This thesis deals with the development of scanning probe microscopes. Mechanical requirements for microscopes using measuring methods of scanning tunneling microscopy (STM) and atomic force microscopy (AFM) under enviroments of an ultrahigh vacuum (UHV) and variable temperatures are specified. Mechanical designs of two microscopes are discussed and their control electronics described. A special chapter is devoted to description of linear piezo manipulators and mechanical design of these prototypes.

Ce travail présente les études, par microscopie à effet tunnel (STM) sous ultravide, d’une part de la formation de réseaux supramoléculaires, résultant de l’auto-assemblage des précurseurs organiques sur les surfaces Cu(111), Au(111), Si(111)-B et HOPG, et d’autre part, de l’étude de réactions chimiques sur les surfaces Cu(111), Au(111) et HOPG. Le premier chapitre décrit l’état de l’art des réseaux supramoléculaires ainsi que les réactions chimiques sur les surfaces. Le deuxième chapitre présente le dispositif expérimental et les théories sous-jacentes, ainsi que les préparations des substrats, de la pointe et la méthode de déposition des molécules.Le troisième chapitre présente les réseaux supramoléculaires formés par les dépositions des molécules fonctionnalisées par des atomes de brome ou d’azote sur les surfaces Cu(111) et Si(111)-B. Dans tous les cas, le rôle de la surface est prédominant lors de la formation des réseaux. Sur Cu(111), deux réseaux linéaires sont stabilisés par des interactions organométalliques entre les adatomes de Cu et les molécules organiques. Sur Si(111)-B, les réseaux formés sont commensurables avec la reconstruction √3 × √3 de la surface. En fonction de la compétition entre les interactions intermoléculaires et molécule-surface, les réseaux peuvent être 2D ou 1D.Le quatrième chapitre présent le premier exemple de polymérisation radicalaire sur une surface. Pour ce faire, quatre molécules de type arylalkyléthers et deux molécules arylalkanes furent synthétisées et déposées sur les surfaces de Cu (111), Au (111) et HOPG. Le mécanisme proposé pour cette réaction débute par une étape d’initialisation grâce à un processus de transfert inélastique d’électron tunnel (IET), générant des radicaux libres qui peuvent ensuite polymérisés par voie radicalaire sur la surface. / This work deals with the investigation, by means of scanning tunneling microscopy under ultra-high vacuum, of supramolecular networks resulting from the self-assembly of organic precursors on surfaces such as Cu(111), Au(111), Si(111)-B and HOPG, but also the investigation of on-surface reactions. The first chapter describes the state-of-the-art of supramolecular networks and on-surface reactions on surfaces. The second chapter presents the experimental setup and theoretical concepts, as well as the preparations of the substrates, the probe tip and the method of molecular deposition.The third chapter presents the supramolecular networks formed by the depositions of molecules functionalized by bromine atoms or nitrogen atoms on the Cu(111) and Si(111)-B surfaces. For both cases, the surface plays a key role in the formation of networks: on Cu(111), the two linear networks are stabilized by metal-organic interactions between the Cu adatoms and the organic molecules; on Si(111)-B, the nanoarchitectures are commensurable with the reconstruction √3 × √3 of the surface. As function of the competition between the intramolecular and intermolecular interactions, the networks could be 2D or 1D.The fourth chapter presents the first example of on-surface radical polymerization, which is developed by the tandem synthetic method. For this end, four arylalkylether molecules and two arylalkane molecules are synthetized and deposited on different types of surfaces such as Cu (111), Au (111) and HOPG. The proposed mechanism suggests that this reaction is initialized by the inelastic electron tunneling (IET) process, which provides the free and stable radicals for the further on surface radical polymerization.

The adsorption of biologically active molecules, such as the DNA bases, amino acids, on solid surfaces has been the subject of a number of experimental and theoretical studies in the past years. The understanding of the self-assembly mechanism of bioactive molecules on surfaces not only is fundamentally important in the preparation of bioactive surfaces, but also provides us insight into the origins of life and homo-chirality in nature. In this thesis, the adsorption behaviour of adenine and phenylglycine molecules on the Cu(110) surface has been investigated in order to understand the effect of experimental parameters like coverage, annealing temperature etc. on the molecular orientation and the ordering of the adlayer structures. The thesis is organised in six parts: Chapter I gives an introduction to the relevance of surface sciences studies, describing the phenomena of surface chirality and molecular adsorption behaviours on surfaces. Chapter II gives an overview of the experimental techniques and introduces basic concepts of theoretical calculation. Chapter III investigates the effect of experimental parameters, e.g. surface coverage, annealing temperature and substrate temperature on molecular diffusion, molecular orientation and ordering of the adlayer structures. LT-STM examination of the contrast variations of adenine chains and isolated adsorbate as a function of the tip-sample bias voltage is also presented with the aim to understand the tunnelling mechanism. Chapter IV shows RAIR spectra studies of the evolution of phenylglycine molecular orientation as a function of surface coverage at room temperature. The adsorption geometry and binding nature of phenylglycine is discussed. Chapter V concerns with the adsorption behaviours of phenylglycine and adenine on Cu(110) surface pre-covered with oxygen. Chapter VI summarises the conclusions and describes the outlook of some future work.