Growth and characterization of dichloro tetrakis thiourea nickel single crystals

Thiourea has a large dipole moment and has an ability to form extensive network of hydrogen bonds. In the course of our studies on new semiorganic NLO materials, thiourea is selected to combine with nickel chloride. Single crystals of tetrakis thiourea nickel chloride are grown using silica gel. Green transparent crystals of NTC (nickel thiourea chloride) of dimension 8x4x3 mm³ are grown in a period of 45 days. Single crystal XRD shows that the crystal belongs to body centered tetragonal symmetry class I4. The UV‐Vis‐NIR spectrum establishes the transmission range to be 300 nm to 2500 nm, with a sharp absorption peak at the red end of the visible region, which is due to the colour of the crystal. Photoconductivity and dielectric studies are also carried out. The mechanical strength of the crystal is estimated by Vickers hardness test. The crystal starts decomposing after about 200°C. Thus, we confirm from our present investigation that NTC is a suitable candidate for NLO applications. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth,optical and thermal studies of nonlinear optical L‐arginine perchlorate single crystals

A potentially useful semiorganic nonlinear optical (NLO) material, L‐arginine perchlorate, has been synthesized and bulk crystals have been grown by slow cooling technique. The grown crystals were characterized by single crystal X‐ray diffraction, UV‐Vis‐NIR spectroscopy, FT‐IR, thermal analysis and SHG measurements. The grown crystals were thermally stable upto 153°C and exhibit SHG efficiency of about 0.17 with respect of Urea. The etching studies have been carried out on the grown crystal. LAPC has good optical transmission not only in the visible range, however, also in the near UV part of the spectra and hence it is a potential material for nonlinear frequency conversion. The refractive index was measured by the Brewster's angle method. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single crystal growth and properties of semiorganic nonlinear optical L‐arginine hydrochloride monohydrate crystals

L‐arginine hydrochloride monohydrate (LAHCl.H₂O) has been synthesized and single crystals have been grown from its aqueous solution by slow evaporation and slow cooling methods. The solubility of the material was measured at various temperatures and bulk crystals of size 26×13×11 mm³ have been grown by optimizing the growth parameters. The grown crystals have been subjected to single crystal XRD studies to confirm the structure and to estimate the lattice parameters. FTIR analysis indicate the mode of vibrations of different molecular groups present in LAHCl and confirm the protonation of guanidyl, amino groups and deprotonation of COO^‐ groups. UV‐Vis transmission spectrum revealed the linear optical properties of the grown crystals with a transparency of 65% over the entire visible range upto 300 nm. Thermal behavior of the grown crystal was investigated from DTA and TGA measurements. Dielectric studies have been carried out on the grown crystals. Kurtz and Perry powder SHG technique confirms the NLO property of the grown crystal. The SHG efficiency of LAHCl was found to be 0.38 with respect to KDP. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of semiorganic NLO crystals of LAHClBr

Single crystals of non‐linear optical (NLO) LAHClBr were grown by slow evaporation technique from its aqueous solution. Good optical quality crystals having dimensions up to 12 × 9 × 7 mm³ were obtained. The lattice parameters and morphology for the grown crystals were determined using single crystal XRD. The crystals were characterized by FT‐Raman, optical absorption, thermal (DTA and TGA) and dielectric studies. LAHClBr was found to be thermally stable up to 124.3°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of pure and Hg2+ doped thiosemicarbazide cadmium chloride crystals

Semiorganic single crystals of thiosemicarbazide cadmium chloride (TSCCC) and mercury ions doped thiosemicarbazide cadmium chloride were synthesized by slow solvent evaporation technique. The grown crystals were subjected to powder X‐ray analysis and both the crystals were found to crystallize in the monoclinic system. EDAX analysis was carried out for chemical analysis of the grown crystals. The UV‐Vis‐NIR spectrum shows that both the materials have wide transparency window in the visible and near IR region. The dielectric studies were carried out to estimate the dielectric constant and dielectric loss with respect to frequency for both the crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of succinic acid single crystals

Single crystals of ferroelectric succinic acid were grown from aqueous solution by low temperature solution growth technique. The cell parameters and space group are found using powder X‐ray diffraction analysis. The presence of the functional groups has been estimated qualitatively by FTIR analysis. The UV‐Visible spectrum shows the cut‐off wavelength at 240 nm. The thermal stability of the crystal was studied by TG/DTA. The dielectric constant of the crystal studied as a function of frequency shows the pyroelectric property. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of glycine lithium sulphate single crystal

Single crystal of glycine lithium sulphate, a nonlinear optical material, was grown from aqua solution by temperature reduction method. The solubility and metastable zonewidth of glycine lithium sulphate were estimated using aqueous solution. The cell parameters of the grown crystal were estimated by single crystal X‐ ray diffraction analysis. The presence of functional groups was identified from FTIR spectrum. Thermal analysis was performed to study the thermal stability of the grown crystal. The transmission and absorption spectra of this crystal show that the lower cut off wavelength lies at 330 nm. Powder Second Harmonic Generation efficiency of the grown crystal measured by Kurtz technique is 0.75 times that of potassium dihydrogen orthophosphate. Vickers microhardness study was carried out on the well developed (011) face of the grown crystal. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of semi organic nonlinear optical LHPCL crystals

The growth of single crystals of L‐histidinium perchlorate (LHPCL), a semi organic nonlinear optical material with dimension upto 5 × 6 × 2.5 mm³ is reported. Good optical quality single crystals were grown from aqueous solution by slow solvent evaporation technique. The grown crystals were characterized by single crystal X‐ray diffraction (XRD), FT‐IR and optical transmission studies. Thermal studies confirm that LHPCL has a fairly high thermal stability (272°C) when compared with other members of histidine family. The scanning electron microscopy (SEM) provides information on the quality of the samples and grain distribution over the surface of the sample. The dielectric constant and dielectric loss of the compound were measured at different frequencies, and also at varying temperatures and the results of these experiments are discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Linear and nonlinear optical properties of tris thiourea zinc sulphate single crystals

Optical absorption of tris thiourea zinc sulphate (ZTS) single crystals has been measured and its direct band gap was found to be 3.6 eV. Theoretical calculations were carried out to determine the linear optical constants such as extinction coefficient and refractive index. Further the optical nonlinearties of ZTS have been investigated by Z‐scan technique with He‐Ne laser at 632.8 nm. The nonlinear refractive index, absorption coefficient and third order susceptibility is found to be in the order of –5.36 ± 0.26 × 10^–12 cm²/W, 4.24 ± 0.21 × 10^–4 cm/W, 3.5 ± 0.17 × 10^–4 esu respectively. Thus optical characterization of ZTS reveals the various industrial application oriented properties of the material. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of the nonlinear optical crystal: L‐arginine trifluoroacetate

Single crystal growth of the organic nonlinear optical crystal, L‐arginine trifluoroacetate (L‐Arg·CF₃COOH, abbreviated as LATF) is reported. Low temperature solution growth method is employed for the growth of bulk single crystals. The cell parameters are verified by single crystal diffraction. Fourier transform infrared (FT‐IR) and Fourier transform Raman analysis are used to confirm the presence of various functional groups in the grown crystal. The thermal properties of the grown crystals are studied by thermogravimetric analysis and differential scanning calorinetry analysis (TGA/DSC). Second harmonic generation (SHG) measurement confirms the NLO properties of the grown crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,growth, morphology of the semiorganic nonlinear optical crystal L‐glutamic acid hydrochloride and its structural,thermal and SHG characterizations

One of the halide derivatives of L ‐glutamic acid which was identified as a semiorganic nonlinear optical material, L ‐glutamic acid hydrochloride [HOOC(CH₂)₂CH(NH₂)COOH.HCl], was grown as bulk single crystal and its significant properties were characterized. The stoichiometric title compound was synthesized and the solubility of its recrystallized form in DD water was determined in the temperature range 30–80 °C by gravimetric method. Structural confirmation was carried out by powder X ‐ray diffraction study through lattice parameter verification. Optical quality smaller dimension single crystals were grown from aqueous solution by self nucleation through slow evaporation of solvent method and a large dimension single crystal was grown by slow cooling method with reversible seed rotation technique. Morphological importances of different growth facets of the as grown crystals were studied through optical goniometry. Unit cell structure of the grown crystal was refined by single crystal X ‐ray diffraction analysis, functional groups present in the crystal responsible for various modes of vibrations were confirmed by FTIR spectroscopy analysis, thermal stability of the grown crytal was analysed by TG/DTA and DSC and second harmonic generation (SHG) of a fundamental Nd:YAG laser beam by Kurtz technique. Results indicate that the grown crystal is in stoichiometric composition and has significant improvement in its thermal and SHG properties when compared to pure L ‐glutamic acid polymorphs.     

Growth and characterization of glycine doped bis thiourea cadmium chloride single crystal

Single crystal of 2 mol% glycine doped Bis Thiourea Cadmium Chloride, a semi organic nonlinear optical material has been grown by slow evaporation technique. Good quality single crystal with dimension 14 × 12 × 5 mm³ was harvested after 35 days. The influence of amino acid glycine was studied for 1, 2 and 3 mol% glycine doped Bis Thiourea Cadmium Chloride by Kurtz and Perry powder second harmonic generation test and compared with pure Bis Thiourea Cadmium Chloride which confirms the enhancement of second harmonic generation property of glycine doped Bis Thiourea Cadmium Chloride. The large enhancement was found for 2 mol% glycine doping. The grown crystal was characterized by various characterizations viz. single crystal X‐ray diffraction, energy dispersive X‐ray (EDAX), Fourier Transform Infrared Spectroscopy (FTIR) analysis, UV‐visible absorption, thermo gravimetric analysis (TGA). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Organic inclusion complex strategy for designing nonlinear optical crystals for ultraviolet applications

Based on Molecular Engineering and Crystal Engineering concepts, a new method for designing nonlinear optical (NLO) crystal materials, the Organic Inclusion Complex (OIC) method has been demonstrated. In defining an appropriate optical transparent range with respect to the Molecular Engineering method, small organic molecules containing n-π conjugation were selected as “second order harmonic generation (SHG)-active units”(guests). Together with the Crystal Engineering method, chiral molecules were used as “molecular scaffolding” (hosts) to combine with the “SHG-active units” by hydrogen bonds. The former can provide a nonlinear optical effect. The latter leads to the OIC with a noncentrosymmetric structure and are expected to enhance the macroscopic nonlinearity in a synergistic mode of guest and host by inducing the guest molecular dipole alignment as well as other properties, such as thermal stability, mechanical strength and ease of growth. Here, we report two new inclusion complex crystals, urea-(d)tartaric acid (UDT) and urea-(dl)tartaric acid (UDLT) (here, d means dextral and dl means racemic). UDT and UDLT crystals belong to P2,2,2, and P2, space group, respectively. Bulk size crystals with high optical quality were successfully obtained from aqueous solution by using a temperature-lowering method. The experimental results show that these two crystals demonstrate higher NLO effects and shorter wavelength cutoff.     

Nucleation kinetics and growth of nonlinear optical bis (dimethyl sulfoxide) manganese mercury thiocyanate single crystals

Nonlinear optical (NLO) material of bis (dimethyl sulfoxide) manganese mercury thiocyanate (MMTD) was synthesized by two step reaction method. The solubility and metastable zonewidth were experimentally determined in order to optimize the growth parameters. Bulk crystals of MMTD were grown by slow cooling and slow evaporation methods. The structure of the grown crystal was confirmed by X‐ray diffraction analysis. Presence of functional groups and the coordination of Lewis base ligand of dimethyl sulfoxide (DMSO) were confirmed by FT‐IR analysis. Optical transparency of the grown crystals was studied by UV‐Vis spectroscopy. Nonlinear optical property of the grown crystal was confirmed by Kurtz powder method. Etching studies reveal the formation of triangular hillock etch patterns, indicative of 2D nucleation mechanism. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of pure and doped nonlinear optical l‐arginine acetate single crystals

Single crystals of organic nonlinear optical material of pure, Cu²⁺ and Mg²⁺ doped L‐arginine acetate (LAA) were successfully grown by slow evaporation method at room temperature. The UV‐Vis‐NIR spectra of pure and doped LAA indicate that these crystals possess a wide optical transmission window from 240‐1600 nm. Non‐linear optical studies reveal that the SHG efficiency of LAA is nearly three times that of KDP. The dielectric response of the samples was studied in the frequency region 100 Hz to 2 MHz and the influence of Cu²⁺ and Mg²⁺ substitution on the dielectric behaviour had been investigated. Photoconductivity study proves that both pure and Cu²⁺ and Mg²⁺ doped LAA crystal exhibit positive photoconductivity. It is evident from the Vickers hardness study that the hardness of the crystal decreases with increasing load both for pure and doped samples. ESR studies confirmed the incorporation of Cu²⁺ into LAA and the value of g‐factor was found to be 2.1654. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of 4‐Aminopyridinium‐4‐nitro phenolate single crystals

Organic optical material 4‐Aminopyridinium‐4‐nitro phenolate (4AP4NP) has been synthesized, and single crystals of size 20 x 14 x 6 mm³ have been grown from acetone solvent at room temperature by solvent evaporation technique. The grown crystals have been characterized by X‐ray diffraction to determine the cell parameters, and by FT‐IR technique to confirm the formation of the expected compound. The crystal belongs to monoclinic crystal system with space group P2₁/a.The structural perfection of the grown crystals has been analyzed by high‐resolution X‐ray diffraction (HRXRD) rocking curve measurements. The thermal stability of the compound has been determined by TG‐DTA curves. The transmittance of 4AP4NP has been used to determine the refractive index n; the extinction coefficient K and both the real ε_r and imaginary ε_i components of the dielectric constant as functions of photon energy. The optical band gap of 4AP4NP is 2.4 eV. The dielectric and mechanical behavior of the specimen was also studied. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,growth and characterization of organic nonlinear optical bis-glycine maleate (BGM) single crystals

A new organic compound of bis-glycine maleate was synthesized in the alkaline medium of 10% ammonium hydroxide solution. The bulk single crystals of Bis-Glycine Maleate (BGM) have been grown by slow cooling method. The grown crystals were characterized by employing single crystal and powder X-ray diffraction, Fourier transform infrared, optical absorption spectral studies and thermo gravimetric analysis. The microhardness studies confirmed that the BGM has a fairly high Vicker’s hardness number value (41 kg mm⁻²) in comparison to other organic NLO crystals. Second harmonic generation efficiency of the crystal measured by Kurtz–Perry powder method using Nd:YAG laser is found to be comparable to that of potassium dihydrogen phosphate (KDP). Frequency dependent dielectric studies were carried out along the major growth axis.     

Influence of La3+ ions on growth and NLO properties of KDP single crystals

Single crystals of pure and Lanthanum added KDP crystals were grown from aqueous solution. The influence of La³⁺ ions in KDP crystals is studied. Isolated centers are formed by La³⁺ ions in KDP structure along (100) plane. La³⁺ ions incorporated into superficial crystal growth layer and slightly affect the growth process as they generate weak lattice stresses. The creation of these weak lattice stress is confirmed by Vickers's micro hardness test. The HRXRD analysis showed reduced structural defects in the La added KDP in the (100) plane than pure KDP. The incorporation of La in the crystal was confirmed by EDAX analysis. The Kurtz's powder SHG efficiency was found to be 1.5 times that of pure KDP. The UV‐Vis transmission spectra of La added KDP showed excellent transmittance from 1100 nm to 340 nm and did not show any change in lower cutoff wavelength with respect to pure KDP. Laser damage threshold value has been determined using Q‐switched Nd:YAG laser operating at 1064 nm and with 65 ns pulses in single shot mode. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,growth and characterization of a new nonlinear optical crystal: l‐arginine maleate dihydrate

A new nonlinear optical material L‐arginine maleate dihydrate, C₆H₁₄N₄O₂,C₄H₄O₄,2H₂O (LAMD) was synthesized and single crystals were grown by slow cooling and also by slow evaporation method at constant temperature from its aqueous solution. Quality and size of the crystals are found to be dependent on pH of the solution and best crystals were obtained at pH = 4. Single crystal X‐ray diffraction analysis reveal that the crystal lattice of LAMD is triclinic with unit cell parameters a = 5.264(3)Å, b = 8.039(3)Å, c = 9.784(3)Å, α = 106.19(3)°, β = 97.24(3)°, γ = 101.66(2)°. Second harmonic generation efficiency is found to be about 6.8 times that of quartz. It is optically transparent down to 300 nm and possesses a large optical window between 300–2000 nm. The compound is thermally stable up to 93.4 °C. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of thiourea mixed cadmium – lead chloride – a nonlinear optical crystal

Nonlinear optical (NLO) crystal of thiourea mixed cadmium–lead chloride dihydrate Cd[(PbCl₃)(NH₂CSNH₂)].2H₂O (TCCPC) have been grown in solution by slow evaporation technique at room temperature. The powder X‐ray diffraction pattern has been recorded and indexed. The UV‐Vis‐NIR transmittance and FT‐IR spectrum have been recorded in the range 200‐1090 nm and 400‐4000 cm^‐1, respectively. The lower cut‐off wavelength is 280 nm in the UV region, which is higher than that of pure Cd(PbCl₃) (CCPC) crystal. The presence of functional groups has been confirmed by FT‐IR analysis. The TCCPC crystal was characterized by SEM and EDX spectrum. The second harmonic generation (SHG) of the thiourea mixed cadmium–lead chloride (TCCPC) crystal is demonstrated by the Kurtz Perry method using Nd:YAG laser and the results confirm that the grown crystal is roughly three times more efficient than ADP. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)