Agnese Abrusci

Dual electron donor/electron acceptor character of a conjugated polymer in efficient photovoltaic diodes

The authors report efficient photovoltaic diodes which use poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl) (F8TBT) both as electron acceptor, in blends with poly(3-hexylthiophene), and as hole acceptor, in blends with (6,6)-phenyl C61-butyric acid methyl ester. In both cases external quantum efficiencies of over 25% are achieved, with a power conversion efficiency of 1.8% under simulated sunlight for optimized F8TBT/poly(3-hexylthiophene) devices. The ambipolar nature of F8TBT is also demonstrated by the operation of light-emitting F8TBT transistors. The equivalent p- and n-type operation in this conjugated polymer represent an important extension of the range of useful n-type materials which may be developed.

Facile infiltration of semiconducting polymer into mesoporous electrodes for hybrid solar cells

Hybrid composites of semiconducting polymers and metal oxides are promising combinations for solar cells. However, forming a well-controlled nanostructure with bicontinuous interpenetrating networks throughout the photoactive film is difficult to achieve. Pre-structured “mesoporous” metal oxide electrodes can act as a well-defined template for latter polymer infiltration. However, the long range infiltration of polymer chains into contorted porous channels has appeared to elude the scientific community, limiting the advancement of this technology. Here we present a structural and electronic characterisation of poly(3-hexylthiophene) (P3HT) infiltrated into mesoporous dye-sensitized TiO2. Through a combination of techniques we achieve uniform pore filling of P3HT up to depths of over 4 μm, but the volumetric fraction of the pores filled with polymer is less than 24%. Despite this low pore-filling, exceptionally efficient charge collection is demonstrated, illustrating that pore filling is not the critical issue for mesoporous hybrid solar cells.

Hyperbranched quasi-1D nanostructures for solid-state dye-sensitized solar cells.

In this work we demonstrate hyperbranched nanostructures, grown by pulsed laser deposition, composed of one-dimensional anatase single crystals assembled in arrays of high aspect ratio hierarchical mesostructures. The proposed growth mechanism relies on a two-step process: self-assembly from the gas phase of amorphous TiO2 clusters in a forest of tree-shaped hierarchical mesostructures with high aspect ratio; oriented crystallization of the branches upon thermal treatment. Structural and morphological characteristics can be optimized to achieve both high specific surface area for optimal dye uptake and broadband light scattering thanks to the microscopic feature size. Solid-state dye sensitized solar cells fabricated with arrays of hyperbranched TiO2 nanostructures on FTO-glass sensitized with D102 dye showed a significant 66% increase in efficiency with respect to a reference mesoporous photoanode and reached a maximum efficiency of 3.96% (among the highest reported for this system). This result was achieved mainly thanks to an increase in photogenerated current directly resulting from improved light harvesting efficiency of the hierarchical photoanode. The proposed photoanode overcomes typical limitations of 1D TiO2 nanostructures applied to ss-DSC and emerges as a promising foundation for next-generation high-efficiency solid-state devices comprosed of dyes, polymers, or quantum dots as sensitizers.

Trap-Induced Losses in Hybrid Photovoltaics

We investigate the loss mechanisms in hybrid photovoltaics based on blends of poly(3-hexylthiophene) with CdSe nanocrystals of various sizes. By combining the spectroscopic and electrical measurements on working devices as well as films, we identify that high trap-mediated recombination is responsible for the loss of photogenerated charge carriers in devices with small nanocrystals. In addition, we demonstrate that the reduced open-circuit voltage for devices with small nanocrystals is also caused by the traps.

The effect of selective interactions at the interface of polymer–oxide hybrid solar cells

The working mechanisms of excitonic solar cells are strongly dominated by interface processes, which influence the final device efficiency. However, it is still very challenging to clearly track the effects of inter-molecular processes at a mesoscopic level. We report on the realization of polymer-based hybrid solar cells made of prototypical materials, namely, poly(3-hexylthiophene) (P3HT) finely infiltrated in a TiO2 scaffold, with power conversion efficiency exceeding 1%. A step-change improvement in the device performance is enabled by engineering the hybrid interface by the insertion of an appropriate molecular interlayer. An unprecedented set of characterization techniques, including time-resolved optical spectroscopy, X-ray photoemission spectroscopy, positron annihilation spectroscopy and atomistic simulations, allows us to rationalize our findings. We show that a suitable chemical structure of the interlayer molecule induces selective intermolecular interactions, and thus a preferential surface energetic landscape and morphological order at the interface which consequently drives a strong improvement in charge generation and a decrease in recombination losses.

Effect of polymer morphology on P3HT-based solid-state dye sensitized solar cells: an ultrafast spectroscopic investigation

Solid-state dye sensitized solar cell devices are fabricated with poly(3-hexylthiophene) (P3HT) as the hole transporting layer. Upon annealing treatment we obtained ≈ 70% increase in the device efficiency compared to un-annealed devices. Our investigation, by means of ultrafast transient absorption spectroscopic characterization, correlates the increased device performances to a more efficient hole-transfer at the dye/polymer interface in the thermally treated P3HT.

Multiscale simulation of solid state dye sensitized solar cells including morphology effects

In this work we present a multiscale simulation of a solid state dye sensitized solar cell including the real morphology of the active layer. In order to include the real morphology the device domain is split into two different regions: one treated using an effective material approximation and another one using the real structure of the blend. The real morphology has been measured using electron tomography to reconstruct the mesoporous TiO2. The geometry was inserted into a mesher and used to solve a drift-diffusion model using finite element method. The simulation is used to cast light over morphology effects in solid state dye solar cells.

Quantitative electron tomography investigation of a TiO2 based solar cell photoanode

The development of efficient thin film solar cells requires a deep knowledge of the nanoscale morphology of the active layers. While conventional investigation is usually limited to 2D information, here we use electron tomography to unravel a complex particle network in a non-ambiguous, 3D reconstruction. We present our study of a dye sensitised solar cell, based on a nanostructured TiO2 photoanode produced by pulsed laser deposition (PLD) and displaying a hierarchical, quasi-1D arrangement. We prepare the sample for electron tomography using focused ion beam (FIB) milling to obtain a micro-pillar, instead of a conventional TEM lamella. This approach has the advantage of allowing higher quality tomographic reconstructions of complex morphologies due to the increased tilt range available and the constant thickness of the section. We analyse the resulting reconstruction to quantitatively investigate the geometry of the TiO2 network. We compare the findings with a photoanode based on a conventional TiO2 paste, determining the anisotropy of the PLD-grown film. To complement our nanoscale TEM characterization, we also employ FIB tomography, to obtain a complete structural characterisation of the photoanode at different length scales.