Diffusion and chemical reaction in the porous structures of solid oxide fuel cells

The Rolls-Royce Integrated-Planar Solid Oxide Fuel Cell (IP-SOFC) consists of ceramic modules which have electrochemical cells printed on the outer surfaces. The cathodes are the outermost layer of each cell and are supplied with oxygen from air flowing over the outside of the module. The anodes are in direct contact with the ceramic structure and are supplied with fuel from internal gas channels. Natural gas is reformed into hydrogen for use by the fuel cells in a separate reformer module of similar design except that the fuel cells are replaced by a reforming catalyst layer. The performance of the modules is intrinsically linked to the behaviour of the gas flows within their porous structures. Because the porous layers are very thin, a one-dimensional flow model provides a good representation of the flow property variations between fuel channel and fuel cell or reforming catalyst. The multi-component convective-diffusive flows are simulated using a new theory of flow in porous material, the Cylindrical Pore Interpolation Model. The effects of the catalysed methane reforming and water-gas shift chemical reactions are also considered using appropriate kinetic models. It is found that the shift reaction, which is catalysed by the anode material, has certain beneficial effects on the fuel cell module performance. In the reformer module it was found that the flow resistance of the porous support structure makes it difficult to sustain a high methane conversion rate. Although the analysis is based on IP-SOFC geometry, the modelling approach and general conclusions are applicable to other types of SOFC.

Integrating vertically aligned carbon nanotubes on micromechanical structures

The integration of high yield, uniform and preferential growth of vertically aligned carbon nanotubes (VACNT) on low stress micromechanical structures was analyzed. A combination of electron-beam crosslinked surface micromachining and direct current plasma enhanced chemical vapor deposition of electric field aligned carbon nanotubes was used for the analysis. The selective placement of high yield and uniform VACNTs on a partially suspended Ni/SiO2/Ti microstructure was also demonstrated.

Three-dimensional carbon nanowall structures

The authors report the growth of carbon nanowalls in freestanding, three-dimensional aggregates by microwave plasma-enhanced chemical vapor deposition. Carbon nanowalls extrude from plasma sites into three-dimensional space. The growth is catalyst-free and not limited by nucleating surfaces. The growth mechanism is discussed and compared with similar carbon nanomaterials. High surface area of as-grown carbon nanowalls indicates a potential for electrochemical applications. Field emission measurements show a low field turn-on and long-term stability. The results establish a scalable production method and possible applications using field emission or high surface area. © 2007 American Institute of Physics.

Plasma enhanced chemical vapour deposition carbon nanotubes/nanofibres - How uniform do they grow?

The ability to grow carbon nanotubes/nanofibres (CNs) with a high degree of uniformity is desirable in many applications. In this paper, the structural uniformity of CNs produced by plasma enhanced chemical vapour deposition is evaluated for field emission applications. When single isolated CNs were deposited using this technology, the structures exhibited remarkable uniformity in terms of diameter and height (standard deviations were 4.1 and 6.3% respectively of the average diameter and height). The lithographic conditions to achieve a high yield of single CNs are also discussed. Using the height and diameter uniformity statistics, we show that it is indeed possible to accurately predict the average field enhancement factor and the distribution of enhancement factors of the structures, which was confirmed by electrical emission measurements on individual CNs in an array.

Electrical and field emission investigation of individual carbon nanotubes from plasma enhanced chemical vapour deposition

Plasma enhanced chemical vapour deposition (PECVD) is a controlled technique for the production of vertically aligned multiwall carbon nanotubes for field emission applications. In this paper, we investigate the electrical properties of individual carbon nanotubes which is important for designing field emission devices. PECVD nanotubes exhibit a room temperature resistance of 1-10 kΩ/μm length (resistivity 10-6 to 10-5 Ω m) and have a maximum current carrying capability of 0.2-2 mA (current density 107-108 A/cm2). The field emission characteristics show that the field enhancement of the structures is strongly related to the geometry (height/radius) of the structures and maximum emission currents of ∼ 10 μA were obtained. The failure of nanotubes under field emission is also discussed. © 2002 Elsevier Science B.V. All rights reserved.

Study of multi-walled carbon nanotube structures fabricated by PMMA suspended dispersion

We report on the electrical characteristics of plasma enhanced chemical vapour deposition (PECVD)-grown, multi-walled carbon nanotube (MWCNT) devices made by a new fabrication method, PMMA suspended dispersion. This method makes it possible to suspend nanotubes between metal electrodes and to remove unwanted nanotubes from the substrate. The measurements show that the MWCNTs are metallic and able to maintain a current density ∼2×106 A/cm2 for more than 15 days with a maximum current density of ∼1.8×107 A/cm2. This high current density and reliability will make PECVD-grown MWCNTs applicable to field emission cathodes. © 2002 Elsevier Science B.V. All rights reserved.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Deposition of diamond-like carbon films by photon-enhanced chemical vapour deposition of methane using a windowless hydrogen lamp

Thin films of diamond-like carbon (DLC) have been deposited using a novel photon-enhanced chemical vapour deposition (photo-CVD) method. This low energy method may be a way to produce better interfaces in electronic devices by reducing damage due to ion bombardment. Methane requires high energy photons for photolysis to take place and these are not transmitted in most photo-CVD methods owing to the presence of a window between the lamp and the deposition environment. In our photo-CVD system there is no window and all the high energy photons are transmitted into the reaction gas. Initial work has proved promising and this paper presents recent results. Films have been characterized by measuring electron energy loss spectra, by ellipsometry and by fabricating and testing diode structures. Results indicate that the films are of a largely amorphous nature and are semiconducting. Diode structures have on/off current ratios of up to 106.

The use of C-V techniques to investigate instability mechanisms in M-I-S structures

In the field of flat panel displays, the current leading technology is the Active Matrix liquid Crystal Display; this uses a-Si:H based thin film transistors (TFTs) as the switching element in each pixel. However, under gate bias a-Si:H TFTs suffer from instability, as is evidenced by a shift in the gate threshold voltage. The shift in the gate threshold voltage is generally measured from the gate transfer characteristics, after subjecting the TFT to prolonged gate bias. However, a major drawback of this measurement method is that it cannot distinguish whether the shift is caused by the change in the midgap states in the a-Si:H channel or by charge trapping in the gate insulator. In view of this, we have developed a capacitance-voltage (C-V) method to measure the shift in threshold voltage. We employ Metal-Insulator-Semiconductor (MIS) structures to investigate the threshold voltage shift as they are simpler to fabricate than TFTs. We have investigated a large of number Metal/a-Si:H/Si3N4/Si+n structures using our C-V technique. From, the C-V data for the MIS structures, we have found that the relationship between the thermal energy and threshold voltage shift is similar to that reported by Wehrspohn et. al in a-Si:H TFTs (J Appl. Phys, 144, 87, 2000). The a-Si:H and Si3N4 layers were grown using the radio-frequency plasma-enhanced chemical vapour deposition technique.

Hierarchical electrohydrodynamic structures for surface-enhanced Raman scattering.

Surface enhanced Raman scattering (SERS) is a well-established spectroscopic technique that requires nanoscale metal structures to achieve high signal sensitivity. While most SERS substrates are manufactured by conventional lithographic methods, the development of a cost-effective approach to create nanostructured surfaces is a much sought-after goal in the SERS community. Here, a method is established to create controlled, self-organized, hierarchical nanostructures using electrohydrodynamic (HEHD) instabilities. The created structures are readily fine-tuned, which is an important requirement for optimizing SERS to obtain the highest enhancements. HEHD pattern formation enables the fabrication of multiscale 3D structured arrays as SERS-active platforms. Importantly, each of the HEHD-patterned individual structural units yield a considerable SERS enhancement. This enables each single unit to function as an isolated sensor. Each of the formed structures can be effectively tuned and tailored to provide high SERS enhancement, while arising from different HEHD morphologies. The HEHD fabrication of sub-micrometer architectures is straightforward and robust, providing an elegant route for high-throughput biological and chemical sensing.

Co-catalytic absorption layers for controlled laser-induced chemical vapor deposition of carbon nanotubes.

The concept of co-catalytic layer structures for controlled laser-induced chemical vapor deposition of carbon nanotubes is established, in which a thin Ta support layer chemically aids the initial Fe catalyst reduction. This enables a significant reduction in laser power, preventing detrimental positive optical feedback and allowing improved growth control. Systematic study of experimental parameters combined with simple thermostatic modeling establishes general guidelines for the effective design of such catalyst/absorption layer combinations. Local growth of vertically aligned carbon nanotube forests directly on flexible polyimide substrates is demonstrated, opening up new routes for nanodevice design and fabrication.