Rational Design of a LiNbO₃-like Nonlinear Optical Crystal, Li₂ZrTeO₆, with High Laser-Damage Threshold and Wide Mid-IR Transparency Window

Abstract

With existing and emerging technologies urgently demanding the expansion of the laser wavelengths, high-performance nonlinear optical (NLO) crystals are becoming indispensable. Here, a prospective NLO crystal, LiZrTeO, is rationally designed by the element substitution of Nb for Zr and Te from LiNbO, which has been recognized as one of the most commercial NLO crystals. LiZrTeO with R3 symmetry inherits the structural merits of LiNbO (space group R3 c) and thus meets the requirements for NLO applications, including noncentrosymmetric crystal structure, moderate birefringence, and phase-matchability. Moreover, it can be exploited to achieve more outstanding optical damage resistant behavior (>1.3 GW cm), exceeding 22 times that of LiNbO, which is more suitable for high-energy laser applications. Notably, this compound displays the widest IR absorption edge (7.4 μm) among all of the noncentrosymmetric tellurates reported so far. These excellent attributes suggest that LiZrTeO is a promising candidate for providing high NLO performance. The substitution of Nb for Zr and Te from LiNbO demonstrates a viable strategy toward the rational design of NLO crystals with anticipated properties.

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials

“…An emerging very effective approach for developing highperformance mid-IR NLO materials is to introduce special kinds of oxide-based systems containing relatively heavy atoms which can expand the IR transparent range.Promoted by this design strategy,several NLO oxides such as NaI 3 O 8 , [49] Pb 17 O 8 Cl 18 , [50] Bi(IO 3 )F 2 , [51] Li 3 VO 4 , [52] Cs 2 LiVO 4 , [53] La 3 SnGa 5 O 14 , [54] Li 2 ZrTeO 6 , [55] Rb 4 [57] and ABi 2 (IO 3 ) 2 F 5 (A = K, Rb,a nd Cs) [58] were proposed as attractive mid-IR NLO candidates. Although the transparent range of most of the reported NLO oxides only cover the atmospheric window of 3-5 mm, La 3 SnGa 5 O 14 and Pb 17 O 8 Cl 18 possess much wider IR transparencyu pt o1 2and 13.9 mm, respectively,w hich can be comparable to that of AgGaS 2 (13 mm We have paid special attention to lead mixed oxyhalide systems according to the following considerations:(1) As lead is av ery heavy element, the lead-oxygen and lead-halogen bonds have quite low vibration frequencies;t hus,c onsiderably wide IR transparencycan be attained.…”

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

“…Our studies propose that three-site aliovalent substitution is af acile route for the discovery of good NLO materials.Noncentrosymmetric (NCS) oxide materials have extensively excited academic interest owing to their probable properties with applications in second-order nonlinear optics (NLO) as well as in pyroelectrics,f erroelectrics,a nd piezoelectrics. [1][2][3][4][5][6] To the best of our knowledge,a ne xcellent second-order NLO material should feature al arge second harmonic generation (SHG) coefficient, ahigh relevant laserinduced damage threshold (LDT), appropriate optical transmittance range,m oderate birefringence for achieving phase matching,and good thermal stability.Inaddition, it should be free of moisture and accessible by af acile synthetic method. [7][8][9] Metal iodates currently attract extensive research interest due to their potential outstanding SHG response.…”

A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design

“…[2] However,t he fabrication of utilizable NLO materials still remains challenging due to rigorous requirements including ap hase-matching capability,arelatively strong SHG response,awide transparencyw indow, ahigh laser damage threshold (LDT) and good physicochemical stability. [3] Thus,continuing endeavors have been focusing on the development of methods to design novel NCS crystal structures and explore potentially utilizable NLO materials.Ad esired purpose can be difficult to achieve in the development of au niversal method for the synthesis of new NCS crystal materials.F rom the view of molecular engineering, it is not possible to directly control the arrangement of atoms or molecules in acrystal structure. [4] In spite of this,an effective strategy for obtaining NCS crystal materials is to introduce d 0 transition-metal cations (for example,T i 4+ ,V 5+ , Mo 6+ ,Nb 5+ ,W 6+ ,T a 5+ )orlone pair cations (for example,I 5+ , Se 4+ ,T e 4+ )into the crystal structure,because these cations are susceptible to the second-order Jahn-Teller (SOJT) effect.…”

“…[2] However,t he fabrication of utilizable NLO materials still remains challenging due to rigorous requirements including ap hase-matching capability,arelatively strong SHG response,awide transparencyw indow, ahigh laser damage threshold (LDT) and good physicochemical stability. [3] Thus,continuing endeavors have been focusing on the development of methods to design novel NCS crystal structures and explore potentially utilizable NLO materials.…”

“…Reactions (1) and (2) are easily achieved, [15] while reactions (3) and (4) can only happen in aw ater-free environment [13] and reaction (5) was not reported until now. [14, 15b] To the best of our knowledge,the IO 3 unit can be stable in H 2 SO 4 below 240 8 8C.…”