation has been demonstrated in both absorptive and transparent materials, and causing surface modification. Micromachining in absorptive materials have been applied to hole drilling, removal of surface defects, and photolithographic mask repair [34]. In addition, micromachining in transparent materials has found applications in the fabrication of microfluidic channels [16,17]. 2.2.2 Brief history Optical breakdown is a process by which energy is transferred from an optical field to a material, causing ionization of a large number of electrons. In solids, the electrons transfer energy to the lattice and permanent structural damage results. Laser-induced optical breakdown has been studied since the first demonstration of
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the laser. In 1962, researchers at Ford Motor Company discovered that light from a Q-switched ruby laser could ionize air, creating a very bright spark [*, Mazur, Cerami ]. Several years later laser damage in glass was observed a discovery with practical implications for laser experiments, as optical components are typically made from glass. These discoveries prompted investigations into how laser light interacts with gases and solid materials, a research field that remains active to this day. As lasers capable of generating pulses of shorter and shorter duration were developed, it became necessary to improve the understanding of light-matter interactions. Pulsed lasers achieve much higher intensities than continuous wave lasers and therefore their interactions with materials are very different in nature. The unique interaction of femtosecond lasers pulses with materials, in particular, has given rise to an extensive and productive research area over the last fifteen to twenty years. The first demonstrations of microstructuring in bulk glass using femtosecond laser pulses occurred in 1996 by two separate research groups [35,36]. One group reported the fabrication of waveguides inside of a piece of glass using a 120-fs, 200-kHz Ti:sapphire laser system. The other group demonstrated the ability to modify the refractive index of submicrometer-sized volumes inside a variety of transparent materials using a similar laser

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system. Soon after, it was shown that a micro-explosion caused by the high intensity of the laser can create small voids in the bulk of transparent samples [37]. The early experiments all used amplified femtosecond laser systems with pulse energies on the order of microjoules to achieve the required high intensity. In 2001, however, micromachining using only nanojoules of energy was demonstrated, presenting new opportunities for microstructuring in glass. More recently, micromachining in bulk polymers has gained interest. Around the same time that bulk damage was first demonstrated in glass, the effect of amplified femtosecond laser pulses on absorptive materials was already being studied. The ablation of the surface of absorptive materials with femtosecond pulses was first used for microstructuring in 1995 [1]. In these experiments, submicrometer diameter holes were drilled in a metal film. Longer pulses had been previously used to ablate metal surfaces, but with different results.

2.3 Femtosecond laser pulse ablation The processes governing ultrashort pulsed laser ablation are not completely understood at the moment. Actually, several studies on the mechanisms of laser absorption and material excitation, as well as its removal and expansion, has been done, but none of them can be considered conclusive. This section of the chapter describes the basic processes occurring during the irradiation of solid targets with
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ultrashort, subpicosecond laser pulses. The detailed course of the very complex phenomenon occurring during the interaction depends strongly on the parameters of the laser pulse and the target material. Typical intensities used in the femtosecond laser ablation and deposition experiments are in the range of 10121014 W/cm2. At these intensities, the basic processes occurring during laser ablation such as excitation, melting and material removal are temporally separated allowing a separate description of each of them. Excitation takes place on a timescale comparable with the duration of the laser pulse (<< 1ps), as a consequence of absorption of photons by the electronic subsystem of the material. This stage is then followed by melting, which roughly occur in the picosecond regime, and by the removal of material (ablation), whose establishment may require up to several nanoseconds. The expansion of the formed plasma plume, then, follows on much longer timescales. Consequently, three regimes can be described separately, which can be considered as :

(1) optical excitation of the system; (2) lattice modifications; (3) material removal and expansion. Each of them is discussed in the framework of several competing mechanisms, which time by time come into play for semiconductors.
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Chapter 3
3.1 Laser-matter interaction in semiconductors Since the focus of this thesis has been on semiconductors, laser-matter interactions between semiconductors and femtosecond pulses will be considered mainly. In semiconductors, the optical excitation of carriers can be pictured as follows. Initially, one-photon excitation generates electron-hole pairs by promoting electrons from the valence band to the conduction band through interband transitions, provided that the photon energy (h) is higher than the material bandgap energy, Eg (single photon absorption). For intense laser pulses, onephoton excitation will saturate, due to band filling, but multiphoton excitation and free-carrier absorption (through intraband transitions) will create more, and more energetic, carriers. Such processes are also the main absorption mechanisms when the photon energy is less than the material bandgap, h< Eg. Since several photons must be absorbed simultaneously, multiphoton absorption is not very probable compared with single photon absorption. However, its rate increases as I*N , where I is the laser intensity and N is the number of photons involved in the transition, thus becoming an important process when the exciting pulse is very short and intense. On the other hand, once carriers have been generated, they can absorb photons and move to higher energy states; this free
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carrier absorption increases the energy of the free carrier population but not the number of free carriers. The highly energetic carriers thus generated, in turn, can create additional carriers through impact ionization. In this process, which is due to Coulomb interactions between carriers, an excited electron loses energy and falls lower in the conduction band, while an excited hole could move higher in the valence band. As a result, the energy released excites an electronhole pair. Therefore, impact ionization increases the number of free carriers but does not affect their total energy. Figure[ ] reports a schematics of the absorption processes just described.

Figure [enter ] : different types of excitation methods from valence band to the conduction band. Once the laser energy is delivered to the system, the carriers quickly relax through several processes occurring over different time scales. First
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of all, carrier-carrier scattering causes thermalization of the non-equilibrium electron distribution created by the laser pulse. This process occurs on a timescale of tens of fs and leads to a redistribution of the carriers energy over the conduction band. Afterwards, inelastic carrier-phonon scattering lowers the carriers energy and leads to the lattice heating. This process typically occurs on a timescale of several ps and, if the absorbed laser intensity is high enough, may induce a phase transition from the solid to the liquid, or directly to the vapor state. Carrier-lattice thermalization brings the temperatures of the free carriers and the lattice to the same value. The electrons form a Fermi-Dirac distribution around the Fermi level, whose width increases with temperature. However, if there is an energy gap, the free electrons and holes have Fermi-Dirac distributions about different Fermi levels. These distributions have the same temperature as that of the lattice, but there is still an excess of free carriers compared to the true Thermodynamic equilibrium.

These carriers can be removed in two ways: Recombination of electrons and holes or diffusion of carriers away from the photoexcited region. When an electron and hole recombine, the excess energy must be removed. There are several possible avenues for this energy, the primary ones being photon emission, other free carriers (Auger recombination) and defect or
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surface states. The first of these mechanisms is called radiative recombination while the last two are non-radiative processes. At this point, it is worth noticing that during the years essentially two models were accounted for the experimentally observed phase transition induced by focusing intense laser radiation on semiconductors. The first one, known as the thermal model, describes the structural changes as a thermal melting process, assuming that the hot equilibrated electron well equilibrates with the lattice through electron phonon scattering; this, in turn, induces a thermal solid-to-liquid transition on a ps time scale. The other model, known as the nonthermal or plasma model, takes into account the destabilization of the covalent bonds due to the high electronic excitation. This process seems to induce an ultrafast melting, arising from a strong modification of the inter-atomic forces owing to laser-induced promotion of a large fraction (10% or more) of the valence electrons to the conduction band. The atoms, not screened any more, immediately begin to move and rapidly gain sufficient kinetic energy to induce a fast melting, lasting on a several hundreds of fs time scale much faster than the several picoseconds required to convert the electronic energy into thermal motions. That is why, this mechanism is also referred as electronic melting. This ultrafast photoexcitation can thus give the atoms enhanced mobility, without increasing their thermal energy; structural modifications can occur while the electronic and the lattice subsystems are not in
40

thermal equilibrium with each other, even if each of them could be in internal quasi-equilibrium. As experimentally demonstrated by several groups, these processes both characterize the ablation of semiconductors by ultrashort pulses, depending on the excitation energy. These experiments validated previous theoretical studies, which set a lower limit of approximately 1022 carriers/cm3 to induce lattice instability; below this threshold, thermal effects result also to be important. During ultrashort irradiation of semiconductors materials, such a high carrier density is easily obtained owing to the extremely high laser intensity; for instance, in the case of GaAs a laser fluence (energy density on the target) of 0.15 J/cm2 is required to induce ultrafast non-thermal melting, a value readily attainable by the common ultrashort laser sources available at the moment. Normal thermal melting occurs heterogeneously by nucleation and growth of the liquid phase. The boundary separating the phases moves from the liquid into the solid. The times to melt a layer of solid material are relatively long, because the upper limit of the velocity of the solidliquid interface should be of the order of the speed of sound. For example, it takes typically 50 to 100 ps to melt a 20 nm surface layer of silicon using picosecond laser pulses. On the contrary, non thermal melting due to surface instability occurs homogeneously, wherever the stability limit is exceeded.
41

Because of the interplay of all these excitation and relaxation mechanisms, it is difficult to estimate the temporal evolution of the carrier density created by the laser pulse. It should be noted that, the reflectivity as well as the absorption coefficient change during the laser pulse irradiation as a consequence of the varying transient electron density. At the high intensities reached by focusing ultrashort laser radiation this can be also influenced by photo and thermal emission of electrons from the target surface. Energy balance equations for electrons and lattice subsystems, similar to the TTM (Two Temperature Model) diffusion equations but with the phonon excitation/relaxation separated into the optical and acoustic modes of the lattice response, have been used by Choi and Grigoropoulos [ ] in the case of a silicon target irradiated by 800 nm, 100 fs laser pulses. By solving this set of coupled equations, space and temporal evolutions of the electron and lattice temperatures for the first few ps of material evolution were obtained. They found that carrier reach thermal equilibrium with the lattice subsystem on a time scale of about 10 ps, by emitting optical phonons and degenerating into acoustic phonons; moreover, after the laser irradiation a significant emission of electrons from the surface occurs, as a consequence of photo and thermal emission processes. On a longer time scale, all the relaxation mechanisms previously mentioned should be taken into account to correctly

42

describe the main features of semiconductor response to the ultrashort laser irradiation. 3.2. Material removal processes and expansion In the previous section, we showed that the thermalization of the laser energy in the irradiated material (metals and semiconductors) typically takes few picoseconds. This time interval is too short for significant expansion to occur. In fact, the expansion velocity of the atomic layers is determined by the pressure gradients set by the laser radiation inside the material, with respect to the external vacuum; this velocity is limited by the material sound velocity thus resulting, within a ps timescale, in a negligible expansion. Thus, ultrashort laser pulses heat a material to high temperature and pressure states, before significant expansion starts, often creating a supercritical material at solid density. The starting point to describe plume expansion dynamics can be considered as a solid density material with an initial temperature determined by the amount of deposited energy.

Figure [ ] : P-V Diagram of vapor plume at various stages and the critical point. The primary reaction of the system to the absorption of the pulse is to expand in order to relieve the important thermoelastic pressure build-up induced by the constant-volume heating of the target. However, the material also relaxes by

43

emitting strong pressure waves which could play an important role in the ablation process. As shown by equations [ ] and [ ] the energy density inside the material following the laser irradiation decreases exponentially with depth, thus allowing the coexistence of various distinct ablation regimes. In fact, laser ablation in the shortpulse regime involves both thermal and mechanical processes, which are effective at different deposited energy densities and, hence, different depths under the surface of the target. Ablation typically occurs hundreds of picoseconds after the absorption of the pulse, much later than the time required for the equilibrium between electronic and atomic degrees of freedom to establish. Hence, the details of the complex non-thermal processes which occur shortly after the absorption of the pulse are not expected to play a crucial role in the material removal. Ablation should thus be dominated by the thermodynamics or by processes occurring on a mesoscopic scale. Along this way, Perez and Lewis developed a Molecular Dynamics (MD) simulation to describe the relaxation of a two-dimensional Lennard-Jones fluid, after the irradiation by femtosecond laser pulse. They followed separately the evolution of the thermodynamic states of the condensed and gaseous phases, starting from the laser heating assumed to be instantaneous at the solid density, going through adiabatic plume expansion and decomposition, up to its final de-excitation. Thus, they were able to distinguish four different
44

mechanisms to account for material ablation. Figure[ ] shows a schematic temperature-density diagram of a material and the thermodynamic pathways corresponding to the four different mechanisms following ultrashort laser irradiation. The characteristics of each of these processes are discussed in the following. 3.2.1 Photo-mechanical processes: Spallation This results from the loss of stability of the solid target following the passage of a tensile pressure wave. After the laser energy delivery to the target, the surface temperature increases dramatically, and a strong compressive stress is generated on the surface and penetrates into the target. Spallation is the result of internal failure due to the creation of defects induced by tensile stresses and is effective at low fluences (close to the ablation threshold), when strong compressive pressure waves are running through the system, inducing fractures parallel to the surface of the sample and ejection of complete layers of material which constitute the main part of the plume.

The isochoric heating takes the system to a supercritical state still in the solid phase space; then it relaxes by cooling down and enters the solid-vapor region of the phase diagram, below the triple point. These phase changes are driven by the stretching of the solid induced by the tensile compressive wave (negative pressure
45

wave) propagating inside the material, which pushes the system into a mechanically unstable state which finally degenerates in the fracture of the solid. As fluence increases, the amplitude of the tensile wave propagating inside the sample decreases and eventually vanishes. As this occurs, the contribution of spallation to the total yield diminishes to the profit of homogeneous nucleation. Spallation-like ablation has been reported by several studies, as experiments on gels and biological tissues, or MD simulations of ablation of organic solids.

3.2.2 Phase explosion It comes from homogeneous nucleation of gas bubbles inside a superheated, metastable liquid. When the energy delivered to the system increases, relaxation can push the material into the liquid-vapor coexistence region up to crossing the binodal line between the triple point and the critical point. Lets recall that if a nonequilibrium liquid system has enough time to relax towards an equilibrium state, its thermodynamic path in the phase diagram follows the bimodal line, which is the coexistence locus between the liquid and vapour phases. On the contrary, when such a system is, for instance, rapidly heated it can undergo superheating (when its temperature exceeds the boiling point at the given pressure), thus entering the region of the metastable states which, in a temperature-density (T, ) phase diagram, is the region delimited by the binodal line and the spinodal line (see Fig.
46

[ ]). In this region, the free-energy of the gas phase becomes lower than that in the liquid phase, which means that the homogeneous liquid is no longer the most stable configuration. For long enough waiting times or a high enough degree of metastability, gas bubbles are expected to form inside the metastable liquid by a process called homogeneous nucleation. For high nucleation rates, the liquid can rapidly decompose into an equilibrium mixture of liquid droplets and monomers (Figure [ ] in Chapter[ ]) ; this stage is called phase explosion. In a (T, ) diagram, the spinodal line and the line T=0 delimit the region of the unstable states which are thermodynamically prohibited. The closer is the system to the spinodal line (high degree of metastability), the higher is the nucleation rate and, thus the more efficient is the phase explosion mechanism. Thus, if the system enters deeply in the metastable region, high nucleation rates are reached and ablation can be induced by the rapid transition from a superheated liquid state to a mixture of vapor and liquid droplets through phase explosion. The condensed phase gradually converts into gas by nucleation and growth of gas regions; since the timescale for this transformation to take place is very long, liquid droplets can persist in the plume for a very long time. At this point, it should be noted that the emission of liquid droplets from the solid target could be obtained also through heterogeneous nucleation, where the new phase appears on the material surface, at impurity particles, etc. . Nevertheless,
47

Kelly and Miotello [ ] pointed out that for high fluences and very short pulses the target is unable to boil because the time scale does not permit the necessary heterogeneously nuclei to form. Thus, the system can be rapidly heated up to the thermodynamic critical point and even more, without experiencing any heterogeneous phase transition. Several authors suggested that a sufficient condition for homogeneous nuclei to form is that the system has to be heated up to 90% of the critical temperature TC. Perez and Lewis [ ] pointed out that this criterion is rigorously correct for slow heating rates at nearly constant pressure but not for isochoric heating following short-pulse laser ablation because here the system is actually pushed away from the metastable region in the first place. In this case, the occurrence of homogeneous nucleation depends, rather, on the relaxation path followed during the expansion by the ablated material and, in particular, on its degree of metastability (how deep in the metastable region the system enters). In fact, the rate of homogeneous nucleation (nuclei cm-3s-1) is given by Equation [ ] where G is the free-energy barrier for homogeneous nucleation to occur. Since this barrier vanishes at the spinodal line, the actual determining parameter for efficient nucleation is just the degree of vicinity to the spinodal. It is worth noticing that the free energy vanishing in the vicinity of the critical point may result in the establishing of an another relaxation mechanism, known as spinodal decomposition [ ]. It consists of the development of inhomogeneous
48

structures inside the relaxing fluid as a result of thermodynamic instabilities (small density fluctuations). On a thermodynamic point of view, this mechanism is strongly different from classical nucleation theory and, up to now, it has been addressed as a fundamental ablation mechanism only by Vidal et al [ ].

3.2.3 Fragmentation of a highly strained supercritical fluid. As the laser energy is further increased, the system relaxation path falls well above the critical point, thus leading to ablation outside the vapor-liquid metastable region. Nucleation cannot be addressed as the main ablation mechanism and, given the large number of clusters present in the plume, vaporization must also be excluded. Ablation is therefore not caused by a entirely a photothermal process, but may have in this case, a mechanical origin. Fragmentation results from the conversion of the internal stress stored in the expanding target into surface energy: when the elastic energy stored in a region of the target is equal to the surface energy it would have if isolated, the excess elastic energy is converted into surface energy and fragments are created. The material decomposes into a collection of small clusters as a consequence of the extremely high stresses superimposed by the laser superheating. It does not require any change of phase, nor the crossing of a metastability or instability limit, and thus can occur in supercritical conditions where phase explosion and spinodal
49

decomposition are not possible. The thermodynamic relaxation paths proceed above the critical point, then crossing the binodal curve at sub-critical densities, far enough from the critical point to avoid the restoration of any thermal decomposition process. This phenomenon has been frequently observed in systems subjected to large strain rates, as small droplets under isochoric heating, free-jet expansion of liquids, etc., as well as numerically described by means of hydrodynamic codes. In particular, Glover [ ] modelled the adiabatic plume expansion by means of the compressible non-dissipative equations for mass, momentum and energy conservation (the Euler equations) in the planar case for a silicon target. The Euler equations must be augmented by an equation of state. Glover imposed similar solutions in the ideal gas approximation, thus finding that the material undergoes a very strong cooling due to expansion, with a quenching rate much higher than the rate at which the bulk surface is initially quenched. Besides, the plume is subjected to very strong velocity gradients due to its vacuum expansion, and the strain associated with them leads to mechanical bond breaking and, thus, to fragment -ation. For the fragmentation process to develop, it is necessary to overcome the energy costs to create additional surface area. This allows an estimation of the mean cluster size (diameter d), simply by balancing the kinetic energy of expansion and
50

the required energy for additional surface area creation, thus obtaining for spherical fragments : Equation [ ] being S the surface to volume ratio and the surface energy. Equation [ ] gives mean fragment sizes of 10 nm for the typical lattice temperature attained during ultrashort laser irradiation. It is worth considering that a more reliable description of the fluid relaxation paths could be obtained by substituting the ideal gas equation of state with a caloric equation of state (which is the equation of state for an ideal gas with a non constant pressureto-volume specific heat ratio) or, even more, by the generalized Van der Waals equation of state. Vaporization If the energy delivered by the laser is high enough, the surface layers of the target are completely atomized since the corresponding thermodynamic relaxation paths never cross the liquid-vapor coexistence curve or crosses it far away from the critical point. In this regime, only a small percentage (some percent) of the total amount of atoms is contained in clusters. In conclusion, as depicted by the Two Temperature Model (TTM) Equation [ ], the spatial energy distribution built up inside the target by the laser irradiation and subsequent e-ph thermalization decreases exponentially with depth. Thus, atomic layers placed at different depths below the surface are characterized by different absorbed energy densities and, hence, by different temperature histories. The material at different depths
51

subsequently undergo adiabatic relaxation following different thermodynamic pathways, which depend on the initial local temperature. Therefore ultrashort laser ablated plumes could be made of several species, from neutral atoms to aggregates of particles, as a consequence of the complex interactions of several different processes. Vacuum expansion of the plume could be described by means of the threedimensional hydrodynamic model proposed by Anisimov et al [ ]. The model, which we are not going to describe in detail here (since we analyze this model in detail in Chapter 3), starts from the solution of the gas-dynamic equations assuming an adiabatic expansion of the plasma plume into vacuum and allows an estimation of several key parameters such as kinetic energy (temperature) of the species or plume divergence.

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Chapter 4.
4.1 The evolution of the plume with time

Figure [ ] : Sideview of the plume

The formation of nanoparticle aggregates in Silicon started at a pulse frequency of about 2MHz. Until this pulse frequency, the formation of fibrous nanoparticle aggregates was not evident. At 2MHz, aggregates are short and co-exist with large amount of molten droplets.

53

Figure [ ] Nanoparticles produced at low repetition rates [high energy]

As the pulse frequency increases, the amount of molten droplets reduces and the aggregates grow longer, and finally form fibrous structures. For graphite the formation of aggregates begins at 1MHz. On the graphite target surface, the fibrous nanoparticle aggregates were denser at 1MHz than those on a silicon wafer surface at 2MHz. The experimental results show that the minimum required pulse frequency to observe nanoparticle aggregates is material-dependent.

Repetition Rate (pulse to pulse duration) Vs Nanofiber growth :

At 1030nm

(above) Formation of nanofibers at 2MHz

54

Formation of nanofibers at 4MHz

(above) Formation of nanofibers at 8MHz

(Left) Formation at 13MHz

Enlarging a formed area at 13MHz

55

Rough estimate of width ; 3070 Microns

To understand the formation of nanoparticle aggregates it is important to understand how they evolve with time after the laser ablation. Characterizing our experimental results with an SEM we observed that individual nanoparticles are bonded with eachother to form nanoparticle aggregates, Figure [ ]. As illustrated in figure ??, during the laser ablation the material inside the plume evolves through several physical states before condensation. In the first step the laser light is absorbed by free electrons due to inverse Bremsstrahlung process in the semiconductor at the top layer. This is followed by a fast energy transfer to the lattice owing to electron-phonon coupling. After the energy transfer, a high temperature is reached in the lattice. The interaction of intense ultrashort light pulses with the target leads to a phase transformation (melting of surface, evaporation and plasma formation). At first the very high heating rates cause a rapid melting and the transition to an overcritical fluid. An overcritical fluid occurs when the material is in a non-equilibrium state of high pressure and high temperature. The rapidly increasing vapor pressure near the surface creates a large driving force for vapor expansion. The high temperature and density leads to pressures far exceeding the background gas pressure (of the order of 10100 atm). The unusually high fluid pressure causes the plume front to expand very rapidly with time in a highly forward-directed pattern.
56

4.2 The plume expansion and nucleation

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At early times, the plume front is spherical in nature, but as time evolves the plume front becomes sharpened Figure ??. Along with sharpening, the expanding plume front splits into a fast and slow moving cloud indicating plume splitting [3-6]. The expanding plume brings the hot vaporized material from the target to a critical state by a process known as supercooling (cooling below the freezing point). Supercooling causes the vaporized material inside the plume to saturate and then form nuclei. The critical vapor within the plume (Figure ??) becomes supersaturated, leading to nanoparticle formation via condensation of nuclei. It has been shown by several researchers that nanoparticles bond together linearly and form similar structures to the fibers in nanoparticle aggregates [??] obtained by our experiments. The fundamental parts of the creation and evolution of the plume are shown in figure ??. During condensation stage primarily formed nanoparticles may coalesce incompletely, which leads to formation of aggregates [ ], such as nanoparticle aggregates or nanofiber aggregates etc. Nanoparticle aggregates have the structure of web like material shown in Figures [ ]. At low pulse frequencies, in the range of KHz, condensates have a structure of spherical nanoparticles. Just after the condensation material that is still at an elevated temperature. The cooling process down to ambient temperature is very slow. This slow cooling process determines
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the physical structure of the condensates according to the pulse frequency that the target is subjected to.

4.3 A theoretical analysis of nanoparticle aggregate creation

It was found that the specific features of cluster formation within the expanding plume are related to dynamics of supercooling, which is affected simultaneously by plume expansion and release of heat of phase transition. This self consistent problem was first solved by Raizer[12] and it was shown that the degree of condensation, number and size of particles strongly depend on the velocity of the vapor expansion which, in turn, depends on the initial size of the vapor cloud, evaporated mass, and internal energy. Later this theory was generalized for non-uniform laser plasma conditions under low pressure conditions. This model is also of interest in the ablation at higher pressure, because directly after the laser pulse, the influence of the surrounding atmosphere can be neglected due to the fact that the pressure ahead of the shock wave can be neglected in comparison with the pressure behind the shock wave. The plasma expansion model, which has been used in the low pressure case, is based on particular solution of gas dynamic equations. The description of the expanding plasma as a self-similar blastwave disregards phenomena as the transition from the free-flight to the shock
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wave regime, the internal homogenization of the plasma due to internal rarefaction waves, and the mixing between plume material and ambient atmosphere. Measurements show that for typical analytical conditions the model gives a reasonable description of the hydrodynamic expansion of the shock at later stages. Other possible models exist which are more precise regarding the external expansion dynamics. However, they lack the internal shock wave structure, which changes considerably the density and temperature distribution in the plume. Especially, the internal density distribution of ablated material must be taken into account as will be shown later. Subsequently, after the shock wave fades away the motion of particles are governed by diffusion.

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Chapter 5
5.1 Raizer-Zeldovich theory of hydrodynamics (RZ theory)

Figure [ ]. Simulation by Monte-Carlo method of the region on the right.

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Figure [ ] simulation of heat dissipation in laser ablation

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The hydrodynamic expansion of the plume is separated into two distinctive regimes. Shortly after the laser pulse, when the internal energy is high enough to dominate the expansion process, it is described by free flight expansion. During this early period the ambient atmosphere does not influence the dynamics. The later expansion, when the shock wave has fully developed can be described as a strong explosion. The two regimes are clearly distinguish-able by the given criterion.

[mass in the plume] = [ mass in the external shock wave]

An intermediate transitional regime is not considered. In the following, it will be shown that during the free flight regime of the plasma nucleation and condensation takes place and is practically terminated at the end of the free flight period. The following period, described by shock wave expansion is
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dominated by coalescence of previously condensed particles. It is this correlation of free flight and shock wave expansion with nucleation, condensation and coalescence, respectively, which makes the problem analytically possible. In our analysis, M is the total vapor mass, E is the initial internal vapor energy, R0 is the initial plume radius, and our is the initial velocity of vapor expansion. The main supposition required for the subsequent analysis is that the liquid droplets will be thought to be moving together with the vapor. Initially, the vapor expansion proceeds along the Poisson adiabat with :
PV =

const.
by the Clausius-

During expansion the vapor cools and comes into the saturation (the Poisson adiabat crosses the saturation adiabat defined

Clapeyron equation). The condensation sets in from this point in time. The corresp-onding temperature is defined as Tc.

Figure : P-V diagram with the Causius-Clapeyron equation

64

To calculate the time at which nuclei are ejected into the vapor, the nucleation time te, it is assumed that the plasma follows Poisson adiabat. Then, the degree of supercooling is calculated as the difference between the temperature along the one-phase and the two-phase adiabat until the nuclei are ejected. The supercooling reaches it maximum at (d/dt)t=te =0

Based on this criterion an equation determining te can be found. The rate of nucleation is taken along the Poisson adiabat. To solve the self-consistent equations the condensation x(t) has to be given. It can be written as : x(t) = (t).g(t) Condensation rate dx/dt

the first term describes the change of condensation due to the formation of

nuclei, while the second one describes the change of condensation caused by cluster growth. Based on nucleation theory the rate of nucleation can be written as [ ]
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Nucleation rate - d/dt

To look at the formation of nanofibers we have to look at the nucleation rate d/dt. The behavior of the nucleation rate is an extreme sharp function of supercooling and is proportional to [12 ] :

exp[ - (T/T)(1/2)]
In the case of Silicon and Graphite, a theoretical plot for nucleation tion time is graphed using Excel :

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Figure [ ]. Results pertain to the plume center. Repetition rate is in s. These results are further substantiated by S.Anisimisov et al.
1 = 1 . exp 2 = 2 .
3

Eqn 1

= 16

2 3k B 3 qL

= (Teq T)/ Teq = 16 3 2 3 3

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Figure : Numerically integrated Eqn 1. By Animisov et al. that gives close values for the time of steep nucleation rate as in Figure. It can be also seen that Teq cally where the adiabat in the P-V diagram in Figure [ ] happens to touch the Causius-Clapeyron equation at the same time.

L = Density of liquid material M = Molecular weight x = Degree of condensation kB = Boltzmann constant q = Heat of vaporization = Surface tension

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Supercooling Parameter

Cluster dimension variation

Vapor condensation

Number of atoms in a cluster

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Silicon nanoparticle aggregates 2 MHz

Silicon nanoparticle aggregates 4 MHz

Silicon nanoparticle aggregates 13 MHz

Figure [ ]. Silicon nanoparticle aggregate growth with laser pulse frequency

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Graphite nanoparticle aggregates at 1 MHz

Graphite nanoparticle aggregates at 4 MHz

Graphite nanoparticle aggregates at 13 MHz

Figure[ ]. Graphite nanoparticle aggregate growth with laser pulse frequency

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5.3 Experimental proof of RZ theory using laser ablation

Since we are only interested in finding the minimum repetition rate to form nanoparticle aggregates for Graphite and Silicon for beginning nucleation, we analyze only the time parameter of equation[1]. Theoretically we can see that the corresponding time where nucleation reaches its maximum can be graphically represented Figure[9]. By separating the exponential part of the equation we have. 1 exp 2 The figure ?? shows that nucleation starts just above 0.65s for Silicon. This critical time to nucleation corresponds to a laser pulse frequency of 1.53MHz, which agrees well with our experimental observations where the silicon nanoparticle aggregates start to form at the pulse frequency of 2 MHz. The calculation also shows that Graphite has a longer critical time of 1.11 s, which is longer than that of Silicons. If the critical time to nucleation is the time to make minimum aggregations of the target material, pulse frequency at which Graphite nanoparticles starts to aggregate should be lower than that of Silicons. Again, the experimental results on graphite target support this hypothesis and agree with the RZ theory.

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Pulse frequency has a significant effect in creating nanofiber aggregates and keeping them continually forming. For high pulse frequencies, ablation from consecutive pulses happen before the material on the surface of the target cools down. Therefore the material that is ejected by a new pulse can have its ablated material condense (or bond) with the ablated material from the previous pulse which is still at a very high temperature. This is a possible explanation for how the nanoparticle structures are built dense and vertically in Figures [3,4]. In our research, we measured the critical times required to form nanoparticle aggregates for Graphite and Silicon experimentally. We have elaborated how our experimental measurements for both materials agreed well with those predicted by RZ theory. Although the RZ theory has been previously supported experimentally by a few other researchers using particle sizes and atomic front velocity etc., there is no definitive evidence that gives strong experimental results to support the theory. One of the most important features of this theory is the ability to predict the critical time for nucleation. We showed how this important theoretical parameter (time for nucleation during phase transformation) agreed with experiment. Therefore, experimental evidence have shown that Raizer-Zeldovich theory has been proven for the first time at its most fundamental level in terms of time scale to a phase transition.
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The initial value of the density is denoted by start . The equation for growth of clusters can be written under the assumptions of kinetically controlled regime, temperature equilibrium between gas and droplet, and accommodation coefficient equal to unity. These considerations give : Nucleus growth rate [from 59] - dg/dt

Here jd, je are fluxes of deposition and evaporation of atoms.

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5.3.1 After nucleation has taken place

The further condensation is governed by the two-phase adiabat. Under equilibrium condition and slow expansion the system should start to condensate a temperature Tc and follow the adiabat for a two-phase system (liquid + vapor) as it was given by Zeldovich and Raizer.[ ]

During condensation the latent heat of evaporation is released. The vapor temperature is therefore determined by the competition of two effects: The cooling related to the plume expansion, and the heating due to vapor condensation. Following Raizer [ ], the corresponding equation can be written in the adiabatic approximation proceeding from the local energy balance in the two-phase vapor liquid system. We now define the degree of vapor

75

condensation x, as the ratio between the number of molecules in the liquid and the total number of molecules. Then, the adiabatic approximation leads to the equation. The numerically solved equation can be seen in Figure :

and the plume expansion. Here, a distinction must be made between a

temporal period which is approximated by the vacuum expansion [ ]

and a later stage determined by the shock wave model [59]The explicit calculations show that this is possible and physically meaningful. Even more, it is verified that particle growth due to condensation is practically finished after the free flight expansion stage. [Anisimov 12, Hergenroder 59]
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Chapter 6.
6.1 Physical properties of nanoparticle aggregates The principal parameters of nanoparticles are their shape (including aspect ratios where appropriate), size, and the morphological sub-structure of the substance. Nanoparticles are presented as an aerosol (mostly solid or liquid phase in air), a suspension (mostly solid in liquids) or an emulsion (two liquid phases). In the presence of chemical agents (surfactants), the surface and interfacial properties may be modified. Indirectly such agents can stabilize against coagulation or aggregation by conserving particle charge and by modifying the outmost layer of the particle. Depending on the growth history and the lifetime of a nanoparticle, very complex compositions, possibly with complex mixtures of adsorbents, have to be expected. In the typical history of a combustion nanoparticle, for example, many different agents are prone to condensation on the particle while it cools down and is exposed to different ambient atmospheres. Complex surface chemical processes are to be expected and have been identified only for a small number of
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particulate model systems. At the nanoparticle - liquid interface, polyelectrolytes have been utilized to modify surface properties and the interactions between particles and their environment. They have been used in a wide range of technologies, including adhesion, lubrication, stabilization, and controlled flocculation of colloidal dispersions (Liufu et al 2004). At some point between the Angstrom level and the micrometer scale, the simple picture of a nanoparticle as a ball or droplet changes. Both physical and chemical properties are derived from atomic and molecular origin in a complex way. For example the electronic and optical properties and the chemical reactivity of small clusters are completely different from the better known property of each component in the bulk or at extended surfaces. Complex quantum mechanical models are required to predict the evolution of such properties with particle size, and typically very well defined conditions are needed to compare experiments and theoretical predictions.

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6.1.2 Nanoparticle Interaction and bonding At the nanoscale, particle-particle interactions are either dominated by weak Van der Waals forces, stronger polar and electrostatic interactions or covalent interactions. Depending on the viscosity and polarisability of the fluid, particle aggregation is determined by the interparticle interaction. By the modification of the surface layer, the tendency of a colloid to coagulate can be enhanced or hindered. For nanoparticles suspended in air, charges can be accumulated by physical processes such as glow discharge or photoemission. In liquids, particle charge can be stabilised by electrochemical processes at surfaces. The details of nanoparticle nanoparticle interaction forces and nanoparticle fluid interactions are of key importance to describe physical and chemical processes, and the temporal evolution of free nanoparticles. They remain difficult to characterise due to the small amount of molecules involved in the surface active layer. Both surface energy, charge and solvation are
79

relevant parameters to be considered. Due to the crucial role of the nanoparticle nanoparticle interaction and the nanoparticle fluid interaction, the term free nanoparticle can be easily misunderstood. The interaction forces, either attractive or repulsive, crucially determine the fate of individual and collective nanoparticles. This interaction between nanoparticles resulting in aggregates and/or agglomerates may influence on their behaviour. In gas suspensions, aggregation is crucially determined by the size and diffusion, and coagulation typically occurs faster than in the liquid phase as the sticking coefficient is closer to unity than in liquids.

6.3 Variation of nanoparticle sizes with pulse frequency

Crystal nucleation has been studied extensively by many researchers, yet the rate of crystal nucleation and the distribution of sizes is exceedingly difficult to predict. According to semi-classical nucleation theory, the total free energy cost to form a spherical radial distribution of nanoparticles is given by [Ref 2, Anisimov et al]. The initial radii of the nanoparticles after condensation following the vacuum expansion is given by the equation [a] derived in [Ref.25,

80

Hergenroeder]. Here g(t) is the number of particles in a cluster given as a function of time. The numerical values for g(t) has been used from 4 to 180 Reference [27]. Using equation [a] the individual thicknesses of nanoparticles can be calculated and compared with experimental results as in Figure [5]. Equation[a] gives average fragment sizes of 50-550 nm for the typical lattice temperature attained during femtosecond laser irradiation. It is possible to prove that the theoretical sizes predicted by equation [a], closely agree with the measured experimental values Figure [5].

(Density) x (Vol. of a cluster) = (Num. of clusters) x (Weight of a single cluster)

4 3 = 3

: ()

3 j = . . / 4 L

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Figure [6] Variation of particle width against pulse frequency The following methodology has been used to measure the widths of the nanowires.

Figure [?] Measuring width : Nanoparticles are connected together to build nanoparticle aggregates (as beads above). To measure the thickness of the

nanoparticle aggregates, the thickness of several locations are measured and then averaged.
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Nanoparticles are connected together to build nanoparticle aggregates (as beads above). To measure the thickness of the nanoparticle aggregates, the thickness of several locations are measured and then averaged.

2MHz repetition rate (diameter 540 nm)

4MHz repetition rate (diameter 370 nm)

8MHz pulse frequency (diameter 130 nm)

13MHz pulse frequency (diameter 50 nm)

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13MHz X20,000

13MHz pulse frequency

(measuring 50 nm diameter) Figure[ ] Effect of increasing repetition rate on Si.

It was observed that the 3D fractal nanoparticle aggregates from 2MHz until 13 MHz. According to the experimental data, the average thickness, decreases with increasing pulse frequency.

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6.3.2 Size variation due to changing pulse pulse widths

Effect of laser pulse-width on nanoparticle size.

13MHz - 300fs 70nm (width)

13MHz - 600fs 140nm (width)

13MHz - 1000fs 180nm (width)

13MHz - 5000fs 220nm (width)

Figure [ ] In pictures above we show the effects on our Silicon sample due to the pulse-width of the laser while keeping a constant pulse frequency of 13MHz.

85

Figure[ ] Variation of particle size with pulse-width

For longer pulse-widths, energy is transferred to the lattice in longer times. Lower energy would result in lower vibrational frequencies transferred to the lattice and to the ablated Silicon vapor. This would result in larger elements being created in the plume as their feature size is inversely proportional to energy absorbed. This can be confirmed by applying de Broglies law of wave-particle duality to Planks law of radiation. Low pulse-width is associated with higher amount of energy being delivered by the pulses to the lattice which makes the lattice vibrate at a higher frequency. The size of the ablated material would be

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proportional to the lattice vibrational frequency 1/ . The above graph, which has been drawn with experimental data summarizes these postulates.

() = .

(Planks Law)

If

1 < 2 ( )

1 < 2

(small particle sizes) 2 < 1 (large particle sizes)

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7.1 Magnetic Field Controlled Nanofiber Generation

ABSTRACT

It is important to manipulate the density of nanoparticles on a substrate subjected to laser ablation. In this paper we have summarized our approach for changing the projected paths of nanoparticles by using a static magnetic field. This enables us to change the concentration of nanoparticles diverted into specific areas which also enable us to control their density and their self assembly into nanofibers on the substrate. The concentration of nanoparticles can also be redirected towards a magnetic lens (a quadrapole lens) and use them in various other applications. We experimentally showed that the nanoparticle aggregates were concentrated at locations consistent with Lorentz force. We have also explained this phenomenon with a modern approach that gives more accurate estimate for the direction of nanoparticles and where these nanoparticles would create nanofibers. Therefore our findings can be used to understand how nanoparticles react under the influence of magnetic fields from a modern perspective and control their growth in designated areas of a two dimensional substrate.

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7.1 Nanoparticle production in Magnetic fields

Nanoparticles have attracted much interest in the nanotechnology applications due to their huge potentials in medicine and new engineering materials. Several methods have been developed to generate nanoparticles in large quantities, among which laser ablation is desired because of simplicity in configuration and short process time. Recently, femtosecond laser ablation has been investigated for nanoparticle generation and it was observed that the nanoparticles generated by femtosecond laser ablation presents unique characteristics, compared to nanoparticles that are generated with conventional long pulsed lasers. The differences in ablation characteristics among femtosecond, picosecond and nanosecond lasers are discussed in detail in the reference [1]. Our recent research revealed that fibrous nanoparticle aggregates can be created by laser ablation of a target material in ambient atmosphere at room temperature [2] with femtosecond laser ablation.

EXPERIMENTAL SETUP We used a femtosecond laser capable of producing variable pulse widths and pulse frequency. The laser source is an all-diode-pumped, direct-diode pumped Ybdoped fiber oscillator and amplifier system capable of producing variable pulse energies up to 10 mJ at a pulse frequency between 200 kHz and 25 MHz. Average
89

power varies between 0-20W. The samples obtained were characterized using scanning electrical microscopy (SEM, TEM and Raman Spectroscopy). In the current analysis for this paper our SEM results provided a wider aerial view of the ablated substrate which gave us enough information for characterization.

Figure [1] : Setup for investigating the magnetic effects on the sample.

EXPERIMENTAL RESULTS We observed that the formation of nanoparticle aggregates in Silicon were deviated to either the left or the right half around the ablated area if the magnetic field is directed upward or downward shows a clear difference between the two sides. When the Lorentz force law is applied to Figure[2], the higher concentration on the substrate depended on the direction of velocity of the plasma and the magnetic field.

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(a)

(b) Figure [2] : Femtosecond laser ablation under the influence of magnetic field. Large amounts of fibrous nanostructures were observed, as shown in Figure [2] left hand side. (b) Femtosecond laser ablation without the influence of magnetic field. Fibrous structures have formed uniformly.

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The asymmetric result seen in figure 2 can be explained using a classical viewpoint. The Lorentz force can be written as F = +nq (V X B) where v is the velocity toward the top of the page. Where V is the upward velocity of the plume, perpendicular to the substrate. Taken the vector product with B (towards top of the page as in Figures 2 and 3) gives the force F to the left for a single ion in the plasma. The outward ejection pattern of nanoparticles are further evident when the ablated points are zoomed outward as below in Figure [3].

Figure [3] : Influence of the magnetic field on nanoparticle direction. The same test was repeated many times to confirm that the deviated particles to the top occurred as a result of non other than the magnetic field.

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Discussion Basic phenomenology of bulk magnetism By using quantum mechanics, it is possible to explain how magnetic fields can control nanofiber generation through crystal-field interaction, exchange interaction and spin-orbit coupling [ ]. When a material is exposed to a magnetic field H, a magnetization M = H is induced. The susceptibility , defining the response of the system, depends on the nature of the atoms and in the environment to which they are exposed to. In order to explain in a qualitative way the magnetic behavior of matter, it is sufficient, in first approximation, to treat each atom as a single, independent magnetic dipole. This dipole can be intrinsic (as in metals at room temperature), and it can be induced by the external field H. If the atoms do not possess a magnetic moment, the effect of an applied magnetic field will be the generation of an induced moment with opposite orientation. In this Larmor case diamagnetism occurs. This effect is encountered in every material. However due to its small absolute value, it is often hidden by other stronger magnetic responses and it is observable only in those materials in which all electronic shells are filled. The diamagnetic susceptibility is negative and of the order of 105. If the atoms consists of intrinsic magnetic moments, they will be randomly oriented if H = 0, but they will align when an external field is applied.
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This paramagnetic response will be positive and much stronger ( 1/1000 ) with respect to the diamagnetic component. The magnetization from a small field H to absolute temperature T ratio is given by the susceptibility, described by Curies law :

Finally, if the intrinsic magnetic moments interact with each other, their energy is minimized for parallel (ferromagnet) or antiparallel (antiferromagnet) alignment. However, in the ferromagnetic case a complete alignment of all magnetic moments would produce too high a total magnetostatic energy for it to be the equilibrium configuration. As a consequence, magnetic domains are created: in each domain all moments are rigidly coupled but different domains can be oriented in different directions. The total magnetization can thus average zero. When a magnetic field is applied, in each domain, all moments start to align parallel to it until a saturation magnetization Ms, is obtained. Until now, an assumption has been made that every atom behaves as if it were isolated. This condition is not satisfied in metals, where the conduction electrons are delocalized over the whole crystal. The origin of magnetic behavior in this case is more complex and strongly related to the quantum mechanical features of the constituent atoms. In order to understand the development of
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magnetism in bulk metals, it is, necessary to understand the origin of the atomic magnetic moment.

7.2 The origin of atomic magnetic moment First let us look at the origin of magnetism in bulk matter, first let us look at the formation of magnetic moments in atoms. Let us consider an atom in a homogeneous magnetic field H described by a vector potential A [where A = -1/2 (r H)]. The Hamiltonian for the Z electrons, each having an intrinsic spin magnetic moment m = 2B s and a momentum l, is :

Where all the terms containing the magnetic field have been grouped in H ( 1 ), that can be treated as a perturbation of H ( 0 ). Hence the energy of the ground state, in 2nd order perturbation theory:

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Magnetic term Where the first term represents the paramagnetic response and is five orders of magnitude greater then the following ones that are the diamagnetic and the van Vleck paramagnetic term respectively. These two terms describe the magnetic polarization induced by the magnetic field and give no contribution to the permanent magnetic moment. Consequently the magnetic moment of the atom can be written as:

[A] This result shows that in order for the magnetic moment of an atom to be zero, both the total angular momentum L and the total spin S need to vanish. We can conclude that only those atoms for which all the l-sub-shells are filled with 2(2l +
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1) electrons, do not carry a magnetic moment, and this condition is fulfilled for very few elements of the periodic table. A unit volume has an energy of :

[B] The force on a unit volume is :

[C]

7.2.1. Magnetism in Clusters We have reviewed the basic concepts of atomic and bulk magnetism. However the system under study does not belong to either of these two classes. When the characteristic lengths of a magnetic system are reduced to the nanometric scale, both extrinsic and intrinsic properties are affected and, furthermore, surface and finite size effects need to be considered. A comprehensive discussion of all the phenomena that originate from reducing the dimension and the dimensionality of a magnet is beyond the scope of this paper. The fact that magnetism, as other cluster properties (cf. section 2), is very sensitive to the geometrical arrangement has the consequence that every atom will give, depending on the number and distance of its nearest neighbors, a different
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contribution to the total magnetic moment. The atomic magnetic moment is in fact determined by the spin orbit coupling and the contribution that each atom will give to the total moment will be determined by its coordination number. This topic will be discussed further since super-paramagnetism is the starting point for the interpretation of the magnetic behavior of cluster assembled materials

Figure [4] (a) Langevin Function describing the magnetization (b) Equivalent of a double well potential function. Higher the energy of the nanoparticle ensemble more chaotic is the system. Lower energies become stable and magnetic moments uni-directional.

Superparamagnetism In a cluster every atom has a magnetic moment of the order of B and all atomic moments are aligned, giving rise to a total magnetic moment . Because of quantization, the projection of along a fixed arbitrary direction, can assume only discrete values but, if is sufficiently big, these values can be considered
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continuous and a semiclassical treatment is justified. The cluster magnetic moment can, in this approximation, point in any direction of space. Let us now consider an ensemble of identical particles; the total magnetization of the system M, is given by the vectorial sum of all single magnetic moments. As for the atomic magnetic moments in a paramagnet, the average magnetization will be zero in the absence of magnetic field since all magnetic moments are randomly directed in space. When a magnetic field H is applied, the magnetic moments will orient in the direction of the field and give rise to a net magnetization. The Hamiltonian of a single macro-spin can then be written as : H = Hcos where is the angle between the magnetic moment and the axis of the magnetic field, that is assumed to be z. The total magnetization can be found averaging over the ensemble: 7.3 On the substrate How do we control the direction of nanoparticles?

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The nanoparticles move in the direction where the paramagnetization potential energy given by equation [B] is minimized. It can be seen from Figure [2] that nanoparticles travelled perpendicular to the direction of the magnetic field. Since MH = MH Cos ) when M is Perpendicular to H ( ~ /2 and gives a minimum value for U. This reasoning explains why the nanoparticle would travel in the direction where the force is minimized for the same conditions. It can be seen from the equation below that increasing flux of the magnetic field H will increase the Paramagnetic potential energy U.

Or in other words the location of the nanoparticles can be expressed as moving in a two dimensional coordinate system as below in Figure [5]. It was explained before in Figure [1] that the most stable direction for nanoparticles to have unidirectional magnetic moments, Figure [4]. In the above equation M is the magnetization of a nanoparticle and H is the magnetic field through the ablated plasma. And the force on a unit volume of nanoparticles is given by :
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Figure [5] : The Nanoparticle will travel in the direction where the force is minimized in the Paramagnetization potential energy contour diagram.

The Fundamental Theorem of Calculus for line integrals implies that if U[x,y] can be defined in the following way, Fi [x,y] = - U [x,y] So that U[x,y] is a scalar potential of the conservative force vector Fi [x,y] for the ith nanoparticle. In our case U[x,y] is defined as a Paramagnetic potential function that depends entirely on the applied static magnetic field and the Magnetization vector. By manipulating M given by Eqn[A] , the magnetization direction and H it is possible to find a far more accurate estimation of force F than that given by the Lorentz Force F= +nq (V X B).
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Figure [6] Simulations that predict the trajectory of nanoparticles (a)..(b). (c) Potential graph and the nanoparticle trajectories (d) Formation of fibers in the highest negative change in the potential function.

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Conclusion : In our research we proved how the Raizer-Zeldovich theory (RZ theory) for plasma hydrodynamics could explain the femtosecond laser ablation results we obtained experimentally for producing nanofibers. The nanofibers we produced had a unique texture compared to what other researchers previously obtained. As far as we know no other researchers used the

repetition rate of the femtosecond laser to provide experiment support for the RZ theory. Since most researchers use low repetition rate femtosecond lasers, they have not seen the phenomenon of nanofibers. Through our research we mainly focused on manipulating the direction of the nanoparticles and understanding what parameters control their direction. The material manipulation was done while the vaporized material was still at a plasma stage. Since crystallization occurs after condensation of plasma [68], we believe that the nanoparticle crystals are arranged according to some Si paramagnetization [69] to make nanofibers. This enhancement effect in chosen locations by laser ablation along with the magnetic field gives us the ability to control their growth and collect them for other applications such as in nanoelectronics, nano-device fabrication and many other areas mentioned in Chapter 1.

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Author : Sid Senadheera

sid.senadheera@gmail.com

Chapter 8
Quantum Mechanical and Gravitational Effects on a Nanoparticle
Gravitational effects on a nanoparticle has been combined with the Hamiltonian for second order perturbations in the Schrodinger wave equation in quantum mechanics. The stress energy tensor in the Einstein field equations is added as a perturbation on top of the well known Newtonian gravitational potential function. The experimental proof for the theory can be showing the masses of the particles are quantized according to De Broglie hypothesis. And the magnitude of the energy in quantization change according to the theoretically derived result in this work.

Theory : First let us look at the formation of magnetic moments in atoms. Let us consider an atom in a homogeneous magnetic field H described by a vector

potential A [where A = -1/2 (r H)]. The Hamiltonian for the Z electrons, each having an intrinsic spin magnetic moment m = 2B s and a momentum l, is :

Where all the terms containing the magnetic field have been grouped in H (1), that can be treated as a perturbation of H (0). The nanoparticles in this case deviated from their paths due to para-

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magnetism. Therefore the paramagnetic term is isolated E(p) excluding all other terms. The analysis of particle in a field in the Stern Gerlarch experiment can be similarly carried out.

The energy and force on a particle by a gravitational field will have a similar derivation. In this case the Newtonian gravitational potential (used as U = mgz) has a perturbation term in the energy by the Einsteins stress energy tensor Tt,x,y,z.

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Particle in a Gravitational Field. Pages (1-6 with topics that mention [REVISED]) gives a brief introduction to Tensors, Gravitation and Stress Energy Tensor that gives the energy in a unit volume of space.
Particle Energy derived by Geodesic Deviations [REVISED] The Einstein field equations (EFE) or Einstein's equations are a set of ten equations in Einstein's theory of general relativity which describe the fundamental interaction of gravitation as a result of spacetime being curved by matter and energy. First published by Albert Einstein in 1915 as a tensor equation, the EFE equate spacetime curvature (expressed by the Einstein tensor G
t,x,y,z.)

with the energy and momentum within that spacetime (expressed by the stress-energy

tensor Tt,x,y,z ).

Here we are mostly interested in the Tt,x,y,z tensor. For simplicity we are expressing this tensor in Cartesian coordinates, although it has to be expressed in spherical coordinates. In gravitation, energy is in the curvature of space-time. The relationship between the metric tensor and the Einstein tensor allows the EFE to be written as a set of non-linear partial differential equations when used in this way. The solutions of the EFE are the components of the metric tensor. The trajectories of particles and radiation (geodesics) in the resulting geometry are then calculated using the geodesic equation.

The metric tensor

can be solved by the above equation, which would result in.

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Physicists usually work in local coordinates (i.e. coordinates defined on some local patch of M). In local coordinates x (where is an index which runs from 0 to 3) the metric can be written in the form

The factors dx are one-form gradients of the scalar coordinate fields x. The metric is thus a linear combination of tensor products of one-form gradients of coordinates. The

coefficients g are a set of 16 real-valued functions (since the tensor g is actually a tensor field defined at all points of a space-time manifold). In order for the metric to be symmetric we must have

giving 10 independent coefficients. If we denote the symmetric tensor product by juxtaposition (so that dxdx = dxdx) we can write the metric in the form

If the local coordinates are specified, or understood from context, the metric can be written as a 44 symmetric matrix with entries g. The nondegeneracy of g means that this matrix is nonsingular (i.e. has non-vanishing determinant), while the Lorentzian signature of g implies that the matrix has one negative and three positive eigenvalues.

Curvature [Revised]
The metric g completely determines the curvature of spacetime. According to the fundamental theorem of Riemannian geometry, there is a unique connection on any Lorentzian manifold that is compatible with the metric and torsion-free. This connection is called the LeviCivita connection. The Christoffel symbols of this connection are given in terms of partial derivatives of the metric in local coordinates x by the formula

. The curvature of spacetime is then given by the Riemann curvature tensor which is defined in terms of the Levi-Civita connection . In local coordinates this tensor is given by:

The curvature is then expressible purely in terms of the metric g and its derivatives.

Einstein's equations [Revised]

One of the core ideas of general relativity is that the metric (and the associated geometry of spacetime) is determined by the matter and energy content of spacetime. Einstein's field equations:

Where :

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relate the metric (and the associated curvature tensors) to the stress-energy tensor T. This tensor equation is a complicated set of nonlinear partial differential equations for the metric components. Exact solutions of Einstein's field equations are very difficult to find.

Introductory Quantum Mechanics : In Three Dimensions and Four Dimensions To extend the discussion to more than one dimension is easy. The potential energy becomes U(x,y,z) and we add partial derivatives with respect to y and z. The S-E then becomes

There is a corresponding change in the TISE. The set of derivatives in ( ) above is usually denoted by a special symbol:

The normalization condition becomes

Of course, coordinate systems other than Cartesian can be used. For central force problems (such as the hydrogen atom) it is better to use spherical coordinates.

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Evidence for Quantized Gravitational States of the Neutron

Main Reference : T. J. Bowles, "Quantum effects of gravity," Nature 415 267-268 (2002). Particle confinement and the wave-like properties of matter lead, according to quantum mechanical principles, to self-interference which is the origin of energy quantization. The particle-in-a-box problem is used in introductory quantum mechanics courses to illustrate this fundamental quantum effect. Terrestrial objects are confined by the Earth's gravitational field, but the quantum effects of gravity are not observed in the macro-world because the gravitational interaction is weak. Thus, the gravitational energy levels are very closely spaced and for all practical purposes form a continuum. In spite of the lack of evidence for quantized gravitational energy levels, the "quantum bouncer" has been a favorite example in the repertoire of solvable one-dimensional problems for those who teach quantum chemistry and quantum physics. Schrdinger's equation for the quantum bouncer near the surface of the Earth is,

where the particle is confined by the impenetrable potential barrier of the Earth's surface (V = ) and the attractive gravitational interaction (V = mgz for z > 0).

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The energy eigenvalues for the quantum bouncer are (1,2,3),

where ai are the roots of the Airy function. The first five roots are 2.33810, 4.08794, 5.52055, 6.78670, and 7.94413. The associated eigenfunctions are,

where

Because there is no analytical expression for the eigenfunctions each one must be normalized using a numeric algorithm. Very recently an international team at the Institute Laue-Langevin in Grenoble France lead by V. Nesvizhevsky (4) published evidence for the quantized gravitational states of the neutron. To read a short summary of this experiment in Nature Magazine by Thomas Bowles (5) click here. Another summary has just been published in Physics Today. (6) To appreciate the significance of this accomplishment we calculate the neutron's ground state energy and wave function in the Earth's gravitational field using the equations above. The mass of the neutron is 1.675x10-27 kg which yields a ground-state energy of E1 = 2.254x10-31 J. This

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corresponds to a classical vertical velocity of 1.6 cm/s. Thus gravitational confinement requires a source of ultra-cold neutrons (UCNs). Furthermore, the energy of the first excited state is 3.941x10-31 J, so the energy difference between the ground state and the first excited state is equivalent to photon with a wavelength of 1.2x106 m. Clearly traditional spectroscopic methods cannot be used to establish the existence of quantized gravitational states for the neutron. The probability distributions, Y(z)2, for the ground and first excited states are shown in Figures 1 and 4. They hold the key to the experimental design that Nesvizhevsky's and his group used to establish that the neutron's gravitational states are quantized. To down-load a Mathcad file that will generate the neutron eigenstates numerically click here.

Figure 1 A schematic of the experiment that Nesvizhevsky's team used to gather evidence for quantized neutron gravitational states is shown in Figure 2. The neutron is confined by the attractive

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gravitational field and the repulsive reflecting mirror surface. Ultra-cold neutrons (UCNs) with total velocities less than 8 m/s are "lobbed" into the apparatus. In the vertical direction the neutrons are subject to the gravitational interaction with the Earth, but there are no forces in the horizontal direction. The vertical and horizontal degrees of freedom are independent of one another in the design of this experiment, because care has been taken to eliminate vibrations, and extraneous electric and magnetic fields.

Figure 2 [ Nature (Volume 415 page 267) copyright 2002 Macmillan Publishers Ltd.]

The apparatus shown in Figure 2 records neutron throughput as a function of absorber height. The data collected are shown in Figure 3. The shaded circles are the actual data points. We will not be concerned with the solid, dashed, or dotted lines in the figure. The most important feature of the data for this analysis is the sharp increase in neutron throughput at about 20 mm.

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Figure 3 [ Nature (Volume 415 page 299) copyright 2002 Macmillan Publishers Ltd.] The argument will be made that the neutron wave function shown in Figure 1 is consistent with the data presented in Figure 3. To demonstrate this we calculate the probability that the groundstate neutron will be found in the absorber for a variety of absorber heights. This requires numerical evaluation of

where az is the absorber height. These calculations are presented in the table given below. Probability Absorber in height/mm Absorber

10

0.380

15

0.089

20

0.012

25

0.001

It is clear from these calculations and Figure 1 that the probability of finding the neutron in the absorber falls off sharply at about 20 mm. This analysis, therefore, is consistent with the sharp increase in neutron throughput at this absorber height.

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Many neutron gravitational states besides the ground state are occupied and it is therefore necessary to explore the experimental implications of this fact. The first excited state is, as mentioned previously, shown in Figure 4. This wave function extends further in the z-direction than the ground state function, going to zero around 35 mm. The experimental significance of this is that the neutron throughput should show another abrupt increase in the neighborhood of 30 mm, an absorber height for which, the first excited state neutrons have a low probability of being absorbed. This phenomena should be repeated for all other occupied excited states as the absorber reaches the spatial extent of each excited state wave function.

Figure 4 With regard to this expected effect Bowles has commented (5) The data show some hint of stepped increases at the values corresponding to higher energy states, consistent with the existence of these states, but they are not yet conclusive. Nonetheless, the evidence for the existence of the first energy state is convincing and confirms that a quantum

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effect occurs in the gravitational trap. The difficulty of this measurement should not be underestimated. The researchers are measuring a quantum effect caused by gravity that requires a resolution of 10-15 eV. Interactions of the neutrons with other fields would normally obscure such a tiny effect, but the neutron's lack of electric charge and the low kinetic energy of the UCNs make such observations possible. In summary, thanks to Nesvizhevsky and his team, we now have some direct evidence for quantized gravitational states. The "quantum bouncer", previously a purely academic exercise, can now be applied to a real-life example. Literature cited: 1. P. W. Langhoff, "Schrdinger particle in a gravitational well," Am. J. Phys. 39, 954-957 (1971). 2. R. L. Gibbs, "The quantum bouncer," Am. J. Phys. 43, 25-28 (1975). 3. J. Gea-Banacloche, "A quantum bouncing ball," Am. J. Phys. 67, 776-782 (1999). 4. V. Nesvizhevsky, et al., "Quantum states of neutrons in the Earth's gravitational field," Nature 415 297-299 (2002). 5. T. J. Bowles, "Quantum effects of gravity," Nature 415 267-268 (2002). 6. B. Schwartzchild, "Ultracold Neutrons Exhibit Quantum States in the Earth's Gravitational Field," Physics Today 55 (3) 20-23 (2002). 7. Experimental Evidence of particle - gravitational interaction http://physicsworld.com/cws/article/news/3525

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In the 4D case : The Schrodinger wave equation can be written as :

g is the metric tensor in spherical coordinates, usually takes the form around a massive object
e.g. Sun as Schwarzschild space-time geometry (below). The previous S-E equation, in 3D space treated space-time as uniform (with no curvature in space) and only the distance from the center of the earth to the particle was taken as the variable in the magnitude of gravitational potential energy. In the new derivation in 4D space a new variable is introduced to the gravitational potential as a perturbation. That is the amount of energy in a unit volume of space due to the curvature of space-time as below.

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Gives the path of an object (a neutron or a nanoparticle) in 4-D spacetime geometry related to the Einsteins Stress Energy Tensor Tt,x,y,z

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First and second order corrections for energy can be written as :

Only the following two components change if the mgz primary energy term is kept constant.

In vacuum, curvature due to mass (or energy) :

At lower energies quantization levels should come close together. The Force on a Nanoparticle in 4-D space can be written as : {where is defined here as the 4-D gradient}

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Taking the equation that gives energy from the perturbation, derived earlier :

If

As a first approximation

Where

In Schwarzschild geometry, which is appropriate for the sun, the above equation gives the variation of energy in a (nano)particle or a neutron due to the space-time curvature.

Metric Tensor is given by...

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Experimental Predictions
(1) Under highly controlled conditions measure the masses of a random sample of nanoparticles. The sample should have a discrete distribution of energies from the derived theory. Since the energy and mass are related by De Broglie equation, the sample of particles have discrete masses as the perturbation term varies in gravitational potential energy. (2) If the masses could be deviated as a mass spectrometer, a fringe pattern should result taking into account the following equation for deflecting forces. Since the energy of the particle is quantized, the deflecting forces on them are quantized as well.

Conclusion: It can be shown using general theory of relativity [GR] and 1st and 2nd order perturbation theory in Quantum mechanics, that nanoparticles have quantized energy levels while travelling on a geodesic [from GR] that has minimum gravitational potential energy. This would prove that nanoparticles cannot come in all sizes by the De Broglie hypothesis. Their sizes are restricted by quantization. Their increase of energy is not continuous but, discrete too. This also proves that the gravitation is quantized as well, where the particle is immersed. And space-time curvature is quantized too. This is an indirect proof for quantum-gravity. Several methods have been suggested to experimentally to prove the above theory.

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APPENDIX [A] Relaxation time of electrons (general definition) From : Sci-Tech Encyclopedia: The characteristic time for a distribution of electrons in a solid to approach or relax to equilibrium after a disturbance is removed. A familiar example is the property of electrical conductivity, in which an applied electric field generates an electron current which relaxes to an equilibrium zero current after the field is turned off. In the case of a femtosecond laser, electrons are displaced by thermal fluctuations. The conductivity of a material is directly proportional to this relaxation time; highly conductive materials have relatively long relaxation times. The closely related concept of a lifetime is the mean time that an electron will reside in a given quantum state before changing state as a result of collision with another particle or intrinsic excitation. This lifetime is related to equilibrium properties of the material, whereas the relaxation time relates to the thermal and electrical transport properties. The average distance that an electron travels before a collision is called the mean free path. Although typical collision times in metals are quite short (on the order of 1014s at room temperature), mean free paths range from about 100 atomic distances at room temperature to 106 atomic distances in pure metals near absolute zero temperature. Considering the very dense packing of atoms in a solid, these surprisingly long electron path lengths are analogous to the unlikely event that a rifle bullet might travel for miles through a dense forest without hitting a tree. The detailed explanation of the electron mean free path in metals is a major success of the modern
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theory of solids. A relaxation time appears in the simplest expression for the transport property of electrical conductivity, which states that the electrical conductivity equals the product of the relaxation time, the density of conduction electrons, and the square of the electron charge, divided by the electron effective mass in the solid. The conduction process is a steady-state balance between the accelerating force of an electric field and the decelerating friction of electron collisions which occur on the time scale of the relaxation time.

References (some numbers will change) 1. Laser Ablation for Materials Synthesis (MRS Symp. Proc., Vol. 191, Eds D C Paine, J C Bravman) (Pittsburgh, Pa.: Materials Res. Soc.,1990) 2. Laser Ablation: Mechanisms and Applications (Lecture Notes in Physics, Vol. 389, Eds J C Miller, R F Haglund, Jr.) (Berlin: Springer-Verlag, 1991) 3. Laser Ablation of Electronic Materials: Basic Mechanisms and Applications (Proc. European Materials Res., Vol. 4, Eds E Fogarassy, S Lazare) (Amsterdam: North-Holland, 1992) 4. Laser Ablation: Principles and Applications (Springer Series in Mater. Sci., Vol. 28, Ed. J C Miller) (Berlin: Springer-Verlag, 1994)

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14. Ba uerle D et al., in Excimer Lasers (NATO ASI Series, Ser. E, Vol. 265, Ed. L D Laude) (Dordrecht: Kluwer Academic Publ., 1994) p. 39 15. El'yashevich M A et al. ``Razrushenie metallov pod de stviem izlucheniya opticheskogo kvantovogo generatora'' (Breakdown of metals exposed to laser radiation) Report No. KE -14 (Minsk: Physics Institute, Belarussian SSR Academy of Sciences, 1963) 16. Anisimov S I et al. De|stvie Izlucheniya Bol'sho| Moshchnosti na Metally (Action of High-Power Radiation on Metals) (Eds A M Bonch-Bruevich, M A El'yashevich) (Moscow: Nauka, 1970); Action of High-Power Radiation on Metals (Springfield, V.A.: National Technical Information Service, 1971) 17. Ready J F Effects of High-Power Laser Radiation (New York: Academic Press, 1971) 18. Anisimov S I et al. Zh. Tekh. Fiz. 36 1273 (1966) 19. Anisimov S I Teplofiz. Vys. Temp. 6 110 (1968) 20. Lyubov B Ya, Sobol' E N, in De|stvie Kontsentrirovannykh Potokov Energii na Materialy (Action of Concentrated Energy Fluxes on Materials) (Ed. N N Rykalin) (Moscow: Nauka, 1985) p. 226
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30. Arnold N, Luk'yanchuk B, BityurinNAppl. Surf. Sci. 127, 129, 184 (1998) 31. Brunco D P et al. J. Appl. Phys. 72 4344 (1992) 32. Arnold N et al. Laser Phys. 8 47 (1998) 33. Arnold N et al. Proc. SPIE 3343 484 (1998) 39. Goetz T, StukeM Appl. Phys. A 64 539 (1997) 48. Wang X Y et al. Phys. Rev. B 50 8016 (1994) 49. Sun C-K et al. Phys. Rev. B 50 15337 (1994) 50. Groeneveld R H M, Sprik R, Lagendijk A Phys. Rev. B 51 11433 (1995) 51. Hohlfeld J et al. Appl. Phys. B 64 387 (1997) 52. Falkovsky L A, Mishchenko EGZh. Eksp. Teor. Fiz. 115 149 (1999) [JETP 88 84 (1999)] 53. Anisimov S I, Rethfeld B Izv. Ross. Akad. Nauk Ser. Fiz. 61 1642 (1997) 54. Gudde J et al. Appl. Surf. Sci. 127 129 40 (1998) 55. Wellershoff S-S et al. Appl. Phys. A 69 (Suppl.) S99 (1999) 56. Luk'yanchuk B S, Anisimov S I, Lu Y F Proc. SPIE 4423 141 (2001) 57. Rethfeld B et al. Appl. Phys. A 69 (Suppl.) S109 (1999) 58. Anisimov S I, Makshantsev B I, Barsukov A V Opt. Acoust. Rev. 1251 (1991) 59.R Hergenroder, Journal of Analytical Atomic Spectrometry [2006],1016, 21
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[67] B. S. Luk'yanchuk, W. Marine, S I. Anisimov, G. A. Simakina Condensation of vapor and nanoclusters formation within the vapor plume produced by nanosecond laser ablation of Si, Ge and C. Proc.SPIE 3618, 434 (1999) [68] B. Pivac, B. Rakvin, R. Boskovic, L. Pavesi Paramagnetic centers at and near the Si/SiOx interface in porous silicon Appl. Phys. Lett., Vol. 65, No. 25, (1994) [69] X.J.Wu, T.Q.Jia, F.L.Zhao, M.Huang, N.S.Xu, H.Kuroda and Z.Z.Xu "Formation mechanisms of uniform arrays of periodic nanoparticles and nanoripples on 6H-SiC crystal surface induced by femtosecond laser ablation" Applied Physics A: Materials Science & Processing, Volume 86, Number 4 (2007) [70] Min Seo, Dai Kim, Hyun Kim, and Sae Chae Jeoung Polarization-induced size control and ablation dynamics of Ge nanostructures formed by a femtosecond laser Optics Express, Vol. 14, Issue 8, pp. 3694-369 (2006) [71] D. Eversole, B. Lukyanchuk, A. Ben-yakar, Plasmonic laser nanoablation of silicon by the scattering of femtosecond pulses near gold nanospheres Appl.Phys.A89, 283291 (2007)

(Please note that these references have to be edited in correct order) 75. P.P. Pronko, S.K.Dutta,JSquier "Machining of Submicron Holes using Femtosecond laser at 800 nm Optics Communications 114, 106-110 (1995)

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[60] K. Venkatakrishnan and B. Tan Synthesis of Fibrous Nanostructures Using Ultrafast Laser Ablation under Ambient Condition and at Mega Hertz Pulse Frequency, Optics Express in press. [61]Chichkov B.N. et al. Femtosecond,Picosecond and nanosecond laser ablation of solids Applied Physics A. 63,109-115(1996) [62] J. D. Jackson, Classical Electrodynamics John Wiley, New York (Second Edition - 1975). [63] M. Vanzeeland et al., Production of Alfven waves by a rapidly expanding dense plasma, Phys. Rev. Lett., vol. 87, no. 105 001, (2001) [64] S. S. Harilal et al. "Fast Photography of a Laser Generated Plasma Expanding Across a Transverse Magnetic Field" IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 33, April (2005) [65] Hitz, B. Visualizing a laser's polarization Photonics Spectra, v 42, n 4, April, p 21-23 (2008) [66] Susumu Horita,a Hirokazu Kaki, and Kensuke Nishioka Surface modification of an amorphous Si thin film crystallized by a linearly polarized Nd:YAG pulse laser beam JOURNAL OF APPLIED PHYSICS 102, 013501 (2007)

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If the ith particle has a potential energy Ui then a collection of plasma made up of +ni ions would have the same localized potential energy. This +n i collection would move in the same direction as the other differential volume elements self

assembling similar to the above fundamental principle to reduce energy. The final result would be strands of nanofibers in a location controlled by the experiment.

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76. E. N. Glezer, M. Milosavljevic, L. Huang, R. J. Finlay, T. H. Her, J. P. Callan, and E. Mazur, "Threedimensional optical storage inside transparent materials," Optics Letters 21, 2023-2025 (1996). 77. K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, "Writing Waveguides in Glass with a Femtosecond Laser," Optics Letters 21, 1729-1731 (1996). 78. E. N. Glezer, and E. Mazur, "Ultrafast-laser driven micro-explosions in transparent materials," Applied Physics Letters 71, 882-884 (1997).

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The final equation from my PhD thesis is simplified to show that the shortest distance measurable in space is the Plank Wavelength and the corresponding is Plank Energy : This is a correct result that can be derived from the Heisenberg Uncertainty Principle as well. If the theoretical work done in my thesis has any inconsistency this result cannot be obtained.

Taking only the first order perturbation from the above equation

When n = 2 1

The final equation from my PhD thesis is simplified to show that the shortest distance measurable in space is the Plank Wavelength and the corresponding energy is Plank Energy This is a correct result that can be derived from the Heisenberg Uncertainty Principle as well. If the theoretical work done in my thesis has any inconsistency this result cannot be obtained.

Schwarzschild Metric Tensor can be written

------------------------------------------------------------------------------------------------------------------

..

To simplify consider only the r coordinate and t coordinate and the first order perturbation

When the wavelength [ Limit n 1 ] in discrete steps

For a particle [with diameter d] falling under a gravitational field, this is the Energy required to measure when

By Sid Senadheera copyright reserved