In contrast to regular J-and H-aggregates, thin film squaraine aggregates usually have broad absorption spectra containing both J-and H-like features, which are favorable for organic photovoltaics. Despite being successfully applied in organic photovoltaics for years, a clear interpretation of these optical properties by relating them to specific excited states and an underlying aggregate structure has not been made. In this work, by static and transient absorption spectroscopy on aggregated n-butyl anilino squaraines, we provide evidence that both the red-and blue-shifted peaks can be explained by assuming an ensemble of aggregates with intermolecular dipole−dipole resonance interactions and structural disorder deriving from the four different nearest neighbor alignments�in sharp contrast to previous association of the peaks with intermolecular charge-transfer interactions. In our model, the next-nearest neighbor dipole−dipole interactions may be negative or positive, which leads to the occurrence of J-and Hlike features in the absorption spectrum. Upon femtosecond pulse excitation of the aggregated sample, a transient absorption spectrum deviating from the absorbance spectrum emerges. The deviation finds its origin in the excitation of two-exciton states by the probe pulse. The lifetime of the exciton is confirmed by the band integral dynamics, featuring a single-exponential decay with a lifetime of 205 ps. Our results disclose the aggregated structure and the origin of red-and blue-shifted peaks and explain the absence of photoluminescence in squaraine thin films. Our findings underline the important role of structural disorder of molecular aggregates for photovoltaic applications.

Exciton intervalley scattering, annihilation, relaxation dynamics, and diffusive transport in monolayer transition metal dichalcogenides are central to the functionality of devices based on them. Here, these properties in a large-size exfoliated high-quality monolayer MoSe 2 are addressed directly using heterodyned transient grating spectroscopy at room temperature. While the free exciton population is found to be long-lived (≈230 ps), an extremely fast intervalley scattering (≤170 fs) is observed, leading to a negligible valley polarization, consistent with steady state photoluminescence measurements and theoretical calculation. The exciton population decay shows an appreciable contribution from the exciton-exciton annihilation, with an annihilation rate of ≈0.01 cm 2 s −1. The annihilation process also leads to a significant distortion of the transient grating evolution. Taking this distortion into account, consistent exciton diffusion constants D ≈ 1.4 cm 2 s −1 are found by a model simulation in the excitation density range of 10 11-10 12 cm −2. The presented results highlight the importance of correctly considering the many-body annihilation processes to obtain a pronounced understanding of the excitonic properties of monolayer transition metal dichalcogenides.

Monolayer transition metal dichalcogenides (TMDCs) hold the best promise for next generation optoelectronic and valleytronic devices. However, their actual performance is usually largely affected by the presence of inevitable defects. Therefore, a detailed understanding of the influence of defects on the dynamic properties is crucial for optimizing near future implementations. Here, the exciton population and valley scattering dynamics in a chemical vapor deposition grown large size monolayer WSe2 with naturally abundant vacancy and boundary defects were systematically investigated using polarization controlled heterodyned transient grating spectroscopy at different excitation wavelengths and temperatures. Slow and multi-exponential decay dynamics of the exciton population were observed while no sign of any micron scale diffusive transport was identified, consistent with the effect of exciton trapping by defects. In general, two different kinds of exciton species were identified: one with short population lifetime (∼10 ps) and extremely fast intervalley scattering dynamics (<200 fs) and in contrast another one with a long population lifetime (>1 ns) and very slow intervalley scattering dynamics exceeding 100 ps. We assign the former to non-trapped excitons in the nanometer scale and the latter to defect-bound excitons. Temperature dependent intervalley scattering dynamics of the trapped excitons can be understood in terms of a two optical phonon dominated process at the K point in momentum space. Our findings highlight the importance of the intrinsic defects in monolayer TMDCs for manipulating exciton valley polarization and population lifetimes, which is key for future device applications.

Exciton intervalley scattering, annihilation, relaxation dynamics, and diffusive transport in monolayer transition metal dichalcogenides (TMDCs) are central to the functionality of devices based on them. In article number 2000029 by Jingyi Zhu, Paul H. M. van Loosdrecht, and co‐workers investigate exciton‐exciton annihilation dynamics and its effect in the distortion of the diffusion grating in an exfoliated monolayer TMDC, MoSe2.

Long linear carbon chains are attracting intense interest arising from their remarkable properties, such as the tunable direct energy gap, the high mechanical hardness, and the high Raman response cross section, which would play a great role in their potential applications in future nanotechnology. Here the excitonic transitions and the associated relaxation dynamics of nanotube confined long linear carbon chains are comprehensively interrogated by using steady state and time‐resolved Raman spectroscopies. The exciton relaxation dynamics of the confined carbon chains occurs on a hundred of picoseconds timescale, in strong contrast to the host dynamics that occurs on a few picoseconds’ timescale. A prominent time‐resolved Raman response is observed over a broad energy range extending from 1.2 to 2.8 eV, which includes the strong Raman resonance region around 2.2 eV. Strong coupling between the chain and the nanotube host is found from the dynamics at high excitation energies which provides clear evidence for an efficient energy transfer from the host carbon nanotube to the chain. The experimental study presents the first unique characterization of the long linear carbon chain exciton dynamics, providing indispensable knowledge for the understanding of the interactions between different carbon allotropes.