The gravure printing technique is currently under investigation as a possible method for the roll-to-roll production of OLEDs in the 6th framework EU funded project entitled ROLLED - "Roll-to-roll manufacturing technology for flexible OLED devices and arbitrary size and shape displays". The objective in the project is to fabricate an entire OLED structure by using roll-to-roll manufacturing methods and to examine, how the commercial production could be set up and integrated into an existing printing process. In order to attain a roll-to-roll compatibility, all the materials, inks and device structures need to be suitable for printing. Since, such OLED device structures are very sensitive to moisture and oxygen, high barrier materials to be applied as wet chemical coatings on transparent polymer films such as PET by common roll-to-roll coating techniques have been investigated. The barrier films on their respective substrates act as front and back side encapsulation materials, where the front side encapsulation material is to be used as a transparent and flexible substrate for OLED fabrication. The transmission rates to be achieved for both front and back side encapsulation for oxygen and water vapour are 5 mg m-2day-1 (corresponding to 7 cm3m-2day-1 for O2). In this paper, we show how light-emitting devices manufactured by gravure printing operate compared to the ones manufactured by traditional methods. Furthermore, we present recent results on the development of ITO nanoparticle coatings, cathode inks and flexible barrier materials.
Transparent conducting coatings and patterns of ITO (indium tin oxide) were deposited by a direct gravure printing on PET foils using nanoparticle-based UV-curable inks. Solid areas with thicknesses ranging between 300 and >1000 nm were obtained by varying the ink composition (e.g. ITO content, solvents) and fundamental parameters of the printing plate such as the line density. The best ITO coating patterns showed a sheet resistance of 3 to 10 kΩ□ and a transmission of up to 88 % with a haze of less than 1 %. One of the most crucial steps during film formation is the drying of the wet film as it changes the rheology and polarity of the ink and in consequence decisively influences the film formation. Typical fields of application of the gravure-printed ITO patterned electrodes include smart windows, flexible displays and printed electronics.
The paper focuses on a systematic study of the influence of water on the electrochemical and optical properties of CeO2-TiO2 amd WO3 sol-gel coatings as well as devices made with these layers. The coatings were studied electrochemically in 1 M LiC1O4 in propylene carbonate electrolyte with water content up to 3 wt%. The intercalculated and deintercalated charge was measured during Cyclic Voltammetry (CV) and Chronoamperometric (CA) cycles up to 500 cycles (TiO2-CeO2) and 7000 cycles (WO3). For CeO2-TiO2 it was found to increase from 3mC/cm2 (dry electrolyte) up to 11 mC/cm2 (3 wt% water). This increase is important for the coloration of EC-devices because the charge capacity of this counter electrode is known to be a limiting factor for the transmission change of the EC-devices. For WO3 coatings, the transmission change (Tcolored-Tbleached)is higher in wet electrolytes (1 wt% water) than dry electrolyte and above all remains constant (74%). These improvements are essentially due to an increase of the kinetics of the intercalation and deintercalation of Li+ ions. The electro-optical behavior of solid state EC-devices with and without incorporation of water in the solid electrolyte measured up to 500000 CA cycles is also presented and discussed.
The conventional dip coating techinques, as it is used for flat surfaces, cannot be applied to deposit homogeneous coatings in optical quality inside tubes. The resulting coatings exhibit large variations in thickness and roughness over the length of the tube and show a morphology with a network of cracks. The main reason for these problems seem to be a delayed and restricted solvent evaporation due to the impediment of a laminar flow and the progressive saturation of the atmosphere in the tube. A modified dip coating technique was therefore developed to allow forced flow conditions inside the tubes by an additional exhausting tube. By means of this modification transparent conducting coatings of sol-gel SnO2:Sb (antimony-doped tin oxide - ATO) could be deposited on both sides of borosilicate glass tubes (300 mm, inner diamters down to 11 mm) with excellent thickness uniformity and low roughness (Ra≈1nm). After a heat treatment at temperatures up to 500°C, the prepared ATO coatings are mechanically stable and highly transparent (>85% transmission) with a sheet resistance down to 10 kΩ. The coatings can be used as electrodes for electronic devices and electrical heaters or to give antistatic properties to the substrate.
Single and multilayer sol-gel coatings of transparent antimony-doped tin oxide (SnO2:Sb) have been prepared on borosilicate and fused silica substrates using either a 5 mole% SbCl3 doped 0.5 M solution of SnCl2(OAc)2 in ethanol or a water suspension of crystalline Sb-doped tin oxide nanoparticles. The nanoscale morphology and the electrical parameters of the layers have been determined after different firing procedures and heating rates varying from 0.2 to 4300 K/s obtained either in a furnace or by cw carbon- dioxide laser irradiation. For a given sintering temperature (approximately 540 degrees Celsius) a slow heating process in furnace leads to porous, homogeneous single and multilayers consisting of small crystallites. They present a high resistivity of about (rho) equals 4 multiplied by 10-2 (Omega) cm. With increasing heating rate the layers become denser with larger crystallites and the resistivity value decrease down to approximately 7 X 10-3 (Omega) cm for 4300 K/s (carbon-dioxide laser sintering). It is proposed that the densification of the coatings is determined by a competition between nucleation at low temperatures and the growth of the crystallites at high temperatures.
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