Understanding the interplay between the kinetics and energetics of photophysical processes in perovskite-chromophore hybrid systems is crucial for realizing their potential in optoelectronics, photocatalysis, and light-harvesting applications. By combining steady-state optical characterizations and transient absorption spectroscopy, we have investigated the mechanism of interfacial charge transfer (CT) between colloidal CsPbBr₃ nanoplatelets (NPLs) and surface-anchored perylene derivatives and have explored the possibility of controlling the CT rate by tuning the driving force. The CT driving force was tuned systematically by attaching acceptors with different electron affinities and by varying the bandgap of NPLs via thickness-controlled quantum confinement. Our data show that the charge-separated state is formed by selectively exciting either the electron donors or acceptors in the same system. Upon exciting attached acceptors, hole transfer from perylene derivatives to CsPbBr₃ NPLs takes place on a picosecond time scale, showing an energetic behavior in line with the Marcus normal regime. Interestingly, such energetic behavior is absent upon exciting the electron donor, suggesting that the dominant CT mechanism is energy transfer followed by ultrafast hole transfer. Our findings not only elucidate the photophysics of perovskite-molecule systems but also provide guidelines for tailoring such hybrid systems for specific applications.

Spatiotemporal pH imaging using fluorescence lifetime imaging microscopy (FLIM) is an excellent technique for investigating dynamic (electro)chemical processes. However, probes that are responsive at high pH values are not available. Here, we describe the development and application of dedicated pH probes based on the 1-methyl-7-amino-quinolinium fluorophore. The high fluorescence lifetime and quantum yield, the high (photo)stability, and the inherent water solubility make the quinolinium fluorophore well suited for the development of FLIM probes. Due to the flexible fluorophore-spacer-receptor architecture, probe lifetimes are tunable in the pH range between 5.5 and 11. An additional fluorescence lifetime response, at tunable pH values between 11 and 13, is achieved by deprotonation of the aromatic amine at the quinolinium core. Probe lifetimes are hardly affected by temperature and the presence of most inorganic ions, thus making FLIM imaging highly reliable and convenient. At 0.1 mM probe concentrations, imaging at rates of 3 images per second, at a resolution of 4 μm, while measuring pH values up to 12 is achieved. This enables the pH imaging of dynamic electrochemical processes involving chemical reactions and mass transport.

3D hybrid perovskites (APbX₃) have made a significant impact on the field of optoelectronic materials due to their excellent performance combined with facile solution deposition and up-scalable device fabrication. Nonetheless, these materials suffer from environmental instability. To increase material stability, the organic cation (A) is substituted by the non-volatile cesium cation. However, the desired photoactive cesium lead(II) iodide black phase is metastable in ambient conditions and spontaneously converts into the photo-inactive yellow δ-phase. In this work, the black phase is stabilized by the formation of a quasi-2D perovskite containing a benzothieno[3,2-b]benzothiophene (BTBT) large organic ammonium cation. Thermal analysis shows that degradation of the butylammonium (BA)-based quasi-2D perovskite (BA)₂CsPb₂I₇ sets in at ≈130 °C, while (BTBT)₂CsPb₂I₇ is phase-stable until ≈230 °C. Additionally, the (BTBT)₂CsPb₂I₇ film does not show any sign of degradation after exposure to 77% Relative Humidity in the dark for 152 days, while (BA)₂CsPb₂I₇ degrades in a single day. Photoconductor-type detectors based on (BTBT)₂CsPb₂I₇ demonstrate an increased external quantum efficiency and a similar specific detectivity compared to the BA-based reference detectors. The results demonstrate the utility of employing a BTBT cation within the organic layer of quasi-2D perovskites to significantly enhance the stability while maintaining the optoelectronic performance.

One of the most promising properties of lead halide perovskite nanocrystals (NCs) is their defect tolerance. It is often argued that, due to the electronic structure of the conduction and valence bands, undercoordinated ions can only form localized levels inside or close to the band edges (i.e., shallow traps). However, multiple studies have shown that dangling bonds on surface Br- can still create deep trap states. Here, we argue that the traditional picture of defect tolerance is incomplete and that deep Br- traps can be explained by considering the local environment of the trap states. Using density functional theory calculations, we show that surface Br- sites experience a destabilizing local electrostatic potential that pushes their dangling orbitals into the bandgap. These deep trap states can be electrostatically passivated through the addition of ions that stabilize the dangling orbitals via ionic interactions without covalently binding to the NC surface. These results shed light on the formation of deep traps in perovskite NCs and provide strategies to remove them from the bandgap.

Switching effects are key elements in the design and characterization of nanoscale molecular electronics systems. They are used to achieve functionality through the transition between different conducting states. In this study, we analyze the presence of switching events in reference molecular systems, which are not designed to have switching behavior, such as oligo(phenylene ethynylene)s and alkanes, using the mechanically controllable break junction technique. These events can be classified in two groups, depending on whether the breaking trace shows exponential decay or plateau-like features before the switch happens. We argue that the former correspond to junctions forming after rupture of the gold atomic point contact, while the latter can be related to a change in the contact geometry of the junction. These results highlight how a proper choice of anchoring group and careful comparison with reference compounds are essential to understanding the origin of switching in molecular break junctions.

A series of three perylenemonoimide-p-oligophenylene-dimethylaniline molecular dyads undergo photoinduced charge separation (CS) with anomalous distance dependence as a function of increasing donor-acceptor (DA) distances. A comprehensive experimental and computational investigation of the photodynamics in the donor-bridge-acceptor (DBA) chromophores reveals a clear demarcation concerning the nature of the CS accessed at shorter (bridgeless) and longer DA distances. At the shortest distance, a strong DA interaction and ground-state charge delocalization populate a hot excited state (ES) with prominent charge transfer (CT) character, via Franck-Condon vertical excitation. The presence of such a CT-polarized hot ES enables a subpicosecond CS in the bridgeless dyad. The incorporation of the p-oligophenylene bridge effectively decouples the donor and the acceptor units in the ground state and consequentially suppresses the CT polarization in the hot ES. Theoretically, this should render a slower CS at longer distances. However, the transient absorption measurement reveals a fast CS process at the longer distance, contrary to the anticipated exponential distance dependence of the CS rates. A closer look into the excited-state dynamics suggests that the hot ES undergoes ultrafast geometry relaxation (τ < 1 ps) to create a relaxed ES. As compared to a decoupled, twisted geometry in the hot ES, the geometry of the relaxed ES exhibits a more planar conformation of the p-oligophenylene bridges. Planarization of the bridge endorses an increased charge delocalization and a prominent CT character in the relaxed ES and forms the origin for the evident fast CS at the longest distance. Thus, the relaxation of the hot ES and the concomitantly enhanced charge delocalization adds a new caveat to the classic nature of distance-dependent CS in artificial DBA chromophores and recommends a cautious treatment of the attenuation factor (β) while discussing anomalous CS trends.

The control of local order in polymer semiconductors using non-covalent interactions may be used to engineer materials with interesting combinations of mechanical and optoelectronic properties. To investigate the possibility of preparing n-type polymer semiconductors in which hydrogen bonding plays an important role in structural order and stability, we have used solution-phase polycondensation to incorporate dicyanoperylene bisimide repeat units into an aliphatic polyamide chain backbone. The morphology and thermomechanical characteristics of the resulting polyamides, in which the aliphatic spacer length was varied systematically, were comparable with those of existing semiaromatic engineering polyamides. At the same time, the charge carrier mobility as determined by pulse-radiolysis time-resolved microwave conductivity measurements was found to be about 10-2 cm2 V-1 s-1, which is similar to that reported for low molecular weight perylene bisimides. Our results hence demonstrate that it is possible to use hydrogen bonding interactions as a means to introduce promising optoelectronic properties into high-performance engineering polymers.

Donor-bridge-acceptor systems based on boron dipyrromethene (BODIPY) are attractive candidates for bio-imagining and sensing applications because of their sensitivity to temperature, micro-viscosity and solvent polarity. The optimization of the properties of such molecular sensors requires a detailed knowledge of the relation between the structure and the photophysical behavior in different environments. In this work we have investigated the excited-state dynamics of three acceptor-donor-acceptor molecules based on benzodithiophene and BODIPY in solvents of different polarities using a combination of ultrafast spectroscopy and DFT-based electronic structure calculations. Transient absorption spectra show that upon photoexcitation an initial excited species with an induced absorption band in the near-infrared regime is formed independent of the solvent polarity. The subsequent photophysical processes strongly depend on the solvent polarity. In non-polar toluene this initial excited state undergoes a structural relaxation leading to a delocalized state with partial charge transfer character, while in the more polar tetrahydrofuran a fully charge separated state is formed. The results clearly show how factors such as donor-acceptor distance and restricted rotational motion by steric hindrance can be used to tune the excited state photophysics to optimize such systems for specific applications.

Low-dimensional hybrid perovskites have emerged as promising materials for optoelectronic applications. Although these materials have already demonstrated enhanced stability as compared to their three-dimensional perovskite analogues, their functionality has been limited by the insulating character of the organic moieties that primarily play a structure-directing role. This is particularly the case for the layered (2D) perovskite materials based on formamidinium lead iodide (FAPbI3) that remain scarce. We demonstrate a low-dimensional hybrid perovskite material based on a SPbI4 composition incorporating an electroactive naphthalenediimide (NDI) moiety as an organic spacer (S) between the perovskite slabs and evidence the propensity of the spacer to stabilize the α-FAPbI3 perovskite phase in hybrid low-dimensional SFAn-1PbnI3n+1 perovskite compositions. This has been investigated by means of solid-state nuclear magnetic resonance spectroscopy in conjunction with molecular dynamics simulations and density functional theory calculations. Theoretical calculations suggest an electronic contribution of the organic spacer to the resulting optoelectronic properties, which was confirmed by transient absorption spectroscopy. We have further analyzed these materials by time-resolved microwave conductivity measurements, revealing challenges for their application in photovoltaics.

Solution-processed quasi-2D perovskites are promising for stable and efficient solar cells because of their superior environmental stability compared to 3D perovskites and tunable optoelectronic properties. Changing the number of inorganic layers (n) sandwiched between the organic spacers allows for tuning of the bandgap. However, narrowing the phase distribution around a specific n-value is a challenge. In-situ UV–vis–NIR absorption spectroscopy is used to time-resolve the crystallization dynamics of quasi-2D butylammonium-based (BA) perovskites with <n> = 4, processed from N,N-dimethylformamide (DMF) in the presence of different co-solvents. By combining with photoluminescence, transient absorption, and grazing-incidence wide-angle X-ray scattering, the crystallization is correlated to the distribution of phases with different n-values. Infrared spectroscopy and density functional theory reveal that the phase distribution correlates with perovskite precursor—co-solvent interaction energies and that stronger interactions shift the phase distribution towards smaller n-values. Careful tuning of the solvent/co-solvent ratio provides a more homogeneous phase distribution, with highly oriented perovskite crystals and suppressed formation of n = 1–2 phases, providing a power conversion efficiency for BA₂MA₃Pb₄I₁₃ solar cells that increases from 3.5% when processed from DMF to over 11% and 10% when processed from DMF/dimethyl sulfoxide and DMF/N-methyl-2-pyrrolidone mixtures, respectively.

In this contribution we demonstrate a solid-state approach to triplet-triplet annihilation upconversion for application in a solar cell device in which absorption of near-infrared light is followed by direct electron injection into an inorganic substrate. We use time-resolved microwave photoconductivity experiments to study the injection of electrons into the electron-accepting substrate (TiO₂) in a trilayer device consisting of a triplet sensitizer (fluorinated zinc phthalocyanine), triplet acceptor (methyl subsituted perylenediimide), and smooth polycrystalline TiO₂. Absorption of light at 700 nm leads to the almost quantitative generation of triplet excited states by intersystem crossing. This is followed by Dexter energy transfer to the triplet acceptor layer where triplet annihilation occurs and concludes by injection of an electron into TiO₂ from the upconverted singlet excited state.

Formamidinium (FA) lead iodide perovskite materials feature promising photovoltaic performances and superior thermal stabilities. However, conversion of the perovskite α-FAPbI₃ phase to the thermodynamically stable yet photovoltaically inactive δ-FAPbI₃ phase compromises the photovoltaic performance. A strategy is presented to address this challenge by using low-dimensional hybrid perovskite materials comprising guaninium (G) organic spacer layers that act as stabilizers of the three-dimensional α-FAPbI₃ phase. The underlying mode of interaction at the atomic level is unraveled by means of solid-state nuclear magnetic resonance spectroscopy, X-ray crystallography, transmission electron microscopy, molecular dynamics simulations, and DFT calculations. Low-dimensional-phase-containing hybrid FAPbI₃ perovskite solar cells are obtained with improved performance and enhanced long-term stability.

In recent years, a wide range of single-molecule devices has been realized, enabled by technological advances combined with the versatility offered by synthetic chemistry. In particular, single-molecule diodes have attracted significant attention with an ongoing effort to increase the rectification ratio between the forward and reverse current. Various mechanisms have been investigated to improve rectification, either based on molecule-intrinsic properties or by engineering the coupling of the molecule to the electrodes. In this perspective, we first provide an overview of the current experimental approaches reported in literature to achieve rectification at the single-molecule level. We then proceed with our recent efforts in this direction, exploiting the internal structure of multi-site molecules, yielding the highest rectification ratio based on a molecule-intrinsic mechanism. We introduce the theoretical framework for multi-site molecules and infer general design guidelines from this. Based on these guidelines, a series of two-site molecules have been developed and integrated into devices. Using two- and three-terminal mechanically controllable break junction measurements, we show that depending on the on-site energies, which are tunable by chemical design, the devices either exhibit pronounced negative differential conductance, or behave as highly-efficient rectifiers. Finally, we propose a design of a single-molecule diode with a theoretical rectification ratio exceeding a million.

Recently two-dimensional (2D) hybrid organic-inorganic perovskites have attracted a lot of interest as more stable analogues of their three-dimensional counterparts for optoelectronic applications. However, a thorough understanding of the effect that this reduced dimensionality has on dynamical and structural behavior of individual parts of the perovskite is currently lacking. We have used molecular dynamics simulations to investigate the structure and dynamics of 2D Ruddlesden-Popper perovskite with the general formula BA2MAn-1PbnI3n+1, where BA is butylammonium, MA is methylammonium, and n is the number of lead-iodide layers. We discuss the dynamic behavior of both the inorganic and the organic part and compare between the different 2D structures. We show that the rigidness of the inorganic layer markedly increases with the number of lead-iodide layers and that low-temperature structural phase changes accompanied by tilting of the octahedra occurs in some but not all structures. Furthermore, the dynamic behavior of the MA ion is significantly affected by the number of inorganic layers, involving changes both in the reorientation times and in the occurrence of specific preferred orientations.

Two-dimensional (2D) hybrid perovskites make up an emerging class of materials for optoelectronic applications in which inorganic octahedral layers are separated by nonconductive large organic cations. This leads to a high-dimensional and dielectric confinement and hence a high exciton binding energy, which severely limits their application in devices in which charge carrier separation is required. In this work, we achieve improved charge separation by replacing nonconductive organic cations with organic charge-transfer complexes consisting of a pyrene donor and a tetracyanoquinodimethane acceptor. Steady-state absorption measurements show that these materials exhibit optical features that match with the absorption of the organic charge-transfer complexes. Using microwave conductivity and femtosecond transient absorption, we show that photoexcitation of these charge-transfer states leads to long-lived mobile charges in the inorganic layers. While the efficiency of charge separation is relatively low, these experiments demonstrate that it is possible to induce charge separation in solid-state 2D perovskites by engineering the organic layer.

Two-dimensional (2D) hybrid organic-inorganic perovskites are an interesting class of semi-conducting materials. One of their main advantages is the large freedom in the nature of the organic spacer molecules that separates the individual inorganic layers. The nature of the organic layer can significantly affect the structure and dynamics of the 2D material; however, there is currently no clear understanding of the effect of the organic component on the structural parameters. In this work, we have used molecular dynamics simulations to investigate the structure and dynamics of a 2D Ruddlesden-Popper perovskite with a single inorganic layer (n = 1) and varying organic cations. We discuss the dynamic behavior of both the inorganic and the organic part of the materials as well as the interplay between the two and compare the different materials. We show that both aromaticity and the length of the flexible linker between the aromatic unit and the amide have a clear effect on the dynamics of both the organic and the inorganic part of the structures, highlighting the importance of the organic cation in the design of 2D perovskites.

Metal halide perovskite solar cells (PSCs) are of interest for high altitude and space applications due to their lightweight and versatile form factor. However, their resilience toward the particle spectrum encountered in space is still of concern. For space cells, the effect of these particles is condensed into an equivalent 1 MeV electron fluence. The effect of high doses of 1 MeV e-beam radiation up to an accumulated fluence to 10¹⁶ e⁻ cm⁻² on methylammonium lead iodide perovskite thin films and solar cells is probed. By using substrate and encapsulation materials that are stable under the high energy e-beam radiation, its net effect on the perovskite film and solar cells can be studied. The quartz substrate-based PSCs are stable under the high doses of 1 MeV e-beam irradiation. Time-resolved microwave conductivity analysis on pristine and irradiated films indicates that there is a small reduction in the charge carrier diffusion length upon irradiation. Nevertheless, this diffusion length remains larger than the perovskite film thickness used in the solar cells, even for the highest accumulated fluence of 10¹⁶ e⁻ cm⁻². This demonstrates that PSCs are promising candidates for space applications.

Structure-property relationships of donor-π-acceptor (D-π-A) type molecular dyad (pp-AD) and triads (pp-ADA and Me-pp-ADA) based on benzodithiophene and BODIPY with biphenyl spacers have been reported. Rotors pp-AD and pp-ADA showed efficient twisted intramolecular charge transfer (TICT) with near infrared (NIR) emissions at ∼712 nm and ∼725 nm with (pseudo-)Stokes shifts of ∼208 nm and ∼221 nm, respectively, and prominent solvatochromism. A structurally similar triad, Me-pp-ADA, with tetramethyl substituents on the BODIPY core instead was TICT inactive and exhibited excitation energy transfer with a transfer efficiency of ∼88% as revealed using steady state emission and transient absorption measurements. Rotors pp-AD and pp-ADA showed NIR emission with an enhancement in intensity with the addition of water in THF solution as well as a pronounced change in emission intensity with temperature and viscosity variations, which justify their utility as temperature and viscosity sensors. Furthermore, the linear correlation of lifetime with fluorescence intensity ratios of the donor and acceptor justifies the rigidochromic behaviour of these rotors. This journal is

2D layered hybrid perovskites are currently in the spotlight for applications such as solar cells, light-emitting diodes, transistors and photodetectors. The structural freedom of 2D layered perovskites allows for the incorporation of organic cations that can potentially possess properties contributing to the performance of the hybrid as a whole. In this study, we incorporated a benzothieno[3,2-b]benzothiophene (BTBT) alkylammonium cation into the organic layer of a 2D layered lead iodide perovskite. The formation and degradation of this material are discussed in detail. It is shown that the use of a solvent vapour annealing method significantly enhances the absorption, emission and crystallinity of films of this 2D layered perovskite as compared to regular thermal annealing. The photoconductivity of the films was determined using time-resolved microwave conductivity (TRMC) as well as in a device. In both cases, the solvent vapour annealed films show markedly higher photoconductivity than the films obtained using the regular thermal annealing approach.