Incorporating rare-earth cations with moderate electropositivity into iodates for the optimized second-order nonlinear optical performance,Inorganic Chemistry Frontiers

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Incorporating rare-earth cations with moderate electropositivity into iodates for the optimized second-order nonlinear optical performance
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020-03-17 , DOI: 10.1039/d0qi00162g
Lin Lin _{1,

2,

3,

4,

5} , Longhua Li _{6,

7,

8,

9} , Chao Wu _{1,

2,

3,

4,

5} , Zhipeng Huang _{1,

2,

3,

4,

5} , Mark G. Humphrey _{10,

11,

12,

13} , Chi Zhang _{1,

2,

3,

4,

5}

Affiliation

Infrared (IR) nonlinear optical (NLO) materials have attracted tremendous interest for civil and military applications, but it remains a great contemporary challenge to develop high-efficiency NLO crystals that possess sufficiently high second-harmonic generation (SHG) efficiencies coupled to wide transparency ranges and high laser damage thresholds. A series of new hydrous rare-earth iodates RE(IO₃)₃·(H₂O) (RE = Y 1, Eu 2) and La₂(IO₃)₆(H₂O) (3) have been synthesized through facile hydrothermal methods. 1 and 2 are isostructural, crystallizing in the polar space group P2₁, while 3 crystallizes in the polar space group Pc. 1–3 feature three-dimensional (3D) frameworks composed of alternately connected corner-shared distorted [REO_x] polyhedra (RE = Y, Eu, and La; x = 8, 9) and [IO₃]⁻ groups. Optical studies showed that 1–3 exhibit good NLO properties, including strong SHG intensities (3.0 × (1), 4.5 × (2), and 1.5 × KH₂PO₄ (3)), large band gaps (4.12 (1), 4.36 (2), and 4.24 eV (3), with 2 possessing the largest band gap among the known SHG-active rare-earth-based iodates, high laser damage thresholds (LDT) (53 × (1), 43 × (2), and 44 × AgGaS₂ (3)), and wide transparency ranges (ca. 3.0–11.3 μm) in the mid-IR region covering two critical IR transparency windows; 1–3 are therefore potential candidate NLO materials. Density functional theory calculations on 1–3 confirm that their strong SHG responses and large band gaps are mainly derived from the synergistic effect of [IO₃]⁻ groups and rare-earth oxide polyhedra [REO_x] in their 3D frameworks. We conclude that the introduction of rare-earth cations with moderate electropositivity into iodates may optimize the balance between SHG efficiency and optical band gaps, the key requirement for high-performance NLO materials for practical applications.

中文翻译：

将具有中等正电性的稀土阳离子掺入碘酸盐中，以优化二阶非线性光学性能

红外（IR）非线性光学（NLO）材料引起了民用和军事应用的巨大兴趣，但是，开发具有足够高的二次谐波生成（SHG）效率和宽泛的透明度的高效NLO晶体仍然是当今的巨大挑战。范围和较高的激光损伤阈值。通过合成了一系列新型的含水碘酸盐稀土离子RE（IO ₃）₃ ·（H ₂ O）（RE = Y 1，Eu 2）和La ₂（IO ₃）₆（H ₂ O）（3）。简便的水热法。1和2在极性空间群P 2 _1中结晶的是同构的，而在极性空间群Pc中结晶的是3。1-3具有三维（3D）框架，该框架由交替连接的角共享扭曲的[REO _x ]多面体（RE = Y，Eu和La；x = 8、9）和[IO ₃ ] ^-组组成。光学研究表明1–3具有良好的NLO性质，包括较强的SHG强度（3.0×（1），4.5×（2）和1.5×KH ₂ PO ₄（3）），较大的带隙（4.12（1），4.36（2）和4.24 eV（3），其中2个在已知的SHG活性稀土基碘酸盐中带隙最大，激光损伤阈值（LDT）高（53×（1），43 ×（2）和44×AgGaS ₂（3）），并且在中红外区域覆盖两个关键的IR透明窗口的透明范围宽（约3.0-11.3μm）；因此，1-3是潜在的NLO候选材料。在1–3上进行的密度泛函理论计算证实，它们强大的SHG响应和较大的带隙主要来自[IO ₃ ] ^-的协同效应。组和稀土氧化物多面体[REO _x ]在其3D框架中。我们得出结论，在碘酸盐中引入具有正电性的稀土阳离子可以优化SHG效率和光学带隙之间的平衡，SHG效率和光学带隙是高性能NLO材料在实际应用中的关键要求。

更新日期：2020-03-17

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