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Quasi‐2D lead‐halide perovskites consist of conducting inorganic layers with tunable thickness (n) separated by large organic spacer cations. Typically, domains with different n and bandgaps are formed within a single film. Here, the crystallization of the films is tuned by mixing Dion‐Jacobson (DJ) with Ruddlesden‐Popper (RP) spacer cations. Compared to the quasi‐2D perovskite film based on solely the DJ type spacer 1,4‐phenylenedimethylammonium (PDMA), a film with less defects and more vertically aligned crystallization is achieved by addition of the RP type spacer propylammonium (PA). As the film structure plays an important role in the photophysics, time‐resolved photoluminescence (TRPL) and femtosecond transient absorption (TA) are used to investigate the impact of mixing these spacer cations on the dynamics of hot carrier cooling, the occurrence and directionality of energy or electron transfer between the different domains, and the exciton and charge carrier dynamics. Exciton transfer from low‐n to high‐n domains occurs at a favorable faster rate for the PDMA‐based film (0.0640 ps−1) compared to the PA‐based film (0.0365 ps−1), while the mixed spacer film demonstrates intermediate behavior (0.0473 ps−1). This study facilitates the design of advanced materials with optimized photophysical characteristics for a next generation of optoelectronic devices. [ABSTRACT FROM AUTHOR]

The donor–acceptor (D–A) dye 4‐(bis‐4‐(5‐(2,2‐dicyano‐vinyl)‐thiophene‐2‐yl)‐phenyl‐amino)‐benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1 dye is steered on NiO by co‐adsorption of tetradecanoic acid (C14, myristic acid (MA)). Density Functional Theory and time‐resolved photoluminescence studies confirm that twisting lowers the energy levels of the photoexcited D–A dye. The apolar environment provided by the MA suppresses photoinduced D–A twisting, retards charge recombination following photoinduced charge separation between P1 and NiO, and provides a larger electrochemical potential increasing the photocurrent. Very interestingly, co‐adsorption of MA induces H2 evolution upon photoexcitation without the presence of an H2 evolution catalyst. Based on prior art, the formation of H2 is assigned to the dissolution of Ni2+, followed by reduction and re‐deposition of Ni nanoparticles acting as the catalytically active site. It propose that only excited P1 with suppressed twisting provides the sufficient electrochemical potential to induce deposition of Ni nanoparticles. The work illustrates the importance of understanding the effects of photoinduced intramolecular twisting and highlights the promise of designing twisting‐limited D–A dyes to create efficient solar fuel devices. [ABSTRACT FROM AUTHOR]

Quasi-2D perovskites have attracted attention as potential solar energy absorber materials due to their balanced efficiency and stability and their unique quantum-well structures. In order to facilitate directional excitons and charge carrier transport and preferential energy transfer landscape in photovoltaic thin films, the phase distribution formed by different types of microstructural domains should be regulated. In this work, the Dion–Jacobson-type spacer 1,4-phenylenedimethanammonium (PDMA) was used, and different strategies were pursued to control the phase distribution in formamidinium-based (FA) quasi-2D perovskites based on the composition of (PDMA)FA4Pb5I16. In general, doping with FACl modulated the crystallization kinetics, forming 2D low-n crystals on the top surface or a reversed-gradient phase distribution, depending on whether excess or substitutional doping was employed. Alternatively, mixing with a Ruddlesden–Popper spacer helped bridging to adjacent octahedra in pure PDMA-based perovskites and improved crystallization, while regulating the quantum-well structures to give a normal-gradient phase distribution, where 2D domains resided on the bottom side. By combining FACl doping and spacer mixing, the film showed both a reversed-gradient phase distribution and larger vertically aligned grains. This work contributes to the knowledge of how to manipulate and regulate the phase distribution in FA-based quasi-2D perovskites and further paves the way for fabricating corresponding devices with high efficiency and stability. [ABSTRACT FROM AUTHOR]

A supramolecular photovoltaic strategy is applied to enhance power conversion efficiencies (PCE) of photoelectrochemical devices by suppressing electron–hole recombination after photoinduced electron transfer (PET). Here, the author exploit supramolecular localization of the redox mediator—in close proximity to the dye—through a rotaxane topology, reducing electron–hole recombination in p‐type dye‐sensitized solar cells (p‐DSSCs). Dye PRotaxane features 1,5‐dioxynaphthalene recognition sites (DNP‐arms) with a mechanically‐interlocked macrocyclic redox mediator naphthalene diimide macrocycle (3‐NDI‐ring), stoppering synthetically via click chemistry. The control molecule PStopper has stoppered DNP‐arms, preventing rotaxane formation with the 3‐NDI‐ring. Transient absorption and time‐resolved fluorescence spectroscopy studies show ultrafast (211 ± 7 fs and 2.92 ± 0.05 ps) PET from the dye‐moiety of PRotaxane to its mechanically interlocked 3‐NDI‐ring‐acceptor, slowing down the electron–hole recombination on NiO surfaces compared to the analogue. p‐DSSCs employing PRotaxane (PCE = 0.07%) demonstrate a 30% PCE increase compared to PStopper (PCE = 0.05%) devices, combining enhancements in both open‐circuit voltages (VOC = 0.43 vs 0.36 V) and short‐circuit photocurrent density (JSC = −0.39 vs −0.34 mA cm−2). Electrochemical impedance spectroscopy shows that PRotaxane devices exhibit hole lifetimes (τh) approaching 1 s, a 16‐fold improvement compared to traditional I−/I3−‐based systems (τh = 50 ms), demonstrating the benefits obtained upon nanoengineering of interfacial dye‐regeneration at the photocathode. [ABSTRACT FROM AUTHOR]

P‐type metal oxides, and in particular NiO, are typically used as hole accepting layers in dye‐sensitized photocathodes. Delafossites (CuMO2) with M=B, Al, Cr or Ga have recently been proposed as attractive substitutes for NiO, with theoretically a higher hole mobility than NiO, therefore allowing a higher efficiency when the photocathode is applied in solar to fuel devices. We have experimentally validated the photoelectrochemical performance of photocathodes consisting of nanoporous CuBO2 (CBO) on Fluorine‐doped Tin Oxide substrates, photosensitized with a light absorbing P1 dye. Femtosecond transient absorption and time‐resolved photoluminescence studies show that light‐induced hole injection occurs from the P1 dye into the CBO in a few ps, comparable to the time constant observed for NiO‐based photocathodes. Importantly, the CBO‐based photocathode shows significantly slower charge recombination than the NiO‐based analogue. These results illustrate the promise of CBO as a p‐type semiconductor in solar energy conversion devices. [ABSTRACT FROM AUTHOR]

The self-assembled natural chromosomal chromophores are used for realizing a long exciton length in an artificial light-harvesting system. The larger exciton diffusion coefficient for ZnOP has originated from a strong excitonic coupling for interstack dand the energy transfer is strongly affected by the molecular organization.

The photoinduced charge separation efficiency in porphyrin/TiO(sub 2) bilayers was determined using the time-resolved microwave conductivity technique and porphyrins investigated are unsubstituted mesotetphenylporphyrin (TPP) and meso-tetra(4-ethylphenyl)porphyrin (TEPP). Exciton diffusion lengths of 7A for TPP and 75 A for TEPP are obtained from fitting a model for the charge separation efficiency to the experimental data and the exciton diffusion coefficients, determined from the exciton diffusion length and the exciton lifetime, are found to be 2.10(Super -9) M(super 2)/s for TPP and 7.10(super -8) m(super 2)/s for TEPP.

We report transient absorption spectroscopic studies on the hybrid material composed of porphyrin molecules covalently attached to graphene for investigating the mechanism underlying the reported fluorescence quenching of porphyrin in the hybrid [1]. Excited state dynamics of pure graphene suspension and porphyrin have also been studied as reference samples. A fast excited state decay was observed in the hybrid.

The exciton root-mean-square displacement (ΛD) in regioregular poly(3-hexylthiophene) (P3HT) deposited onto meso-tetrakis (n-methyl-4-pyridyl) porphyrin tetrachloride (H2TMPyP) has been determined from the photovoltaic response of a device based on these materials in a bilayer configuration. Excitons formed on illumination that reach the interface between H2TMPyP and P3HT can undergo interfacial charge separation by electron injection into the H2TMPyP and hole injection into the P3HT. The incident photon to current efficiency (IPCE) exceeds 20% over a broad wavelength regime. The theoretical analysis of the IPCE values gives a value for ΛD in H2TMPyP that amounts to 14 nm, while for P3HT a value of 18 nm is obtained. The latter value exceeds literature values reported for P3HT by almost a factor of 3. X-ray diffraction analysis shows that in the studied bilayer the P3HT backbones are aligned parallel to the interface with H2TMPyP. In contrast, in the case of P3HT deposited onto TiO2, for which ΛD has been reported to equal only 7 nm, hardly any organization of the P3HT backbones is observed. The excitonic coupling between P3HT backbones deposited onto H2TMPyP is as high as 125 cm-1, a factor of 3 larger than the excitonic coupling between the disordered P3HT backbones that amounts to 47 cm-1. The difference illustrates the importance of controlling the molecular organization for the realization of efficient energy transfer in organic optoelectronics. [ABSTRACT FROM AUTHOR]

The exciton diffusion length in a nematically organized meso-tetra(4-n-butylhenyl)porphyrin (TnBuPP) layer has exceeded 40 nm at a temperature of 90 K. The absence of polaronic self-trapping has shown that the exciton diffusion coefficient can be increased by improvement of structural order and rigidity of the material.