Fast computation of the Kohn-Sham susceptibility of large systems

For hybrid systems, such as molecules grafted onto solid surfaces, the calculation of linear response in time dependent density functional theory is slowed down by the need to calculate, in N^4 operations, the susceptibility of N non interacting Kohn-Sham reference electrons. We show how this susceptibility can be calculated N times faster within finite precision. By itself or in combination with previous methods, this should facilitate the calculation of TDDFT response and optical spectra of hybrid systems.Comment: submitted 25/1/200

Photovoltaic performance of injection solar cells and other applications of nanocrystalline oxide layers

The direct conversion of sunlight to electricity via photoelectrochemical solar cells is an attractive option that has been pursued for nearly two decades in several laboratories. In this paper, we review the principles and performance features of very efficient solar cells that are being developed in our laboratories. These are based on the concept of dye-sensitization of wide bandgap semiconductors used in the form of mesoporous nanocrystalline membrane-type films. The key feature is charge injection from the excited state of an anchored dye to the conduction band of an oxide semiconductor such as TiO2. In the use of the semiconductor in the form of high surface area, highly porous film offers several unique advantages: monomeric distribution of a large quantity of the dye in a compact (few micron thick) film, efficient charge collection and drastic inhibition of charge recombination (‘capture of charge carriers by oxidized dye'). Near quantitative efficiency for charge collection for monochromatic light excitation gives rise to sunlight conversion efficiency in the range of 8-10% This has led to fruitful collaboration with several industrial partners. Possible applications and commercialization of these solar cells and also other practical applications of nanosized films are briefly outline

Efficient photosynthesis of carbon monoxide from CO2 using perovskite photovoltaics

Artificial photosynthesis, mimicking nature in its efforts to store solar energy, has received considerable attention from the research community. Most of these attempts target the production of H2 as a fuel and our group recently demonstrated solar-to-hydrogen conversion at 12.3% efficiency. Here, in an effort to take this approach closer to real photosynthesis, which is based on the conversion of CO2, we demonstrate the efficient reduction of CO2 to carbon monoxide driven solely by simulated sunlight using water as the electron source. Employing series-connected perovskite photovoltaics and high-performance catalyst electrodes, we reach a solar-to-CO efficiency exceeding 6.5%, which represents a new benchmark in sunlight-driven CO2 conversion. Considering hydrogen as a secondary product, an efficiency exceeding 7% is observed. Furthermore, this study represents one of the first demonstrations of extended, stable operation of perovskite photovoltaics, whose large open-circuit voltage is shown to be particularly suited for this process

An investigation of the roles furan versus thiophene π-bridges play in donor–π-acceptor porphyrin based DSSCs

Dye-sensitized solar cells (DSSCs) continue to attract interest due to their lower cost production compared to silicon based solar cells and their improving power conversion efficiencies. Porphyrin-based sensitizers have become an important sub-class due to their strong absorption characteristics in the visible region, convenient modulation of properties through synthetic manipulation and class-leading power conversion efficiencies. In this article, we report the synthesis and characterization of two porphyrin-based dyes and their application as sensitizers in DSSCs. A thiophene and a furan moiety have been incorporated into the push–pull architecture as a π-bridge, allowing the systematic investigation of how these moieties influence the physical properties of the dyes and the performance of their resulting DSSCs. A significant difference in PCEs has been observed, with the furan containing dye (PorF, PCE = 4.5%) being more efficient than the thiophene-based analogue (PorT, PCE = 3.6%) in conjunction with the iodide/triiodide redox electrolyte

Solar energy conversion

If solar energy is to become a practical alternative to fossil fuels, we must have efficient ways to convert photons into electricity, fuel, and heat. The need for better conversion technologies is a driving force behind many recent developments in biology, materials, and especially nanoscience

Highly efficient planar perovskite solar cells through band alignment engineering

The simplification of perovskite solar cells (PSCs), by replacing the mesoporous electron selective layer (ESL) with a planar one, is advantageous for large-scale manufacturing. PSCs with a planar TiO2 ESL have been demonstrated, but these exhibit unstabilized power conversion efficiencies (PCEs). Herein we show that planar PSCs using TiO2 are inherently limited due to conduction band misalignment and demonstrate, with a variety of characterization techniques, for the first time that SnO2 achieves a barrier-free energetic configuration, obtaining almost hysteresis-free PCEs of over 18% with record high voltages of up to 1.19 V

New Strategies for Defect Passivation in High-Efficiency Perovskite Solar Cells

Lead halide perovskite solar cells now show excellent efficiencies and encouraging levels of stability. Further improvements in performance require better control of the trap states which are considered to be associated with vacancies and defects at crystallite surfaces. Herein, a reflection on the ways in which these traps can be mitigated is presented by improving the quality of the perovskite layer and interfaces in fully assembled device configurations. In this review, the most recent design strategies reported in the literature, which have been explored to tune grain orientation, to passivate defects, and to improve charge-carrier lifetimes, are presented. Specifically, the advances made with single-cation, mixed-cation and/or mixed-halide, and 3D/2D bilayer-based light absorbers are discussed. The interfacial, compositional, and band alignment engineering along with their consequent effects on the open-circuit voltage, power conversion efficiency, and stability are a particular focus

Novel room temperature ionic liquids of hexaalkyl substituted guanidinium salts for dye-sensitized solar cells

A novel family of room temperature ionic liquids, N,N-diethyl-N′,N′-dipropyl-N′′-hexyl-N′′-methylguanidinium iodide (SGI) and N,N,N′,N′-tetramethyl-N′′,N′′-dipentylguanidinium tricyanomethanide (SGTM) were designed and synthesized. Due to the strong charge delocalization on the tricyanomethanide anion and, thus, weaker ion-pairing, SGTM has a lower viscosity than SGI salt that has iodide as an anion. SGI was successfully used as an iodide resource for dye-sensitized nanocrystalline solar cells. The device with a solvent-free, SGI-based electrolyte achieved a 5.9% power conversion efficiency under an air mass 1.5 incident light of 9.47mW/cm

Non-aggregated Zn(ii)octa(2,6-diphenylphenoxy) phthalocyanine as a hole transporting material for efficient perovskite solar cells

A non-aggregated Zn(ii)octa(2,6-diphenylphenoxy) phthalocyanine (coded as TT80) has been used as a hole-transporting material for perovskite solar cells. The cells were fabricated under three different configurations by changing the uptake solvent (chlorobenzene or toluene) and incorporating additives (bis(trifluoromethane) sulfonimide lithium salt (LiTFSI) and 4-tert-butylpyridine (TBP). A power conversion efficiency of 6.7% (AM1.5G standard conditions) was achieved for the best cell under optimized configurationWe are grateful for the financial support of the MEC, Spain (CTQ2014-52869/BQU), Comunidad de Madrid, Spain (FOTOCARBON, S2013/MIT-2841), and the European Union within the FP7-ENERGY-2012-1, nr. 309194-2, GLOBALSOL project. M. K. N. thanks the European Union for funding within the Seventh Framework Program [FP7/2007–2013] under the grant agreement no. 604032 of the MESO projec