Growth and characterization of an organic nonlinear optical crystal: Glycinium trichloroacetate

Single crystal of glycinium trichloroacetate, an organic nonlinear optic (NLO) material, has been grown by slow solvent evaporation technique at room temperature. The grown crystal was subjected to single crystal X-ray diffraction for confirming the coordination formed, and the presence of various functional groups was studied by FTIR in the range 4000–450 cm⁻¹. UV–Visible transmittance studies were performed to analyze optical transparency of the crystal and second harmonic generation was investigated to explore the NLO property of the material. Thermogravimetric and differential thermal analysis have been performed to study thermal properties of the grown crystal. Dielectric constant and dielectric loss were studied at different temperatures and frequencies. Vicker's microhardness testing was carried out on the as grown crystal to reveal the mechanical properties of the crystal. Etching studies were made on the as grown crystal to analyze the structural imperfection of the crystal.     

Studies on the growth and physical properties of nonlinear optical crystal: 2-Amino-5-nitropyridinium-toluenesulfonate

Single crystals of 2-amino-5-nitropyridinium-toluenesulfonate (2A5NPT) were grown by the slow cooling method. The unit cell dimensions were determined from single crystal X-ray diffraction studies. The thermal parameters - thermal diffusivity (α), thermal effusivity (e), thermal conductivity (K) and heat capacity (C_p) of 2A5NPT were measured by an improved photopyroelectric technique at room temperature. Single and multiple shot experiments performed on the grown crystals for the second harmonic of pulsed Nd:YAG laser (532 nm) show that it exhibits a high laser damage threshold which is a favorable property for nonlinear optical applications. Dielectric constant and dielectric loss of the grown crystal were evaluated for the frequency range 1 kHz-1 MHz in the temperature region 40-130 °C. Hardness values were measured using Vickers hardness measurement.     

Studies on the synthesis, structure, growth and physical properties of an organic NLO crystal: 2-Amino-5-nitropyridinium Phenolsulfonate

A noncentrosymmetric crystal was prepared from 2-amino-5-nitropyridine (2A5NP) and p-Phenolsulfonic acid, which was designed for second harmonic generation. Good quality single crystals of 2-amino-5-nitropyridinium Phenolsulfonate (2A5NPP) were successfully grown by the slow evaporation method with dimensions 10 × 4 × 3 mm³. The unit cell dimensions were determined from single crystal X-ray diffraction studies. The structural perfection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. Fourier transform infrared (FTIR) spectral studies have been performed to identify the functional groups. The optical transmittance window and the lower cutoff wavelength of the 2A5NPP have been identified by UV-vis-NIR studies. Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study its thermal properties. Powder test with Nd:YAG laser radiation shows a high second harmonic generation. The laser induced surface damage threshold for the grown crystal was measured using Nd:YAG laser.     

Studies on growth and characterization of an NLO crystal: L-alanine hydrogen chloride (LAHC)

A nonlinear optical (NLO) salt viz. L-alanine hydrogen chloride (LAHC) has been synthesized and solubility of the synthesized salt in de-ionized water was determined at different temperatures. Single crystals of L-alanine hydrogen chloride (LAHC) salt were grown by solution method with slow evaporation technique. The grown crystals were characterized by single crystal X-ray diffraction (XRD) and powder XRD analyses to study the crystal structure. The crystallinity of LAHC crystal was confirmed by the powder X-ray diffraction study and diffraction peaks were indexed. FTIR study was used to confirm the presence of various functional groups in the grown crystals. UV–visible transmittance spectrum was recorded to study the optical transparency of LAHC crystal. The nonlinear optical (NLO) property of the grown crystal was confirmed by Kurtz–Perry powder test. The density of LAHC crystal was determined by floatation method. The mechanical strength of the crystal was estimated by Vickers hardness test. The grown crystals were subjected to TG/DTA analyses. The dielectric behavior of the sample was also studied.     

Growth, thermal, dielectric and mechanical studies of triglycine zinc chloride, a semiorganic nonlinear optical material

Triglycine zinc chloride, a semiorganic material, has been grown by slow solvent evaporation technique from a mixture of aqueous solution of glycine and zinc chloride in 2:1 molar ratio at room temperature. The grown crystal is up to the dimension of 45 × 23 × 18 mm³. Characterization of the crystals was made using single-crystal X-ray diffraction for obtaining unit cell parameters. Powder X-ray diffraction was recorded and the major peaks were indexed. Simultaneous thermogravimetric analysis and differential thermal analysis were carried out for the as grown crystals to determine the thermal stability of the crystal. The crystals were further characterized by UV-Vis-NIR transmission spectrum in the range of 200 to 1100 nm. Dielectric constant and dielectric loss measurements were carried out at different temperatures and frequencies. Mechanical studies were carried out on the as grown crystal.     

Spectroscopic, thermal and mechanical behavior of allylthiourea cadmium chloride single crystals

Allylthiourea cadmium chloride, a promising non-linear optical material was grown from aqueous solution by slow evaporation technique. Single crystal X-ray diffraction studies reveal that the crystal is trigonal structure with R3C space group. The spectroscopic properties were investigated by recording the Fourier transform infrared and optical absorption spectra. The dielectric studies of the sample were carried out at varying temperatures in the frequency range from 50 Hz to 5 MHz. The thermal properties were studied using thermogravimetric analyses and photopyroelectric technique. It is evident from the thermal studies that the decomposition of the crystal begins around 200 °C. The microhardness test conducted on the grown crystal suggests that the crystal has a relatively high mechanical strength. The second harmonic generation efficiency of the crystal was studied and found to be nearly 1.5 times that of urea.     

Effect of magnesium chloride on growth,crystalline perfection,structural, optical,thermal and NLO behavior of γ-glycine crystals

In the present study, single crystals of γ-glycine possessing excellent non-linear optical properties were successfully grown at room temperature in the presence of magnesium chloride (MgCl₂) for the first time by using the slow solvent evaporation method. The second harmonic conversion efficiency of γ-glycine crystal was determined using Kurtz powder technique with Nd:YAG laser and was found to be 6 times greater than that of the standard inorganic sample potassium dihydrogen phosphate (KDP). The crystalline perfection of the grown crystal was analyzed using high-resolution X-ray diffraction (HRXRD) rocking curve measurements. The grown crystal was subjected to single crystal XRD and powder XRD, which confirmed that the crystal has hexagonal structure and belongs to space group P3₁. Inductively coupled plasma optical emission spectrometry (ICP-OES) was carried out to quantify the concentration of Mg element in the grown γ-glycine single crystal. Fourier transform infrared (FTIR) spectral studies were made to identify the functional groups. The optical band gap was likewise estimated for γ-glycine crystal using UV–vis–NIR study. The optical measurements of γ-glycine crystal helped to calculate the optical constants such as refractive index (n), the extinction coefficient (K), electric susceptibility (χ_c) and both the real (∈_r) and imaginary (∈_i) components of the dielectric permittivity functions of photon energy, which is essentially required to develop optoelectronic devices. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study thermal stability and decomposition point of the grown crystal.     

Crystal growth and characterization of new nonlinear optical single crystals of l-alaninium fumarate

Amino acid based crystals exhibit excellent nonlinear and electro optical properties. A new nonlinear optical single crystal l-alaninium fumarate (LAF) belonging to the amino acid group was grown by slow evaporation solution growth technique. Single crystal X-ray diffraction study showed that LAF belongs to orthorhombic crystal system. The UV-Vis-NIR spectrum of LAF showed very good transparency in the region from 300 nm to 1100 nm. Fourier transform infrared is used to confirm the presence of various functional groups in the grown crystal. Thermal properties of the LAF crystal were carried out 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 as 267.5 °C by melting point apparatus. The existence of nonlinear optical (NLO) property of LAF was confirmed by second harmonic generation test using Nd:YAG laser fundamental wavelength of 1064 nm.     

Growth, thermal and mechanical properties of new nonlinear optical barium bis-paranitrophenolate paranitrophenol tetrahydrate single crystal

Barium bis paranitrophenolate paranitrophenol tetrahydrate, a new semiorganic nonlinear optical single crystal has been grown by slow evaporation solution growth technique at room temperature of 30 °C. Crystal of dimensions of 29 mm × 11 mm × 5 mm was obtained in a period of 30 days. X-ray diffraction analysis reveal the newness of the crystal structure belonging to the orthorhombic class with lattice parameters a = 19.899(5) Å, b = 28.019(8) Å, c = 10.745(4) Å and α = β = γ = 90°. The grown crystal is examined for its nonlinear optical nature with Kurtz powder technique after being sieved for particle sizes between 5 and 100 μm and analyzed for its thermal and mechanical properties. The effective nonlinear optical coefficient being 16 times greater than that of KDP crystal, good thermal stability up to 120 °C with the Meyer's constant n < 2 helps fashion the crystal towards device geometry.     

Crystal structure and characterization of a novel organic optical crystal: 2-Aminopyridinium trichloroacetate

2-Aminopyridinium trichloroacetate, a novel organic optical material has been synthesized and crystals were grown from aqueous solution employing the technique of controlled evaporation. 2-Aminopyridinium trichloroacetate crystallizes in monoclinic system with space group P2₁/c and the lattice parameters are a = 8.598(5) Å, b = 11.336(2) Å, c = 11.023(2) Å, β = 102.83(1)° and volume = 1047.5(3) Å³. High-resolution X-ray diffraction measurements were performed to analyze the structural perfection of the grown crystals. Thermal analysis shows a sharp endothermic peak at 124 °C due to melting reaction of 2-aminopyridinium trichloroacetate. UV-vis-NIR studies reveal that 2-aminopyridinium trichloroacetate has UV cutoff wavelength at 354 nm. Dielectric studies show that dielectric constant and dielectric loss decreases with increasing frequency and finally it becomes almost a constant at higher frequencies for all temperatures. The negative nonlinear optical parameters of 2-aminopyridinium trichloroacetate were derived by the Z-scan technique.     

Crystal growth, thermal and optical studies of semiorganic nonlinear optical material: l-lysine hydrochloride dihydrate

Single crystals of l-lysine hydrochloride dihydrate (LLHCD), a nonlinear optical material, have been grown by slow cooling technique from its aqueous solution. LLHCD was found to be highly soluble in water. The grown crystals have been subjected to single crystal X-ray diffraction to confirm the structure and to estimate the lattice parameters. The vibrational structure of the molecule is elucidated from FTIR spectra. Thermal analysis revealed the thermal stability of the grown crystals. The optical transmittance spectrum shows that the material possesses good optical transparency in the entire visible region with a UV cut-off wavelength at 228 nm. The mechanical properties of the grown crystal have been studied using Vicker's microhardness test. The laser damage threshold of 52.25 MW/cm² has been measured by irradiating Q-switched Nd:YAG laser (1064 nm).     

Optical, structural and microhardness properties of KDP crystals grown from urea-doped solutions

Potassium dihydrophosphate single crystals were grown from aqueous solutions onto a point seed using temperature reduction method by doping with different molar values of urea. The characterization of the grown crystals was made by visible and Fourier transform infrared spectroscopy, Vicker's hardness studies, X-ray powder diffraction, non-linear optical and laser damage threshold measurements. By comparing these crystals with the ones grown from the pure solution, it is shown that 0.2-2.0 M of the urea additive enhances the laser damage threshold and the second harmonic efficiency more than by 25 and 20%, respectively. By means of the Bond method using a multipurpose three-crystal X-ray diffractometer it is shown that the presence of urea additive increases the crystal lattice parameter c of the grown crystals, whereas the lattice parameter a is by an order less sensitive to the changing urea concentration in the solution. The Vicker's hardness studies at room temperature carried out on (1 0 0) and (0 0 1) crystallographic planes show an increased hardness of the doped crystals (grown in the presence of urea additive) on the plane (0 0 1) in comparison with that of pure potassium dihydrophosphate crystal.     

Crystal structure and characterization of a novel organic crystal: 4-Dimethylaminobenzophenone

Single crystals of a novel organic material, dimethylaminobenzophenone were grown from aqueous solution employing the technique of controlled evaporation. Dimethylaminobenzophenone belongs to the monoclinic system, with a = 12.5755(7) Å, b = 7.9749(4) Å, c = 13.0946(7) Å, α = 90°, β = 111.6380(10)° and γ = 90°. Fourier transform infrared study has been performed to identify the functional groups. The transmittance of dimethylaminobenzophenone has been used to calculate the refractive index n; the extinction coefficient K and both the real ?_r and imaginary ?_i components of the dielectric constant as functions of photon energy. The optical band gap of dimethylaminobenzophenone is 2.9 eV. The structural prefection of the grown crystals has been analyzed by high-resolution X-ray diffraction rocking curve measurements. Thermo gravimetric analysis and differential thermal analysis have also been carried out, and the thermal behavior of dimethylaminobenzophenone crystal has been studied. The dielectric properties and mechanical properties have been investigated.     

Feasibility study on Czochralski (Cz) growth of 3-methoxy 4-hydroxy benzaldehyde (MHBA) single crystals for nonlinear optical applications

Reported large nonlinear optical coefficients such as d₂₂ = 23.8d₃₆^KDP, d₂₁ = 13.5d₃₆^KDP, d₂₃ = 29.1d₃₆^KDP, d₂₅ = 12.8d₃₆^KDP of 3-methoxy 4-hydroxy benzaldehyde (MHBA) attract research on its bulk crystal growth for device application. The X-ray rocking and X-ray topographic studies of Cz-grown organic monoclinic crystals invariably reveal closely aligned sub-crystals which made melt growth difficult. In this context, the single crystal growth of MHBA by Czochralski pulling technique has been successfully demonstrated for the first time in the literature. Comparison study of obtained X-ray powder diffraction data with the literature confirmed the monoclinic structure. High-resolution X-ray diffraction (HRXRD) study confirms the better crystalline perfection of the grown crystal in comparison to that of solution-grown crystals and revealed the optimization of the growth process along [211¯] direction. TG, DTA and optical transmission studies carried out on the grown crystal exhibit its thermal and optical properties for SHG application.     

Study of optimum growth condition of Zinc Cadmium Thiocyanate (ZCTC) single crystals in silica gel

Some bimetallic thiocyanate complexes exhibit excellent nonlinear optical properties. Single crystals of one such material Zinc Cadmium Thiocyanate ZnCd(SCN)₄ abbreviated as ZCTC have been grown in Silica gel using gel technique by the process of diffusion. Colorless transparent crystals of size 12 mm × 2 mm × 1.3 mm have been obtained. Structural analysis has been carried out in powder form and for single crystal using X-ray diffractometer. Single crystal X-ray diffraction analysis reveals that the crystal lattice of ZCTC is tetragonal. From powder X-ray diffraction analysis the diffraction planes have been identified and unit cell parameters are determined.     

Growth by SR method and characterization of bis(thiourea)zinc(II) chloride single crystals

Large size single crystals of bis(thiourea)zinc(II) chloride (BTZC), a potential nonlinear optical material, have been grown successfully by the Sankaranarayanan-Ramasamy (SR) method. Powder X-ray diffraction and Fourier transform infrared analyses confirmed the material of the grown crystal. Thermal stability was assessed by the thermogravimetric/differential thermal analysis. The high-resolution X-ray diffraction and dielectric measurements indicate that the crystal grown by the SR method has good crystalline perfection and low density of defects.     

Studies on the nonlinear optical single crystal: Ammonium d,l-tartrate (C4H9NO6)

The organic nonlinear optical material ammonium d,l-tartrate single crystal has been successfully grown by slow evaporation solution technique (SEST). The grown crystals were characterized by single crystal XRD and the lattice parameters have been confirmed. The structural perfection of the grown crystal was analyzed by high-resolution X-ray diffraction measurement. The optical transmittance spectrum shows that the material has a good optical transparency in the entire visible region with the UV cut-off wavelength at 234 nm. Thermogravimetric and differential scanning calorimetric measurements were performed to study the thermal properties of the grown crystal. Chemical etching studies were attempted to determine the dislocation density of the grown crystal. Mechanical behavior was assessed using Vickers hardness testing carried out on (0 0 1) crystallographic plane. The Kurtz–Perry powder SHG technique confirms the NLO property of the grown crystal and the efficiency of AMT crystal was found to be 1.3 times that of standard KDP crystal.     

Growth and characterization of 4-dimethylamino-N-methyl 4-stilbazolium tosylate (DAST) single crystals grown by nucleation reduction method

Good quality single crystal 4-dimethylamino-N-methyl 4-stilbazolium tosylate (DAST) has been grown by novel nucleation reduction method instead of regular slope nucleation technique (SNT). The grown crystal was subjected to high resolution X-ray diffraction (HRXRD) studies, the perfection of the crystal was found to be better than the crystal grown by slope nucleation technique and slow cooling method. The UV-vis-NIR spectrum was recorded for the grown crystal and relative second harmonic generation (SHG) efficiency was investigated to explore the nonlinear optical (NLO) property. The dielectric and thermal behaviour of the crystal were also studied. The nuclear magnetic resonance (NMR) studies also performed for the identification of different modes present in the compound. The photoluminescence and mechanical were carried out and the results were discussed in detail.     

Synthesis, structure, growth and physical properties of a novel organic NLO crystal: 1,3-Dimethylurea dimethylammonium picrate

A novel noncentrosymmetric crystal was prepared from 1,3-dimethylurea dimethylammonium picrate, C₁₁H₁₈N₆O₈ (DMUP), which was designed for second harmonic generation. DMUP crystals exist in noncentro symmetric space group Cmc2₁ with unit cell dimensions a = 14.288(4) Å, b = 17.023(5) Å, c = 6.8268(13) Å, α = β = γ = 90° and volume = 1660.5(8) Å³. The crystal structure of DMUP has been determined using single crystal X-ray diffraction studies. The single crystals of DMUP were successfully grown by the slow evaporation method with dimensions 10 mm × 4 mm × 3 mm using dimethylformamide as solvent. The structural perfection of the grown crystals has been analysed by High-resolution X-ray diffraction (HRXRD) rocking curve measurements. Powder test with Neodymium-doped Yttrium aluminum garnet (Nd:YAG) laser radiation shows a high second harmonic generation (SHG). The laser induced surface damage threshold for the grown crystal was measured using Nd:YAG laser.     

Study of optimum growth condition and characterization of zinc mercury thiocyanate (ZMTC) single crystals in silica gel

Some bimetallic thiocyanate complexes exhibit excellent nonlinear optical properties. Single crystals of one such material, zinc mercury thiocyanate ZnHg(SCN)₄ have been grown in silica gel with gel technique by the process of diffusions and the optimum growth condition has been studied. Crystals of 4 mm length have been obtained. Their structural, optical and thermal properties have been studied. Structural analysis was carried out using an X-ray diffractometer and the crystal structure was confirmed to be tetragonal. Fourier transform infrared spectrum was obtained to confirm the functional groups. Transmission spectrum has been recorded in the solution state and the cut-off wavelength has been determined. Thermal stability of the grown crystal has been investigated by thermogravimetric and differential thermal analyses. Nonlinear optical property of the crystal has been confirmed using the Kurtz powder technique and a study of its second harmonic generation efficiency in comparison with urea has been made.