Lisanne M. Einhaus

Quasi-two-dimensional (quasi-2D) lead halide perovskites with alternating cations in the interlayer (ACI) space represent a promising type of material for optoelectronics. Similar to the Ruddlesden–Popper and Dion–Jacobson types of perovskites, domains with different thicknesses (n) and bandgaps are formed within a single film. This work focuses on ⟨n⟩ = 5 ACI perovskites based on guanidinium (GA⁺) and methylammonium (MA⁺) cations and investigates the influence of the GA:MA ratio in the interlayer space on the photophysical processes after photoexcitation. Using a combination of time-resolved photoluminescence (TRPL) and femtosecond transient absorption (TA) spectroscopy, hot carrier cooling, the occurrence and directionality of energy or charge transfer between the different domains, and the exciton and charge carrier dynamics are studied and modeled using target analysis. After the thermalization of hot carriers and excitons, exciton transfer from low-n to high-low-n domains occurs within 10 ps, after which they dissociate into free charges. From there, charge transfer into the intermediate-n domains occurs in about 22–54 ps. In the layers with excess GA, this process possibly occurs in an undesirable competition with self-trapped exciton (STE) formation. From the intermediate-n domains, charges are transferred into the high-n domains in 95–159 ps, which process occurs the fastest in the GA-MA layer. Finally, charge carriers decay intrinsically on the nanosecond scale with the longest lifetimes for the GA-MA and GA-2MA systems, which is beneficial for PV applications.

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.

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.

The diammonium precursor 1,4-phenylenedimethanammonium (PDMA) was used as a large organic spacer for the preparation of Dion-Jacobson-type quasi-2D perovskites (PDMA)(MA)_n-1Pb_nI_3n+1 (MA = methylammonium). Films with composition ⟨n⟩ = 5 comprised randomly orientated grains and multiple microstructural domains with locally differing n values. However, by mixing the Dion-Jacobson-type spacer PDMA and the Ruddlesden-Popper-type spacer propylammonium (PA), the crystal orientation in both the vertical and the horizonal directions became regulated. High crystallinity owing to well-matched interlayer distances was observed. Combining this spacer-engineering approach with the addition of methylammonium chloride (MACl) led to full vertical alignment of the crystal orientation. Moreover, the microstructural domains at the substrate interface changed from low-n (n = 1, 2, 3) to high-n (n = 4, 5), which may be beneficial for hole extraction at the interface between perovskite and hole transport layer due to a more finely tuned band alignment. Our work sheds light on manipulating the crystallization behavior of quasi-2D perovskite and further paves the way for highly stable and efficient perovskite devices.

In the present study, we investigate the effects of the applied external potential on a dye-sensitized NiO photocathode by time-resolved photoluminescence and femtosecond transient absorption spectroscopy under operating conditions. Instead of the anticipated acceleration of photoinduced hole injection from dye into NiO at a more negative applied potential, we observe that both hole injection and charge recombination are slowed down. We cautiously assign this effect to a variation in OH- ion concentration in the inner Helmholtz plane of the electrochemical double layer with applied potential, warranting further investigation for the realization of efficient solar fuel devices.

Quasi-two-dimensional (2D) metal halide perovskites (MHPs) are promising photovoltaic (PV) materials because of their impressive optical and optoelectronic properties and improved stability compared to their 3D counterparts. The presence of domains with varying numbers of inorganic layers between the organic spacers (n-phases), each with different bandgaps, makes the photoinduced carrier dynamics in films of these materials complex and intriguing. Existing interpretations of the ultrafast femto- or picosecond spectroscopy data have been inconsistent, most of them focusing either on exciton/charge transfer from low-n to high-n phases or on hot carrier cooling, but not combined. Here, we present a comprehensive study of the carrier dynamics in the Dion-Jacobson type (PDMA)(MA)_(n-1)Pb_nI_(3n+1) (PDMA = 1,4-phenylenedimethylammonium, MA = methylammonium) perovskite, stoichiometrically prepared as ⟨n⟩ = 5. Within the film, a coexistence of various n-phases is observed instead of solely the n = 5 phase, resulting in an interesting energy landscape for the motion of excitons and charge carriers. We disentangle hot carrier cooling from exciton transfer between low-n and high-n phases using ultrafast time-resolved photoluminescence and transient absorption spectroscopy. Photophysical modeling by target analysis shows that carrier cooling occurring on a subpicosecond time scale is followed by exciton transfer from low-n into high-n phases in ca. 35 ps when the film is excited by 532 or 490 nm light. Carriers in the high-n phase are much longer lived and decay in a ns time window. Overall, our results provide a comprehensive understanding of the photophysics of this material, which helps to optimize quasi-2D MHP materials for a new generation of PV devices.

We report on a photonic system capable of collimating diffuse light in free space. In this system, photons are absorbed by luminophores (lumogen red) embedded in a PMMA waveguide and subsequently emitted with red-shifted wavelength. These photons are allowed to exit the waveguide if their trajectory falls within the emission cone dictated by a spectro-angular notch filter at the front of the device. We experimentally observed an 18% higher photon emission than an ideal Lambertian reflector at an angle normal to the system surface, thereby confirming our previously established analytical model for the collimation of diffused light in free space.

In present study we investigate the effect of the external potential on a dye-sensitized NiO photocathode on the light-induced charge carrier dynamics by time-resolved photoluminescence and femtosecond transient absorption spectroscopy under operating conditions. Instead of the anticipated acceleration of photoinduced hole injection from dye into NiO at more negative applied potential, we observe that both hole injection and charge recombination are slowed down. We assign this effect to a variation in OH- ion concentration in the inner Helmholtz plane (IHP) of the electrochemical double layer with applied potential, showing that ion adsorption and desorption onto the NiO surface play an essential role as a relay in light-induced charge transfer and recombination. Our work highlights the key role of ions at the electrode surface and in the electrolyte in the realization of efficient solar to fuel devices.