Abstract: |
The continuous advancement of technologies across various fields, from communication to medicine, is driven by exploring new materials and techniques in nonlinear optics (NLO) [1]. Despite significant progress, NLO materials continue to present challenges and innovation opportunities. Among the materials that have gained prominence in this area are semiconductors, particularly perovskites, which have shown great potential for applications in solar cells and other photonics devices [2]. Their nonlinear properties, particularly third-order nonlinearities, have demonstrated promising results, especially in lead-based halide perovskites [3]. Additionally, due to the high toxicity of lead, developing lead-free perovskites with comparable optoelectronic properties has become essential, with lead-free double perovskites emerging as a promising alternative [4]. This study focuses on the linear and nonlinear optical properties of 〖Cs〗_2 AgIn_0,9 Bi_0,1 Cl_6, a lead-free double perovskite, in its pure form and modified with rare earth ions (Er^(3+)and Eu^(3+)). Emphasis is placed on first-order hyperpolarizability (𝛽), a microscopic property related to macroscopic second-order susceptibility χ^((2)), which is crucial for processes like second harmonic generation (SHG), which is relevant to numerous applications. Hyper-Rayleigh scattering (HRS) was employed for spectral analysis, complemented by additional measurements such as Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) to examine structural modifications in greater detail and their correlation with HRS. These perovskites show promising nonlinear properties, enhanced by structural octahedral modifications in pure, Er-doped, and Eu-doped samples. Both dopants induce asymmetry and alter bond angles, impacting HRS response uniquely, each contributing distinct variations in HRS intensity and wavelength. Raman analysis further reveals shifts in vibrational modes, confirming changes in local bonding environments. HRS measurements present an increase in 𝛽 magnitude with the modification, underscoring their potential for photonics applications.
References
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[2] J. Xu, X. Li, J. Xiong, C. Yuan, S. Semin, T. Rasing, X.-H. Bu, Halide Perovskites for Nonlinear Optics. Adv. Mater. 2020, 32, 1806736. https://doi.org/10.1002/adma.201806736
[3] Sousa, C. A.; Bonato, L. G.; Gonçalves, E. S.; Alo, A.; Vale, B. R. C.; Almeida, D. B.; Nogueira, A. F.; Zagonel, L. F.; Padilha, L. A. Addressing the Magnitude of the Nonlinear Refraction Response in Perovskite Nanocrystals. ACS Photon. 2023, 10, 1334– 1340, DOI: 10.1021/acsphotonics.2c01985
[4] Manna, D., Das, T. K., & Yella, A. (2019). Tunable and Stable White Light Emission in Bi3+ Alloyed Cs2AgInCl6 Double Perovskite Nanocrystals. Chemistry of Materials. doi:10.1021/acs.chemmater.9b02973. |