ITO (tin doped indium oxide) coatings with a sheet resistance of 2 to 3 kΩ(square) were produced by gravure printing process
on PET and PEN foil. The printing paste consisted of ITO nanoparticles which were dispersed in a solvent by using a
surfactant. The dispersion was mixed with a binder and a photo initiator before printing. The printed films were hardened
under UV-irradiation at low temperatures (< 130°C). The sheet resistance could be decreased by heat treatment at 120°C
under forming gas atmosphere (N2/H2) to 1.5 kΩ(square). The transmission of the ITO coated PET and PEN foils is more than
80 % in the visible range.
The ITO films were directly used as the bottom electrode in an organic photodiode (OPD). The setup of the OPD
originates from the well known Tang photodiode, consisting of a stacked layer of copper phthalocyanine (p-type
material) and perylene tetracarboxylic bisbenzimidazole (n-type material). The photodiodes are characterised via current-voltage
(I-V) characteristics. The performance of the photodiodes with printed ITO on plastic substrates could be
improved by the deposition of a PEDOT/PSS layer (Baytron(R) P) on the ITO coated foils and was then comparable to the
performance of photodiodes with semi-transparent gold as anode on PET substrates. These results demonstrate the
suitability of the printed ITO layers as anode for organic photodiodes.
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 impedance spectra of non-sensitized and Ru(II)-sensitized Nb2O5 nanoporous coatings have been measured in the dark and under solar illumination using an electroactive electrolyte. All the Nyquist plots consist of a high and a low frequency depressed semicircle. The results have been modeled and fitted by an equivalent electric circuit consisting of a resistor Rs in the series with two parallel RC circuits containing both a constant phase element (CPE). The resistor Rs describes the total resistance of the electrolyte and conducting electrodes (SnO2:F). The high frequency semicircule (f<1kHz) describes the capacitance and resistance of the semiconducting materials (grain boundaries and interfaces). The low frequency cycle (f < 1 kHz) is related to the formation of a double charge layer capacitance at the nanoparticle/electrolyte interface and a charge transfer resistance. Both values are strongly dependant of the experimental conditions, in particular of the applied potential and the state of illumination. The evolution of the electric elements is presented and discussed. It is shown in particular that the measurements in the dark cannot be directly compared to those under illumination as in teh latter all the Nb2O5-film is accessed.
CeO2-TiO2 sol-gel coatings are well known as Li-ion storage electrode in electrochromic (EC) devices of the form glass/ TE /WO3/ electrolyte/ CeO2-TiO2/ TE/ glass (TE: transparent electrode, e.g. SnO2:F, FTO). The charge capacity of the CeO2-TiO2 coating is a limiting factor to get a high coloration intensity of such devices. In order to improve the charge capacity of these electrodes, new routes for the preparation of thick porous CeO2-TiO2 sol-gel layers were tested.
One route was the preparation of thick porous TiO2 coatings on a conducting glass support (FTO) using a solution of colloidal TiO2 particles. After heat treatment at temperatures up to 550°C the coatings were soaked in a solution of a cerium-IV (Ce(NH4)2(NO3)6) or a cerium-III salt (Ce(NO3)3 6H2O) and heat treated again. Another route was the preparation of sols by mixing a solution of the cerium-IV or cerium-III salt or a colloidal CeO2-sol with the colloidal solution of TiO2. After dip coating on FTO-glass the coatings were also heat treated at temperatures up to 500°C. ALl these coatings were studied electrochemically in 1 M LiC1O4 in propylene carbonate electrolyte. Although thick porous single coatings could be obtained, typically 450 nm for TiO2 and 600 nm for cerium-titanium oxide, the intercalated and deintercalcated Li+ charges remain small and lie in the range of 2 mC/cm2 to 3 mC/cm2. The reasons for such low charge capacity is discussed.
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