Applications of two-dimensional (2D) perovskites have significantly outpaced the understanding of many fundamental aspects of their photophysics. The optical response of 2D lead halide perovskites is dominated by strongly bound excitonic states. However, a comprehensive experimental verification of the exciton fine structure splitting and associated transition symmetries remains elusive. Here we employ low temperature magneto-optical spectroscopy to reveal the exciton fine structure of (PEA) 2 PbI 4 (here PEA is phenylethylammonium) single crystals. We observe two orthogonally polarized bright in-plane free exciton (FX) states, both accompanied by a manifold of phonon-dressed states that preserve the polarization of the corresponding FX state. Introducing a magnetic field perpendicular to the 2D plane, we resolve the lowest energy dark exciton state, which although theoretically predicted, has systematically escaped experimental observation (in Faraday configuration) until now. These results corroborate standard multiband, effective-mass theories for the exciton fine structure in 2D perovskites and provide valuable quantification of the fine structure splitting in (PEA) 2 PbI 4 .
The optical response of bulk germanium sulfide (GeS) is investigated systematically using different polarization-resolved experimental techniques, such as photoluminescence (PL), reflectance contrast (RC), and Raman scattering (RS). It is shown that while the low-temperature (T = 5 K) optical band-gap absorption is governed by a single resonance related to the neutral exciton, the corresponding emission is dominated by the disorder/impurity- and/or phonon-assisted recombination processes. Both the RC and PL spectra are found to be linearly polarized along the armchair direction. The measured RS spectra over a broad range from 5 to 300 K consist of six Raman peaks identified with the help of Density Functional Theory (DFT) calculations: Ag1, Ag2, Ag3, Ag4, B1g1, and B1g2, which polarization properties are studied under four different excitation energies. We found that the polarization orientations of the Ag2 and Ag4 modes under specific excitation energy can be useful tools to determine the GeS crystallographic directions: armchair and zigzag.
The temperature evolution of the resonant Raman scattering from high-quality bilayer 2H-MoS$$_{2}$$ 2 encapsulated in hexagonal BN flakes is presented. The observed resonant Raman scattering spectrum as initiated by the laser energy of 1.96 eV, close to the A excitonic resonance, shows rich and distinct vibrational features that are otherwise not observed in non-resonant scattering. The appearance of 1st and 2nd order phonon modes is unambiguously observed in a broad range of temperatures from 5 to 320 K. The spectrum includes the Raman-active modes, i.e. E$$_{\text {1g}}^{2}$$ 1g 2 ($$\Gamma$$ Γ ) and A$$_{\text {1g}}$$ 1g ($$\Gamma$$ Γ ) along with their Davydov-split counterparts, i.e. E$$_{\text {1u}}$$ 1u ($$\Gamma$$ Γ ) and B$$_{\text {1u}}$$ 1u ($$\Gamma$$ Γ ). The temperature evolution of the Raman scattering spectrum brings forward key observations, as the integrated intensity profiles of different phonon modes show diverse trends. The Raman-active A$$_{\text {1g}}$$ 1g ($$\Gamma$$ Γ ) mode, which dominates the Raman scattering spectrum at T = 5 K quenches with increasing temperature. Surprisingly, at room temperature the B$$_{\text {1u}}$$ 1u ($$\Gamma$$ Γ ) mode, which is infrared-active in the bilayer, is substantially stronger than its nominally Raman-active A$$_{\text {1g}}$$ 1g ($$\Gamma$$ Γ ) counterpart.
Abstract2D Ruddlesden‐Popper metal‐halide perovskites feature particularly strong excitonic effects, making them a fascinating playground for studying exciton physics. A complete understanding of the properties of this quasi‐particle is crucial to fully exploit the tremendous potential of 2D perovskites (2DP) in light emission applications. Despite intense investigations, some of the exciton properties remain elusive to date, for example, the energy‐ordering of the exciton states within the so‐called fine structure manifold. Using optical spectroscopy, it demonstrates that in the archetypical 2DP (PEA)2PbI4, in contradiction to theoretical predictions, the energy of the bright out‐of‐plane exciton state is higher than that of two in‐plane states. Having elucidated the order of exciton fine structure, it determines the g‐factor of the dark exciton transition, together with the values of the electron and hole g‐factors in the direction parallel to the c‐axis of the crystal. In this way, it provides for the first time, a complete picture of the exciton fine structure in (PEA)2PbI4 2DP.
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