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Title Page

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Contents

1. INTRODUCTION 14

1.1. Electron beam irradiation and annealing process 14

1.2. Investigation on the origin of brown color of diamonds 16

2. LITERATURE REVIEW AND TECHNICAL BACKGROUND 18

2.1. Properties of Diamond 18

2.1.1. Structure 19

2.1.2. Electronic structure 21

2.1.3. Classification 24

2.2. Defects in Diamond 26

2.2.1. Point defects 26

2.2.2. Extended defects 30

2.3. Brown coloration of diamond 33

2.4. The mechanisms of damage by electron irradiation 35

2.4.1. Rutherford scattering 35

2.4.2. Knock-on atoms 38

2.4.3. Energy lost to ionization 39

2.5. Heat treatment 40

3. EXPERIMENTAL TOOLS AND TECHNIQUES 41

3.1. Experimental tools 41

3.1.1. Photoluminescence spectroscopy 41

3.1.2. Ultraviolet-visible (UV-Vis) spectroscopy 45

3.1.3. Infrared (IR) spectroscopy 49

3.2. Experimental procedure 52

4. RESULTS AND DISCUSSION 53

4.1. Effects of electron beam irradiation and heat treatment in color center in natural colorless diamond 53

4.2. Correlation of vacancy formation and amber center in natural brown diamonds 71

5. CONCLUSION 103

5.1. Colorless type IaAB, synthetic type IIa, synthetic type Ib, pretreated(unknown) type IaABC diamond 103

5.2. Brown type Ia (A, A＞B, A＝B, A＜B, B) diamonds 105

REFERENCES 106

ABSTRACT 110

List of Tables

Table 2.1.1. The types and subtypes of diamond, with their main defects and colors 25

Table 2.2.1. Point defects in diamond, and their known properties. 30

Table 4.1.1. Description of the peaks of the FT-IR absorption spectrum observed in various... 55

Table 4.1.2. Description of the peak of the PL absorption spectrum observed in various types... 59

Table 4.1.3. Average bond dissociation energies, D. 61

Table 4.1.4. Description of the peaks of the PL absorption spectrum observed in e-beam... 67

Table 4.2.1. Description of the peaks of the 325 ㎚ laser PL absorption spectrum observed in... 83

Table 4.2.2. Description of the peaks of the 514 ㎚ PL absorption spectrum observed in... 87

Table 4.2.3. Description of the peaks of the FT-IR absorption spectrum observed in various... 94

Table 4.2.4. Description of the peaks of the 325 ㎚ He-Cd laser PL absorption spectrum... 102

List of Figures

Fig. 2.1.1. The Face Centered Cubic lattice, with lattice points represented by black spheres.... 20

Fig. 2.1.2. The diamond structure, with the basis atoms added to the FCC lattice. The... 20

Fig. 2.1.3. The electronic band structure of diamond, with the valence band top set to 0 eV.... 23

Fig. 2.1.4. Band structure of bulk diamond calculated using both the screened exchange... 23

Fig. 2.2.1. A perfect edge dislocation, with the Burgers circuit shown in (a) and the... 32

Fig. 2.2.2. The perfect screw dislocation, with the Burgers vector b parallel to the line... 32

Fig. 2.4.1. Variation of Rutherford cross-section with electron energy, for three values of the... 37

Fig. 3.1.1. Schematic of Photoluminescence in a direct-gap semiconductor. 43

Fig. 3.1.2. Phonon-assisted PL in an indirect-gap semiconductor. The conservation of... 43

Fig. 3.1.3. Exciton effects in Photoluminescence. The reduced energy due to electron-hole... 44

Fig. 3.1.4. Schematics illustration of the setup for UV-Vis measurement with on line irradiation. 48

Fig. 3.1.5. Schematic illustration of the FT-IR measurement system. 51

Fig. 4.1.1. Comparison of the FT-IR spectra of the various types of diamonds before and after e-... 54

Fig. 4.1.2. Comparison of the UV-Vis-NIR spectra of the various types of diamonds with and... 57

Fig. 4.1.3. Comparison of the vacancy peaks of the various types of e-beam irradiated diamonds... 58

Fig. 4.1.4. The arrangement of nitrogen and carbon atoms depending on diamond type. 63

Fig. 4.1.5. The effect of annealing on the PL spectra of an e-beam irradiated natural type Ia... 65

Fig. 4.1.6. PL spectra (325 ㎚ source) of the treated type Ia diamond subjected to e-beam... 66

Fig. 4.1.7. Variation of the PL (325 ㎚ source) peak intensities of the natural type IaAB diamond... 69

Fig. 4.1.8. PL spectra (514 ㎚ source) of the irradiated natural type Ia diamond for various electron... 70

Fig. 4.2.1. Infrared absorption spectra for natural brown diamonds before e-beam irradiation 75

Fig. 4.2.2. Infrared absorption spectra for typical five diamonds classified depending on the nitrogen... 77

Fig. 4.2.3. Comparison of the FT-IR spectra of brown diamonds before and after e-beam irradiation 79

Fig. 4.2.4. The 325 ㎚ laser PL spectra of brown diamonds before and after e-beam irradiation 82

Fig. 4.2.5. The 514 ㎚ laser PL spectra of brown diamonds before and after e-beam irradiation 86

Fig. 4.2.6. Comparison of the FT-IR spectra of brown diamonds before and after e-beam irradiation 91

Fig. 4.2.7. Comparison of the FT-IR spectra of brown diamonds before and after e-beam irradiation 93

Fig. 4.2.8. Comparison of the FT-IR spectra of brown diamonds before and after e-beam irradiation 96

Fig. 4.2.9. The 514 ㎚ laser PL spectra of brown diamonds after e-beam irradiation and annealing 99

Fig. 4.2.10. The 325 ㎚ He-Cd laser PL spectra of brown diamonds after e-beam irradiation and... 101

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