Synthesis,crystal growth and characterization of organic NLO material: 4-Bromo-4′-hydroxybenzylidene aniline

One of the novel benzylidene aniline derivatives, 4-bromo-4′-hydroxybenzylidene aniline (BHBA) was synthesized and single crystal of BHBA was grown from solution following slow evaporation method at room temperature. Unit cell parameters of the grown crystal were determined from single crystal X-ray diffraction studies. Functional groups of BHBA were identified from Fourier transform infrared spectral study. UV–vis-NIR analysis of BHBA showed that the crystal is transparent between wavelengths 400 and 1100 nm. Thermal stability of the title compound was examined by thermogravimetric and differential scanning calorimetric studies. Fluorescence spectrum of the grown crystal recorded using spectrofluorometer shows emission peak at 450 nm. The second harmonic generation efficiency of BHBA estimated by Nd:YAG pulsed laser employing the Kurtz powder technique is ∼1.3 times that of potassium dihydrogen orthophosphate. Microhardness studies reveal that BHBA possesses high Vickers hardness value. The dielectric measurements were carried out at different temperatures and frequencies and the results are discussed.     

Studies on the growth,structural, optical and laser damage threshold properties of 4-aminopyridinium p-aminobenzenesulfonate p-ammoniobenzenesulfonate monohydrate crystal

An organic nonlinear optical crystal 4-aminopyridinium 4-aminobenzenesulfonate 4-ammoniobenzenesulfonate monohydrate (4APABS) was grown by slow evaporation solution growth technique. The cell parameters of grown crystal were confirmed by single crystal X-ray diffraction analysis. High resolution X-ray diffraction studies revealed the crystalline perfection of grown crystal. The functional groups present in title compound were confirmed by FTIR spectral studies. UV–vis spectral studies revealed that the grown crystal is transparent in the entire visible region. Single and multiple shots laser induced surface damage threshold values of the grown crystal were measured using Nd:YAG laser. The relative second harmonic generation efficiency of grown crystal was found to be 2.2 times that of KDP crystal.     

Growth and characterization of an efficient semi organic single crystal: Sodium hydrogen oxalate monohydrate

A highly proficient nonlinear optical compound Sodium Hydrogen Oxalate Monohydrate (SHOM) single crystal under semi organic category has been grown-up by the process of slow solvent evaporation. The triclinic structure and cell parameters of SHOM was revealed from X-ray diffraction analysis. The examination of FTIR was done to determine the existence of various functional groups present in the SHOM crystal. The mechanical stability is evaluated from Vicker's microhardness tester and related mechanical parameters were assessed. The multiple shot laser damage threshold was examined to be 2.65 GW/cm². TG/DTA analysis is carried out to appraise the thermal limit of the grown material. The absorbance spectrum was analyzed from UV–vis analysis which verifies high transparency of the grown crystal and various optical constants were also estimated. The third order nonlinearity, two-photon absorption and self-defocussing effect of the grown material was established from the Z-Scan approach. The results favoring the materials suitability over nonlinear optical applications are reported.     

Enhancement of second harmonic generation efficiency: Growth and characterization of magnesium(II)-doped tetrakis(thiourea)nickel(II) chloride crystals

The influence of magnesium doping on the properties of tetrakis(thiourea)nickel(II) chloride crystals has been described. The reduction in the intensity observed in powder X-ray diffraction of doped specimen and slight shifts in vibrational frequencies confirm the lattice stress as a result of doping. Surface morphological changes due to doping of the alkaline earth metal are observed by scanning electron microscopy. The incorporation of Mg(II) into the crystal lattice was confirmed by energy dispersive X-ray spectroscopy. Lattice parameters are determined by single crystal XRD analysis. The thermogravimetric and differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. The crystal is further characterized by Kurtz powder technique and dielectric studies.     

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.     

Synthesis,growth and characterization of non-linear optical material: l-Tryptophan p-nitrophenol (LTPNP) single crystal

A new nonlinear optical organic crystal l-tryptophan p-nitrophenol (LTPNP) of dimension 19 mm × 2 mm × 1.5 mm has been grown from an aqueous solution for the first time by slow evaporation technique at ambient temperature. The crystal structure of LTPNP was confirmed by single crystal X-ray diffraction. LTPNP crystallizes in non-centrosymmetric monoclinic system with space group P₂₁. The recorded FTIR spectrum confirms the presence of various functional groups in the grown crystal and confirms the formation of LTPNP. Thermal stability and melting temperature of the LTPNP crystal were identified from TG/DTA analysis. The optical absorption study confirms the suitability of the crystal for device applications. LTPNP exhibits SHG efficiency over 1.7 orders of magnitude higher than that of urea and 4 orders of magnitude higher than that of KDP.     

Growth,crystal perfection,optical and electrical properties of organic crystal: Brucinium 5-sulfosalicylate trihydrate

Single crystals of brucinium 5-sulfosalicylate trihydrate (B5ST) were grown from ethanol–water (1:1) mixed solvent by slow evaporation method. Structure and crystallinity of the grown crystal were confirmed by single-crystal X-ray diffraction analysis. Presence of functional groups and coordination of brucine and 5-sulfosalicylic acid (5SSA) were confirmed by FT-IR and FT-Raman analyses. Optical transmittance spectrum shows the crystal having 90% transmittance in the visible region. The laser-induced surface damage threshold for the grown crystal was measured as 13.64 GW cm⁻² with Nd:YAG laser assembly. Dielectric study was performed on the single crystal to study the power dissipation of the material in the presence of alternating electric field. Crystal defects and surface morphology are studied by dissolution solvent technique and it reveals the layer growth mechanism for B5ST compound.     

Growth and characterization of semi organic nonlinear optical l-Valine Ferric Chloride single crystal by solution growth technique

l-Valine Ferric Chloride single crystal is a new semi organic nonlinear optical material. It has been grown from a mixture of aqueous solutions of l-Valine and Ferric Chloride by slow evaporation solution growth technique at room temperature for the first time. Single crystal XRD analysis revealed that the crystal system belongs to Cubic P with cell parameters are a = 24.38 Å, b = 24.38 Å, c = 24.38 Å and volume is 14,485 Å³. The UV spectrum shows existence of wide transparency window suitable for optoelectronic applications. Thermal stability and melting temperature of the as grown crystal was identified from TG-DTA analysis. Spectroscopic studies have been carried out for analyzing the presence of functional groups, thermal stability and phase transition of the grown crystal. The dielectric loss and the dielectric constant of the crystals were measured as a function of frequency. Photoluminescence study was carried out for grown crystals and the maximum emission occurs has good optical transmission in the entire visible region. Second harmonic generation (SHG) conversion efficiency has been estimated.     

Crystal growth and characterization of l-phenylalaninium trichloroacetate—A new organic nonlinear optical material

Amino acid based crystals exhibit excellent nonlinear and electro-optical properties. A new nonlinear optical single crystal l-phenylalaninium trichloroacetate (LPTCA) belonging to the amino acid group was grown by the slow evaporation solution growth method. The grown crystals have been subjected to powder X-ray diffraction studies to identify the crystalline nature. Single crystal X-ray diffraction study showed that LPTCA belongs to monoclinic crystal system. Fourier transform infrared study is used to confirm the presence of various functional groups in the grown crystal. Optical transparency of the grown crystals was investigated by UV-vis-NIR spectrum. The lower optical cutoff wavelength for this crystal is observed at 254 nm and energy band gap is 4.89 eV. Thermal properties of the LPTCA crystal were studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques, which indicate that the material does not decompose before melting. The melting point of grown crystal was observed to be 136 °C in a melting point apparatus. The existence of nonlinear optical (NLO) property of LPTCA was confirmed by second harmonic generation test using Nd:YAG laser fundamental wavelength of 1064 nm.     

Growth and characterization of L-phenylalanine nitric acid (LPN) and tris L-(phenylalanine)-phenylalanininum nitrate (TPLPN) as second and third order nonlinear optical materials

We synthesized noncentrosymmetric single crystals of L-phenylalanine nitrate (LPN) and tris L-(phenylalanine) L-phenylalaninium nitrate (TPLPN) by slow solvent evaporation technique. Both crystallized in monoclinic system with different acentric space groups namely P2₁ (LPN) and C2 (TPLPN) respectively. The IR and Raman spectral investigation was done for LPN and TPLPN and discussed. The UV-vis-studies accomplished the excitation wavelength of the grown crystals suitable to exhibit second harmonic generation signal. From the absorption data, remarkable optical properties such as direct band gap energy, Urbach energy, extinction coefficient were evaluated. The mechanical strength of the grown crystal was examined by Vickers micro hardness test. The temperature of decomposition was confirmed by TG/DSC analysis. Fluorescence emission spectrum of LPN and TPLPN were recorded and lifetime was also studied. The dielectric constant and dielectric loss of LPN and TPLPN has been determined as a function of frequency and temperature. Also the surface topologies of the crystallized salts were assessed by SEM studies. The third-order nonlinearities of LPN and TPLPN were determined by Z-scan technique with Nd: YAG at 532?nm and thereby from closed and open Z-scan data, third-order susceptibilities were calculated to be χ⁽³⁾?=?8.826?×?10^?6 esu for LPN and χ⁽³⁾?=?2.552?×?10^?7 esu for TPLPN.     

Growth,optical, mechanical,dielectric and theoretical properties of picolinium maleate NLO single crystal

Nonlinear optical single crystals of picolinium maleate (PM) were grown by slow evaporation method. The grown crystal was subjected to single crystal X-ray diffraction analysis to confirm that the crystal belongs to the monoclinic crystal structure with space group P2₁/c. The optical transmission range of the grown crystal was measured by UV–Vis–NIR region with the lower cut-off wavelength as 330 nm. The optical bandgap is found to be 3.75 eV. Mechanical strength of the grown crystal was analyzed using Vickers microhardness tester. Dielectric constant and dielectric loss of picolinium maleate are measured in the frequency range from 50 Hz to 5 MHz at different temperatures. Further, electronic properties, such as valence electron plasma energy, Penn gap, Fermi energy and electronic polarizability of the grown crystal have been estimated.     

2-Phenylethylammonium p-hydroxybenzoate: Growth,structural, spectral,thermal, optical and mechanical characterization

An efficient nonlinear optical single crystal of 2-phenylethylammonium p-hydroxybenzoate (2PPHB) was grown from aqueous solution by slow evaporation solution growth method. Single crystal X-ray diffraction studies confirmed that 2PPHB crystallizes in orthorhombic crystal system with non-centrosymmetric space group of Pna2₁. The presence of functional groups in the synthesized compound was identified by FTIR spectral analysis. The grown crystals were thermally stable up to 155 °C. UV–vis absorption, photoluminescence and birefringence optical properties of grown crystal were explored. The laser induced surface damage threshold and relative second harmonic generation properties of the grown crystal were studied using Q-switched Nd:YAG laser. The variation of dielectric properties of the grown crystal with frequency was investigated for different temperatures. The mechanical response of the crystal was studied by Vicker's microhardness technique.     

Unidirectional growth,optical, mechanical and dielectric studies on a novel NLO crystal: l-Arginine 4-nitrophenolate 4-nitrophenol dihydrate

The bulk single crystal of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP), an efficient organic NLO material of size 74 mm in length, 18 mm in diameter, was grown successfully by Sankaranarayanan–Ramasamy (SR) method. Single crystal X-ray diffraction study reveals that LAPP crystallizes into monoclinic system with the space group P2₁. The unidirectional growth along the plane (1 1 0) was confirmed from the powder XRD pattern with the sharp peak having maximum intensity. Optical absorption spectrum shows that LAPP has highly transparent in the entire visible and IR region with a wide band gap of 3.9 eV for large photon absorption. Vickers micro hardness measurement was performed to know the mechanical strength of the crystal. Dielectric profile of LAPP at room temperature brings forth low value of dielectric loss and dielectric constant at higher frequencies. Photoluminescence study reveals that LAPP exhibit green emission in the wavelength region 538 nm. The SHG efficiency of the crystal is measured by Kurtz's powder test using Nd:YAG Laser.     

Synthesis,spectral and thermal characterization of Bis(diethylammonium) tetrachloromercurate(II)-An nonlinear optical material

A new semiorganic compound, bis(diethylammonium) tetrachloromercurate(II) was grown by slow evaporation solution growth technique at ambient temperature from its aqueous solution. The crystal system and the cell parameters have been identified from the powder X-ray diffraction pattern. The UV–visible absorption of the compound shows absorption at 246 nm and there is absorption observed in the entire visible region indicates that the compound can be used as a nonlinear optical material. The UV–visible transmittance spectrum of grown crystal shows a lower cut-off wavelength at 275 nm and it was found that the crystal is suitable for optoelectronic applications. Thermal studies were carried out to find out the thermal stability and confirm the stoichiometric ratio of the compound. The thermal anomalies in DSC study indicate the occurrence of first order transition in the compound at low temperatures. The FTIR spectrum of the compound characterizes various functional groups. The various kinds of protons and carbons were assigned through NMR (¹H and ¹³C) spectroscopic techniques. The SHG efficiency of the compound was studied by Kurtz-Perry power technique and observed that it has SHG efficiency 1.5 times greater than that of potassium dihydrogen phosphate (KDP). The dielectric constant and dielectric loss of the compound decreases with increase in frequency.     

Synthesis, crystal growth and characterization of 1,5-diphenylpenta-1,4-dien-3-one: An organic crystal

1,5-Diphenylpenta-1,4-dien-3-one ( dibenzalacetone, DBA) was synthesized by a base-catalyzed aldol condensation reaction between benzaldehyde and acetone. High quality single crystals have been grown by the slow evaporation of ethanol solution and the crystal belongs to monoclinic system with centrosymmetric space group C 2/c. The DBA crystals are transparent in the entire visible region and have a lower optical cutoff at ∼440 nm. It is stable up to 119 °C and has a good chemical stability. The high resolution X-ray diffraction curve (DC) indicates that the specimen is free from structural grain boundaries. Molecular packing leads to a centrosymmetric arrangement resulting in zero second harmonic generation (SHG; χ⁽²⁾=0) efficiency.     

Studies on the electrical, linear and nonlinear optical properties of Manganese mercury thiocyanate bis-dimethyl sulfoxide, an efficient NLO crystal

Manganese mercury thiocyanate bis-dimethyl sulfoxide (MMTD), a novel organo-metallic nonlinear optical (NLO) crystal, was grown by a slow evaporation technique over a period of 30 days. The grown crystal was subjected to single crystal X-ray diffraction to determine the unit cell parameters. The optical properties of MMTD were investigated by UV-Vis-NIR, FTIR and FT-Raman spectroscopic techniques. The second harmonic generation (SHG) efficiency of the sample was measured using a Q-switched, mode-locked Nd:YAG laser and the results were compared with urea and manganese mercury thiocyanate (MMTC). The thermal parameters, such as the thermal diffusivity (α), thermal effusivity (e), thermal conductivity (k) and heat capacity (c_p) of MMTD were measured by the photopyroelectric (PPE) technique and the results are discussed. The dielectric response and mechanical properties of MMTD have also been investigated and reported.     

Growth aspects,spectral, thermal and hardness studies of rare earth cerium(III)nitrate doped zinc(tris) thiourea sulphate single crystals

Single crystals of pure and cerium(III)nitrate doped zinc(tris) thiourea sulphate (ZTS) were grown from aqueous solution by slow evaporation method. The cell parameters of the grown crystals were determined by single crystal X-ray diffraction analysis. Powder X-ray diffraction patterns were recorded and indexed for the structural confirmation. The presence of functional group in the compound has been confirmed by FTIR analysis. UV–vis absorption spectrum has been recorded to determine the cut-off wavelength of the crystal. TGA/DTA studies show thermal stability of the grown crystals. SEM-EDX analysis revealed the incorporation of the impurity (Ce³⁺) into ZTS crystals. The microhardness study reveals that the hardness number (H_v) increases with load for all the grown crystals of this work. From the values of work hardening coefficients, it was concluded that pure and cerium nitrate doped ZTS crystals belong to the category of soft materials. The second harmonic generation of cerium(III)nitrate doped ZTS crystals was confirmed by Kurtz–Perry powder method using Nd:YAG laser.     

Studies on the growth aspects and characterization of sodium para-nitro phenolate single crystals for nonlinear optical applications

Using slow evaporation solution growth technique, single crystals of sodium para nitro phenolate have been grown from the solutions prepared from three different molecular ratios of para-nitro phenol and sodium hydroxide. Structural analyses were carried out by powder X-ray diffraction and Fourier transform infrared spectrum to conform the grown crystals. Thermal stability of the grown crystals was studied by thermogravimetric (TG) and differential thermal analyses (DTA). UV–vis spectral analysis has been carried out to find the cut off wavelength of the grown crystals. Variations in the cut off wavelengths have been observed. Nonlinear optical property has been confirmed by Kurtz powder technique. The observed optical properties have confirmed that the molar concentration of para nitro phenol influenced significantly on the linear and nonlinear optical properties.     

Growth, optical, dielectric and ESR studies on tetrathiourea mercury(II) tetrathiocyanato manganate(II): An organometallic complex NLO crystal

Single crystals of tetrathiourea mercury(II) tetrathiocyanato manganate(II); Hg(N₂H₄CS)₄Mn(SCN)₄, (TMTM) were grown by slow solvent evaporation technique. The grown crystals were confirmed by single crystal and powder X-ray diffraction analysis. The optical absorption spectrum of TMTM in a mixed solvent of acetone and water shows the near ultra-violet cut-off wavelength corresponding to the absorption maximum as 335 nm. FT-IR spectrum identifies the characteristic absorption bands of thiourea and thiocyanate in both middle and far infrared regions, which further confirm the incorporation of both the ligands in the resulting compound. The electron spin resonance spectrum of TMTM was recorded both at room temperature and −196 °C, which reveals that the Mn environment is symmetrical with respect to the NCS ligand distribution. It is also interesting to note that there is no hyperfine coupling between Mn nucleus and its free electrons at both room temperature and −196 °C. The dielectric constant as well as dielectric loss of the sample were calculated for varying frequencies under different temperatures.     

Studies on physico-chemical properties of hydroxyethylammonium (l) tartrate monohydrate single crystals

In this paper, we report the growth and characterization of hydroxyethylammonium (l) tartrate monohydrate single crystals grown by slow evaporation solution technique. The X-ray diffraction analysis reveals that the crystal belongs to the monoclinic system having P2₁ space group. Photoinduced optical absorption effects were studied on the crystalline samples irradiated with CW 532 nm (green) and 689 nm (red) laser wavelengths. The relative second harmonic generation efficiency of the title crystal was found to be 1.4 times larger than that of KDP crystal. The thermal, mechanical, dielectric and optical studies of the single crystals were carried out to propose the material for useful applications. The reflectance and refractive indices were also evaluated from optical transmission spectrum. Further the electronic excitation calculations were carried out to understand the charge transfer mechanisms.