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Substoichiometric molybdenum oxide (MoOx) has good potential as a hole-collecting layer in solar cells. In this paper, we report on the application of ultrathin evaporated MoOx as a hole collector at the back side of two distinct photovoltaic technologies: polymeric and silicon heterojunction (SHJ). In the case of polymer solar cells, we test MoOx as a hole transport layer in devices with inverted architecture. The higher transparency of the MoOx film, compared to the commonly used poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), allows an enhanced back reflected light into the photoactive layer, thus boosting the photogeneration, as found from the illuminated J-V and external quantum efficiency (EQE) curves. The higher fill factor (FF) of the MoOx-based device also suggests an improved charge collection efficiency compared to the cells with PEDOT:PSS. As for SHJ solar cells, we show that MoOx offers the means for dopant-free hole collection with both p-type and n-type Si wafers. In the present comparison over planar test structures with Ag back reflecting electrodes, we observe an efficiency gain of approximately 1% absolute against a baseline with a conventional p-type amorphous silicon hole collector. The gain is linked to the increased VOC, which is likely due to the reduced recombination at the Si wafer.

The relationships between the structure and the viscoelastic properties of freeze/thaw PVA hydrogels obtained by repeatedly freezing and thawing dilute solutions of PVA in D 2 O(11% w/w PVA) in as-prepared and rehydrated states are investigated. Our results indicate that the PVA chains and solvent molecules are organized at different hierarchical length scales, which include the presence of micro-and macro-pores, into a network scaffolding. The porous network is ensured by the presence of crystallites, which act as knots interconnected by portions of PVA chains swollen by the solvent. X-ray diffraction and SANS techniques are used to obtain structural information at short (angstroms) and medium (nanometers) ranges of length scales, concerning the crystallinity, the size of small crystalline aggregates and the average distance between crystallites in PVA hydrogels. Indirect information concerning the structural organization on the large length scales (microns) are provided by viscoelastic measurements. The dynamic shear elastic moduli at low frequency and low strain amplitude, G', are determined and related to the degree of crystallinity. These data indicate that a minimum crystallinity of 1% is required for these PVA samples to exhibit gel behaviour and have allowed obtaining the order of magnitude of the average mesh size in these gels. Finally, it is shown that the negative effect of aging, inducing worse physical and mechanical properties in these systems, may be prevented using a drying/re-hydration protocol able to keep the physical properties of the as-prepared PVA hydrogels.

The structure and rheological behavior of atactic poly(vinyl alcohol) (a-PVA) hydrogels prepared by freeze/thaw cycles were investigated as a function of polymer concentration and number of freeze/thaw cycles. The presence of phases with different mobilities was observed using 13 C CP/MAS and DP/MAS NMR experiments. The degree of crystallinity of the a-PVA-rich phase was determined by 1 H NMR free decay experiments. Measurements of the shear storage and loss modulus were performed at a fixed frequency of 1 Hz and a strain value of 0.1%, i.e. under conditions where the deformation imposed on the gel structure is entirely reversible. Results thus obtained showed that an increase in the number of freeze/thaw cycles induces an increase in the degree of crystallinity in the polymer-rich phase together with an increase in the storage modulus. The a-PVA hydrogels became more fragile as the number of freeze/thaw cycles was increased. Moreover, both the percentage of protons in a rigid environment measured by 1 H NMR and the storage modulus values tended to a limiting value after six freeze/thaw cycles. These results show that the first five or six freeze/thaw cycles play a very important role in determining the hydrogel structure and rheological properties. A more detailed comparison of NMR and rheological data led to the conclusion that the storage modulus is mainly controlled by the a-PVA crystallinity while the hydrogen bond interactions have a much smaller contribution.