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Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides

基于氟化功能基团的d0过渡金属氟氧化物中红外非线性光学材料设计研究

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Abstract

Exploration of new infrared (IR) nonlinear optical (NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formidable challenge is to balance the contradiction between wide band gaps and large second harmonic generation (SHG) effects in IR NLO materials. In the present work, we proposed new kinds of NLO active units, d0 transition metal fluorooxo-functional groups for designing mid-IR NLO materials. By studying a series of d0 transition metal oxyfluorides (TMOFs), the influences of fluorooxo-functional groups with different d0 configuration cations on the band gap and SHG responses were explored. The results reveal that the fluorooxo-functional groups with different d0 configuration cations can enlarge band gaps in mid-IR NLO materials. The first-principles calculations demonstrate that the nine alkali/alkaline earth metals d0 TMOFs exhibit wide band gaps (all the band gaps > 3.0 eV), large birefringence Δn (> 0.07), and two W/Mo TMOFs also exhibit large SHG responses. Moreover, by comparing with other fluorooxo-functional groups, it is found that introducing fluorine into building units is an effective way to enhance optical performance. These d0 TMOFs with superior fluorooxo-functional groups represent a new exploration family of the mid-IR region, which sheds light on the design of mid-IR NLO materials possessing large band gap.

摘要

红外非线性光学晶体在光电器件、资源勘探和长距离激光通讯等领域具有极其重要的应用, 因此探索性能优异的新型红外非线性光学晶体材料已成为该领域的一个重要方向. 当前, 该领域面临的主要挑战之一是如何实现宽带隙和大倍频效应之间的平衡. 本文中, 我们提出一种设计策略, 即引入d0过渡金属的氟化功能基团作为活性基元, 设计中红外非线性光学晶体材料. 通过对含d0过 渡金属氟氧化物的系统研究, 我们探索了这类氟化功能基团对带隙和倍频响应的影响机制. 研究发现d0过渡金属的氟化功能基团有利于产生较大的带隙. 基于第一性原理计算, 我们分析了碱金属/碱土金属d0过渡金属氟氧化物的光学性能, 它们具有宽的带隙(> 3.0 eV)和大的双折射率(>0.07),其中2个分别含W和Mo的氟氧化物也呈现了较强的倍频效应. 此外, 我们对比分析了其他氟化功能基团, 发现在基本构筑基元中引入氟离子有利于光学性能的提升. 由此说明, 这种具有优异氟化功能基团的d0过渡金属氟氧化物, 可以作为探索新型中红外非线性光学的潜在体系.

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Acknowledgements

This work is supported by Tianshan Innovation Team Program (2018D14001), the National Natural Science Foundation of China (51922014 and 11774414), Shanghai Cooperation Organization Science and Technology Partnership Program (2017E01013), Xinjiang Program of Introducing High-Level Talents, Fujian Institute of Innovation, Chinese Academy of Sciences (FJCXY18010202), and the Western Light Foundation of CAS (2017-XBQNXZ-B-006 and 2016-QNXZ-B-9).

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Authors and Affiliations

  1. CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS; Xinjiang Key Laboratory of Electronic Information Materials and Devices, Urumqi, 830011, China

    Junben Huang  (黄君本), Siru Guo  (郭思茹), Zhizhong Zhang  (张志忠), Zhihua Yang  (杨志华) & Shilie Pan  (潘世烈)

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Junben Huang  (黄君本), Siru Guo  (郭思茹) & Zhizhong Zhang  (张志忠)

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  1. Junben Huang  (黄君本)
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Author contributions Huang J, Guo S and Zhang Z performed the theoretical data analysis; Huang J and Yang Z wrote the paper; Yang Z and Pan S designed the concept and supervised the theoretical data. All authors contributed to the general discussion.

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Correspondence to Zhihua Yang  (杨志华) or Shilie Pan  (潘世烈).

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Junben Huang received his BSc degree in Hexi University in 2014 and MSc degree in Xinjiang University in 2017. From 2018 to 2019, he was a research assistant in Technical Institute of Physics & Chemistry (XTIPC), Chinese Academy of Sciences (CAS). Now, he joined Professor Gemei Cai’s research group as a PhD student at Central South University. He is currently focusing on the optical materials.

Zhihuang Yang completed her PhD under the supervision of Professor Jianhui Dai in Zhejiang University in 2008. From 2009 to 2011, she was a post-doctoral fellow at Sungkyunkwan University in Korea. From 2011, she worked as a full professor at XTIPC, CAS. Her current research interests focus on the response mechanism, structure prediction, design and synthesis of new optical functional materials.

Shilie Pan completed his PhD under the supervision of Professor Yicheng Wu (Academician) at the University of Science & Technology of China in 2002. From 2002 to 2004, he was a postdoctoral fellow at Technical Institute of Physics & Chemistry of CAS in the laboratory of Professor Chuangtian Chen (Academician). From 2004 to 2007, he was a post-doctoral fellow at Northwestern University in the laboratory of Professor Kenneth R. Poeppelmeier in USA. Since 2007, he has worked as a full professor at XTIPC, CAS. His current research interests include the design, synthesis, crystal growth and evaluation of new optical-electronic functional materials.

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Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides

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Huang, J., Guo, S., Zhang, Z. et al. Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides. Sci. China Mater. 62, 1798–1806 (2019). https://doi.org/10.1007/s40843-019-1201-5

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