Name: Abdulrahman Khalaf Ali Thesis Title: (Preparation of Ag and Au Nanoparticles by Pulsed Laser Ablation in Liquids) Supervisor: Ass.

Prof. Dr. Dayah N. Raouf Date: 2010 No. of Pages: 114 Abstract: This thesis has presented an alternative-novel, easy, fast and one-step method for the preparation of pure and stable noble metal versatile nanoparticles NPs in a high ablation rate and size-selected manner with a high concentration, long period of stability, less aggregation, non toxic and contamination. Noble metals silver and gold NPs were synthesized by pulsed (Q-switched, 1064 or 532nm doubled frequency-Nd: YAG) laser ablation of silver and gold metal plates immersed in double distilled and deionised water DDDW or other aqueous solutions such as: NaCl, sodium and dodecyl sulphate SDS, various

polyvinylpyrrolidone PVP, Ethanol concentrations.

Acetone, each with

The optimum preparation parameters had been optimized for the best formation efficiency of pulsed laser ablation in liquids (PLAL) process, which are: laser shots is 15 and 10 pulses, laser energy is 600 and 500 mJ, liquid depth is 8 and 7 mm, laser fluence is 47.4 and 105.8 J/cm2 for silver and gold, respectively. Moreover, the optimum ablation laser wavelength was 1064 nm. The formation efficiency of PLAL process was quantified in term of the surface plasmon extinction SPE peaks and it was enhanced greater than 220 times, as well as the concentration of ablated Ag NPs which obtained via AAS; however it was estimated to be about 8.66 g/pulse, and it was increased about 21 times.
I

The SPE spectra shows a sharp and single peaks around 400 or 526 nm, indicating the production of pure and spherical Ag and Au NPs with average size of 14 nm, respectively. All the size measurements have been confirmed by TEM. There is a simultaneous possibility of on-line observation of the nanoparticles formation via measuring the variation in nanoparticles absorption at the peaks of SPE using 532nm, 1mW diode laser. The optimum concentration for the formation of Ag nanoparticles in various solutions were: NaCl (2.5 mM), SDS (25 mM) and PVP (5 mM) which optimize the formation efficiency, reduces the size and size distribution, enhance dispersity and prevents aggregation of the prepared nanoparticles. Resizing and reshaping of Ag and Au nanoparticles have been performed using pulsed Nd-YAG laser, =532nm; the average particle size dropped from 14 to 8nm. Novel bimetallic of AuAg core-shell nanoalloys were synthesized. The nanoalloys appear to be nearly spherical with average size of 19 nm. The irradiation process has been done by Nd-YAG laser, with =532nm and E=900 mJ.

Keyword: Pulsed, Nanoparticles, Ag, Au, liquid, Nd: YAG

II

Preparation of Ag and Au Nanoparticles by Pulsed Laser Ablation in Liquids

By

Abdulrahman Khalaf Ali

A Thesis
Submitted to the Department of Applied Sciences at the University of Technology as a Partial Fulfilment ulfilment of the Requirement for the Degree egree of Doctor of Philosophy in Laser Physics

Supervised by

Assistant istant Prof. Dr.Dayah N. Raouf

Baghdad (2010)



)( -

II

Supervisor Certification

I certify that this thesis entitled: (Preparation of Ag and Au Nanoparticles by Pulsed Laser Ablation in Liquids) was prepared under my supervision at the University of Technology, department of applied sciences, in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Laser Physics.

Signature: Name: Dr. Dayah N. Raouf Title: Assistant Professor Date: / / 2010

III

Linguistic Certification

I certify that this thesis entitled: (Preparation of Ag and Au Nanoparticles by Pulsed Laser Ablation in Liquids) was prepared under my linguistic supervision. It was amended to meet the style of the English language.

Signature: Name: Dr. Mohamed Saleh Ahmed Title: Assistant Professor Date: / / 2010

IV

Examination Committee Certificate

We certify that we have read this thesis entitled (Preparation of Ag and Au Nanoparticles by Pulsed Laser Ablation in Liquids) and as an examining committee examined the student '' Abdulrahman Khalaf Ali'' in its contents and that in our opinion; it meets the requirements of awarding the degree of Doctor of Philosophy of Science in Laser Physics.

Signature: Name: Dr. Bassam G. Rasheed Title: Assistant Professor (Member) Date: / / 2010

Signature: Name: Dr. Khawla Salah Khashan Title: Assistant Professor (Member) Date: / / 2010

Signature: Name: Dr. Adawiya J. Haider Title: Professor (Member) Date: / / 2010

Signature: Name: Dr. Nadir Fadhil Habbubi Title: Professor (Member) Date: / / 2010

Signature: Name: Dr. Dayah N. Raouf Title: Assistant Professor (Supervisor) Date: / / 2010

Signature: Name: Dr. Mazin M. Elias Title: Professor (Chairman) Date: / / 2010

Approved by the School of Applied Sciences, University of Technology.

Signature: Name: Kassim S. Kassim Title: Head of School of Applied Sciences Date: / / 2010
V

Acknowledgment

After thanks my glorious ALLAH, I am pleased to acknowledge the assistance and support for many people whom had support me in completion of this work. First I would like to thank my supervisor Dr. Dayah N. Raouf for skilful scientific guidance, who always supported my research effort, during the long period time of this project. I would like to present my spatial thanks and great gratitude to Dr. Bassam G. Rashid, the head of laser branch, for his unlimited support for the experimental requirements. Also, I would like to express my deep appreciation and respect to all the department of applied science staff, especially of laser branch. I am indebted to the electronic microscope centre-collage of medicine/ AlNahrain University for their helpful in TEM measurements. I am also grateful to the chemical Lab.-collage of science/ Baghdad University for unlimited assistant in AAS measurements.

Abdulrahman 15-1-2010

VI

Dedication

I would like to dedicate my Doctoral Thesis to my family: parent, wife, brothers and sisters.

VII

Abstract
This thesis has presented an alternative-novel, easy, fast and one-step method for the preparation of pure and stable noble metal versatile nanoparticles NPs in a high ablation rate and size-selected manner with a high concentration, long period of stability, less aggregation, non toxic and contamination. Noble metals silver and gold NPs were synthesized by pulsed (Q-switched, 1064 or 532nm doubled frequency-Nd: YAG) laser ablation of silver and gold metal plates immersed in double distilled and deionised water DDDW or other aqueous solutions such as: NaCl, sodium dodecyl sulphate SDS, polyvinylpyrrolidone PVP, Ethanol and Acetone, each with various concentrations. The optimum preparation parameters had been optimized for the best formation efficiency of pulsed laser ablation in liquids (PLAL) process, which are: laser shots is 15 and 10 pulses, laser energy is 600 and 500 mJ, liquid depth is 8 and 7 mm, laser fluence is 47.4 and 105.8 J/cm2 for silver and gold, respectively. Moreover, the optimum ablation laser wavelength was 1064 nm. The formation efficiency of PLAL process was quantified in term of the surface plasmon extinction SPE peaks and it was enhanced greater than 220 times, as well as the concentration of ablated Ag NPs which obtained via AAS; however it was estimated to be about 8.66 g/pulse, and it was increased about 21 times. The SPE spectra shows a sharp and single peaks around 400 or 526 nm, indicating the production of pure and spherical Ag and Au NPs with average size of 14 nm, respectively. All the size measurements have been confirmed by TEM. There is a simultaneous possibility of on-line observation of the nanoparticles formation via measuring the variation in nanoparticles absorption at the peaks of SPE using 532nm, 1mW diode laser. The optimum concentration for the formation of Ag nanoparticles in various solutions were: NaCl (2.5 mM), SDS (25 mM) and PVP (5 mM) which optimize the formation efficiency, reduces the size and size distribution, enhance dispersity and prevents aggregation of the prepared nanoparticles. Resizing and reshaping of Ag and Au nanoparticles have been performed using pulsed Nd-YAG laser, =532nm; the average particle size dropped from 14 to 8nm. Novel bimetallic of AuAg core-shell nanoalloys were synthesized. The nanoalloys appear to be nearly spherical with average size of 19 nm. The irradiation process has been done by Nd-YAG laser, with =532nm and E=900 mJ.
VIII

List of Abbreviations
AAS AD AgNPs Au-Ag AuNPs BC DDDW e.g. et al. i.e. LISR LSPR NP (NPs) PLA PLAL PVP SDS SERS SPE SPR TEM Atomic Absorption Spectroscopy After Date Silver Nanoparticles Bimetallic of GoldSilver Nanoalloys Gold Nanoparticles Before Christ Double Distilled and Deionised Water for example (exempli gratia) and others (et alia) That is (id est) Laser Induced Size Reduction Localized Surface Plasmon Resonance Nanoparticle (Nanoparticles) Pulsed Laser Ablation Pulsed Laser Ablation in Liquids Polyvinylpyrrolidone Sodium Dodecyl Sulphate Surface Enhanced Raman Scattering Surface Plasmon Extinction Surface Plasmon Resonance Transmission Electron Microscope

List of Symbols
C 0 k M Pa S Absorption Coefficient Concentration Complex dielectric constant Vacuum permittivity (dielectric constant) Extinction Coefficient Molary: (number of moles per litre) Pascal (=10-5 bar =10-5 atm.=76010-5 mmHg=76010-5 torr) Specific Surface Area cm-1 g/l or Molary (M) J-1C2m-1 J-1C2m-1 cm-1 mol/l N/m2 m2/g

IX

Contents
CHAPTER ONE: INTRODUCTION
1-1 Nanotechnology 1-2 Noble Metal Nanoparticles 1-3 Advantage of Pulsed Laser Ablation in Liquid Media 1-4 Literatures Review 1-5 Scientific Problems 1-6 Aims of the Work 1-7 Thesis Outline

Page
1 3 4 6 11 12 12

CHAPTER TWO: THEORETICAL CONSIDERATIOS

2-1 Introduction 2-2 Laser ablation and Particle Generation 2-2-1 Laser-Induced Heating and Melting 2-2-2 Explosive Boiling 2-2-3 Evaporization 2-2-4 Plasma Formation 2-2-5 Solid Exfoliation 2-2-6 Hydrodynamic Sputtering 2-2-7 particle Ejection (Spallation) 2-2-8 Nucleation and Condensation 2-2-9 Coagulation and Agglomerates (Groth) 2-3 Nanoparticles-Liquid Reaction 2-4 Nanoparticles Suspension 2-5 Synthesis of Nanoparticles 2-5-1 Dispersion Methods 2-5-2 Reduction Methods 2-6 Colloids 2-7 Pulsed laser Ablation in Liquid Medium 2-8 Nanoparticles Formation Mechanism 2-9 Interaction of Light with Noble Metal Nanoparticles 2-9-1 Surface Plasmon Resonance in Metal Nanoparticles (SPR) 2-9-2 Mie Theory 2-10 Modification of Metal Nanoparticles 2-10-1 Size Reduction: Secondary Laser Irradiation 2-10-2 Mechanism of Size Reduction Process 2-10-3 Laser-Induced Growth Tuneable Nanoparticles 2-10-4 Target Modification 2-11 Surface Area of Nanoparticles 2-12 Properties of Nanoparticles 2-12-1 Optical Properties 2-12-2 Thermal Properties 2-12-3 Catalytic Properties 2-13 Application of Nanoparticles 2-13-1 Antibacterial of Silver Nanoparticles Agent 2-13-2 Surface Enhanced Raman Scattering X 13 13 14 14 15 15 16 16 17 18 18 19 20 21 21 21 22 22 23 25 25 28 29 29 30 31 32 33 34 34 35 35 36 36 37

2-13-3 Diabetic Delayed Wound Healing 2-13-4 Cooling Challenge

39 39

CHAPTER THREE: EXPERIMENTAL WORKS

3-1 Laser Ablation System 3-2 Laser Source and Measurements Device 3-2-1 Nd-YAG Laser 3-2-2 Semiconductor Laser 3-2-3 Transmission Electron Microscope 3-2-4 Spectrophotometer 3-2-5 Atomic Absorption Spectroscopy 3-2-6 Optical Microscope 3-2-7 Evaporation System 3-3 Materials 3-3-1 Target Materials 3-3-2 Distilled and Deionised Water 3-3-3 Chemical Solution Preparation 3-4 General Experimental Process for Nanoparticles Formation 40 41 41 41 41 42 42 42 42 43 43 43 43 44

CHAPTER FOUR: RESULTS AND DISCUSSION

4-1 Introduction 4-2 Effect of Laser Shots 4-2-1 Silver Nanoparticles Concentration 4-2-2 Ablation Monitoring 4-3 Effect of Laser Energy 4-4 Effect of Laser Fluence 4-5 Effect of Liquid Depth 4-6 Effect of Laser Wavelength 4-7 Effect of Chemical Solutions 4-7-1 Effect of NaCl Solution 4-7-2 Effect of SDS Solution 4-7-3 Effect of PVP Solution 4-7-4 Effect of Organic Solutions 4-8 Effect of Temperature 4-9 Effect of Aging Time 4-10 Nanoparticles Modification and Size Controlling 4-11 Nanoalloys: Core-Shell Nanostructure Synthesis 4-12 Color Changing: Indicator 4-13 Thin Films Deposition 4-13-1 Bulk Thin Films 4-13-2 Nanoparticles Thin Films 4-14 Target Effects 45 45 50 54 55 61 64 67 70 70 73 77 82 85 87 91 95 97 98 98 99 103

CHAPTER FIVE: CONCLUSIONS AND FUTURE WORK

5-1 Conclusions 5-2 Suggestion for Future Works References XI 106 106 107

...

XII


- . 1064 nm 532 nm DDDW (polyvinylpyrrolidone PVP, sodium dodecyl sulfate SDS, NaCl Ethanol, (Acetone . PLAL : 600 mJ 500 mJ mm 7 mm 47.4 J/cm2 105.8 J/cm2 . 1064 .nm PLAL (surface plasmon extinction) SPE AAS 8.66 g/pulse . SPE 400nm 526 nm .13 nm . TEM SPE 532nm .1 mW NaCl 2.5 mM SDS 25 mM PVP 5 mM . PLAL 532 nm 14 nm .8 nm . .19 nm nm . 900 mJ
XIII

Chapter One: Introduction

1-1 Nanotechnology
When Neil Armstrong stepped onto the moon, he called it small step for man and giant leap for mankind. Nano may represent another giant leap for mankind, but with step so small that it makes Neil Armstrong look the size of solar system! However, nanoscience and nanotechnology are steering mankind into new realms of efficient and miniature tools and gadgetry [1]. Clusters of metals are known from ancient times. It is widely known that the brilliant colors of noble metals like gold or silver have fascinated the human being from the very beginning of mankind. They were employed to dye glass and fabrics and as a therapeutic aid in treatment of arthritis. While the most ancient use colloidal Au is believed to have been BC in Egypt by alchemists [2], the brilliant colors of nanosized colloidal particles of Ag and Au were used in ancient Romans glass artefact dated to 4th century AD, that appears red in transmitted light and green in reflected light was found to be due to Au and Ag nanocrystals impregnated in glass. These metals were already used to decorate glass, exhibited in the British Museum shows. This technique to color glass was extensively used in the 10th century AD for the many cathedrals in Europe [3]. The history of metal nanoparticles begins with Faradays study of gold colloids, as early as 1857 [4]. He established that several dyes were indeed made of metal particles. After a thorough study of gold sols, Faraday concluded The introduction into a ray of separate particles [...]The gold is reduced in exceedingly fine particles which becoming diffuse, produce a beautiful fluid[. . .] the various preparations of gold, whether ruby, green, violet or blue[...]consist of that substance in a metallic divided state known phenomena appeared to indicate that a mere variation in the size of its particles gave rise to a variety of resultant colours. The British physicist Michael Faraday recognized that this variety of colors was due to the interaction of light with
1

small metal particles. [3]. In 1908, Mie explained the origin of the bright colors to the colloid by solving Maxwell's electromagnetic equation for the interaction of light with spherical particles (d<<) [2,5].On December 29 1959, Nobel Prize winner, physicist Feynman said in his famous speech There is Plenty of Room at the Bottom [6]. The term Nanotechnology has been in use as early as 1974. It was defined by Taniguchi [7]. Additionally, the definition of nanoscience and nanotechnology as it is given by the US National Nanotechnology Initiative NNI, in 2000[6]: nanoscience or nanotechnology are Development at the atomic levels in the length scale of approximately 1-100 nanometer range, to provide a fundamental understanding of phenomena and materials at the nanoscale and to create and use structures, devices and systems that have novel properties and functions. The term Nano refers to 10-9 meter is so small that things smaller than it can only be molecules, clusters of atoms or particles in the quantum world [8]. The term Nanoparticle is referring to a particle where all the three dimensions are nanometer in scale; contain small enough a number of constituent atoms or molecules that they differ from the properties inherent in their bulk counterparts, exist in diverse shapes such as spherical, triangular, cubical, pentagonal, rod-shaped, shells, ellipsoidal and so forth[8]. The term Colloid is more elusive, the particle size can range from nanometers to several hundreds of micrometers. The term Cluster is usually used for small nanoparticles that have well-defined composition and surface structure as finite aggregates of atoms or molecules which are bound by forces of metallic, covalent, ionic, hydrogen bonded or van der Waals [9]. Nanomaterials display unique, superior and indispensable properties and have attracted much attention for their distinct characteristics that are unavailable in conventional macroscopic materials. Their uniqueness arises specifically from higher surface to volume ratio and increased percentage of atoms at the grain boundaries. They represent an important class of materials in
2
th

the development of novel devices that can be used in various physical, biological, biomedical and pharmaceutical applications [10]. Therefore are an objects of active research in various applications such as: photo-thermal therapy[11], surface-enhanced Raman spectroscopy[12], biochemical

sensors[13], nanophotonics devices[14], biology[15], carrier systems for drug delivery[16] , biosensing in vivo or in vitro diagnostic[17], solar cells[18], optoelectronic device[19], diabetic healing[20], cooling system[21],

antibacterial against[10], cancer treatment[2], catalysis[3], sensor[22], imaging, sensing, biology and medicine[23], inkjet-printer[24]... etc.

1-2 Noble Metal Nanoparticles

Noble metal nanoparticles such as Ag and Au NPs have been a source of great interest due to their novel electrical, optical, physical, chemical and magnetic properties [25,26]. They were very attractive for biophysical, biochemical, and biotechnological applications due to their unusual physical properties, especially due to their sharp plasmon absorption peak at the visible region. Another important advantage Ag and Au nanoparticles prepared by PLAL process were stable for a period of months. Additionally, Gold and silver nanoparticles are chemically stable and typically exhibit surface enhanced Raman scattering SERS in the visible wavelength range, where they may cause a tremendous increase in various optical cross-sections. The resonance frequencies strongly depend on particle shape and size as well as on the optical properties of the material within the near-field of the particle [14]. Silver, for example, has been for thousands of years, used as a disinfectant; from the other side nobody can neglect its value as a catalyst [27]. On the other hand, Gold nanoparticles have gained considerable attention in recent years for potential applications in nanomedicine due to their interesting size dependent chemical, electronic and optical properties. Also, gold nanoparticles show promise in
3

enhancing the effectiveness of various targeted cancer treatments such as radiotherapy and photothermal therapy [8]. However, the field of nanotechnology has received much attention, specially gold and silver nanoparticles with the number of publications of growing exponentially (as shown in Fig. 1-1)[28].
6000

.
5000

4000

Articles

3000

2000

1000

0 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004

years

Fig. 1-1: Articles published on gold and silver NPs from 1990 to 2005[28].

1-3 Advantage of Pulsed Laser Ablation in Liquids

Nanoparticles have been prepared by a wide variety of techniques such as pulsed laser deposition[29], flame metal combustion[30], chemical reduction [31], photo-reduction[32], electrochemical reduction[33], solvothermal[34], electrolysis[27], green method[35], Microwave-induced[36], sono-

electrochemical[37], aerosol flow reactor[38], photochemical reduction[40], chemical fluid deposition[41], spray pyrolysis[39,42] , and spark discharge[43]. Among them, the pulsed laser ablation in liquids PLAL has become an increasingly popular top-down approach [44] for producing nanoparticles. It's a relatively new method that was first introduced by Fojtik et al. in 1993[45] as is a promising technique for the controlled fabrication of nanomaterials via rapid
4

reactive quenching of ablated species at the interface between the plasma and liquid with high-quality nanoparticles free from chemical reagents. Therefore, PLAL process has received much attention as a novel NPs production technique. In general, there are an ability to prepare various kinds of nanoparticles such as metals[46,47], noble metals[48], semiconductors[49,50], nanoalloys[51], oxides[52], magnetic[53], biaxial heterostructures[54] and coreshell nanostructure[55]. Moreover, the interesting feature of this technique, which distinguishes it from laser ablation in gas or vacuum, is the influence of the surrounding solvent. The solvent can provide (i) physical effects such as confinement and cooling, in addition to (ii) chemical reactions effects such as oxidation or reduction and control on the size and the aggregation state of nanoparticles NPs by changing the surface charge of the nuclei. In addition, the surfactant molecules can prevent particle size increase by their adsorption on the nanoparticles as (iii) coating reagents effect [56]. Crystallized NPs can easily be obtained in one-step procedures without subsequent heat-treatments, because of the high energetic state of ablated species. Certain pure NPs colloidal solutions can be formed without the formation of by-products. Resizing and reshaping of colloidal NPs synthesized by other technique are also possible through melting and fragmentation technique by laser irradiation. The production system is easy, simple and cheap, does not require costly vacuum chambers [3,57]. The ejected nanoparticles completely collected in solutions forming thus a colloidal solution make them very easier to handle as suspended or powder (by centrifuged) [58]. Moeover, the PLAL method is free of any reducing agents, which are potential impurities no pollution and contamination [59]. However the strong confinement of the expanding plasma produced by laser ablation of a target in solution, which can realize extremely high temperature and high pressure [56]. Another interesting feature is the weak dependence of the size of generated NPs on the duration of laser pulse. For laser ablation in vacuum, the generated NPs are almost immediately deposited in the
5

chamber walls or on a substrate and do not absorb forthcoming laser pulses. In liquids, NP remains in liquid and can therefore appear in the laser beam path upon convective motion of the liquid [60]. In addition, the physical approach feature was originally used to produce colloidal metal nanoparticles with controlled size and shape. There is ability to surface modification as partial oxidation, charge distribution, coating ...etc, using a surfactant solution in a simple one step process. Moreover, there is an ability to disperse the aggregated nanoparticles, as: (i) changing the pH value of suspension; (ii) using surface activator and dispersants [13] (iii) using ultrasonic vibration to deagglomeration [61,62].

1-4 Literatures Review

This review aims to summarize recent research has attracted much attention during last decade on the preparation of noble metal NPs using PLAL method. In 2000, Mafune et al. [63] produced silver nanoparticles by laser ablation of a silver plate in water or SDS. The laser wavelength and laser shots are 532 nm and 50000 pulses, respectively. He found that the size distribution of the nanoparticles shifts to a smaller size with increase in the concentration of SDS. In 2001, Tsuji et al. [64] studied the influence of the laser wavelength, focusing conditions on the ablation efficiency of silver and copper targets in water to prepare nanoparticles. It was finding that the ablation efficiency at shorter wavelengths was higher at low fluence, while the ablation efficiency at longer wavelengths was higher at high fluence. In 2002, Dolgaev et al.[65] reported the formation of Ag and Au nanoparticles under pulsed laser ablation metal target in liquid environment (H2O, C2H5OH, C2H4Cl2) by using Cu vapour laser (=510nm). This method allow high rate of nanoparticles formation. Tsuji et al.[66] studied the influences of laser wavelength of 1064, 532, or 355 nm laser in order to prepare
6

silver nanoparticles in water. It was found that the ablation efficiency decrease with decrease the laser wavelength. In 2003, Kabashin et al.[67] reported two different mechanisms of material ablation in the liquid environment to produce gold nanoparticles. The first, associated with thermal-free femtosecond ablation, manifests itself at relatively low laser fluences F,400 J/cm2 and leads to small ~310 nm. The second one, attributed to the plasma-induced heating and ablation of the target, takes place. Tsuji et al.[68] studied the preparation of Ag NP by laser ablation in water with femtosecond laser pulses at 800 nm. The formation efficiency for femtosecond pulses was significantly lower than nanoseconds pulse. In 2004, Sylvestre et al.[69] reported the femtosecond laser ablation of a gold target in aqueous solutions to produce Au nanoparticles with controlled surface chemistry. A detailed chemical analysis showed that the nanoparticles formed were partially oxidized by the oxygen present in solution. In 2005, Pyatenko et al.[70] prepared silver nanoparticles with 8 nm, by irradiating a silver colloid, prepared via the citric reduction method, using 532 nm Nd:YAG laser, with laser fluence more than about 0.2 J/cm2. Tarasenko et al.[71] studied effects of laser irradiation of silver colloids prepared by laser ablation technique in acetone at different wavelengths (532, 266, 400 and 800 nm). The experimental conditions favoured a dimension reduction of the initial particles and a formation of spherical size-controlled nanoparticles. In 2006, Kawasaki et al.[72] studied the laser-induced fragmentation of thin Au and Ag flakes in acetone by 1064-nm nanosecond laser (with the fluence typically about 2 J/cm2) potentially offers a highly productive pathway to stable metal nanoparticles, at a remarkable high production rate of 1.1 mg/min in liquid. Zhao et al.[73] synthesized of Ag NP by laser ablation in water with excitation of 532 and 248 nm. It is proved that all of them are effective SERS-active substrates. Zhu et al.[74] investigated the pulsed laser
7

ablation of Ag bulk in distilled water to synthesize Ag colloid nanoparticles. Amendola et al.[75] Prepared of free and functionalized gold nanoparticles laser ablation of a gold metal plate immersed in dimethyl sulfoxide, acetonitrile, and tetrahydrofuran. It is possible to have significant control of the concentration, aggregation, and size of the particles by varying few parameters. Kazakevich et al. [60] presented of new nanoparticles formation under laser ablation of Ag, Au, and Cu-containing solid targets in liquid environments (H2O, C2H5OH and C2H4Cl2). The Formation of alloyed AuAg and AgCu nanoparticles is reported under laser exposure of a mixture of individual nanoparticles. Yamada et al.[76] presented of new Gold nanoparticles with an average diameter of 8 nm were irradiated with a tightly focused pulse laser at 355 nm in an aqueous solution of SDS. Tarasenko et al.[77] reported the formation of gold nanoparticles during laser ablation of gold target in water by pulsed Nd:YAG laser, operating at the second (532 nm, 10 ns, 10 Hz), or the fourth harmonic (266 nm) wavelengths. The properties of the nanoparticles were found to be both the mean size of the nanoparticles and their stability to the additional 532 and 266 nm laser irradiation. Mafune et al.[78] produced silver nanoparticles by laser ablation of a metal silver plate in SDS. The concentration dependence of the abundance implies that the surfactant coverage and the charge state on the nanoparticle surface are closely related to the stability of the nanoparticles in the solutions. In 2007, Zheng et al.[79] presented a new method for the tunable production of monodisperse silver nanoparticles by different laser wavelengths to irradiate an initial solution of seed crystals, the size and shape of the products can be controlled. The absorption maximum shifts to longer wavelengths and broadens, indicating an increase in particle size and size dispersion. They found that the final size and shape are depending on laser wavelength and power. Muto et al.[80] prepared of partially oxidized gold nanoparticles by laser ablation of a gold metal plate in water. The nanoparticles are negatively charged
8

because the surface atoms are partially oxidized to Au-O. It was found that the surfactant cations attach to the particle surface, neutralizing the particle charge. Phuoc et al.[61] fabricated the multi-pulse Nd-YAG lasers operating at 1064 nm laser ablation of silver in deionized water, arranged in a cross-beam configuration. Its found that the cross-beam ablation can increase the ablation rate and promote reduction of the particle sizes and particle size distribution. Kim et al.[81] synthesized metal and oxide nanoparticles(Ag, Al and Cu) by pulsed laser ablation of the compacted metal microparticles using a Q-switched Nd:YAG laser in water. It was shown that the process is effective for preparing nanoparticle suspensions having relatively uniform size distributions. Truong et al.[82] studied the formation of dense arrays of nanospikes occurs under laser ablation of bulk targets (Ag, Au, Ta, Ti) immersed in liquids. The effect is observed with sufficiently short laser pulses, either a 350 ps or a 90 ps Nd:YAG lasers. The nanostructured Ag surface shows enhanced Raman scattering. Giusti et al.[83] reported the preparation of Au nanoparticles by picosecond laser ablation in water, with the fundamental and second harmonic of a picoseconds Nd:YAG laser. The ablation process at 532 nm reached early saturation because of both linear and nonlinear absorption mechanisms, accompanied by fragmentation of existing nanoparticles. Compagnini et al.[51] synthesized Au/Ag colloidal nano-alloys by laser ablation of single metal targets in water and a re-irradiation of mixed colloidal suspensions. In 2008, Werner et al.[84] studied the formation of silver nanoparticles by nanosecond pulsed-laser irradiation (1064 and 532 nm, at 1 J/cm2) of silver flakes in alcohols such as methanol and ethanol, the NPs are extremely unstable and easily settled down to form precipitates. Siskova et al.[85] synthesized Ag nanoparticles by laser ablation of a Ag target immersed in water and in aqueous electrolyte solutions (HCl, NaCl, NaOH) as stabilization of the resulting Ag nanoparticles. Tsuji et al.[86] prepared silver nanoparticles by laser ablation of a silver plate in PVP aqueous solutions. Secondary laser irradiation onto the
9

prepared colloidal solutions was also carried out. It was found that the formation efficiency was increased by addition of PVP as well as the stability of nanoparticles with fine particles no more than 4 nm. Smejkal et al.[87] showed that the laser fragmentation of Ag nanoparticles proceeds during first 20 pulses and then reaches saturation. Fluences above 303 mJ/cm2 caused the formation of less stable, aggregating nanoparticles, while fluences below 90 mJ/cm2 do not provide sufficient energy for efficient fragmentation. Muto et al.[88] prepared of gold nanoparticles by laser ablation of a gold metal plate in an SDS aqueous solution with an average diameter of about 11 nm. Jimenez et al.[89] introduced novel technique, which consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO3 or HAuCl4. Compagnini et al.[55] prepared a novel Au-core Ag-shell nanoparticles by irradiated of mixed AuAg nanoparticles, were obtained by pulsed laser ablation of metallic targets in liquid medium. In 2009, Yang et al.[90] fabricated the Ag nanostructured films, based on electrophoretic deposition EPD in the Ag colloidal solution produced by laser ablation in water, under a constant current deposition mode. It has been found that the obtained films are of tunable and controllable morphologies and structures depending on EPD parameters. Pyatenko et al.[91] presented mechanisms for silver and gold particle size reduction by laser (1064nm) irradiation. The results presented here will be useful to all specialists using lasers in particle size controlling, resizing, and reshaping. Petersen et al.[17] studied the generation of gold NPs using a femtosecond laser system delivering 120 fs laser pulses at a wavelength of 800 nm at a repetition rate of 5 kHz. In 2010, Manjon et al.[92] studied the influences of temperature variation on the hydrodynamic diameter of the resulting colloidal nanoparticles when a gold target is ablated by an IR femtosecond laser in water at different stabilized liquid temperatures in the range of 283-353 K. The maximum hydrodynamic
10

diameter was observed at 330 K, the temperature at which the compressibility of water reaches its minimum. Karimzadeh et al.[48] synthesized silver nanoparticles by nanosecond pulsed laser ablation of silver plate in distilled water. The results showed narrow size distribution of the nanoparticles with radius centered at about 9 nm with a standard deviation of 3 nm.

1-5 Scientific Problems

As reported in previous literatures, we found that the preparation of metal nanoparticles via PLAL method suffers from low production yields. However, have not been sufficiently explored until very recently, though Kawasaki [72] and Kim [81] recently shown that a suspension of fine metal powders as the target material for a 1064-nm laser could largely improve the production yield. To effectively prepare metal nanoparticles of high ablation rate quantities, it is necessary to understand how the laser parameters affect the final nanoparticle product mass yield. We suggest that the rate of NP generation depends on different experimental parameters such as the metal reflectivity at the laser wavelength, the liquid depth, energy...etc, not only on the laser fluence as reported. These last parameters have been studied only in marginal until now. Another disadvantage is that the size distribution of the NPs prepared by this technique tends to be broadened due to agglomeration of nanoclusters and to the possible ejection of the relatively large target fragments during the laser ablation process. The formation mechanism and methods to control the properties have not been sufficiently explored until very recently. To achieve that, the particle-size reduction accomplished by re-irradiation, it was one of the most important mechanisms. To date, to the best of our knowledge, only one report has described laser ablation of metal in a PVP solution recently by Tsuji et al.[86]. However, because that study specifically examined the optical properties of Ag nanoparticles, other essential information about the influences
11

of PVP on the properties of produced nanoparticles such as formation efficiency were not reported. In general, the PLAL process is not controlled; we refer to on-line monitoring of nanoparticles formation as a topic of great present interest study. We regard as a pioneer study in our thesis.

1-6 Aims of the Work

To prepare pure silver and gold nanoparticles in easy, fast and one step method via PLAL process. On-line monitoring to controlling on the formation process of nanoparticles. To optimise the PLAL process and improve the formation rate of nanoparticles by studying the effects of experimental parameters. To controlling and optimise the formation rate, NPs size, size distribution, dispersity and aggregation of Ag NPs by studying the effect of surfactants solutions, as capping agent Modification and size controlling of the noble metal nanoparticles by reirradiation to narrow the size and size distribution of metal nanoparticles. Synthesis novel composite of Au-Ag core-shell nanoalloys in two steps. Study the stability of nanoparticles upon ages.

1-7 Thesis Outline

This thesis is divided into five chapters. The First Chapter describes the metal nanoparticles and their literature review. Chapter Two explains in detail a theoretical background approach to characterize the properties of nanoparticles and their interaction with light. Chapter Three gives the experimental procedures and methodologies adopted in synthesis. Chapter Four describes the experimental results of the studies and its discussions. Chapter Five gives the summary the conclusions for the current work and future pathways.
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Chapter Two: Theoretical Considerations

2-1 Introduction
Production of nanoparticles under laser ablation of solids either in gas or in vacuum has been extensively explored during two last decades. A new methodology based on laser ablation in liquids has received much attention as a novel nanoparticle-production technique. Laser ablation represents dramatic laser-material-interaction phenomenon. The amount of mass removed was depending on the laser parameters such as: pulse duration, energy, wavelength, target properties and the surrounding environment [93,94]

2-2 Laser ablation and Particle Formation

When a laser pulse reaches a sample surface, some of the energy is reflected by the surface. It is noted that the reflectivity depends on the material and laser wavelength [95]. The energy absorbed by the sample is transferred from optical photons to electrons and then to the lattice, which then diffuses the energy into the material [93]. Extremely high energy pulses may cause photochemical reactions which remove atoms and molecules from the surface. The heated surface can reach temperatures close to the critical temperature and cause rapid vaporization process. The vaporization resulting in plasma that consists of ionized vaporized atoms and electrons. It is possible that the plasma cloud absorbs some of the incident laser energy and thereby only allows a fraction of the laser energy to reach the surface (plasma shielding). The plasma expands and is heated by photon absorption. Later the vapour cools and aerosol particles begin to form. The rest of the energy diffuses into the material via heat transfer. Depending on the applied laser energy, the surface may be melted into a liquid with a moving solid-liquid interface. Liquid may be removed from the molten pool as droplets that result in a higher ablation rate. However, a series of events during laser ablation has been take place, can be discussed as follows [93,95].
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2-2-1 Laser-Induced Heating and Melting

The absorption of laser light by metal nanoparticles gives rise to a succession of energy transformation processes. These involve the successive excitation and relaxation of the metal electrons, its interaction with the lattice, i.e. electron-phonon relaxation and the phonon-phonon thermalization. Afterwards, several thermal processes like melting or evaporation can be activated. As discussed above, in the case of nanosecond-pulsed laser light, the heat diffusion from the metal particle to the support takes place on a time scale much shorter than the pulse width. This enables a simple thermodynamic treatment of the laser induced temperature rise [3,96]. The laser energy was not vaporized the material, heats it and raises their temperature, propagates via heat conduction inside the material. The temperature distribution is governed by the heat conduction equation [93]:

where , Cp, K, T: represent density, specific heat, thermal conductivity and 1 represents the source term which is the laser energy absorbed by the material

( ) + ( )  

(2-1)

temperature, respectively. The second term on the right hand side of equation 2-

at a depth z from the surface, where R is the surface reflectivity, and I0 is the laser irradiance and is the absorption coefficient (the imaginary part of the complex refractive index, assumed to be constant) [93,97]

2-2-2 Explosive Boiling

When a very high-energy fluence laser pulse is applied on the target surface, a dramatic change of crater shape and volume is reported. The ablation rate measured from the crater depth changes abruptly when the energy power density is larger than a critical value. This mechanism has been analyzed based on classical thermodynamics. When the surface region is heated beyond the limit of its
14

thermodynamic stability during short-pulse laser irradiation, the surface is presumed to undergo a rapid transition from a superheated liquid to a mixture of vapour and liquid droplets. Experimental results of the existence of well-defined threshold fluence for the onset of the droplet ejection, as well as a steep increase of the ablation rate at the threshold, have been reported and interpreted as evidence of the transition from normal vaporization to phase explosion [93,98].

2-2-3 Evaporation
The mass evaporated from the target forms a vapour plume and moves away from the surface with a high temperature and pressure. The surface temperature primarily determines the vaporization rate. The evaporation rate from a liquid surface is given by [93]:
 

Where n is the number of atoms per unit volume, the subscripts l and v represent liquid and vapour, respectively, and are the latent heat of vaporization hlv and Tv temperature of the vapour, ma is the atomic mass and kB is the Boltzmann constant. The first term in equation (2-2) represents the evaporization rate from a liquid surface temperature and the second term represents the condensation rate of molecules back to the liquid surface. The sticking coefficient s is the probability that a vapour atom returning to the liquid surface is adsorbed [93,99].

(2-2)

2-2-4 Plasma Formation

The laser-irradiated region on the target surface is heated to high temperatures. The large portion of the absorbed laser energy is used to evaporate the atoms of the target material thereby reducing the energy transport into the interior of the target material. The front of the vapour formed plasma contacts the environment and forms a shockwave, which travels faster than the speed of sound. The vapour plasma is in a strong nonequilibrium state with an
15

ions density reaching 10161018 ions/cm3. The characteristic time for the cloud formation is about 10-7 sec. The temperature inside the plasma can reach several tens of thousands of K when all of the atoms or molecules are ionized [100,101].

2-2-5 Solid Exfoliation

Exfoliation is the removal of fractured material in the solid state caused by photomechanical effects due to strong laser-induced thermal expansion and stress. This kind of removal is particularly important for brittle, refractory materials such as single crystal materials including silicon, graphite or glass type materials. The magnitude of the laser-induced stresses becomes significant under conditions of stress confinement, when the laser pulse duration is shorter than the time needed for mechanical equilibration of the absorbing volume. The particles are usually cleaved along crystallographic planes. The particles are of large size and evidently irregular shape. The sample surface after an exfoliation process can also be easily identified by the shape of the crater [93].

2-2-6 Hydrodynamic Sputtering

The term hydrodynamic sputtering is refer to a range of processes in which large droplets are ejected as a result of a transient melting and motion of a liquid caused by steep thermal gradients and relaxation of the laser induced pressure. However, even though it is easy to identify those particles that are ejected in the liquid state, there are several different mechanisms that could cause the liquid to leave the surface. Among them, hydrodynamic sputtering which is caused by cyclic heating and cooling of the surface which is frequently observed in laser ablation. When the laser fluence is sufficient to melt the surface, cyclic heating and cooling of the surface leads to the growth of perturbations and produces finger-like or ridge-like surface structures. Liquid droplets could be ejected from a melted layer as the acceleration of a liquid asperity (protrusion which is related to thermal expansion) exceeds the force holding the liquid to the surface [102].
16

2-2-7 Particle Ejection (Spallation)

The spherical shape of the particles demonstrates its origin from the liquid state. The large particles are formed from the liquid-solid interface. In the regime of stress confinement the laser-induced stresses can exceed the dynamic tensile strength of the target material, causing disruption of a liquid-solid interface. When the high-energy laser pulse, caused fast heating and vaporized of target material, results in the formation of thermomechanically stressed state. Its unloading may cause frontal cavitation of subsurface layer. The compression wave propagating deep into material hits the rear-side of the target with the formation of rarefaction wave. The last may produce cracks and rear-side spallation[103]. However, the vaporized material generated a vapour plume that propagated outward in the ambient. The pressure and temperature of the plume are very large especially in the initial stage of the vapour plume formation. The high pressure may push the liquid melt out from the centre of the laser-heated region and after the melt is cooled form a volcano-shaped crater (Fig.2-1). When the pressure is sufficiently large the resulting momentum surpasses the surface tension, which is holding the liquid to the surface, and droplets are ejected [93, 95,103, 104].

Fig. 2-1: Material removal via vaporization (left), pressure induced melt displacement (middle) and explosive melt ejection (right) [104].
17

2-2-8 Nucleation and Condensation

As the vapour plume propagates outward and starts to cool, the cooler front of the plume cloud allows aerosol particles to form. The characteristic times for particle formation are typically on the order of nanoseconds (10-9 sec), which is much shorter than the duration time of the cloud. The much shorter time scale for the particle formation ensures that the vapour will be transformed into particles. Condensation of the vaporized atoms is the mechanism for the generation of nanosized particles. The ambient pressure, gas properties and temperature are critical factors in condensation processes. Most numerical studies that have been made of this process calculate the shock location and the gas properties. Condensation processes were predicted when the plasma temperature decreased to a sufficiently low value related to the vapour number density. The molecules collide with each other and form larger aerosols; however the probability of forming particles as large as microns is very low since extremely high collision frequencies and atom number densities would be required [93,105].

2-2-9 Coagulation and Agglomeration (Growth)

Besides the main particle generation mechanisms there are several minor mechanisms, which will not generate particles but may alter the particle size distribution or the total particle number concentrations. These processes as coagulation can occur from several nanoseconds to several milliseconds after the laser pulse. Two most important processes were coagulation and agglomeration, which would usually increase the final particle size. Particles after forming from laser ablation collide with each other in the gas ambient, and if the momentum is large enough or the participant particles are in liquid phase, particles coalesce to form new large particles. This process is called coagulation and usually happens in the later time stage. Agglomerates are formed as early soon condensation starts, when the nanosizes aerosols are formed from vapour, they are strongly charged with electrons existing in the plasma. The charged particles then attach to each
18

other by the electronic bond and the agglomerates are identifiable by their chain or web shape. Figure 2-2 shows several images of particles ejecting from silver target that were ablated in liquid medium [86,93].
0 s

Fig.2-2: 10-ns resolved shadowgraph images of laser ablation phenomena observed for the 18 mM PVP solution. Some remarkable phenomena were selected: (a) optical emissions, (b) shockwave, (c) cavitations bubble and (d) secondary shockwave generated at the bubble collapse [86].

2-3 Nanoparticles-Liquid Reaction

Strong chemical reactions and physical processes will take place among the laser ablated metal species in the aqueous solution, such as the reaction between water molecules with the ablated species (as charge-transfer interaction and electrostatic forces), since the ablated active species are electronically excited and hence highly reactive, which induces the formation of nanoparticles in solution. The structure, morphology, size, and hence properties of nanoparticles will differ for different media including solvent and surfactant [106]. So, the properties of nanoparticles can be controlled by solution composition; On the other hand, the effect of such aqueous oxidation should be controllable through surface modification by surfactant coverage and manipulation of laser parameters. Hereby, it is possible to obtain the metal oxide metal composite NPs by rapid reactive quenching with surfactant aqueous solution [52,107]
19

2-4 Nanoparticles Suspension

Nanosized particles suspensions provide many advantages: (1) Nano-sized particles can have a surface force that balances the gravity force keeping the particles from being sunk or floated, thus nano-sized particles dispersions can form a stable systems with very little settling in static conditions; the mechanism of stability of nanoparticles was shown in Fig.(2-3) [85]. (2) The thermal, optical, mechanical, electrical, rheological, and magnetic properties of nanoparticles depend significantly on size and shape and they are superior to those of the base material. Thus, a variety of different nanofluids with significant properties can be designed to be environmentally friendly for a wide range of applications. Recent experiments have shown some promising nanofluids with amazing properties such as fluids with advanced heat transfer, drag reduction, binders for sand consolidation, gels, products for wettability alteration, and anti corrosive coatings For heat transfer applications, the presence of these nanoparticles has been shown to increase the static thermal conductivity of the base fluid by as much as 160% with the addition of carbon nanotubes.

Fig.2-3: Electrostatic repulsion between the outer parts of the electric bilayer enveloping each of the two Ag nanoparticles adapted for the case of Ag [85].
20

2-5 Synthesis of Nanoparticles

Synthesis techniques to generate metal nanoparticles depend on isolation of small amounts of a material. There are two general strategies mechanism to obtain materials on the nanoscale; I-The top down method (dispersion method) is where material is removed from the bulk material, leaving only the desired nanostructures. II-The bottom up method (reduction method) is one where the atoms produced from reduction of ions, are assembled to generate nanostructures [28,108].

2-5-1 Dispersion Methods (Top down method) The Top down method typically starting from bulk, involves laser ablation [47], arc discharge [43], etc... Nucleation takes place starting from the plume and continues till a solid substrate comes in its way. Control of particle size is achieved by tuning the fluence, wavelength irradiation time ...etc. The above crude method may be modified by altering the design of the cluster. Top down techniques suffer from the need to remove large amounts of material [28, 108].

2-5-2 Reduction Methods (bottom up method) The bottom up method starting from atoms, include chemical [31], electrochemical [33], sono-chemical[37], thermal and photochemical reduction [32,40,109],...etc, have been used to generate nanoparticles. Bottom up synthesis techniques usually employ an agent to stop growth of the particle at the nanoscale. Capping materials, such as a surfactant or polymer are used to prevent aggregation and precipitation of the metal nanoparticles out of solution. Choice of the reduction technique, time, and capping material determine the size and shape of the nanoparticles generated. Spheres, rods, cubes, disks,

wires, tubes, branched, triangular prisms and tetrahedral nanoparticles have been generated in gold, silver and platinum with various reduction techniques and capping materials [28,108,109].
21

2-6 Colloids
Nanosized particles of metals are ordinary insoluble in organic or organic solvent, but if they can be prepared in colloidal form, they can function more readily as catalysts. A colloid is a suspension of particles in range from 1 nm to 1 m in size. Many colloidal particles can, however, be detected by the way the scatter light, such as dust particles in air. This particles are in state of constant random movement (Brownian motion) arising from collisions with solvent molecules, which themselves are in motion. Particles are kept in suspension by repulsive electrostatic forces between them. The addition of salt to a colloid can weaken these forces and cause the suspended particles to gather into aggregates, and eventually they collect as sediment at the bottom of the solvent. This process of the settling out of colloid is called flocculation. Some of colloidal systems to be discussed are colloidal dispersions of insoluble materials (nanoparticles) in organic liquids, and these are called organsols. Analogous colloidal dispersions in water are called hydrosols [67,110].

2-7 Pulsed Laser Ablation in Liquids

Pulsed laser ablation in liquids PLAL is currently explored as a prospective top-down (dispersion method) strategy of metals nanoparticles preparation [70]. Its simple no chemistry is involved and basically free from limitations because it can generate nanoparticles without counter-ions or surface-active substances [61]. When a high-power pulsed laser beam irradiates on a metal target in a transparent liquid, a local plasma, with super high temperature (about 6000 K) and high pressure (about 1 GPa)[60,93], will instantly be produced on the solid-liquid interface and quench quickly after one pulse due to adiabatic expansion of the plasma and its interaction with surrounding media. The whole process is finished in about some microsecond. The thickness of the molten layer on the target is about 300 nm [60]. The
22

formation of nanostructures can be mainly attributed to the combination of ultrafast quenching of hot plasma produced via evaporated of molten thin layer and its interaction with surrounding media [111]. Moreover the nanoparticles ejected with velocity about 200 m/s[112].

2-8 Nanoparticles Formation Mechanisms

The complexity of the mechanisms of metal nanoparticle formation during PLAL includes various reactions in high-temperature and high-pressure plasma which are nonequilibrium process [60]. Upon laser ablation, various materials such as metal atoms, ions, clusters, fracture and droplets [113] are emitted from the metal plate. Nanoparticles are formed via nucleation, phase transition, and crystal growth of these emitted substances [86]. On the basis of that mentioned above, the formation of nanoparticles could be described in three mechanisms and every mechanism started with three steps :(I) After the interaction between pulsed laser and the metal target, the electronphonon coupling leads to a transfer of the electronic excess energy into lattice heat. The high-temperature and high-pressure of plasma (without solvent) is produced in the solid-liquid interface quickly after the interaction between pulsed laser and the metal target. (II) The subsequent ultrasonic and adiabatic expansion of the high temperature and high-pressure metal plasma leads to cooling of the metal plume region and hence to formation of metal clusters. (III) With the extinguishment of the plasma, the formed metal clusters encounter the solvent and surfactant molecules in the solution, which induces some chemical reactions and capping effects. The final structure and morphology of the particles are dependent on the surfactant concentration in solution or on the competition between aqueous oxidation of metals particles and surfactant protection [107]. However, The first mechanism, associated with aggregation of the ablated atoms and clusters into small embryonic nanoparticles and their growth by
23

assembling the clusters and attachment of free atoms. The density of ablated species (atoms) plays an important role in the nanoparticles growth, can be changed by adjusting the laser fluence. By controlling the density of the ablated species it is possible to control the final size of the formed nanoparticles [104]. The second mechanism attributed to the plasma-induced, with super high temperature and high pressure, plasma expanding result in ablation of particulates as fragment from the target or crater walls. Moreover, exfoliation as removal of fractured material in the solid state caused by photomechanical effects due to strong laser-induced thermal expansion and stress [93]. It should be noted that the second mechanism gives rise to much larger particle sizes and broader size distributions [46,104]. The third mechanism started when the solid at the focal point initially melts and is vaporized above ablation threshold (explosive boiling). The thin liquid layer adjacent to the solid surface is heated to the same temperature of the solid. The liquid is vaporized and in the vapour phase. Expanding vapours of the liquid splash this reservoir resulting in the removal of the molten layer. This molten drops and fractures split into nano-sized droplets, which are super cooled by the surrounding liquid [111]. Note that formation of NP via evaporation of the metal is unlikely, since the pressure of metal vapour at temperature close to melting is too low compared to vapour pressure of surrounding liquid. Surface tension stabilizes the molten drop of the metal, while the pressure of surrounding vapour of the liquid tends to split this drops [60,104,112]. It was source of the bimodal distributions was attributed to nanoparticles formed from ejected species from the initial ultrafast, nonthermal laser target interaction and thermal vaporization due to plasma heating of the target the bimodal distributions found here are attributed to thermally induced vaporization and explosive boiling. We identify the larger-sized mode of the distribution as arising from explosive boiling that ejects molten nanoparticles directly and the small size from thermal vaporization [112].
24

2-9 Interaction of Light with Noble Metal Nanoparticles

The intensity of light which propagates through a medium containing small particles is reduced by scattering and absorption. The extinction of the light beam is given by [3]: I(z) = I0 exp(n0extz), (2-3)

where I(z) is the intensity of the incoming beam after a distance z, n0 the number of particles per unit volume and ext the extinction cross section of a single particle. It holds [3]: ext = abs +sca, (2-4) where abs and sca: is the absorption and scattering cross sections of a single particle, respectively. The optical properties of such particles, as a consequence of their reduced dimensions, are dominated by a coherent collective oscillation of their conduction band electrons. As a result, the absorption cross section, which scales with their volume, can reach values several orders of magnitude larger compared to common organic dye molecules. Such collective oscillation is known as surface plasmon resonance [3].

2-9-1 Surface Plasmon Resonance in Metal Nanostructures (SPR)

The term plasmon is used to refer to plasma oscillations in metals, i.e. collective oscillation of conductive electron driven by light. The term resonance refers to a plasma oscillation excited by electromagnetic waves and the term surface is used because a surface polarization is the origin of the plasma oscillation [11]. For this purpose, the Surface Plasmon Resonance SPR in metal nanoparticles is an oscillation plasmon absorbs or scatters light resonantly of certain wavelength, also is known as surface plasmon extinction SPE, localized surface plasmon resonance LSPR, polariton resonance or Mie resonance.

25

For electromagnetic wave at a certain frequency () incident on a spherical nanoparticles much smaller than the wavelength of light (R), which induce a resonant, coherent oscillation of metal free electrons across the nanoparticles (Fig.2-4-a). Since the diameter of the particle is on the order of a few nanometers, and the penetration depth of electromagnetism waves in metals is of about 30 nm, the incident light is able to propagate through the particle. The propagated electric field inside the particle drives the conduction band electrons collectively with respect to the fixed positive lattice ions. As a result, a net charge difference appears on the surface at one side of the particle. Its attraction with the lattice ions on the opposite side leads to a restoring force. The resonance frequency is mainly determined by the strength of the restoring force. This force depends on the separation of the surface charges, i.e. the particle dimensions, and the polarizability of the medium between and around the charges. In other words the frequency, intensity and bandwidth of the SPR absorption and scattering depend on the incident wave, metal composition, nanoparticles size and shape, dielectric properties of surrounding

medium/substrate [114], spaced particles inter-particle interaction and particleto-particle interactions [23]. A photon confined to the small size of the nanostructure, constituting an intense electric field around the particle. The surface plasmon oscillation decays by radiating its energy resulting in light scattering or decays non-radiatively as a result of conversion of absorbed light to heat. The alternating surface charges form an oscillating dipole, which radiates electromagnetic waves. This oscillation is known as SPR (SPE), the resonance that lays at visible frequency for noble metals as Au and Ag, given those intense colours and interesting optical properties, as reflected are due to their unique interaction with light. Some of the photons will be released with the same frequency in all directions and this process is known as scattering. At the same time, some of the photons will be converted into phonons or vibrations of the lattice and this process is referred to as absorption. In general, the SPR peak
26

of metal nanostructure should include both scattering and absorption components. If the frequency of the incident light is in resonance with this surface plasmon oscillation of metal electrons, results in strong enhancement of absorption and scattering of electromagnetic radiation [3]. This simple model for particle plasmons is reminiscent of an optical antenna such that all the conduction electrons move in-phase producing only dipole-type oscillations manifested by a single, narrow peak in the SPR spectrum (Fig. 24b). As the size increases, the field across the particle becomes nonuniform, and this phase retardation broadens the dipole resonance and excites higher multipole resonances, such as the quadrupole, octupole, etc. (Fig 2-4-c) leading to several peaks in the spectra [3,114].

Fig. 2-4: Interaction of a small metal nanoparticle with light (R) (a), particle dipolar radiation(b) and quadrupole radiation of larger particles (c) [3].
27

2-9-2 Mie Theory

The general solution of the interaction problem of a single homogeneous sphere, of the radius R, and of arbitrary material with an incident electromagnetic field was first given by Mie in 1908[5]. Mie presented a solution to Maxwells equations that describes the extinction spectra of spherical particles of arbitrary size embedded in a homogeneous medium. One of the reasons why Mies theory has remained important for so long is that it is the only simple, exact solution to Maxwells equations that is relevant to particles. It is also worth mentioning that in his calculation, he introduces the dielectric function (,R) at the angular frequency to treat the material problem, which can incorporate all the size effects. The spherical symmetry suggests the use of a multipole extension of the fields, giving Mies calculations a series of multipole oscillations (dipole, quadrupole, etc.) for the absorption and the scattering cross section of the particles as a function of the particle radius. The extinction spectrum is then composed of the sum of absorption and scattering modes, each of which has a contribution that depends on the particle size. Higher-order modes become more dominant with increasing particle size. Physically, this can be explained by the fact that for larger particles, the light cannot polarize the nanoparticles homogeneously and retardation effects lead to the excitation of higher-order modes. Mies theory and experimental spectra agree well until for bulk metals, the normal incidence absorption no longer shows a plasmon resonance. Although his theory describes accurately the optical extinction spectra of metal nanoparticles, it does not explain the physical process, i.e. the collective oscillation of the conduction band electrons. The term plasmon for the Mie resonances was proposed first by Schopper in 1931[2,5,115].

28

2-10 Modification of Metal Nanoparticles

One of the most important challenges in the preparation of metal nanoparticles is the control of their size, shape and morphology. Laser-induced modification of the size and shape of nanoparticles are powerful tooling to enhancement the properties. Since the plasmon frequency of each single particle is determined by its dimension and shape, the optical absorption profiles of the whole distributions are inhomogeneously broadened. Therefore, irradiation of colloids with laser (pulsed or CW) of definite photon energy yields resonant plasmon excitation in particles with specific size and shape. By changing the excitation wavelength it is possible to selectively excite particles within a range of sizes and/or shapes. The observed changes in the absorption spectra caused by laser irradiation appear to correspond to changes in the size of the particles. Experimental parameters such as laser fluence, wavelength and irradiation time were found to influence the efficiency of the modification process [71,79,116].

2-10-1 Size Reduction- Secondary Laser Irradiation

Laser-induced modification of the size and shape of nanoparticles carried out when the surface Plasmon of nanoparticles in solution is excited under irradiation of a 532-nm laser, the photon energy is readily converted to the internal modes of the nanoparticles as heat [76]. During a single laser pulse (5 ns), one nanoparticle is considered to absorb consecutively more than one thousand photons, and its temperature rises significantly so that the nanoparticle starts to fragment. After the single laser pulse, the heat diffuses into the solution and the temperature of the nanoparticles returns to room temperature before the next one arrives. The heating and cooling of the nanoparticles occur in every laser pulse. We employed irradiate the growth solution containing silver nanoparticles. However that size was influenced by the frequency and power of the incident light. The optical properties of the prepared nanoparticles were
29

linearly dependent on the excitation wavelength [117]. So, the laser irradiation onto metal colloids induces both fragmentation and fusion of the colloidal particles [79,86].

2-10-2 Mechanism of Size Reduction Process

The efficiency of coupling of radiation to NP depends on the proximately of laser wavelength to plasmon frequency of charge carriers. The energy from electrons to the lattice is transferred within 35 ps, and the temperature T of the nanoparticles can be estimated on the basis of conventional heat diffusion equation. For small NP one obtains [60]:

Here r, I0, , Kl are: radius of nanoparticles, peak power of the laser, laser wavelength, and thermal conductivity of surrounding liquid, respectively. In this approximation, the temperature of the nanoparticle in the laser beam is proportional to its geometric cross-section r2. The extinction coefficient kex under large detuning from the plasmon resonance is close to that of the bulk metal. However, in the vicinity of plasmon resonance k = k() shows resonant behaviour, as well as the temperature T of the particle. Note that T is proportional to the peak power I0 of the laser beam, which is due to its small size. Fragmentation of NP occurs under their melting. As one can see from Eq.(2-5) the temperature T depends on the particle radius and can be lower than the melting point of its bulk material. At given value of laser peak power further fragmentation of nanoparticles stops as soon as they reach some critical size. Also, the temperature of a nanoparticle in the laser beam depends on the detuning of its plasmon resonance from the laser wavelength. This factor determines the efficiency of interaction of laser beam with nanoparticles generated by laser ablation of solid targets in liquids [60,118,].

(2-5)

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2-10-3 Laser-Induced Growth Tuneable Nanoparticles

The correlations between the SPE properties of silver or gold nanoparticles, their size, and their morphology have become an important subject. Preparation of tuneable nanoparticles were employed various laser lines as the exciting source to irradiate the growth solution containing nanoparticles. As the growth proceeds, the SPE peaks shifts to longer wavelength and broadens. Size, shape and optical properties of the prepared nanoparticles are influenced by the frequency and power of the incident light. Fig. 2-5 shows samples of the prepared silver colloids by using different laser lines as the incident light and their corresponding UV-VIS spectra. The vials marked from a to e, as shown in Fig. 2-5-A, correspond to the samples prepared with the excitation wavelengths of 514.5, 501, 488, 476.5, and 457.9 nm. The vial marked f is the original growth solution. These samples together display a series of colors, from mauve to faint yellow, due to differences in the size and shape of the prepared nanoparticles in the final colloid solution. The corresponding UV-VIS spectra, shown in Fig.2-5-B, display a series of absorption bands in the range from 480 to 560 nm, which implies that the optical properties of the prepared nanoparticles can be finely adjusted by changing the excitation wavelength surface of nanoseeds that impelled the growth of silver nanoparticles and formation of specific shape and size [79].

Fig. 2-5: (A) Optical pictures of the final products prepared by the irradiation of laser beam with different excitation wavelengths. (B) Corresponding UV-VIS absorption spectra of the final products, from a to e, with the excitation at 514.5, 501, 488, 476.5, and 457.9 nm, respectively. Spectrum f corresponds to the growth (parent) solution [79].
31

2-10-4 Target Modification

For instance, exposure of a solid by a stationary laser beam produces a crater (Fig. 2-6-a) [58,119]. If a scanning laser beam is used, then a new type of periodic structure arises (Fig.2-6-b). The formation of periodic structures under laser ablation of solid targets (such as Cu, brass) in liquids can be explained as follows [58,82]. During the laser pulse the target material melts and expelled from the pit by the recoil pressure of vapours of surrounding liquid. If the scanning velocity of the laser beam is small enough, then the laser radiation is captured by the pit in a sense that the side walls of the pit reflect the laser beam into the pit. The formation of the adjacent pit is therefore inhibited until the laser spot crosses the first pit, and the cycle repeats. The recoil pressure of vapours induces the melt motion along the pit surface. The molten material is partially ejected into surrounding liquid as nanoparticles. Then the melt solidifies, and one can see it in the form of small protrusions on the tips of structures. The gaps between the adjacent structures are of special interest. Their width rapidly decreases with depth down to few m and is therefore much smaller than the laser spot size. The formation of these channels attributed to the instability of a flat front of a melt under high recoil pressure [58,120]. The channels become hot spots due to reflection of laser light by side walls of the cones into in the target where the intensity of the laser beam may exceed by far the initial value of intensity on a flat target surface. [58].

Fig. 2-6: Typical craters on the gold target in water after 5000 laser pulses at F=60 (a) and F=1000 J/cm2 (b) [67]. And SEM view of periodic structures formed under scanning laser ablation in ethanol of bronze (c), and brass (d). A Cu vapour laser, fluence of 50 J/cm2 (c). An Nd: YAG laser, fluence of 16 J/cm2 (d)[58].
32

2-11 Surface Area of Nanoparticles

A number of properties of materials composed of nanometres-sized particles depend strongly on the surface area. For example, the chemical activity of conventional heterogeneous catalyst is proportional to the overall specific surface area per unit volume, so the high areas of nanoparticles provide them with the possibility of functioning as efficient catalysts. Fig. (2-7) shows an interest depended on the surface area on the nanoparticles size. The specific surface area (S) of sphere nanoparticles with diameter r is given by:[121].

Where: and r are the density (g/cm3) and nanoparticles size, respectively.

Using the units square meters per gram (m2/g) (2-6)

It is of interest to examine how the specific surface area depends on the shape of nanoparticles. Consider cube of side d with the same volume as a sphere of radius r, that 4/3r3=d3, we obtain for this case Scub=1.24 Ssph., so a cube has more specific surface than a sphere in same volume. In summary, the efficient way to increase the surface area of material is to decrease its particle size or shape. Another way to increase the surface area is to fill material with void or empty spaces, as porous material [121].
300 Surface Area per Weight(m2/g) 250 200 150 100 50 0 0 10 20 30 40 50 60 size of nanopaticle (nm) 70 80 90 100

Fig. 2-7: The surfaces area of GaAs nanoparticles as a function of their size [121].
33

2-12 Properties of Nanoparticles

2-12-1 Optical Properties
In small nanoclusters the effect of reduced dimensionality on electronic structure has the most profound effect on the energies of the highest occupied molecular orbital, essentially the valence band, and the lowest unoccupied molecular orbital, essentially the conduction band. Optical emission and absorption depend on transitions between these states; semiconductors and metals, in particular, show large changes in optical properties, such as colour, as a function of particle size. Colloidal solutions of gold nanoparticles have a deep red colour which becomes progressively more yellow as the particle size increases. Fig.2-8 shows the images for colloidal gold and silver nanoparticles of varying shape and sizes. Other properties which may be affected by reduced dimensionality include photocatalysis, photoconductivity, photoemission and electroluminescence

[63,122,123,124].

Fig. 2-8: Synthetic tunability of noble metal nanoparticles. Transmission electron micrographs of (a) Au nanospheres, (b) Au nanorods, and (c) Ag nanoprisms(Left). Photographs of colloidal dispersions of (d) Au-Ag alloy nanoparticles with increasing Au concentration, (e) Au nanorods of increasing aspect ratio, and (f) Ag nanoprisms with increasing lateral size(Right) [2].
34

2-12-2 Thermal Properties The large increase in surface energy and the change in interatomic spacing as a function of nanoparticle size have a marked effect on material properties. For instance, the melting point of gold particles, which is really a bulk thermodynamic characteristic, has been observed to decrease rapidly for particle sizes less than 10 nm, as shown in Fig. 2-9. There is evidence that for metallic nanocrystals embedded in a continuous matrix the opposite behaviour is true; i.e., smaller particles have higher melting points [123].
1400 1300 Meltig Temperature(K) 1200 1100 1000 900 800 0 5 10 15 20 25 30 35 size of nanopaticle (nm)

Bulk

Fig. 2-9: variation in melting point of gold NPs as a function of particle size [123].

2-12-3 Catalytic Properties Catalysis involve the modification of the rate of a chemical reaction, usually speeding up or acceleration of the reaction rate , by the addition of a substance, called a catalyst, that is not consumed during the reaction. Ordinary the catalyst participates in the reaction by combining with one or more of the reactants, and at the end the process it is regenerated without change. The catalyst is being constantly recycled as the reaction progresses. When two or more chemical reactions are proceeding in sequins or in parallel, a catalyst can play the role of selectively accelerating one reaction relative to other. [121,125].
35

2-13 Applications of Nanoparticles

Gold and silver nanoparticles exhibit strong optical extinction at visible and near-infrared wavelengths which can be tuned by adjusting the size. With recent advances in their high-yield synthesis, stabilization, functionalization and bioconjugation, gold nanoparticles are an increasingly applied nanomaterial. Bulk gold is well known for being inert; however, the nanoparticulate sizes of gold display astronomically high chemical reactivity [3,109].

2-13-1 Antibacterial of Silver Nanoparticles Agent

Synthesis of nanosized drug particles with tailored physical and chemical properties is of great interest in the development of new pharmaceutical products. Investigations have shown encouraging results about the activity of different drugs and antimicrobial formulation in the form of nanoparticles. However silver is a nontoxic, safe inorganic antibacterial agent used for centuries and is capable of killing about 650 types of diseases causing microorganisms. Silver has been ability to exert a bactericidal effect at minute. It has a significant potential for a wide range of biological applications such as antifungal agent, antibacterial agents for antibiotic resistant bacteria, preventing infections, healing wounds and anti-inflammatory. Silver ions (Ag+) and its compounds are highly toxic to microorganisms exhibiting strong biocidal effects on many species of bacteria but have a low toxicity towards animal cells. Therefore, silver ions, being antibacterial component, are employed in formulation of dental resin composites, bone cement, ion exchange fibers and coatings for medical devices. Bactericidal behaviour of nanoparticles is attributed to the presence of electronic effects that are brought about as a result of changes in local electronic structures of the surfaces due to smaller sizes. These effects are considered to be contributing towards enhancement of reactivity of silver nanoparticles surfaces. Ionic silver strongly interacts with
36

vital enzymes and inactivates them. It has been suggested that DNA loses its replication ability once the bacterium are treated with silver ions. Two dimensional electrophoresis and proteins identification analysis of antibacterial action of silver nanoparticles have disclosed accumulation of envelope proteins precursors. Silver nanoparticles destabilize plasma membrane potential and depletion of levels of intracellular adenosine triphosphate by targeting bacterial membrane resulting in bacterial cell death. Antibacterial activity of these silver nanoparticles as a function of particles concentration against gram-negative bacterium Escherichia coli (E: coli), that silver nanoparticles after interaction with E: coli have adhered to and penetrated into the bacterial cells. Antibacterial properties of silver nanoparticles are attributed to their total surface area, as a larger surface to volume ratio of nanoparticles provides more efficient means for enhanced antibacterial activity [10].

2-13-2 Surface Enhanced Raman Scattering

Noble metallic nanostructures exhibit a phenomenon known as surfaceenhanced Raman scattering SERS. The SERS technique is a powerful analytical tool in the fields of surface science, electrochemistry, biology, analytical chemistry, biochemistry, catalysis, and materials research. The excellent sensitivity and selectivity of SERS allow for the determination of chemical information from single monolayer on planar surfaces and extend the possibilities of surface vibrational spectroscopy to solve a wide array of problems [53]. In which, the intensity of Raman spectroscopy are dramatically enhanced through adsorbing the molecules onto metal surfaces. The aggregate of noble metal particles is prerequisite for stronger SERS enhancement. This is due to the existence of so-called hot spots having intense local electromagnetic fields in which highly efficient Raman scattering can be obtained [126].The sensitivity of SERS obtained from noble metal nanoparticles
37

strongly depends on the size and shape [127]. The basic theory of Raman Effect was developed before its discovery in 1928. Briefly, in this effect, incident light is inelastically scattered by molecules and shifted in frequency by the energy of the characteristic molecular vibrations. Raman scattering provides information about vibrational levels of molecules or, in other words, its structural fingerprint. However, the applications of Raman scattering are strongly limited by the weak intensity of the Raman-scattered light. When light is scattered from an atom or a molecule, most photons are elastically scattered (Rayleigh scattering), and only a small fraction is scattered at frequencies different from that of the incident photons [8]. When molecules deposited on rough noble metal surfaces showed greatly enhanced Raman scattering. Rough surfaces are decorated with nanoparticle shapes with surface plasmon oscillations. Also Surface Enhanced Raman Scattering occurs when the molecule is either absorbed or is in close proximity of metallic nanostructures (Fig. 2-10). The enhancement in the Raman signal in SERS is thought to occur due to two mechanisms: chemical (electronic) enhancement and electromagnetic

enhancement [8,128].

+
Biomolecules: Raman Signal is weak Metallic Nanoparticles NPs Biomolecule Adsorbed on the NPs: Enhancement Raman Signal

Fig. 2-10: Schematic of SERS process [8].

38

2-13-3 Diabetic Delayed Wound Healing

Diabetes mellitus is most common disease of the altered glucose homeostasis. One of the common degenerative diseases affecting people in the world today is diabetes mellitus. People with diabetes mellitus have five times the risk of having heart disease as people without diabetes. Diabetics have impaired wound healing and impaired formation of coronary collaterals. The abnormal apoptosis or angiogenesis may cause many of the clinical manifestations of diabetes. Silver has been known to have effective bactericidal properties for centuries. Nowadays, silver-based topical dressings have been widely used as a treatment for infections in burns, open wounds, and chronic ulcers. Silver nanoparticles are novel nanosized and highly crystalline antibacterial agent which carries Ag+ ions by ion-exchanging [20].

2-13-4 Cooling Challenge

Ultrahigh- performance cooling is one of the most vital needs of many industrial technologies. However, inherently low thermal conductivity is a primary limitation in developing energy-efficient heat transfer fluids that are required for ultrahigh-performance cooling. Nanofluids are engineered by suspending nanoparticles in traditional heat transfer fluids such as water, oil...etc. A very small amount of guest nanoparticles, when dispersed uniformly and suspended stably in host fluids, can provide dramatic improvements in the thermal properties of host fluids. Cooling is indispensable for maintaining the desired performance and reliability of a wide variety of products, such as computers, power electronics, car engines, and high-powered lasers or x-rays. With the unprecedented increase in heat loads (in some cases exceeding 25 kW) and heat fluxes (in some cases exceeding 2000 W/cm2) caused by more power and/or smaller feature sizes for these products, cooling is one of the top technical challenges facing high-tech industries such as microelectronics, transportation, and defence. Nanoparticles used in nanofluids have been made of various materials, such as (Ag, and Au) [21].
39

Chapter Three- Experimental Works

3-1 Laser Ablation System
Fig. 3-1 shows the experimental setup for laser ablation of solid metal target immersed in water or aqueous solution, which includes two lasers: Nd-YAG laser 1064nm and/or 532 nm (frequency doubled) wavelength was used for laser ablation process. A diode laser, 532 nm wavelengths, was used for on-line monitoring the formation and growth advance of nanoparticles. The measurement system consists of a detector type RS BPW 21 was connected to an electric circuit that convert the electric signal into transmittance/absorbance values; the calibration measurement was done as in reference [133]. The NdYAG laser beam was focused by using a lens onto a metallic target. The ablation process was typically done for 1 minute at room temperature. The target is fixed by a holder at the bottom of a quartz container.

Nd-YAG laser 1064 or 532 nm Laser beam Absorbance meter Lens Quartz container Diode laser(532nm) Detector Target
Liquid (NPs solution)

Electronic circuit

Target holder Magnetic stirrer

Plasma Melting layer

Fig. 3-1: Experimental setup for nanoparticles synthesis, by laser ablation technique.
40

3-2 Laser Source and Measurements Device 3-2-1 Nd-YAG Laser

Q-switched Nd/YAG laser system type HUAFEI providing pulses of 1064nm and 532 nm(frequency doubled) wavelength with maximum energy per pulse of 1000 mJ, pulse width of 10 ns, repetition rate of 10 Hz and effective beam diameter of 5 mm, was used for laser ablation. The laser is applied with a lens with 110 mm focal length is used to achieve high laser fluence.

3-2-2 Semiconductor Laser

Diode laser type IIIB laser product- 21CFR, Taiwan, was used. Its wavelength is 532nm; maximum output power is 10 mW. The beam diameter and divergence angle were experimentally measured about 2 mm and 3 mRad, respectively.

3-2-3 Transmission Electron Microscope

Samples of nanoparticles were identified by the transmission electron microscope TEM type CM10 pw6020, Philips-Germany (electronic microscope centre-collage of medicine/ Al-Nahrien University). The test samples were prepared by placing a drop of suspension of interest on a copper mesh coated with an amorphous carbon film. The drop was dried with an infrared lamp (Philips, 100 W) until all the solvent had evaporated. This process was repeated three to four times. The TEM carbon grids were loaded into the sample. The images were obtained at an accelerating voltage of 60 kV, with maximum magnification of 25000x-450000x. The diameter of produced was calculated from the following equation (taken from CM10 TEM sheet):


Where; D, d and M are: nanoparticle diameter, real diameter on image, and magnification of TEM respectively.
41

(nm)

(3-1)

3-2-4 Spectrophotometer
Absorbance spectra (SPE spectra) of NPs solution were measured by UVVIS double beam spectrophotometers, CECIL C. 7200 (France) and SHIMADZU. All spectra were measured at room-temperature in a quartz cell with 1 cm optical path. Additionally, spectrophotometer was used to estimate of metals nanoparticles [129].

3-2-5 Atomic Absorption Spectroscopy

Atomic absorption spectroscopy AAS measurement was carried out for the prepared samples using AAS spectrometer model GBS 933, Australia. Standard solution with concentration 1000 g/l of silver was prepared by dissolving 1.57 g of AgNO3 powder in 10 ml of HNO3 (40%), then the solution completed to 1 litre by adding distilled water. To obtain the calibration curve of silver, five standard samples were prepared ranged from (1.5, to 5.5 g/ml). The corresponding absorbance values of the above samples were measured by AAS.

3-2-6 Optical Microscope

The optical microscope, type KRUSS-OPTICAL IV (Germany) and KRUSS-OPTRONIC, with amplification of (1000x, 1600x), were used to observe morphology of metals target and thin films.

3-2-7 Evaporation System

The bulk silver and gold have been deposited on glass slides using thermal evaporation technique. The evaporation system is Edwards (UK). The deposition rate was 1 nm/sec. The vacuum chamber evacuated down to 10-5 torr using rotary pump and diffusion pump simultaneously. The thickness of the thin films has been evaluated about 20 nm, using the interference method.
42

3-3 Materials 3-3-1 Target Materials

Metals plates silver and gold ounces are purchased from Al-Rafedian bank, with high purity listed of (99.999) for Ag and Au foil. The plates were polished, washed in ethanol and DDDW and cut off to pieces with dimensions to suite the experimental arrangement. The surface of the noble metals plate (ounce) was polished with 600-grade emery paper and applying to ultrasonically rinse in organic solvents before being prior to each experiment.

3-3-2 Distilled and Deionised Water

Double distilled and deionised water DDDW is necessary for the preparation of all samples and solution in this work. Even such water is entirely pure; however, it is contaminated by salts ions, dissolved gases and dissolved materials. Deionised water prepared in Mansur factory-Baghdad by process of ion exchange [130]. The dissolved gases were removed by boiling the water at 100 0C for 10 minutes. Filter papers used to filter out and remove particulate matter. Distilled and Redistilled (duple distilled) water was prepared in our laboratory in glasses containers to avoid the contamination. After that preparation, the pH and resistance of water were measured to be near 7 and 5106 ohms/cm respectively.

3-3-3 Chemical Solution Preparation

Aqueous solution containing sodium dodecyl sulphate SDS, (M.W 289 C12H25SO4Na) (Kanto Chemical Co., Inc., 96%), as a surfactant (ionic detergent) is determined by particle growth by the laser ablation and its termination by SDS coating. Evidently, SDS plays an important role in determining stability and size of the nanoparticles. It is negatively charged, has
43

lathering properties [78,131]. SDS solution was prepared by adding 0.3 g of pure SDS powder to 10 ml DDDW and shake carefully. Then different concentrations samples (5-100 mM) are prepared by dilution procedure. Polyvinylpyrrolidone PVP (C6H9NO)x aqueous solution is a typical polymer (M.W.5000) that is used extensively as a stabilizing agent of metal colloids. In addition, since because PVP will also interact with ablated matter (atoms, clusters, and droplets) produced by laser ablation and prevent their aggregation, it is expected that PVP will affect on the particle size [85]. PVP solutions are prepared by adding 0.5 g of pure PVP powder to 10 ml of DDDW and shake carefully. Different concentrations samples (2-8 mM) are prepared.

3-4 General Experimental Process for Nanoparticles Formation

Silver and gold NPs were synthesized by pulsed laser ablation of a piece of silver and gold metal plates (ounces: 99.999%) placed on the bottom of quartz vessel containing 1ml of DDDW, or different solution such as NaCl, SDS, PVP, Ethanol and acetone. Those solutions have analytical grade were prepared in DDDW. The Nd-YAG laser was utilized as an. The spot size of the laser beam on the surface of the metal plate was varied in the range of 0.4-2.37 mm in diameter by changing the distance between the focusing lens and the metal plate. The laser

fluence was varied in the range from 477.7 to 13.6 J/cm2. The pulse energy was
varied in the range (100-900 mJ). The pulse duration and the repetition rate of the laser pulse were 10 ns and 10 Hz respectively. The liquid thickness was changed in the range from 2-14 mm. The liquid thickness adjusted by using different dimensions of cells. The number of laser shots applied for the metal target ranged from 5 to 90 pulses. A TEM was employed to take the electron micrographs of the solutions studied. SPE spectra of the nanoparticles solution were measured by UVVIS double beam spectrophotometer.
44

Chapter Four: Results and Discussion

4-1 Introduction
Laser ablation of bulk target immersed in liquid environment [48] which is simple method, recently has attracted much attention. The characteristics of the metal nanoparticles formed and the ablation efficiency strongly depend upon many parameters such as the wavelength[64,71] of the laser impinging the metallic target[60], the duration of the laser pulses[68], the laser fluence[67], the ablation time duration[85] and the effective liquid medium[65], with or without the presence of surfactants[86]. Moreover, nanoparticles can be modified in shape and size due to their further interaction with the laser light passing through it [1]. However, the SPR is a collective excitation of the electrons in the conduction band near the nanoparticle surface. Electrons are limited to specific vibration modes by particle size and shape [109]. Therefore, metallic NPs have characteristic SPE spectra in the UVVIS region and the SPE position is relates to particle size [117].

4-2 Effects of Laser Shots

Fig. 4-1 (A and B) shows the SPE spectra of silver and gold nanoparticles solutions, respectively, synthesized by pulsed laser ablation of a piece of silver and gold plate placed on the bottom of quartz vessel containing 1ml of ultra pure DDDW. The liquid depth was selected 8 and 7 mm above the target for silver and gold, respectively. The piece of metal was irradiated by focused energy of 600 mJ/pulse and 1064 nm Nd: YAG laser. The beam spot diameter at the metal surface was 1.27 and 0.85 mm for silver and gold, respectively. The number of pulses applied for the metal target ranged from 5 to 90 pulses. When the laser pulse struck the metal surface immersed in liquid; it created a spark plume with a strong shockwave that propagated in all directions. The spark emitted light and cracking noise, which were followed by a visible cloud of metal particles oozing out of the metal surface and dispersed slowly in all directions floating in liquid, easily noticed by naked eye. The colour of solution was changed and the intensity was
45

increased when advancing in the laser shots, showing the formation of colloidal metals nanoparticles. The SPE peaks in visible region are the characteristic metals NPs formation [3] while confinement in nanoscale was proved by blue shift in plasmon absorption peak relative to the bulk[114] (Fig. 4-42, sec. 4-15-1). When an increase in laser shots results in an increase in the SPE intensity, while the peak position remaining practically constant. The height and the width of the SPE peaks were found to be dependent upon the laser shots. This spectral change indicates that the abundance of the NPs is enhanced more under irradiation of the laser. Fig 4-1-A shows the SPE spectrum of the silver nanoparticles solution, displays a quasisymmetric absorption band centred at 400 nm, which indicates that the nanoparticles in the growth solution are quasispherical approximately 8 nm in size [79]. The silver nanoparticles, was faint yellow in color. Fig 4-1-B shows the plasmon peak position of AuNPs was around 525535 nm indicating the formation of particles with dimensions of 530 nm in the solution for laser energy used in the experiment. The formation of the gold nanoparticles in the solution was also verified by the TEM results, which are discussed below. The presence of the single surface plasmon peak implied that the formed nanoparticles were nearly spherical; in the case of ellipsoidal particles the absorption spectrum would have two plasmon peaks [77]. The height and the width of the SPR peaks were found to be dependent upon the laser shots. The gold nanoparticles, was faint pink in color, due to plasmon absorption [3]. The losses in the ablation of Au compared with Ag is attributed to the large reflectivity from the metal surface[112] The inset in Fig. 4-1-A shows the SPE band of Ag nanoparticles has been performed at 10 Hz pulses, band a, and, alternatively, in stepwise ablation (4 sec. break) band b, for 15 pulses. The SPE band of Ag NPs in spectrum (b) is more intense, narrower and more symmetrical than in spectrum (a), and its maximum is located at shorter wavelengths. In particular, the SPE peaks have been increased

from 0.69 to 0.83. That attributed to the mobility of generated particles which are much lower in solution than in gas [117], they can stay in the light-path of subsequent laser pulses, and then attenuate the laser energy.
46

3.5 3 2.5 2

A
Ag Nanoparticles
5 Pulses 10 P 15 P 30 P 45 P 60 P 75 P 90 P

15 Pulses
(a)

SPE

Laser Shots (Pulses)

(b)

SPE

0 350 400 (nm) 450 500

1.5 1 0.5 0 325

350

375

400

425

450

475

500

525

Wavelength (nm)

Au Nanoparticles
Laser shots
10 Pulses 15 Pulses 30 Pulses 40 Pulses 60 Pulses 90 Pulses

0.8

0.6

SPE

0.4

0.2

0 390 415 440 465 490 515 540 565 590 615 640

Wavelength (nm)

Figure 4-1: The SPE spectra of the plasmon band of Ag (A), and Au NPs (B), obtained by laser ablation of metal plates immersed in DDDW. The laser shots are changed in the range 5 to 90 pulses at laser energy of 600 mJ and =1064 nm. The inset shows the difference in SPE values between 10 Hz (a) and stepwise ablation (b), for 15 pulses.

47

Also it was attributed to a more efficient redistribution of nanoparticles due to long period time and efficient electric bilayer [85] build-up around the nanoparticles. It was noticed the stepwise laser ablation in pure water actually provides better results than of 10 Hz pulses ablation. Figure 4-2(A and B) shows the SPE peaks of silver and gold nanoparticles at 400 nm and 526 nm, respectively, as a function of the laser shot. As shown, the peaks were found to increase exponentially and saturate at more number of laser shots, attributed to the effect of accumulated nanoparticles to attenuate the laser intensity. The ejected NP remains in the liquid that surrounds the target resulting in formation of so called colloidal solution and prolonged interaction with laser radiation proceeds via its absorption by free electrons is possible. Thus, the particles have a considerable extinction coefficient at wavelength of laser light, they can absorb energy of laser light and the intensity of the incident laser light will be reduced. However, when the number of laser shots increases, the concentration of the atoms ejected in solution increases, whereas the ejection rate decreases. The degree of the reduction must depend on the concentrations of the nanoparticles. We expect that the ablation efficiency reduced and effected by three opposite parameters: a change of the polarizability of the solution [59], increase scattering due to present high concentration of nanoparticles and surface defect.
3.5 3 2.5 SPE Peaks SPE Peaks 2 1.5 1 0.5 0 0 15 30 45 60 75 90 Laser Shots 1.2

Ag Nanoparticles

1 0.8 0.6 0.4 0.2 0 0

Au Nanoparticles

15

30

45

60

75

90

Laser Shots

Fig. 4-2: SPE peaks as a function of number of laser shots for silver (A) and gold nanoparticles (B), respectively
48

Fig. 4-3 shows the PLAL efficiency, in terms of the SPE peaks, as a function of laser shot. It was found that ablation efficiency of samples is very weak, and found increases with the number of laser shot until 15 pulses, then turns to decrease. The linearly increase of the efficiency is interpreted as that initially the target surface of gold and silver was smooth and very shining, so that it reflects some of incident photon and reduces the ablation efficiency . But after application of the first few laser shots 2 to 3 pulses, the surface roughness and area increase. The decrease in ablation efficiency above 15 laser pulses was attributed to absorbance effect by advance laser shots [134]. Here the concentration of ejected NPs in solution increases, whereas the ejection rate decreases. The degree of the reduction must depend on the concentrations of the nanoparticles. It observed that, the laser shots of 15 pulses is the optimum, therefore it was selected to be applied as an effective parameter in following experimental study. Under our optimum parameters for Ag nanoparticles (liquid depth=8 mm, spot size=1.27, laser energy=600 mJ and laser wavelength =1064 nm), the formation efficiency was enhanced and estimated to be 30 times greater compared with results was reported by Siskova [85], 50 times as reported by Smejkal[132], 220 times as reported by Tsuji[64] and 700 times as reported by Tsuji[68]. This change in formation rate attributed to different parameters, one of them was our optimizations.
0.4 Ablation Efficiency (a.u) 0.12

A
Ablation Efficiency (a.u) 0.3

Ag Nanoparticles

0.1 0.08 0.06 0.04 0.02 0

Au Nanoparticles

0.2

0.1

0 0 10 20 30 40 50 60 70 80 90 100 Laser Shots

0 10 20 30 40 50 60 70 80 90 100 Laser Shots

Fig. 4-3: PLAL efficiency as a function of laser shots for silver (A) and gold nanoparticles (B), obtained by laser ablation of metal plates immersed in DDDW.
49

4-2-1 Silver Nanoparticles Concentration

To obtain the concentration of silver nanoparticles in liquid, atomic absorption spectrometer AAS was employed. Fig. 4-4-A shows the calibration curve, referring to atomic absorbance values obtained from AAS, as a function of silver standard concentration samples. The silver concentration exhibited an almost linear increase with atomic absorption. Fig. 4-4-B shows the amounts of ablated silver nanoparticles as a function of laser shots, corresponding to the samples shown in Fig. 4-1-A. The amount of ablated silver nanoparticles in agreement with SPE peaks as in Fig. 4-2-A. Under our optimum conditions, the rate of nanoparticles formation for silver and gold was enhanced. For examples, the formation rate of Ag nanoparticles is estimated to be 5200 g/min in one step, compared with 240 g/min, has been reported by Smejkal et al.[132], and 1100 g/min as reported by Kawasaki et al.[72] in two steps (at 10 Hz of laser ablation).
0.3 Atomic Absorbance 0.25 0.2 0.15 0.1 0.05 0 0 1 2 3 4 5 6 Ag standard concentration (g/ml) 600 Calibration Curve Ablated Ag (g/ml) 500 400 300 200 100 0 0 15 30 45 60 75 90 105 laser Shots

Ag Nanoparticles

y = 0.05x

Fig. 4-4: Calibration curve of atomic absorbance as a function of Ag standard concentration (A) and ablated concentration of Ag nanoparticles as a function of laser shots (B), obtained by laser ablation of silver plate immersed in DDDW.

From the observations of the electric potential of Ag colloid, the mechanism of desperation and aggregation depending on the pH value of solution [135]. The
50

Ag nanoparticles having negative surface charge can demonstrate a highly dispersed state without aggregation because of the electrostatic repulsion between the Ag NPs. However the Zeta potential inversely proportional with pH[80,135]. So that, because of their negative charges among the nanoparticles, the repulsive forces are likely to exceed the van der Waals attractive forces leading to coalescence[59], and hence, the nanoparticles are present in a solution without being coalesced even under centrifuge application Fig.4-5-A shows good agreement and correlation between the

concentrations of ablated Ag nanoparticles was determined by AAS and SPE peaks obtained by spectrophotometer. These results have two important features.
First it is suggested that we obtain coherent result for quantify the PLAL efficiency in terms of SPE peak, as well as of the amount of ablated silver nanoparticles. The second feature, one can estimate the amount of silver nanoparticles produced from the spectrophotometer measurements without need to AAS. Fig.4-5-B shows the

ablation efficiency in term of the concentration of ablated Ag nanoparticles. These results are in agreement with efficiency obtained in term of the SPE peaks; it has been proven by Fig. 4-5-A.
600 Ablated Ag concentrations (g/ml) 500 400 300 200 100 0 0 0.5 1 1.5 2 2.5 3 0.6

Ag Nanoparticles Ablation Efficiency (a.u)

0.5 0.4 0.3 0.2 0.1 0 0

Ag Nanoparticles

y = 179.2x

15

30

45

60

75

90

Maximum Absorbance (SPE)

laser Shots

Fig. 4-5: Amount of ablated Ag nanoparticles as a function of SPE peaks (A) and ablation efficiency in terms of the amount of ablated Ag nanoparticles (B), as a function of laser shots.
51

Figure 4-6(A and B) shows the TEM images and the corresponding size distributions of silver nanoparticles produced by laser ablation of a silver plate immersed in 1 ml of DDDW, at 15 pulses (A) and 90 pulses (B), respectively. The Nd-YAG laser of 1064 nm and energy of 600 mJ was used. The nanoparticles thus produced were calculated to have an average diameter of 1 and 15 nm at 15 and 90 pulses, respectively. The result revealed that the average diameter of nanoparticles increase with an increase in laser shots.
40 35 30 25

15 pulses Ag Nanoparticles

Frecuency (%)

20 15 10 5 0 5 10 15 20 25 30 35 40 45 50 55 60

200 nm
28 24 20

Nanoparticle Diameter (nm)

90 pulses Ag Nanoparticles

Frequency (%)

16 12 8 4 0

200 nm

10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

Fig. 4-6: TEM images and size distribution of silver nanoparticles produced by 1064-nm laser ablation (E=600 mJ/pulse) of silver plate immersed in 1ml of DDDW. The laser shots set of 15 pulses (A) and 90 pulses (B), respectively.

52

Figure 4-7(A and B) shows a typical TEM images and the corresponding size distributions of gold nanoparticles produced by laser ablation of gold plate immersed in 1 ml of DDDW, at different laser shots of 15 (A) and 90 pulses (B), respectively. The nanoparticles thus produced were calculated to have the average diameters of 1 and 16 nm at 15 and 90 pulses, respectively. The result shows that the average diameter increases with an increase of the laser number of shots. However, laser irradiation of the nanoparticles can stimulate further change of their morphology or can change the rate of their aggregation [77].
25

15 Pulses Au Nanoparticles

20

Frecuency (%) 200 nm

15

10

0 5 10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

25

90 Pulses Au Nanoparticles

20

15

Frecuincy (%) 200 nm

10

0 5 10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

Fig.4-7: TEM images and size distribution of Au nanoparticles produced by laser ablation of Au plate immersed in DDDW. The laser shots set of 15 pulses (A) and 90 pulses (B).
53

4-2-2 Ablation Monitoring

The SPE spectra of Au nanoparticles solution has an intense peaks centering at 525-535 nm (Fig 4-1-B). So that when the gold nanoparticles solution is excited under irradiation of 532-nm diode laser (1 mW, CW), the wavelength is in the vicinity of the SPE. The photon energy is interact [3] with nanoparticles solution can be result of absorb by nanoparticles. Therefore, when PLAL is take place, the Au nanoparticles formation was on-line monitored by simultaneous measurements SPE at the peaks via diode laser (Fig.4-8-A) for sample have of 15 pulses . It was found that the absorption values increased at more pulses,
indicating an increase in particle abundance. Fig.4-8-B shows a fairly good linear correlation between SPE peaks obtained by spectrophotometer and laser; therefore we suggest a relationship and agreement between them. Remarkably, all the calibration and correlation between laser and spectrophotometer measurements were done in reference [133]. These results are very important for testing and providing good reference to comparison with other results for evaluation of PLAL efficiency. It was believed that the result of the SPE peaks obtained by laser is a good tool to investigate the ablation efficiency. The on-line monitoring of Au nanoparticles formation represents a topic of great present interest in our study.
0.3 SPE (Obtained by laser) SPE(Obtained by Laser) 0.25 0.2 0.15 0.1 0.05 0 0 2 4 6 8 10 Laser Shots 12 14 16 1

Au Nanoparticles

0.8 0.6 0.4 0.2 0 0

Au Nanoparticles

y = 0.9806x

0.5 SPE (Obtained by Spectrophtpmeter)

Fig.4-8: The SPE peaks obtained by laser as a function of laser shots (A), and the correlation of between the SPE peaks obtained by laser and spectrophotometer(B).
54

4-3 Effects of Laser Energy

Another parameter having an important effect on the formation of metal nanoparticles is the laser energy. Fig. 4-9(A and B), shows SPE spectra of Ag and Au samples, respectively, prepared at different laser ablation energies. The Nd-YAG laser of 1064 nm was utilized as an ablation source. The pulse energy at the target surface was varied in the range (100-900 mJ) and the beam was focused to have a diameter near the outer edges of the target of 1.27 and 0.85 mm for Ag and Au, respectively. The metal plate was fixed in a glass vessel filled with 1 ml DDDW thus the smokelike colloids above the metal plate was observed. The plate was located at 8 and 7 mm from the liquid surface for Ag and Au, respectively. Laser ablation listed for 15 pulses and the solution gradually turned to coloured with the increase of the number of laser pulses. We measure a sensible increase in the SPR intensity, accompanied by a slight change in bandwidth and maximum wavelength, when increasing in the laser energy. This enhancement in intensity can be explained by the increase in the concentration of metals nanoparticles formed in solution during the ablation process. The height and the width of the SPR peaks were found also to be dependent upon the laser energy. Fig. 4-9(A) shows the SPE peaks that occurred at around 400 nm is the characteristic SPE signature of Ag nanoparticles [74], the SPR intensity increase broadens and slightly shifts to the red. This effect could be an indication of the formation of Ag nanoparticles with larger average size [93]. Fig 4-9-B shows broad band with the SPR peak around 526 nm with the peak position remaining practically constant, that indicates the production of gold nanoparticles [77]. We observed a visible coloration of the solution after several pulses of the experiment. The solution was coloured with faint pink. In the absorption spectra of the solutions, the surface plasmon related peak could be clearly distinguished. This peak was around 520530 nm, which was consistent with the presence of small 330 nm particles in the solution [136].

55

Ag Nanoparticles
Laser Energy (mJ)
100 mJ 300 mJ

0.8

0.6

500 mJ 600 mJ 700 mJ 900 mJ

SPE

0.4

0.2

0 350 375 400 425 450 475 500

Wavelength(nm)

0.35

B
0.3 0.25 0.2

Au Nanoparticles
Laser energy (mJ)
100 mJ 300 mJ 500 mJ 600 mJ 700 mJ 900 mJ

SPE

0.15 0.1 0.05 0 390 415 440 465 490 515 540 565 590 615

640

Wavelength(nm)

Fig. 4-9: SPE spectra of the plasmon band of silver nanoparticles (A), and gold NPs (B), obtained by laser ablation of metal plates immersed in DDDW with laser energy of (100 to 900 mJ, laser shots of 15 pulses and wave length is 1064 nm of Nd-YAG.
56

Fig. 4-10(A and B) shows the SPE peaks of ablated metals nanoparticles were increased as a function of laser energy. These absorption processes increase as number of particles increase in the solution. The curve shows linear increase as a function of energy, until the energy reaches 600 and 500 mJ for silver and gold, respectively, then the curve seems to saturate at high energies. This is attributed to the ejection rate that is reduced because: (1) The laser light is absorbed by nanoparticles present over the metal plate [59] and the ablation efficiency is reduced, (2) the surface properties of the metal plate are changed by the high laser pulses, and the ablation efficiency reduced drastically, (3) change of the polarizability of the solution in the presence of the nanoparticles [59], that causes the ablation efficiency to decrease. On the other hand, silver nanoparticles shows faster saturated compared with gold nanoparticles. It was attributed to abundance of silver nanoparticles is greater than that in gold at same parameters.

1.2 1 0.8 SPE Peaks SPE Peaks 0.6 0.4 0.2 0 0 200 400 600 800 1000 Laser Energy (mJ)

0.35

Ag Nanoparticles

0.3 0.25 0.2 0.15 0.1 0.05 0 0

Au Nanoparticles

250

500

750

1000

Laser Energy (mJ)

Fig. 4-10: Intensity of the SPE peaks as a function of laser energy, for silver (A) and gold (B) NPs, respectively, obtained by laser ablation of metal plates immersed in DDDW, laser shots is 15 pulses at =1064 nm.

57

Figure 4-11(A and B) shows electron micrographs and corresponding size distributions of silver nanoparticles, produced by laser ablation of silver plate immersed in pure water. The laser wavelength is 1064 nm and energies of 300 (A) and 900 mJ (B), respectively. The nanoparticles thus produced were calculated to have the average diameters of 13 and 17 nm at 300 and 900 mJ, respectively. It is observed that the average diameter and size distribution was increased with the increase of the laser energy.

12 10 8

300 mJ Ag Nanoparticles

Frquency(%) 200 nm

6 4 2 0 5 10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

9 8 7 6

900 mJ Ag Nanoparticles

Frequency (%) 200 nm

5 4 3 2 1 0 5 10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

Fig. 4-11: TEM images and size distributions of the silver nanoparticles, produced by laser ablation of silver plate immersed in DDDW. The laser energies are 300 mJ (A) and 900 mJ (B) , respectively(=1064 nm, laser shots of 15 pulses).

58

Figure 4-12(A and B) shows TEM pictures and size distributions of gold nanoparticles, produced by laser ablation of metal plates immersed in DDDW; the laser wavelength is 1064 nm. The nanoparticles thus produced were calculated to have the average diameters of 14 and 17 nm at the laser energies of 300 and 900 mJ, respectively. The average particles sizes increase and the size distribution broadens with an increase of applied laser energy. The origin of the surface morphology of the irregularly shaped particles in case of high energy can be explained by absorption by defects and thermally induced pressure pulses which cause cracking [47].
28 24 20

300 mJ Au Nanoparticles

Frequency (%)

16 12 8 4 0

200 nm
20

10 15 20 25 30 35 40 45 50 55 60

Particle Diameter (nm)

B
16 12

900 mJ
Au Nanoparticles

Frequency (%)

200 nm

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Particle Diameter (nm)

Fig. 4-12: TEM images and size distributions of gold nanoparticles, produced by laser ablation of metal plats immersed in DDDW, (=1064 nm and laser shots of 15 pulses). The laser energies are 300 (A) and 900 mJ (B), respectively.
59

The TEM data shows a drastic particle size reduction under the laser fluence decrease. Indeed, the mean particle size dropped from 18 to 13 nm as energy decreased from 900 to 300 mJ, as shown in Fig (5-12). Our result is in an agreement with Phuoc et al. [61] and Said et al [137]. However, increasing the fluence means delivering more energy that implies ablating larger amount of material. The strong effect of the laser intensity on the particle size and size distribution observed by our present study suggests that these parameters depend strongly on the plasma conditions in particular temperature, pressure, and species density [112]. However in ablation mechanism, the laser pulse produces melting and evaporating mass. The evaporated mass is an optimum case to produce soft nanoparticles by aggregation of evaporated atoms. On the other hand, in case of melting mass, small metal droplets are ejected [46] and nanoparticles formed as fragment of these droplets with large diameter and broad particles distribution, so that it is undesirable for application. At high energy ablation caused melting mass of the target surface with less evaporation, therefore it is not preferred in ablation mechanism. Therefore increase in size distribution at high energy can be attributing to that high energy laser caused target melting and expanding vapours splashes the liquid this solid melt and fractures into large nano-sized drops [112], which are super cooled by the surrounding liquid. At high energy, the inter- absorption of laser light is also taken place during the ablation, which retards the efficiency of ablation and minimize rate of nanoparticles production. These absorption processes increase as number of particles in the solution rise at small size. The melting and fragmentation mechanism of larger particles and formation of smaller ones could also be taken place due to the absorption of laser light [118,138]. This fragmentation mechanism explained the variation in size distribution. Therefore the population of particles smaller than 5 nm increased markedly in solution when laser energy at 900 mJ, compared to 300 mJ. However the density of the ablated species can be changed by adjusting the laser energy.
60

4-4 Effects of Laser Fluence

Fig. 4-13(A and B) shows the absorption spectra of colloidal solutions prepared by ablating silver and gold target respectively in ultra pure water ambient. The laser fluence was varied in the range from 477.7 to 13.6 J/cm2. The effective spot diameter of the laser beam on the surface of the metal plate was varied in the range of (0.4-2.37 mm). The laser energy was adjusted at 600 mJ, and the ablation was made by 15 pulses of laser. The metal plate was placed on the bottom of a glass vessel filled with 1 ml of pure water. The liquid depth was selected 8 and 7 mm for silver and gold, respectively, above the target. The metal plate was irradiated with a focused output of the fundamental (1064 nm) of Nd-YAG laser. Upon irradiating the target by the laser beam, the solution was gradually turned into contamination in nanoparticles. The spectra consist of strong absorption varied drastically with our conditions, due to plasmon band around visible region. Figure 4-14(A and B), shows the SPE peaks of silver and gold nanoparticles at 400 and 526 nm respectively, as a function of the laser fluence. the SPE peaks was found to increase linearly with the laser fluence, until (optimum) 47.4 and 105.8 J/cm2 for silver and gold, respectively, and then turns to decrease exponentially. A drastic change in the SPE peaks was occurred, when the spot diameter is slightly changed. An interesting phenomenon was found in our study that the lowest efficiency was obtained at the focal length of used lens (i.e. at the minimum spot size, 0.4 mm). Moreover, our results shows high formation rate compared with similar studies were prepared of Ag NPs at spot size of 2 mm over the Ag target, as reported by Zhao et al. [73] and 0.2 mm as reported by Tsuji et al.[64]. Both literatures shows low formation rate. These can be attributed to the effects of spot size on the metal surface. It is obvious

that, by decreasing in spot diameter less than an optimum values decrease the formation rate. That attributed to enhancement of blast wave.
61

1 0.9 0.8 0.7 0.6

(A) Ag Nanoparticles

Laser Fluence(J/cm2)
447.7 68.4 47.4 34 20.5 13.6

SPE

0.5 0.4 0.3 0.2 0.1 0 350 375 400 425 Wavelength(nm) 450 475

500

0.3

(B) Au Nanoparticles
0.25 0.2

Laser Fluence (J/cm2)

477.7 156 105.8 47.4 13.6

SPE
0.15 0.1 0.05 0 390 415 440 465 490 515 540 565 590

615

640

Wavelength(nm)

Figure 4-13: SPE spectra of the SPE band of silver (A), and gold nanoparticles (B), obtained by laser ablation of metal plates immersed in DDDW. The laser fluence was varied in the range from 477.7 to 13.6 J/cm2 with spot diameter ranged of (0.4-2.371 mm), respectively. The laser energy is 600 mJ and laser shots are 15 pulses.
62

Because the laser power is much higher than the focusing threshold, a blast wave is induced as a result of the high pressure exerted by the hightemperature filament like plasma [101].On the other hand, increase the spot size upon the target surface the radiation intensity is decreased and thus enlarges the radiation spot. This weakened the plasma intensity and thus minimized the impact of plasma-related ablation effects [69], which were found to broaden the size distribution of the ablated nanoparticles and reduce the ablation efficiently. However, the optimum adjusted laser fluence was very impotent parameter to increase ablation efficiency both in silver and gold.

1 0.8

A
Ag Nanoparticles

0.3 0.25 0.2

B
Au Nanoparticles

SPE Peaks

SPE Peaks
0 100 200 Laser 300 400 500

0.6 0.4 0.2 0 Fluence(J/cm2)

0.15 0.1 0.05 0 0 100 200 Laser 300 400 500 Fluence(J/cm2)

Fig. 4-14: Intensity of the SPE peaks as a function of laser fluence, of silver (A) and gold nanoparticles (B), respectively, obtained by laser ablation of metal plates immersed in DDDW with an laser energy of 600 mJ, laser shots are 15 pulses and =1064 nm.

63

4-5 Effects of Liquid Depth

Liquid depth above the metal target is very important parameter that enhanced the ablation efficiency of nanoparticles that confirm by absorbance measurement for the ablated suspended solution. Fig. 4-15 (A and B) shows the UV-VIS absorption spectra that indicated the characteristic SPE feature of silver and gold nanoparticles, respectively. This was carried out by PLAL of a metal plate in DDDW. The liquid depth was changed in the range from 2 to 14 mm. A focused Nd-YAG laser operated at 1 Hz with a wavelength of 1064 nm was vertically irradiated onto a metal plate placed in the aqueous solution. The beam diameter was selected at 1.27 and 0.85 mm for silver and gold plate, respectively. The ablating energy of 600 mJ was employed to ablate a target for 15 pulses. The products formed in the ambient liquid were transparent just after ablation, and then changed to contaminated ones after more application of NPs. We noticed a drastic change in the SPE peak found by few change in liquid depth. Fig. 415-A shows UVVIS absorption spectra of Ag NPs. All the spectra exhibit a characteristic peak around 400 nm, indicating the formation of Ag nanocolloids [139]. Fig. 4-15-B shows absorption spectra of gold nanoparticles, the surface plasmon related peak could be clearly distinguished. This peak was around 520530 nm, which was consistent with the presence of small 330 nm Au nanoparticles in the solution [67]. We observed a visible coloration of the solution after several pulses during the experiment. The color of solutions is faint pink.

64

(A) Ag Nanoparticles
0.8

Liquid Depth (mm)

2 mm 4 mm 6 mm

0.6

8 mm 10 mm 14 mm

SPE
0.4 0.2 0 350 375 400 425 Wavelength(nm) 0.3 450 475

500

(B) Au Nanoparticles
0.25 0.2 0.15 0.1 0.05 0 390 415 440 465 490 515 540 565

Liquid Depth (mm)

2 mm 4 mm 7 mm 8 mm 10 mm 14 mm

SPE

590

615

640

Wavelength(nm)

Fig. 5-15: SPE spectra of the plasmon band of Ag (A), and Au nanoparticles (B), obtained by laser ablation of metal plates immersed in DDDW with laser energy of 600 mJ, laser shots of 15 pulses and =1064 nm. The liquid depth varied in the range of (214 mm).

65

Figure 4-16 (A and B), shows the SPE peaks for silver and gold nanoparticles around 526 and 400 nm respectively, as a function of the liquid depth. We notice drastic changes in SPE when a little changes in liquid depth. The peak of SPR tends to increase linearly with the increase of depth, to reach 8 and 7 mm for silver and gold, respectively, and then turns to decrease exponentially, attributed to high absorption of IR wavelength by water. However, these values which were considered as optimum depths only in our study, as energy and wavelength ...etc.
Since the laser burst were greater than 8mm below the liquid surface, the expanding plume was always confined within the liquid, no water splashing was observed due to strong pressure and shockwave propagation. The reduction in formation rate observed when the liquid depth less than 4 mm attributed to water droplet as well as plasma splashing out of the liquid ambit at struck pulse. By compared with our result, Tsuji et al.[64] and Zhu et al.[74] reported low formation rate. These attributed to different parameters, one of them the depth of water layer was selected 15 mm and 5 mm by Tsuji and Zhu, respectively; compared with 8 mm was reported in our study.
1 0.8 0.6 SPE Peaks 0.4 0.2 0 0 1 Liquid Depth (cm) 2

0.4 Ag Nanoparticles 0.35 0.3 0.25 SPE Peaks 0.2 0.15 0.1 0.05 0 0

Au Nanoparticles

0.2 0.4 0.6 0.8

1.2 1.4 1.6

Lquid Depth (cm)

Fig 4-16: Intensity of the SPE peaks as a function of liquid depth, of silver (A) and gold nanoparticles (B), respectively, obtained by laser ablation of metal plates immersed in DDDW with an laser energy of 600 mJ and laser shots 15 pulses at =1064 nm.
66

4-6 Effects of Laser Wavelength

Fig. 4-17(A and B), shows the SPE spectra for Ag and Au samples, respectively, that were the nanoparticles synthesized by PLAL technique. The Nd-YAG laser of wavelength 1064nm and 532 nm(frequency doubled) with energies of 600 mJ per pulse in either wavelength. The beam was focused with near the target surface to of 1.27 mm for Ag, and 0.85 mm for Au. The metal plate was fixed in a glass vessel filled with 1 ml DDDW. After the laser ablation process is advanced, so that smokelike colloids above the metal plate were observed. The plate is located at 8 mm from the liquid surface for silver, and 7 mm for gold. Laser ablation listed for 15 pulses and the solution gradually turned to coloured with the increase of the number of pulses. An interesting phenomenon is observed that is the color of water is changed faster for the laser wavelength of 1064 nm than 532 nm at the same laser energy. Fig. 4-17-A shows UVVIS absorption spectra of Ag and Au nanoparticles, respectively. The spectra exhibit a characteristic peak around 400nm, indicating formation of Ag and Au nanocolloids, respectively [139]. It was found that augment is broadening in spectrum and decreased in the maximal value of absorption peak, when 532nm takes place (band -b). Fig 4-17-B shows broad band with the SPR peak around 526 nm with the peak position remaining practically constant, that indicates production of gold nanoparticles. However it was found that the SPE peaks of samples produced at 532 nm laser wavelengths is lower than that produced at 1064 nm as shown in Fig. 4-17. Therefore, it suggests that the particle densities of samples prepared at 1064 nm laser wavelength are an optimum. It may be concluded that laser wavelength of 532 nm is less efficient in fabricating nanoparticles in water. It is obvious that the efficiency of nanoparticle production increases when the wavelength decreases. By comparison of the SPE peaks of noble metals nanoparticles produced by PLAL at laser wavelength of 1064 and/or 532nm, indicates that the efficiency
67

of PLAL obtained by 1064 nm is largely exceeded that of 532 nm pulses. In particular, the maximum efficiencies of Ag ablated by 1064 nm pulses are greater than that obtained by using the same parameters with the 532 nm pulses for Ag and Au nanoparticles, respectively. There are some factors that can be attributing to the changes in PLAL efficiency between the two wavelengths. First, it may be contributing to light absorption properties of the target materials. The Ag and Au target have the capability to absorb the longwavelength (specifically1064 nm) laser energy as efficiently as at 532 nm. At laser wavelength 532 nm, the value of the abortion coefficient k of bulk noble metals (silver or gold) is less than that at wavelength 1064 nm [70]. Another factor is that at green wavelength, the absorbance by metal hydrosol is substantially higher than that at the 1064 nm. Although the visible wavelength exhibits a lower ablation threshold than that of the infrared one, the ablation process at 532 nm reaches early saturation because of both linear and nonlinear absorption mechanisms, accompanied by fragmentation of existing nanoparticles [83].
1 0.8 0.6

(A)

0.4 Ag Nanoparticles
(a)-1064 nm (b)-0532 nm

(B)
0.3

Au Nanoparticles
(c)-1064 nm (d) -0532 nm

SPE

0.4 0.2 0 350 400 450 500 Wavelength(nm)

SPE

0.2

0.1

0 390 430 470 510 550 590 Wavelength(nm)

Fig. 4-17: SPE spectra of the plasmon band of silver (A), and gold nanoparticles (B), obtained by laser ablation of metal plates immersed in DDDW exposed by 15 laser pulses, with laser energy 600 mJ, at laser wavelength of 1064 nm (band a and c), and 532 nm (bands b and d), respectively.
68

Fig. 4-18(A and B) shows TEM images and the corresponding size distributions of silver and gold nanoparticles, respectively. The laser wave length is 532 nm. The nanoparticles thus produced were calculated to have the average diameters of 16 and 18 for silver and gold, respectively. The result shows that the average diameter and size distribution increase with the decrease of wavelength. The average sizes increases and the distribution broadens with decrease in the laser wavelength.
25

Ag Nanoparticles

20

15

Frequency (%) 150 nm

10

0 5 10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

20 18 16 14 12

Au Nanoparticles

Frequency (%) 150 nm

10 8 6 4 2 0 5 10 15 20 25 30 35 40 45 50 55 60

Particle Diameter (nm)

Fig. 4-18: TEM images and size distributions of the silver (A) and gold nanoparticles (B), respectively, produced by laser ablation of metal plates immersed in DDDW, (laser energy of 600 mJ/pulse and laser wavelength is 532 nm).

69

4-7 Effects of Chemical Solutions

4-7-1 Effects of NaCl Solution
Fig. 4-19 shows the SPE spectra of colloidal solutions obtained by laser ablation of a silver plate in neat water and NaCl solutions at various concentrations. The absorption intensity of the plasmon band at 400 nm corresponding to the SPE, were increased by addition of NaCl. On the other hand, the spectral shapes of the plasmon bands were almost identical among those colloidal solutions. For that reason, the increase in the absorption intensity of the plasmon bands implies that the formation efficiency of nanoparticles was increased by addition NaCl. The SPE spectrum of Ag nanoparticles produced at 15 mM NaCl was characterized by a much weaker plasmon-related peak, which is shifted to 404 nm, this suggesting both a relatively large nanoparticle sizes and size dispersions, this is confirmed by TEM analysis The inset in Fig. 4-19 shows the SPE peaks of Ag nanoparticles are rapidly increased and reaching a maximum value of 1.23, when NaCl concentration changed from 0 to 2.5 mM, and then gradually decreased for higher concentrations. We believe that the abundance of silver nanoparticles is attributed to the presence of Cl ions, which in particular increase of the efficiency of the formation of Ag NPs [140]. Also it was noticed that the formation efficiency decreases with the increase of the concentration of NaCl from 2.5 to 15 mM. According to our result the optimum NaCl concentration to produce maximum amount of Ag NPs is 2.5 mM. We believe that convenient amount of NaCl in water will enhance the efficiency of nanoparticles formation, reduce the size, and prevent the aggregation. The increase in the absorption intensity of the plasmon bands implies that the formation efficiency of nanoparticles was increased; this fact was confirmed by Tsuji et al. [86]. The presence of Cl has a positive effect on the progress and the outcome of laser ablation, since they prevent the formation of large Ag nanoparticles and their aggregations, as witnessed by sharp, of narrow and nearly symmetric SPE bands with maxima in the 390-400 nm regions. This effect was
70

attributed to an efficient adsorption of Cl ions by the Ag nanoparticle surfaces and an efficient build-up of the electric bilayer around particles [85]. However the Cl increases the absolute value of this negative charge. The highly negatively charged nanoparticles produced in basic solution will tend to repel each other, thus limiting particle coalescence. Metal NPs surface reacted efficiently with Cl- and to

augment its net surface charge. This limited the coalescence of the particles, due to electrostatic repulsion, and led to a significant reduction of their size. Taking advantage of the repulsion effect, efficient size control is achieved. Metal surface was also suitable for surface modification through both covalent and electrostatic interactions during particle formation [69]. This was confirmed by TEM analysis indicating the absence of any reduction effect compared to that of pure deionised water.
1.4

NaCl Concentration (mM)

1.2 1 0.8 DDDW SPE peaks 0.5 mM 2.5 mM 5 mM 10 mM 15 mM

1.5 1.3 1.1 0.9 0.7 0.5 0.3 0.1 -1 1 3 5 7

NaCl Solution
Ag Nanoparticles

SPE
0.6 0.4 0.2 0 350 375 400 425

11

13

15

NaCl Concentration (mM)

450

475

500

525

Wavelength(nm)

Fig. 4-19: SPE spectra of silver colloids prepared by laser ablation of a silver plate immersed in DDDW or in NaCl solutions at various concentrations, ranged as (0.5 - 15 mM), for laser energy of 600 mJ, =1064 nm and laser shots is 15 pulses. The inset illustrates the change in the SPE peaks as a function of NaCl concentration.
71

Fig. 4-20 shows TEM and the corresponding size distributions of Ag NPs produced by laser ablation of a Ag plate immersed in NaCl solutions, the laser energy of 600 mJ/pulse. The nanoparticles that produced were calculated, have an average particle diameters of 11 and 13 nm in the 2.5 and 15 mM solutions respectively. The result shows that the average diameter and size distribution were decreased with the increase of NaCl. Ag nanoparticles are prepared in 2.5 mM faceted disperse without aggregation and do not have irregular shapes. However, at higher concentrations of NaCl (>10 mM), we observed quite different colloidal solution properties. In these cases, agglomeration of nanoparticles was occurred.
16 14 12

2.5 mM

Frequency (%)

10 8 6 4 2 0

Ag Nanoparticles

200 nm
28 24 20

10 15 20 25 30 35 40 45 50 55 60

Particle Diameter (nm)

15 mM
Ag Nanoparticles

Frequency (%)

16 12 8 4 0

200 nm

10 15 20 25 30 35 40 45 50 55 60

Particle Diameter (nm)

Fig. 4-20: TEM images and size distributions of the Ag NPs produced by laser ablation (E=600 mJ/pulse, laser shots of 15 pulses) in 2.5 mM (A) and 15 mM (B) of NaCl solution, respectively.
72

4-7-2 Effects of SDS Solution

Metal nanoparticles have a tendency to agglomerate, and therefore, it is necessary to protect those using surfactants or polymers [63,78,131,141]. The surfactant which surrounds each nanoparticle prevents direct contact of the other nanoparticles. Fig. 4-21 shows a typical optical SPE spectrum of silver nanoparticles produced in different concentrations of sodium dodecyl sulphate SDS and pure water respectively. So that the laser ablation in an aqueous solution containing SDS: C12H25SO4Na, (M.W 289), as a surfactant is determined by particle growth in a plume by the laser ablation and its termination by SDS coating. The formation mechanism of silver nanoparticles in the solution was examined by changing the concentration of SDS. Laser ablation was carried out with a Nd:YAG laser 1064 nm, maximum energy 600mJ/pulse, during all of the experiments. The silver target was placed on the bottom of a 1ml quartz vessel filled with 1 ml of aqueous solution. The depth of the deionised water layer above the target was 8 mm. The focal plane was adjusted to 1.27 mm beyond the target surface to decrease the radiation intensity on its surface and enlarge the radiation spot. This weakened the plasma intensity and thus minimized them impact of plasma-related ablation effects that were found to broaden the size distribution of the ablated nanoparticles [69]. All aqueous solutions used as ablation environments were prepared from double distilled deionised water. The extinction band of capped silver colloid suspended in SDS solution has SPE peaks at 402 nm. The spectrum exhibits a broad band extending toward the long wavelength range while the extinction band of uncapped silver colloid (suspension in water) has a maximum at 400 nm. This is the characteristic of silver colloid [142]. It is observed that a shift in the SPE peaks between capped and uncapped Ag nanoparticles is almost 2 nm. It may be concluded that the SPE depending on a number of parameters involving not only the particles size and shape but also the environmental dielectric function, the surface coating,
73

and the particle- particle interaction [110]. The red shift of the SPE peaks could be explained as formation of the chemical band between SDS ions and silver atom [142].The shapes and the intensities of the plasmon bands in the absorption spectra depended on the regime of laser operation. The inset shows the peaks of SPE of the Ag nanoparticles as a function of the SDS concentration corresponding to be the samples shown in same figure. The peak of SPE tends to increased linearly by addition of SDS, until 25 mM, and then turns to decrease gradually. According to our result the optimum SDS concentration to produce maximum amount of Ag nanoparticles is 25 mM. Note that the optimum concentration depends on the experimental parameters. Evidently, SDS plays an important role in determining the stability and size of the nanoparticles, because the termination of the nanoparticle growth is controlled by the diffusion and the attachment rates of SDS on the NPs.
1.4 1.2 1 0.8

SDS Concentration (mM)

DDDW 5 mM 10 mM 25 mM 50 mM 100 mM

1.5

SDS
SPE Peaks
1.25 1 0.75 0.5 0.25 -2 8 18 28 38 48

SPE

0.6 0.4 0.2 0 350 375 400 425

SDS Concentration (mM)

450

475

500

525

Wavelength (nm)

Fig. 4-21: SPE spectra of silver colloids prepared by laser ablation of a silver plate immersed in DDDW and SDS solutions at various concentrations (5, 10, 25, 50 and 100 mM) .The pulsed laser parameters are (E=600 mJ, =1064 nm and 15 laser pulses).The inset shows intensity of the SPE peak as a function of SDS concentrations (5-50 mM).
74

Fig. 4-22(A and B) shows TEM images and corresponding size distributions of silver nanoparticles produced by laser ablation (the wavelength of 1064 nm, 600 mJ/pulse) of a silver plate immersed in aqueous solutions of SDS having concentrations of 25 mM (A) and 50 mM (B),respectively. The nanoparticles thus produced were calculated to have an average diameter of 9 and 7 nm for 25, and 50 mM solutions, respectively. These results show that the average diameter reduction occurred when the SDS concentration is increased. The products are composed of the particles with nearly spherical shape. It is expected that the size distribution and the stability of the nanoparticles depend critically on the properties of the surfactant employed.
48 44 40 36 32 28 24 20 16 12 8 4 0 5 10 15 20 25 30 35 40 45 50 55 60

25 mM

200 nm
60 54 48

Frequency (%)

Ag Nanoparticles

Particle Diameter (nm)

50 mM

Frequency (%)

42 36 30 24 18 12 6 0 5 10 15 20 25 30 35 40 45 50 55 60

Ag Nanoparticles

200 nm

Particle Diameter (nm)

Fig. 4-22: TEM images and size distributions of the Ag NPs produced by laser ablation of silver plate immersed in 25 mM (A) and 50 mM (B) of SDS aqueous solution, respectively.
75

For the samples prepared in SDS solution, the particles are covered with surfactant (especially for high SDS concentration). It can be seen that with the increasing of SDS concentration, the size distribution width becomes narrow. TEM data, revealed a drastic particle size reduction as SDS concentration increased. Indeed, the mean particle size dropped from 14 to 7 nm as SDS concentration increased to 50 mM (Fig. 4-22). Highly negative charged nanoparticles can repel each other more effectively, thus allowing the SDS molecules to cover them before contact occurs. These kinetics considerations are expected to limit the coalescence of the forming clusters, leading to smaller particles. SDS which interact with the nanoparticles during the condensation and, thus, prevent them from further coalescence and agglomeration, have been used to effectively stabilize and reduce the size of Ag nanoparticles covered with SDS could be problematical for intended biosensing applications, because this surfactant might interfere with the subsequent biomolecule immobilization step[44]. At SDS concentrations of 10 mM, silver nanoparticles are born to be coated by a sufficient number of SDS molecules and are negatively charged. The repulsive force exerted among the negatively charged nanoparticles exceeds the van der Waals attractive force among them, so that they are dispersed stably in the solution and resistive against the aggregation. In a much higher concentration region (greater than 50 mM), the adsorption reduces the surface charge, increasing the van der Waals attractive interaction between the metal surfaces, and resulting in the attractive interaction. The attraction among metal nanoparticles acts as driving factors for the fusing process. The metal nanoparticles in higher concentration have been reported to show a tendency to fuse [126]. This phenomenon is explained by reduction of the negative charge on the nanoparticles because of neutralization on the nanoparticles by an excess amount of SDS .The repulsive forces among the different nanoparticles are weakened [59,141], so that, the Ag nanoparticles are tendency to coagulated.
76

4-7-3 Effects of PVP Solution

Fig. 4-23 shows the SPE spectra of silver nanoparticles produced by laser ablation of a silver plate immersed in neat water or in PVP aqueous solutions at various concentrations of 2, 4, 5, 8, 10 mM. Already, PVP is a typical polymer that is used extensively as a stabilizing agent of metal colloids [46] (as capping agent). Therefore, it is expected that colloids obtained in PVP solution will be more stable than those obtained in neat water. In addition, because PVP will also interact with ablated matter (atoms, clusters and droplets) produced by laser ablation and prevent their aggregation, it is expected that PVP will also affect on the particle size. Laser ablation was carried out with a Nd:YAG, (wavelength 1064 nm). The laser energy is fixed at 600 mJ/pulse and using 15 laser pulses during all experiments. The depth of the deionised water layer above the target was 8 mm, typically the focal plane was adjusted to 1.27 mm beyond the target surface to decrease the radiation intensity on its surface and enlarge the radiation spot. This weakened the plasma intensity and thus minimized their impact of plasmarelated ablation effects that were found to broaden the size distribution of the ablated nanoparticles. The SPE peaks are sensitive by PVP concentration. The plasmon absorption peak at 400 nm is the characteristic plasmon absorption peak of silver nanoparticles [74]. The position of the plasmon absorption peak depends on the particle size and shape and the adsorption of surfactant to the particle surface. It was noticed that the plasmon absorption peak shifts toward longer wavelengths (red shift) as we increased PVP concentration, usually is associated with an increase in particle size [143].

77

1.2

Ag Nanoparticles
1

PVP Concentration (mM)

DDDW 2 mM

0.8

4 mM 5 mM

0.6

8 mM 10 mM

SPE
0.4 0.2 0 350 375 400 425 Wavelength(nm) 450 475

500

Fig. 4-23: SPE spectra of silver nanoparticles prepared by laser ablation of a silver plate immersed in DDDW and PVP solutions at various concentrations. The laser energy is 600 mJ, laser wavelength is1064 nm and laser shots of 15 pulses.

Fig. 4-24: Shows the SPE peaks (A) and peak position (B), respectively, as a function of PVP concentration corresponding to the samples shown in Fig. 423. The SPE peaks of silver nanoparticles increased linearly by the addition of PVP, until 5 mM and then gradually decreased at higher concentrations. The formation efficiency, as a function of SPE peaks, is increased by 12% by the increase of the concentration of PVP from 0 to 5 mM. We believe that the concentration of silver nanoparticles are increased, which is attributes to high viscosity in particular increase the plasma confinement and enhancing the shockwave, that increase the efficiency of the formation of Ag nanoparticles. At high concentration of PVP greater than 5 mM, the formation efficiency of the formation of Ag nanoparticles decreased, that attributed to the production of
78

nanoparticle with large size. According to our result the optimum PVP concentration to produce maximum amount of Ag NPs is 5 mM. We note that the optimum concentration that depends on the experimental parameters as pulse energy, laser fluence wavelength... etc. The results described above indicate that the addition of PVP enhanced the formation efficiency of silver nanoparticle.
1.2 420

A
1 0.8 SPE Peaks 0.6 0.4 0.2 -1 1 3

Ag Nanoparticles

415 410 SPE Locaction 405 400 395 390

Ag Nanoparticles

11

-1

11

PVP Concentration (mM)

PVP Concentration (mM)

Fig. 4-24: Intensity of the SPE peaks (A) and SPE location (B), respectively, as a function of PVP concentrations of silver NPs obtained by laser ablation of Ag plate immersed in DDDW, the laser energy of 600 mJ, laser shots is 15 pulses at laser wavelength of 1064 nm.

Fig. 4-25 shows a typical TEM images and the particle size distributions of silver nanoparticles produced by laser ablation (=1064 nm and laser energy of 600 mJ/pulse) of a silver plate immersed in PVP aqueous solution. The Ag nanoparticles have an average diameter of 12 and 16 nm were produced in 5 and 10 mM PVP aqueous solution, respectively. The silver nanoparticles prepared in PVP solutions were more dispersed on the TEM grids than those prepared in neat water and the particle size was clearly decreased by addition of PVP compared with pure water (Fig. 4-6-A). It was found that, the size distribution increased by addition of PVP. The products are composed of the particles with
79

nearly spherical shape. For the samples prepared in PVP solution, the particles are covered with surfactant (especially for high PVP concentration). It can be seen that with the PVP concentration increasing, the size distribution increased. According to our result the optimum size was obtained when PVP concentration was at 5 mM. Note that the optimum size was depending on the experimental parameters. However, the size that decreases by addition of PVP is attributable to the interaction between PVP molecules and materials emitted by laser ablation.
32 28 24 20

5 mM
Ag Nanoparticles

Frequency (%)

16 12 8 4 0

200 nm
24 20 16

5 10 15 20 25 30 35 40 45 50 55 60 65 70

Particle Diameter (nm)

10 mM
Ag Nanoparticles

Frequency (%)

12 8 4 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 80

200 nm

Particle Diameter (nm)

Fig. 4-25: TEM images and size distributions of the silver nanoparticles produced by laser ablation of silver plate immersed in PVP aqueous solution have the concentration of 5 mM (A) and 10 mM (B) respectively. The laser parameters are (E=600 mJ, =1064 nm and laser shots is 15 pulses).
80

Throughout the laser ablation process, various materials such as silver atoms, clusters, and droplets are emitted from the silver plate. Nanoparticles are formed via nucleation phase transition, and crystal growth of these emitted substances. As for the PVP concentration dependence of the particle size, it can be attributed to the capping effect of PVP on the particles. The commercially available PVP molecules are terminated in the hydroxyl group due to the involvement of water and hydrogen, so that PVP in solution adsorbs on the nanoparticles and prevent their aggregation and growth. Such surface capping will prevent not only growth of the particles but also the coalescence among particles due to the repulsive interaction [111], leading to stable colloidal solution and small sized particles. Obviously, the higher PVP concentration will lead to more PVP molecules in solution attaching on the surface of the nanoparticles, inducing more stable colloidal solution and smaller particle size. On the other hand, the TEM images shows significant two type of nanoparticles, the first one larger than 50 nm and smaller than 10 nm were very similar in all PVP solutions samples. These phenomena attributed to thermal vaporization and explosive boiling mechanisms [112]. It was shown that the size distribution of particles formed after thermal vaporization is relatively small and constant in size and. We suggest this is due to the strong confinement of the ablation plume by the liquid atmosphere resulting in a nearly constant vapour density at the onset of nanoparticle growth. The explosive mode resulted in larger nanoparticles with a wide distribution with a significantly larger yield. Size control is an important measure of the quality of the nanomaterials synthesis. For synthesis, laser ablation of silver in PVP is a trade-off of i- larger nanoparticle yields at the expense of a much larger size distribution and less control in the final product or ii- lower yields of smaller, narrower size distribution. Additionally, the vapour plume also expands faster at higher PVP concentration. These reasons contribute to more irregular shape [112].

81

4-7-4 Effects of Organic Solutions

Fig. 4-26 shows the compression of optical SPE spectra of solutions (H2O, Ethanol and acetone) of Ag nanoparticles, respectively. The characteristic peak of the Ag colloid prepared in different organic solution centred around 400 nm. There colloids were prepared by pulsed laser ablation of a piece of silver plate immersed in 1ml of ultra DDDW or organic solution. The liquid depth and spot size above the target was selected 8 mm and 1.27 mm, respectively. The laser energy of 600 mJ/pulse, =1064nm of Nd: YAG laser operating at 1 Hz.
0.9 0.8 0.7 0.6

Ag nanoparticles
(i) DDDW (ii) Ethanol (iii) Acetone

SPE

0.5 0.4 0.3 0.2 0.1 0 350 375 400 425 Wavelength (nm) 450 475 500

Fig. 4-26: SPE spectra of silver colloids prepared by laser ablation of a silver plate immersed in DDW (i), ethanol (ii) and acetone (iii).The laser parameter are (laser energy of 600 mJ, =1064 nm and laser shots of 15 laser pulses)

Fig.4-27 shows typical electron micrographs and corresponding size distribution of silver nanoparticles produced by laser ablation (=1064 nm, laser energy 600 mJ/pulse and 15 laser pulses) of a silver plate immersed in ethanol (A), acetone (B). The nanoparticles thus produced were calculated to have the average diameters of 15 and 12 for ethanol and acetone, respectively.
82

28 24 20 16 12 8 4 0

(A)

Ethanol
Ag Nanoparticles

Frequency (%)

200 nm
28 24 20 16 12 8 4 0

10 15 20 25 30 35 40 45 50 55 60

Particle Diameter (nm)

(B)

Acetone
Ag Nanoparticles

Frequency (%)

200 nm

10 15 20 25 30 35 40 45 50 55 60

Particle Diameter (nm)

Fig. 4-27: TEM images and size distributions of the silver nanoparticles produced by laser ablation (=1064-nm, laser energy is 600 mJ/pulse and laser shots of 15 pulses) of silver plate immersed in ethanol (A), and acetone (B).

a- Ethanol Effects During laser ablation of silver in ethanol small bubbles can be observed in the solution, while in water no bubbles were observed. It is found that the SPE of samples produced in ethanol is lower than that produced in water. The lower of SPE indicates lower abundance of particles in solution. Thus, it implies that the ablation efficiency in ethanol is lower. After coupling of pulse energy to the surface of target, plasma species with very high temperature are generated. A
83

thin layer of solution at the interface of ablated area is vaporized to high temperature that far beyond its boiling point and to a high pressure of orders of tens atmospheres. The thermal conductivity of ethanol is 0.17 W/mK at 25 oC, which is much smaller than that of water (0.60 W/mK at 25 oC) [53]. Ethanol solution can be easily vaporized to such an enhanced condition. At high pressure and high temperature, ethanol can decompose to form permanent gases. The formed permanent gases in ethanol solution aggregate to bubbles that can be seen during laser ablation. The gases bubbles in the path of laser beam in combination with ablated plasma and formed nanoparticles in earlier pulses weaken the laser light that couples to the target. The nanoparticle generation reduces into a lower nanoparticle concentration. It suggests that no oxidation occurs under the protection of ethanol solution. Therefore, ethanol is proposed to be an optimal substitute of water for fabricating pure metals colloid.

b- Acetone Effects Acetone is preserving good dispersity of the nanoparticles. This superior function of acetone most probably stems from the interaction between the acetone carbonyl group and the metal nanoparticle surface. Strong interaction of the carbonyl group with nanoparticle surface is occurred. This interaction most probably involves a net charge transfer between the metal surface and the carbonyl oxygen atom. When the acetone molecules are adsorbed in this manner around the metal nanoparticle, they develop a protective surface dipole layer with the methyl groups in the outermost plane. This is probably how the interactions between nanoparticles become overall repulsive in the acetone medium [72]. Therefore acetone is good stabilizing power, serves as a superior liquid medium that keeps fine metal nanoparticles free from precipitation and oxidation.

84

4-8 Effects of Temperature

Fig. 4-28 band a-d shows the optical SPE spectra of four kinds of Ag nanoparticles in the colloids, respectively. The characteristic peak of the Ag colloid measured in different temperature treatment as denoted by inset caption for same colloids. The growth solution was synthesis by pulsed laser ablation of a piece of metals plates immersed in 1ml of ultra DDDW. The piece of metal was irradiated with the focused 700 mJ/pulse, 1064nm Nd: YAG laser. Fig.4-28 band a shows the SPE spectra of fresh (growth) solution, have a peak at 400 nm, and then it increase in intensity and shifted to 405 nm for storage of 15 days at room temperature (band b). This phenomenon attributed to a laser-ablated plume containing of an atoms [113] and small clusters during the ablation process. This phenomena was discussed as pioneer study by Tarasenko et al.[77] only in short period time along 60 minutes for gold nanoparticles. The ablated atoms and clusters tend to aggregate into small embryonic nanoparticles. These nanoparticles continue to grow by assembling the clusters and attachment of free atoms to the nanoparticles until all atoms in the vicinity of embryonic nanoparticles are consumed. Therefore the density of ablated species as atoms in the gas phase plays an important role in the nanoparticle growth, leading to a formation of new particles [51,77,136]. On the other hand band (c) shows reduce and red shift of the plasmon frequency of virgin nanoparticles solution, when heated for 5 minutes at 900C. This is characteristic for increase of the size. It is attributed to increase the kinetic energy of nanoparticles, lead to increase collision between nanoparticles that caused fusion. By compared with a, the band (d) is narrowed and the relative intensity of the plasma peak is enhanced and blue shift observed. The difference in the shape of the plasmon band suggested the change in particle size under frizzing treatment. An interesting phenomenon is observed that after frizzing, the ice of nanoparticles is slightly expand that caused a broken of contact points between nanoparticle that make it in small size.
85

1.2 Ag NPs 1 Fresh NPs 0.8 Keeping(15 Days) Heating(90 C. Dgree)

SPE

0.6

Freezing (3 Months)

0.4

0.2

0 350 375 400 425 Wavelength(nm) 450 475 500

Fig 4-28: SPE spectra of silver NPs prepared by laser ablation of Ag plate immersed in DDDW. The laser energy was selected of 700 mJ/pulse and wavelength is 1064 nm.

Fig. 4-29: shows TEM images and corresponding size distributions of silver nanoparticles after freezing it a long period of 3 months. The nanoparticles were calculated have the average diameters of 11 nm. The result shows that the average size and size distribution decreases at freezing and more dispersed.
36 32 28

Three Months of Freezing

Ag Nanoparticles

Frequency (%)

24 20 16 12 8 4 0

200 nm

5 10 15 20 25 30 35 40 45 50 55 60 65 70

Particle Diameter (nm)

Fig. 4-29: TEM image and size distributions of the silver nanoparticles after frizzing it along period of 3 months, produced by laser ablation of Ag plate immersed in DDDW.
86

4-9 Effects of Aging Time

To examine a stability of the prepared nanoparticles, the changes in the absorption spectrum with time were studied. Fig. 4-30 shows the change in the SPE of AgNPs, the plasmon bands at 400 nm became noticeable on the time scale of several months. The growth solution of nanoparticles was prepared by PLAL process in optimum condition at laser energy of 700 mJ. We noticed that the width of the 400-nm peak is broadened and the height is getting lowered for a longer time periods. This spectral change indicates that the diameters of the nanoparticles are increased more under by aging effect; which is interpreted to the metal nanoparticles are aggregated and fused by and hence the number of nanoparticles which are available decreased for as long time storage. Note that the nanoparticles in the solution fuse sufficiently fast that the spatial distribution of the nanoparticles is regarded as homogeneous.
1.2

Ag Nanoparticles
1

Storage Time (Month) Fresh 2 Months 4 Months 6 Months 8 Months

0.8

0.6

SPE
0.4 0.2 0 350 375 400 425 Wavelength (nm) 450 475

500

Fig. 4-30: SPE spectra of the plasmon band of silver NPs, obtained by laser ablation in DDDW with various aging time ranges from, 2 to 8 months using laser energy ,700 mJ, =1064 nm and 15 laser pulses.
87

Another significant change, red shifts is by observing in the absorption maximum that is shifted to longer wavelengths and broadening bandwidths until, on completion, a final size which is relatively broaden, indicating an increase in particle size and size dispersion remarkably [140]. We observed changes in color of the solution after several months of the experiment. The color of initial solutions was yellow for silver, whereas the aging solution looked red-yellow tint. This spectral change implies that the diameters of the nanoparticles increased. The decreased absorption intensity is caused by the sedimentation of the colloidal particles. The agglomeration of silver nanoparticles at first four months occurred fast than after six months. Fig. 4-31(A and B) shows peak intensity and the peak position (inset), for silver and gold, respectively, as a function of storage time (months); it was reduced and shifted to the longer wavelengths. These spectral changes attributed to that the metal nanoparticles tend to aggregate slowly with time in the solution [77,140]. The nanoparticles grow by collecting the small nanofragments. As a result the optical spectrum changes with time, the peak position of silver slightly shifted to the longer wavelengths and then stops after approximately 5 months.
1.05

Peak position(nm)

Peak Position(nm)

414 410 406 402 398 394 -1 1 3 5 7 Time (Month) 9

0.28

A
0.245

560 550 540 530 520 -1 1 3 5 7 Time (Month)

SPE Peaks

0.95

SPE Peaks

0.21

0.9

AgNPs

0.175

AuNPs

0.85 -1 0 1 2 3 4 5 6 7 8 9

0.14 -1 1

Time (Month)

Time (Month)

Fig. 4-31: Peaks intensity and peak position (inset) of the SPE of silver (A) and gold nanoparticles (B) as a function of storage time (months) obtained by laser ablation in DDDW with laser energy of 700 mJ, laser shots is 15 pulses at =1064 nm.
88

Fig. 4-32 shows TEM images and corresponding size distributions of Ag nanoparticles, produced by laser ablation of Ag metal plate immersed in 1 ml DDDW. The silver nanoparticles were storage at room temperature for one year before carrying out TEM measurement, without addition of any surfactants .The nanoparticles thus produced were calculated to have the average diameter of 20 nm. The result shows that the average diameter and size distribution increased with aging time. The nanoparticles where strongly aggregated due to a small electrostatic repulsive force between them, since the absolute value of the potential was small. When the aggregation and precipitation of Ag nanoparticles occurs, the color of colloidal solution changed. The SPR intensity diminishes, broadens and shifts to the red. On the other hand, bigger particles can precipitate more easily than much smaller ones due to the larger weight overcoming the interaction forces among particles and the buoyancy force of water. An interesting phenomena was noticed that the stability of the Ag nanoparticles in water decreases very slowly with the time compared with gold, a half-life time period is estimated about >720 days). That attributed formation of a partially oxide layer [84] on the surface of Ag nanoparticles that hampers further aggregation of Ag NPs.
25

Ag Ag Nanoparticles

20

Frecuency (%)

15

10

200 nm

10 15 20 25 30 35 40 45 50 55 60

Nanoparticle Diameter (nm)

Fig. 4-32: Selected TEM image and size distributions of the AgNPs after one year from preparation, produced by 1064-nm laser ablation (E=700 mJ/pulse and 15 pulses).
89

Fig. 4-33: summarize the stability of the colloidal nanoparticles solution prepared (in previous sections at the optimum parameters) by laser ablation of silver plates immersed in DDDW (a), NaCl (b), SDS (c), acetone (d), PVP (e) and ethanol (f). Its shows the change in the absorption intensity of the plasmon bands at 400 nm as a function of the months after the preparation to observe the stability of the colloids. The sedimentation of silver nanoparticles in the PVP, acetone and ethanol solutions occurred very fast than in neat water. Consequently, these data show that colloidal particles obtained in Ethanol solutions are less stable than those obtained in neat water. Consequently, these data show that colloidal particles obtained in NaCl solutions are less stable than those obtained in neat water.
1.3

1.1

Ag Nanoparticles
a=DDDW b=NaCl(2.5mM)

0.9

SPE Peaks

0.7
c=SDS(25mM)

0.5

d=Acetone e=PVP(5mM)

0.3

f=Ethanol

0.1 -1 0 1 2 3 4 5 6 7 8 9 10 11 Time ( Months)

Fig. 4-33: Peak intensity of the SPE of silver nanoparticles as a function of storage time (months) obtained by laser ablation of silver plate immersed in DDDW (a), NaCl (b), SDS (c),acetone(d) PVP (e)and ethanol (f) with laser energy of 600 mJ, laser shots is 15 pulses and at =1064 nm.
90

4-10 Nanoparticles Modification and Size Controlling

To obtain the laser induced size reduction LISR onto the produced metals nanoparticles was carried out by irradiation of unfocused pulsed 532 nm (second harmonic). After the laser ablation, the metal plate was removed from the solution and prepared colloids were put in tube with diameter of 5 mm under the laser beam irradiated 20 pulses unfocused double frequency 532 nm beams of the same Nd:YAG laser. The maximal laser irradiation energy was 900 mJ. Fig 4-34 shows the SPE spectrum of the fresh solution of silver nanoparticles, displays a quasi-symmetric absorption band centered at 400 nm (band a), which indicates that the nanoparticle in the virgin solution are quasispherical nanoparticles. By irradiating an initial solution of silver colloid, prepared via PLAL method, using the second harmonic of a Nd-YAG laser 532 nm, at laser energy of 900mJ. The size and shape of the products can be controlled; we prepared a colloid consisting of small spherical silver nanoparticles with average size of 8 nm. By monitoring the absorption

spectrum during growth, it is found that initially the solution irradiated displays symmetric absorption band centered at 395 nm (band b), which indicates that the nanoparticle in the embryonic solution are spherical nanoparticles and of darken yellow in color. The absorption maximum shifts to shorter wavelengths and narrower bandwidths until, on completion, a final size and relatively narrow is obtained, indicating a decrease in particle size and size dispersion remarkably [136]. Since the plasmon frequency of each single particle is determined by its dimension and shape, the optical absorption profiles of the whole distributions are inhomogeneously broadened. Therefore, irradiation of colloids with laser pulses of definite photon energy yields resonant plasmon excitation in particles with specific size and shape. By changing the excitation wavelength it is possible to selectively excite particles within a range of sizes and/or shapes [71].The ability to fabricate nanoparticles of varying shape and size, is a
91

hopefully improvement. So by irradiation of nanoparticles with a laser beam, which wavelength is in the vicinity of the surface plasmon excitation the laserinduced size reduction can be caused in result of the interaction between pulsed laser light and particles, the heating effect was suggested to be the cause in the case of the gold nanoparticles. We can prepare silver nanoparticles with wellcontrolled size, shape, and tunable SPR properties. This suggests that there must be a relationship between the excitation wavelength and the corresponding SPR absorption band of the prepared nanoparticles [77]. The final size and shape is found to depend on irradiation pulses. Our result in agreement with Smejkal et al.[87], study the effects of laser fluence and laser shots on fragmentation process. The full width at half-maximum FWHM of band (b) was decreased and the profile narrowed and became monosymmetric.
1

Ag Nanoparticles
0.8 (a) Virgin Nanoparticles (b) Embryonic Nanoparticles 0.6

SPE
0.4 0.2 0 350 375 400 425 Wavelength(nm) 450 475 500

Fig. 4-34: SPE of Ag nanoparticles produced by laser ablation of 1064 nm (600 mJ) in water (band a) and after irradiation (band b) by pulsed 532 nm laser, having laser energy of 900 mJ for laser shots of 20 pulses.

92

Figure 4-35 shows the SPE spectra of gold NPs produced in water before (band a) and after irradiation (band b) by a pulsed 1064 and 532 nm laser, having energies of 600 and 900 mJ, respectively. The spectra of virgin solution exhibit the characteristic peak of the surface plasmon band at 526 nm (band a). The embryonic nanoparticles exhibit the characteristic peak of the surface plasmon band at 520 nm (band b). The width of the 520-nm peak is broadened and the height is lowered more greatly by introducing more laser shots. This spectral change indicates that the diameters of the nanoparticles are reduced more [77] under irradiation of the laser with a more laser shots. Another significant change is observed is the blue shifts. According to the Mies theory, the peak shift to be observed in an absorption spectrum when the mean diameter of the particles changes. It was observed that the Au NPs with smaller diameter exhibit SPE at the shorter wavelengths. Therefore, we observed spectral changes imply that the initial nanoparticles were most likely fragmented by the laser irradiation.
0.3 (a) Virgin Nanoparticles (b) Embryonic Nanoparticles

Au Nanoparticles
0.25

0.2

SPE
0.15 0.1 0.05 390 415 440 465 490 515 540 565 590 615 640

Wavelength(nm)

Fig. 4-35: SPE spectra of gold nanoparticles produced by laser ablation of 1064 nm (600 mJ) in water (band a) and after irradiation (band b) by pulsed 532 nm laser, the laser energy is 900 mJ and laser shots of 20 pulses.
93

Figure 4-36 shows the TEM image and corresponding size distribution of nanoparticles products prepared by the irradiation of unfocused 532 nm laser for 20 pulses with excitation energy of 900 mJ. The TEM image shows that the nanoparticles in the embryonic colloid solution are spherical in shape, with the average diameter of 9 and 8 nm for silver and gold respectively. The parent silver and gold nanoparticles were shifted to a small diameter and sizedistribution is narrowed by the size reduction because the smallest possible.
40 36 32 28 24

A
Ag Nanoparticles

Frequency (%)

20 16 12 8 4 0 5 10 15 20 25 30 35 40 45 50 55 60

200 nm
48 44 40 36 32 28

Nanoparticles Diameter (nm)

B
Au Nanoparticles

Frequency (%)

24 20 16 12 8 4 0 5 10 15 20 25 30 35 40 45 50 55 60

200 nm

Nanoparticle Diameter (nm)

Fig. 4-36: TEM images and size distributions of the embryonic silver (A) and gold (B) nanoparticles, produced by laser irradiation virgin nanoparticles with laser pulsed at =532 nm, E=900 mJ and laser shots of 20 pulses. (The virgin NPs prepared by 1064-nm laser ablation (E=600 mJ/pulse, =1064 nm) of metals plats immersed in DDDW.
94

We noticed that the population of particles smaller than 5 nm increased markedly in solution after the secondary laser irradiation; large particles should be pulverized to small particles, which revealed a drastic particle size reduction under the laser fluence decrease. Our results are in agreement with Tsuji et al. [86]. Moreover, metal NPs are much smaller than the wavelength of the exciting light so that all conduction elections of particles are excited in phase. The collective electron motion (plasmon) inside the metal clusters arouses strong interaction of metal clusters with the exciting light at their SPE frequency [144]. We expect that the reduction size efficiency must be reached to saturation limit. It was attributed to smaller particles show time constants of heat dissipation that are proportional to the square of their radius [75]. So that smaller nanoparticles show, therefore, fast heat dissipation and they are less expected to reach a temperature sufficient for reduction. Therefore, smaller nanoparticles can be pulverized even by weak laser energy [117,136]. Similar study was reported by Pyatenko et al.[91].

4-11 Nanoalloys: Core-Shell Nanostructure Synthesis

Pure Ag and Au nanoparticles were synthesised by pulsed laser ablation of metallic targets in liquid media, subsequently, mixing in same volume ratio and re-irradiating by unfocused and pulsed Nd-YAG laser. The laser energy, laser wavelength and shots are 900 mJ, 532 nm and 25 pulses, respectively. Fig (437) reports the extinction spectra of two sets of Ag (band a) and Au NPs (band b) samples. The SPE spectra (band c) of irradiated Ag-Au mixed nanoparticles solution show double peaks, indicating the presence of discrete-pure silver and gold particles [51], respectively. On the other hand, the SPE reduced and the tow peaks at 400 and 525 nm were shifted to the red and blue, respectively, indicating of producing of bimetallic AuAg core-shell nanoalloys [55] instead of separate Ag and Au nanoparticles. This phenomenon was confirmed by TEM. However, the Ag NPs have been observed to melt at significantly lower temperatures than the melting temperature of bulk Ag [145].
95

0.9 0.8 0.7 0.6 0.5 (a) Ag Nanoparticles (b) Au Nanoparticles (c) As Irradiated(532 nm)

Au-Ag Core-Shell Nanostructure

SPE

0.4 0.3 0.2 0.1 0 340 380 420 460

500

540

580

Wavelength (nm)

Fig. (4-37): SPE spectra of pure Ag (a), pure Au (b) and as mixed and irradiated (=532 nm, laser shots of 25 pulses and E=900 mJ) of Au-Ag core-shell nanostructure (c).

Fig. 4-38 shows the TEM images and corresponding size distribution of colloid obtained after laser irradiation. The clusters appear to be nearly spherical with average sizes of 19 nm. Similar study was reported in [51,55,146].
24

200 nm
20 16

Size Distribution Au-Ag Core-Shell: Nanostructure

Frequency (%)

12 8 4 0 5 10 15 20 25 30 35 40 45 50 55 60

Au-core

Ag-shell

30 nm

Particle Diameter (nm)

Fig. 4-38: TEM image and corresponding size distribution of Au-Ag core-shell nanostructure solution, prepared via laser irradiation of mixed Ag-Au nanoparticles solution. The lighter particles are Ag ones while darker ones are Au. The irradiated laser parameters are:(=532 nm, E=900 mJ and laser shots is 25 pulses).
96

4-12 Color Changing: nging: Indicator

During the laser ablation of noble metal target, it was observed that the color of solution changed from light yellow and pink for Ag and Au, respectively, and then finally deep. The deeper color indicates higher concentration of noble metal nanoparticles. Fig.(4-39) shows the color changing as a function of nanoparticles concentration by changing some parameter as mentioned in each vial vial. The interesting optical is attributes of metal nanoparticles, as scattered red in their bright intense colors [3]. . In the presence of the oscillating electromagnetic field of the light, the free electrons of the metal nanoparticle undergo a co collective coherent oscillation with respect to the positive metallic lattice. This process is resonant at a particular frequency of the light and is termed the SPR oscillation (SPE) [114]. This electronic oscillation can be simply visualized as a photon confined to the small size of the nanostructure, constituting an intense electric fie field around the particle. The SPR oscillation decays by radiating its energy resulting in light scattering [23]. Whose hose color and color intensity can be determined both their particle size and concentration, respectively. Therefore, the color of the colloidal solution is a good indicator of the particle size and solution concentration [69]. The color of metal nanoparticle is resulted from the coherent oscillation of the conduction band electrons for metallic nanoparticles can be induc induced by the interacting electromagnetic field, which is named as SPE [46].

Fig.4-39: Photo-pictures pictures of the final products of NPs solutions prepared by PLAL.
97

4-13 Thin Films Deposition

4-13-1 Bulk Thin Films
To estimate the absorbance behaviour of bulk noble metals target as a function of incident wavelength, silver and gold thin films have been prepared by deposited on glass substrates using thermal evaporation technique. The thickness of the thin films was 20 nm, has been evaluated using interference method. We noted that the surface is smooth because the thickness of the Ag and gold films was only 20 nm. The optical spectra of the films were investigated in the wavelength range of 3501200 nm by a spectrophotometer. Fig. 4-40 shows the absorption spectra of the Ag and Au films deposited for 20 sec. The Ag thin films deposited, which exhibit a linear increase in absorbance intensity with the increasing of the wavelength and have flat absorption peak around 600 nm, suggesting that the Ag films are homogeneous according to Moore et al. [147] .The Au thin film shows decrease in absorbance intensity, when the wavelength is increased until 500 nm, then will be increased and it is subsequently saturated.
0.8 0.7 0.6 0.5 Absorbance 0.4 0.3 0.2 0.1 0 300 400 500 600 700 800 900 1000 1100 1200 Silver thin film Gold thin film

Thin Film

Wavelength (nm)

Fig.4-40: Absorption spectra of silver and gold bulk thin films as a function of wavelength.
98

4-13-2 Nanoparticles Thin Films

Two-dimensional nanostructures have been studied and categorized as thin films. Because of their confinement to the nanoscale, they have been developed for use in fields as diverse as electronic devices and photovoltaic applications, due to their large surface area [148]. Therefore transparent thin films were prepared by precipitated nanoparticles solutions on glass substrate by drying at room temperature in an auto-dry method. The nanoparticles solutions were synthesized by pulsed laser ablation of metal plates immersed in DDDW. This method is dependent by Kazakevich et al [58]. On the other hand, deposition of noble metal nanoparticle via PLD in liquid has been reported by Cui et al.[12]. Fig. 4-41 shows the optical microscope images of silver (a-g) and gold (h-o) NPs thin films, respectively. These thin films are prepared by precipitate of liquid nanoparticles samples (produced by PLAL in previous section). However the SPE peaks of the silver nanoparticles solutions in panels a-g are 0.4-2.2, increased by 0.3, and the SPE peaks of the gold nanoparticles solutions in panels h-o are 0.170.87, increased by 0.1. The thickness of the nanoparticles thin films was 20 nm in panels a and h for silver and gold respectively, has been evaluated using interference method. Correspondingly, the films structure changes from discontinuous film, consisting of the isolated aggregates of the building blocks, to the dense film. Further experiments have revealed that formation of the irregularly shaped building blocks is attributed to the randomly growth of the nanoparticles. We noted that the surface is not quite smooth because the films prepared in an auto-dry precipitation. We suggest that the relatively large roughness of the thin films is a result from two aspects. Firstly, the films were deposited at room temperature. Secondly, the films were grown at long period time about 5 days, which may give rise to some particles during the depositing process, affecting on surface roughness. The metal film shows a shiny and metallic appearance may be come from the agglomerating into bulk metal [32]. The coloration is due to plasmon oscillations of free electrons in nanoprotrusions structure [82,149].
99

50 m

Fig.4-41: Optical microscope images of silver a-g and gold h-o nanoparticles thin films. All the images were done in the same magnification.
100

On the other hand, metal films which contain large networks of elongated nano- voids, granular films with a small quantity of voids, and finally dense void free films which however have properties which differ from the bulk due to their nano-grain. The corresponding UV-VIS absorption spectra of silver (panel a) and gold (panel h) in Fig. 4-41, are shown in Fig. 4-42. All the spectra exhibit bands due to the SPE, the position and intensity depending on several factors such as the diameter of the nanocrystals, the nature of the light and the refractive index of the surrounding medium. Fig. 4-42(A and B) shows the SPE of silver and gold nanoparticles, respectively, in case of solution and thin film. Band (i) in Fig 4-42-A shows the SPE spectrum of the silver nanoparticles solution, displays a quasisymmetric absorption band centred at 400 nm, which indicates that the nanoparticles in the growth solution are quasispherical nanoparticles approximately 8 nm in size[79]. Band (ii) shows the UV-VIS absorption spectrum that the thin film silver nanoparticles, displays asymmetric absorption band centred at 430 nm which indicates that the nanoparticle in the thin film are hemispherical nanoparticles. The absorption maximum shifts to longer wavelengths and broadening bandwidths, a final size and relatively expand, indicating an increase in particle size and size dispersion [86], is in good agreement with the red shift and widening of the SPR peak with the increase in the thickness of nanostructured Ag films prepared by PLD, reported by Alonso et al.[150]. Band (iii) shows the SPE spectrum of the gold nanoparticles solution, was around 525535 nm, indicating the formation of particles with dimensions of 530 nm[151]. The presence of the single surface plasmon peak implied that the formed nanoparticles were nearly spherical. In the case of ellipsoidal particles the absorption spectrum would have two plasmon's peaks [77]. Band (iv) shows the SPE spectrum of the thin film gold nanoparticles. The spectra exhibit the
101

characteristic peak at 545 nm compared with Thomas et al. was reported a broad band centred at 575 nm [108]. The width of the 545-nm peak is broadened and the height is lowered more greatly. This spectral change indicates that the diameters of the nanoparticles are increased more under precipitation [136]. The increase in size is interpreted as those gold nanoparticles are fusion by precipitation and hence the number of nanoparticles which are available to the fusion decreases. Note that the nanoparticles in thin film fused sufficiently fast that the spatial distribution of the nanoparticles is regarded as inhomogeneous. Another significant change is observed red shifts. According to the Mies theory, the peak shift to be observed in an absorption spectrum when the mean diameter of the particles changes [136]. Gold nanoparticles with larger diameter exhibit maximum absorption at the longer wavelengths. However, the thin film shows a strong decrease of the UV-VIS absorbance appeared in the absorption spectrum, which corresponds to the decrease concentration of the Au atoms in thin film. On the other hand broadening of the red tail of the plasmon resonance band can be attributed to the fusion of the particle aggregates. The SPR peak shifts to longer wavelengths with increasing thickness which is consistent with our previous work on Donnelly et al. [29].
0.5 0.4 0.3 0.22

(A)

Silver Nanoparticles
(i) Solution (ii) Thin Film 0.18

(B)

Gold Nanoparticles
(iii) Solution (iv)Thin Film

SPE

0.2 0.1 0 350 375 400 425 450 475 500

SPE

0.14

0.1

0.06

390

440

490

540

590

Wavelength(nm)

Wavelength(nm)

Fig. 4-42: SPE spectra of silver (A) and gold nanoparticles (B), respectively, in case of solutions (i, iii) and thin films (ii, iv).
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4-14 Target Effects

Pulsed Laser ablation (desorption) of solid targets in liquids has attracted much attention not only for nanoparticles formation but also due to possibility to fabricate debris -free microstructures on various solids. Fig. 4-43 shows the surface morphology of Ag target, panels a-i and Au, panels j-o, respectively, was studied using optical microscope. All experimental parameters

corresponding to panels a-m are mentioned in table (4-l). The structures are closely packed periodic micro-grooves with deep ablation, depending on some parameters such as laser wavelength, fluence and environment liquid. The surface of the target undergoes eyevisible changes. Namely, the exposed areas of the Ag and Au substrate take on a yellow coloration, suggesting (1) its relevance to the plasmon resonance of metal NPs and (2) the formation of a nanostructure directly on the metal substrate as a result of laser exposure in water.
Table 4-1: Shows the ablation stateous of figure a-o as a function of target type, environment solution, laser shots, energy and wavelength, respectively. Figure a b c d e f g h i j k l m n o Target Silver Silver Silver Silver Silver Silver Silver Silver Silver Gold Gold Gold Gold Gold Gold medium H2 O H2 O NaCl H2 O H2 O H2 O Ethanol PVP SDS H2 O H2 O H2 O H2 O H2 O Ethanol Laser shots 15 15 15 15 5 90 15 15 15 15 15 15 15 90 15 Energy (mJ) 600 600 600 900 600 600 600 600 600 600 600 900 300 600 600
103

Wavelength (nm) 1064 532 1064 1064 1064 1064 1064 1064 1064 1064 532 1064 1064 1064 1064

Ablation Stateous Homogeneous Shallow, homogeneous Homogeneous Inhomogeneous, melt drops Partially, inhomogeneous Deep, inhomogeneous Partially, inhomogeneous Deep, inhomogeneous Deep, inhomogeneous Homogeneous, Shallow, Homogeneous Deep, Homogeneous Partially, inhomogeneous Deep, inhomogeneous Partially, inhomogeneous

The formation of the structures is attributed to the instability of the flat front of the melt under recoil pressure of vapours of surrounding liquid. One can see that the periodic ripples on the Ag and Au target are predominantly (Fig. 4-43). Formation of these ripples is typical of the interaction of a laser radiation of sub-nanosecond duration with the surface electromagnetic wave induced in the material. However, the formation of microstructures on a rough metal surface subjected to laser ablation in water is due to the modification of the topology of the molten area upon decreasing the laser fluence. At high laser energy (900 mJ, Fig 5-43-d), the molten area is continuous, and this melt is effectively dispersed as nanoparticles by the recoil pressure of the surrounding liquid. At lower laser energy (300 mJ, Fig. 5-43-n), the melting occurs in the areas with weak thermal bounding to the substrate, e.g. summits of the initial micro- relief, edges of scratches, etc. Therefore, at low laser fluence the molten area is a discontinuous set of small molten areas. The recoil pressure of the vapour surrounding the target pushes these molten areas from the target and generates a microstructure. In other words, formation of microstructure is a result of hydrodynamic instability at the interface liquid vapourmelt characterized by very small period of order of hundreds of nanometers. The described mechanism is independent on the target material, and similar nanostructures may be grown on silver or gold target that absorb at laser wavelength. Typically the period of ripples is close to laser wavelength, which is 1064 or 532 nm in our work. However, ripples on Ag and Au have the period about of 1000 nm (Fig.4-43-a, j) and 500 nm (Fig.4-43-b, k) corresponding to ablation wavelength. This discrepancy should be assigned to the elevated refractive index of surrounding water compared to air or vacuum. Yellowish coloration of laser-treated areas is also observed in the case of Ag or Au target, though its origin is not clear.

104

50 m Fig. 4-43: Surface morphology of Ag, panels a-i and Au target, panels j-o, respectively, after ablation by Nd-YAG laser at the parameters was mentioned in table 4-1. All the images were done in the same magnification. 105

Chapter Five: Conclusions and Future Works

5-1 Conclusions
1-Certain pure NP colloidal solutions can be formed. In addition, surfactants can be added to liquids in order to control the size and the aggregation state. 2-The formation rate, mean particle size and stability could be controlled by proper selection of the laser parameters. 3-On-line monitoring is regarded as a good tool to controlling on PLAL process. 4- There is an agreement in the PLAL efficiency was quantified in term of the SPE peaks as well as of the concentration of Ag NPs. 5-Metals nanoparticles can be produced at laser wavelength of 1064-nm laser energy more efficiently than at 532 nm. 6-The silver nanoparticles are shifts to a smaller size due to increasing in SDS concentration; slow particle growth is due to SDS coating. 7-The Cl ions were formed of a negatively charged electric bilayer which enhances dispersity and prevents the aggregation. 8-The PVP solution enhanced the formation efficiency of Ag NPs and prevents aggregates (as capping agent). 9-LISR (modification) is caused by heating, melting and evaporation of the initial particles, which reduced the size and size distribution. 10-We have successfully prepared of AuAg core-shell NPs in two steps. 11-The SPE properties as peak position and peak intensity is reliable indicator for identify the size and concentration. 12-Fabrication of metal nanostructured films using auto-dry deposition provides a new method to tuning the morphology and thickness.

5-2 Suggestion for Future Works

1. Using the produced nanoparticles in practices application such as: solar cell,
sensor, cancer treatment and antibacterial reagent.

2. Study the effect of NaOH solution on the size and size distribution of metal NPs.
106

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