STM Investigation of Molecular Architectures of Porphyrinoids on a Ag(111) Surface (eBook)

Supervisor’s Foreword 8
Acknowledgments 10
Contents 11
List of Abbreviations 15
List of Figures 16
1 Introduction 27
References 28
2 Fundamentals 30
2.1…Principle of the STM 30
2.2…Origin of the Tunneling Current 32
2.3…Scanning Tunneling Spectroscopy 34
2.4…Contrast Mechanism of Molecular Adsorbates 35
2.5…Temperature Programmed Desorption 37
2.6…Low Energy Electron Diffraction 39
References 40
3 Experimental Setup 41
3.1…UHV System 41
3.2…Scanning Tunneling Microscope 42
3.3…Control Electronics and Vibration Isolation 45
3.4…Ag(111) 46
3.5…Porphyrinoids 48
3.6…Preparation of thin Porphyrinoid Layers 49
3.7…Vapor-deposition of Cobalt and Iron 51
References 52
Part IResults 53
4 Self-Assembly and Individual Appearance of Tetraphenylporphyrins on Ag(111) 54
4.1…Introduction 54
4.2…Epitaxial Growth 55
4.3…Appearance and Intramolecular Conformation 59
4.4…Ordering Aspects 60
4.5…Conclusion 66
References 67
5 Self-Assembly and Individual Appearance of Cobalt(II)-Tetrakisditertbutylphenylporphyrins on Ag(111) 69
5.1…Polymorphism of CoTTBPP 69
5.1.1 Conclusion 81
5.2…Polarity-Dependent Appearance 82
5.2.1 Conclusion 83
References 84
6 Coordination of Iron and Cobalt Atoms by Tetraphenylporphyrin Monolayers on Ag(111) and Formation of Metal(II)-Tetraphenylporphyrin 85
6.1…Introduction 85
6.2…Coordination of Post-deposited Iron Atoms by Tetraphenylporphyrin Monolayers 86
6.2.1 Conclusion 90
6.3…Coordination of Pre-deposited Iron Atoms by Tetraphenylporphyrin Monolayers 90
6.3.1 Conclusion 93
6.4…Coordination of Post-deposited Cobalt Atoms by Tetraphenylporphyrin Monolayers 93
6.4.1 Conclusion 97
6.5…Discussion of the Metalation Reaction 97
References 99
7 Different Aspects of 2H-Tetrakis-di-tert-butylphenylporphyrin on Ag(111) 101
7.1…Introduction 101
7.2…Monolayer Preparation 102
7.3…Arrangement of 2HTTBPP 104
7.3.1 Conclusion 107
7.4…Voltage-Dependent Appearance 108
7.4.1 Conclusion 109
7.5…Direct Metalation of 2HTTBPP with Co-adsorbed Iron 109
7.5.1 Conclusion 110
References 111
8 Direct Metalation of a Phthalocyanine Monolayer on Ag(111) with Co-adsorbed Iron Atoms 112
8.1…Introduction 112
8.2…Results 113
8.3…Conclusion 119
References 119
9 Multicomponent Adlayers of Tetraphenylporphyrins on Ag(111) 121
9.1…Understanding the Contrast Mechanism in STM Images of Cobalt Tetraphenylporphyrin on Ag(111) 121
9.1.1 Introduction 122
9.1.2 Results 122
9.1.3 Conclusion 128
9.2…Fingerprints of Different Porphyrins 129
9.2.1 Introduction 129
9.2.2 Results 131
9.2.3 Conclusion 140
9.3…Addressing Molecular Orbitals of Cobalt- and Iron-Tetraphenylporphyrins by Continuous Imaging Tunneling Spectroscopy 141
9.3.1 Introduction 141
9.3.2 Results 142
9.3.3 Conclusion 147
References 147
10 Modification of the Growth of Iron on Ag(111) by Predeposited Organic Monolayers 149
10.1…Introduction 149
10.1.1 Growth of Fe on Ag(111) 150
10.1.2 Growth of Fe on Ag(111) Precovered with Different Tetrapyrrolic Monolayers 152
10.2…Conclusion 159
References 159
11 Geometric and Electronic Aspects of CoTPP upon Dosage of NO 161
11.1…Introduction 161
11.2…In Situ Observation of the Rearrangement of CoTPP on Ag(111) 162
11.3…Conclusion 166
11.4…Modification of the Appearance of CoTPP upon Formation of NO-CoTPP 167
11.5…Conclusion 170
References 171
12 Self-Assembly and Voltage-Dependent Appearance of Octaethylporphyrins 172
12.1…Introduction 172
12.2…Results 173
12.3…Conclusion 177
References 178
13 Summary and Outlook 179
13.1…Molecular Ordering and Intramolecular Conformation 179
13.2…Coordination of Metal Atoms by Free Base Porphyrinoids 180
13.3…Electronic Properties of Porphyrins 181
13.4…Interaction with Small Molecules 181
13.5…Outlook 182