From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies Irma Čustovic To cite this version: Irma Čustovic. From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies. Micro and nanotechnologies/Microelectronics. Université Bourgogne Franche- Comté, 2020. English. NNT : 2020UBFCD044. tel-03128924 HAL Id: tel-03128924 https://tel.archives-ouvertes.fr/tel-03128924 Submitted on 2 Feb 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THESE DE DOCTORAT DE L’ETABLISSEMENT UNIVERSITE BOURGOGNE FRANCHE-COMTE PREPAREE A l’UNIVERSITE DE FRANCHE-COMTE Ecole doctorale : n°37 ED SPIM Doctorat de Sciences pour l'ingénieur Par Irma Custovic De l’auto-assemblage supramoléculaire à la synthèse sur surface : études par microscopie à champ proche From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies Soutenue à Montbéliard, le 9/11/2020 devant le jury composé de Rapporteur MASSON, Laurence Pr., Aix-Marseille Université, Marseille, France Rapporteur TEJEDA, Antonio Dr. CNRS, Laboratoire de Physique des Solides, Orsay, France PIRRI, Carmelo Pr., Université de Haute Alsace, Mulhouse, France Président De WOLF, Peter Dr. AD, Bruker Nano Surfaces and Metrology, Nimes, France Examinateur BRIOIS, Pascal Dr. Maitre de Conférences, Univérsite Technologique Belfort-Montbéliard Examinateur CHERIOUX, Fréderic Dr. CNRS, FEMTO-ST, Besançon, France Directeur PALMINO, Frank Pr., Univeristé de Franche-Comté, France Co-directeur THESIS TO OBTAIN THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY BOURGOGNE FRANCHE-COMTE PREPARED AT University of Bourgogne Franche-Comte Doctoral School n°37 ED SPIM Engineering sciences and Microtechnology Thesis in 2020 By Irma Custovic Thesis title: From supramolecular self-assemblies to on-surface synthesis monitored by Scanning Probe Microscopies Defended in Montbéliard, the 9th November, 2020 Defence committee: Chairman Pr. Carmelo Pirri MASSON, Laurence Pr., Aix-Marseille Université, Marseille, France Reviewer TEJEDA, Antonio Dr. CNRS, Laboratoire de Physique des Solides, Orsay, France Reviewer PIRRI, Carmelo Pr., Université de Haute Alsace, Mulhouse, France Jury member De WOLF, Peter Dr. AD, Bruker Nano Surfaces and Metrology, Nimes, France Jury member BRIOIS, Pascal Dr. Maitre de Conférences, Univérsite Technologique Belfort-Montbéliard Jury member CHERIOUX, Fréderic Dr. CNRS, FEMTO-ST, Besançon, France Supervisor PALMINO, Frank Pr., Univeristé de Franche-Comté, France Co-supervisor Acknowledgements I would like to express my appreciation to the director and co-director of my thesis, Dr. Frédéric Chérioux and Professor Frank Palmino, for providing me this opportunity to join their research group and for their enthusiastic, cooperative and indispensable guidance and supervision. I would like to thank them for enrolling me in the world of science and research and for sharing their experience, knowledge and scientific discussion that I will carry with myself in a long- term life pathway. I owe my deep sense of gratitude to the members of jury for devoting their time and assessment to this thesis. I would also extend my special thanks to Professor Laurence Masson and Dr. Antonio Tejeda, for accepting to be the reviewers of my thesis and to Professor Carmelo Pirri and Dr. Peter de Wolf for their acceptation to be the examiners of my thesis. A great thanks are devoted to the collaborators which were enrolled in my work, Professor Christian Loppacher, Professor Alain Rochefort, Hamed Abbasian, as well as members of our group, Judicael Jeannoutot, Katia Verbeke and Guillaume Levasseur. Following part of Acknowledgements are dedicated to the intimate appreciation that I own to the people who were encouraged support during three years of my thesis. First, my personal thanks are dedicated to Dr. Muamer Kadic, for his enormous help, advise and support since the beginning of my thesis. I am grateful that I met you and have you as my friend. Thank you for pushing me forward towards this important part of my life. In addition, I would thank to Myriam Carrillat for her companion, friendship and for giving me opportunity to collaborate with her as a teaching assistant. My deep gratitude goes to my best friend, Elie Geagea, in a way that words are not sufficient to describe my appreciation for your unconditional support and help in one of the most difficult periods I had been through. Knowing you is the evidence that still good people exist and thank you for being by my side. Thank you for sharing with me the eternal life lectures and thank you for being my true friend. Finally, a deep gratitude goes to my family, my mother Edina, my father Edhem and my brother Irfan. Without your love, comprehension and support I would never achieve my dreams and my goals. I am happy to be daughter and sister to the most amazing persons I have ever known. Dedication of the thesis I dedicate this thesis to my grandmother “Sika”, my eternal support and inspiration. The joy of my life! General introduction General introduction “There’s Plenty of Room at the Bottom: An Invitation to Enter a New field of Physics” was a famous lecture given by Richard P. Feynman at the annual American Physical Society meeting at Caltech, 1959 [1] . In his lecture, Feynman settled the inception for the field which was based on his vision of computer and machine miniaturization to the atomic scale where a huge amount of information could be storage and encoded onto increasingly small spaces. His speech significantly influenced the commencement of the nanotechnology and nanoscience which aim refers to the study and manipulation of a matter and particles on nanometer scale for a development of new nanomaterials and nanocomponents. The development of molecular electronics involves study and implementation of molecules as primary building blocks for the fabrication of the nanoscale devices. One of the fascinating examples regarding the given opportunity to the molecular integration into an electronic circuit was reported in work of Nongjian Tao and Bingqian Xu in 2003, who addressed electrode–molecule–electrode junctions presented by the conductance peaks for the set of organic molecules [2]. In this issue, an efficient current junction method which studies the conductivity of various organic molecules, quested to be deeply understood and controlled, not by using any another technique but by basic principle of chemistry: understanding the relationship between molecular structure and function which will enable the synthesis of molecules with improved properties. Therefore, the organic nanostructures with desired properties could be studied by “bottom-up” approach which is inspired by “nature autonomous order phenomena” and refers to the fabrication of ordered nanostructures by using chemical or physical bonds operating at the nanoscale to the molecular building blocks which results into self-organized supramolecular growth or so-called self-assembled nanostructures [3]. The major advantage of the investigation of supramolecular self-assembly relays on efficient tuning of the resulting self-assembled properties (structural, electrical, photophysical etc.) just by shifting the structure-specific part of utilised molecular building blocks. In such a way, the variations in supramolecular self- assembled properties are contemplated by existence of different interactions between the building blocks. The breakthrough example of the development of 3D organic nanostructures based on self-assembly which are influenced by intermolecular interactions is presented by Jean-Marie Lehn, Donald Cram and Charles Pedersen, awarded by the Nobel prize in chemistry in 1987 for development and use of “molecules with structure-specific interactions of high selectivity” [4]. General introduction a) b) c) d) Figure 1.1 a) Atomic scale view of nanostructure growth on surfaces. Atoms and molecules are deposited from vapor phase. The type of growth depends of ratio between diffusion D and deposition flux F. b) When F is larger than D (blue arrow) the growth is determined by kinetics individual processes mostly recognized in formation of metallic islands onto metal surfaces upper image presents Cu chains on anisotropic Pd(110) surface and down image presents Ag dendrites on Pt(111) surface). c) When D is equal to F, complex interplay between kinetics and thermodynamics affects nanostructure growth. This condition is recognized for semiconductor nanostructures: upper right and upper left panels show pyramidal and dome-shaped Ge semiconductor quantum dots grown on Si(100). Lower panel of figure 1.1 c) presents boron- nitride nanomesh on Rh(111). d) If the D is higher than F (red arrow), it allows thermodynamic conditions to be set at equilibrium state which is recognized at self-assembly of organic molecules on metal surfaces and shows self-assembly in formation of rod-like benzoic acid molecules on Ag(111) surface. Images adapted from [5]. The idea of supramolecular self-assembly was extended in