Strong Infrared NLO Tellurides with Multifunction: CsX(II)4In5Te12 (X(II) = Mn, Zn, Cd).

Chalcogenides are the most promising mid- and far-infrared materials for nonlinear optical (NLO) applications. Yet, most of them are sulfides and selenides, and tellurides are still rare. Herein, we report three new KCd4Ga5S12-structure type NLO-active tellurides, CsX(II)4In5Te12 (X(II) = Mn, Zn, Cd), synthesized by solid-state reactions. The structure features a 3D diamond-like framework constructed by vertex-sharing asymmetric MTe4 tetrahedra that are stacked along the c-axis. CsCd4In5Te12 exhibits the strongest powder second-harmonic generation (SHG) intensity at 2050 nm (0.61 eV) among tellurides to date, 9 × benchmark AgGaS2 in the range of 46-74 µm particle size. The primary studies reveal the 1.42 eV direct band gap and high absorption coefficient in the visible spectral region for CsCd4In5Te12, suggesting it is a new potential solar cell absorber material. In addition, CsMn4In5Te12 also displays a spin-canted antiferromagnetic property below 50 K.

Syntheses, Characterization, and Optical Properties of Centrosymmetric Ba3(BS3)1.5(MS3)0.5 and Noncentrosymmetric Ba3(BQ3)(SbQ3).

The most advanced UV-vis and IR NLO materials are usually borates and chalcogenides, respectively. But thioborates, especially thio-borometalates, are extremely rare. Here, four new such compounds are discovered by solid state reactions representing 0D structures constructed by isolated BQ3 trigonal planes and discrete MQ3 pyramids with Ba(2+) cations filling among them, centrosymmetric monoclinic P21/c Ba3(BS3)1.5(MS3)0.5 (M = Sb, Bi) 1, 2 with a = 12.9255(9), 12.946(2) Å; b = 21.139(2), 21.170(2)Å; c = 8.4194(6), 8.4207(8) Å; ß = 101.739(5), 101.688(7)°; V = 2252.3(3), 2259.9(3) Å(3) and noncentrosymmetric hexagonal P6̅2m Ba3(BQ3)(SbQ3) (Q = S, Se) 3, 4 with a = b = 17.0560(9), 17.720(4) Å; c = 10.9040(9), 11.251(3) Å; V = 2747.1(3), 3060(2) Å(3). 3 exhibits the strongest SHG among thioborates that is about three times that of the benchmark AgGaS2 at 2.05 µm. 1 and 3 also show an interesting structure relationship correlated to the size mismatching of the anionic building units that can be controlled by the experimental loading ratio of B:Sb. Syntheses, structure characterizations, and electronic structures based on the density functional theory calculations are reported.

Deep-ultraviolet nonlinear optical crystals: Ba3P3O10X (X = Cl, Br).

Deep-ultraviolet nonlinear optical (deep-UV NLO) crystals are of worldwide interest for the generation of coherent light with wavelength below 200 nm by the direct second-harmonic generation (SHG) output from solid-state lasers. The unprecedented deep-UV NLO phosphates representing their own structure types, Ba3P3O10Cl (BPOC), Ba3P3O10Br (BPOB), have been discovered, which display moderate powder SHG intensities in type I phase matchable behaviors with a short UV cutoff edge of 180 nm (measured by a single crystal, one of the shortest values among phosphates to date). Insightfully, the geometry and polarization of the C1-P3O10(5-) building unit are affected by the crystal packing. DFT calculations and cutoff energy dependent SHG coefficient analyses reveal that the SHG origin is from the cooperation of asymmetric C1-P3O10(5-) anion, Ba(2+) cation, and Cl(-)/Br(-) anion.

SiC2 siligraphene and nanotubes: novel donor materials in excitonic solar cells.

In excitonic solar cells (XSC), power conversion efficiency (PCE) depends critically on the interface band alignment between donor and acceptor materials. Graphene or silicene is not suitable for donor materials due to their semimetallic features (zero band gaps); it is therefore highly desired to open an energy gap in graphene or silicene to extend their application in optoelectronic devices, especially in photovoltaics. In this paper, based on the global particle-swarm optimization algorithm and the density functional theory methods, we predict a novel SiC2 siligraphene (g-SiC2) with a direct band gap of 1.09 eV showing infinite planar geometry, in which Si and C atoms adopt sp(2) hybridization and C atoms form delocalized 4 C-domains that are periodically separated by Si atoms. Such a g-SiC2 siligraphene (with a global minimum of energy) is 0.41 eV/atom lower and thermally stabler than the isomeric pt-SiC2 silagraphene containing planar 4-fold coordinated silicon (3000 K vs 1000 K). Interestingly, the derivative (n, 0), (n, n) nanotubes (with diameters greater than 8.0 Å) have band gaps about 1.09 eV, which are independent of the chirality and diameter. Besides, a series of g-SiC2/GaN bilayer and g-SiC2 nanotube/ZnO monolayer XSCs have been proposed, which exhibit considerably high PCEs in the range of 12-20%.

Functionalization based on the substitutional flexibility: strong middle IR nonlinear optical selenides AX(II)(4)X(III)(5)Se12.

Seven nonlinear optical (NLO) active selenides in the middle IR region, AX(II)4X(III)5Se12 (A = K(+)-Cs(+); X(II) = Mn(2+), Cd(2+); X(III) = Ga(3+), In(3+)) adopting the KCd4Ga5S12-type structure, have been synthesized by high-temperature solid-state reaction of an elemental mixture with ACl flux. Their three-dimensional network structures are stacked by M9Se24-layers of vertex sharing MSe4 tetrahedra, of which each center is jointly occupied by X(II) and X(III) atoms. Studies suggest that such tetrahedral building units can be regarded as the "multi-functional sites", on which the Cd(2+)/Ga(3+) pair gives rise to the coexistence of NLO and thermochromic properties, and the Mn(2+)/In(3+) pair leads to the coexistence of NLO and magnetic properties. The density functional theory (DFT) studies and the cutoff-energy-dependent NLO coefficient analyses reveal that such "multi-functional sites" contribute to the origin of the second harmonic generation (SHG) that is ascribed to the electronic transitions from the Se-4p states to the ns, np states of X(II) and X(III) atoms. Remarkably, title compounds show very strong SHG at an incident wavelength of 2.05 µm, roughly 16-40 times that of commercial AgGaS2; among them, ACd4In5Se12 (A = Rb, Cs) represents the strongest SHG among chalcogenides to date.

Syntheses, structures, and nonlinear optical properties of quaternary chalcogenides: Pb4Ga4GeQ12 (Q = S, Se).

Two noncentrosymmetric isostructural compounds Pb4Ga4GeQ12 (Q = S, Se) with their own structure type have been synthesized by solid-state reactions at high temperature. They crystallize in the tetragonal space group P42(1)c (No. 114) with a = 12.673(2) Å and c = 6.128(2) Å, and a = 13.064(7) Å and c = 6.310(5) Å, respectively, and Z = 2. The major structure motif features a three-dimensional framework constructed by chains of GaQ4 tetrahedra that are interconnected by separated GeQ4 tetrahedra at regular intervals. Interestingly, such a [Ga4GeQ12](8-) framework is flexible to allow the addition of Ag(+) or Li(+) to occupy the embedded A- or B-type of vacancies to generate the previously reported [AgGa5Q12](7-) or [LiGa5Q12](7-) interstitial compounds without symmetry breaking. The title compounds (Q = S, Se) have optical band gaps of 2.35 and 1.91 eV, respectively, and wide IR transparent regions of 0.80-22.5 and 0.75-22.5 µm, respectively. Significantly, the powder Pb4Ga4GeSe12 sample exhibits a strong second-harmonic-generation (SHG) response that is ∼2 times that of the benchmark AgGaS2 at a laser radiation of 2.05 µm with a non phase-matchable behavior. The calculated d36 coefficient agrees well with the experimental observation. The density functional theory (DFT) calculations suggest that the SHG response originates from the electronic transitions from Se 4p states to Pb 6p, Ga 4p, and Ge 4p states.

Noncentrosymmetric inorganic open-framework chalcohalides with strong middle IR SHG and red emission: Ba3AGa5Se10Cl2 (A = Cs, Rb, K).

Novel SHG effective inorganic open-framework chalcohalides, Ba(3)AGa(5)Se(10)Cl(2) (A = Cs, Rb and K), have been synthesized by high temperature solid state reactions. These compounds crystallize in the tetragonal space group I ̅4 (No.82) with a = b = 8.7348(6) - 8.6341(7) Å, c = 15.697(3) - 15.644(2) Å, V = 1197.6(3) - 1166.2(2) Å(3) on going from Cs to K. The polar framework of (3)(∞)[Ga(5)Se(10)](5-) is constructed by nonpolar GaSe(4)(5- )tetrahedron (T1) and polar supertetrahedral cluster Ga(4)Se(10)(8-) (T2) in a zinc-blende topological structure with Ba/A cations and Cl anions residing in the tunnels. Remarkably, Ba(3)CsGa(5)Se(10)Cl(2) exhibits the strongest intensity at 2.05 µm (about 100 times that of the benchmark AgGaS(2) in the particle size of 30-46 µm) among chalcogenides, halides, and chalcohalides. Furthermore, these compounds are also the first open-framework compounds with red photoluminescent emissions. The Vienna ab initio theoretical studies analyze electronic structures and linear and nonlinear optical properties.

Disconnection enhances the second harmonic generation response: synthesis and characterization of Ba23Ga8Sb2S38.

An unusual zero-dimensional quaternary sulfide, Ba(23)Ga(8)Sb(2)S(38), that crystallizes in the noncentrosymmetric polar space group Cmc2(1) was discovered by solid-state reaction of an elemental mixture. The involvement of a second building unit consisting of SbS(3) pyramid and constituting 20% of the structure helped to realize the disconnection of the asymmetric GaS(4) tetrahedra. Such a disconnection leads to the strongest powder second harmonic generation intensity in the IR region among sulfides to date, ~22 times that of commercial AgGaS(2) at an incident laser wavelength of 2.05 µm with the same particle size of 46-74 µm.

Quaternary tellurides with different valent Ge centers: Cs2Ge3M6Te14 (M = Ga, In).

New quaternary tellurides, Cs(2)Ge(3)M(6)Te(14) (M = Ga, In), were discovered by solid-state reactions. These compounds crystallize in space group P3ml (No. 164), with a = b = 8.2475(2) Å, c = 14.2734(8) Å, and V = 840.82(6) Å(3) (Z = 1) for Cs(2)Ge(3)Ga(6)Te(14) (1) and a = b = 8.5404(2) Å, c = 14.6766(8) Å, and V = 927.07(6) Å(3) (Z = 1) for Cs(2)Ge(3)In(6)Te(14) (2). The remarkable structural feature is the novel three-dimensional [Ge(3)M(6)Te(14)](2-) anionic framework made by condensed In(6)Te(14) (or Ga(6)Te(14)) layers that are connected alternately by dimeric Ge(3+)(2)Te(6) units and Ge(2+)Te(6) octahedra along the c direction. The presence of Ge centers with different oxidation states is also supported by the results of the electron localization function calculation and X-ray photoelectron spectroscopy measurement.

Structure change induced by terminal sulfur in noncentrosymmetric La2Ga2GeS8 and Eu2Ga2GeS7 and nonlinear-optical responses in middle infrared.

Two new noncentrosymmetric quaternary sulfides, La(2)Ga(2)GeS(8) (1) and Eu(2)Ga(2)GeS(7) (2), have been synthesized by high-temperature solid-state reactions. The structure change on going from 1 to 2 to the known Li(2)Ga(2)GeS(6) (3) nicely shows that the reduced cation charge-compensation requirement causes a decrease in the number of terminal S atoms per formula, which is a key to determining the connectivity of the GaS(4) and GeS(4) building units. Powder sample 2 exhibits a strong second-harmonic-generation (SHG) response of about 1.6 times the benchmark AgGaS(2) at 2.05 µm laser radiation, a non type I phase-matchable behavior, and a comparable transparency region. The SHG intensities of these compounds originate from the electronic transitions from S 3p states to La/Eu/Li-S, Ga-S, and Ge-S antibonding states according to Vienna ab initio simulation package studies.

A hybrid with uniaxial negative thermal expansion behaviour: the synergistic role of organic and inorganic components.

Presented is an inorganic-organic hybrid compound Mn2(api)Sb2S5 (1) with uniaxial NTE behaviour. The NTE of reflects a strong synergistic role of organic and inorganic components, which results from the novel zigzag linkage of interlamellar organic ligands. An "elevator-platform" expansion mechanism was proposed, with implications for future design of sensitive hybrid thermomechanical actuators.

Novel mercury selenidoantimonates with structures ranging from one-dimensional ribbon to three-dimensional open-framework.

With a transition metal (TM) complex or a protonated organic amine as a structure-directing agent (SDA), five novel Hg-Sb-Se compounds with the architectures ranging from one-dimensional (1D) ribbon, two-dimensional (2D) layer, to three-dimensional (3D) open-framework have been solvothermally synthesized and structurally characterized. The compounds [Ni(1,2-pda)3]HgSb2Se5 (1) (1,2-pda = 1,2-diaminopropane) and [Mn(dien)2]HgSb2Se5 (2) (dien = diethylenetriamine) feature a 1D-[HgSb2Se5]n(2n-) ribbon assembled by the {HgSb2Se5} groups. The compounds [Ni(en)3]Hg2Sb2Se6 (3) (en = ethylenediamine) and [Ni(en)(teta)]Hg2Sb2Se6 (4) (teta = triethylenetetramine) feature a 2D-[Hg2Sb2Se6]n(2n-) layer constructed by the combination of the {HgSbSe3}n ribbons. The compound [(Me)2NH2][Hg3Sb3Se8] (5) contains the dimeric {Sb2Se5} groups and {Hg3SbSe7}n layers, which are interconnected into a 3D-[Hg3Sb3Se8]n(n-) anionic framework with [(Me)2NH2](+) ions located in the channels. Furthermore, the comparison between 2 and recently reported [Mn(tren)]HgSb2Se5 based on the optical diffuse-reflectance measurements and band structure calculations indicates that the Mn(2+) ions with different coordination environments make distinct contributions to the CBM of the band structure.

Assembly of novel organic-decorated quaternary TM-Hg-Sb-Q compounds (TM = Mn, Fe, Co; Q = S, Se) by the combination of three types of metal coordination geometries.

Four organic-decorated quaternary TM-Hg-Sb-Q compounds, namely, [Mn(phen)](2)HgSb(2)S(6) (phen = 1,10-phenanthroline) (1) and isomorphic [TM(tren)]HgSb(2)Se(5) (TM = Mn (2), Fe (3), Co (4); tren = tris(2-aminoethyl)amine) have been solvothermally prepared, and structurally characterized by single crystal X-ray diffraction analyses. 1 and 2 (3, 4) feature distinct one-dimensional neutral infinite ribbon-like structures constructed by the combination of Sb(3+), Hg(2+) and TM(2+), the latter two of which adopt different coordination modes. In compound 1, organic-decorated {[Mn(phen)](2)Sb(2)S(6)} clusters assembled by {MnS(4)N(2)} octhedra and {SbS(3)} pyramids are bridged by the {HgS(2)} groups in a linear fashion. Differently, the {SbSe(3)} pyramids, {HgSe(4)} tetrahedra and {TMSeN(4)} trigonal-bipyramids in 2 (3, 4) are combined to form novel {[TM(tren)](2)Hg(2)Sb(4)Se(12)} clusters, which are interconnected to form {[TM(tren)]HgSb(2)Se(5)}(n) ribbons. The results of optical diffuse-reflectance measurements and band structure calculations based on DFT methods indicate that 1 and 2 (3, 4) are indirect and direct semiconductors, respectively. Photocatalytic experiments have shown the ability of 2 in photodegradation of Rhodamine B (RhB).