Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship

Abstract

Mid-infrared (IR) nonlinear optical (NLO) materials with high performance are vital to expanding the laser wavelengths into the mid-IR region and have important technological applications in many civil and military fields. For the last two decades metal chalcogenides have attracted great attention since many of them possess a large NLO effect, wide transparent range, moderate birefringence, and high resistance to laser damage. However, the discovery of superior mid-IR NLO metal chalcogenides is still a big challenge mainly due to the difficulty of achieving a good balance between the NLO effect and laser damage threshold (LDT). In this review, metal chalcogenides are catalogued according to the different types of microscopic building blocks. These groups include triangle planar units, tetrahedral metal-centered units, polyhedra with second-order John-Teller cations, and polyhedra with stereochemically active lone electron pairs cations, rare-earth cations, and/ or halogen anions. The determinations of these microscopic structures on mid-IR NLO properties in metal chalcogenides are summarized and analyzed combined with available experimental data and first-principle calculations. From the deduced structure−property relationship, the searching directions for new metal chalcogenides that have good mid-IR NLO performances, especially for achieving the balance between large NLO effect and high LDT, are discussed.

Synthesis, Crystal Structures, Optical Properties and Theoretical Calculations of Two Metal Chalcogenides Ba2AlSbS5 and Ba2GaBiSe5

“…Metal chalcogenides have been used as critical materials in the development of modern science and technology because of their structural complexities and fascinating properties [1][2][3][4][5][6][7][8][9][10][11][12]. Among them, many trivalent cations (such as M III ': As, Sb, or Bi) containing chalcogenides have been discovered and shown to have various application prospects.…”

Coexistence of Strong Second Harmonic Generation Response and Wide Band Gap in AZn4Ga5S12 (A=K, Rb, Cs) with 3D Diamond‐like Frameworks

“…[1][2][3][4][5][6] However,t he lack of good performance MIR NLO materials is ab ig issue. [1][2][3][4][5][6] However,t he lack of good performance MIR NLO materials is ab ig issue.…”

Langasite Family Midinfrared Nonlinear Optical Oxide Materials: Structure, Property, and Applications

“…(i) Growing large-size crystals: although many new mid-IR materials possess excellent SHG properties, largesize crystals for practical applications have not been obtained [16]. Many important physical measurements require large-size crystals, including IR absorption edge, LDT value, and SHG tensor component.…”

“…In general, optional midinfrared nonlinear optical materials, in addition to having a noncentral symmetric structure, should meet the following conditions [15,16]: (1) a wider range of transmission bands that can cover important atmospheric transparent windows of 3-5 m; (2) a large nonlinear optical coefficient, because the power of the output light is proportional to the effective nonlinear optical coefficient; (3) high LDT, which essentially depends on the wide bandgap of the material; (4) moderate birefringence Δ to achieve a phase-matchable condition; (5) good growth habit and high optical quality; and (6) good physical and chemical stabilities for convenient applications.…”

“…Accordingly, there is a pressing need to develop new metal oxides with relatively low phonon vibrational frequency and wide mid-IR transparency window. Notably, the phonon subsystem plays a negligible role in determining the SHG coefficients of wide bandgap oxides (>4.0 eV) and the "anionic group theory" is still suitable [16]. In addition, the phonon vibrational frequency of M-O bond is negatively related to the atomic mass of M and the bond length of M-O bond.…”