La démonstration de la première diode laser organique reste un défi majeur en opto-électronique organique. Parmi les nombreuses problématiques à étudier, l’aspect « matériau » (gain et pertes) est capital. Par exemple, la limite théorique basse du seuil laser en pompage électrique pourrait être connue s’il existait une méthode d’estimation fiable du seuil laser en pompage optique. Dans cette thèse nous avons étudié le gain et la polarisation de lasers basés sur des couches minces de polymère dopées par des colorants organiques. L’originalité de ce travail repose sur l’étude des propriétés du matériau organique à travers l’analyse des caractéristiques de microlasers. Cela permet aussi de s’intéresser aux problématiques de couplage gain-mode et aux systèmes ouverts. Nous proposons une description quantitative du processus d’amplification dans les matériaux organiques. Une relation liant gain, pertes et seuil est établie dans le cas d’une cavité Fabry-Perot, ce qui permet par la suite l’étude de l’amplification optique et de l’extraction de la lumière dans les cavités diélectriques à travers la mesure précise du seuil laser. Nous avons exploré différentes formes de cavités, comme les carrés où la lumière est couplée vers l’extérieur par diffraction au niveau des coins. Nous avons démontré que l’anisotropie de fluorescence intrinsèque des molécules de colorant gouverne la polarisation de tels systèmes lasers. Nous avons développé à cette occasion un modèle original incluant la distribution non-isotrope des molécules dans le polymère. Nous avons aussi étudié le rôle de la géométrie de la cavité sur l’état de polarisation du laser, et différents moyens de contrôler cet état. / The demonstration of an electrically pumped organic laser remains a major issue of organic optoelectronics for several decades. This goal requires an improved device configuration so as to reduce losses which are intrinsically higher under electrical excitation compared to optical pumping. Moreover a systematic investigation of the material properties is still missing and should lead to a reliable estimate of the lasing threshold under optical pumping, and then to a lower limit for electrical pumping. In this thesis we addressed the issue of gain and polarization properties of organic materials in the case of dye-doped polymer thin films. The originality of this work lies in the study of materials via the features of dielectric micro-lasers, allowing to investigate the issues of gain and mode coupling and the physics of open systems. We propose a quantitative description of amplification in organic materials. The “gain-loss-threshold” relation was developed and demonstrated for a Fabry-Perot type cavity, opening the way to study both amplification in organic materials and light out-coupling in dielectric micro-cavities via the lasing threshold. Within this context, different cavity shapes were studied, for instance squares, where light out-coupling takes place by diffraction at dielectric corners. We evidence that polarization properties of such lasing system originate from the intrinsic fluorescence anisotropy of dyes, which required to develop a specific anisotropic model going beyond the existing theory. We also investigated the role of the cavity geometry on the polarization states of the micro-lasers and proposed different ways to influence these features.

The demonstration of an electrically pumped organic laser remains a major issue of organic optoelectronics for several decades. This goal requires an improved device configuration so as to reduce losses which are intrinsically higher under electrical excitation compared to optical pumping. Moreover a systematic investigation of the material properties is still missing and should lead to a reliable estimate of the lasing threshold under optical pumping, and then to a lower limit for electrical pumping. In this thesis we addressed the issue of gain and polarization properties of organic materials in the case of dye-doped polymer thin films. The originality of this work lies in the study of materials via the features of dielectric micro-lasers, allowing to investigate the issues of gain and mode coupling and the physics of open systems. We propose a quantitative description of amplification in organic materials. The "gain-loss-threshold" relation was developed and demonstrated for a Fabry-Perot type cavity, opening the way to study both amplification in organic materials and light out-coupling in dielectric micro-cavities via the lasing threshold. Within this context, different cavity shapes were studied, for instance squares, where light out-coupling takes place by diffraction at dielectric corners. We evidence that polarization properties of such lasing system originate from the intrinsic fluorescence anisotropy of dyes, which required to develop a specific anisotropic model going beyond the existing theory. We also investigated the role of the cavity geometry on the polarization states of the micro-lasers and proposed different ways to influence these features.

Le contrôle des polluants environnementaux présents à faible concentration a conduit à la création de détecteurs miniaturisés, à bas coûts et ultra-sensibles, capables d’identifier spécifiquement certaines substances. Dans cette thèse, la méthode de détection explorée repose sur la sensibilité de micro-lasers polymères à une variation d’indice de réfraction. Cette approche a été mise en application pour détecter des métaux lourds (mercure – Hg2+, cadmium – Cd2+ et plomb – Pb2+) dans l’eau potable. En effet les fréquences de résonance de ces micro-cavités sont particulièrement sensibles à l’indice de réfraction du milieu extérieur et se déplacent lorsque celui-ci est modifié. Ce système permet ainsi une détection sans marqueur (« label ») en recouvrant la cavité d’une couche de reconnaissance spécifique de l’espèce recherchée. L’originalité de ce travail repose sur l’utilisation de micro-cavités actives, ou micro-lasers, fabriquées avec des polymères dopés par des colorants lasers. En effet les micro-lasers permettent d’augmenter le rapport signal/bruit et de profiter de pics de résonance étroits, même pour des facteurs de qualité de l’ordre de quelques milliers seulement. Le choix de matériaux organiques comme milieu à gain a été dicté par les nombreux avantages qu’ils offrent. Contrairement aux semi-conducteurs inorganiques, les polymères peuvent être fonctionnalisés de manière relativement aisée et l’utilisation de matériaux poreux devrait augmenter la sensibilité en faisant circuler le fluide à tester à l’intérieur même du résonateur. De plus le protocole de fabrication des micro-lasers organiques reste d’un coût modéré et permet une intégration aisée en micro-fluidique. Deux voies différentes ont été explorées dans cette thèse : détection d’une variation d’indice de réfraction avec des cavités non-fonctionnalisées et détection d’ions lourds avec des cavités fonctionnalisées. Dans le premier cas, la sensibilité obtenue est comparable à ce qui est publié pour des micro-résonateurs passifs. Dans le second cas, nous avons réussi à mettre en évidence la présence d’ions mercure jusqu’à 10-6 M. Quelques approches ont été envisagées pour diminuer encore le seuil de détection dont certaines ont été vérifiées expérimentalement. Ainsi, cette étude propose un prototype de composant sur puce pour la détection d’espèces chimiques ou biologiques. / Monitoring of environmental pollutants present at low concentrations requires creation of miniature, low-cost, and highly sensitive detectors that are capable to specifically identify target substances. In this thesis, a detection approach based on refractive index sensing with polymer micro-lasers is proposed and its application to the detection of heavy metal pollutants in water (mercury – Hg2+, cadmium – Cd2+ and lead – Pb2+) is studied. The resonance frequencies of the microcavity are highly sensitive to the refractive indices of the resonator surrounding: the resonances shift by a small amount when the surface refractive index changes, resulting from the interaction of the mode evanescent field with the surrounding medium. This permits label-free detection by coating the resonator with a suitable recognition species. The originality of this work lies in the utilization of active microcavities, or microlasers, created of the dye-doped polymers. Active microcavities offer an enhanced signal/noise ratio as compared to the passive ones and very narrow resonance peaks even at moderate quality factors (Q &#8805- 6000). The choice of polymers as an active medium is connected with a number of advantages they offer: as opposite to semiconductors, polymers can be easily functionalized, integrated in microfluidic circuits and are cheaper in processing. Moreover, the use of porous polymer matrices may allow accumulation of analyte ions inside the microcavity and thus enhance the sensitivity. Two possible applications of microlasers are investigated in the thesis: refractive index variation sensing with non-functionalized cavities and heavy metal ion detection with functionalized cavities. In the first case, the sensitivity values have been obtained, comparable with the reported in literature for planar passive microresonators. In the second case, the experimental proofs of specific detection of mercury ions in liquid are presented. The ways of sensitivity improvement are discussed and verified and a foundation is layed for the creation of integrated Lab-on-Chip microfluidic biochemical detector.

Monitoring of environmental pollutants present at low concentrations requires creation of miniature, low-cost, and highly sensitive detectors that are capable to specifically identify target substances. In this thesis, a detection approach based on refractive index sensing with polymer micro-lasers is proposed and its application to the detection of heavy metal pollutants in water (mercury - Hg2+, cadmium - Cd2+ and lead - Pb2+) is studied. The resonance frequencies of the microcavity are highly sensitive to the refractive indices of the resonator surrounding: the resonances shift by a small amount when the surface refractive index changes, resulting from the interaction of the mode evanescent field with the surrounding medium. This permits label-free detection by coating the resonator with a suitable recognition species. The originality of this work lies in the utilization of active microcavities, or microlasers, created of the dye-doped polymers. Active microcavities offer an enhanced signal/noise ratio as compared to the passive ones and very narrow resonance peaks even at moderate quality factors (Q &#8805- 6000). The choice of polymers as an active medium is connected with a number of advantages they offer: as opposite to semiconductors, polymers can be easily functionalized, integrated in microfluidic circuits and are cheaper in processing. Moreover, the use of porous polymer matrices may allow accumulation of analyte ions inside the microcavity and thus enhance the sensitivity. Two possible applications of microlasers are investigated in the thesis: refractive index variation sensing with non-functionalized cavities and heavy metal ion detection with functionalized cavities. In the first case, the sensitivity values have been obtained, comparable with the reported in literature for planar passive microresonators. In the second case, the experimental proofs of specific detection of mercury ions in liquid are presented. The ways of sensitivity improvement are discussed and verified and a foundation is layed for the creation of integrated Lab-on-Chip microfluidic biochemical detector.

The scope of this work is an in-depth investigation of dielectric mirror microcavities with central organic dye layers, which are preferably modified in at least one lateral dimension. The large quality factor of the planar resonator in conjunction with comparatively stable and spectrally broad emitting molecules allows for a detailed analysis of several aspects of microresonator systems. Their optical properties are analyzed both with transmission and luminescence measurements as well as in the lasing regime. The first part presents the resonant mode properties of planar and laterally structured microcavities. With the help of a high-resolution imaging micro-photoluminescence setup, working either in the spatial (near field) or vectorial (far field) regime, the polarization splitting is studied in a detuned microcavity, containing the dye 4,4'-bis[(N-carbazole)styryl]biphenyl (BSB-Cz) in a matrix of 4,4'-di(N-carbazolyl)- biphenyl (CBP). With the help of a thickness gradient, a relation between the large spectral distance of the cross-polarized states and the mode position within the stop band is investigated. In shadow-mask prepared, laterally restricted devices (5x5 µm2 square boxes), the three-dimensional confinement introduces sets of discrete modes, which experience a similar polarization splitting. The origin in this case is a different phase shift of electromagnetic waves during internal total reflection at a boundary. By using a concentration gradient planar microcavity sample of the dye 4-(dicyanomethylene)-2-methyl-6-(4-(dimethylamino)styryl)-4H-pyran (DCM) in a tris-(8-hydroxyquinoline)aluminum (Alq3) matrix, the influence of the number of emitters on the lasing characteristics is subsequently analyzed. Depending on the pumping conditions, and thus the involvement of the Förster resonant energy transfer, an optimal composition is identified. After a qualitative evaluation of the long-term stability upon various excitation energies, the attention is focussed to the modification of the stimulated emission properties of photonic boxes. The stronger field concentration and altered density of states leads to a significant improvement of the values for the coupling factor fi and the threshold levels. Furthermore, new properties arise, namely simultaneous multimode and off-axis laser emission. With an inhomogeneous excitation of the box, it is possible to selectively excite single modes above the threshold. The work ends with experimental results of metal structures as additional optical element in the organic microcavity layer. Here, the aim is is to understand the passive influence of these possible contact- devices on the lasing performance. For this purpose, the lasing is studied at an interface of an areal thin metal layer, which is incorporated in the organic layer.:List of publication Introduction Optical properties of dielectric microresonator systems Sample fabrication and characterization Resonant mode properties of dielectric mirror microcavities Lasing from laterally modified organic cavity systems Conclusion and outlook Bibliography