Optimizing the energy offset between dye and hole-transporting material in solid-state dye-sensitized solar cells

The power-conversion efficiency of solid-state dye-sensitized solar cells can be optimized by reducing the energy offset between the highest occupied molecular orbital (HOMO) levels of dye and hole-transporting material (HTM) to minimize the loss-in-potential. Here, we report a study of three novel HTMs with HOMO levels slightly above and below the one of the commonly used HTM 2,2′,7,7′- tetrakis(N,N-di-p-methoxyphenylamino)-9,9′- spirobifluorene (spiro-OMeTAD) to systematically explore this possibility. Using transient absorption spectroscopy and employing the ruthenium based dye Z907 as sensitizer, it is shown that, despite one new HTM showing a 100% hole-transfer yield, all devices based on the new HTMs performed worse than those incorporating spiro-OMeTAD. We further demonstrate that the design of the HTM has an additional impact on the electronic density of states present at the TiO2 electrode surface and hence influences not only hole- but also electron-transfer from the sensitizer. These results provide insight into the complex influence of the HTM on charge transfer and provide guidance for the molecular design of new materials. © 2013 American Chemical Society.

Dependence of dye regeneration and charge collection on the pore-filling fraction in solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells rely on effective infiltration of a solid-state hole-transporting material into the pores of a nanoporous TiO 2 network to allow for dye regeneration and hole extraction. Using microsecond transient absorption spectroscopy and femtosecond photoluminescence upconversion spectroscopy, the hole-transfer yield from the dye to the hole-transporting material 2,2′,7,7′-tetrakis(N,N-di-p- methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) is shown to rise rapidly with higher pore-filling fractions as the dye-coated pore surface is increasingly covered with hole-transporting material. Once a pore-filling fraction of ≈30% is reached, further increases do not significantly change the hole-transfer yield. Using simple models of infiltration of spiro-OMeTAD into the TiO2 porous network, it is shown that this pore-filling fraction is less than the amount required to cover the dye surface with at least a single layer of hole-transporting material, suggesting that charge diffusion through the dye monolayer network precedes transfer to the hole-transporting material. Comparison of these results with device parameters shows that improvements of the power-conversion efficiency beyond ≈30% pore filling are not caused by a higher hole-transfer yield, but by a higher charge-collection efficiency, which is found to occur in steps. The observed sharp onsets in photocurrent and power-conversion efficiencies with increasing pore-filling fraction correlate well with percolation theory, predicting the points of cohesive pathway formation in successive spiro-OMeTAD layers adhered to the pore walls. From percolation theory it is predicted that, for standard mesoporous TiO2 with 20 nm pore size, the photocurrent should show no further improvement beyond an ≈83% pore-filling fraction. Solid-state dye-sensitized solar cells capable of complete hole transfer with pore-filling fractions as low as ∼30% are demonstrated. Improvements of device efficiencies beyond ∼30% are explained by a stepwise increase in charge-collection efficiency in agreement with percolation theory. Furthermore, it is predicted that, for a 20 nm pore size, the photocurrent reaches a maximum at ∼83% pore-filling fraction. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The plastic collapse and energy absorption capacity of egg-box panels

The plastic collapse response of aluminium egg-box panels subjected to out-of-plane compression has been measured and modelled. It is observed that the collapse strength and energy absorption are sensitive to the level of in-plane constraint, with collapse dictated either by plastic buckling or by a travelling plastic knuckle mechanism. Drop weight tests have been performed at speeds of up to 6 m s-1, and an elevation in strength with impact velocity is noted. A 3D finite element shell model is needed in order to reproduce the observed behaviours. Additional calculations using an axisymmetric finite element model give the correct collapse modes but are less accurate than the more sophisticated 3D model. The finite element simulations suggest that the observed velocity dependence of strength is primarily due to strain-rate sensitivity of the aluminium sheet, with material inertia playing a negligible role. Finally, it is shown that the energy absorption capacity of the egg-box material is comparable to that of metallic foams. © 2003 Elsevier Ltd. All rights reserved.

Transient natural ventilation of a space with localised heating

The natural ventilation of a well-mixed, pre-heated room with a point source of heating, and openings at the base and roof is investigated. The transient draining associated with the room being warmer than the exterior combined with the convective ow produced by the point source of heat leads to a fascinating series of transient ow regimes as the system evolves to the two-layer steady-state regime described by Linden, Lane-Ser_ and Smeed [1]. As the room begins to ventilate, a turbulent plume rises from the point source of heat to the ceiling, and typically forms a deepening layer of hot air. However, with a weak heat source, then at some point the ascending plume will intrude beneath the layer of original uid. Otherwise, the ascending plume always reaches the top of the room as the system evolves to a steady state. We develop a simpli_ed model of the transient evolution and test this with some new laboratory experiments. We conclude with a discussion of the implications of our results for real buildings.

Transient Ventilation Dynamics Following a Change in Strength of a Point Source of Heat

We investigate the transient ventilation flow within a confined ventilated space, with high- and low-level openings, when the strength of a low-level point source of heat is changed instantaneously. The steady-flow regime in the space involves a turbulent buoyant plume, which rises from the point source to a well-mixed warm upper layer. The steady-state height of the interface between this layer and the lower layer of exterior fluid is independent of the heat flux, but the upper layer becomes progressively warmer with heat flux. New analogue laboratory experiments of the transient adjustment between steady states identify that if the heat flux is increased, the continuing plume propagates to the top of the room forming a new, warmer layer. This layer gradually deepens, and as the turbulent plume entrains fluid from the original warm layer, the original layer is gradually depleted and disappears, and a new steady state is established. In contrast, if the source buoyancy flux is decreased, the continuing plume is cooler than the original plume, so that on reaching the interface it is of intermediate density between the original warm layer and the external fluid. The plume supplies a new intermediate layer, which gradually deepens with the continuing flow. In turn, the original upper layer becomes depleted, both as a result of being vented through the upper opening of the space, but also due to some penetrative entrainment of this layer by the plume, as the plume overshoots the interface before falling back to supply the new intermediate layer. We develop quantitative models which are in good accord with our experimental data, by combining classical plume theory with models of the penetrative entrainment for the case of a decrease in heating. Typically, we find that the effect of penetrative entrainment on the density of the intruding layer is relatively weak, provided the change in source strength is sufficiently large. However, penetrative entrainment measurably increases the rate at which the depth of the draining layer decreases. We conclude with a discussion of the importance of these results for the control of naturally ventilated spaces.

Transient Natural Ventilation of a Room with a Distributed Heat Source

We report on an experimental and theoretical study of the transient flows which develop as a naturally ventilated room adjusts from one temperature to another. We focus on a room heated from below by a uniform heat source, with both high- and low-level ventilation openings. Depending on the initial temperature of the room relative to (i) the final equilibrium temperature and (ii) the exterior temperature, three different modes of ventilation may develop. First, if the room temperature lies between the exterior and the equilibrium temperature, the interior remains well-mixed and gradually heats up to the equilibrium temperature. Secondly, if the room is initially warmer than the equilibrium temperature, then a thermal stratification develops in which the upper layer of originally hot air is displaced upwards by a lower layer of relatively cool inflowing air. At the interface, some mixing occurs owing to the effects of penetrative convection. Thirdly, if the room is initially cooler than the exterior, then on opening the vents, the original air is displaced downwards and a layer of ambient air deepens from above. As this lower layer drains, it is eventually heated to the ambient temperature, and is then able to mix into the overlying layer of external air, and the room becomes well-mixed. For each case, we present new laboratory experiments and compare these with some new quantitative models of the transient flows. We conclude by considering the implications of our work for natural ventilation of large auditoria.

Carbon onions: Carriers of the 217.5 nm interstellar absorption feature

The UV-VIS characteristics of carbon ions fabricated by an arch discharge in water or liquid nitrogen show characteristics that are similar to the interstellar absorption feature. Thus, high purity and well separated carbon onion samples prepared by annealing the as-fabricated powder in air at 600°C for 60 showed a constant absorption peak at 4.6 μm-1 with a variable width ranging from 1.2-1.6 μm-1. In addition to the UV-VIS data, the origin of the absorption feature at 4.6 μm-1 in carbon onions can be attributed to the collective excitations of π plasmons.