Organic Materials for Photonics: Properties and Applications

Photonics will play a key-role for the future development of ICT and healthcare and organic semiconductors are promising candidates to fulfil the capacity of photonics and deliver on its promises. This “photonics revolution” relies on novel and more performing materials, tailored for the specific requirements of real-world applications, and on reliable and cheap technologies, which can attract investments to address the transition from academia to industry. In this dissertation, I will report my findings on conjugated polymers suitable for photonic applications and demonstrate their use into low-cost photonic structures, as proof of concept. The first part is dedicated to the study of an aggregation-induced emission polymer, whose fluorescence is enhanced in the aggregated solid-state thanks to the restrictions of intramolecular rotations in contrast to typical planar conjugated polymers. I will show its exceptional fundamental photophysical properties which enable the reduction of non-radiative pathways and makes it attractive for its use in organic light-emitting diodes. In the second part, I will present the application of conjugated polymers into flexible all-polymer microcavities fabricated through a low-cost process based on spin coating. The incorporation of functional defects in periodic dielectric structures with optical feedback will enable the change in the photonic density of states. I will report the investigation on photonic resonators embedding an aggregation-induced polymer emitting in the visible and a novel near-infrared oligomer, assessing high quality factors and tuning of their radiative rates to achieve low threshold optically pumped lasers. In the last part, I will show the infiltration of conjugated engineered materials into porous silicon microcavities to enable a novel class of photonically-enhanced chips for communications and sensing. A cheap electrochemical technique has been employed to fabricate one-dimensional resonators, which I characterized fully to demonstrate the variation of the photonic density of states and an efficient approach to novel hybrid photonic devices

Diarylethenes in Optically Switchable Organic Light‐Emitting Diodes: Direct Investigation of the Reversible Charge Carrier Trapping Process

The design, fabrication, and characterization of optically switchable organic light-emitting diodes (OSOLEDs) based on the combination of the commercially available light-emitting polymer poly(9,9′-dioctylfluorene-alt-benzothiadiazole), F8BT, doped with a diarylethene derivative is reported. The photochromic activity of the dopant in the solid state has been investigated both via UV/vis absorption and photoluminescence spectroscopy, whereas the morphology of different blends is investigated via atomic force microscopy. OSOLEDs embedding dopant loadings of 1, 5, and 10 wt% exhibit optical responsivity with a maximum reversible optical threshold voltage shift of 4 V. The best performing devices containing 5 wt% dopant show a maximum current density and luminance ON/OFF ratio of ≈20 and ≈90, respectively. For the first time, the impact of the diarylethene isomerization on hole and electron transport has been decoupled and directly investigated, via the design, fabrication, and characterization of single-carrier switchable devices based on the same blends. Not only do these results confirm the photo-responsive trapping activity of the diarylethenes on both charge carriers, but they also demonstrate its asymmetry, with a predominant effect on electron transport that is over 3.4 times larger as compared to hole transport

Low-loss passive waveguides in a generic InP foundry process via local diffusion of zinc

Generic InP foundry processes allow monolithic integration of active and passive elements into a common p-n doped layerstack. The passive loss can be greatly reduced by restricting the p-dopant to active regions. We report on a localized Zn-diffusion process based on MOVPE, which allows to reduce waveguide loss from 2 dB/cm to below 0.4 dB/cm. We confirm this value by fabrication of a 73 mm long spiral ring resonator, with a record quality factor of 1.2 million and an extinction ratio of 9.7 dB.</p

Low-loss passive waveguides in a generic InP foundry process via local diffusion of zinc

Generic InP foundry processes allow monolithic integration of active and passive elements into a common p-n doped layerstack. The passive loss can be greatly reduced by restricting the p-dopant to active regions. We report on a localized Zn-diffusion process based on MOVPE, which allows to reduce waveguide loss from 2 dB/cm to below 0.4 dB/cm. We confirm this value by fabrication of a 73 mm long spiral ring resonator, with a record quality factor of 1.2 million and an extinction ratio of 9.7 dB

Towards efficient near-infrared fluorescent organic light-emitting diodes

The energy gap law (EG-law) and aggregation quenching are the main limitations to overcome in the design of nearinfrared (NIR) organic emitters. Here, we achieve unprecedented results by synergistically addressing both of these limitations. First, we propose porphyrin oligomers with increasing length to attenuate the effects of the EG -law by suppressing the non-radiative rate growth, and to increase the radiative rate via enhancement of the oscillator strength. Second, we design side chains to suppress aggregation quenching. We find that the logarithmic rate of variation in the non-radiative rate vs. EG is suppressed by an order of magnitude with respect to previous studies, and we complement this breakthrough by demonstrating organic light-emitting diodes with an average external quantum efficiency of ~1.1%, which is very promising for a heavy-metal-free 850 nm emitter. We also present a novel quantitative model of the internal quantum efficiency for active layers supporting triplet-to-singlet conversion. These results provide a general strategy for designing high-luminance NIR emitters

Optically switchable organic light-emitting transistors

International audienceOrganic light-emitting transistors are pivotal components for emerging opto- and nanoelectronics applications, such as logic circuitries and smart displays. Within this technology sector, the integration of multiple functionalities in a single electronic device remains the key challenge. Here we show optically switchable organic light-emitting transistors fabricated through a judicious combination of light-emitting semiconductors and photochromic molecules. Irradiation of the solution-processed films at selected wavelengths enables the efficient and reversible tuning of charge transport and electroluminescence simultaneously, with a high degree of modulation (on/off ratios up to 500) in the three primary colours. Different emitting patterns can be written and erased through a non-invasive and mask-free process, on a length scale of a few micrometres in a single device, thereby rendering this technology potentially promising for optically gated highly integrated full-colour displays and active optical memory

Modulating the luminance of organic light-emitting diodes: Via optical stimulation of a photochromic molecular monolayer at transparent oxide electrode

Self-assembled monolayers (SAMs) deposited on bottom electrodes are commonly used to tune charge carrier injection or blocking in optoelectronic devices. Beside the enhancement of device performance, the fabrication of multifunctional devices in which the output can be modulated by multiple external stimuli remains a challenging target. In this work, we report the functionalization of an indium tin oxide (ITO) electrode with a SAM of a diarylethene derivative designed for optically control the electronic properties. Following the demonstration of dense SAM formation and its photochromic activity, as a proof-of-principle, an organic light-emitting diode (OLED) embedding the light-responsive SAM-covered electrode was fabricated and characterized. Optically addressing the two-terminal device by irradiation with ultraviolet light doubles the electroluminescence. The original value can be restored reversibly by irradiation with visible light. This expanded functionality is based on the photoinduced modulation of the electronic structure of the diarylethene isomers, which impact the charge carriers' confinement within the emissive layer. This approach could be successfully exploited in the field of opto-communication technology, for example to fabricate opto-electronic logic circuits. © 2020 The Royal Society of Chemistry

An observational study of functional abilities in infants, children, and adults with type 1 SMA

ObjectiveTo report cross-sectional clinical findings in a large cohort of patients affected by type 1 spinal muscular atrophy.MethodsWe included 122 patients, of age ranging between 3 months and 22 years, 1 month. More than 70% (85/122) were older than 2 years and 25% (31/122) older than 10 years. Patients were classified according to the severity of phenotype and to the number of SMN2 copies.ResultsPatients with the more common and the most severe phenotype older than 2 years were, with few exceptions, on noninvasive ventilation and, with increasing age, more often had tracheostomy or &gt;16-hour ventilation and a gastrostomy inserted. In contrast, 25 of the 28 patients with the mildest phenotype older than 2 years had no need for tracheostomy or other ventilatory or nutritional support. In patients older than 2 years, the Children's Hospital of Philadelphia Infant Test of Neuromuscular Disorders scores were generally lower compared to those found in younger patients and showed distinct levels of functional abilities according to the severity of the phenotype. Similar findings were also observed on the Hammersmith Infant Neurological Examination.ConclusionsOur findings confirm that, after the age of 2 years, patients with type 1 spinal muscular atrophy generally survive only if they have gastrostomy and tracheostomy or noninvasive ventilation &gt;16 hours and have low scores on the functional scales. More variability, however, can be expected in those with the mildest phenotype, who achieve head control. These data provide important baseline information at the time treatments are becoming available