Charge carriers' density, their lifetime, mobility, and the existence of trap states are strongly affected by the microscopic morphologies of perovskite films, and have a direct influence on the ...photovoltaic performance. Here, we report on micro-wrinkled perovskite layers to enhance photocarrier transport performances. By utilizing temperature-dependent miscibility of dimethyl sulfoxide with diethyl ether, the geometry of the microscopic wrinkles of the perovskite films are controlled. Wrinkling is pronounced as temperature of diethyl ether (T
) decreases due to the compressive stress relaxation of the thin rigid film-capped viscoelastic layer. Time-correlated single-photon counting reveals longer carrier lifetime at the hill sites than at the valley sites. The wrinkled morphology formed at T
= 5 °C shows higher power conversion efficiency (PCE) and better stability than the flat one formed at T
= 30 °C. Interfacial and additive engineering improve further PCE to 23.02%. This study provides important insight into correlation between lattice strain and carrier properties in perovskite photovoltaics.
In this Letter, we investigate the temperature dependence of the optical properties of methylammonium lead iodide (MAPbI3 = CH3NH3PbI3) from room temperature to 6 K. In both the tetragonal (T > 163 ...K) and the orthorhombic (T < 163 K) phases of MAPbI3, the band gap (from both absorption and photoluminescence (PL) measurements) decreases with decrease in temperature, in contrast to what is normally seen for many inorganic semiconductors, such as Si, GaAs, GaN, etc. We show that in the perovskites reported here, the temperature coefficient of thermal expansion is large and accounts for the positive temperature coefficient of the band gap. A detailed analysis of the exciton line width allows us to distinguish between static and dynamic disorder. The low-energy tail of the exciton absorption is reminiscent of Urbach absorption. The Urbach energy is a measure of the disorder, which is modeled using thermal and static disorder for both the phases separately. The static disorder component, manifested in the exciton line width at low temperature, is small. Above 60 K, thermal disorder increases the line width. Both these features are a measure of the high crystal quality and low disorder of the perovskite films even though they are produced from solution.
In an endeavor to correlate the optoelectronic properties of π-conjugated polymers with their structural properties, we investigated the aggregation of P3HT in THF solution within a temperature range ...from 300 to 5 K. By detailed steady-state, site-selective, and time-resolved fluorescence spectroscopy combined with Franck–Condon analyses, we show that below a certain transition temperature (265 K) aggregates are formed that prevail in different polymorphs. At 5 K, we can spectroscopically identify two H-type aggregates with planar polymer backbones yet different degree of order regarding their side chains. Upon heating, the H-character of the aggregates becomes gradually eroded, until just below the transition temperature the prevailing “aggregate” structure is that of still phase-separated, yet disordered main and side chains. These conclusions are derived by analyzing the vibrational structure of the spectra and from comparing the solution spectra with those obtained from thin films that were cooled slowly from the melting temperature to room temperature and that had been analyzed previously by various X-ray techniques. In addition, site selectively recorded fluorescence spectra show that there isdependent on temperatureenergy transfer from higher energy to lower energy aggregates. This suggests that they must form clusters with dimensions of the exciton diffusion length, i.e., several nanometers in diameter.
Recent developments in the field of high efficiency perovskite solar cells are based on stabilization of the perovskite crystal structure of FAPbI3 while preserving its excellent optoelectronic ...properties. Compositional engineering of, for example, MA or Br mixed into FAPbI3 results in the desired effects, but detailed knowledge of local structural features, such as local (dis)order or cation interactions of formamidinium (FA) and methylammonium (MA), is still limited. This knowledge is, however, crucial for their further development. Here, we shed light on the microscopic distribution of MA and FA in mixed perovskites MA1–x FA x PbI3 and MA0.15FA0.85PbI2.55Br0.45 by combining high-resolution double-quantum 1H solid-state nuclear magnetic resonance (NMR) spectroscopy with state-of-the-art near-first-principles accuracy molecular dynamics (MD) simulations using machine-learning force-fields (MLFFs). We show that on a small local scale, partial MA and FA clustering takes place over the whole MA/FA compositional range. A reasonable driving force for the clustering might be an increase of the dynamical freedom of FA cations in FA-rich regions. While MA0.15FA0.85PbI2.55Br0.45 displays similar MA and FA ordering as the MA1–x FA x PbI3 systems, the average cation–cation interaction strength increased significantly in this double mixed material, indicating a restriction of the space accessible to the cations or their partial immobilization upon Br– incorporation. Our results shed light on the heterogeneities in cation composition of mixed halide perovskites, helping to exploit their full optoelectronic potential.
We show that mechanochemically synthesized halide perovskite powders from a ball milling approach can be employed to fabricate a variety of lead halide perovskites with exceptional intrinsic ...stability. Our MAPbI3 powder exhibits higher thermal stability than conventionally processed thin films, without degradation after more than two and a half years of storage and only negligible degradation after heat treatment at 220 °C for 14 h. We further show facile recovery strategies of nonphase-pure powders by simple remilling or mild heat treatment. Moreover, we demonstrate the mechanochemical synthesis of phase-pure mixed perovskite powders, such as (Cs0.05FA0.95PbI3)0.85(MAPbBr3)0.15, from either the individual metal and organic halides or from readily prepared ternary perovskites, regardless of the precursor phase purity. Adding potassium iodide (KI) to the milling process successfully passivated the powders. We also succeeded in preparing a precursor solution on the basis of the powders and obtained uniform thin films for integration into efficient perovskite solar cells from spin-coating this solution. We find the KI passivation remains in the devices, leading to improved performance and significantly reduced hysteresis. Our work thus demonstrates the potential of mechanochemically synthesized halide perovskite powders for long-time storage and upscaling, further paving the way toward commercialization of perovskite-based optoelectronic devices.
Conjugated poly(3-hexylthiophene) (P3HT) chains are known to exist at least in two distinct conformations: a coiled phase and a better ordered aggregated phase. Employing steady state absorption and ...fluorescence spectroscopy, we measure the course of aggregation of P3HT in tetrahydrofuran (THF) solution within a temperature range of 300 K to 170 K. We show that aggregation is a temperature controlled process, driven by a thermodynamic order–disorder transition. The transition temperature increases with the molecular weight of the chains and can be rationalized in the theory of Sanchez. This implies a smearing out of the phase transition in samples with increasing polydispersity and erodes the signature of a first order phase transition. The detection of a hysteresis when undergoing cooling/heating cycles further substantiates this reasoning.
Halide perovskites have undergone an impressive development and could be used in a wide range of optoelectronic devices, where some of them are already at the edge of commercialization, e.g., ...perovskite solar cells. Recently, interest in perovskites in powder form has increased, as for example, they are found to exhibit high stability and allow for easy production of large quantities. Accordingly, also the topic of processing thin and thick films on the basis of perovskite powders is currently gaining momentum. Here, perovskite powder can form the basis for both, typical wet and solvent‐based processing approaches, as well as for dry processes. In this Progress Report, the recent developments of halide perovskites in powder form and of film processing approaches are summarized that are based on them. The advantages and opportunities of the different processing methods are highlighted, but their individual drawbacks and limitations are also discussed. Prospects are also pointed out and possible steps necessary to unlock the full potential of powder‐based processing methods for producing high quality thick and thin perovskite layers in the future are discussed.
In this progress report, the recent developments of halide perovskites in powder form and their film processing approaches are focused on. The current limitations of these methods are shown, and the advantages and opportunities of powder‐based halide perovskite processing are also highlighted.
We present the successful fabrication of CH₃NH₃PbI₃ perovskite layers by the aerosol deposition method (ADM). The layers show high structural purity and compactness, thus making them suitable for ...application in perovskite-based optoelectronic devices. By using the aerosol deposition method we are able to decouple material synthesis from layer processing. Our results therefore allow for enhanced and easy control over the fabrication of perovskite-based devices, further paving the way for their commercialization.
In situ measurement techniques, applied during the solution processing of novel semiconductors such as organic semiconductors or hybrid perovskites, have become more and more important to understand ...their film formation. In that context, it is crucial to determine how the optical properties, namely photoluminescence (PL) and absorption, evolve during processing. However, until now PL and absorption have mostly been investigated independently, significantly reducing the potential insights into film formation dynamics. To tackle this issue we present the development of a detection system that allows simultaneous measurement of full absorption and PL spectra during solution processing of the investigated film. We also present a spin-coater system attachable to the detection system, where the temperature of the substrate on which the film is processed can be changed. We performed test measurements by spin coating the well-known conjugated polymer P3HT demonstrating the potential of this technique. By considering absorption and corresponding PL, we extract the PL quantum yield (PLQY) during processing, which decreases with substrate temperature. Furthermore, we identify a significant red shift of the PL just prior to the onset of the aggregation process, indicating the importance of chain planarization prior to solid film formation.
The aggregation of π-conjugated materials significantly impacts the photophysics and performance of optoelectronic devices. Nevertheless, little is known about the laws governing aggregate formation ...of π-conjugated materials from solution. In this Perspective, we compare, discuss, and summarize how aggregates form for three different types of compounds, that is, homopolymers, donor–acceptor type polymers, and low molecular weight compounds. To this end, we employ temperature-dependent optical spectroscopy, which is a simple yet powerful tool to investigate aggregate formation. We show how optical spectra can be analyzed to identify distinct conformational states. We find aggregate formation to proceed the same in all these compounds by a coil-to-globule-like first-order phase transition. Notably, the chain expands before it collapses into a highly ordered dense state. The role of side chains and the impact of changes in environmental polarization are addressed.
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