Charge selective contacts, mobile ions and anomalous hysteresis in organic-inorganic perovskite solar cells
Materials Horizons Royal Society of Chemistry 2:3 (2015) 315-322
Abstract:
High-efficiency perovskite solar cells typically employ an organic–inorganic metal halide perovskite material as light absorber and charge transporter, sandwiched between a p-type electron-blocking organic hole-transporting layer and an n-type hole-blocking electron collection titania compact layer. Some device configurations also include a thin mesoporous layer of TiO2 or Al2O3 which is infiltrated and capped with the perovskite absorber. Herein, we demonstrate that it is possible to fabricate planar and mesoporous perovskite solar cells devoid of an electron selective hole-blocking titania compact layer, which momentarily exhibit power conversion efficiencies (PCEs) of over 13%. This performance is however not sustained and is related to the previously observed anomalous hysteresis in perovskite solar cells. The “compact layer-free” meso-superstructured perovskite devices yield a stabilised PCE of only 2.7% while the compact layer-free planar heterojunction devices display no measurable steady state power output when devoid of an electron selective contact. In contrast, devices including the titania compact layer exhibit stabilised efficiency close to that derived from the current voltage measurements. We propose that under forward bias the perovskite diode becomes polarised, providing a beneficial field, allowing accumulation of positive and negative space charge near the contacts, which enables more efficient charge extraction. This provides the required built-in potential and selective charge extraction at each contact to temporarily enable efficient operation of the perovskite solar cells even in the absence of charge selective n- and p-type contact layers. The polarisation of the material is consistent with long range migration and accumulation of ionic species within the perovskite to the regions near the contacts. When the external field is reduced under working conditions, the ions can slowly diffuse away from the contacts redistributing throughout the film, reducing the field asymmetry and the effectiveness of the operation of the solar cells. We note that in light of recent publications showing high efficiency in devices devoid of charge selective contacts, this work reaffirms the absolute necessity to measure and report the stabilised power output under load when characterizing perovskite solar cells.Structure-directed exciton dynamics in templated molecular nanorings
journal of physical chemistry. C, Nanomaterials and interfaces American Chemical Society 119:11 (2015) 6414-6420
Abstract:
Conjugated polymers with cyclic structures are interesting because their symmetry leads to unique electronic properties. Recent advances in Vernier templating now allow large shape-persistent fully conjugated porphyrin nanorings to be synthesized, exhibiting unique electronic properties. We examine the impact of different conformations on exciton delocalization and emission depolarization in a range of different porphyrin nanoring topologies with comparable spatial extent. Low photoluminescence anisotropy values are found to occur within the first few hundred femtoseconds after pulsed excitation, suggesting ultrafast delocalization of excitons across the nanoring structures. Molecular dynamics simulations show that further polarization memory loss is caused by out-of-plane distortions associated with twisting and bending of the templated nanoring topologies.Ultrafast delocalization of excitation in synthetic light-harvesting nanorings
Chemical Science Royal Society of Chemistry 6:1 (2015) 181-189
Abstract:
Rings of chlorophyll molecules harvest sunlight remarkably efficiently during photosynthesis in purple bacteria. The key to their efficiency lies in their highly delocalized excited states that allow for ultrafast energy migration. Here we show that a family of synthetic nanorings mimic the ultrafast energy transfer and delocalization observed in nature. π-Conjugated nanorings with diameters of up to 10 nm, consisting of up to 24 porphyrin units, are found to exhibit excitation delocalization within the first 200 fs of light absorption. Transitions from the first singlet excited state of the circular nanorings are dipole-forbidden as a result of symmetry constraints, but these selection rules can be lifted through static and dynamic distortions of the rings. The increase in the radiative emission rate in the larger nanorings correlates with an increase in static disorder expected from Monte Carlo simulations. For highly symmetric rings, the radiative rate is found to increase with increasing temperature. Although this type of thermally activated superradiance has been theoretically predicted in circular chromophore arrays, it has not previously been observed in any natural or synthetic systems. As expected, the activation energy for emission increases when a nanoring is fixed in a circular conformation by coordination to a radial template. These nanorings offer extended chromophores with high excitation delocalization that is remarkably stable against thermally induced disorder. Such findings open new opportunities for exploring coherence effects in nanometer molecular rings and for implementing these biomimetic light-harvesters in man-made devices. This journal isUltrafast transient terahertz conductivity of monolayer MoS₂ and WSe₂ grown by chemical vapor deposition
ACS nano American Chemical Society 8:11 (2014) 11147-11153
Abstract:
We have measured ultrafast charge carrier dynamics in monolayers and trilayers of the transition metal dichalcogenides MoS2 and WSe2 using a combination of time-resolved photoluminescence and terahertz spectroscopy. We recorded a photoconductivity and photoluminescence response time of just 350 fs from CVD-grown monolayer MoS2, and 1 ps from trilayer MoS2 and monolayer WSe2. Our results indicate the potential of these materials as high-speed optoelectronic materials.Electron mobilities approaching bulk limits in "surface-free" GaAs nanowires.
Nano letters American Chemical Society 14:10 (2014) 5989-5994