Organic solar cells promise electricity generation at very low cost, and higher installation flexibility as compared to inorganic solar cells. The lower cost is achieved by cheaper semiconductors and easier manufacturing processes. The flexibility is naturally given by these ultra-thin, amorphous layers. Also the power conversion efficiency can be high enough for many applications. The organic molecules have to withstand the constant excitation by photons, transport of energy in form of excitons and charge. A small but significant amount of these photons has energy over the absorption gap, the excess of energy must be released without breaking the molecular bonds. In consequence, the solar cells can also heat up to temperatures at above 80°C. The objective of this work is to answer the question if the small molecules organic solar cells can be stable enough to operate under a very long time. The stability of organic doped layers in an organic solar cell is also addressed. This work starts with a general introduction followed by the description of the experimental procedures. The aging experiments of the solar cell were done with a self developed equipment. The fabrication of this equipment (a set of measurement boxes) was necessary to maintain the conditions, under which a solar cell can be aged, as constant as possible. The measurement boxes were used to control the electrical load of the cell, its temperature, the illumination intensity, and its electric connection to the IxV measurement equipment. A software package was also developed to control the equipment and to facilitate the work and visualization of the high volume of collected data. The model solar cells chosen for the aging experiments were donor-acceptor heterojunctions devices formed with the well-known materials C60 and ZnPc. Two basic different structures were analyzed, because they offered reasonable performance and potentially long lifetime: the flat heterojunction (FHJ) and the mixed heterojunction in a Metal-Insulator-p-Semiconductor (m-i-p) configuration. Variations of the FHJ and of the m-i-p structures are also used to verify the limits of the stability of electrically p- and n- doped organic semiconducting layers. The least stable solar cells are the FHJ devices. These devices show a fast initial decrease of all their characteristic conversion parameters but the Voc. After a few hundred hours, the saturation current (current under a reverse bias of 1 V) was almost stable. The saturation current is related to the number of absorbing centers, the decrease indicates that the degradation of the absorbing centers has stopped. With wavelength resolved external quantum efficiency measurements and chemical analysis, it was found that the degradation is related to the oxidation of C60. It was also shown that the use of organic dopants do not significantly affect the lifetime. The results show that the m-i-p solar cells are more stable than the FHJ devices. They are also stable under high temperatures up to 105°C. Outdoor testing also showed that the solar cells remained chemically, electrically and mechanically stable during a 900 h test.

Le contexte actuel de forte croissance des besoins en énergie dans le monde nécessite une diversification de sa production, notamment vers des sources renouvelables tout en limitant autant qu’il est possible l’émission de gaz à effet de serre. Parmi les énergies renouvelables une des plus prometteuses et abondantes est l’énergie solaire et il apparaît évident que l’énergie solaire, thermique ou photovoltaïque, représente un enjeu crucial pour diminuer la consommation d’énergie fossile. Actuellement 90 % des générateurs solaires sont élaborés en silicium cristallin, ce qui pose un problème d’approvisionnement en matière première, les producteurs de silicium n’ayant pas su anticiper la forte expansion de la filière solaire. Des concepts innovants présentent une forte potentialité en termes de coût de production et d’application, notamment les filières organiques et hybrides (organique/oxyde métallique). En Europe, la France est très active dans ce domaine de recherche, en particulier en ce qui concerne l’utilisation de nouveaux matériaux nanostructurés organiques ou de structures hybrides. C'est pourquoi Disasolar, une start-up française spécialisée dans le photovoltaïque souple, souhaite développer cette activité en élaborant des modules solaires souples par impression jet d'encre. Les objectifs de cette thèse sont d'étudier des nouveaux matériaux d'interface imprimables et d'évaluer l'effet de la dimension des nanoparticules sur la topologie et les performances des dispositifs. Et dans un deuxième temps l'étude portera sur l'impression des matériaux d'interface et la stabilité des cellules solaires organiques. / The current context of strong growth in energy demands in the world requires diversification of its production, in particular towards renewable sources while limiting as far as possible the emission of greenhouse gases. Among the most promising and abundant renewable energies is solar energy and it is evident that solar, thermal or photovoltaic energy represents a crucial issue to reduce the consumption of fossil energy. Currently 90% of the solar generators are made of crystalline silicon, which poses a problem of supply of raw material, as silicon producers did not know how to anticipate the strong expansion of the solar sector. Innovative concepts present a high potential in terms of cost of production and application, in particular organic and hybrid (organic / metal oxide) dies. In Europe, France is very active in this area of research, particularly with regard to the use of new organic nanostructured materials or hybrid structures. This is why Disasolar, a French start-up specializing in flexible photovoltaics, wants to develop this activity by developing flexible solar modules by inkjet printing. The objectives of this thesis are to study new printable interface materials and to evaluate the effect of nanoparticle size on the topology and performance of devices. And secondly, the study will focus on the printing of interface materials and the stability of organic solar cells.

Les travaux de cette thèse sont en rapport avec la caractérisation de cellules solaires organiques et se déclinent suivant 3 axes :- Dans le cadre du projet IMPCELPHOTOR, nous avons développé un banc de caractérisation LBIC/LBIV permettant de cartographier des dispositifs OPV afin de visualiser et d’identifier les défauts de fonctionnement.- Dans le cadre du projet Européen SPrinTronics, nous avons travaillé sur l’amélioration des électrodes. Pour l’électrode collectrice d’électrons, nous avons sélectionné, testé et validé des encres métalliques à base de nanoparticules d’argent compatibles avec l’impression jet d’encre et permettant de réaliser des dispositifs OPV fonctionnels. Pour l’électrode collectrice de trous, nous avons testé des encres à base de nanofils d’argent et de nanotubes de carbone afin de remplacer l’ITO. Des résultats satisfaisants ont été obtenus avec une encre à base de nanofils d’argent. Cette dernière permet de réaliser des cellules semi-transparentes fonctionnelles sur verre et sur plastique. - Un travail sur l’aspect couleur d’un dispositif OPV a été mené au sein du projet PHASME. Nous avons mis en œuvre différentes techniques afin de modifier la couleur d’un dispositif OPV sans détruire ses performances photovoltaïques, le but étant de réaliser des modules polychromes. Nous avons développé simultanément un logiciel de colorimétrie permettant de contrôler et de prévoir le rendu de couleur dû à l’ajout de filtre coloré sur le dispositif OPV. / The work of this thesis is related to the characterization of organic solar cells and is structured in three independant parts :- Within the IMPCELPHOTOR project, we developed an experimental bench based on LBIC/ LBIV mapping, in order to visualize and identify defects within OPV device and modules.- Within the European SPrinTronics project, we worked on the improvement of OPV electrodes. For the top electrode, we selected, tested, and validated metallic inks based on silver nanoparticles compatible with inkjet printing. For the bottom electrode, we tested silver nanowires and carbon nanotubes inks to replace ITO. Satisfactory results have been obtained with an ink based on silver nanowires, which allowed us to obtain functional semi-transparent cells on glass and plastic.- Within the PHASME project, we worked on the visual aspect of a coloured OPV device. We implemented various strategies to change the color of an OPV device without altering its photovoltaic performance, the aim being to achieve full color modules. Simultaneously, we developed a colorimetric software to control and predict the color rendering on the final device (OPV plus filter).