Interface Play between Perovskite and Hole Selective Layer on the Performance and Stability of Perovskite Solar Cells

Perovskite solar cells with variety of hole selective contacts such as 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD), poly(3-hexylthiophene-2,5-diyl), poly[bis(4-phenyl)(2,5,6-trimentlyphenyl)amine], 5,10,15-trihexyl-3,8,13-tris (4-methoxyphenyl) -10,15-dihydro-SH-diindolo [3,2-a:3',2'-c]carbazole (HMPDI), and 2',7'-bis(bis(4-methoxyphenyl)-amino)spiro [cyclopenta[2,1-b:3,4-b']dithiophene-4,9'-fluorene] were employed to elucidate its role at the interface of perovskite and metallic cathode. Microscopy images revealed Spiro-OMeTAD and HMPDI produce smoother and intimate contact between perovskite/hole transporting materials (HTM) interfaces among others evaluated here. This morphological feature appears to be connected with three fiindamental facts: (1) hole injection to the HTM is much more efficient as evidenced by photoluminescence measurements, (2) recombination losses are less important as evidenced by intensity-modulated photovoltage spectroscopy and impedance spectroscopy measurements, and (3) fabricated solar cells are much more robust against degradation by moisture. Devices with higher open-circuit photovoltages are characterized by higher values of the recombination resistance extracted from the impedance data. The variation in device hysteresis behavior can be ascribed mainly due to the molecular interaction and the core of HTM employed. In all cases, this fact is related with a larger value of the low-frequency capacitance, which indicates that the HTM can induce specific slow processes of ion accumulation at the interface. Notably, these processes tend to slowly relax in time, as hysteresis is substantially reduced for aged devices

Highly efficient flexible cathodes for dye sensitized solar cells to complement Pt@TCO coatings

Solution-processed, semi-transparent, conductive electrodes based on PEDOT: PSS [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)] using silver grids were developed on a plastic support. The flexible electrode (flextrode) was employed as a cathode in dye sensitized solar cells (DSSCs) and acts in two-fold manner: the PEDOT layer will yield a high surface area for effective electrocatalysis, while the silver grid will decrease the series resistance to rival transparent conducting oxide (TCO) coatings. DSSCs fabricated with Y123 dye and the developed cathodes show power conversion efficiencies of 7%, which are comparable to the reference device (6.9%) using Pt@FTO (F-doped SnO2) coatings on glass under the same conditions. A flexible and cost effective electrode will help to penetrate the market for DSSCs and hybrid-organic-inorganic photovoltaics. Electrochemical impedance spectroscopy and modelling results confirm similar values of the series resistance and charge transfer resistance of the cathodes both in Pt-based and PEDOT-based cells, as well as the limited impact on the I-V curve from the modification of the charge transfer parameters in the PEDOT-based cells

Effect of different photoanode nanostructures on the initial charge separation and electron injection process in dye sensitized solar cells: a photophysical study with indoline dyes

Ultrafast and fast charge separation processes were investigated for complete cells based on several ZnO-based photoanode nanostructures and standard TiO2 nanoparticle layers sensitized with the indoline dye coded D358. Different ZnO morphologies (nanoparticles, nanowires, mesoporous), synthesis methods (hydrothermal, gas-phase, electrodeposition in aqueous media and ionic liquid media) and coatings (ZnO -ZnO core-shell, ZnO-TiO2 core-shell) were measured by transient absorption techniques in the time scale from 100 fs to 100 ps and in the visible and near-infrared spectral range. All of ZnO cells show worse electron injection yields with respect to those with standard TiO2 material. Lower refractive index of ZnO than that of TiO2 is suggested to be an additional factor, not considered so far, that can decrease the performance of ZnO-based solar cells. Evidence of the participation of the excited charge transfer state of the dye in the charge separation process is provided here. The lifetime of this state in fully working devices extends from several ps to several tens of ps, which is much longer than the typically postulated electron injection times in all-organic dye-sensitized solar cells. The results here provided, comprising a wide variety of morphologies and preparation methods, point to the universality of the poor performance of ZnO as photoanode material with respect to standard TiO2. (C) 2015 Elsevier B.V. All rights reserved

Understanding the Interfaces between Triple-Cation Perovskite and Electron or Hole Transporting Material

The properties of efficient solar cells fabricated with triple-cation perovskite placed between a mesoporous titania layer and a spiro-OMeTAD layer are studied by using devices either prepared under water-free drybox conditions or fabricated under ambient room humidity. The morphological studies indicate that the content of unreacted PbI2 phase in the perovskite structure is much higher near the interface with titania than near the interface with spiro-OMeTAD. The stationary emission spectra and transient bleach peaks of perovskites show additional long-wavelength features close to the titania side. Time-resolved techniques ranging from femtoseconds to seconds reveal further differences in charge dynamics at both interfaces. The population decay is significantly faster at the titania side than at the spiro-OMeTAD side for the cells prepared under ambient conditions. An increased hole injection rate correlates with higher photocurrent seen in the devices prepared under drybox conditions. The charge recombination loss on the millisecond time scale is found to be slower at the interface with titania than at the interface with spiro-OMeTAD. The ideality factor of the cells is found to increase with increasing DMSO content in the precursor solution, indicating a change in recombination mechanism from bulk to surface recombination. We also found that the charge dynamics are not uniform within the whole perovskite layer. This feature has significant implications for understanding the operation and optimizing the performance of solar devices based on mixed cation perovskites

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation

The main handicap still hindering the eventual exploitation of organometal halide perovskite‐based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid‐state hole conductor (SSHC), i.e., the Spiro‐OMeTAD [2,2′,7,7′‐tetrakis (N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene], and how its dopant‐free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution‐processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light‐emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro‐OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X‐ray diffraction, grazing‐incidence small‐angle X‐ray scattering and grazing‐incidence wide‐angle X‐ray scattering, X‐ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy