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Lead halide perovskites exhibit great potential for light‐emitting devices. Enhanced photoluminescence (PL) is obtained in perovskite materials of reduced dimensionalities due to the large exciton binding energy. However, as the nanocrystal size is reduced, the surface‐to‐volume ratio increases, leading to an abundance of surface defects. Here, a fast PL decay, 3–10 ps, is observed in quasi‐1D CsPbBr3 perovskite nanoplatelets using broadband fluorescence upconversion spectroscopy. This decay is attributed to reversible trapping of band‐edge excitons into dark states that lie close to the band edge. A simplified model is proposed to further confirm the presence of shallow traps and to fit the data obtained by ultrafast spectroscopy for multiple samples. Finally, the presence of deep trap states in aged nanoplatelets is revealed, likely arising from desorption of the organic capping ligands from the surface. Exciton trapping into these states is slower, 20–30 ps, but leads to a decrease in the photoluminescence quantum yield. These results may not only explain the extended luminescence lifetimes that have been reported for perovskite nanocrystals but also demonstrate the potential of combining ultrafast transient absorption and fluorescence up‐conversion to obtain a full description of the spectroscopic properties of the material. [ABSTRACT FROM AUTHOR]

Dye‐sensitized solar cells (DSCs) based on copper(II/I) redox mediators have recently achieved notable performance progress through tailoring the ligand structure of the copper complexes, exploiting cosensitization, and introducing an advanced device structure. In order to further improve the power conversion efficiency (PCE), it is imperative to develop wide spectral‐response photosensitizers compatible with the copper(II/I) redox mediators while attaining a high Voc. Herein, a blue photosensitizer coded R7 is reported, which is purposely designed for highly efficient DSCs with copper‐based electrolytes. R7 features a strong electron‐donating segment of 9,19‐dihydrobenzo[1′,10′ ]phenanthro[3′,4′:4,5]thieno[3,2‐b]benzo[1,10]phenanthro[3,4‐d]thiophene conjugated with a bulky auxiliary donor N‐(2,4′‐bis(hexyloxy)‐[1,1′‐biphenyl]‐4‐yl)‐2,4′‐bis(hexyloxy)‐N‐methyl‐[1,1′‐biphenyl]‐4‐amine and the electron acceptor 4‐(7‐ethynylbenzo[c][1,2,5]thiadiazol‐4‐yl)benzoic acid. The blue dye R7 with bulkier auxiliary donor moiety in the DSC largely outperforms the reference dye R6, which has a smaller bis(4‐(hexyloxy)phenyl)amine donor unit. Transient absorption spectroscopy and electrochemical impedance spectroscopy measurements show that the R7 based DSC has a higher charge separation yield, a higher charge collection efficiency, and lower charge recombination with the copper electrolyte than the R6 based counterpart. A cosensitized system of R7 and Y123 for the DSC presents an outstanding PCE of 12.7% and retains 90% of its initial value after 1000 h of light soaking under 1 sun at 45 °C. [ABSTRACT FROM AUTHOR]

Dye‐sensitized solar cells (DSSCs) based on CuII/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (VOC, more than 1 V). However, their short‐circuit photocurrent density (JSC) has remained modest. Increasing the JSC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO2 film and fast regeneration by the CuI complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64, which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers. [ABSTRACT FROM AUTHOR]

Four organic donor-π-bridge-acceptor dyes containing phenothiazine as a spacer and cyanoacrylic acid as an acceptor were synthesized and tested as sensitizers in dye-sensitized solar cells (DSCs). The influence of iodide- and cobalt-based redox electrolytes on the photovoltaic device performance was investigated. In these new dyes, systematic π-conjugation was extended by inserting one or two phenothiazine moieties and investigated within the context of the resulting photoinduced charge-transfer properties. A detailed investigation, including transient absorption spectroscopy and quantum chemical methods, provided important information on the role of extended π-conjugation on the photophysical properties and photovoltaic device performance. Overall, the results showed that the extension of π-conjugation by one phenothiazine unit resulted in the best device performance owing to reduced recombination rates, whereas extension by two phenothiazine units reduced dye adsorption on TiO2 probably owing to the increase in molecular size. The performance of the dyes in DSCs was found to be a complex interaction between dye structure and size. [ABSTRACT FROM AUTHOR]

In the recent years, the heterojunction solar cells based on quantum dots (QDs) have attracted attention due to strong light absorbing characteristics and the size effect on the bandgap tuning. This paper reports on the kinetics of interfacial charge separation of PbS QDs/(001) TiO2 nanosheets heterojunction solar cells. PbS QDs are deposited using a bifunctional linker molecule on two different TiO2 films, i.e., TiO2 nanosheets (with 001 dominant exposed facet) and TiO2 nanoparticles (with 101 dominant exposed facet). Upon bandgap excitation, electrons are transferred from the PbS QDs conduction band to the lower lying conduction band of TiO2. Based on the ultrafast pump-probe laser spectroscopy technique, the kinetics of charge separation is scrutinized at the PbS/TiO2 interface. The interfacial charge separation at PbS/TiO2 nanosheets films made of (001) dominant exposed facets is five times faster than that on (101) dominant exposed facets TiO2 nanoparticles. The quantum yields for charge injection are higher for the (001) TiO2 nanosheets than the (101) TiO2 nanoparticles due to enhanced interfacial interaction with (001) surface compared to the (101) nanoparticles. The superior interfacial charge separation at PbS/(001) nanosheets respect to PbS/(101) nanoparticles is consistent with the higher photocurrent and enhanced power conversion efficiency in the PbS QDs/(001) TiO2 heterojunction solar cell. The use of (001) TiO2 nanosheets can be a better alternative to conventional mesoporous TiO2 films in QD heterojunction solar cells and perovskites-based heterojunction solar cells. [ABSTRACT FROM AUTHOR]

Ruthenium und Co: Ruthenium(II) ‐ Komplexe sind nach wie vor die „heißesten Kandidaten“ für Farbstoffsolarzellen, doch derzeit bekannte Ru ‐ Sensibilisatoren sind nicht mit CoII/III ‐ Elektrolyten kompatibel. Der Effekt einer Oberflächenisolierung auf die Leistungsfähigkeit einer Zelle wurde durch den Vergleich zweier cyclometallierter RuII ‐ Komplexe studiert. Der Ansatz zeigt ein allgemeines Prinzip für beispiellose Effizienzen bei der Kombination von RuII ‐ Sensibilisatoren mit einem Cobalt ‐ Elektrolyt. [ABSTRACT FROM AUTHOR]

A new series of donor-bridge-acceptor (D-B-A) compounds consisting of π-conjugated oligofluorene (oFL) bridges between a ferrocene (Fc) electron-donor and a fullerene (C60) electron-acceptor have been synthesized. In addition to varying the length of the bridge (i.e., mono- and bi-fluorene derivatives), four different ways of linking ferrocene to the bridge have been examined. The Fc moiety is linked to oFL: 1) directly without any spacer, 2) by an ethynyl linkage, 3) by a vinylene linkage, and 4) by a p-phenylene unit. The electronic interactions between the electroactive species have been characterized by cyclic voltammetry, absorption, fluorescence, and transient absorption spectroscopy in combination with quantum chemical calculations. The calculations reveal exceptionally close energy-matching between the Fc and the oFL units, which results in strong electronic-coupling. Hence, intramolecular charge-transfer may easily occur upon exciting either the oFLs or Fcs. Photoexcitation of Fc-oFL-C60 conjugates results in transient radical-ion-pair states. The mode of linkage of the Fc and FL bridge has a profound effect on the photophysical properties. Whereas intramolecular charge-separation is found to occur rather independently of the distance, the linker between Fc and oFL acts (at least in oFL) as a bottleneck and significantly impacts the intramolecular charge-separation rates, resulting in beta values between βCS 0.08 and 0.19 Å−1. In contrast, charge recombination depends strongly on the electron-donor-acceptor distance, but not at all on the linker. A value of βCR (0.35±0.01 Å−1) was found for all the systems studied. Oligofluorenes prove, therefore, to be excellent bridges for probing how small structural variations affect charge transport in D-B-A systems. [ABSTRACT FROM AUTHOR]