Optimal Sub-Pixel arrangements and coding for ultra-high resolution three-dimensional OLED displays

Information display technology is a rapidly growing research and development field. Using state-of-the-art technology, optical resolution can be increased dramatically by organic light-emitting diode - since the light emitting layer is very thin, under 100nm. The main question is what pixel size is achievable technologically? The next generation of display will considers three-dimensional image display. In 2D , one is considering vertical and horizontal resolutions. In 3D or holographic images, there is another dimension – depth. The major requirement is the high resolution horizontal dimension in order to sustain the third dimension using special lenticular glass or barrier masks, separate views for each eye. The high-resolution 3D display offers hundreds of more different views of objects or landscape. OLEDs have potential to be a key technology for information displays in the future. The display technology presented in this work promises to bring into use bright colour 3D flat panel displays in a unique way. Unlike the conventional TFT matrix, OLED displays have constant brightness and colour, independent from the viewing angle i.e. the observer's position in front of the screen. A sandwich (just 0.1 micron thick) of organic thin films between two conductors makes an OLE Display device. These special materials are named electroluminescent organic semi-conductors (or organic photoconductors (OPC )). When electrical current is applied, a bright light is emitted (electrophosphorescence) from the formed Organic Light-Emitting Diode. Usually for OLED an ITO layer is used as a transparent electrode. Such types of displays were the first for volume manufacture and only a few products are available in the market at present. The key challenges that OLED technology faces in the application areas are: producing high-quality white light achieving low manufacturing costs increasing efficiency and lifetime at high brightness. Looking towards the future, by combining OLED with specially constructed surface lenses and proper image management software it will be possible to achieve 3D images.

Estudo das propriedades de fotogeração e transporte de portadores de cargas em dispositivos optoeletrônicos orgânicos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização e aplicação da Blenda PEDOT : PSS/PVA na construção de eletrodos transparentes e dispositivos eletroluminescentes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Propriedades ópticas e elétricas de materiais híbridos de sílica/orgânico à base de GPTS:TEOS preparados pelo método sol-gel

Fabrication of optoelectronic devices requires the employment of at least one transparent electrode. Usually, commercially transparent electrodes have been made by deposition of indium tin oxide (ITO) films by RF-Sputtering technique. These commercial electrodes have sheet resistance of about 100 Ω/sq and optical transmittance of 77% at the wavelength of 550 nm. The poly(3,4-ethylenedioxythiophene):polystyrene-sulfonate (PEDOT:PSS) is an alternative material to fabricate transparent electrodes due to its high conductivity (about 600 S/cm) and solubility in water. Soluble conductive materials exhibits advantages for processing of electrode layers, however there is a disadvantage during devices fabrication once materials with the same solvent of the electrode material cannot be coated one over the other. Alternatively, organic/Silica hybrid materials prepared by sol-gel process allow producing bulks and films with high chemical durability. In order to obtain transparent electrodes with high chemical durability, we introduced a blended material comprising the high UV-VIS transparency of organic/Silica sol-gel material and a high conductivity polymer PEDOT:PSS. The organic/Silica sol was obtained using two different molar concentrations (1:1 and 4:1), of tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTS). Amounts of PEDOT:PSS solutions were added to the sol material, resulting in different weight fractions of sol and polymer. G:T/P:P were deposit onto glass substrates by spray-coating. In order to perform electrical characterization of the blended material, gold electrodes were thermally evaporated onto the films. The electrical characterization was performed using a Keithley 2410 source/meter unity and the optical characterization, using a Cary50 UV-Vis spectrophotometer. The absorption coefficient and electric conductivity of the different compositions blends, as function of the PEDOT:PSS concentration, were...

An alternative blocking layer for titanium dioxide (TiO 2) solar cell applications

In hybrid organic solar cells a blocking layer between transparent electrode and nanocrystalline titania particles is essential to prevent short-circuiting and current loss through recombination at the electrode interface. Here the preparation of a uniform hybrid blocking layer which is composed of conducting titania nanoparticles embedded in an insulating polymer derived ceramic is presented. This blocking layer is prepared by sol-gel chemistry where an amphiphilic block copolymer is used as a templating agent. A novel poly(dimethylsiloxane) containing amphiphilic block copolymer poly(ethyleneglycol)methylethermethacrylate-block-poly(dimethylsiloxane)-block-poly(ethyleneglycol)methylethermethacrylate has been synthesized to act as the templating agent. Plasma treatment uncovered titania surface from any polymer. Annealing at 450°C under nitrogen resulted in anatase titania with polymer derived silicon oxycarbide ceramic. Electrical characterization by conductive scanning probe microscopy experiments revealed a percolating titania network separated by an insulating ceramic matrix. Scanning Kelvin probe force microscopy showed predominant presence of titania particles on the surface creating a large surface area for dye absorption. The uniformity of the percolating structures was proven by microbeam grazing incidence small angle x-ray scattering. First applications in hybrid organic solar cells in comparison with conventional titanium dioxide blocking layer containing devices revealed 15 fold increases in corresponding efficiencies. Poly(dimethylsiloxane)-block-poly(ethyleneglycol)methylethermethacrylate and poly(ethyleneoxide)-poly(dimethylsiloxane)methylmethacrylate diblock copolymers were also synthesized. Their titania nanocomposite films were compared with the integrated blocking layer. Liner poly(ethyleneoxide) containing diblock copolymer resulted in highly ordered foam like structures. The effect of heating temperature rise to 600°C and 1000°C on titania morphology was investigated by scanning electron and force microscopy and x-ray scattering. Sol-gel contents, hydrochloric acid, titania precursor and amphiphilic triblock copolymer were altered to see their effect on titania morphology. Increase in block copolymer content resulted in titania particles of diameter 15-20 nm.

Application of a hybrid blocking layer in dye-sensitized solar cells

In dye-sensitized solar cells a blocking layer between the transparent electrode and the mesoporous titanium dioxide film is used to prevent short-circuits between the hole-conductor and the front electrode. The conventional approach is to use a compact layer of titanium dioxide prepared by spin coating or spray pyrolysis. The thickness of the blocking layer is critical. On one hand, the layer has to be thick enough to cover the rough substrate completely. On the other hand, the serial resistance increases with increasing film thickness, because the layer acts as an ohmic resistance itself. In this thesis an amphiphilic diblock copolymer is used as a functional template to produce an alternative, hybrid blocking layer. The hybrid blocking layer is thinner than the conventional, compact titanium dioxide film and thereby possesses a higher conductivity. Still, this type of blocking layer covers the rough electrode material completely and avoids current loss through charge recombination. The novel blocking layer is prepared using a tailored, amphiphilic block copolymer in combination with sol-gel chemistry. While the hydrophilic poly(ethylene oxide) part of the polymer coordinates a titanium dioxide precursor to form a percolating network of titania particles, the hydrophobic poly(dimethylsiloxane) part turns into an insulating ceramic layer. With this technique, crack-free films with a thickness down to 24 nm are obtained. The presence of a conductive titanium dioxide network for current flow, which is embedded in an insulating ceramic material, is validated by conductive scanning force microscopy. This is the first time that such a hybrid blocking layer is implemented in a solar cell. With this approach the efficiency could be increased up to 27 % compared to the conventional blocking layer. Thus, it is demonstrated that the hybrid blocking layer represents a competitive alternative to the classical approach.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Oxygen evolution at ultrathin nanostructured Ni(OH)2 layers deposited on conducting glass

Ultrathin and transparent nanostructured Ni(OH)2 films were deposited on conducting glass (F:SnO2) by a urea-based chemical bath deposition method. By controlling the deposition time, the amount of deposited Ni(OH)2 was varied over 7 orders of magnitude. The turnover number for O2 generation, defined as the number of O2 molecules generated per catalytic site (Ni atom) and per second, increases drastically as the electrocatalyst amount decreases. The electrocatalytic activity of the studied samples (measured as the current density at a certain potential) increases with the amount of deposited Ni(OH)2 until a saturation value is already obtained for a thin film of around 1 nm in thickness, composed of Ni(OH)2 nanoplatelets lying flat on the conductive support. The deposition of additional amounts of catalyst generates a porous honeycomb structure that does not improve (only maintains) the electrocatalytic activity. The optimized ultrathin electrodes show a remarkable stability, which indicates that the preparation of highly transparent electrodes, efficient for oxygen evolution, with a minimum amount of nickel is possible.

Mechanisms for triggering high-voltage breakdown in vacuum

The electrical and optical characteristics of a cylindrical alumina insulator (94% Al203) have been measured under ultra-high vacuum (P < 10-8 mBar) conditions. A high-resolution CCD camera was used to make real-time optical recordings of DC prebreakdown luminescence from the ceramic, under conditions where DC current magnitudes were limited to less than 50μA. Two concentric metallized rings formed a pair of co-axial electrodes, on the end-face of the alumina tube; a third 'transparent' electrode was employed to study the effect of an orthogonal electric field upon the radial conduction processes within the metallized alumina specimen. The wavelength-spectra of the emitted light was quantified using a high-speed scanning monochromator and photo-multiplier tube detector. Concurrent electrical measurements were made alongside the recording of optical-emission images. An observed time-dependence of the photon-emission is correlated with a time-variation observed in the DC current-voltage characteristics of the alumina. Optical images were also recorded of pulsed-field surface-flashover events on the alumina ceramic. An intensified high-speed video technique provided 1ms frames of surface-flashover events, whilst 100ns frames were achieved using an ultra high-speed fast-framing camera. By coupling this fast-frame camera to a digital storage oscilloscope, it was possible to establish a temporal correlation between the application of a voltage-pulse to the ceramic and the evolution of photonic emissions from the subsequent surface-flashover event. The electro-optical DC prebreakdown characteristics of the alumina are discussed in terms of solid-state photon-emission processes, that are believed to arise from radiative electron-recombination at vacancy-defects and substitutional impurity centres within the surface-layers of the ceramic. The physical nature of vacancy-defects within an alumina dielectric is extensively explored, with a particular focus placed upon the trapped electron energy-levels that may be present at these defect centres. Finally, consideration is given to the practical application of alumina in the trigger-ceramic of a sealed triggered vacuum gap (TVG) switch. For this purpose, a physical model describing the initiation of electrical breakdown within the TVG regime is proposed, and is based upon the explosive destabilisation of trapped charge within the alumina ceramic, triggering the onset of surface-flashover along the insulator. In the main-gap prebreakdown phase, it is suggested that the electrical-breakdown of the TVG is initiated by the low-field 'stripping' of prebreakdown electrons from vacancy-defects in the ceramic under the influence of an orthogonal main-gap electric field.

Enhanced zinc oxide and graphene nanostructures for electronics and sensing applications

Zinc oxide and graphene nanostructures are important technological materials because of their unique properties and potential applications in future generation of electronic and sensing devices. This dissertation investigates a brief account of the strategies to grow zinc oxide nanostructures (thin film and nanowire) and graphene, and their applications as enhanced field effect transistors, chemical sensors and transparent flexible electrodes. Nanostructured zinc oxide (ZnO) and low-gallium doped zinc oxide (GZO) thin films were synthesized by a magnetron sputtering process. Zinc oxide nanowires (ZNWs) were grown by a chemical vapor deposition method. Field effect transistors (FETs) of ZnO and GZO thin films and ZNWs were fabricated by standard photo and electron beam lithography processes. Electrical characteristics of these devices were investigated by nondestructive surface cleaning, ultraviolet irradiation treatment at high temperature and under vacuum. GZO thin film transistors showed a mobility of ∼5.7 cm2/V·s at low operation voltage of <5 V and a low turn-on voltage of ∼0.5 V with a sub threshold swing of ∼85 mV/decade. Bottom gated FET fabricated from ZNWs exhibit a very high on-to-off ratio (∼106) and mobility (∼28 cm2/V·s). A bottom gated FET showed large hysteresis of ∼5.0 to 8.0 V which was significantly reduced to ∼1.0 V by the surface treatment process. The results demonstrate charge transport in ZnO nanostructures strongly depends on its surface environmental conditions and can be explained by formation of depletion layer at the surface by various surface states. A nitric oxide (NO) gas sensor using single ZNW, functionalized with Cr nanoparticles was developed. The sensor exhibited average sensitivity of ∼46% and a minimum detection limit of ∼1.5 ppm for NO gas. The sensor also is selective towards NO gas as demonstrated by a cross sensitivity test with N2, CO and CO2 gases. Graphene film on copper foil was synthesized by chemical vapor deposition method. A hot press lamination process was developed for transferring graphene film to flexible polymer substrate. The graphene/polymer film exhibited a high quality, flexible transparent conductive structure with unique electrical-mechanical properties; ∼88.80% light transmittance and ∼1.1742Ω/sq k sheet resistance. The application of a graphene/polymer film as a flexible and transparent electrode for field emission displays was demonstrated.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Transparent nanostructured electrode by centrifuge coating

We employ a new solution-based coating process, centrifuge coating, to fabricate nanostructured conductive layers over large areas. This coating procedure allows fast quenching of the metastable dispersed state of nanomaterials, which minimizes material wastes by mitigate the effects of particle re-aggregation. Using this method, we fabricate SWNT coatings on different substrates such as PET (polyethylene terephthalate), PDMS (polydimethylsiloxane), and an acrylic elastomer. The effects of the choice of solvents on the morphology and subsequent performance of the coating network are studied. © 2012 IEEE.