Jiale Xue,Shuyao Wang,Xiande Peng,Zhengyan Lin,Xuehua Dong,Liling Cao,Ling Huang,Guohong Zou
We present two novel antimony(III)-based tellurite sulfate crystals, Sb2(TeO3)(SO4)2-P1̅ (I) and Sb2(TeO3)(SO4)2-P21/c (II), synthesized using a dual lone pair strategy that incorporates Sb3+ and Te4+ ions into a sulfate framework. This approach significantly enhances the birefringence of these compounds, with values of 0.11 and 0.10 at 546 nm, respectively, surpassing those of many previously reported mixed alkali metal/alkaline earth metal sulfates and tellurites. Both compounds also exhibit excellent UV transparency with cutoff edges at 292 and 294 nm, making them promising candidates for short-wave UV optical applications. Structural and theoretical analyses reveal that the enhanced birefringence arises from the synergistic effects of the stereochemically active lone pairs of Sb3+ and Te4+, which contribute to the optical anisotropy. This work highlights the potential of dual SCALP elements in improving the optical properties of sulfate-based crystals and provides new insights into designing high-performance optical materials with tailored properties for advanced UV technologies.
YiLin Mao,Jian Zhang,Qiqiong Ren,Maxim S. Molokeev,Guojun Zhou,Xian-Ming Zhang
Low-dimensional metal halides with ns2 lone-pair electrons have been recognized as new generation luminescent emitters for various optoelectronic applications. However, 5s2 configuration tellurium halides have not received substantial attention despite their fascinating photoluminescence (PL) properties. Here, a hybrid tellurium-based double perovskite of (C20H20P)2TeCl6 is developed, in which the [TeCl6]2− octahedra are completely surrounded by [C20H20P]+ organic cations to form a unique zero-dimensional (0D) “host–guest” structure. An uncommon broadband yellow emission peaking at 570 nm with ultra-broad excitation from ultraviolet to blue light is excavated, which originates from the triplet self-trapped exciton (STE) emission of Te4+. Moreover, the 5s2 electronic transition mechanism of Te4+ is systematically revealed in depth, benefiting from the temperature-dependent fluorescence dynamic analysis and auxiliary theoretical calculations. It is concluded that the distortion degree of the [TeCl6]2− octahedron comprehensively affects the full width at half-maximum (FWHM) (positive correlation), Stokes shift (negative correlation) and PL intensity (negative correlation) with increasing temperatures. This work sheds new light on the PL behaviour of Te4+ and opens up a feasible avenue for blue-excitable broadband emissions in low-dimensional organic–inorganic hybrid double perovskites.
Zhiyu Pei,Yeshan Wu,Shuailing Ma,Tian Cui,Laihui Luo,Peng Du
Te 4+ -doped Cs 2 ZrCl 6 vacancy-ordered double perovskites with intense self-trapped excitons emissions were prepared via a rapid room-temperature precipitation method. Utilizing low-temperature engineering, tunable luminescence was realized in the synthesized products, resulting in the maximum temperature relative sensitivities of 0.48% and 0.81% K −1 , respectively, when the emission band centroid and lifetime were employed as thermometric parameters. Moreover, in situ high-pressure Raman spectra and X-ray diffraction patterns confirmed the excellent structural stability and reversibility of the studied samples. When the as-prepared compounds experienced the high-pressure conditions, spectral blue-shift and broadened bandwidth were observed, resulting in the tunable luminescence at high-pressure, which endowed their applications in pressure sensing. Furthermore, via utilizing the emission band centroid and full width at half maximum as manometric parameters, the maximum pressure sensitivities of the final products were 6.30 and 1.86 nm GPa −1 , respectively. Additionally, based on the pressure-related color coordinate, the manometric properties of the resultant products were further investigated, yielding a maximum sensitivity of 4.25% GPa −1 . Our findings did not only propose a rapid synthesis route for the Te 4+ -doped Cs 2 ZrCl 6 vacancy-ordered double perovskites but also highlighted that their luminescence properties can be regulated via extreme conditions engineering, showcasing their feasibilities in advanced optical thermometry and manometry.
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