SYNTHESIS, CHARACTERIZATION AND IRRADIATION OF FULLERENE BASED METAL NANOCOMPOSITES Ph.D. Thesis POOJA SHARMA ID No. 2014RPY9008 DEPARTMENT OF PHYSICS MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY JAIPUR June, 2019 Synthesis, Characterization and Irradiation of Fullerene Based Metal Nanocomposites Submitted in fulfillment of the requirements for the degree of Doctor of Philosophy by Pooja Sharma ID:2014RPY9008 Under the Supervision of Dr. Rahul Singhal Prof. M.K. Banerjee DEPARTMENT OF PHYSICS MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY JAIPUR, June, 2019 © Malaviya National Institute of Technology Jaipur-2019. All rights reserved. This work is dedicated to my beloved sister and brother, Asha and Harimohan Sharma for their eternal love i Scanned by CamScanner Scanned by CamScanner Scanned by CamScanner Scanned by CamScanner Scanned by CamScanner ABSTRACT The present research work entitled “Synthesis, Characterization and Irradiation of Fullerene Based Metal Nanocomposites” envisages the study on the feasibility of using fullerenes, one of the most emerging functional materials as a matrix for the reinforcement of metal nanoparticles. Fullerene matrix nanoparticles embedded composites are found to exhibit surface plasmon resonance (SPR) by virtue of which a significant enhancement of absorbance of the material become possible; the bi- functional property of matrix and metal nanoparticles in a single material makes it highly beneficial and applicable for different optical devices, thereby making it poised for emergence as a lucrative energy material. Understanding that the performance of optical absorbance of nanocomposites is highly influenced by the host microstructure, it has appeared important to monitor the structural conditions of fullerene as matrix material when subjected to such treatments as considered useful for enhancement of SPR due to noble metal particles in nanocomposites. It is further known that ion beam irradiation is most effective in alteration of SPR behavior of nanoparticles of noble metals like Au and Ag. So the present study in chapter 4.1 has contemplated to explore the effect of heavy ion beam irradiation (90 MeV Ni ion) on fullerene C60 thin film. As expected the damage of fullerenes has been fluence dependent and that ion tracks of determinable diameter could be formed by such irradiation. In view of the fact that elaborate studies on fullerene C70 is till due to be reported in literature, the present research work in chapter 4.2 has investigated and reported the effect of irradiation by different ions viz. 90 MeV Si, 55 MeV Si, 90 MeV Ni and 125 MeV Au on fullerene C70 thin films. Based on the results of the above ion beams of different electronic energy loss (Se), the damage cross section has been calculated for each ion beam, compiled and a relationship between damage cross section and electronic energy loss is developed which is supposed to be beneficial in estimating the value of damage cross section for any unknown situation of electronic energy loss within the range of present study. Although the potential of nanoparticles of gold and silver as reinforcement in fullerene C60 and C70 has been amply researched, the potential of copper is yet to receive due research attention in spite of its advantage of interesting mechanical properties, high electrical conductivity, favorable catalytic properties, appropriate melting point, high stability and high natural abundance in nature. Hence, the present thesis work has reported (chapter 5.1) the results of investigation on the incorporation of copper nanoparticles in fullerene C60 matrix subjected to irradiation by low energy ion beams (100 keV Ag ion, 350 keV Ar ion). As a corollary of low energy 100 keV Ag ion irradiation study the widening of absorption range could be observed due to hybridization of copper nanoparticles induced SPR and that due to Ag ions getting implanted within in the silicon substrate. The low cost of Cu over Ag and Au makes it more attractive for applications in various fields of optics, electronics, solar energy conservation, sensors, lubricants and sliding electrical contacts. Effect of high energy (120 MeV Ag) ion irradiation on Cu (18 at. %)-C60 has implicitly demonstrated (chapter 5.2 ) the enhancement of SPR band intensity due to copper nanoparticles; the concurrent growth of copper nanoparticles at increasing fluences has caused a shift in the position of SPR band. The chapter 6 of present study has addressed the research questions related to Cu-C70 nanocomposite thin films under ion irradiation of various energies. The low energy ion beam irradiation (350 keV Ar ion) of Cu (10 at.%)-C70 nanocomposite thin films have been able to exhibit SPR band due to copper only after irradiation at fluence of 1×1015 ions/cm2. The SPR band increases its intensity with increasing fluence and got shifted towards lower wavelength side. This is in contrast with the pristine which has not exhibited any SPR due to copper presumably due to its low concentration. The similar behavior was also exhibited by this composite subjected to high energy ion beam irradiation (120 MeV Ag ion) with the exception that SPR could be obtained only at a higher fluence like 3×1013 ions/cm2. Since any fluence higher than 3×1013 ions/cm2 has not been employed in the present study it is not possible to be conclusive if it would also exhibit a blue shift with still increasing fluence, which, it seems would occur most likely. However, the studies in chapter 6 clearly authenticates that both the concentration of embedded nanoparticles and the change in optical properties of irradiated fullerenes are responsible for determining the intensity and the position of SPR due to copper in fullerene C70 matrix. CONTENTS Chapter Caption of Chapter Page No. No. Chapter 1 Introduction 1-30 1.1 Third allotropic form of carbon-Fullerenes: 1 1.2 Characteristics of fullerenes 1 1.2.1 Structure of fullerene C60 and C70 2 1.2.2 Symmetry and phase transition in C60 and C70 2 1.2.3 Optical behavior 3 1.2.4 Some other physical and chemical behavior 4 1.3 Applications of fullerenes 5 1.4 Nanocomposites 5 1.5 Surface Plasmon Resonance (SPR) 7 1.6 Ion irradiation 9 1.6.1 Matter-Ion Interaction 10 1.6.2 Models 11 1.6.2.1 Thermal spike model 11 1.6.2.2 Coulomb Explosion Model 12 1.6.3 Role of ion irradiation 13 1.7 Objectives in the present thesis work 14 1.8 Motivation of the thesis problem 15 1.9 Organization of thesis 17 References 22 Chapter 2 Literature Review 31-42 2.1 Introduction 31 2.2 Metal nanocomposites thin films, properties and applications 31 2.3 Fullerene based Metal Nanocomposites 33 2.4 Ion irradiation effect in fullerene as a matrix and fullerene 34 based metal nanocomposites References 38 Chapter 3 Experimental Techniques 43-70 3.1 Thin Film Deposition 43 3.1.1 Thermal evaporation Technique 44 3.1.1.1 Resistive Heating Technique 45 3.2 Irradiation 47 3.2.1 Ion Implantation by Low Energy Ion Implanter 47 3.2.2 Low Energy Ion Beam Irradiation 48 3.2.3 High Energy Ion Beam Irradiation 50 3.3 Characterizations 52 3.3.1 UV-visible Absorption Spectroscopy 52 3.3.2 Raman Spectroscopy 53 3.3.3 Rutherford beam scattering (RBS) 55 3.3.4 X-ray diffraction (XRD) 56 3.3.5 Scanning Electron Microscope (SEM) 58 3.3.6 Transmission electron microscopy (TEM) 60 3.3.7 Atomic Force Microscopy (AFM) 62 3.3.8 Conductivity Measurements 64 3.3.9 X-ray photoelectron spectroscopy (XPS) 65 References 68 Chapter 4 Effect of ion irradiation on the structure and properties of 71-114 fullerene C60 and C70 as a matrix of metal reinforced nanocomposites. 4.1 Effect of ion irradiation on the structure and properties of 71 fullerene C60 as a matrix of metal reinforced nanocomposites. 4.1.1 Experimental Details 72 4.1.2 Result Discussions 73 4.1.2.1 RBS Analysis 73 4.1.2.2 Raman Analysis 73 4.1.2.3 UV-visible absorption spectroscopic analysis 77 4.1.2.4 Conductivity measurement 78 4.1.2.5 Surface Analysis 79 4.1.2.6 XRD Analysis 81 4.2 To observe the effect of different energy ion beam irradiation 83 on fullerene C70 thin films: dependence of electronic energy loss. 4.2.1 Experimental Details 85 4.2.1 .1 Methods of preparation, irradiation by 90 MeV Si ion 85 and characterization of C70 thin films. 4.2.1 .2 Methods of preparation, irradiation by 55 MeV Si ion 8 5 and characterization of C70 thin film 4.2.1 .3 Methods of preparation, irradiation by 90 MeV Ni ion 86 and characterization of C70 thin film 4.2.1.4 Methods of preparation, irradiation by 125 MeV Au 86 ion and characterization of C70 thin film 4.2.2 Results and discussion 87 4.2.2.1 C70 thin film irradiated by 90 MeV Si ion beam 87 4.2.2.1.1 Raman analysis 87 4.2.2.1.2 Surface analysis 89 4.2.2.1.3 Contact angle measurement 90 4.2.2.2 C70 thin film irradiated by 55 MeV Si ion beam 92 4.2.2.2.1 Raman analysis 92 4.2.2.2.2 UV-visible absorption spectroscopy 95 4.2.2.2.3 Surface analysis 96 4.2.2.3 C70 thin film irradiated by 90 MeV Ni ion beam 97 4.2.2.3.1 UV-visible absorption spectroscopy 97 4.2.2.3.2 Raman Analysis 99 4.2.2.3.3 SEM analysis 103 4.2.2.3.4 AFM analysis 104 4.2.2.4 C70 thin film irradiated by 125 MeV Au ion beam 105 4.2.2.4.1 UV- visible absorption spectroscopy 105 4.2.2.4.2 Raman analysis 106 4.2.2.5 Ion track radius in fullerene C70 : Dependence of 107 electronic energy loss 4.2.2.5.1 Raman analysis 108 4.3 Conclusions 110 References 112 Chapter 5 Study the effect of low and high energy ion beam 115-156 irradiation on Copper-fullerene C60 nanocomposite thin films.