Piezoelectric energy harvesting is a process in which energy in the form of kinetic movements can be harvested and converted into useful electrical energy using piezoelectric materials. Metal-organic frameworks (MOFs) have a huge potential for piezoelectric energy harvesting owing to their high flexibility, structural tunability, and very low dielectric constants due to their high porosity. The piezoelectric constant d relevant for piezoelectric energy harvesting depends on the piezoelectric constant e and the flexibility of the structure (i.e. mechanical properties). The mechanical properties of MOFs have previously been extensively studied but the piezoelectric constant e was never explored for MOFs. In this work, we generate a database of piezoelectric properties, specifically e for around ∼1608 previously synthesized non-centrosymmetric MOF structures. The calculations were performed using the density functional perturbation theory (DFPT) method. The highest piezoelectric constant e obtained in this work is approximately ∼2.76 C m⁻², which is significantly higher than that of the flexible organic piezoelectric polymer polyvinylidene fluoride (PVDF) and its copolymers. In this work, we analyze and identify structural factors that influence the values of the piezoelectric constant for high-performing MOFs. Based on that, a series of guidelines for the design of MOF structures that can lead to a high piezoelectric constant e are presented. One class of high-performing piezoelectric MOFs is based on polar patterns of O—(short)—Mo—(long)—O unequal bond length, reminiscent of ferroelectric inorganic oxides. This class could have potential for ferroelectricity, meaning that the bond length pattern could be reversed by external electrical field. We substantiate this by showing experimentally via SHG-microscopy that the O—(short)—Mo—(long)—O unequal bond lengths are indeed malleable by external conditions.

Due to significantly lower costs than compound semiconductor counterparts, there is increasing interest in using silicon solar cells for cost-sensitive space missions, particularly in low Earth orbit (LEO). A major concern is, however, that the minority carrier lifetime (lifetime) of silicon solar cells degrades severely under high-energy electron irradiation. Fortunately, thermal and hydrogenation processes can potentially recover all the irradiation losses. This work studies these defects and their recovery using contactless lifetime measurement and deep-level transient spectroscopy (DLTS). Both fired and unfired Ga-doped passivated emitter and rear contact (PERC) solar cell precursors are used in this work. The precursors were irradiated with 1 MeV electrons and annealed at 300 °C and 380 °C, respectively. All the samples exhibited lifetime recovery, with fired samples recovering faster and achieving higher saturated lifetime. After ∼360s of annealing at 380 °C, the irradiated fired samples recovered to their pre-irradiation lifetime, whereas the irradiated non-fired samples required 71.5 times longer (25,740 s). Remarkably, longer annealing caused reductions in lifetime, likely due to surface-related degradation. The DLTS measurements revealed a clear reduction of recombination-active defects after annealing, including V-V⁺ and C_i-C_s in irradiated fired samples and V-V⁺ in irradiated unfired samples. This study demonstrates that the firing process is critical for optimizing the recovery of irradiation damage in silicon solar cells. Hydrogenation of the silicon bulk results in quicker recovery and superior End-of-life performance compared to thermal recovery without hydrogen. Therefore, Ga PERC with bulk hydrogenation can recover radiation-induced damage, rendering it suitable for LEO missions.

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.

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.

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.

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.

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.

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.

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.

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

Layered hybrid perovskites comprising adamantyl spacer (A) cations based on the A₂FA_n−1Pb_nI_3n+1(n= 1-3, FA = formamidinium) compositions have recently been shown to act as promising materials for photovoltaic applications. While the corresponding perovskite solar cells show performances and stabilities that are superior in comparison to other layered two-dimensional formamidinium-based perovskite solar cells, the underlying reasons for their behaviour are not well understood. We provide a comprehensive investigation of the structural and photophysical properties of this unique class of materials, which is complemented by theoretical analysisviamolecular dynamics simulations and density functional theory calculations. We demonstrate the formation of well-defined structures of lower compositional representatives based onn= 1-2 formulations with (1-adamantyl)methanammonium spacer moieties, whereas higher compositional representatives (n> 2) are shown to consist of mixtures of low-dimensional phases evidenced by grazing incidence X-ray scattering. Furthermore, we reveal high photoconductivities of the corresponding hybrid perovskite materials, which is accompanied by long charge carrier lifetimes. This study thereby unravels features that are relevant for the performance of FA-based low-dimensional hybrid perovskites.

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.

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.

In this work we demonstrate a novel approach to achieve efficient charge separation in dimensionally and dielectrically confined two-dimensional perovskite materials. Two-dimensional perovskites generally exhibit large exciton binding energies that limit their application in optoelectronic devices that require charge separation such as solar cells, photo-detectors and in photo-catalysis. Here, we show that by incorporating a strongly electron accepting moiety, perylene diimide organic chromophores, on the surface of the two-dimensional perovskite nanoplatelets it is possible to achieve efficient formation of mobile free charge carriers. These free charge carriers are generated with ten times higher yield and lifetimes of tens of microseconds, which is two orders of magnitude longer than without the peryline diimide acceptor. This opens a novel synergistic approach, where the inorganic perovskite layers are combined with functional organic chromophores in the same material to tune the properties for specific applications.