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)     

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)     

Crystal structure and characterization of a novel organic optical crystal: 4‐chloro‐3‐nitrobenzophenone

Single crystals of a novel organic material, 4‐Chloro‐3‐Nitrobenzophenone (4C3N) were grown from acetone solution employing the technique of controlled evaporation. 4C3N belongs to the Orthorhombic system, with a = 12.9665(11) Å, b = 7.4388(6) Å, c = 24.336(2) Å, α = β = γ = 90°. FT‐IR study has been performed to identify the functional groups. The transmittance of 4C3N has been used to calculate 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 4C3N is 2.7 eV. Thermo gravimetric analysis and differential thermal analysis have also been carried out, and the thermal behavior of 4C3N crystal has been studied. The mechanical properties have been investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Additive induced morphology changes of nano‐crystalline SrWO4

Large‐scale high‐quality SrWO₄ nanocrystals have been synthesized in aqueous solutions under mild hydrothermal conditions with citrate as a simple additive. The crystals undergo an interesting 0‐D to 1‐D and to 0‐D morphology changes and have been characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The results showed that the experimental parameters had great influences on the shape evolution of products. The adjustment of these parameters such as the addition of the citrate and hydrothermal reaction conditions, can lead to obvious morphology changes of products, and the growth mechanism has been proposed. Room‐temperature photoluminescence indicated that the as‐prepared SrWO₄ nanocrystals had strong emission peaks at about 434 and 506 nm, respectively. This facile route could be employed to synthesize more promising nanomaterials with interesting self‐assembly structures. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigations on the growth,optical behaviour and factor group of an NLO crystal: L‐alanine alaninium nitrate

Amino acid family crystals exhibit excellent nonlinear and electro‐optical properties. L‐alanine alaninium nitrate (LAAN) single crystal belonging to the amino acid group was grown by slow cooling solution growth technique. The High resolution X‐ray diffraction (HRXRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, UV‐Vis., Photoluminescence (PL) and Factor group analyses were carried out. The factor group analysis reveals 183 internal vibrations for the title compound. The second harmonic generation property was tested by Kurtz‐Perry powder technique. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth,structure and spectroscopic studies of a novel organic single crystal: L‐lysine p‐nitrophenolate monohydrate (LLNP)

A novel organic crystal, L‐lysine p‐nitrophenolate monohydrate (LLNP) has been grown successfully from an aqueous solution by the slow cooling method. Transparent single crystal of dimensions 22 × 12 × 12 mm³ has been obtained. The single crystal X‐ray diffraction has shown that LLNP belongs to the orthorhombic crystallographic system with space group P2₁2₁2₁. The functional groups and vibrational frequencies of the crystal have been identified using IR and Raman spectra. The proton and carbon configurations have been confirmed through ¹H‐NMR and ¹³C‐NMR spectra analyses. The UV‐Vis‐NIR transmittance spectrum for LLNP crystal has been recorded in the range from 200 to 2500 nm. The second harmonic generation (SHG) intensity of LLNP has been measured by powder SHG method and found to be as 4.2 times as that of KDP. The thermal properties have been studied by using thermo gravimetric (TG) and differential thermal analysis (DTA).     

Synthesis,crystal structure and third order nonlinear optical properties of bis(tetra‐n‐propylammonium) bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)cuprate(II)

A novel bis (dmit) complex of copper (II), [(C₃H₇)₄N]₂[Cu(dmit)₂] ( 1 ), where dmit is 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate, was prepared and structurally characterized by X‐ray single crystal diffraction. The copper (II) atom is tetracoordinated by four dmit S atoms, forming a nearly square planar arrangement. The [Cu(dmit)₂]^2‐ anions and the [(C₃H₇)₄N]⁺ counter‐cations form a three‐dimensional solid‐state structure by C–H…S hydrogen bonds. The third‐order nonlinear optical properties of the complex were determined by picosecond Z‐scan technique at a wavelength of 1064 nm. The results indicate the compound exhibits reverse saturation absorption and self‐defocusing performance. The molecular second‐order hyperpolarizability γ is calculated to be as high as (1.8±0.2)×10^‐30 esu. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Etching and dielectric studies on L‐lysine monohydrochloride dihydrate single crystal

The nonlinear optical single crystals of L‐Lysine monohydrochloride dihydrate (L‐LMHCl) have been grown and examined by High‐resolution X‐ray diffraction and etching studies for their perfection. The vibrational frequencies have been identified by the micro‐Raman studies and the dielectric behaviour has been studied and the results are presented in detail. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation,single crystal growth and characterization of bis(tetrabutylammonium)bis(4,5‐dithiolato‐1,3‐dithiole‐2‐thione)copper

The preparation and single crystal growth of bis(tetrabutylammonium)bis(4,5‐dithiolato‐1,3‐dithiole‐2‐thione)copper, (I), are described. The energy gap Eg of (I) is about 2.38 eV. The nonlinear optical susceptibility χ⁽³⁾ is about 1.3×10^‐3 esu at 1064 nm. The characterization of (I) has been performed by electronic absorption, infrared and X‐ray powder diffraction spectroscopy. The thermal behavior of (I) has been investigated by means of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements in air. (© 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 L‐valine ‐ a nonlinear optical crystal

The growth of a new nonlinear optical material L‐valine by solvent evaporation method is reported here. To grow good quality crystals pH value of growth solution has been optimized and solubility of L‐valine in different solvents and different pH values was determined. The grown crystals were characterized by IR, single crystal XRD, DTA and TGA, optical transmission and second harmonic generation (SHG) efficiency measurement. SHG efficiency of L‐valine was found equivalent to KDP and its transmission is 75%‐80% from ultraviolet to near IR region. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of TGS crystals using uniaxially solution‐crystallization method of Sankaranarayanan‐Ramasamy

The recently discovered crystal growth method called uniaxially solution‐crystallization method of Sankaranarayanan–Ramasamy (SR) is modified in some aspects and used for growth of triglycine sulphate (TGS) crystals. The modification leads to the simplicity, reduction of cost and avoided the temperature fluctuations. The 〈010〉 direction of TGS is very important and used for fabrication of infrared detectors. Using this method, the 〈001〉, 〈010〉 directional crystals of TGS were successfully grown in a glass crystallizer. The grown crystal was characterized by HRXRD, UV‐Visible and dielectric studies. The results prove the suitability of the modified SR method for oriented TGS crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of material,thermal and laser conditioning on the damage threshold of type II tripler‐cut DKDP crystals

By using the traditional temperature‐reduction method, KD₂PO₄ (DKDP) crystals were grown from 85%‐deuterated aqueous solution synthesized by different kind of KH₂PO₄ (KDP) raw materials. An experimental technique was employed to measure the variation of bulk damage threshold in plates of DKDP crystals. Bulk laser damage in unconditioned, thermal‐conditioned and laser‐conditioned type II tripler‐cut DKDP crystals has been studied using 1064 nm (ω) and 355 nm (3ω) laser at pulse lengths of 5ns, 5ns respectively. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and photoluminescence properties of SrWO4 3D microspheres synthesized by the surfactant‐assisted hydrothermal method

In this paper, we report large‐scale high‐quality SrWO₄ 3D microspheres synthesized in aqueous solutions under mild conditions with cetyl trimethyl ammonium bromide as a simple cationic surfactant. These crystals have been characterized by X‐ray diffraction, transmission electron microscopy and field emission scanning electron microscopy techniques. The crystal growth processes were employed to investigate the formation mechanism of SrWO₄ 3D microspheres. Room‐temperature photoluminescence indicated that the as‐prepared SrWO₄ 3D microcrystals had strong emission peaks at about 432 and 505 nm, respectively.     

Growth and thermal studies on pure ADP,KDP and mixed K1‐x(NH4)xH2PO4 crystals

The investigations on the formation of mixed crystals of ammonium dihydrogen orthophosphate (ADP) and potassium dihydrogen orthophosphate (KDP) i.e. potassium ammonium dihydrogen phosphate, K_1‐x(NH₄)_xH₂PO₄ have been presented in this paper. Pure and mixed crystals of ADP and KDP have been grown by slow evaporation technique from the supersaturated solution at an ambient temperature 26±1 °C for ammonium concentration x in the range 0.0 ≤ x ≤ 1.0 in the case of mixed crystals. Crystal compositions were determined by flame atomic absorption spectroscopy and chemical analysis. The results of the X‐ray analysis of the grown crystals are also reported. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the kinetic process of dehydration and the high temperature phase behaviour. DTA showed the distinct thermal events attributed to dehydration of ADP, KDP and K_1‐x(NH₄)_xH₂PO₄. The results of thermal analysis and chemical analysis are consistent with each other. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and thermal characterization of L‐arginine dihydrate ‐ a nonlinear optical material

Crystal structure and thermal stability of the hydrated crystals of the basic amino acid L‐arginine named as L‐arginine dihydrate (LAD), a nonlinear optical material have been reported here. The title compound crystallized in the space group P2₁2₁2₁ with Z=4 and unit cell dimensions a=11.856(2)Å, b=15.694(2)Å, c=5.664(3)Å. The arginine molecule is a zwitterion with the guanidyl group accepting an extra proton from the carboxylate group. DTA‐TG analysis gives an idea about the thermal behaviour of LAD and ruled out the possibility of structural changes independent of mass changes. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Effect of different solvents on the habit of meta‐nitroaniline single crystals

The habit of the organic non‐linear optical material meta‐nitroaniline (mNA) crystallized from different organic solvents such as acetone, benzene, ethyl acetate, n‐hexane, methanol and toluene were studied. Solubility of mNA in these solvents at various temperatures in the range between 288 and 323 K was determined by gravimetric method. Crystals were grown by restricted evaporation of solvents method. Solutions with different solvents having different chemical nature and polarity yielded crystals with different habits: one‐dimensional needles, two‐dimensional rhombic platelets and three‐dimensional octahedral. In addition, the mNA crystals show unidirectional growth behaviour along its polar [001] direction irrespective of the solvents used. All the grown crystals were found to be orthorhombic system with point group mm2 and space group Pbc2₁ which was confirmed by powder X‐ray diffraction study. Optical transmittance study showed that the grown mNA single crystals have optical transparency in the wavelength range between 430 and 1550 nm. SHG efficiency of the grown mNA crystal was 3 times grater than KDP. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improvement of crystal quality of AlN grown on sapphire substrate by MOCVD

The crystalline quality of aluminum nitride (AlN) epilayers grown on sapphire substrates by MOCVD was improved by increasing hydrogen flow rate during the high temperature growth process. The AlN epilayer exhibited a root mean square (rms) of roughness was 1.944 nm from the 2×2 µm² size atomic force microscopy (AFM) images. Full widths at half maximum (FWHMs) of (002) and (102) rocking curves of triple‐axis high resolution X‐ray diffraction (HRXRD) measurements were as narrow as 28.8 arc sec and 868 arc sec, respectively. The optical transmittance spectra showed a sharp absorption edge at a wavelength of 200 nm and strong Fabry‐Perot (FP) oscillations. It is proposed that the improvement in crystalline quality is due to the surface in the low‐temperature aluminum nitride (LT‐AlN) buffer layer is promoted to be stable Al‐polarity by the conditions of increasing hydrogen flow rate and ramping up the growth temperature. Addtionally, the parasitic reactions are effectively suppressed by increasing the hydrogen flow rate during the growth process of high temperature. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Excitation intensity and temperature‐dependent photoluminescence and optical absorption in Tl4Ga3InSe8 layered crystals

Photoluminescence (PL) spectra of Tl₄Ga₃InSe₈ layered crystals grown by Bridgman method have been studied in the wavelength region of 600‐750 nm and in the temperature range of 17‐68 K. A broad PL band centered at 652 nm (1.90 eV) was observed at T = 17 K. Variations of emission band has been studied as a function of excitation laser intensity in the 0.13 to 55.73 mW cm^‐2 range. Radiative transitions from donor level located at 0.19 eV below the bottom of conduction band to shallow acceptor level located at 0.03 eV above the top of the valence band were suggested to be responsible for the observed PL band. From X‐ray powder diffraction and optical absorption study, the parameters of monoclinic unit cell and the energy of indirect band gap were determined, respectively. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spatially resolved X‐ray diffraction as a tool for strain analysis in laterally modulated epitaxial structures

Spatially resolved X‐ray diffraction (SRXRD) is applied for micro‐imaging of strain in laterally modulated epitaxial structures. In GaAs layers grown by liquid phase epitaxial lateral overgrowth (ELO) on SiO₂‐masked GaAs substrates a downward tilt of ELO wings caused by their interaction with the mask is observed. The distribution of the tilt magnitude across the wings width is determined with μm‐scale spatial resolution. This allows measuring of the shape of the lattice planes in individual ELO stripes. If a large area of the sample is studied the X‐ray imaging provides precise information on the tilt of an individual wing and its distribution. In heteroepitaxial GaSb/GaAs ELO layers local mosaicity in the wing area is found. By the SRXRD the size of microblocks and their relative misorientation were analyzed. Finally, the SRXRD technique was applied to study distribution of localized strain in AlGaN epilayers grown by MOVPE on bulk GaN substrates with AlN mask. X‐ray mapping proves that by mask patterning strain in AlGaN layer can be easily engineered, which opens a way to produce thicker, crack‐free AlGaN layers with a higher Al content needed in GaN‐based laser diodes. All these examples show that high spatial and angular resolutions offered by SRXRD makes the technique a powerful tool to study local lattice distortions in semiconductor microstructures. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)