Nonlinear optical properties of La³⁺-Doped tellurite-zinc glasses: Impact of chemical bonding and physical properties via Raman and XPS

Autor(es)

Clabel, H. J. L. ; Valverde, J. V. P. ; Lozano, C. G. ; Marega Jr, E. ; Mastelaro, Valmor R. ; Mendonca, C. R.

• Tipo de documento: Artigo Científico
• Fonte: CERAMICS INTERNATIONAL; v. 51, n. 1, p. 12-pg., 2024-12-24.

Resumo

Understanding the connection between the local environments of lanthanum ions in tellurite glasses and their nonlinear optical (NLO) properties is essential for various technological applications. Rare earth ions can serve as probes for the local environments of the host material if the structure-property correlations are well understood. In this study, we investigated glasses with compositions 70TeO(2) - (30-x)ZnO - (x)La2O3 (mol%) (x = 0, 5, 7, 9) fabricated by the melt-quenching technique. The capabilities of combined Raman and X-ray photoemission (XPS) spectroscopy were used to identify these glasses and define spectral deconvolution for distinguishing them in the formation of bridging oxygens (BO) and non-bridging oxygens (NBO). NLO properties were evaluated using open-aperture (OA) and closed-aperture (CA) Z-scan measurements with femtosecond (fs) laser pulses (similar to 220 fs, 750 Hz) at wavelengths ranging from 600 to 1500 nm. Raman spectra revealed a shift to higher frequencies from 731 to 746 cm(-1), with increasing of La3+ ions, indicating the conversion of TeO4 polyhedra to TeO3 structural units, affecting the Te-O- Zn2+ or Te=O bonds and resulting in a variation of the polarizability. Besides the conventional analysis of oxidation state and chemical shifts of the core-level peaks, XPS spectroscopy included a careful analysis of the type oxygen bridges and metal-oxygen bond length to distinguish otherwise similar spectral contributions of different TZL glasses. Glasses with a high fraction of Zn2+ ions bonded with oxygen form NBO and modify the local structure of the glass network, while La3+ ions coordinate with oxygen atoms or interact with the lone pairs of tellurium atoms. By analyzing the correlation in different concentrations of La3+ ions, the Te-O bonds and NBO/(BO + NBO) ratio were clearly demonstrated. These findings suggest charge compensation between the Zn2+ and La3+ ions, for maintaining structural stability within the glass network. This study also reveals an enhancement of NLO properties as a function of La3+ ions concentration in TZL glasses under fs laser excitation due to resonant nonlinearity. The third-order optical nonlinearities showed an increase in the two-photon absorption coefficient (beta) from 0.26 x 10(-2) cm GW(-1) (TZL5) to 0.62 x 10(-2) cm GW(-1) (TZL9), along with an increase in the nonlinear refractive index (n(2)) from 0.32 x 10(-18) m(2) W-1 to 0.65 x 10(-18) m(2) W-1. This enhancement is attributed to the increased number of NBOs and the high polarizability of La3+ ions. For all-optical switching (AOS) applications, two figures of merit were applied using the n(2), alpha(0), and beta coefficients. The results suggest that the TZL glasses studied are potential candidates for AOS devices. Thus, this work not only elucidates the factors underlying the NLO properties but also highlights the promising potential of these glasses for use in AOS devices. (AU)

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