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

Hetero-Supramolecular Modification of Nanocrystalline TiO₂-Film Electrodes: Photoassisted Electrocatalysis at B₁₂-on-TiO₂

Nanocrystalline TiO2-film electrodes exhibit a unique set of intrinsic properties (transparency for visible light, electric conductivity in the doped state, semiconductor properties, large surface area, surface affinity towards organic anchoring groups). These can be combined with those of TiO2-surface-anchored molecular subunits such as light emitters or absorbers, redoxactive–possibly electrochromic–compounds, and electroactive molecular hosts or catalysts. The number of macroscopic devices resulting from such a hetero-supramolecular architecture includes photovoltaic cells, erasable photochromic devices, electrochromic displays and filters, and electrocatalytically active surfaces. The principals behind these applications are reviewed with special emphasis on a new type of photo assisted electrocatalysis using vitamin B12-modified TiO2

Monolithic CIGS-Perovskite Tandem Cell for an Optimal Light Harvesting Without Current Matching

We present a novel monolithic architecture for optimal light harvesting in multijunction thin film solar cells. In the configuration we consider, formed by a perovskite (PVK) cell overlying a CIGS cell, the current extracted from the two different junctions is decoupled by the insertion of a dielectric nonperiodic photonic multilayer structure. This photonic multilayer is designed by an inverse integration approach to confine the incident sunlight above the PVK band gap in the PVK absorber layer, while increasing the transparency for sunlight below the PVK band gap for an efficient coupling into the CIGS bottom cell. To match the maximum power point voltages in a parallel connection of the PVK and CIGS cells, the latter is divided into two subcells by means of a standard three-laser scribing connection. Using realistic parameters for all the layers in the multijunction architecture we predict power conversion efficiencies of 28%. This represents an improvement of 24% and 26% over the best CIGS and PVK single-junction cells, respectively, while at the same time outperforms the corresponding current-matched standard tandem configuration by more than two percentage points.Peer ReviewedPostprint (author's final draft

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

Facile synthesis of metal-free organic dyes featuring a thienylethynyl spacer for dye sensitized solar cells

In this article, we report the facile synthesis of metal-free dyes 6 and 7, their solution-based optical and redox properties and their use as sensitizers in dye-sensitized solar cells (DSSCs). Our studies indicate that the addition of the second thiophene unit in dye 7, decreases the oxidation and reduction potential and consequently the band gap of the molecule compared to 6. Furthermore, increasing the length of the conjugated spacer also affects on the properties of the DSSCs, with dye 7 providing a higher power conversion efficiency compared to 6 (η = 4.49 versus 3.23%)

All-inorganic core-shell silica-titania mesoporous colloidal nanoparticles showing orthogonal functionality

Colloidal mesoporous silica (CMS) nanoparticles with a thin titania-enriched outer shell showing a spatially resolved functionality were synthesized by a delayed co-condensation approach. The titaniashell can serve as a selective nucleation site for the growth of nanocrystalline anatase clusters. These fully inorganic pure silica-core titania-enriched shell mesoporous nanoparticles show orthogonal functionality, demonstrated through the selective adsorption of a carboxylate-containing ruthenium N3-dye. UV-Vis and fluorescence spectroscopy indicate the strong interaction of the N3-dye with the titania-phase at the outer shell of the CMS nanoparticles. In particular, this interaction and thus the selective functionalization are greatly enhanced when anatase nanocrystallites are nucleated at the titania-enriched shell surface

Efficient and stable CH3NH3PbI3-sensitized ZnO nanorod array solid-state solar cells

We report for the first time the use of a perovskite (CH3NH3PbI3) absorber in combination with ZnO nanorod arrays (NRAs) for solar cell applications. The perovskite material has a higher absorption coefficient than molecular dye sensitizers, gives better solar cell stability, and is therefore more suited as a sensitizer for ZnO NRAs. A solar cell efficiency of 5.0% was achieved under 1000 W m(-2) AM 1.5 G illumination for a solar cell with the structure: ZnO NRA/CH3NH3PbI3/spiro-MeOTAD/Ag. Moreover, the solar cell shows a good long-term stability. Using transient photocurrent and photovoltage measurements it was found that the electron transport time and lifetime vary with the ZnO nanorod length, a trend which is similar to that in dye-sensitized solar cells, DSCs, suggesting a similar charge transfer process in ZnO NRA/CH3NH3PbI3 solar cells as in conventional DSCs. Compared to CH3NH3PbI3/TiO2 solar cells, ZnO shows a lower performance due to more recombination losses

Bilayer Hybrid Solar Cells Based on Triphenylamine−Thienylenevinylene Dye and TiO2

Photoinduced energy conversion from multilayers of organic dye on dense TiO2 films was investigated in bilayer hybrid solar cells. Dye layers of varying thicknesses were prepared by spin-casting the star-shaped dye [tris(dicyano-vinyl-2-thienyl)phenyl]amine (1) from solutions onto dense TiO2 on conducting glass substrates. A spin-cast layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and graphite powder was used for contacting the devices. Excitons generated in the dye multilayer contribute to the power conversion efficiency, reaching a maximum of ca. 0.3% at a dye layer thickness of ca. 8 nm for the devices described herein. For dye layers exceeding 5 nm, the cell performance becomes limited by the exciton diffusion length LED and the hole mobility in the organic layer. Using dye multilayers is a viable way to increase light harvesting in solid-state dye-sensitized solar cells