L'objectif de ce travail est de réaliser des substrats pour l’effet SEIRA (surface enhanced IR absorption) pour mesurer de faibles volumes de gaz ambiants possédant une signature moléculaire de 3,3 μm à 5,1 μm en exploitant la forte amplification de champ électrique due à la résonance plasmon de surface localisés. A cette fin, nous avons démontré la modulation des résonances de plasmon de surface localisées MIR (LSPR) dans les nanocristaux de ZnO dopés (NCs) dopés à Ga ou Al ainsi que dans des nanofils (NWs) de ZnO dopés Ga (GZO) et dans des nanofils coeur/coquille de ZnO/GZO. En ce qui concerne l’accordabilité de MIR LSPR dans les NC, nous avons modulé la résonance plasmon de surface dans des NC de ZnO dopés Ga et Al, de 3 à 5 μm en faisant varier la teneur en Al et en Ga de 3 à 9 at.%. L’incorporation des dopants s’est révélée homogène jusqu’à 6%. Au-delà (9%), l’incorporation était fortement hétérogène, révélant que la limite de solubilité était atteinte. Les NC présentent une faible activation des impuretés. L'activation était aussi faible que 8%. Les LSPR présentaient également un fort élargissement (largeur-à-mi-hauteur FWHM). Pour accroitre l'activation des dopants, nous avons synthétisés les NC dans des conditions pauvres en O et en passivant les NC synthétisés dans des conditions riches en O (en les isolant dans des matrices telles que Al2O3 et SiO2). Nous avons ainsi augmenté l'activation de 8% à 20% pour les deux stratégies. De plus, l'incorporation des NC dans les matrices a réduit l'élargissement spectral de moitié (de 2200 cm-1 pour les NC déposés à 1100 cm-1 pour les NC noyés en matrice). En correspondance, les effets d’auto-assemblage des nanocristaux sur leur LSPR ont été modélisés par simulation FDTD. Cela a fourni des indications quant aux mécanismes responsable de l’élargissement inhomogènes des LSPR de nanocristaux de GZO. Outre les nanoparticules, nous avons étudié des nanofils ZnO dopés Ga (GZO) et coeur/coquille (ZnO/GZO) synthétisés par CVD d’organométalliques . La première conclusion importante est que le gallium produit un fort effet surfacatnt lors de la croissance MOCVD de GZO. Au lieu de former des nanofils de section hexagonale, l’introduction de Ga modifie nettement l’énergie de surface des faces latérales et conduit à al formation de structures de type « sapins de Noël ». Ce constat est aussi valable pour les coquilles de GZO déposées sur coeur de ZnO. Dans ce cas, les coquilles démouillent et forment des structures hiérarchiques en branches. Concernant les propriétés optiques de ces objets, les mesures de FTIR-photo acoustiques ont démontré une signature d’absorption reliée à la présence de Ga et pouvant être accordée selon la teneur en Ga. Cette absorption reproduit le comportement d’une résonance plasmon de surface. Cette résonance a pu être accordée de 1600 à 1900 cm-1. / The scope of this thesis is about developing SEIRA (surface enhanced IR absorption) platform to probe low volumes of environmental gases that possess molecular signature from 3.3 μm to 5.1 μm leveraging the high field amplification of localised surface plasmon resonance (LSPR). To realise SEIRA, we demonstrated tuning MIR LSPR in Al or Ga doped ZnO nanocrystals (NCs) as well as in GZO or core-shell (ZnO/GZO) nanowires (NWs). Regarding tuning MIR LSPR in NCs, we demonstrated tunable MIR LSPR in Ga and Al doped ZnO NCs from 3 to 5 μm varying the Al or Ga content from 3 to 9 at.%. The incorporation of dopant was homogeneous up to 6%. At 9% dopant concentration, the incorporation was inhomogeneous, revealing the solubility limit has been reached. However, the NCs exhibited low activation of impurities. The activation was as low as 8%. The LSPR were characterised by large broadening as well. In order to enhance the dopant activation, we synthesized the NCs in O-poor conditions as well as passivated the NCs fabricated in O-rich condictions (by isolating and embedding them in matrices such as Al2O3 and SiO2 matrices). Both strategies improved the dopant activation from 8% up to 20%. Moreover, for assemblies of NCs dispersed in matrices, the broadening (FWHM) of the LSPR was reduced by half (from 2200 cm-1 in as-deposited NCs to 1100 cm-1 in embedded NCs). Correspondingly, the effect of the self-assembly of the nanocrystals on their LSPR was modeled by FDTD simulation and provided hindsight into the mechanisms responsible for the heterogeneous broadening of the LSPR. Finally, we have studied Ga-doped ZnO (GZO) and core-shell (ZnO/GZO) NW synthesized by MOCVD. The first important conclusion is that Ga plays a major surfactant role during the MOCVD growth of GZO. Instead of leading to hexagonal NWs, the introduction of Ga during the synthesis led to faceted “Christmas-tree” like architectures. The same observation held for core-shell ZnO-GZO nanowires; in the latter case, the GZO shell resulted in a dewetting branched architecture. Regarding their optical properties, photo-acoustic FTIR measurements revealed an absorption feature related to the Ga content, likely to be assigned to a plasmonic effect. This resonance could be tuned from 1600 to 1900 cm.

A firm knowledge about the interaction between the metal surface and adsorbed molecules is imperative for formulating procedures to synthesize nanoparticles (NPs) with predetermined shape and size. The ligand‐metal interaction during NP formation can be mimicked on an electrode surface by electrosorbing ligand molecules on a charged metal surface. Electrochemical methods can provide an ideal platform to study the adsorption behaviour of molecules at the solid‐liquid interface. In addition to classical electrochemical techniques, the combination of spectroscopy with electrochemical methods amplifies mechanistic insights about the surface adsorption processes. The adsorption behaviour of pyridine and one of its derivatives, 4‐dimethylamino pyridine (DMAP) have been well studied due to their potential application in nanoparticle synthesis. However, prior to this work, there has been very limited and conflicting literature available about the adsorption of of pyridine derivatives analogous to DMAP. Among the pyridine derivatives that were studied, some reports indicate that, other than DMAP, only 4‐methoxy pyridine (MOP) can stabilize gold nanoparticles. However, very little is known about the possible differences in the adsorption energy and general behaviour of MOP compared to DMAP. Resolving this knowledge gap is imperative to resolving the conflicting information about pyridine‐based stabilizers for metal nanoparticle applications. The adsorption behaviour of MOP on different crystallographic Au surfaces as a function of pH and surface potential has been investigated in this project. These studied were carried out using classical electrochemical methods including chronocoulometry and differential capacity, as well as modern spectroscopic techniques like Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS). The thermodynamic parameters obtained from electrochemical data shows that adsorption features of MOP is similar to that of DMAP. However, there is a significant difference in the adsorption strength of MOP and DMAP at positive potentials. The SEIRAS data provides much more detailed information about the potential depended orientation of MOP on polycrystalline Au. Cumulative analysis of electrochemical and spectroscopic data provides strong evidence that MOP can stabilize Au(111) facets over wide pH ranges. Moreover, this work provides convincing evidence that the basic nature of substituted pyridine alters the metal to ligand adsorption strength.