PhD Thesis - Sept 2003

Sean R.J. Pearce

"The Synthesis and Characterisation of Carbon Phosphide"


This thesis is available in Acrobat pdf file format. Click on the links below to download each Chapter.


Contents

Title Page
Abstract
Ackowledgements
Table of Contents

1 INTRODUCTION 1 FILMS AND MATERIALS     1
1.1 DIAMOND AND GRAPHITE     1
1.1.1 Introduction     1
1.1.2 Uses of Diamond     7
1.1.3 The Doping of Diamond     8
1.2 DIAMOND LIKE CARBON     9
1.2.1 Introduction     9
1.2.2 Uses of DLC     10
1.2.3 The Doping of DLC     11
1.2.4 The Deposition of DLC     13
1.2.4.1 Ion Beam Deposition Methods (Ion Deposition and Ion Assisted Sputtering)     16
1.2.4.2 Sputtering     17
1.2.4.3 Cathodic Vacuum Arc     18
1.2.4.4 Plasma Enhanced Deposition     18
1.2.4.5 Pulsed Laser Deposition     19
1.3 CARBON NITRIDE     20
1.3.1 The Properties of Carbon Nitride     20
1.3.2 Production of Carbon Nitride     22
1.4 CARBON PHOSPHIDE     24
1.4.1 Introduction     24
1.4.2 The Properties of Carbon Phosphide     24
1.4.3 Experimental Reports of Carbon Phosphide Materials     29
1.5 REFERENCES     32

2 INTRODUCTION 2 - DEPOSITION METHODS     39
2.1 RADIO FREQUENCY PLASMA ASSISTED CHEMICAL VAPOUR DEPOSITION (RF-CVD)     39
2.1.1 Striking and Maintenance of a Plasma     39
2.1.2 The Sheath Region     42
2.1.3 DC-Bias     43
2.1.4 The Average Ion Energy     45
2.2 PULSED LASER ABLATION AT THE SOLID-LIQUID INTERFACE     49
2.3 REFERENCES    55

3 EXPERIMENTAL METHODS     56
3.1 DEPOSITION METHODS     56
3.1.1 Radio Frequency Plasma Enhanced Chemical Vapour Deposition (RFCVD)     56
3.1.2 Pulsed laser ablation at the solid -liquid interface (LP-PLA)     61
3.1.2.1 Manufacture of Mixed Carbon/Phosphorus Targets for Laser Ablation at the Solid-Liquid Interface     64
3.2 PROCESSING METHODS     65
3.2.1 Thermal Annealing     65
3.3 ANALYSIS METHODS     67
3.3.1 X-ray photoelectron spectroscopy (XPS)     67
3.3.1.1 X-ray photoelectron spectroscopy at the Daresbury Laboratory Synchrotron Light Source    71
3.3.2 Secondary Ion Mass Spectrometry (SIMS)     75
3.3.3 Auger Electron Spectroscopy (AES) and Energy Dispersive X-ray Spectroscopy (EDX)     80
3.3.4 Scanning Electron Microscopy (SEM)     82
3.3.5 Transmission Electron Microscopy (TEM)     84
3.3.6 Laser Raman Spectroscopy (LRS)     85
3.3.7 Ultraviolet / visible (UV/Vis) spectroscopy     87
3.3.8 Optical Emission Spectroscopy (OES)     88
3.3.9 X-ray Powder Diffraction (XRD)     89
3.4 REFERENCES     91

4 RESULTS AND DISCUSSION: RF PLASMA ENHANCED CHEMICAL VAPOUR DEPOSITION     92
4.1 DLC AND AMORPHOUS CARBON THIN FILMS     92
4.1.1 Aims     92
4.1.2 Growth and Analysis Parameters     93
4.1.3 Results and Discussion     95
4.2 ADDITION OF PH3 TO THE PROCESS GAS MIXTURE     100
4.2.1 Aims     100
4.2.2 Deposition and Analysis Parameters     100
4.2.3 Results and Discussion     101
4.3 VARIATION OF THE ION ENERGY AND ITS EFFECT ON THE DEPOSITION OF AMORPHOUS CARBON PHOSPHIDE THIN FILMS     120
4.3.1 Aims     120
4.3.2 Deposition and Analysis Parameters     120
4.3.3 As-deposited films     121
4.3.4 Annealed films     124
4.3.5 XPS at the Synchrotron Radiation Light Source     126
4.3.6 Conclusion     128
4.4 THE EFFECT OF SUBSTRATE TEMPERATURE ON THE DEPOSITION OF CARBON PHOSPHIDE THIN FILMS     128
4.4.1 Aims     128
4.4.2 Deposition and analysis parameters     129
4.4.3 Results and discussion     129
4.4.4 Conclusions     135
4.5 REFERENCES     136

5 LASER ABLATION AT THE SOLID/LIQUID INTERFACE     138
5.1 GRAPHITE ABLATED UNDER OXYGEN AND CARBON CONTAINING LIQUIDS     138
5.1.1 Ablation of Graphite Under Water     139
5.1.2 Ablation of Graphite Under Cyclohexane     146
5.1.3 Optical Emission Spectra of the Ablation Plume     150
5.2 PHOSPHORUS ABLATED UNDER CARBON CONTAINING LIQUIDS     152
5.2.1 The Ablation of Phosphorus Under Cyclohexane     152
5.2.2 Ablation of Phosphorus Under Xylene     170
5.2.3 Ablation of mixed (red phosphorus/graphite) targets under cyclohexane.     171
5.3 REFERENCES     174

6 SUMMARY AND CONCLUSIONS     176
6.1 RF-DEPOSITION OF AMORPHOUS CARBON PHOSPHIDE     176
6.2 PULSED LASER ABLATION AT THE SOLID/LIQUID INTERFACE     177
6.3 FURTHER WORK     178
6.4 REFERENCES     178

Appendix 1 The Synthetic Route Towards Carbon Phosphide     A1