Polar Fluorooxoborate, NaB<sub>4</sub>O<sub>6</sub>F: A Promising Material for Ionic Conduction and Nonlinear Optics

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  • Zhizhong Zhang
    CAS Key Laboratory of Functional Materials and Devices for Special Environments Xinjiang Technical Institute of Physics & Chemistry of CAS Xinjiang Key Laboratory of Electronic Information Materials and Devices 40-1 South Beijing Road Urumqi 830011 China
  • Ying Wang
    CAS Key Laboratory of Functional Materials and Devices for Special Environments Xinjiang Technical Institute of Physics & Chemistry of CAS Xinjiang Key Laboratory of Electronic Information Materials and Devices 40-1 South Beijing Road Urumqi 830011 China
  • Bingbing Zhang
    CAS Key Laboratory of Functional Materials and Devices for Special Environments Xinjiang Technical Institute of Physics & Chemistry of CAS Xinjiang Key Laboratory of Electronic Information Materials and Devices 40-1 South Beijing Road Urumqi 830011 China
  • Zhihua Yang
    CAS Key Laboratory of Functional Materials and Devices for Special Environments Xinjiang Technical Institute of Physics & Chemistry of CAS Xinjiang Key Laboratory of Electronic Information Materials and Devices 40-1 South Beijing Road Urumqi 830011 China
  • Shilie Pan
    CAS Key Laboratory of Functional Materials and Devices for Special Environments Xinjiang Technical Institute of Physics & Chemistry of CAS Xinjiang Key Laboratory of Electronic Information Materials and Devices 40-1 South Beijing Road Urumqi 830011 China

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<jats:title>Abstract</jats:title><jats:p>The search of new borates with improved functional properties has attracted considerable attention. Herein, a new polar fluorooxoborate, NaB<jats:sub>4</jats:sub>O<jats:sub>6</jats:sub>F (NBF) was prepared by high‐temperature solid‐state reaction. NBF belongs to the AB<jats:sub>4</jats:sub>O<jats:sub>6</jats:sub>F family (A=alkali metal or ammonium), a series of compounds that undergoes significant cation‐dependent structural changes. NBF is of particular interest owing to the special cation position. Temperature‐dependent ionic conductivity measurements show that NBF is a solid ionic conductor, and it has the lowest active energy of 32.5 kJ mol<jats:sup>−1</jats:sup> of fluorooxoborates. NBF also shows a second‐harmonic generation (SHG) response of 0.9×KH<jats:sub>2</jats:sub>PO<jats:sub>4</jats:sub> and 0.2×β‐BaB<jats:sub>2</jats:sub>O<jats:sub>4</jats:sub>, at 1064 and 532 nm, respectively, and it has a short UV cutoff edge below 180 nm. Based on bond valence (BV) concepts, symmetry analysis, and the first principles calculation, the unique [B<jats:sub>4</jats:sub>O<jats:sub>6</jats:sub>F]<jats:sub>∞</jats:sub> layer can be regarded as the “multifunctional unit”, which is responsible for the observed properties of NBF.</jats:p>

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