Meysam Pazoki

Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells

Lead halide perovskites have attracted considerable interest as photoabsorbers in PV-applications over the last few years. The most studied perovskite material achieving high photovoltaic performance has been methyl ammonium lead iodide, CH3NH3PbI3. Recently the highest solar cell efficiencies have, however, been achieved with mixed perovskites where iodide and methyl ammonium partially have been replaced by bromide and formamidinium. In this work, the mixed perovskites were explored in a systematic way by manufacturing devices where both iodide and methyl ammonium were gradually replaced by bromide and formamidinium. The absorption and the emission behavior as well as the crystallographic properties were explored for the perovskites in this compositional space. The band gaps as well as the crystallographic structures were extracted. Small changes in the composition of the perovskite were found to have a large impact on the properties of the materials and the device performance. In the investigated compositional space, cell efficiencies, for example, vary from a few percent up to 20.7%. From the perspective of applications, exchanging iodide with bromide is especially interesting as it allows tuning of the band gap from 1.5 to 2.3 eV. This is highly beneficial for tandem applications, and an empirical expression for the band gap as a function of composition was determined. Exchanging a small amount of iodide with bromide is found to be highly beneficial, whereas a larger amount of bromide in the perovskite was found to cause intense sub band gap photoemission with detrimental results for the device performance. This could be caused by the formation of a small amount of an iodide rich phase with a lower band gap, even though such a phase was not observed in diffraction experiments. This shows that stabilizing the mixed perovskites will be an important task in order to get the bromide rich perovskites, which has a higher band gap, to reach the same high performance obtained with the best compositions.

The effect of dye coverage on the performance of dye-sensitized solar cells with a cobalt-based electrolyte

The effect of dye coverage of the mesoporous TiO2 electrode on the performance of dye-sensitized solar cells based on the cobalt tris(bipyridine) electrolyte and the D35 dye was studied in detail. The dye coverage was controlled by using a dye bath with different dye concentrations and containing an inert salt, LiClO4, which was found to promote equilibrium conditions in the dye adsorption process. The amount of adsorbed D35 dye on mesoporous TiO2 was reasonably fit using the Langmuir adsorption isotherm, with a binding constant of 55 000 M(-1). Upon increasing the dye coverage on the TiO2 electrode, the electron lifetime in the dye-sensitized solar cell increased remarkably, demonstrating the blocking behavior of the D35 dye at the TiO2-electrolyte interface. Consequently, the solar cell efficiency increased dramatically with the D35 dye coverage.

Understanding interfacial charge transfer between metallic PEDOT counter electrodes and a cobalt redox shuttle in dye-sensitized solar cells

Conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with iron(III) tris-p-toluenesulfonate (PEDOT:Tos) having metallic conductivity was coated onto fluorine-doped tin oxide (FTO) glass and plain glass substrates and used as a counter electrode (CE) in a dye-sensitized solar cell (DSC) with a [Co(bpy)3](3+/2+) complex redox shuttle. DSCs with PEDOT:Tos/glass CE yielded power conversion efficiencies (PCE) of 6.3%, similar to that of DSCs with platinized FTO glass CE (6.1%). The PEDOT:Tos-based counter electrodes had 5 to 10 times lower charge-transfer resistance than the Pt/FTO CE in DSCs, as analyzed by impedance spectroscopy. More detailed studies in symmetrical CE-CE cells showed that the PEDOT:Tos layers are nanoporous. Not all internal area can be used catalytically under solar cell conditions and effective charge-transfer resistance was similar to that of Pt/FTO.

Characterization techniques for dye-sensitized solar cells

Dye-sensitized solar cells (DSCs) have been widely studied in the last two decades and start to be commercialized in the photovoltaic market. Comprehensive characterization is needed to fully understand and optimize the device performance and stability. In this review, we summarize different characterization methods for dye-sensitized solar cells with liquid redox electrolytes or solid state hole transporting materials, most of which can also be used for similar devices such as perovskite based thin film solar cells. Limitations and advantages of relevant methods for studying the energy levels and time scales involved in charge transfer processes as well as charge transport related characteristic lengths are discussed. A summary of recent developments in DSCs and the importance of measured parameters for the device optimization procedure are mentioned at the end.

Probing Photocurrent Generation, Charge Transport, and Recombination Mechanisms in Mesostructured Hybrid Perovskite through Photoconductivity Measurements

Conductivity of methylammonium lead triiodide (MAPbI3) perovskite was measured on different mesoporous metal oxide scaffolds: TiO2, Al2O3, and ZrO2, as a function of incident light irradiation and temperature. It was found that MAPbI3 exhibits intrinsic charge separation, and its conductivity stems from a majority of free charge carriers. The crystal morphology of the MAPbI3 was found to significantly affect the photoconductivity, whereas in the dark the conductivity is governed by the perovskite in the pores of the mesoporous scaffold. The temperature-dependent conductivity measurements also indicate the presence of states within the band gap of the perovskite. Despite a relatively large amount of crystal defects in the measured material, the main recombination mechanism of the photogenerated charges is bimolecular (band-to-band), which suggests that the defect states are rather inactive in the recombination. This may explain the remarkable efficiencies obtained for perovskite solar cells prepared with wet-chemical methods.

Multifunctional Gadolinium‐Doped Mesoporous TiO2 Nanobeads: Photoluminescence, Enhanced Spin Relaxation, and Reactive Oxygen Species Photogeneration, Beneficial for Cancer Diagnosis and Treatment

Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO2 sub-micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd-doped TiO2 exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin-lattice and spin-spin relaxation times. Density functional theory calculations show that Gd3+ ions introduce impurity energy levels inside the bandgap of anatase TiO2 , and also create dipoles that are beneficial for charge separation and decreased electron-hole recombination in the doped lattice. The Gd-doped TiO2 nanobeads (NBs) show enhanced ability for ROS monitored via • OH radical photogeneration, in comparison with undoped TiO2 nanobeads and TiO2 P25, for Gd-doping up to 10%. Cellular internalization and biocompatibility of TiO2 @xGd NBs are tested in vitro on MG-63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation.

Photoinduced Stark Effects and Mechanism of Ion Displacement in Perovskite Solar Cell Materials

Organometallic halide perovskites (OMHPs) have recently emerged as a promising class of materials in photovoltaic technology. Here, we present an in-depth investigation of the physics in these systems by measuring the photoinduced absorption (PIA) in OMHPs as a function of materials composition, excitation wavelength, and modulation frequency. We report a photoinduced Stark effect that depends on the excitation wavelength and on the dipole strength of the monovalent cations in the A position of the ABX3 perovskite. The results presented are corroborated by density functional theory calculations and provide fundamental information about the photoinduced local electric field change under blue and red excitation as well as insights into the mechanism of light-induced ion displacement in OMHPs. For optimized perovskite solar cell devices beyond 19% efficiency, we show that excess thermalization energy of blue photons plays a role in overcoming the activation energy for ion diffusion.

Combined cytotoxic effect of UV-irradiation and TiO2 microbeads in normal urothelial cells, low-grade and high-grade urothelial cancer cells

The differentiation of urothelial cells results in normal terminally differentiated cells or by alternative pathways in low-grade or high-grade urothelial carcinomas. Treatments with traditional surgical and chemotherapeutical approaches are still inadequate and expensive, as bladder tumours are generally highly recurrent. In such situations, alternative approaches, using irradiation of the cells and nanoparticles, are promising. The ways in which urothelial cells, at different differentiation levels, respond to UV-irradiation (photolytic treatment) or to the combination of UV-irradiation and nanoparticles (photocatalytic treatment), are unknown. Here we tested cytotoxicity of UV-irradiation on (i) normal porcine urothelial cells (NPU), (ii) human low-grade urothelial cancer cells (RT4), and (iii) human high-grade urothelial cancer cells (T24). The results have shown that 1 minute of UV-irradiation is enough to kill 90% of the cells in NPU and RT4 cultures, as determined by the live/dead viability assay. On the other hand, the majority of T24 cells survived 1 minute of UV-irradiation. Moreover, even a prolonged UV-irradiation for 30 minutes killed <50% of T24 cells. When T24 cells were pre-supplemented with mesoporous TiO2 microbeads and then UV-irradiated, the viability of these high-grade urothelial cancer cells was reduced to <10%, which points to the highly efficient cytotoxic effects of TiO2 photocatalysis. Using electron microscopy, we confirmed that the mesoporous TiO2 microbeads were internalized into T24 cells, and that the cells ultrastructure was heavily compromised after UV-irradiation. In conclusion, our results show major differences in the sensitivity to UV-irradiation among the urothelial cells with respect to cell differentiation. To achieve an increased cytotoxicity of urothelial cancer cells, the photocatalytic approach is recommended.

Mesoporous TiO2 microbead electrodes for solid state dye-sensitized solar cells

Mesoporous TiO2 microbead films have been investigated as working electrodes for solid state dye sensitized solar cells and 3.5% efficiency was achieved for 4 micrometer thick films under 1 sun illumination. Compared to conventional mesoporous solar cells, microbead films have higher porosity, increased open circuit voltage, lower fill factor and current density, faster transport time and lower electron lifetime. Cross sectional scanning electron microscopy results show that the pore filling of a solid hole conductor (spiro-OMeTAD) inside the entire mesoporous bead film is very good even for 4 micrometer thick films. The high porosity of the microbead film allows good penetration of spiro in thick films, while its high surface area ensures good dye coverage. X-ray photoelectron spectroscopy data reveals a lower density of intra-bandgap trap states for microbead films compared to conventional mesoporous TiO2 films, which could be in part responsible for faster transport of electrons and higher voltage in microbead films. Optimization of microbead films for solid state dye sensitized solar cells can be an interesting possibility for highly efficient and relatively thick film solid state solar cells.

Ab initio study of electronic effects in the ZnO/TiO2 core/shell interface: application in dye sensitized solar cells

Core/shell structure of ZnO nanowires coated with a monolayer of TiO2 is investigated using Density Functional Theory (DFT). The electronic states of the semiconductor is calculated and compared before and after coating of the TiO2 monolayer on a ZnO [10 0] surface. The effect of TiO2 coating induce surface states changes and shifts the conduction and valence band edges to higher energies. Our results, in qualitative agreement with the experimental work of Matt Law et al. (J. Phys. Chem. B, 110, 22652), show an increase in open circuit voltage and a decrease in short circuit current in ZnO/TiO2 core shell dye sensitized solar cells. Regarding the semiconductor density of states (DOS), TiO2 coated ZnO have more conduction band acceptor states and lower electronic back recombination in agreement with experimental results. Surface dipoles are attributed to changes of the local density of states of the surface. This method can be used for more investigation of starting effects of semiconductor interface and helps the study of surface states and their physical origin in dye sensitized solar cells.