Resonance and antiresonance in Raman scattering in GaSe and InSe crystals

The temperature effect on the Raman scattering efficiency is investigated in ε-GaSe and γ-InSe crystals. We found that varying the temperature over a broad range from 5 to 350 K permits to achieve both the resonant conditions and the antiresonance behaviour in Raman scattering of the studied materials. The resonant conditions of Raman scattering are observed at about 270 K under the 1.96 eV excitation for GaSe due to the energy proximity of the optical band gap. In the case of InSe, the resonant Raman spectra are apparent at about 50 and 270 K under correspondingly the 2.41 eV and 2.54 eV excitations as a result of the energy proximity of the so-called B transition. Interestingly, the observed resonances for both materials are followed by an antiresonance behaviour noticeable at higher temperatures than the detected resonances. The significant variations of phonon-modes intensities can be explained in terms of electron-phonon coupling and quantum interference of contributions from different points of the Brillouin zone. Two-dimensional (2D) van der Waals crystals have recently attracted considerable attention due to their unique electronic band structure and functionalities 1,2. The main focus of researchers has been on semiconducting transition metal dichalcogenides (S-TMDs), e.g. MoS 2 , WSe 2 , and MoTe 2 3,4. Currently, another much larger group of layered materials, i.e. semiconducting post-transition metal chalcogenides (S-PTMCs), e.g. SnS, GaS, InSe, and GaTe, has drawn the attention of the 2D community. Among these crystals, Se-based compounds of S-PTMCs, i.e. InSe and GaSe, demonstrate a tunability of their optical response from the near infrared to the visible spectrum with decreasing layer thickness down to monolayers 5-7. Raman scattering (RS) spectroscopy is a powerful and nondestructive tool to get useful information about material properties 8. The RS measurements provide an insight into their vibrational and electronic structures and are of particular importance in studies of layered materials 9. The flake thickness, strain, stability, charge transfer, stoichiometry, and stacking orders of the layers can be accessed by monitoring parameters of the observed pho-non modes 10-17. RS experiments can be performed under non-resonant and resonant excitation conditions: 18. The resonant excitation may lead to a significant enhancement of the RS intensity in S-TMD as well as the activation of otherwise inactive modes. This offers supplementary information on the coupling of particular phonons to electronic transitions of a specific symmetry 19-21. The crossover between the non-resonant and resonant conditions can be achieved not only by the variation of the excitation energy but also by the modulation of temperature as it was recently reported 22-24. In such an approach, it is the band structure that changes with temperature allowing for resonance with particular excitation energy. In this work, we present a comprehensive investigation of the effect of temperature on the Raman scattering in ε-GaSe and γ-InSe crystals. It has been found that the intensity of some phonon modes exhibits a strong variation as a function of temperature under excitation with specific energy due to the resonant conditions of RS. Moreover, a significant antiresonance behaviour accompanies the resonances at higher temperatures, which leads to the vanishing of the modes intensities. The observed effects are discussed in terms of electron-phonon coupling and quantum interference of contributions from different points of the Brillouin zone (BZ)