Noncentrosymmetric materials are of special interest in chemistry owing to their technologically important properties, such as ferroelectricity and second-order nonlinear optical behavior. Over 500 noncentrosymmetric oxides have been compiled categorized by symmetry-dependent property crystal class. In addition, the described transition, or main group, metal coordination environment grouped element. Similarities within between groups discussed, structure−property relationships.

The oxides that contain both a d0 transition metal (Ti4+, Nb5+, W6+, etc.) and lone-pair cation (Sn2+, Se4+, Te4+, are examined to investigate the influence of on intra-octahedral distortion metal. direction magnitude out-of-center also examined. When an is observed, at least one metal−oxide bonds needs either be terminal or should link another With respect distortion, Ti4+, V5+, Nb5+ usually displace toward edge (local C2 direction) corner C4 direction), whereas Mo6+ W6+ observed distorting...

Deep ultraviolet (absorption edge <200 nm, band gap >6.2 eV) nonlinear optical (NLO) materials are of current interest owing to their technological applications and design challenges. Technologically, the used in laser systems, atto-second pulse generation, semiconductor manufacturing, photolithography. Designing synthesizing a deep UV NLO material requires crystallographic non-centrosymmetry, wide transparency range, large second-harmonic generating coefficient (dij > 0.39 pm/V), moderate...

Two new oxides, BaTeMo2O9 and BaTeW2O9, have been synthesized, by standard solid-state techniques, that strong SHG intensities of approximately 600 x SiO2, on the order LiNbO3. Both materials contain cations susceptible to second-order Jahn-Teller (SOJT) distortions, resulting in asymmetric coordination environments. The SOJT distortion polarizes M6+-O Te4+-O bonds. Equally importantly, these polarizations constructively add, large responses. Powder measurements BaTeM2O9 (M = Mo6+ or W6+)...

A new noncentrosymmetric (NCS) and polar material containing two lone-pair cations, Bi(3+) I(5+), exhibiting an Aurivillius-type (Bi(2)O(2))(2+) layer has been synthesized structurally characterized. The material, BiO(IO(3)), exhibits strong second-harmonic generation (SHG), ∼12.5 × KDP (or ∼500 α-SiO(2)), using 1064 nm radiation, is found in the NCS orthorhombic space group Pca2(1) (No. 29). structure consists of cationic layers that are connected to (IO(3))(-) anions. macroscopic polarity,...

More than 750 d0 transition metal oxide octahedra have been examined in order to better understand the out-of-center distortion occurring with these cations. A continuous symmetry measures approach was used quantify magnitude and direction of distortion. Using this we were able divide metals into three categories: strong (Mo6+ V5+), moderate (W6+, Ti4+, Nb5+, Ta5+), weak (Zr4+ Hf4+) distorters. We also discussed directional preference for each cation.

A new deep-ultraviolet nonlinear optical material, RbMgCO3F, has been synthesized and characterized. The achiral nonpolar acentric material is second harmonic generation (SHG) active at both 1064 532 nm, with efficiencies of 160 × α-SiO2 0.6 β-BaB2O4, respectively, exhibits a short UV cutoff, below 190 nm. RbMgCO3F possesses three-dimensional structure corner-shared Mg(CO3)2F2 polyhedra. Unlike other carbonate fluorides, in this example, the inclusion Mg(2+) creates pentagonal channels where...

A new polar noncentrosymmetric material, Li(2)Ti(IO(3))(6), has been synthesized and characterized. The material is built up from a TiO(6) octahedron that linked to six IO(3) polyhedra. These polyhedral groups are separated by Li(+) cations. Ti(4+) I(5+) cations in asymmetric coordination environments attributable second-order Jahn-Teller effects. distortion associated with the cation negligible, since octahedra completely surrounded highly environment its stereoactive lone pair, which was...

Access to the elusive deep-ultraviolet by direct second harmonic generation (SHG) enabled a new beryllium-free zincoborate-phosphate crystal is reported. Ba3(ZnB5O10)PO4, exhibits large SHG responses at 1064 and 532 nm short 180 absorption edge. Centimeter-size crystals are grown, quantum mechanical calculations demonstrate key role played ZnO4 tetrahedra in enhanced optical responses.

We have synthesized a series of new alkali-metal or Tl(+) titanium iodates, A(2)Ti(IO(3))(6) (A = Li, Na, K, Rb, Cs, Tl). Interestingly the Li and Na phases are noncentrosymmetric (NCS) polar, whereas Tl analogues centrosymmetric (CS) nonpolar. able to explain change from NCS polar CS nonpolar using cation-size arguments, coordination requirements, bond valence concepts. The six materials topologically similar, consisting TiO(6) octahedra, each which is bonded IO(3) polyhedra. These...

Noncentrosymmetric mixed-metal carbonate fluorides are promising materials for deep-ultraviolet (DUV) nonlinear optical (NLO) applications. We report on the synthesis, characterization, structure–property relationships, and electronic structure calculations two new DUV NLO materials: KMgCO3F Cs9Mg6(CO3)8F5. Both noncentrosymmetric (NCS). crystallizes in achiral nonpolar NCS space group P6̅2m, whereas Cs9Mg6(CO3)8F5 is found polar Pmn21. The compounds have three-dimensional structures built...

On the basis of their short ultraviolet (UV) absorption edges, phosphates are ideal candidates for deep-UV nonlinear optical (NLO) applications. However, often-weak second-harmonic generating (SHG) responses reduce NLO It has been demonstrated that SHG response in polyphosphates or orthophosphates could be enhanced by highly polymerized P–O groups aligned nonbonding O-2p orbitals isolated PO4 units. Herein, we report on design and synthesis two pyrophosphates, K4Mg4(P2O7)3 Rb4Mg4(P2O7)3,...

Angle phase-matching in nonlinear optical (NLO) materials is critical for technological applications. The purpose of this manuscript to describe the concept synthesis NLO community. Refractive index and birefringence are defined with respect uniaxial biaxial crystal systems. angle wavelength range, Type I II, explained using real materials, K3B6O10Cl (KBOC) Ba3(ZnB5O10)PO4 (BZBP) In addition, we how refractive measurements performed on single crystals resulting impacts phase-matching. Our...

Borate halides are an ideal materials class from which to design high-performance nonlinear optical (NLO) materials. Currently, borate fluorides, chlorides, and bromides extensively investigated while iodide discovery remains rare because of the perceived synthetic challenges. We report a new iodide, Pb2 BO3 I, synthesized by straightforward hydrothermal method. The I chemical formula conceals that compound exhibits structure similar well-established KBe2 F2 (KBBF), we show supports highest...

New inorganic nonlinear-optical (NLO) materials are necessary for solid-state lasers to generate coherent radiation in the ultraviolet (UV) and deep-UV regions. The purpose of this Viewpoint is describe chemical physical requirements such materials, as well current state field. In addition, "birefringence challenge" described a flowchart presented characterizing new second-harmonic-generation materials. Finally, several suggested that may have UV and/or NLO applications.

Abstract Inorganic materials exhibiting second-harmonic generation (SHG) are used to generate coherent radiation at wavelengths where solid-state laser sources not available; that is, the deep UV (DUV) below 200 nm. Here, we describe structure and optical property requirements should be assessed conclusively demonstrate discovery of a functional DUV material for nonlinear (NLO) applications.

Noncentrosymmetric (NCS) structures are of particular interest owing to their symmetry-dependent physical properties, e.g., pyroelectricity, ferroelectricity, piezoelectricity, and nonlinear optical (NLO) behavior. Among them, chiral materials exhibit polarization rotation host topological properties. Borates often contribute NCS via triangular [BO3] tetrahedral [BO4] units numerous superstructure motifs. However, no compound with the linear [BO2] unit has been reported date. Herein, an...

Four new metal methanesulfonates with mixed anionic groups, Bi(SeO3)(CH3SO3) (1), Bi(TeO3)(CH3SO3) (2), Ba(BF4)(CH3SO3) (3), and Ba2(BF4)(CH3SO3)3(H2O)3 (4), have been successfully synthesized. Compounds 1 2 are isomorphic exhibit a two-dimensional (2D) layered structure. Stereoactive lone pairs observed Se4+, Te4+, Bi3+. Compound 3 features three-dimensional (3D) structure formed by connecting [Ba(CH3SO3)]+ layers via BF4 tetrahedra, whereas compound 4 2D structure, where the tetrahedra...

Three new molybdenyl iodates, KMoO3(IO3) (1), RbMoO3(IO3) (2), and CsMoO3(IO3) (3), have been prepared through the hydrothermal reactions of MoO3 with AIO4 (A = K, Rb, or Cs) at 180 C. These compounds are isolated as nearly colorless, air-stable crystals. Single-crystal X-ray diffraction experiments reveal that 1 possesses a corrugated layered structure constructed from molybdenum oxide chains bridged by iodate anions. The puckering layers is caused alignment bent (MoO2(2+)) groups along one...

The synthesis, structure, and characterization of a new noncentrosymmetric molybdenum tellurite, Na2Te3Mo3O16, are reported. Na2Te3Mo3O16 crystallizes in the monoclinic space group I2 (No. 5, cell choice 3) with = 7.3373(10) Å, b 11.2668(16) c 8.2369(18) β 97.387(3)°. material exhibits quasi-one-dimensional crystal each chain consisting edge-shared MoO6 octahedra that connected by TeO3 TeO4 polyhedra. SHG efficiency using 1064 nm radiation, is approximately 500 × α-SiO2 phase-matchable (type...

The synthesis, structure, and characterization of a new noncentrosymmetric tellurite, Na2TeW2O9, is reported. oxide exhibits three-dimensional structure comprising distorted W6+O6 octahedra linked to asymmetric Te4+O3 groups. Both cations are in local acentric environments attributable second-order Jahn−Teller effects. Single crystals Na2TeW2O9 were synthesized through supercritical hydrothermal methods, utilizing NaOH(aq), WO3, TeO2 as reagents. Polycrystalline was by combining...

The semiconductors Li2CdGeS4 and Li2CdSnS4, which are of interest for their nonlinear optical properties, were synthesized using high-temperature solid-state polychalcogenide flux syntheses. Both compounds found to crystallize in Pmn21, with R1 (for all data) = 1.93% 1.86% respectively. structures both diamond-like the tetrahedra pointing same direction along c axis. alignment results structure lacking an inversion center, a prerequisite second-harmonic generation (SHG). A modified Kurtz...

The synthesis and characterization of a noncentrosymmetric tellurium selenate, Te2SeO7, is reported. In addition, the powder second-harmonic-generating (SHG) properties TeO2, Te2O5, TeSeO4 have been measured, using 1064 nm radiation. Through SHG experiments, we are able to determine that TeO2 not phase-matchable, whereas phase-matchable. Also, efficiencies 5, 200, 400, 400 times SiO2, respectively. relative may be understood by examining structure each material. measurements, estimate...

A new thio-germanium sulfide Li2Ga2GeS6 has been synthesized for the first time and its structure was found to be isomorphous with AgGaGeS4, which is well-known as a promising infrared NLO material. The host built of GaS4 tetrahedra linked by corners GeS4 create 3D framework forming tunnels along c-axis, in Li+ ions are located. second harmonic generation (SHG) efficiency determined on powders Li2Ga2GaS6 ∼200 times larger than that α-SiO2. Unlike AgGaS2 observed very stable under prolonged...