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.
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.
A spin-crossover coordination polymer [Fe(L1)(bipy)] (where L = a NO coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4'-bipyridine) was synthesized and exhibits a 48 K wide thermal hysteresis above room temperature (T↑ = 371 K and T↓ = 323 K) that is stable for several cycles. The spin transition was characterized using magnetic measurements, Mössbauer spectroscopy, and DSC measurements. T-dependent X-ray powder diffraction reveals a structural phase transition coupled with the spin transition phenomenon. The dimeric excerpt {(μ-bipy)[FeL1(MeOH)]}·2MeOH of the coordination polymer chain crystallizes in the triclinic space group P1̅ and reveals that the packing of the molecules in the crystal is dominated by hydrogen bonds. Investigation of the emission properties of the complexes with regard to temperature shows that the spin crossover can be tracked by monitoring the emission spectra, since the emission color changes from greenish to a yellow color upon the low spin-to-high spin transition.
We demonstrate that the often observed double peak emission in lead halide perovskites is caused by an extensive self-absorption effect.
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.
We report a systematic investigation on the role of excess PbI content in CHNHPbI perovskite film properties, solar cell parameters and device storage stability. We used the CHNHI vapor assisted method for the preparation of PbI-free CHNHPbI films under a N atmosphere. These pristine CHNHPbI films were annealed at 165 °C for different time intervals in a N atmosphere to generate additional PbI in these films. From XRD measurements, the excess of PbI was quantified. Detailed characterization using scanning electron microscopy, X-ray diffraction, UV-Visible and photoluminescence for continuous aging of CHNHPbI films under ambient condition (50% humidity) is carried out for understanding the influence of different PbI contents on degradation of the CHNHPbI films. We find that the rate of degradation of CHNHPbI is accelerated due to the amount of PbI present in the film. A comparison of solar cell parameters of devices prepared using CHNHPbI samples having different PbI contents reveals a strong influence on the current density-voltage hysteresis as well as storage stability. We demonstrate that CHNHPbI devices do not require any residual PbI for a high performance. Moreover, a small amount of excess PbI, which improves the initial performance of the devices slightly, has undesirable effects on the CHNHPbI film stability as well as on device hysteresis and stability.
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.
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