Aujourd hui encore, malgré l utilisation de techniques spectrochimiques de référence, l aspect quantitatif de la spectroscopie sur plasma induit par laser (LIBS) reste largement en friche du fait d effets de matrice incapacitants. La LIBS sans étalonnage (CF-LIBS) est une des façons considérées par la communauté scientifique afin de relever ce défi. Malgré ses postulats d idéalité du plasma (ETL, homogénéité et stationnarité du plasma), à l heure actuelle peu d études extensives ont été développées afin de réaliser une évaluation critique de la méthode. A l aide d outils théoriques (modèle collisionnel-radiatif développé pour l Aluminium, Argon et Cadmium) et expérimentaux (expérience de Diffusion Thomson) tirant leur origine de la physique des plasmas, ainsi que de cas pratiques d analyses, nous tenterons d établir le cahier des charges le plus favorable à l analyse quantitative par CF-LIBS. L application de cette méthode à l analyse d échantillons complexes (minéraux et sols pollués) sera discutée à l aune de nos résultats et des connaissances actuellement disponibles en la matière.Despite the existence of many benchmarked spectrochemical analysis techniques in the field of Laser-Induced Breakdown Spectroscopy (LIBS), the quantitative analysis holds of the laser induced plasma still holds a huge number of analytical drawbacks, the occurrence of matrix effects not being the slightest among those ones.Calibration-Free LIBS was historically developped to address specifically those aspects, and has already reached a high level of maturation for the analysis of simple metallic or soil samples. Unfortynately, in spite of the strong assumptions that need to be necesserily considered in the CF-LIBS algorithm (such as Local Thermodynamic Equilibrium, and the homogeneity and stationnarity of the plasma), only a few number of contributions have been devoted to the critical assessment of the latter postulates to date. Thanks to the help of several case tests and theoretical (collisionnal-radiative model depicting aluminum, argon and cadmium plasmas) and experimental concepts originating from the field of plasma physics (Thomson-Scattering experiments intended to validate our results), we will focus our study on the research and development of novel experimental criteria that would allow an experimentalist to set up and analyze a CF-LIBS experiment in the least unfavourable theoretical and experimental conditions.We will eventually apply our new considerations on the prediction of the CF-LIBS analysis efficiency, coming to the specific field of interest of analysis of geophysical samples (such as soils polluted by heavy metals). A special interest will be paid on the latest developments appearing nowadays in the field of LIBS, and devote a part of our debate on the expectancies that will have to be fulfilled in order to highen the analysis potential of LIBS.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF