RESUMEN
In this study, fully aromatic polyether sulfones were developed, bearing blue, yellow, and orange-red π-conjugated semiconducting units. Carbazole-, anthracene-, and benzothiadiazole-based fluorophores are copolymerized with a diphenylsulfone moiety. A diphenylpyridine comonomer was additionally utilized, acting as both a solubilizing unit and a weak blue fluorescent group. Using this rationale, fluorescent polyarylethers with high molecular weights, up to 70 kDa, were developed, showing film formation ability and high thermal stability, while preserving excellent solubility in common organic, nonvolatile, and nonchlorinated solvents. Fine-tuning of the emission color was achieved through subtle changes of the comonomers' type and ratio. Single-chromophore-bearing copolymers emitted in the blue or the yellow region of the visible spectrum, while the dual-chromophore-bearing terpolymers emitted throughout the visible spectrum, resulting in white light emission. Solutions of 20 wt% in polar aprotic solvents at ambient conditions allowed the deposition of fluorescent copolyethers and printing from non-chlorinated solvents. All polyethers were evaluated for their structural and optoelectronic properties, and selected copolymers were successfully used in the emitting layer (EML) of organic light-emitting diode (OLED) devices, using either rigid or flexible substrates. Remarkable color stability was displayed in all cases for up to 15 V of bias voltage. The Commission Internationale de L'Eclairage (CIE) of the fabricated devices is located in the blue (0.16, 0.16), yellow (0.44, 0.50), or white region of the visible spectrum (0.33, 0.38) with minimal changes according to the ratio of the comonomers. The versatile methodology toward semiconducting polyethersulfones for polymer light-emitting diodes (PLEDs) developed herein led to the scaled-up production of luminescent polymers of up to 25 g of high-molecular-weight single batches, demonstrating the effectiveness of this approach as a straightforward tool to facilitate the synthesis of flexible and printable EMLs for large-area PLED coverage.
RESUMEN
Titanium nitride (TiN) is a candidate material for several plasmonic applications, and pulsed laser ablation in liquids (PLAL) represents a rapid, scalable, and environmentally friendly approach for the large-scale production of nanomaterials with customized properties. In this work, the nanosecond PLAL process is developed, and we provide a concise understanding of the process parameters, such as the solvent and the laser fluence and pulse wavelength, to the size and structure of the produced TiN nanoparticles (NPs). TiN films of a 0.6 µm thickness developed by direct-current (DC) magnetron sputtering were used as the ablation targets. All laser process parameters lead to the fabrication of spherical NPs, while the laser pulse fluence was used to control the NPs' size. High laser pulse fluence values result in larger TiN NPs (diameter around 42 nm for 5 mJ and 25 nm for 1 mJ), as measured from scanning electron microscopy (SEM). On the other hand, the wavelength of the laser pulse does not affect the mean size of the TiN NPs (24, 26, and 25 nm for 355, 532, and 1064 nm wavelengths, respectively). However, the wavelength plays a vital role in the quality of the produced TiN NPs. Shorter wavelengths result in NPs with fewer defects, as indicated by Raman spectra and XPS analysis. The solvent type also significantly affects the size of the NPs. In aqueous solutions, strong oxidation of the NPs is evident, while organic solvents such as acetone, carbides, and oxides cover the TiN NPs.
RESUMEN
Extensive research has been dedicated to the solution-processable white organic light-emitting diodes (WOLEDs), which can potentially influence future solid-state lighting and full-color flat-panel displays. The proposed strategy based on WOLEDs involves blending two or more emitting polymers or copolymerizing two or more emitting chromophores with different doping concentrations to produce white light emission from a single layer. Toward this direction, the development of blends was conducted using commercial blue poly(9,9-di-n-octylfluorenyl2,7-diyl) (PFO), green poly(9,9-dioctylfluorenealt-benzothiadiazole) (F8BT), and red spiro-copolymer (SPR) light-emitting materials, whereas the synthesized copolymers were based on different chromophores, namely distyryllanthracene, distyrylcarbazole, and distyrylbenzothiadiazole, as yellow, blue, and orange-red emitters, respectively. A comparative study between the two approaches was carried out to examine the main challenge for these doping systems, which is ensuring the proper balance of emissions from all the units to span the entire visible range. The emission characteristics of fabricated WOLEDs will be explored in terms of controlling the emission from each emitter, which depends on two possible mechanisms: energy transfer and carrier trapping. The aim of this work is to achieve pure white emission through the color mixing from different emitters based on different doping concentrations, as well as color stability during the device operation. According to these aspects, the WOLED devices based on the copolymers of two chromophores exhibit the most encouraging results regarding white color emission coordinates (0.28, 0.31) with a CRI value of 82.
RESUMEN
Τhe fabrication of organic light-emitting diodes (OLEDs) from solution involves the major problem of stack integrity, setting the determination of the composition and the characteristics of the resulting interfaces prerequisite for the optimization of the growth processes and the achievement of high devices' performance. In this work, a poly(9,9-dioctylfluorene) (F8) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) blend is used for the emissive layer (EML), poly-3,4-ethylene dioxythiophene; poly-styrene sulfonate (PEDOT:PSS) is used for a hole transport layer (HTL), and Poly(9,9-bis(3'-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluore-ne))dibromide (PFN-Br) for an electron transport layer (ETL) to produce the OLED device. All the layers are developed using the slot-die process, onto indium tin oxide (ITO)-coated polyethylene terephthalate (PET) flexible substrates, whereas Ag cathode was formed by ink-jet printing under ambient conditions. Spectroscopic ellipsometry measurements were performed upon completion of the successive films' growth, in sequential steps, for the multilayer OLED development. Ellipsometry analysis using different models demonstrate the degree of intermixing within the layers and provide information about the interfaces. These interfacial properties are correlated with the emission characteristics as well as the final performance of the OLED devices.
RESUMEN
Obtaining white light from organic LEDs is a considerable challenge and, to realize white light emission, many studies have been conducted, primarily addressing two- or three-color blend systems as a promising strategy. In this work, pristine films, grown by spin coating, consisting of commercial blue Poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO), green Poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT), and red spiro-copolymer (SPR) light-emitting materials, were studied as reference materials. Afterward, binary (SPR doped in host PFO) and ternary (SPR and F8BT doped in host PFO) thin films were successfully prepared with various ratios. The characterization of the as-grown and thermally-treated blend films was focused on their optical and photophysical properties. After, the fabrication of OLED devices on glass substrates was carried out for the evaluation of a blend's composition and annealing in terms of the devices' electrical characteristics and electro-emission properties in order to achieve white light emission. Their analysis provided insights into the energy transfer mechanisms between the constituent materials, which were correlated to host-guest interactions as well as to the structural changes originated by thermal treatment, leading to the crystallization of PFO. Finally, the OLEDs based on ternary blends approach the white light emission with (x, y) of (0.272, 0.346). These fabricated devices also exhibit turn-on voltages as low as 3 V, accompanied by remarkable luminance values above 3000 cd/m2.
RESUMEN
In this study, novel copolymers consisting of blue and red chromophores are presented to induce emission tuning, enabling the definition of white light emission in a single polymeric layer. These aromatic polyether sulfones exhibit high molecular weights, excellent solubility and processability via solution deposition techniques. In addition, by carefully controlling the molar ratios of chromophores composition, the energy transfer mechanism, from blue to red chromophores, takes place enabling us to define properly the emission covering the entire range of the visible spectrum. The optical and photophysical properties of the monomers and copolymers were thoroughly investigated via NIR-Vis-far UV Spectroscopic Ellipsometry (SE), Absorbance and Photoluminescence (PL). These copolymers are used as an emissive layer and applied in solution-processed WOLED devices. The fabricated WOLED devices have been subsequently studied and characterized in terms of their electroluminescence properties. Finally, the WOLED devices possess high color stability and demonstrate CIE Coordinates (0.33, 0.38), which approach closely the pure white light CIE coordinates.
RESUMEN
To study the development, characterisation, and drug release of one- and two-layered thin films based on organic polymers [poly(D,L-lactide-co-glycolide) lactide:glycolide (65:35), poly(D,L-lactide-co-glycolide) lactide:glycolide (75:25), and polycaprolactone] and dexamethasone. To examine their applicability for intraocular lenses (IOLs) and function in intraocular drug delivery systems. Four series of thin films, single and double-layer, were prepared by the spin-coating method on a silicon substrate. The films were studied using atomic force microscopy and spectroscopic ellipsometry. The release rate of dexamethasone was studied for a period of ten weeks. Series A and C demonstrated the formation of large dexamethasone aggregates. The monolayer films of series C and D formed pores, in agreement with previous findings. The spectroscopic ellipsometry study demonstrated that the samples were transparent. The drug release study demonstrated that dexamethasone was released during the first 6 weeks at a desirable rate. The films exhibited properties suitable for use in intraocular drug delivery systems. The single-layer thin films demonstrated a sufficient encapsulation of dexamethasone and appropriate release of the therapeutic substance. Further studies are necessary to investigate the possibility of developing the films directly on the surface of the IOL.
Asunto(s)
Sistemas de Liberación de Medicamentos/métodos , Poliésteres/química , Copolímero de Ácido Poliláctico-Ácido Poliglicólico/química , Dexametasona/química , Dexametasona/farmacocinética , Liberación de Fármacos , Lentes Intraoculares , Modelos Químicos , Soluciones Oftálmicas/química , Soluciones Oftálmicas/farmacocinética , Diseño de PrótesisRESUMEN
Biodegradable polymers can be applied to a variety of implants for controlled and local drug delivery. The aim of this study is to develop a biodegradable and nanoporous polymeric platform for a wide spectrum of drug-eluting implants with special focus on stent-coating applications. It was synthesized by poly(DL-lactide-co-glycolide) (PLGA 65:35, PLGA 75:25) and polycaprolactone (PCL) in a multilayer configuration by means of a spin-coating technique. The antiplatelet drug dipyridamole was loaded into the surface nanopores of the platform. Surface characterization was made by atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). Platelet adhesion and drug-release kinetic studies were then carried out. The study revealed that the multilayer films are highly nanoporous, whereas the single layers of PLGA are atomically smooth and spherulites are formed in PCL. Their nanoporosity (pore diameter, depth, density, surface roughness) can be tailored by tuning the growth parameters (eg, spinning speed, polymer concentration), essential for drug-delivery performance. The origin of pore formation may be attributed to the phase separation of polymer blends via the spinodal decomposition mechanism. SE studies revealed the structural characteristics, film thickness, and optical properties even of the single layers in the triple-layer construct, providing substantial information for drug loading and complement AFM findings. Platelet adhesion studies showed that the dipyridamole-loaded coatings inhibit platelet aggregation that is a prerequisite for clotting. Finally, the films exhibited sustained release profiles of dipyridamole over 70 days. These results indicate that the current multilayer phase therapeutic approach constitutes an effective drug-delivery platform for drug-eluting implants and especially for cardiovascular stent applications.