Achieving high circularly polarized luminescence with push-pull helicenic systems: from rationalized design to top-emission CP-OLED applications.

While the development of chiral molecules displaying circularly polarized luminescence (CPL) has received considerable attention, the corresponding CPL intensity, g lum, hardly exceeds 10-2 at the molecular level owing to the difficulty in optimizing the key parameters governing such a luminescence process. To address this challenge, we report here the synthesis and chiroptical properties of a new family of π-helical push-pull systems based on carbo[6]helicene, where the latter acts as either a chiral electron acceptor or a donor unit. This comprehensive experimental and theoretical investigation shows that the magnitude and relative orientation of the electric (µe ) and magnetic (µ m ) dipole transition moments can be tuned efficiently with regard to the molecular chiroptical properties, which results in high g lum values, i.e. up to 3-4 × 10-2. Our investigations revealed that the optimized mutual orientation of the electric and magnetic dipoles in the excited state is a crucial parameter to achieve intense helicene-mediated exciton coupling, which is a major contributor to the obtained strong CPL. Finally, top-emission CP-OLEDs were fabricated through vapor deposition, which afforded a promising g El of around 8 × 10-3. These results bring about further molecular design guidelines to reach high CPL intensity and offer new insights into the development of innovative CP-OLED architectures.

Optical modulation frequency mediated tunable response time and responsivity in graphene-PbS QD based hybrid photodetectors.

Graphene/lead sulfide (PbS) quantum dot (QD) hybrid infrared photodetectors have gained a lot of attention in recent times due to their high resolution and cost effective fabrication process. In spite of exhibiting remarkably high responsivity, such hybrid detectors are slow as a result of their internal gain mechanism process. In this work, we present a convenient strategy to modulate the correlation between their responsivity and response time giving access to high resolution fast photodetectors in the broadband wavelength range for imaging purpose. Using a layer-by-layer deposition technique including simultaneous ligand exchange and surface passivation at each layer, homogeneous PbS QD films on chemical vapour deposition grown single layer graphene could be achieved. The obtained hybrid phototransistors exhibit a high responsivity of 108A W-1and sensitivity down to 0.1 pW incident light power in the near-infrared wavelength range. By modulating the incident light at a modulation frequency up to 50 kHz, we achieve a response time as low as 5µs while preserving a much higher responsivity (144 A W-1) compared to existing commercial room temperature infrared photodetectors.

Maximizing Chiral Perturbation on Thermally Activated Delayed Fluorescence Emitters and Elaboration of the First Top-Emission Circularly Polarized OLED.

Molecular designs merging circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (CP-TADF) using the concept of chiral perturbation appeared recently as a cornerstone for the development of efficient CP-organic light emitting diodes (CP-OLED). Such devices could strongly increase the energy efficiency and performances of conventional OLED displays, in which 50% of the emitted light is often lost due to the use of antiglare filters. In this context, herein, ten couples of enantiomers derived from novel chiral emitter designs are reported, exhibiting CPL, TADF, and aggregation induced enhancement emission properties (AIEE). Representing the first structure properties relationship investigation for CP-TADF materials, this thorough experimental and theoretical work highlights crucial findings on the key structural and electronic parameters (isomerism, nature of the carbazole substituents) governing the synergy between CPL and TADF properties. To conclude this study, the first top emission CP-OLED is elaborated as a new approach of generating CP light in comparison with classical bottom-emission CP-OLED architecture. Indeed, the top-emission configuration represents the only relevant device architecture for future microdisplay applications. Thereby, in addition to offer molecular guidelines to combine efficiently TADF and CPL properties, this study opens new avenues toward practical applications for CP-OLEDs.

Ultrashort laser pulse splitting upon resonant reflection on a mirror-based waveguide grating.

A resonant waveguide grating based on a high reflectivity mirror causes a 2pi phaseshift of adjustable slope in the spectrum of an ultrashort light pulse, giving rise to a controllable, lossless temporal pulse splitting. This monolithic phase shifter can simply be placed on the path of the beam as a mirror. A functional element was designed and fabricated. Temporal splitting of a femtosecond laser pulse is experimentally demonstrated. The possibility of obtaining variable delay between subpulses is theoretically discussed.

Ultraviolet optical and microstructural properties of MgF2 and LaF3 coatings deposited by ion-beam sputtering and boat and electron-beam evaporation.

Single layers of MgF2 and LaF3 were deposited upon superpolished fused-silica and CaF2 substrates by ion-beam sputtering (IBS) as well as by boat and electron beam (e-beam) evaporation and were characterized by a variety of complementary analytical techniques. Besides undergoing photometric and ellipsometric inspection, the samples were investigated at 193 and 633 nm by an optical scatter measurement facility. The structural properties were assessed with atomic-force microscopy, x-ray diffraction, TEM techniques that involved conventional thinning methods for the layers. For measurement of mechanical stress in the coatings, special silicon substrates were coated and analyzed. The dispersion behavior of both deposition materials, which was determined on the basis of various independent photometric measurements and data reduction techniques, is in good agreement with that published in the literature and with the bulk properties of the materials. The refractive indices of the MgF2 coatings ranged from 1.415 to 1.440 for the wavelength of the ArF excimer laser (193 nm) and from 1.435 to 1.465 for the wavelength of the F2 excimer laser (157 nm). For single layers of LaF3 the refractive indices extended from 1.67 to 1.70 at 193 nm to approximately 1.80 at 157 nm. The IBS process achieves the best homogeneity and the lowest surface roughness values (close to 1 nm(rms)) of the processes compared in the joint experiment. In contrast to MgF2 boat and e-beam evaporated coatings, which exhibit tensile mechanical stress ranging from 300 to 400 MPa, IBS coatings exhibit high compressive stress of as much as 910 MPa. A similar tendency was found for coating stress in LaF3 single layers. Experimental results are discussed with respect to the microstructural and compositional properties as well as to the surface topography of the coatings.

Effect of systematic errors in spectral photometric data on the accuracy of determination of optical parameters of dielectric thin films.

The determination of optical parameters of thin films from experimental data is a typical task in the field of optical-coating technology. The optical characterization of a single layer deposited on a substrate with known optical parameters is widely used for this purpose. Results of optical characterization are dependent on not only the choice of the thin-film model but also on the quality of experimental data. The theoretical results presented highlight the effect of systematic errors in measurement data on the determination of thin-film parameters. Application of these theoretical results is illustrated by the analysis of experimental data for magnesium fluoride thin films.