Picosecond Capture of Photoexcited Electrons Improves Photovoltaic Conversion in MAPbI3 :C70 -Doped Planar and Mesoporous Solar Cells.

In this work, solar cells based on methylammonium lead iodide (MAPbI3 ) doped in solution with C70 fullerene in a mesoporous as well as planar electron-transporting layer (ETL)-free architecture are realized, showcasing in the latter case a record efficiency of 15.7% and an improved open-circuit voltage (VOC ). Contrary to the bulk heterojunction previously reported, the C70 molecules do not phase segregate and they are rather finely dispersed in the perovskite film, possibly infiltrating at the grain boundaries, while assisting the growth of a highly uniform perovskite layer. By means of time-resolved femtosecond-to-nanosecond optical spectroscopy, with an extended spectral coverage, it is observed that electrons photogenerated in the perovskite are transferred to C70 with a time constant of 20 ps. Despite being captured by C70 , electrons are not deeply trapped and can potentially bounce back into the perovskite, as suggested by the high fill factor and enhanced VOC of the MAPbI3 :C70 solar cells, especially in the case of the ETL-free device configuration.

Physicochemical Phenomena and Application in Solar Cells of Perovskite:Fullerene Films.

Beyond the use of fullerenes as electron-transporting layers in perovskite solar cells, their introduction into a perovskite active layer has been ascertained as a very promising strategy for device improvement. In this sense, this Perspective summarizes the studies in which perovskite:fullerene systems were employed, covering the different methodologies for introducing fullerenes inside the perovskite layer. In particular, fill factor was the most benefited parameter, which was ascribed to minimized pinhole density and fullerene passivating role. We discussed the importance of their ability to passivate trap states and, in this regard, focused on the affinity of fullerenes toward these sites. Additionally, the different nature of the fullerene and its environment in the active layer were found to determine the proper distribution of fullerene so that they could passivate the defects along grain boundaries. Understanding this mechanism would provide further insights for new methodologies and fullerene derivatives with enhanced trap-passivating ability.

Molecular Dynamics Analysis of Charge Transport in Ionic-Liquid Electrolytes Containing Added Salt with Mono, Di, and Trivalent Metal Cations.

Among many other applications, room-temperature ionic liquids (ILs) are used as electrolytes for storage and energy-conversion devices. In this work, we investigate, at the microscopic level, the structural and dynamical properties of 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethanesulfonyl) imide [C4 PYR]+ [Tf2 N]- IL-based electrolytes for metal-ion batteries. We carried out molecular dynamics simulations of electrolytes mainly composed of [C4 PYR]+ [Tf2 N]- IL with the addition of Mn+ -[Tf2 N]- metal salts (M=Li+ , Na+ , Ni2+ , Zn2+ , Co2+ , Cd2+ , and Al3+ , n=1, 2, and 3) dissolved in the IL. The addition of low salt concentrations lowers the charge transport and conductivity of the electrolytes. This effect is due to the strong interaction of the metal cations with the [Tf2 N]- anions, which allows for molecular aggregation between them. We analyze how the conformation of the [Tf2 N]- anions surrounding the metal cations determine the charge-transport properties of the electrolyte. We found two main conformations based on the size and charge of the metal cation: monodentate and bidentate (number of oxygen atoms of the anion pointing to the metal atoms). The microscopic local structure of the Mn+ -[Tf2 N]- aggregates influences the microscopic charge transport as well as the macroscopic conductivity of the total electrolyte.

All-in-One Gel-Based Electrochromic Devices: Strengths and Recent Developments.

Electrochromic devices (ECDs) have aroused great interest because of their potential applicability in displays and smart systems, including windows, rearview mirrors, and helmet visors. In the last decades, different device structures and materials have been proposed to meet the requirements of commercial applications to boost market entry. To this end, employing simple device architectures and achieving a competitive electrolyte are crucial to accomplish easily implementable, high-performance ECDs. The present review outlines devices comprising gel electrolytes as a single electroactive layer ("all-in-one") ECD architecture, highlighting some advantages and opportunities they offer over other electrochromic systems. In this context, gel electrolytes not only overcome the drawbacks of liquid and solid electrolytes, such as liquid's low chemical stability and risk of leaking and soil's slow switching and lack of transparency, but also exhibit further strengths. These include easier processability, suitability for flexible substrates, and improved stabilization of the chemical species involved in redox processes, leading to better cyclability and opening wide possibilities to extend the electrochromic color palette, as discussed herein. Finally, conclusions and outlook are provided.

Fullerene-Based Materials as Hole-Transporting/Electron-Blocking Layers: Applications in Perovskite Solar Cells.

Here we report for the first time an efficient fullerene-based compound, FU7, able to act as hole-transporting material (HTM) and electron blocking contact. It has been applied on perovskite solar cells (PSCs), obtaining 0.81 times the efficiency of PSCs with the standard HTM, spiro-OMeTAD, with the additional advantage that this performance is reached without any additive introduced in the HTM layer. Moreover, as a proof of concept, we have described for the first time efficient PSCs in which both selective contacts are fullerene derivatives, to obtain unprecedented "fullerene sandwich" PSCs.

Laponite-Based Surfaces with Holistic Self-Cleaning Functionality by Combining Antistatics and Omniphobicity.

In the present work, perfluoroalkylated laponite nanoparticles with a high degree of functionalization (60 wt %) have been prepared and a methodology to prepare transparent, antistatic, and omniphobic laponite-based films with holistic self-cleaning properties against liquids, solids and liquid-solid mixtures has been developed. The intrinsic electrical and ionic conductivities observed in unmodified laponite coatings are combined with perfluoroalkyl-modified laponite clays. As a result, films with improved self-cleaning functionality based on dust-repellency and omniphobic liquid-repellence (sheet resistance in the range of 107 Ω/□ and contact angles of 106° (H2O) and 93° (oil)) were obtained. These unique films, being capable to repel dust and liquids, were applied to a variety of substrates (i.e., glass and plastics) and tested against solids and liquids of different nature with excellent performance. Bending tests of these holistic self-cleaning films deposited over flexible substrates showed better mechanical performance than unmodified laponite films.

Modified Fullerenes for Efficient Electron Transport Layer-Free Perovskite/Fullerene Blend-Based Solar Cells.

A variety of novel chemically modified fullerenes, showing different electron-accepting capabilities, has been synthesized and used to prepare electron transport layer (ETL)-free solar cells based on perovskite/fullerene blends. In particular, isoxazolino[60] fullerenes are proven to be a good candidate for processing blend films with CH3 NH3 PbI3 and obtaining enhanced power conversion efficiency (PCE) ETL-free perovskite solar cells (PSCs), improving the state-of-the-art PCE (i.e., 14.3 %) for this simplified device architecture. A beneficial effect for pyrazolino and methano[60]fullerene derivatives versus pristine [60]/fullerene is also shown. Furthermore, a clear correlation between the LUMO energy level of the fullerene component and the open circuit voltage of the solar cells is found. Apart from the new knowledge on innovative fullerene derivatives for PSCs, the universality and versatility of perovskite/fullerene blend films to obtain efficient ETL-free PSCs is demonstrated.

Electrochemical Reduction of Oxygen in Aprotic Ionic Liquids Containing Metal Cations: A Case Study on the Na-O2 system.

Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (Mn+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate Mn+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of Mn+ on oxygen reduction. A case study on the Na-O2 system is described in detail. Among other things, the Na+ concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided.

Colorless to Neutral Color Electrochromic Devices Based on Asymmetric Viologens.

Electrochromic materials have extensively been investigated because of their potential fields of application, with a significant growing interest in expanding the provided colorations. However, among all palette of colors, colorless electrochromic devices (ECDs) that provide neutral-grayish colorations with a simple configuration remain a key challenge. The present study reports on the synthesis of asymmetrically 1-alkyl-1'-aryl-substituted viologens and their incorporation in PVA-borax gel polyelectrolytes for ECDs that constitute the simplest device architecture (glass/TCO/EC gel/TCO/glass). We demonstrate herein that these EC gels based on single asymmetric viologens provide more neutral-colored state than their corresponding symmetric viologens (a* and b* ≤ |15|), while maintaining satisfactory colorless bleached state (%Tb > 70% in the whole visible range), transmittance changes (i.e., ∼60%) and cyclability (i.e., ∼15 000 cycles). Additionally, the effect of the solvent on the observed coloration has also been investigated. This easy-to-make neutral-grayish color ECDs may significantly extend the potential of the electrochromic technology, because they adapt better aesthetically to the surrounding environment, as they are easier to implement in different applications.

Electron Transport Layer-Free Solar Cells Based on Perovskite-Fullerene Blend Films with Enhanced Performance and Stability.

The solution processing of pinhole-free methylammonium lead triiodide perovskite-C70 fullerene (MAPbI3 :C70 ) blend films on fluorine-doped tin oxide (FTO)-coated glass substrates is presented. Based on this approach, a simplified and robust protocol for the preparation of efficient electron-transport layer (ETL)-free perovskite solar cells is described. Power conversion efficiency (PCE) of 13.6 % under AM 1.5 G simulated sunlight is demonstrated for these devices. Comparative impedance spectroscopy and photostability analysis of the MAPbI3 :C70 and single MAPbI3 films compared with conventional compact TiO2 ETL-based devices are shown. The beneficial impact of using MAPbI3 :C70 blend films is emphasized.

Determination of Interfacial Charge-Transfer Rate Constants in Perovskite Solar Cells.

A simple protocol to study the dynamics of charge transfer to selective contacts in perovskite solar cells, based on time-resolved laser spectroscopy studies, in which the effect of bimolecular electron-hole recombination has been eliminated, is proposed. Through the proposed procedure, the interfacial charge-transfer rate constants from methylammonium lead iodide perovskite to different contact materials can be determined. Hole transfer is faster for CuSCN (rate constant 0.20 ns(-1) ) than that for 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD; 0.06 ns(-1) ), and electron transfer is faster for mesoporous (0.11 ns(-1) ) than that for compact (0.02 ns(-1) ) TiO2 layers. Despite more rapid charge separation, the photovoltaic performance of CuSCN cells is worse than that of spiro-OMeTAD cells; this is explained by faster charge recombination in CuSCN cells, as revealed by impedance spectroscopy. The proposed direction of studies should be one of the key strategies to explore efficient hole-selective contacts as an alternative to spiro-OMeTAD.

Nanophotoactivity of Porphyrin Functionalized Polycrystalline ZnO Films.

Kelvin probe force microscopy in darkness and under illumination is reported to provide nanoscale-resolved surface photovoltage maps of hybrid materials. In particular, nanoscale charge injection and charge recombination mechanisms occurring in ZnO polycrystalline surfaces functionalized with Protoporphyrin IX (H2PPIX) are analyzed. Local surface potential and surface photovoltage maps not only reveal that upon molecular adsorption the bare ZnO work function increases, but also they allow study of its local dependence. Nanometer-sized regions not correlated with apparent topographic features were identified, presenting values significantly different from the average work function. Depending on the region, the response to the light excitation is different, distinguishing two relaxation processes, one faster than the other. This behavior can be explained in terms of electrons trapped closed to the molecule-semiconductor interface or electrons pushed into the ZnO bulk, respectively. Moreover, the origin of these differences is correlated with the H2PPIX-ZnO bonding and molecules configuration and aggregation. The chenodeoxycholic acid (CDCA) coadsorption leads to a more homogeneous surface potential distribution, confirming the antiaggregate effect of this additive, while the surface photovoltage is mostly dominated by the slow relaxation component. This work reveals the complexity of real device architectures with ill-defined surfaces even in a relatively simple system with only one type of dye molecule and hightlights the importance of nanoscale characterization with appropriate tools.

Multicolor Electrochromics: Rainbow-Like Devices.

Stimuli-responsive reversible coloration-change materials represent a highly demanded type of smart systems useful for a wide variety of applications, with a significant growing interest in multicolor abilities. In particular, electrochromic materials have received a great deal of attention due to their versatility and broad range of industrial uses. However, most of the existing electrochromic technologies provide a single coloration, while achieving multiple colors based on simple approaches remains a challenge. The present article reports on PVA gel-based electrochromic devices, containing a single viologen, providing a colorless and two different well-defined colored states. The successful fabrication of a device, based on two viologens (multi-EC gel) with a simple architecture (glass/TCO/multi-EC gel/TCO/glass), with five different multiswitchable colors based on four-zoned electrodes (rainbow-like ECD) is also demonstrated. This novel easy-to-make multichromic system represents a significant breakthrough toward the generation of full-color devices, expanding the potential of electrochromic technology.

Quantum and Classical Molecular Dynamics of Ionic Liquid Electrolytes for Na/Li-based Batteries: Molecular Origins of the Conductivity Behavior.

Compositional effects on the charge-transport properties of electrolytes for batteries based on room-temperature ionic liquids (RTILs) are well-known. However, further understanding is required about the molecular origins of these effects, in particular regarding the replacement of Li by Na. In this work, we investigate the use of RTILs in batteries, by means of both classical molecular dynamics (MD), which provides information about structure and molecular transport, and ab initio molecular dynamics (AIMD), which provides information about structure. The focus has been placed on the effect of adding either Na(+) or Li(+) to 1-methyl-1-butyl-pyrrolidinium [C4 PYR](+) bis(trifluoromethanesulfonyl)imide [Tf2 N](-) . Radial distribution functions show excellent agreement between MD and AIMD, which ensures the validity of the force fields used in the MD. This is corroborated by the MD results for the density, the diffusion coefficients, and the total conductivity of the electrolytes, which reproduce remarkably well the experimental observations for all studied Na/Li concentrations. By extracting partial conductivities, it is demonstrated that the main contribution to the conductivity is that of [C4 PYR](+) and [Tf2 N](-) . However, addition of Na(+) /Li(+) , although not significant on its own, produces a dramatic decrease in the partial conductivities of the RTIL ions. The origin of this indirect effect can be traced to the modification of the microscopic structure of the liquid as observed from the radial distribution functions, owing to the formation of [Na(Tf2 N)n ]((n-1)-) and [Li(Tf2 N)n ]((n-1)-) clusters at high concentrations. This formation hinders the motion of the large ions, hence reducing the total conductivity. We demonstrate that this clustering effect is common to both Li and Na, showing that both ions behave in a similar manner at a microscopic level in spite of their distinct ionic radii. This is an interesting finding for extending Li-ion and Li-air technologies to their potentially cheaper Na-based counterparts.

Efficient Regular Perovskite Solar Cells Based on Pristine [70]Fullerene as Electron-Selective Contact.

[70]Fullerene is presented as an efficient alternative electron-selective contact (ESC) for regular-architecture perovskite solar cells (PSCs). A smart and simple, well-described solution processing protocol for the preparation of [70]- and [60]fullerene-based solar cells, namely the fullerene saturation approach (FSA), allowed us to obtain similar power conversion efficiencies for both fullerene materials (i.e., 10.4 and 11.4 % for [70]- and [60]fullerene-based devices, respectively). Importantly, despite the low electron mobility and significant visible-light absorption of [70]fullerene, the presented protocol allows the employment of [70]fullerene as an efficient ESC. The [70]fullerene film thickness and its solubility in the perovskite processing solutions are crucial parameters, which can be controlled by the use of this simple solution processing protocol. The damage to the [70]fullerene film through dissolution during the perovskite deposition is avoided through the saturation of the perovskite processing solution with [70]fullerene. Additionally, this fullerene-saturation strategy improves the performance of the perovskite film significantly and enhances the power conversion efficiency of solar cells based on different ESCs (i.e., [60]fullerene, [70]fullerene, and TiO2 ). Therefore, this universal solution processing protocol widens the opportunities for the further development of PSCs.

Control of the recombination rate by changing the polarity of the electrolyte in dye-sensitized solar cells.

Recombination in Dye-sensitized Solar Cells (DSCs) is an electron transfer process critical for high efficiency. The chemical nature of the electron acceptor is known to have an important impact on recombination and, hence, limits the choice of hole conductors in DSCs and related solar cells. In this respect, Room Temperature Ionic liquids (RTILs) have been recognized as an alternative to volatile organic solvents due to their negligible vapor pressure, which offers the chance for long-term stability. However, RTIL-based electrolytes lead to lower performance, a feature that has been attributed to the high viscosity of ionic liquids and the mass-transport limitation associated with it. In this work we show that the origin of the lower performance is also related to an increase in the recombination loss due to the polar nature of the RTIL and the influence of the reorganization energy of the electron acceptor in a polar environment. To investigate this chemical effect, different mixing ratios of RTILs and an organic solvent (acetonitrile) have been considered. The fabricated devices have been characterized by small-perturbation techniques (Impedance Electrochemical Spectroscopy and Intensity-Modulated Photovoltage and Photocurrent Spectroscopies) and Open-Circuit Voltage Decay measurements, which have been used to extract electron lifetimes at different applied voltages. Two different ruthenium dyes (hydrophilic N719 and hydrophobic Z907) and two different cations in the RTIL (imidazolium- and pyrrolidinium-based) have been considered. The results obtained show that for pure ionic liquids the lifetime-voltage curve is exponential, which is a signature of large reorganization energies for electron transfer. In contrast, pure acetonitrile exhibits a non-exponential behavior, which is consistent with relatively low reorganization energy. Interestingly, and as a general rule, we find that recombination is faster in systems with higher reorganization energies. This is interpreted as a consequence of the availability of more acceptor states for electron transfer. In addition, it is found that mixing RTILs and acetonitrile is an interesting strategy to increase the stability of DSCs without significant recombination losses, provided that the right dye and RTIL, in particular, a pyrrolidinium component, are used.

Electrodeposition of antimony selenide thin films and application in semiconductor sensitized solar cells.

Sb2Se3 thin films are proposed as an alternative light harvester for semiconductor sensitized solar cells. An innovative electrodeposition route, based on aqueous alkaline electrolytes, is presented to obtain amorphous Sb2Se3. The amorphous to crystalline phase transition takes place during a soft thermal annealing in Ar atmosphere. The potential of the Sb2Se3 electrodeposited thin films in semiconductor sensitized solar cells is evaluated by preparing TiO2/Sb2Se3/CuSCN planar heterojunction solar cells. The resulting devices generate electricity from the visible and NIR photons, exhibiting the external quantum efficiency onset close to 1050 nm. Although planar architecture is not optimized in terms of charge carrier collection, photocurrent as high as 18 mA/cm(2), under simulated (AM1.5G) solar light, is achieved. Furthermore, the effect of the Sb2Se3 thickness and microstructural properties on the photocurrent is analyzed, suggesting the hole transport is the main limiting mechanism. The present findings provide significant insights to design efficient semiconductor sensitized solar cells based on advanced architectures (e.g., nanostructured and tandem), opening wide possibilities for progresses in this emerging photovoltaics technology.

A sulfide/polysulfide-based ionic liquid electrolyte for quantum dot-sensitized solar cells.

Further development of quantum dot-sensitized solar cells (QDSCs) will require long-term stability in addition to the continuous increase of photovoltaic (PV) conversion efficiency achieved in the last years. We report a robust S(2-)/S(n)(2-) electrolyte that has been specifically designed for compatibility with CdSe quantum dots in sensitized solar cells. The new pyrrolidinium ionic liquid reaches 1.86% efficiency and a short-circuit current close to 14 mA·cm(-2) under air-mass 1.5 global illumination and improves the device lifetime with good photoanode stability over 240 h. PV characterization showed that the solar cell limitations relate to poor catalysis of regeneration at the counter electrode and high recombination. Further improvement of these factors in the robust electrolyte configuration may thus have a significant impact for advancing the state-of-the-art in QDSCs.

Novel ZnO nanostructured electrodes for higher power conversion efficiencies in polymeric solar cells.

1-Dimensional nanostructured ZnO electrodes have been demonstrated to be potentially interesting for their application in solar cells. Herein, we present a novel procedure to control the ZnO nanowire optoelectronic properties by means of surface modification. The nanowire surface is functionalized with ZnO nanoparticles in order to provide an improved contact to the photoactive P3HT:PCBM film that enhances the overall power conversion efficiency of the resulting solar cell. Charge extraction and transient photovoltage measurements have been used to successfully demonstrate that the surface modified nanostructured electrode contributes in enhancing the exciton dissociating ratio and in enlarging the charge lifetime as a consequence of a reduced charge recombination. Under AM1.5G illumination, all these factors contribute to a considerably large increase in photocurrent yielding unusually high conversion efficiencies over 4% and external quantum efficiencies of 87% at 550 nm for commercially available P3HT:PCBM based solar cells. The same approach might be equally used for polymeric materials under development to overcome the record reported efficiencies.

Electrochemical reduction of O2 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid containing Zn2+ cations: deposition of non-polar oriented ZnO nanocrystalline films.

The influence of the Zn(2+) concentration and temperature on the electrochemical reduction of O(2) in a solution of zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)(2)) salt in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR(14)TFSI) ionic liquid is presented. ZnO nanocrystalline films were then electrodeposited, under enhanced O(2) reduction, at temperatures in the 75-150 °C range. Their morphology, chemical composition, structural and optical properties were analyzed. In contrast to the polar-oriented ZnO usually obtained from aqueous and conventional solvent based electrolytes, nanocrystalline films oriented along non-polar directions, (11 ̅10) and (11 ̅20), were obtained from this ionic liquid electrolyte. A significant content of carbon was detected in the films, pointing to the active participation and crucial effect of pyrrolidinium cation (and/or byproducts) during the electrodeposition. The films showed semiconducting behavior with an optical gap between 3.43 and 3.53 eV as measured by optical transmittance. Their room temperature photoluminescence spectra exhibited two different bands centered at ∼3.4 and ∼2.2 eV. The intensity ratio between both bands was found to depend on the deposition temperature. This work demonstrates the great potential of ionic liquids based electrolytes for the electrodeposition of ZnO nanocrystalline thin films with innovative microstructural and optoelectronic properties.