Rational design of infrared nonlinear optical chalcogenides by chemical substitution

Unprecedented mid-infrared nonlinear optical materials achieved by crystal structure engineering, a case study of (KX)P2S6 (X = Sb, Bi, Ba)

“…New research strategy is called for breaking the "3.5 eV wall" with good balance of d ij , Δn, and LDT for MIR NLO. The mixed cations with a combination of two chemically different atoms may increase the structure complexity of the target system, which has a higher chance of forming NCS structures, moderate birefringence for phase-matching behavior, and interactions between cations and anionic groups for better NLO properties [21,[25][26][27][28][29][30] . Our research was firstly inspired by Ba 2 P 2 S 6 , which contains-[P 2 S 6 ] ethane-like motifs and crystallizes in a centrosymmetric structure [31] .…”

“…Mixed cations with a combination of two chemically different atoms may increase the structural complexity of the target system, which has a higher chance of forming NCS structures, moderate birefringence for phase-matching behavior, and interactions between cations and anionic groups for better NLO properties. 21,[25][26][27][28][29][30] Our research was rstly inspired by Ba 2 P 2 S 6 , which contains [P 2 S 6 ] ethane-like motifs and crystallizes in a centrosymmetric structure. 31 The K + cation was selected to replace Ba 2+ cations due to their comparable ionic sizes: 152 pm and 149 pm, respectively.…”

The Combination of Structure Prediction and Experiment for the Exploration of Alkali‐Earth Metal‐Contained Chalcopyrite‐Like IR Nonlinear Optical Material

“…For the design of new IR NLO materials, atomic substitution has been demonstrated as a feasible strategy, and many new compounds have been developed in this way by numerous experimental attempts. [ 21 ] However, the trial‐and‐error processes are time‐consuming, and plenty of attempts are not always effective. [ 22 ] Recently, computer‐aided material fabrication, based on crystal structure prediction, property calculation, and screening techniques, has become an effective way for exploring targeted functional materials like superconducting materials, electrode materials in battery, and ultraviolet NLO materials.…”

Pb4SeBr6: A Congruently Melting Mid‐Infrared Nonlinear Optical Material with Excellent Comprehensive Performance

“…Especially for the aliovalent substitution, it can better balance the functional properties of materials because the target ions feature different charges, sizes, electronegativities and polarizabilities from the substituted one. [35,36] Inspired by this, we have chosen the PbBr 2 as parent template with the partial substitution of Se 2for Br -. A NCS lead chalcohalide, Pb 4 SeBr 6 has been successfully synthesized.…”