Zn₃B₇O₁₃Cl: A New Deep-Ultraviolet Transparency Nonlinear Optical Crystal with Boracite Structure

Abstract

Nonlinear optical crystals play important roles in modern laser science and technology. However, the design and growth of new nonlinear optical (NLO) materials is still a challenging issue for researchers. Due to the excellent performance of Mg 3 B 7 O 13 Cl crystal, we paid attention to the optimization of its structure, in order to find new NLO materials with favorable properties. Here, Zn 3 B 7 O 13 Cl crystals were obtained by a hightemperature solution method. Its structure was determined to be the trigonal symmetry with a polar space group of R3c, which is more highly symmetric than that of Mg 3 B 7 O 13 Cl (Pca2 1 ). The experimental and theoretical investigations demonstrated that the title compound exhibits a short absorption cutoff (band gap ∼6.53 eV), moderate SHG responses (2.2 times that of KDP at 1064 nm), and the improved birefringence, which results from the large distortion and anisotropy of borate groups and zinc polyhedrons. Therefore, the structural modification of Mg 3 B 7 O 13 Cl by zinc cations achieves a balance between the deep-ultraviolet transparency, the nonlinear optical effect, and the moderate birefringence, which is very significant for the design of practical NLO materials.

An excellent lead oxyiodide with a strong second-harmonic generation response and a large birefringence induced by the oriented arrangement of highly distorted [PbO4I2] polyhedra

“…S7, ESI†), which is beneficial for the generation of a strong SHG response and optical anisotropy for disparate polarizations in different directions. 43 In addition, the calculated BVS values of K, Pb, I and O atoms are 0.77–0.98, 1.72, −0.88−0.64 and −2.16, matching with the expected valence states of +1, +2, −1 and −2, respectively.…”

From Phosphate Fluoride to Fluorophosphate: Design of Novel Ultraviolet/Deep-Ultraviolet Nonlinear Optical Materials for BePO3F with Optical Property Enhancement

“…As high-performance computing develops by leaps and bounds, first-principles simulations and crystal structure prediction have been widely used in exploring novel functional materials to accelerate the material discovery. , Particularly, as the key materials for extending the ultraviolet (UV), especially the deep-UV wavelength range provided by conventional laser sources, − nonlinear optical (NLO) crystals have received extensive attention since they are widely used in semiconductor manufacturing, fine processing, medical treatment, optical data storage, and ultrahigh-resolution photoemission spectroscopy. − To date, researchers have made a series of efforts to design and synthesize UV/deep-UV optical materials in borates, − borate halides, − carbonates, − fluorooxoborates, − sulfates, , and phosphates. − However, among the materials we know so far, those that can meet the strict NLO-related property criteria are still scarce. Therefore, the discovery or design of novel UV/deep-UV NLO materials with excellent performance is still a long-term goal.…”

Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect

“…Crystal materials with an ultraviolet (UV) nonlinear-optical (NLO) property can emit coherent and tunable laser beams by cascading second-harmonic-generation (SHG) methods, constituting the core part of solid-state laser systems. − UV laser sources have drawn extensive science and technology applications including laser medical treatment, material micromachining, and semiconductor manufacturing. − To achieve promising UV NLO materials, strict requirements should be satisfied simultaneously: (i) acentric crystal structures to induce a SHG response; (ii) a broad transparency range below a light wavelength (λ) of 300 nm (or E g > 4.13 eV); (iii) a large SHG efficiency [≥1 × KH 2 PO 4 (KDP)] beneficial to increasing the frequency conversion efficiency of the laser; (iv) sufficient birefringence (Δ n ) between about 0.07 and 0.1 for phase-matching ability; (v) high laser-induced damage threshold (LIDT) for a laser system with high power radiation; (vi) an easily grown large single crystal. However, integrating all of the good qualities into one crystal is challenging because a mutually conflicting nature exists between the SHG efficiency and E g and between birefringence and E g .…”