White organic light-emitting diodes with an ultra-thin premixed emitting layer

We described an approach to achieve fine color control of fluorescent White Organic Light-Emitting Diodes (OLED), based on an Ultra-thin Premixed emitting Layer (UPL). The UPL consists of a mixture of two dyes (red-emitting 4-di(4'-tert-butylbiphenyl-4-yl)amino-4'-dicyanovinylbenzene or fvin and green-emitting 4-di(4'-tert-butylbiphenyl-4-yl)aminobenzaldehyde or fcho) premixed in a single evaporation cell: since these two molecules have comparable structures and similar melting temperatures, a blend can be evaporated, giving rise to thin films of identical and reproducible composition compared to those of the pre-mixture. The principle of fine color tuning is demonstrated by evaporating a 1-nm-thick layer of this blend within the hole-transport layer (4,4'-bis[N-(1-naphtyl)-N-phenylamino]biphenyl (\alpha-NPB)) of a standard fluorescent OLED structure. Upon playing on the position of the UPL inside the hole-transport layer, as well as on the premix composition, two independent parameters are available to finely control the emitted color. Combined with blue emission from the heterojunction, white light with Commission Internationale de l'Eclairage 1931 color coordinates (0.34, 0.34) was obtained, with excellent color stability with the injected current. The spectrum reveals that the fcho material does not emit light due to efficient energy transfer to the red-emitting fvin compound but plays the role of a host matrix for fvin, allowing for a very precise adjustment of the red dopant amount in the device

Small molecule-based photocrosslinkable fluorescent materials toward multilayered and high-resolution emissive patterning

International audiencea Solution-processable green and red-emitting fluorophores possessing photopolymerizable acrylate units have been synthesized. Photocrosslinking was successfully performed in neat thin films at room temperature under low-dose UV irradiation at 365 nm. No further curing step was necessary to achieve insoluble emissive thin films displaying high optical quality. Up to 80% of the green emitting material processed as a non-doped thin film remained after photopolymerization. Despite competitive energy transfer occurring between the excited photoinitiator and the radiative excited state of red-emitting materials, up to 40% of the initial thickness could be achieved after development. The very low RMS roughness of the green and red photocrosslinked thin films after development (RMS o 0.7 nm) allowed us to fabricate multicolored stacks again with high optical quality (RMS roughness o 1.3 nm) after two cycles of irradiation and development involving successively red and green emitters. Resolved patterns as small as 600 nm in width could be obtained upon photolithography performed under an air atmosphere. High adhesion of the photocrosslinked materials on surfaces makes the resulting emissive thin films very promising for realizing complex emissive structures on flat or bend substrates as required in multiple applications such as optical data storage, organic lasers, organic light emitting diodes or counterfeiting

Enhanced Rates of Photoinduced Molecular Orientation in a Series of Molecular Glassy Thin Films.

Photoinduced orientation in a series of molecular glasses made of small push-pull azo derivatives is dynamically investigated for the first time. Birefringence measurements at 632.8 nm are conducted with a temporal resolution of 100 ms to probe the fast rate of the azo orientation induced under polarized light and its temporal stability over several consecutive cycles. To better evaluate the influence of the azo chemical substituents and their electronic properties on the orientation of the whole molecule, a series of push-pull azo derivatives involving a triphenylaminoazo core substituted with distinct electron-withdrawing moieties is studied. All resulting thin films are probed using polarization modulation infrared spectroscopy that yields dynamical linear dichroism measurements during a cycle of orientation followed by relaxation. We show here in particular that the orientation rates of small molecule-based azo materials are systematically increased up to 7-fold compared to those of a reference polymer counterpart. For specific compounds, the percentage of remnant orientation is also higher, which makes these materials of great interest and promising alternatives to azobenzene-containing polymers for a variety of applications requiring a fast response and absolute control over the molecular weight

Red-emitting fluorescent Organic Light emitting Diodes with low sensitivity to self-quenching

International audienceConcentration quenching is a major impediment to efficient organic light-emitting devices. We herein report on Organic Light-Emitting Diodes (OLEDs) based on a fluorescent amorphous red-emitting starbust triarylamine molecule (4-di(4'-tert-butylbiphenyl-4-yl)amino-4'-dicyanovinylbenzene, named FVIN), exhibiting a very small sensitivity to concentration quenching. OLEDs are fabricated with various doping levels of FVIN into Alq3, and show a remarkably stable external quantum efficiency of 1.5% for doping rates ranging from 5% up to 40%, which strongly relaxes the technological constraints on the doping accuracy. An efficiency of 1% is obtained for a pure undoped active region, along with deep red emission (x=0.6; y=0.35 CIE coordinates). A comparison of FVIN with the archetypal DCM dye is presented in an identical multilayer OLED structure

Exploiting Light Interferences to Generate Micrometer-High Superstructures from Monomeric Azo Materials with Extensive Orientational Mobility

Photochromic azo materials have stirred considerable interest for their ability to mechanically respond to polarized light through large photo-induced migration and orientation processes. In order to apprehend the microscopic dynamics behind the extensive mass transport occurring under interferential illumination, two azo compounds differing by their propen-sity to form hydrogen bonds are synthesized and processed as nondoped glassy thin films. Interferential irradiation using polarization and intensity patterns reveals fully distinct responses. Regular nanometer-high surface relief gratings transform into micrometer superstructures with an ampli-tude ten times higher than the initial film thickness when using the latter polarization. Systematic comparisons between the azo materials in terms of thermal properties, photochromism in solution and in the solid state, and photomigration are carried out. The progressive formation of super-structures is ascribed to two successive processes. The first one relates to fast photoinduced migration due to the impinging structured light, and the second one is promoted by slower thermally activated “zig-zag”-like diffu-sion and Z-E thermal relaxation, which in turn requests high orientational mobility of the azo compounds and causes large nanomechanical changes. Such studies should provide novel structural guidelines in terms of material fluidity to rapidly achieve highly structured and rewritable materials at lilogwht irradiance

Photoinduced Surface Relief Grating Formation for a Single Crystal of 4-Aminoazobenzene

Photoinduced surface relief grating (SRG) formation for a single crystal of 4-aminoazobenzene was investigated. It was found that SRG could be inscribed on the (001) surface of the crystal, which might suggest that the photoinduced SRG formation is a general phenomenon observed for single crystals of azobenzene-based molecules as well as for azobenzene-based amorphous systems. In addition, the dependences of the SRG formation upon the orientation of the sample crystal and upon the polarization of the writing beams were found to be different from those observed for previously reported crystalline systems

Tunable double photochromism of a family of bis-DTE bipyridine ligands and their dipolar Zn complexes.

International audienceThe photoinduced ring-closure/ring-opening reactions of a series of bis-dithienylethene derivatives, as free ligands and Zn(II)-complexes, are investigated by resorting to theoretical (time-dependent density functional theory) and kinetic analyses in solution. The originality of the system stems from the tunability of the photoreaction quantum yields and conversion yields as a function of the electronic structure. The latter could be varied by modifying the electron-donating character of the DTE-end substituents L(a-d) (o,o) (a, D = H; b, D = OMe; c, D = NMe(2); d, D = NBu(2)) and/or the Lewis character of the metal ion center L(a-d)ZnX(2) (o,o) (L(a-c), X = OAc; L(d), X = Cl). The orbital description of the doubly-open form (o,o) and half-closed form (o,c) predicts that double closure to the form (c,c) would occur using UV irradiation. Photokinetic studies on the complete series demonstrate that photocyclization proceeds following a sequential ring closure mechanism. They clearly point out distinct quantum yields for the first and second ring closures, the latter being characterized by a significantly lower value. Dramatic decrease in both the quantum yields of the ring-closure and ring-opening processes is demonstrated for the complex L(d)ZnCl(2) exhibiting the strongest charge-transfer character in the series investigated. These studies show that this series of DTE derivatives provides an efficient strategy to tune the photochromic properties through the combination of the electron-donor and electron-acceptor (D-A) groups

A "reverse interrupter": the novel molecular design of a fluorescent photochromic DTE-based bipyridine

International audienceAn original design of a fluorescent dithienylethene (DTE)-based bipyridine, where donor (D) and acceptor (A) groups are located on the same thiophene ring of the DTE unit, is reported; in non-polar solvents, UV or visible excitation triggers a photochromic reaction, disrupting the conjugation and quenching the fluorescence

Highly cohesive dual nanoassemblies for complementary multiscale bioimaging

International audienceInnovative nanostructures made of a high payload of fluorophores and superparamagnetic nanoparticles (NPs) have simply been fabricated upon self-assembling in a two-step process. The resulting hybrid supraparticles displayed a dense shell of iron oxide nanoparticles tightly attached through an appropriate polyelectrolyte to a highly emissive non-doped nanocore made of more than 10 5 small organic molecules. Cooperative magnetic dipole interactions arose due to the closely packed magnetic NPs at the nanoarchitecture surface, causing enhanced NMR transverse relaxivity. Large in vivo MRI T 2 contrast was thus obtained with unusually diluted solutions after intravenous injection in small rodents. Two-photon excited fluorescence imaging could be performed, achieving unprecedented location resolution for agents combining both magnetic nanoparticles and fluorescence properties. Finally, TEM imaging of the sectioned mouse tissue succeeded in isolating the core–shell structures, which represents the first image of intact complex magnetic and fluorescent nanoassemblies upon in vivo injection. Such highly cohesive dual nanoarchitectures should open great horizons toward the assessment with high spatial resolution of the drug or labeled stem cell biodistribution