Growth,structure and optical properties of an efficient NLO crystal-aqua maleatocopper(II)

A promising non-linear optical (NLO) crystal, aqua maleatocopper(II) (CuC₄H₂O₄·H₂O), was grown at room temperature by the controlled ionic diffusion technique. Fourier transform infrared spectrum could identify the various functional groups in the crystal. Structural analysis using single crystal XRD revealed that the compound crystallizes in the monoclinic system with space group P2₁ and unit cell parameters a = 7.7277(5) Å, b = 5.2967(3) Å, c = 7.7179(4) Å, α = γ = 109.170(5)°, β = 111.995(2)°. The thermal stability and decomposition pattern of the material were explored using thermogravimetry (TG) and differential thermal analysis (DTA). The optical band gap energy of the material was estimated as 2.2 eV from the diffuse reflectance spectroscopy. The Kurtz and Perry powder technique established the crystal to be an efficient non-linear optical (NLO) material.     

Optical,spectral and thermal properties of organic nonlinear optical single crystal: 2,3-Dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate

The potential organic nonlinear optical single crystal of 2,3-dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate has been grown by slow evaporation solution growth technique (SEST) using ethanol–water solution at room temperature. The powder X-ray diffraction study reveals that the crystal belongs to orthorhombic system with non-centrosymmetric space group P2₁2₁2₁ and the cell parameters are a = 7.61 Å, b = 10.73 Å, c = 29.49 Å, V = 2410.75 Å³. The functional groups of the synthesized compound have been identified by FT-Raman and FTIR analyses. Photoluminescence spectroscopy study is determined to explore its efficacy towards device fabrications. Birefringence measurement has been carried out in order to analyze the optical homogeneity of the grown crystal. The optical constants such as reflectance (R) and extinction coefficient (K) have been determined from the transmittance data. The relative second harmonic efficiency of the compound is found to be 4 times greater than that of KDP. DTA-DSC measurements indicate that the crystal is thermally stable up to 174 °C.     

Growth and characterization of a novel organic nonlinear optical material: l-alanine 2-furoic acid

l-alanine 2-furoic acid (LA2FA), a novel organic third order nonlinear optical material was grown by slow solvent evaporation technique at room temperature. The grown single crystals were characterized by XRD, spectral, thermal, optical, dielectric and third order nonlinear properties. LA2FA crystallizes into triclinic system with the space group P1. The cell parameters are found to be a = 3.97 Å, b = 7.09 Å, c = 10.69 Å, α = 73.61°, β = 83.57°, γ = 84.21° and V = 286 Å3. The modes of vibrations of different molecular groups present in LA2FA were identified by FTIR studies. The optical transparency of the grown crystals was investigated by UV–visible spectrum. The absorption spectrum reveals that the crystal has a high UV cut off of 245 nm and photonic band gap of 2.5 eV. The scanning electron microscope (SEM) study has been carried out to determine the surface morphology of the grown crystal. The thermal behavior of the crystal investigated using thermo gravimetric (TG) and differential thermal analysis (DTA) indicates that the material does not decompose before melting. The third order NLO property was studied in detail by z-scan technique.     

Studies on the optical and mechanical properties of organic nonlinear optical 1-(4-fluorostyryl)-4-nitrostilbene (FNS) single crystal

A new organic nonlinear optical material 1-(4-fluorostyryl)-4-nitrostilbene (FNS) has been synthesized and single crystals of FNS were grown using solvent evaporation solution growth technique (SESGT) by 2-butanon solvent. Single crystal x-ray diffraction analysis reveals the unit cell parameters of the grown crystal are a = 9.494(4) Å, b = 9.864(2) Å, c = 19.501(7) Å and it belongs to monoclinic system with noncentrosymmetric space group. Optical transmittance of the grown crystal has been studied by UV-Vis-NIR spectrum. The optical properties of FNS have been studied by means of optical transmittance measurements in the wavelength range of 190–1100 nm The optical constants were calculated from the optical transmittance (T) data such as refractive index (n), extinction coefficient (k) and reflectance (R). The optical band gap (E_g) of FNS is 3.27 eV with direct transition. The complex dielectric (?) constant of the grown FNS crystal was determined. The second harmonic generation (SHG) efficiency of the grown FNS crystal has been studied by using Kurtz-Perry powder technique and it shows 12 times relatively greater than KDP.     

Studies on vibrational, dielectric, mechanical and thermal properties of organic nonlinear optical co-crystal: 2,6-diaminopyridinium-4-nitrophenolate-4-nitrophenol

This article presents the vibrational, dielectric, mechanical and thermal properties of 2,6-diaminopyridine-4-nitrophenolate-4-nitrophenol co-crystals (DAP:NP) grown by slow evaporation solution growth technique. It crystallizes in orthorhombic noncentrosymmetric space group Pna2₁ with cell dimension a=10.86 Å, b=12.00 Å and c=13.53 Å; α=β=γ=90° with V=1764 Å³. Functional groups present in the molecule have been identified from FTIR study. Dielectric constant (ε_r), dielectric loss (tanδ) and ac conductivity (σ_ac) behaviors of the crystals have been studied at different temperatures. Presence of piezoelectric resonance peaks at lower frequency in dielectric measurements may increase the electro-optic coefficient of the crystals. Mechanical strength and its parameters of the grown crystals have been determined by Vickers microhardness test. TG/DTA analysis shows the melting point of the material is 150 °C and it undergoes two stages of decomposition.     

Growth and physical properties of an organic crystal for NLO applications: Guanidinium phenyl arsonate (GPA)

Single crystals of organic material guanidinium phenyl arsonate (GPA) of size 28 × 14 × 10 mm³ were grown from propanol–water mixed solvent by slow solvent evaporation technique. The crystal belongs to monoclinic system with noncentrosymmetric space group Cc. The lattice parameter values of GPA crystals are a = 18.453 Å, b = 7.609 Å, c = 12.592 Å and β = 121.856°. The grown crystal was subjected to X-ray diffraction (XRD) study to identify its morphology and structure. Chemical etching study using propanol–water as etchant reveals the mechanism of growth. The formation of synthesized compound was confirmed by Fourier transform infrared (FT-IR) spectroscopy analysis. Optical transmittance and second harmonic generation (SHG) of the grown crystals were studied by UV–vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of GPA has been used to calculate the refractive index ‘n’ and the extinction coefficient ‘k’. The laser induced surface damage threshold for the grown crystal was determined using Nd:YAG laser. The mechanical behavior of GPA was analyzed using Vickers microhardness test.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Synthesis, growth, and characterization of a non-linear optical crystal-glycine lithium chloride

A new non-linear optical material, glycine lithium chloride, was synthesized and single crystals were grown by slow evaporation solution growth technique at constant temperature from its aqueous solution. Transparent and well-crystallized hexagonal prisms were obtained by controlled evaporation at a constant temperature of 45 °C. The grown crystals were characterized by X-ray diffraction methods, Fourier transforms infrared spectroscopy, and optical absorption spectrum. Single crystal X-ray diffraction analysis revealed that the crystal lattice of glycine lithium chloride is hexagonal with unit cell a = b = 7.023 Å, c = 5.478 Å, α = β = 90°, γ = 120°, V = 234 Å³. The dielectric response of the crystal with varying frequencies was studied. The second harmonic generation efficiency of the crystal was studied and is found to be larger than KDP.     

Structural phase transitions at high-temperature in double perovskite Sr2GdRuO6

The crystal structure evolution of the Sr₂GdRuO₆ complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K≤T≤1273 K. Powder X-ray diffraction measurements at room temperature and Rietveld analysis show that this compounds crystallizes in a monoclinic perovskite-type structure with P2₁/n (#14) space group and the 1:1 ordered arrangement of Ru⁵⁺ and Gd³⁺ cations over the six-coordinate M sites, with lattice parameters a=5.81032(8) Å, b=5.82341(4) Å, c=8.21939(7) Å, V=278.11(6) Å³ and angle β=90.311(2)^o. The high-temperature analysis shows that this material suffers two-phase transitions. At 373 K it adopts a monoclinic perovskite structure with I2/m space group, and lattice parameters a=5.81383(2) Å, b=5.82526(4) Å, c=8.22486(1) Å, V=278.56(2) Å³ and angle β=90.28(2)^o. Above of 773 K, it suffers a phase transition from monoclinic I2/m to tetragonal I4/m, with lattice parameters a=5.84779(1) Å, c=8.27261(1) Å, V=282.89(5) Å³ and angle β=90.02(9)^o. The high-temperature phase transition from monoclinic I2/m to tetragonal I4/m is characterized by strongly anisotropic displacements of the anions.     

Investigation of crystal structure and nonlinear optical properties of 2-methoxyanilinium nitrate

Single crystals of a new hybrid compound salt: 2-methoxyanilinium nitrate were prepared by slow evaporation at room temperature of diluted aqueous solutions containing 2-methoxyaniline with nitric acids. The compound crystallizes in a space group Pcab of orthorhombic system with cell parameters a = 8.8784 (6) Å, b = 10.6348 (7) Å, c = 18.3045 (7) Å, V = 1728.31 (17) ų at T = 100 K and Z = 8. The structure has been refined to an R-value of 0.044 for 1956 observed reflections using three-dimensional X-ray diffraction data. Third-order nonlinear optical susceptibility (χ^〈3〉) was measured by degenerate four wave mixing (DFWM) method at 532 nm. Third harmonic generation (THG) measurements at the 1064 nm were carried out for the 2-methoxyanilinium nitrate crystal with the following dimensions: 4 × 9 × 0.5 mm.     

A new sodium samarium borate Na3Sm2(BO3)3

A new sodium samarium borate with composition Na₃Sm₂(BO₃)₃ (NSBO) has been synthesized by high temperature solid state reaction. The yellowish transparent single crystals of Na₃Sm₂(BO₃)₃ have been grown from the Na₂CO₃-H₃BO₃ flux system using the top-seeded solution growth (TSSG) method. X-ray diffraction analysis demonstrated that the NSBO crystals belong to orthorhombic systems and lattice parameters are a=5.0585 Å, b=11.0421 Å, c=7.0316 Å. The measurement of the infrared spectrum indicated that the basic anionic groups are the BO³⁻₃ groups. Furthermore, Na₃Sm₂(BO₃)₃ exhibits an optical second harmonic generation effect which is close to that of KDP (KH₂PO₄).     

Synthesis, growth and characterization of novel second harmonic nonlinear chalcone crystal

Nonlinear optical (NLO) materials are useful in many of the industrial applications. New NLO chalcone derivative (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (4N4MSP) crystals have been grown by slow evaporation technique at ambient temperature. The grown crystals were subjected to single crystal X-ray diffraction study. The crystal has noncentrosymmetric structure in the orthorhombic system with space group Aba2 and unit cell parameters a=14.0647(15) Å, b=33.738(4) Å and c=6.0039(6) Å. To confirm the presence of various functional groups in the compound, FT-IR spectrum was recorded. The crystal was subjected to TGA/DTA analysis to find its thermal stability. The grown crystals were characterized for their optical transmission and mechanical hardness. The second harmonic generation (SHG) efficiency of the crystal is obtained by classical powdered technique using Nd:YAG laser and its value is 28.57 times that of urea. The laser damage threshold for 4N4MSP crystal was determined using Q-switched Nd:YAG laser. The refractive index values for green and red wavelengths were measured by Brewster angle technique. The dielectric and electrical measurements were carried out to study the different polarization mechanism and conductivity of the crystal. Good thermal, mechanical, transmission and SHG response make it desirable for the NLO applications.     

Synthesis,growth, structure,spectral, thermal and first-order molecular hyperpolarizability of benzophenone-2-furoyl hydrazone single crystal

Single crystals of benzophenone-2-furoyl hydrazone are grown by slow evaporation solution growth technique from ethanol at room temperature. It belongs to monoclinic system with the space group P2₁/c and the cell parameters are, a = 6.1631(3) Å, b = 13.1397(8) Å, c = 18.0030(11) Å and V = 1457.72(14) Å³. NMR spectral studies reveal the structure and powder XRD indicates the crystallinity of the specimen. The characteristic functional groups present in the molecule are confirmed by Fourier transform infrared spectroscopy. The crystals are transparent in the visible region having a lower optical cut-off at ∼406 nm and the band gap energies are estimated by the application of Kubelka–Munk algorithm. Thermal analysis by TG/DTA indicates the stability of the material. The scanning electron microscopy studies reveal the surface morphology of the as-grown crystal. Theoretical calculations were performed using Hartree–Fock method with 6-31G(d,p) as the basis set for to derive the optimized geometry, dipole moment and first-order molecular hyperpolarizability (β) values.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Structural, dielectric, optical and ferroelectric property of urea succinic acid crystals grown in aqueous solution containing maleic acid

Urea-succinic acid crystals have been grown at room temperature from aqueous solution in the presence of maleic acid by a slow evaporation technique. The structural parameters were determined using powder X-ray diffraction (XRD) and found to have monoclinic symmetry (space group P2₁/m) with a=9.902, b=17.510, c=5.555 Å and α=γ=90°, β=96.46°. The transparency and optical analysis were carried out using UV-vis analysis. The optical band gap is found to be 4.71 eV. The presence of various functional groups was confirmed by FTIR analysis. The samples have shown piezoelectric behavior with a fairly good piezoelectric charge coefficient (d₃₃) of 5 pC/N, when it is poled at 7 kV/cm. The hysteresis loop was plotted and the remnant polarization and coercive field were found to be 2.8 μC/cm² and 4 kV/cm, respectively. The dielectric analysis was carried out as a function of temperature at various frequencies and the results were also discussed.     

Synthesis and hydrolysis of octacalcium phosphate and its characterization by electron microscopy and X-ray diffraction

Octacalcium phosphate (OCP) powder was produced by precipitating 250 mL Ca(CH₃COO)₂ 0.04 M into 750 L of phosphate solution (5 mmol Na₂HPO₄ and 5 mmol NaH₂PO₄) at a constant temperature of 60 °C and pH 5, which resulted in a dry white powder. X-ray diffraction (XRD), transmission electron microscopy (TEM) analysis, and the electron diffraction pattern (SAED) all showed only OCP. Hydroxyapatite (HAP) was directly obtained through hydrolysis of the powder. The total transformation of OCP into HAP was registered over a period of 6 h. During the first 30 min of hydrolysis both phases coexisted. The two phases and the OCP-HAP interface were structurally analyzed through XRD and TEM. OCP parameters (calculated by the Rietveld method) are a=19.70, b=9.50, c=6.85 Å; α=90.03°, β=92.48°, γ=108.32° (triclinic P-1) with average crystal size of 13.5±0.2 nm, while HAP parameters were a=9.45, c=6.87 Å (hexagonal P6₃/m) with average crystal size of 16.9±0.2 nm.     

Syntheses, crystal structures, visible and near-IR luminescent properties of ternary lanthanide (Dy, Tm) complexes containing 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline

The ligands 4,4,4-trifluoro-1-phenyl-1,3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)₃phen and Tm(bfa)₃phen]. Crystal data: Dy(bfa)₃phen C₄₂H₂₆F₉N₂O₆Dy, triclinic, P1¯, a=9.9450(6) Å, b=14.0944(9) Å, c=14.6043(9) Å, α=82.104(1)°, β=87.006(1)°, γ=76.490(1)°, V=1971.1(2) Å³, Z=2; Tm(bfa)₃phen C₄₂H₂₆F₉N₂O₆Tm, triclinic, P1¯, a=9.898(5) Å, b=13.918(5) Å, c=14.753(5) Å, α=83.517(5)°, β=86.899(5)°, γ=76.818(5)°, V=1965.3(14) Å³, Z=2. The coordination number of the central Ln³⁺ (Ln=Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand. The photophysical properties of the two complexes were studied by absorption spectra, diffuse reflectance spectra, and emission spectra. They show the characteristic luminescence of the corresponding Ln³⁺ ion in both visible and near-IR (NIR) region. Additionally, the energy transfer mechanisms between the ligands and central Ln³⁺ ions were discussed.     

Crystal structure,ionic conductivity and dielectric relaxation studies in the (C5H10N)2BiBr5 compound

The synthesis and crystal structure of the bis (3-dimethylammonium-1-propyne) pentabromobismuthate(III) salt are given in the present paper. After an X-ray investigation, it has been shown that the title compound crystallizes at 298 K in a centrosymmetric monoclinic system, in the space group C₂/c with the following lattice parameters a=12.9034(3) Å, b=19.4505(6) Å, c=8.5188(2) Å, β=102.449(2). Not only were the impedance spectroscopy measurements of (C₅H₁₀N)₂BiBr₅ carried out from 209 Hz to 5 MHz over the temperature range of 318 K–373 K, but also its ac conductivity evaluated. Besides, the dielectric relaxation was examined using the modulus formalism. Actually, the near values of activation energies obtained from the impedance and modulus spectra confirms that the transport is of an ion hopping mechanism, dominated by the motion of the H⁺ ions in the structure of the investigated material.     

Growth and characterization of new semi-organic l-proline strontium chloride monohydrate single crystals

The present communication deals with the synthesis, single crystal growth and characterization of a new nonlinear optical material l-proline strontium chloride monohydrate (l-PSCM). Single crystals have been grown using the slow solvent evaporation technique. Single crystal XRD analysis confirmed that the crystal belongs to the orthorhombic structure with lattice parameter a=6.6966(3) Å, b=12.4530(5) Å, c=15.2432(5) Å and space group P2₁2₁2₁. Presence of various functional groups in l-PSCM and protonation of the ions were confirmed by Fourier transform infrared spectroscopy (FT-IR) analysis. The melting point of the single crystal was found to be 126 °C using DSC. Ultraviolet-visible spectral analyses showed that the crystal has low UV cut-off at 226 nm combined with very good transparency of 90% in a wide range. The optical band gap was estimated to be 5.82 eV. Capacitance and dielectric-loss measurements were carried out at different temperatures in the frequency range 1 kHz-2 MHz. The dielectric constant and loss factor were found to be 21 and 0.03 at 1 kHz at room temperature, respectively. Microhardness mechanical studies show that hardness number (H_v) increases with load for l-PSCM single crystals the by Vickers microhardness method. Second harmonic generation (SHG) efficiency was found to be 0.078 times the value of KDP.