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.

High temperature robust SOI ethanol sensor

In this paper we present a robust SOI-CMOS ethanol sensor based on a tungsten-doped lanthanum iron oxide sensing material. The device shows response to gas, has low power consumption, good uniformity, high temperature stability and can be manufactured at low cost and with integrated circuitry. The platform is a tungsten-based CMOS micro-hotplate that has been shown to be stable for over two thousand hours at a high temperature (600°C) in a form of accelerated life test. The tungsten-doped lanthanum iron oxide was deposited on the micro-hotplate as a slurry with terpineol using a syringe, dried and annealed. Preliminary gas testing was done and the material shows response to ethanol vapour. These results are promising and we believe that this combination of a robust CMOS micro-hotplate and a good sensing material can form the basis for a commercial CMOS gas sensor. © 2011 Published by Elsevier Ltd.

Controllable synthesis of metal hydroxide and oxide nanostructures by ionic liquids assisted electrochemical corrosion method

Cu(OH)(2) nanowires have been synthesized by anodic oxidation of copper through a simple electrolysis process employing ionic liquid as an electrolyte. Controlling the electrochemical conditions can qualitatively modulate the lengths, amounts, and shapes of Cu(OH)(2) nanostructures. A rational mechanism based on coordination self-assembly and oriented attachment is proposed for the selective formation of the polycrystalline Cu(OH)(2) nanowires. In addition, the FeOOH nanoribbons, Ni(OH)(2) nanosheets, and ZnO nanospheres were also synthesized by this route, indicative of the universality of the electrochemical route presented herein. The morphologies and structures of the synthesized nanostructures have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), powder X-ray diffraction (XRD). Fourier transform infrared spectra (FT-IR), and thermogravimetric (TG). (C) 2007 Elsevier Masson SAS. All rights reserved

Effects of divalent metal ions on electrochemiluminescence sensor with Ru(bPY)(3)(2+) immobilized in Eastman-AQ membrane

Different effects of divalent metal ions on electrochemiluminescence (ECL) sensor with Ru(bPY)(3)(2+) immobilized in Eastman-AQ membrane were investigated. Mg2+,Ca2+ and Fe2+ can elevate the ECL of Ru(bpY)(3)(2+)/proline; while metal ions that underwent redox reactions on the electrode such as Mn2+ and Co2+ presented intensive quenching effects on Ru(bpy)(3)(2+) ECL. Also, the quenching effect of Mn2+ on the ECL sensor with Ru(bpY)(3)(2+) immobilized in Eastman-AQ membrane enhanced to about 30-folds compared with the case that Ru(bpy)(3)(2+) was dissolved in phosphate buffer, and the enhanced quenching effects of Mn2+ were studied.

Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

Low power predictable memory and processing architectures

Great demand in power optimized devices shows promising economic potential and draws lots of attention in industry and research area. Due to the continuously shrinking CMOS process, not only dynamic power but also static power has emerged as a big concern in power reduction. Other than power optimization, average-case power estimation is quite significant for power budget allocation but also challenging in terms of time and effort. In this thesis, we will introduce a methodology to support modular quantitative analysis in order to estimate average power of circuits, on the basis of two concepts named Random Bag Preserving and Linear Compositionality. It can shorten simulation time and sustain high accuracy, resulting in increasing the feasibility of power estimation of big systems. For power saving, firstly, we take advantages of the low power characteristic of adiabatic logic and asynchronous logic to achieve ultra-low dynamic and static power. We will propose two memory cells, which could run in adiabatic and non-adiabatic mode. About 90% dynamic power can be saved in adiabatic mode when compared to other up-to-date designs. About 90% leakage power is saved. Secondly, a novel logic, named Asynchronous Charge Sharing Logic (ACSL), will be introduced. The realization of completion detection is simplified considerably. Not just the power reduction improvement, ACSL brings another promising feature in average power estimation called data-independency where this characteristic would make power estimation effortless and be meaningful for modular quantitative average case analysis. Finally, a new asynchronous Arithmetic Logic Unit (ALU) with a ripple carry adder implemented using the logically reversible/bidirectional characteristic exhibiting ultra-low power dissipation with sub-threshold region operating point will be presented. The proposed adder is able to operate multi-functionally.

Magnetic impurities in nanostructured materials

Os resultados apresentados aqui foram alcançados no âmbito do programa de doutoramento intitulado “Impurezas Magnéticas em Materiais Nanoestruturados”. O objectivo do estudo foi a síntese e caracterização de óxido contendo impurezas magnéticas. Durante este trabalho, sínteses de sol-gel não-aquoso têm sido desenvolvidos para a síntese de óxidos dopados com metais de transição (ZnO e ZrO2). A dopagem uniforme é particularmente importante no estudo de semicondutores magnéticos diluídos (DMSs) e o ponto principal deste estudo foi verificar o estado de oxidação e a estrutura local do dopante e para excluir a existência de uma fase secundária como a origem do ferromagnetismo. Para alargar o âmbito da investigação e explorar plenamente o conceito de "impurezas magnéticas em materiais nanoestruturados" estudamos as propriedades de nanopartículas magnéticas dispersas em uma matriz de óxido. As nanopartículas (ferrita de cobalto) foram depositadas como um filme e cobertas com um óxido metálico semicondutor ou dielétrico (ZnO, TiO2). Estes hetero-sistemas podem ser considerados como a dispersão de impurezas magnéticas em um óxido. As caracterizações exigidas por estes nanomateriais têm sido conduzidas na Universidade de Aveiro e Universidade de Montpellier, devido ao equipamento complementar.

THEORY OF NON-STEADY-STATE ELECTRICAL CHARACTERISTICS OF METAL-INSULATOR-METAL STRUCTURES WITH SCHOTTKY BARRIERS AND UNIFORMLY DISTRIBUTED INTERFACE IMPURITY STATES

The metal-insulator (or amorphous semiconductor) blocking contact is still not well understood. In the present paper, we discuss the non steady state characteristics of Metal-lnsulator-Metal Structure with non-intimate blocking contacts (i.e. Metal-Oxide-Insulator-Metal Structure). We consider a uniform distribution (in energy) of impurity states in addition to impurity states at a single energy level within the depletion region. We discuss thermal as well as isothermal characteristics and present expressions for the temperature of maximum current (T-m) and a method to calculate the density of uniformly distributed impurity states. The variation of mobility with electrical field has also been considered. Finally we plot the theoretical curves under different conditions. The present results are closing into available experimental results.

A generalized theory of electrical characteristics of schottky barriers for amorphous materials

In the present paper, we discuss a generalized theory of electrical characteristics for amorphous semiconductor (or insulator) Schottky barriers, considering: (i) surface states, (ii) doping impurity states at a single energy level and (iii) energetically distributed bulk impurity states. We also consider a thin oxide layer (≈10 Å) between metal and semiconductor. We develop current versus applied potential characteristics considering the variation of the Fermi level very close to contact inside the semiconductor and decrease in barrier height due to the image force effect as well as potential fall on the oxide layer. Finally, we discuss the importance of each parameter, i.e. surface states, distributed impurity states, doping impurity states, thickness of oxide layer etc. on the log I versus applied potential characteristics. The present theory is also applicable for intimate contact, i.e. metal-semiconductor contact, crystalline material structures or for Schottky barriers in insulators or polymers.

From polymer precursors to metal oxides

We report on a strategy to prepare metal oxides including binary oxide and mixed metal oxide (MMO) in form of nanometer-sized particles using polymer as precursor. Zinc oxide nanoparticles are prepared as an example. The obtained zinc polyacrylate precursor is amorphous as confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The conversion from polymer precursor to ZnO nanocrystals by thermal pyrolysis was investigated by means of XRD, thermogravimetric analysis (TGA) and electron microscopy. The as-synthesized ZnO consists of many individual particles with a diameter around 40 nm as shown by scanning electron microscopy (SEM). The photoluminescence (PL) and electron paramagnetic (EPR) properties of the material are investigated, too. Employing this method, ZnO nanocrystalline films are fabricated via pyrolysis of a zinc polyacrylate precursor film on solid substrate like silicon and quartz glass. The results of XRD, absorption spectra as well as TEM prove that both the ZnO nanopowder and film undergo same evolution process. Comparing the PL properties of films fabricated in different gas atmosphere, it is assigned that the blue emission of the ZnO films is due to crystal defect of zinc vacancy and green emission from oxygen vacancy. Two kinds of ZnO-based mixed metal oxide (Zn1-xMgxO and Zn1-xCoxO) particles with very precise stoichiometry are prepared by controlled pyrolysis of the corresponding polymer precursor at 550 oC. The MMO crystal particles are typically 20-50 nm in diameter. Doping of Mg in ZnO lattice causes shrinkage of lattice parameter c, while it remains unchanged with Co incorporation. Effects of bandgap engineering are seen in the Mg:ZnO system. The photoluminescence in the visible is enhanced by incorporation of magnesium on zinc lattice sites, while the emission is suppressed in the Co:ZnO system. Magnetic property of cobalt doped-ZnO is checked too and ferromagnetic ordering was not found in our samples. An alternative way to prepare zinc oxide nanoparticles is presented upon calcination of zinc-loaded polymer precursors, which is synthesized via inverse miniemulsion polymerization of the mixture of the acrylic acid and zinc nitrate. The as-prepared ZnO product is compared with that obtained from polymer-salt complex method. The obtained ZnO nanoparticles undergo surface modification via a phosphate modifier applying ultrasonication. The morphology of the modified particles is checked by SEM. And stability of the ZnO nanoparticles in aqueous dispersion is enhanced as indicated by the zeta-potential results.

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.

Low-cost flight control system for a small autonomous helicopter

In this paper we describe a low-cost flight control system for a small (60 class) helicopter which is part of a larger project to develop an autonomous flying vehicle. Our approach differs from that of others in not using an expensive inertial/GPS sensing system. The primary sensors for vehicle stabilization are a low-cost inertial sensor and a pair of CMOS cameras. We describe the architecture of our flight control system, the inertial and visual sensing subsystems and present some flight control results.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Non-aqueous synthesis of hexagonal ZnO nanopyramids : gas sensing properties

Zinc oxide (ZnO) nanopyramids were synthesized by a one-pot route in a non-aqueous and surfactantfree environment. The synthesized metal oxide was characterized using SEM, XRD, and TEM to investigate the surface morphology and crystallographic phase of the nanostructures. It was observed that the ZnO nanopyramids were of uniform size and symmetrical, with a hexagonal base and height of ∼100 nm. Gas sensing characterization of the ZnO nanopyramids when deposited as thin-film onto conductometric transducers were performed towards NOx and C2H5OH vapor of different concentrations over a temperature range of 22–350 ◦C. It was observed that the sensors responded towards NO2 (10 ppm) and C2H5OH(250 ppm) analytes best at temperatures of 200 and 260 ◦C with a sensor response of 14.5 and 5.72, respectively. The sensors showed satisfactory sensitivity, repeatability as well as fast response and recovery towards both the oxidizing and the reducing analyte. The good performance was attributed to the low amount of organic impurities, large surface-to-volume ratio and high crystallinity of the solvothermally synthesized ZnO nanopyramids.

A comparison study on hydrogen sensing performance of Pt/MoO3 nanoplatelets coated with a thin layer of Ta2O5 or La2O3

In this work, we investigate how hydrogen sensing performance of thermally evaporated MoO3 nanoplatelets can be further improved by RF sputtering a thin layer of tantalum oxide (Ta2O5) or lanthanum oxide (La2O3). We show that dissociated hydrogen atoms cause the thin film layer to be polarised, inducing a measurable potential difference greater than that as reported previously. We attribute these observations to the presence of numerous traps in the thin layer; their states allow a stronger trapping of charge at the Pt-thin film oxide interface as compared to the MoO3 sensors without the coating. Under exposure to H2 (10 000 ppm) the maximum change in dielectric constant of 45.6 (at 260 °C) for the Ta2O5/MoO3 nanoplatelets and 31.6 (at 220 °C) for La2O3/MoO3 nanoplatelets. Subsequently, the maximum sensitivity for the Ta2O5/MoO3 is 16.87 (at 260 °C) and La2O3/MoO3 is 7.52 (at 300 °C).