Low temperature (< 100 °c) deposited P-type cuprous oxide thin films: Importance of controlled oxygen and deposition energy

With the emergence of transparent electronics, there has been considerable advancement in n-type transparent semiconducting oxide (TSO) materials, such as ZnO, InGaZnO, and InSnO. Comparatively, the availability of p-type TSO materials is more scarce and the available materials are less mature. The development of p-type semiconductors is one of the key technologies needed to push transparent electronics and systems to the next frontier, particularly for implementing p-n junctions for solar cells and p-type transistors for complementary logic/circuits applications. Cuprous oxide (Cu2O) is one of the most promising candidates for p-type TSO materials. This paper reports the deposition of Cu2O thin films without substrate heating using a high deposition rate reactive sputtering technique, called high target utilisation sputtering (HiTUS). This technique allows independent control of the remote plasma density and the ion energy, thus providing finer control of the film properties and microstructure as well as reducing film stress. The effect of deposition parameters, including oxygen flow rate, plasma power and target power, on the properties of Cu2O films are reported. It is known from previously published work that the formation of pure Cu2O film is often difficult, due to the more ready formation or co-formation of cupric oxide (CuO). From our investigation, we established two key concurrent criteria needed for attaining Cu2O thin films (as opposed to CuO or mixed phase CuO/Cu2O films). First, the oxygen flow rate must be kept low to avoid over-oxidation of Cu2O to CuO and to ensure a non-oxidised/non-poisoned metallic copper target in the reactive sputtering environment. Secondly, the energy of the sputtered copper species must be kept low as higher reaction energy tends to favour the formation of CuO. The unique design of the HiTUS system enables the provision of a high density of low energy sputtered copper radicals/ions, and when combined with a controlled amount of oxygen, can produce good quality p-type transparent Cu2O films with electrical resistivity ranging from 102 to 104 Ω-cm, hole mobility of 1-10 cm2/V-s, and optical band-gap of 2.0-2.6 eV. These material properties make this low temperature deposited HiTUS Cu 2O film suitable for fabrication of p-type metal oxide thin film transistors. Furthermore, the capability to deposit Cu2O films with low film stress at low temperatures on plastic substrates renders this approach favourable for fabrication of flexible p-n junction solar cells. © 2011 Elsevier B.V. All rights reserved.

Thermal plasma synthesis of superparamagnetic iron oxide nanoparticles

Superparamagnetic iron oxide nanoparticles were synthesized by injecting ferrocene vapor and oxygen into an argon/helium DC thermal plasma. Size distributions of particles in the reactor exhaust were measured online using an aerosol extraction probe interfaced to a scanning mobility particle sizer, and particles were collected on transmission electron microscopy (TEM) grids and glass fiber filters for off-line characterization. The morphology, chemical and phase composition of the nanoparticles were characterized using TEM and X-ray diffraction, and the magnetic properties of the particles were analyzed with a vibrating sample magnetometer and a magnetic property measurement system. Aerosol at the reactor exhaust consisted of both single nanocrystals and small agglomerates, with a modal mobility diameter of 8-9 nm. Powder synthesized with optimum oxygen flow rate consisted primarily of magnetite (Fe 3O 4), and had a room-temperature saturation magnetization of 40.15 emu/g, with a coercivity and remanence of 26 Oe and 1.5 emu/g, respectively. © Springer Science+Business Media, LLC 2011.

High-density remote plasma sputtering of high-dielectric-constant amorphous hafnium oxide films

Hafnium oxide (HfOx) is a high dielectric constant (k) oxide which has been identified as being suitable for use as the gate dielectric in thin film transistors (TFTs). Amorphous materials are preferred for a gate dielectric, but it has been an ongoing challenge to produce amorphous HfOx while maintaining a high dielectric constant. A technique called high target utilization sputtering (HiTUS) is demonstrated to be capable of depositing high-k amorphous HfOx thin films at room temperature. The plasma is generated in a remote chamber, allowing higher rate deposition of films with minimal ion damage. Compared to a conventional sputtering system, the HiTUS technique allows finer control of the thin film microstructure. Using a conventional reactive rf magnetron sputtering technique, monoclinic nanocrystalline HfOx thin films have been deposited at a rate of ∼1.6nmmin-1 at room temperature, with a resistivity of 1013Ωcm, a breakdown strength of 3.5MVcm-1 and a dielectric constant of ∼18.2. By comparison, using the HiTUS process, amorphous HfOx (x=2.1) thin films which appear to have a cubic-like short-range order have been deposited at a high deposition rate of ∼25nmmin-1 with a high resistivity of 1014Ωcm, a breakdown strength of 3MVcm-1 and a high dielectric constant of ∼30. Two key conditions must be satisfied in the HiTUS system for high-k HfOx to be produced. Firstly, the correct oxygen flow rate is required for a given sputtering rate from the metallic target. Secondly, there must be an absence of energetic oxygen ion bombardment to maintain an amorphous microstructure and a high flux of medium energy species emitted from the metallic sputtering target to induce a cubic-like short range order. This HfOx is very attractive as a dielectric material for large-area electronic applications on flexible substrates. A remote plasma sputtering process (high target utilization sputtering, HiTUS) has been used to deposit amorphous hafnium oxide with a very high dielectric constant (∼30). X-ray diffraction shows that this material has a microstructure in which the atoms have a cubic-like short-range order, whereas radio frequency (rf) magnetron sputtering produced a monoclinic polycrystalline microstructure. This is correlated to the difference in the energetics of remote plasma and rf magnetron sputtering processes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The attrition behaviour of oxygen-carriers under inert and reacting conditions

The attrition of two potential oxygen-carriers for chemical-looping, 100. wt% mechanically-mixed, unsupported iron oxide (400-600 μm diameter) and 25. wt% copper oxide impregnated on alumina (600-900 μm diameter), has been studied. The rates of attrition of batches of these particles whilst they were being fluidised and subjected to successive cycles of reduction and oxidation were determined by measuring the rate of production of fine particles elutriated from the bed, as well as progressive changes in the distribution of particle sizes retained in the bed. The ability of the particles to withstand impacts was also investigated by examining the degree of fragmentation of 1. g of reacted particles of known size on projecting them at a target at various velocities. It was found that the mechanical strength of the iron oxide particles deteriorated significantly after repeated cycles of oxidation and reduction. Thus, the rate of elutriation increased ~35-fold between the 1st and 10th cycle. At an impact velocity of 38. m/s, the amount of fragmentation in the impact test, viz. mass fraction of particles after impact having a size less than that before impact, increased from ~2.3. wt% (fresh particles) to 98. wt% after the 10th cycle. The CuO particles, in comparison, were able to withstand repeated reaction: no signs of increased rates of elutriation or fragmentation were observed over ten cycles. These results highlight the importance of selecting a durable support for oxygen-carriers. © 2011 Elsevier Ltd.

Steady-state modelling of the universal exhaust gas oxygen (UEGO) sensor

The universal exhaust gas oxygen (UEGO) sensor is a well-established device which was developed for the measurement of relative air fuel ratio in internal combustion engines. There is, however, little information available which allows for the prediction of the UEGO's behaviour when exposed to arbitrary gas mixtures, pressures and temperatures. Here we present a steady-state model for the sensor, based on a solution of the Stefan-Maxwell equation, and which includes a momentum balance. The response of the sensor is dominated by a diffusion barrier, which controls the rate of diffusion of gas species between the exhaust and a cavity. Determination of the diffusion barrier characteristics, especially the mean pore size, porosity and tortuosity, is essential for the purposes of modelling, and a measurement technique based on identification of the sensor pressure giving zero temperature sensitivity is shown to be a convenient method of achieving this. The model, suitably calibrated, is shown to make good predictions of sensor behaviour for large variations of pressure, temperature and gas composition. © 2012 IOP Publishing Ltd.

The influence of turbine stator well coolant flow rate and passage configuration on cooling effectiveness

Market competitiveness for aero engine power plant dictates that improvements in engine performance and reliability are guaranteed a priori by manufacturers. The requirement to accurately predict the life of engine components makes exacting demands of the internal air system, which must provide effective cooling over the engine duty cycle with the minimum consumption of compressor section air. Tests have been conducted at the University of Sussex using a turbine test facility which comprises a two stage turbine with an individual stage pressure ratio of 1.7:1. Main annulus air is supplied by an adapted Rolls-Royce Dart compressor at up to 440 K and 4.8 kg s-1. Cooling flow rates ranging from 0.71 to 1.46 Cw, ent, a disc entrainment parameter, have been used to allow ingress or egress dominated stator well flow conditions. The mechanical design of the test section allows internal cooling geometry to be rapidly re-configured, allowing the effect of jet momentum and coolant trajectory to be investigated. An important facet to this investigation is the use of CFD to model and analyse the flow structures associated with the cavity conditions tested, as well as to inform the design of cooling path geometry. This paper reports on the effectiveness of stator well coolant flow rate and delivery configurations using experimental data and also CFD analysis to better quantify the effect of stator well flow distribution on component temperatures. Copyright © 2011 by Rolls-Royce plc.

Creep and oxygen diffusion in magnetite

The creep rate of polycrystalline Fe3O4 has been measured as a fonction of stress and oxygen partial pressure in the temperature range 480-1100°C. A regime of power law creep is found at high stress, with a stress exponent of ≈- 3.1 and an activation energy of 264 kJ/mol. A regime of diffusional flow is found at lower stresses and is interpreted as Nabarro-Herring creep. The data for the two regimes are combined to deduce an oxygen diffusion coefficient of ≈-10-5 exp(-264 kJ/mol/RT) m2s-1, with oxygen vacancies suggested as the mobile species. © 1990.

CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product CO2 from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.

Application of fast oxygen sensors for investigations into air-path dynamics and EGR distribution in a diesel engine

The control of NOX emissions by exhaust gas recirculation (EGR) is of widespread application. However, despite dramatic improvements in all aspects of engine control, the subtle mixing processes that determine the cylinder-to-cylinder distribution of the recirculated gas often results in a mal-distribution that is still an issue for the engine designer and calibrator. In this paper we demonstrate the application of a relatively straightforward technique for the measurement of the absolute and relative dilution quantity in both steady state and transient operation. This was achieved by the use of oxygen sensors based on standard UEGO (universal exhaust gas oxygen) sensors but packaged so as to give good frequency response (∼ 10 ms time constant) and be completely insensitivity to the sample pressure and temperature. Measurements can be made at almost any location of interest, for example exhaust and inlet manifolds as well as EGR path(s), with virtually no flow disturbance. At the same time, the measurements yield insights into air-path dynamics. We argue that "dilution", as indicated by the deviation of the oxygen concentration from that of air, is a more appropriate parameter than EGR rate in the context of NOX control, especially for diesel engines. Experimental results are presented for the EGR distribution in a current production light duty 4-cylinder diesel engine in which significant differences were found in the proportion of the recirculated gas that reached each cylinder. Even the individual inlet runners of the cylinders exhibited very different dilution rates - differences of nearly 50% were observed at some conditions. An application of such data may be in the improvement of calibration and validation of CFD and other modelling techniques. Copyright © 2014 SAE International.