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.

Frame assisted H2O electrolysis induced H2 bubbling transfer of large area graphene grown by chemical vapor deposition on Cu

An improved technique for transferring large area graphene grown by chemical vapor deposition on copper is presented. It is based on mechanical separation of the graphene/copper by H2 bubbles during H2O electrolysis, which only takes a few tens of seconds while leaving the copper cathode intact. A semi-rigid plastic frame in combination with thin polymer layer span on graphene gives a convenient way of handling- and avoiding wrinkles and holes in graphene. Optical and electrical characterizations prove the graphene quality is better than that obtained by traditional wet etching transfer. This technique appears to be highly reproducible and cost efficient. © 2013 American Institute of Physics.

Near-field characterization of chemical vapor deposition graphene in the microwave regime

Near-field measurements were performed at X-band frequencies for graphene on copper microstrip transmission lines. An improvement in radiation of 0.88 dB at 10.2 GHz is exhibited from the monolayer graphene antenna which has dc sheet resistivity of 985 Ω/sq. Emission characteristics were validated via ab initio simulations and compared to empirical findings of geometrically comparable copper patches. This study contributes to the current knowledge of the electronic properties of graphene. © 2013 AIP Publishing LLC.

Observing graphene grow: catalyst-graphene interactions during scalable graphene growth on polycrystalline copper.

Complementary in situ X-ray photoelectron spectroscopy (XPS), X-ray diffractometry, and environmental scanning electron microscopy are used to fingerprint the entire graphene chemical vapor deposition process on technologically important polycrystalline Cu catalysts to address the current lack of understanding of the underlying fundamental growth mechanisms and catalyst interactions. Graphene forms directly on metallic Cu during the high-temperature hydrocarbon exposure, whereby an upshift in the binding energies of the corresponding C1s XPS core level signatures is indicative of coupling between the Cu catalyst and the growing graphene. Minor carbon uptake into Cu can under certain conditions manifest itself as carbon precipitation upon cooling. Postgrowth, ambient air exposure even at room temperature decouples the graphene from Cu by (reversible) oxygen intercalation. The importance of these dynamic interactions is discussed for graphene growth, processing, and device integration.

Heterojunction ambipolar organic transistors fabricated by a two-step vacuum-deposition process

Ambipolar organic field-effect transistors (OFETs) are produced, based on organic heterojunctions fabricated by a two-step vacuum-deposition process. Copper phthalocyanine (CuPc) deposited at a high temperature (250 degrees C) acts as the first (p-type component) layer, and hexadecafluorophthalocyaninatocopper (F16CuPc) deposited at room temperature (25 degrees C) acts as the second (n-type component) layer. A heterojunction with an interpenetrating network is obtained as the active layer for the OFETs. These heterojunction devices display significant ambipolar charge transport with symmetric electron and hole mobilities of the order of 10(-4) cm(2) V-1 s(-1) in air. Conductive channels are at the interface between the F16CuPc and CuPc domains in the interpenetrating networks. Electrons are transported in the F16CuPc regions, and holes in the CuPc regions. The molecular arrangement in the heterojunction is well ordered, resulting in a balance of the two carrier densities responsible for the ambipolar electrical characteristics. The thin-film morphology of the organic heterojunction with its interpenetrating network structure can be controlled well by the vacuum-deposition process.

Fabrication of integrated microelectrodes for electrochemical detection on electrophoresis microchip by electroless deposition and micromolding in capillary technique

A new method for the fabrication of an integrated microelectrode for electrochemical detection (ECD) on an electrophoresis microchip is described. The pattern of the microelectrode was directly made on the surface of a microscope slide through an electroless deposition procedure. The surface of the slide was first selectively coated with a thin layer of sodium silicate through a micromolding in capillary technique provided by a poly(dimethylsiloxane) (PDMS) microchannel; this left a rough patterned area for the anchoring of catalytic particles. A metal layer was deposited on the pattern guided by these catalytic particles and was used as the working electrode. Factors influencing the fabrication procedure were discussed. The whole chip was built by reversibly sealing the slide to another PDMS layer with electrophoresis microchannels at room temperature. This approach eliminates the need of clean room facilities and expensive apparatus such as for vacuum deposition or sputtering and makes it possible to produce patterned electrodes suitable for ECD on microchip under ordinary chemistry laboratory conditions. Also once the micropattern is ready, it allows the researchers to rebuild the electrode in a short period of time when an electrode failure occurs. Copper and gold microelectrodes were fabricated by this technique. Glucose, dopamine, and catechol as model analytes were tested.

Preparation and gas sensitivity of octa-n-butoxy-2,3-naphthalocyanine copper(II) Langmuir-Blodgett film

The formation process of monolayer of octa-n-butoxy-2,3-naphthalocyanine copper ( I), [CuNc(OBu)(8)], on water subphase was studied. Its multilayers were successifully deposited on the hydrophilic substrates by Z-type deposition mode using LB technique. Stable solid film with a limiting molecular area of 0.74 nm(2) and a collapse pressure of 55 mN/m were formed. The LB film structure was characterized by IR and electronic absorption spectra. Macrocycle of CuNc (OBu)(8) molecules have a face-to-face arrangement in the multilayers. These films have good sensitivities to vapor of alcohols, with the following sequence of sensitivities: i-PrOH>EtOH>MeOH. The response time and recovery time of the LB films to vapor of MeOH, EtOH and i-PrOH[volume fraction (1-5) X 10(-5)] were within 2 and 5 seconds respectively, while those of the LB films to ammonia(1 X 10(-4)) were 30-60 seconds and 4-5 minutes respectively.

THE CHARACTERIZATION OF 2 COPPER PHTHALOCYANINE LANGMUIR-BLODGETT-FILMS AND THEIR GAS-SENSITIVE PROPERTIES

The monolayer and deposition behaviour of a symmetrically substituted copper tetra-4-(2, 4-di-t-amylphenoxy) phthalocyanine (tapCuPc) and an asymmetrically substituted copper [tri-4-(2, 4-di-t-amylphenoxy)-mono-4-(-2-methoxyethoxy)]phthalocyanine (AsyCuPc) were investigated. The results on monolayer behaviour and spectroscopic characterization of the LB films show that both CuPc molecules in a monolayer at the air-water interface and the LB films are stacked and inclined. The gas-sensitive properties show that the responding speed of AsyCuPc LB film is faster than that of tapCuPc LB film.

Preparation of Dendritic Copper Nanostructures and Their Characterization for Electroreduction

Dendritic copper nanostructures of different morphologies were synthesized by a surfactant-free electrochemical method. Single crystal nature of the nanostructures was revealed from their X-ray diffraction and electron diffraction patterns. Mechanism of dendrite formation was discussed from thermodynamic aspects using the concept of supersaturation. Supersaturation of the copper metal reduced on the surface of the electrode was the crucial factor for the generation of different morphologies. Effects of applied potential, temperature, and the solution concentration on the supersaturation were studied. The NO3- and H2O2 electroreduction ability of the dendritic materials was tested. Use of copper dendrite-modified electrode as NO3- sensor was demonstrated.

Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry

Jenkins, Tudor; Brieva, A.C.; Jones, D.G.; Evans, D.A., (2006) 'Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry', Journal of Applied Physics 99 pp.73504 RAE2008

Modelling the performance of lead-Free solder interconnects for copper bumped flip-chip devices

Traditionally, before flip chips can be assembled the dies have to be attached with solder bumps. This process involves the deposition of metal layers on the Al pads on the dies and this is called the under bump metallurgy (UBM). In an alternative process, however, Copper (Cu) columns can be used to replace solder bumps and the UBM process may be omitted altogether. After the bumping process, the bumped dies can be assembled on to the printed circuit board (PCB) by using either solder or conductive adhesives. In this work, the reliability issues of flip chips with Cu column bumped dies have been studied. The flip chip lifetime associated with the solder fatigue failure has been modeled for a range of geometric parameters. The relative importance of these parameters is given and solder volume has been identified as the most important design parameter for long-term reliability. Another important problem that has been studied in this work is the dissolution of protection metals on the pad and Cu column in the reflow process. For small solder joints the amount of Cu which dissolves into the molten solder after the protection layers have worn out may significantly affect solder joint properties.

A more direct way to make catalysts: one-pot ligand-assisted aerobic stripping and electrodeposition of copper on graphite

Electrodeposition of metals onto conductive supports such as graphite potentially provides a lower-waste method to form heterogeneous catalysts than the standard methods such as wet impregnation. Copper electrodeposition onto pressed graphite disc electrodes was investigated from aqueous CuSO4-ethylenediamine solutions by chronoamperometry with scanning electron microscopy used to ascertain the particle sizes obtained by this method. The particle size was studied as a function of pH, CuSO4-ethylenediamine concentration, and electrodeposition time. It was observed that decreasing the pH, copper-ethylenediamine concentration and time each decreased the size of the copper particles observed, with the smallest obtained being around 5-20 nm. Furthermore, electroless aerobic oxidation of copper metal in the presence of ethylenediamine was successfully coupled with the electrodeposition in the same vessel. In this way, deposition was achieved sequentially on up to twenty different graphite discs using the same ethylenediamine solution, demonstrating the recyclability of the ligand. The materials thus prepared were shown to be catalytically active for the mineralisation of phenol by hydrogen peroxide. Overall, the results provide a proof-of-principle that by making use of aerobic oxidation coupled with electrochemical deposition, elemental base metals can be used directly as starting materials to form heterogeneous catalysts without the need to use metal salts as catalyst precursors.

Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen

Amorphous Selenium films using CBD: A Novel Selenisation technique for preparing lndium Selenide and Copper lndium Selenide Thin Films

In the present work, we describe our efforts to develop device quality CuInSe2, films through low cost, simple and eco-friendly hybrid techniques. The most important point to be highlighted here is that the method fully avoids the use of poisonous gases such as H2Se/Se vapour. Instead, selenisation is achieved through solid state reaction between amorphous selenium and polycrystalline metal layers resulting in both binary and ternary selenides. Thin films of amorphous selenium (a-Se) used for this is deposited using Chemical Bath Deposition (CBD). CulnSe2 films are prepared through the selenisation process. Another PV material, indium selenide (In2Se3) thin films are also prepared using this process.

Optimization of electroless copper plating on polyethylene films modified by surface grafting of vinyl ether of monoethanolamine

Metallized plastics have recently received significant interest for their useful applications in electronic devices such as for integrated circuits, packaging, printed circuits and sensor applications. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. There are several techniques for metal deposition on surface of polymers such as evaporation, sputtering, electroless plating and electrolysis. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. Polyethylene films were subjected to gamma-radiation induced surface graft copolymerization with vinyl ether of monoethanolamine. Electroless copper plating was carried out effectively on the modified films. The catalytic processes for the electroless copper plating in the presence and the absence of SnCl2 sensitization were studied and the optimum activation conditions that give the highest plating rate were determined. The effect of grafting degree on the plating rate is studied. Electroless plating conditions (bath additives, pH and temperature) were optimized. Plating rate was determined gravimetrically and spectrophotometrically at different grafting degrees. The results reveal that plating rate is a function of degree of grafting and increases with increasing grafted vinyl ether of monoethanolamine onto polyethylene. It was found that pH 13 of electroless bath and plating temperature 40°C are the optimal conditions for the plating process. The increasing of grafting degree results in faster plating rate at the same pH and temperature. The surface morphology of the metallized films was investigated using scanning electron microscopy (SEM). The adhesion strength between the metallized layer and grafted polymer was studied using tensile machine. SEM photos and adhesion measurements clarified that uniform and adhered deposits were obtained under optimum conditions.