Experiments in thin film deposition: Plasma-based fabrication of Carbon Nanotubes and Magnesium Diboride thin films Dirk Coetsee Submitted in fulfilment of the requirement for the degree of Master of Science in Engineering Date: 20/12/2004 Supervisor: Mr. A.L.L Jarvis Co-supervisor: Prof. T.B. Doyle As the candidate's Supervisor I have/have not approved this thesis/dissertation for submission Sig natl.lLe~::=::j:::::::::::==::::> Name: ~.L.L. -~(J~.) Date: 54'" Apr, \ ').oo~ 11 Acknowledgements I am deeply indebted to a great many people without whom this work would have certainly been a dismal failure. On the technical side, I owe Tony Roos a thousand favours for the endless milling, turning, welding and machining he has done at short notice (not to mention for all the surfing tips...). Thanks must also go to Peter Siegling for all the glasswork. Divesh Maharaj and Gregory Moodley from electronic and chemistry stores have also done me innumerable favours by supplying me with the necessary equipment and chemicals to make things work. Chris van der Merwe and Mike Witcomb are also duly thanked for all the work they put into helping me with SEM and TEM use in the analysis stage of this project. And of course, I really do owe my supervisor, who for some reason let me often have my way in the course of this work and suffered the consequences... As cliched as it may be, my mother deserves a most special thank-you for tirelessly putting up with me (and feeding me) all this time. And of course, above all I thank God, truly. In the end, He bailed me out oftrouble yet again. One last thank-you to Goku, Gohan, Cloud and Yakumo Fujii for their incredible inspiration and determination. When the going gets tough, they grind the axe. When all is lost, they rise again. The contribution ofthe National Research Foundation is gratefully acknowledged. 111 Abstract A simple, low-cost plasma reactor was developed for the purpose of carrying out thin film deposition experiments. The reactor is based largely on the Atmospheric Pressure Nonequilibrium Plasma (APNEP) design with a simple modification. It was used in an attempt to fabricate magnesium diboride thin films via a novel, but unsuccessful CVD process where plasma etching provides a precursor boron flux. Carbon nanotubes were successfully synthesised with the apparatus using a plasma-based variation of the floating catalyst or vapour phase growth method. The affect of various parameters and chemicals on the quality of nanotube production was assessed. IV Table of Contents INTRODUCTION I 2 MAGNESIUM DIBORlDE THIN FILMS 2 2.1 INTRODUCTION 2 2.2 SUPERCONDUCTIVITy 2 2.3 MAGNESIUM DIBORIDE 3 2.3.1 Introduction . 3 2.3.2 Structure and Properties . 4 2.4 THfN FILMS 7 2.4. I Types ofmethods..... 7 2.4.2 Pulsed Laser Deposition (PLD). 8 2.4.3 Sputtering, e-beam evaporation and sublimation 12 2.4.4 Chemical Vapour Deposition (CVD) .14 2.4.5 Molecular Beam Epitaxy (MBE)......................................................... 15 2.4.6 Other methods......... 15 2.4.7 Thermodynamics ofthe MgB2 system.......... 16 2.4.8 Hybrid Physical Chemical Vapour Deposition (HPCVD).................................. 18 2.5 EXPERIMENTAL - THE BASIC PREMISE 18 2.6 ALTERNATIVES 19 2.6. I Evaporation....... 19 2.6.2 PLD............ 19 2.6.3 Plasma processes... 20 2.6.4 Heat Pipe . 21 2.7 CONCLUSION 23 3 PLASMA SOURCES 24 3. I PLASMAS 24 3.1.1 Introduction . 24 3. 1.2 Some basic properties 24 3.2 SOURCES 25 3.2.1 Capacitively-coupled, 13.56 MH= RFsources 26 3.2.2 Inductively Coupled Plasma (ICP) . 26 3.2.3 Torche ainjection axiale (TIA).. ... 27 3.2.4 Microwave Plasma Torch (MPT) ... 28 3.2.5 CoronaDischarge. ~.............. ..29 3.2.6 Dielectric Barrier Discharge (DBD) . 30 3.2.7 Atmospheric Pressure Plasma Jet (APPJ) . 30 3.2.8 Thermal Plasma Torch -tube in waveguide . 31 3.2.9 Microwave plasma Jet with no==le . 32 3210 Fused Hollow Cathode (FHC) . 32 3.2.1 I Atmospheric Pressure Nonequilibrium Plasma (APNEP) .. 34 3.2. 12 Persistent Ionisation in Air (PIA) in a microwave oven 36 3. 2.13 Summary.............. .. 37 4 DEVELOPMENT OF THE PLASMA APPARATUS 38 4.1 INTRODUCTION 38 4.2 INITIAL ATTEMPTS 38 4.3 MARK 11 42 4.4 PLASMA LOCALISATION 45 4.5 MARK Ill 46 4.6 MORE LOCALISATION AND SAMPLE LOADfNG 50 4.7 OTHER APPARA TUS 54 4.7.1 Substrate Heater . 54 4.7.2 Cooling . 57 4.7.3 Microwave Power Contro!. 59 4.7.4 Second Magnetron . 60 4.8 CONCLUSION 60 5 EXPERIMENTAL: THIN FILM DEPOSITION 62 v 5. 1 INTRODUCTION 62 5.2 EARLY WORK 62 5.3 FIRST ATTEMPTS 63 5.4 SECOND ATTEMPTS 64 5.5 DISCONTfNUATION 66 6 CARBON NANOTUBES 68 6.1 INTRODUCTION 68 6.2 DISCOVERY 68 6.3 STRUCTURE AND CHEMiSTRy 69 6.4 PROPERTIES 72 6.4.1 Electrical.. 72 6.4.2 Mechanical............................. .. 72 6.4.3 Heat conduction..... 73 6.4.4 Summary............. .. .. 73 6.5 ApPLICATIONS 73 6.5.1 Bullet ProofVests... .. .. 73 6.5.2 Memory........................................ 73 6.5.3 Field Emitters . 74 6.5.4 Visible light aerial..................... 74 6.5.5 Energy Storage 74 6.5.6 Motor Shaft............................................................................................. ............. 74 6.5. 7 SummQly 75 6.6 SYNTHESIS 76 6.7 ARC DISCHARGE 76 6.7.1 Addition ofcatalyst . 77 6.7.2 Optimisation ofprocess parameters 77 6.7.3 Temperature control. .. 78 6.7.4 Liquid Nitrogen.. 78 6.7.5 Coal........ 79 6.7.6 Effect ofgas environment .. 79 6.7.7 Arc in water .. 80 6.7.8 Considerations.... 80 6.8 CHEMICAL VAPOUR DEPOSITION 80 6.8.1 The basic process....... .. 81 6.8.2 Growth Mechanism .. 82 6.8.3 Effect ofTemperature . .. 83 6.8.4 Effect ofPressure....... .. 84 6.8.5 Effect ofSubstrate and supported nanoparticles .. 84 6. 8. 6 Plasma Enhanced Chemical Vapour Deposition.... .. 85 6. 8.7 Thermal plasma torches........ .. .. 87 6.8.8 Promoters.............. .. 88 6.8.9 Precursor choice.... .. 89 6.8.10 Hydrogen.. 90 6.8.11 Considerations..... 90 6.9 LASER ABLATION 91 6.9.1 Basic Process .. .. 9/ 6.9.2 Method ofgrowth............... 91 6.9.3 Advances .. .. 92 6.9.4 Considerations .93 6.10 ALTERNATIVE METHODS 93 6.10.1 Solar Production . 93 6.10.2 Solvothermal Synthesis .. 93 6.103 Catalytic Pyrolysis.. .. 93 6./0.4 Annealing....... .. 94 6.11 SUMMARY 94 7 EXPERIMENTAL: NANOTUBES 97 7.1 ApPARATUS 97 7.1.1 Plasma Chamber 97 VI 712 Aerial............... 98 7 I. 3 Gases and vacuum system . J00 71.4 Soot Collection.. 101 7.2 £XPERIMENTS 102 8 RESULTS: NANOTUBES 105 8.1 £1 105 8.2 £2 107 8.3 £3 11 I 8.4 £4 112 8.5 £5 114 8.6 £6 115 8.7 £7 119 8.8 £8 119 8.9 £9 122 8.10 £10 122 8.11 SUMMARY 125 9 CONCLUSIONS AND FUTURE WORK 128 9.! NANOTUBES 128 9.2 THEApPARATUS 129 9.3 MGB z 130 9.4 FUTURE WORK 130 9.5 CLOSING THOUGHTS 131 1 : DESIGN OF 16-BIT DATA ACQUISITION BOARD FOR LITHOGRAPHY 133 A.l £LECTRON-BEAM LITHOGRAPHY 133 A.2 HARDWARE DESIGN: CIRCUITRY 135 A.3 USB 136 A.4 Bus STRUCTURE 137 A.5 FIFOs 137 A.6 DAC OUTPUT 138 A.7 SCALEANDOFFSET 139 A.8 OUTPUT FILTERING 140 A.9 GENERAL NOISE PRECAUTIONS 142 A.9.J Circuit level precautions . 142 A.9.2 Printed Circuit Board Precautions........ 145 A.IO DUAL DIGITAL RAILS 150 A. 11 IN CIRCUIT DEBUGGER (lCD) 150 A. 12 CLOCK MATCHING (INTERFACING) 150 A.13 DAUGHTERCARD 15! 2 : SOFTWARE DESIGN 158 B. I PC SOFTWARE 158 B.2 CAD FILE READING 159 B.3 GENERATINGDATAPOINTS 159 8.4 READING IMAGES 161 8.5 CONFIGURING THE MiCROSCOPE 162 8.6 TOOLBAR 164 8.7 FIRMWARE 165 B.8 CONCLUSiON 166 3 BIBLIOGRAPHY 167 vii Table of Figures FIGURE 2-1: HEXAGONAL, GRAPHITE-LIKE LAYERS OF BORON (SMALL MOLECULES) SANDWICHED BETWEEN HCP MAGNESIUM 4 FIGURE 2-2: BASIC PLD APPARATUS 8 FIGURE 2-3: RESISTIVE HEATING - THE MOST SIMPLE FORM OF PVD 12 FIGURE 2-4: BASIC SPUTTER PROCESS. IONS (WHITE) ARE ACCELERATED TOWARDS A SUBSTRATE ON THE CATHODE WHICH DISLODGE SURFACE ATOMS (GREY) 13 FIGURE 2-5: BASIC CVD PROCESS. MOLECULES OF AN INCOMING GAS STREAM ARE DISSOCIATED TO YIELD UP A DESIRED PRODUCT (REPRESENTED BY DARK GREY CIRCLES) 14 FIGURE 2-6: PHASE DIAGRAMS OF MGB2 SYSTEM FOR DIFFERENT PRESSURES (Lru ET AL., 2001 ) 16 FIGURE 2-7: STATES OF MGB2 SYSTEM FOR TEMPERATURE OF 850°C (Lru ET AL., 2001) 17 FIGURE 2-8: BASIC SCHEMATIC OF HPCVD EXPERIMENT 18 FIGURE 2-9: POSSIBLE ALTERNATIVE TO DIBORANE SOURCE FOR B FLUX 19 FIGURE 2-1 0: BASIC PROCESS OF ETCHING. ACTIVE SPECIES IN THE PLASMA (DARK GREY CIRCLES) MOVE TO THE SUBSTRATE SURFACE WHERE THEY ATTACH CHEMICALLY TO SURFACE ATOMS OF TH E SUBSTRATE (LIGHT CIRCLES). THE RESULTING MOLECULE WILL ULTIMATELY BE DISPOSED OF VIA THE VACUUM 20 FIGURE 2-11: SHOWING IDEA BEHIND PLASMA ETCH ROUTE TO BORON FLUX GENERATION 21 FIGURE 2-12: BASIC OPERATION OF HEAT PIPE OVEN. REDRAWN FROM (LRI, 2001). LIQUID MG IS SHOWN IN GREY, MG VAPOUR IS SHOWN IN LIGHT BLUE.. 21 FIGURE 2-13: CROSS-CONCENTRIC HEAT PIPE OVEN. MG LIQUID IS SHOWN IN DARKER BLUE. MG VAPOUR IS SHOWN IN LIGHTER BLUE. THE PURPLE REPRESENTS A DIFFERENT METAL IN THE OUTER HEAT PIPE..22 FIGURE 3-1: BARREL TYPE (LEFT) AND PARALLEL-PLATE (RIGHT) ETCHERS 26 FIGURE 3-2: BASIC TORCH USED IN ICP-MASS SPECTROSCOPY (THOMAS, 2001) 27 FIGURE 3-3: BASIC DESIGN OF TIA APPARATUS.