Networks on Metal Surfaces through Amine Reactions.

160 Pages·2012·14.81 MB·English

Strategies for the Formation of Covalently Bonded Nano-
Networks on Metal Surfaces through Amine Reactions.

A thesis for the degree of
PHILOSOPHIAE DOCTOR

Presented to
DUBLIN CITY UNIVERSITY
Ollscoil Chathair Bhaile Átha Cliath

by

Hooi Ling Lee,
M.Sc., B. App. Sci.(Hons)
School of Physical Sciences
Dublin City University

Research Supervisor:
Dr. A. A. Cafolla

External Examiner: Prof. Andrew Evans
Internal Examiner: Prof. Greg Hughes

May 2012
Declaration

I hereby certify that this material, which I now submit for assessment on the programme of
study leading to the award of Doctor of Philosophy is entirely my own work, that I have
exercised reasonable care to ensure that the work is original, and does not to the best of my
knowledge breach any law of copyright, and has not been taken from the work of others
save and to the extent that such work has been cited and acknowledged within the text of
my work.

-------------------------------
Hooi Ling Lee
ID No: 58125361
April, 2012.
ii
Acknowledgements

First of all, I wish to convey my heartfelt gratitude to my Ph.D supervisor, Dr. Tony
Cafolla for his patience and guidance throughout my doctorate study. I am thankful to my
colleagues in my laboratory particularly Dr. John P. Cuniffe, Mr. John P. Beggan, Ms.
Catherine Doyle, Ms. Nina Berner and Mr. Thomas Carpy. It has been a wonderful
experience working with all of you. I also wish to thank academicians and staff support in
Dublin City University especially School of Physical Sciences for their assistance.

My deepest appreciation is also dedicated to all my collaborators who have contributed
enormously in my research work. I am truly honoured to have had the opportunity to work
with the following collaborators who are specialised in their own field:
1. Prof. Louis Porte, Dr. Luca Giovanelli, Dr. Mathieu Abel, Dr. Mathieu Koudia, Dr.
Sylvain Clair from IM2NP-CNRS, Aix-Marseille Université, Marseille, France.
2. Dr. Corinne Dufaure from ENSIACET/CIRIMAT, Toulouse, France.
3. Dr. Zheshen Li from The Institute for Storage Rings Facilities (ISA), Aarhus, Denmark.
4. Dr. Alexei B. Preobrajenski from MAX Lab, University of Lund, Sweden.

To all my friends who know me, thank you for your friendships and care.

Last but not least, thank you to my family especially my parents in Malaysia. Without their
continuous faith, I would never make it until this stage. In short, it has been a very
humbling journey.

This Ph.D work was funded by Science Foundation Ireland (SFI) under grant number
08/RFP/PHY1366. My synchrotron trip to ISA laboratory was supported by the EU grant.
The travelling grant to IM2NP was awarded by Ulysses Grant 2011 from Irish Research
Council for Sciences, Engineering and Technology, IRCSET-Embark Initiative. Their
financial supports are gratefully acknowledged.

Thank you.
Terima kasih.
Go raibh maith agat.
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For my parents

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Table of Contents

Declaration ii
Acknowledgements iii
Dedication iv
Table of Contents v
List of Poster Publications ix
List of Acronyms x
Abstract xi

Chapter 1: Introduction and Literature Review.
1.0 Introduction. 1
1.1 Literature Review. 1
1.1.1 Supramolecular Chemistry and Self-Assembly. 1
1.2 Porphyrin and Porphyrin Derivatives. 5
1.2.1 Electronic Properties of Porphyrin and Porphyrin Derivatives. 7
1.3 Motivation 8
1.4 Outline of the Thesis. 8
References. 10

Chapter 2: Methodologies.
2.0 Experimental Methods. 13
2.1 The Ultra High Vacuum (UHV) System. 13
2.2 Scanning Tunneling Microscopy (STM). 14
2.2.1 Basic Operational Principles. 15
2.2.2 Scanning Tunnelling Microscopy: Apparatus. 19
2.2.3 Preparation of STM Tip. 21
2.3 X-ray Photoelectron Spectroscopy (XPS). 22
2.4 Ultraviolet Photoelectron Spectroscopy (UPS). 26
2.5 Synchrotron Radiation Techniques. 28
2.5.1 X-ray Absorption Spectroscopy (XAS). 30
2.6 Low Energy Electron Diffraction (LEED). 31
v
2.7 Metal Surfaces. 35
2.7.1 The (22 x 3) on Au(111) Reconstruction. 35
2.7.2 Cu(111) and Ag(111) Surfaces. 35
2.8 Sample Preparation. 36
References. 37

Chapter 3: The Formation of Surface Supported Covalently Bonded TAPP
Networks on Au(111), Ag(111) and Cu(111) Surfaces.
3.0 Introduction. 39
3.1 Experimental. 40
3.2 Results and Discussion. 41
3.2.1 STM of TAPP on Au(111) Surface at Room Temperature (RT). 41
3.2.2 Synchrotron based XPS of TAPP on Au(111) Surface at Room 44
Temperature (RT).
3.2.3 XAS of TAPP on Au(111) Surface at Room Temperature (RT). 47
3.2.4 STM of TAPP on Au(111) Surface at Elevated Temperature. 49
3.2.5 XPS of TAPP on Au(111) Surface at Elevated Temperature. 51
3.2.6 STM of TAPP on Cu(111) Surface at Room Temperature (RT). 52
3.2.7 XPS of TAPP on Cu(111) Surface at Room Temperature (RT). 53
3.2.8 STM of TAPP on Cu(111) Surface at Elevated Temperature. 55
3.2.9 XPS of TAPP on Cu(111) Surface at Elevated Temperature. 56
3.2.10 STM of TAPP Self-assembled on Ag(111) Surface at Room 57
Temperature (RT).
3.2.11 XPS of TAPP on Ag(111) Surface at Room Temperature (RT). 59
3.2.12 STM of TAPP on Ag(111) Surface at Elevated Temperature. 60
3.2.13 XPS of TAPP on Ag(111) Surface at Elevated Temperature. 61
3.3 Summary 62
References 64

Chapter 4: UPS Measurements on TAPP Molecules on Au(111) and Cu(111).
4.0 Introduction. 66
4.1 Experimental. 67
4.2 Results and Discussion 68
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4.2.1 d Valence Band Spectra as a Function of Coverage on Au(111). 68
4.2.2 UPS Study of the Polymerisation of TAPP on Au(111). 73
4.2.3 Work Function Measurements of TAPP/Au(111) Interface. 76
4.2.4 Valence Band Spectra as a Function of Coverage on Cu(111). 78
4.2.5 UPS Study of the Polymerisation of TAPP on Cu(111). 81
4.2.6 Work Function Measurements of TAPP/Cu(111) Interface. 83
4.3 Summary. 84
References. 86

Chapter 5: Covalent bonding of TAPP and PTCDA on Au(111) Surface.
5.0 Introduction 88
5.1 Materials and Experimental. 89
5.1.1 3, 4, 9, 10-perylene tetracarboxylic dianhydride (PTCDA). 89
5.1.2 Methodology. 89
5.2 Results and Discussion. 90
5.2.1 STM of PTCDA on Au(111). 90
5.2.2 LEED of PTCDA on Reconstructed Au(111). 93
5.2.3 Synchrotron based XPS of PTCDA on Au(111). 95
5.2.4 XAS of PTCDA on Au(111). 97
5.2.5 STM of the bimolecular TAPP-PTCDA on Au(111) Surface. 99
5.2.6 Synchrotron based XPS of the bimolecular TAPP-PTCDA on 101
Au(111) Surface.
5.2.7 XAS of the bimolecular TAPP-PTCDA on Au(111) Surface. 102
5.3 Summary. 104
References. 105

Chapter 6: STM Studies of TAPB molecules on Noble Metal Surfaces and
Covalent bonding of TAPB and PTCDA on Ag(111) Surface.
6.0 Introduction. 107
6.1 Experimental. 109
6.2 Results and Discussion. 110
6.2.1 STM of TAPB on Au(111) at Room Temperature (RT). 110
6.2.2 XPS of TAPB on Au(111) at Room Temperature (RT). 111
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6.2.3 STM of TAPB on Au(111) at Elevated Temperature. 112
6.2.4 XPS of TAPB on Au(111) at Elevated Temperature. 116
6.2.5 STM of TAPB on Ag(111) at Room Temperature (RT). 117
6.2.6 XPS of TAPB on Ag(111) at Room Temperature (RT). 118
6.2.7 STM of TAPB on Ag(111) at Elevated Temperature. 119
6.2.8 XPS of TAPB on Ag(111) at Elevated Temperature. 121
6.2.9 STM and LEED Studies of PTCDA on Ag(111). 124
6.2.10 XPS Study of PTCDA on Ag(111). 125
6.2.11 STM of Co-deposited of TAPB and PTCDA on Ag(111). 127
6.2.12 XPS of Co-deposited of TAPB and PTCDA on Ag(111). 134
6.3 Summary. 136
References. 138

Chapter 7: Conclusions and Future Work.
7.1 Conclusions. 140
7.2 Future Work. 143
7.2.1 Research Work with TAPB. 143
7.2.2 Self-assembly and Covalent Reaction of BCPP and PTCDA on 143
Au(111).
7.2.3 Synchrotron Radiation Techniques on TAPB Molecules. 145
7.2.4 Density Functional Theory (DFT) Calculations. 145
7.2.5 Fullerene (C60) and TAPP Molecules Studies on Au(111). 145
References 147

Appendix A – Thermogravimetric Analysis (TGA) Spectrum of TAPP. 148
Appendix B – Thermogravimetric Analysis (TGA) Spectrum of TAPB. 149

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List of Poster Presentations

BOC POSTER COMPETITION
The formation of surface supported covalently bonded 5,10,15,20-tetrakis(4-
aminophenyl)-porphyrin (TAPP) networks.
School of Physical Sciences, Dublin City University, 13th April, 2012.

ECOSS28
The formation of surface supported covalently bonded 5,10,15,20-tetrakis(4-
aminophenyl)-porphyrin (TAPP) networks.
Wroclaw, Poland, 28th August, 2011 – 2nd September, 2011.

BOC POSTER COMPETITION
The formation of surface supported covalently bonded porphyrin networks through
polyimidisation.
School of Physical Sciences, Dublin City University, 24th September, 2010.
-won 3rd prize in the poster competition.

ECOSS27
The formation of surface supported covalently bonded porphyrin networks through
polyimidisation.
th th
Groningen, The Netherlands, 29 August, 2009 – 3 September, 2009.
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List of Acronym.
E Pass energy
p
BE Binding energy
EBD Electron beam deposition
EDC Energy distribution curve
ESCA Electron Spectroscopy for Chemical Analysis
FWHM Full width half maximum
GI Grazing incidence
HOMO Highest occupied molecular orbital
hν Photon energy
KE Kinetic energy
LEED Low energy electron diffraction
LUMO Lowest occupied molecular orbital
MFP Mean free path
ML Monolayer
MO Molecular orbital
NE Normal emission
NI Normal incidence
PES Photoelectron spectroscopy
PTCDA 3, 4, 9, 10-perylene tetracarboxylic dianhydride
RT Room temperature
SECO Secondary electrons cut-off
STM Scanning tunnelling microscopy
STS Scanning tunnelling spectroscopy
TAPB 1,3,6-tris(4-aminophenel)benzene
TAPP 5,10, 15,20-tetrakis(4-aminophenyl)porphyrin
TPP Tetra(4-aminophenyl)porphyrin
UHV Ultra high vacuum
UPS Ultraviolet photoelectron spectroscopy
VB Valence band
WF Workfunction
XAS X-ray absorption spectroscopy
XPS X-ray photoelectron spectroscopy

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