Growth and characterization of pure and doped bis thiourea zinc acetate: Semiorganic nonlinear optical single crystals

Metal–organic coordination complex single crystals bis thiourea zinc acetate (BTZA) and Cd²⁺ doped BTZA have been synthesized and grown successfully by slow-cooling technique from their aqueous solutions. Single crystals of pure and Cd²⁺ doped BTZA with dimensions of 35 × 4 × 2 mm³ and 10 × 5 × 6 mm³, respectively were obtained with well defined morphology. The as grown single crystals are characterized by single crystal XRD studies and melting point measurements which reveal the incorporation of metallic dopants has not changed the structure of the parent crystal. The powder X-ray diffractogram of the grown crystals has been recorded and the various planes of reflection identified shows shift in the peak positions. The metal coordination with thiourea through sulphur in pure and Cd²⁺ doped BTZA were ascertained by FTIR studies and optical absorption study to identify the UV cut-off range. The presence of metals in pure and Cd²⁺ doped BTZA crystal lattice were confirmed by atomic absorption spectroscopy (AAS). The thermal decomposition of pure and Cd²⁺ doped BTZA crystals were investigated by thermo gravimetric analyses (TGA) and differential thermal analysis (DTA) indicate that doped crystals are more stable than pure crystals. The dielectric response of the crystals were studied in the frequency range 100 Hz–5 MHz at different temperatures and the results are discussed. Second harmonic generation (SHG) measurement confirms that the pure and Cd²⁺ doped BTZA have nonlinear optical (NLO) property. Laser damage threshold value of 12.44 MW/cm² has been determined using Q-switched Nd:YAG laser operating at 1064 nm and with 8 ns pulses in single shot mode for pure BTZA single crystal is reported for the first time.     

Synthesis and growth of sodium bitartrate monohydrate a new organometallic nonlinear optical single crystal

Sodium bitartrate monohydrate (SBTMH) a new organometallic nonlinear optical material, with molecular formula, [C₄H₅NaO₆ · H₂O] has been synthesized at ambient temperature. Spectral, thermal and optical techniques have been employed to characterize the new material. Bulk single crystals of size 13 × 4 × 4 mm³ of SBTMH have been grown by slow cooling method. The unit cell parameters of the grown crystal were determined by single crystal XRD. Functional groups present in the sample were identified by FTIR spectral analysis. Thermal stability of SBTMH was determined using TGA/DTA. The grown crystals exhibit nonlinear properties. The dielectric response of the crystal with varying frequencies was studied. The optical transparency range and the lower cut-off wavelength of the material were identified from the UV–vis–NIR absorption spectrum.     

Experimental and theoretical studies on bis(glycine) lithium nitrate (BGLiN): A physico-chemical approach

Good quality and bulk size single crystal (size: 20×13×8 mm³) of bis(glycine) lithium nitrate (BGLiN) was grown by a slow evaporation solution technique from the aqueous solutions at constant temperature i.e. 27 °C using synthesized materials. Crystal system and lattice parameters were determined by single crystals as well as powder X-ray diffraction analysis. The lattice parameters of the titled compound are a=10.0223 Å, b=5.0343 Å, c=17.0510 Å, and V=860.312 Å³ and it crystallized in an orthorhombic system with space group Pca2₁ obtained by single crystal XRD. Elemental composition was confirmed by energy dispersive X-ray spectroscopic analysis. Optical absorption spectrum was recorded and various optical parameters such as optical transmission (~60%), and optical band gap (4.998 eV) were calculated. Photoluminescence study shows that the grown crystal is free from major defects. Crystalline perfection of the grown crystal was assessed and found good. Ground state optimized geometry has been obtained by using DFT with 6-31G(d,p) basis set. HOMO and LUMO energy gap was found to be 6.01 eV and dipole moment was 1.65 D.     

Structural,optical and mechanical property analysis of magnesium sulphate admixtured l-Threonine: A novel optoelectronic material

l-Threonine is an important amino acid and famous due to their property of frequency conversion and electro optic modulation. Single crystals of magnesium sulphate admixtured l-Threonine was grown by slow evaporation technique. Good quality single crystal with dimension 58 × 5 × 10 mm³ was harvested after 60 days. The powder X-ray diffraction pattern of the grown crystal has been indexed. The optical transmission spectrum shows that the magnesium sulphate admixtured l-Threonine possess good optical transparency in the entire visible region with Ultra Violet cut-off wavelength at 250 nm. The presence of fundamental functional groups was identified by Fourier Transform Infra Red spectral analysis. The structure of the grown crystal was established using Fourier Transform-Nuclear Magnetic Resonance spectral analysis. The thermal behaviour of the crystal has been discussed by Thermal Gravimetric Analysis and Differential Thermal Analysis. Magnesium sulphate admixtured l-Threonine was characterized by Energy dispersive analysis of X-ray. The second harmonic generation efficiency of magnesium sulphate admixtured l-Threonine crystal is found to be same as that of potassium dihydrogen phosphate crystal.     

Structural,optical and electrical characteristics of a new NLO crystal

A new nonlinear optical (NLO) organic crystal 1-[4-({(E)-[4-(methylsulfanyl)phenyl]methylidene}amino)phenyl]ethanone (MMP) has been grown by slow evaporation technique at ambient temperature. The crystal structure of MMP was determined by single crystal X-ray diffraction. MMP crystallizes in non-centrosymmetric monoclinic system with space group P2₁. The FT-IR spectrum recorded for new crystal confirmed the presence of various functional groups in the material. MMP was found to be thermally stable up to 300 °C. The grown crystal was optically transparent in the wavelength range of 400–1100 nm. The second harmonic generation (SHG) efficiency of the crystal was measured by the classical powder technique using Nd:YAG laser and was found to be 4.13 times more efficient than reference material, urea. Third order nonlinear parameters were measured by employing the Z-scan technique. The laser damage threshold for MMP crystal was determined to be 4.26 GW/cm². The Brewster angle technique was employed to measure the refractive index of the crystal and the values for green and red wavelengths were found to be 1.35 and 1.33, respectively. The dielectric and electrical measurements were carried out to study the different polarization mechanisms and conductivity of the crystal.     

Linear and nonlinear optical properties of N-(3-nitrophenyl) acetamide single crystals

Optically transparent nonlinear optical bulk single crystal of N-(3-nitrophenyl) acetamide (3NAA) of dimension 7 mm × 6 mm × 5 mm has been grown from its aqueous solution by slow solvent evaporation technique. The grown crystal was characterized by powder X-ray diffraction to confirm the crystal structure. Investigation has been carried out to assign the vibrational frequencies of the grown crystals by Fourier Transform Infrared Spectroscopy and FT-NMR technique. Thermal behaviour of the grown crystals was studied by thermogravimetric analysis. The second harmonic generation efficiency of 3NAA was determined by Kurtz and Perry powder technique. The optical absorption study confirms the suitability of the crystal for device applications. The mechanical properties of the grown crystals have been studied using Vickers microhardness tester. Dielectric, microhardness and photoconductivity studies also carried out for the grown sample.     

Studies on the optical and mechanical properties of non-linear optical 3-aminophenol orthophosphoric acid (3-amphph) single crystal

Single crystals of semiorganic material 3-aminophenol orthophosphoric acid (denoted as 3-amphph) of size 29 × 17 × 4 mm³ have been grown by the slow evaporation of an aqueous solution of deionized water at 50 °C. The crystal belongs to orthorhombic system with the non centrosymmetric space group P2₁2₁2₁. The lattice parameter values of 3-amphph crystal are a = 4.481(2) Å, b = 9.782(4) Å and c = 18.326(4) Å. The grown crystals are subjected to single crystal XRD studies to identify its morphology and structure. Optical transmittance and second harmonic generation of the grown crystals have been studied by UV–Vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of 3-amphph crystal has been used to calculate the refractive index n, the extinction coefficient k, reflectance R and both the real (?_r) and imaginary (?_i) components of the dielectric constant as a function of wavelength. The optical band gap of 3-amphph is 4.05 eV with direct transition. The anisotropic mechanical behavior of 3-amphph has been analyzed using Vickers microhardness test. The mechanism of growth is revealed by carrying out chemical etching using water as etchant.     

Growth of 〈1 0 0〉 directed ADP crystal with slotted ampoule

Good quality ammonium dihydrogen phosphate single crystals have been grown by: (i) Sankaranarayanan–Ramasamy (SR) method and (ii) SR method with slotted ampoule. The grown crystals were subjected to UV–Vis spectroscopy, high-resolution X-ray diffractometer, dielectric, piezoelectric and laser damage threshold studies. Compared to the (1 0 0) plane of the conventional method grown ADP crystal and 〈1 0 0〉 directed SR method grown ADP crystal, the crystal grown by SR method with slotted ampoule has higher growth rate, higher optical transparency, high crystalline perfection, low dielectric loss, high piezoelectric charge coefficient and high laser damage threshold due to diffusion of segregated impurities away from the growing crystal in the slotted ampoule growth.     

Structural and vibrational properties of PVT grown Bi2Te3 microcrystals

High-quality Bi₂Te₃ microcrystals have been grown by physical vapor transport (PVT) method without using a foreign transport agent. The microcrystals grown under optimal temperature gradient are well facetted and they have dimensions up to ～100 μm. The phase composition of grown crystals has been identified by X-ray single crystal structure analysis in space group R3?m, a=4.3896(2) Å, b=30.5019(10) Å, Z=3 (R=0.0271). Raman microspectrometry has been used to describe the vibration parameters of Bi₂Te₃ microcrystals. The FWHM parameters obtained for representative Raman lines at 61 cm^?1 and 101 cm^?1 are as low as 3.5 cm^?1 and 4.5 cm^?1, respectively.     

Spectroscopy and efficient laser emission of Yb3+: LuAG single crystal grown by μ-PD

A LuAG shaped rod crystal, doped with Yb³⁺, has been grown by μ-PD technique. The crystal diameter was about 3 mm and the length around 130 mm. A complete spectroscopic investigation in the temperature range 10–300 K is reported and data has been utilized to model the laser behavior. In the laser experiment the Yb:LuAG sample was placed in an X cavity and pumped longitudinally obtaining an efficient CW laser emission. The Yb:LuAG laser yielded a maximum output power of 23 mW with a slope efficiency of 32% and a threshold around 35 mW, at lasing wavelength of 1030 nm. No significant depolarization effects were observed, indicating a crystal growth with negligible stress. The output beam profile was investigated, yielding M² ≈ 1.0 in both directions, further confirming the good optical quality of the sample.     

Growth and characterization of Nd:Bi12SiO20 single crystal

A Nd:Bi₁₂SiO₂₀ crystal was grown by the Czochralski method. The thermal properties of the crystal were systematically studied. The thermal expansion coefficient was measured to be α=11.42×10^?6 K^?1 over the temperature range of 295–775 K, and the specific heat and thermal diffusion coefficient were measured to be 0.243 Jg^?1 k^?1 and 0.584 mm²/s, respectively at 302 K. The density was measured to be 9.361 g/cm³ by the buoyancy method. The thermal conductivity of Nd:Bi₁₂SiO₂₀ was calculated to be 1.328 Wm^?1 K^?1 at room temperature (302 K). The refractive index of Nd:Bi₁₂SiO₂₀ was measured at room temperature at eight different wavelengths. The absorption and emission spectra were also measured at room temperature. Continuous-wave (CW) laser output of a Nd:Bi₁₂SiO₂₀ crystal pumped by a laser diode (LD) at 1071.5 nm was achieved with an output power of 65 mW. To our knowledge, this is the first time LD pumped laser output in this crystal has been obtained. These results show that Nd:Bi₁₂SiO₂₀ can serve as a laser crystal.     

Growth,structural, optical and mechanical studies on acid mixed glycine metal salt (GABN) crystal as potential NLO material

Transparent crystals of α-glycine with ammonium nitrate and barium nitrate (GABN) have been grown from aqueous solution by slow evaporation technique at room temperature. Crystals of size 11 × 7 × 4 mm³ have been obtained in about 3–4 weeks time. The solubility of GABN has been determined in water. The grown crystal belongs to orthorhombic system with cell parameters a = 7.317 A.U, b = 12.154 A.U and c = 5.468 A.U with a unit cell volume 486.35 (A.U)³. The presence of chemical components/groups has been identified by CHN, EDAX and NMR analysis. Comparative IR and Raman studies indicate a molecule with a lack of centre of symmetry. A wide transparency window useful for optoelectronic applications is indicated by the UV Studies. Using a Nd-YAG laser (1064 nm), the optical second harmonic generation (SHG) conversion efficiency of GABN is found to be 1.406 times of that of standard KDP. On exposure to light the GABN crystals are found to exhibit negative photoconductivity. I–V characteristics, SEM studies, dielectrics studies, and Vickers micro hardness measurement have been carried out.     

Synthesis,crystal growth and characterization of a semiorganic material: Calcium dibromide bis(glycine) tetrahydrate

Single crystals of semiorganic material calcium dibromide bis(glycine) tetrahydrate were grown from aqueous solution. The crystal belongs to monoclinic system, with a = 13.261(5) Å, b = 6.792(2) Å, c = 15.671(9) Å and β = 91.68(4)°. The presence of the elements in the title compound was confirmed by energy dispersive X-ray analysis. The solubility and metastable zone width were found. The grown crystals were tested by powder XRD, FTIR, Thermo Gravimetric and Differential Thermal Analysis, UV–vis–NIR analysis, dielectrical and mechanical studies. The transmittance of calcium dibromide bis(glycine) tetrahydrate crystal has been used to calculate the refractive index n, the extinction coefficient K and both the real ɛ_r and imaginary ɛ_i components of the dielectric constant as functions of wavelength. The optical band gap of calcium dibromide bis(glycine) tetrahydrate is 3.23 eV.     

Crystal growth,spectral and NMR studies of nonlinear optical crystal: L-valinium picrate

Organic nonlinear optical material, L-valinium picrate (LVP) was synthesized by slow evaporation solution growth method. The synthesized material was purified by repeated recrystallization. Single crystals of LVP were grown by slow evaporation method using water as solvent. The cell dimensions were obtained by X-ray diffraction study and crystal system was confirmed as monoclinic. The transmission spectrum of LVP was recorded by UV–Vis-NIR spectrometer in the range between 190 nm and 1100 nm which addressed the high percentage of transmission of the sample in the entire visible region. The presence of functional groups was studied by FT-IR analysis. The chemical environment of carbon and hydrogen in the proposed structure of LVP crystal was confirmed by FT NMR studies. The Kurtz-Perry powder SHG measurement was confirmed the frequency doubling of the crystal.     

Growth,structural, mechanical,spectral and dielectric characterization of NaCl-added Triglycine sulfate single crystals

Pure and sodium chloride (NaCl)-added Triglycine sulfate (TGS) crystals were grown from aqueous solutions by slow evaporation technique. The values of concentration of dopants in the mother solution were 0.2, 0.6 and 1 mol%. The solubility of the grown samples have been found out at various temperatures. The determination of unit cell parameters was carried out by single crystal XRD method and found that the grown crystals crystallize in monoclinic structure. The dielectric characterization for the pure and NaCl-doped TGS crystals was performed by measuring the dielectric parameters like dielectric constant and dielectric loss with various frequencies in the range 10²–10⁶ Hz and with the temperatures ranging from 30 to 70 °C and this study reveals an increase of dielectric constant and loss with the increase of NaCl concentration. Studies on mechanical properties like microhardness and density of the grown pure and NaCl-doped TGS crystals were carried out. UV–Visible transmittance studies were carried out for the grown samples. A sharp fall in the transmittance is observed at 228 nm for pure and NaCl-doped TGS crystals. Atomic absorption spectroscopic (AAS) study was done on the NaCl-doped TGS crystals to ascertain the presence of Na⁺ ions in the lattice.     

Synthesis,growth and characterization of a semiorganic nonlinear optical single crystal: L-Valine cadmium bromide

A semiorganic nonlinear optical material L-valine cadmium bromide was synthesized and single crystal grown from an aqueous solution by the method of slow evaporation technique at room temperature. The grown crystal was characterized by Powder X-ray diffraction and FT IR studies. The LVCB crystallizes in monoclinic system with cell parameters a = 10.144(2) Å, b = 5.54(1) Å, c = 12.07(2) Å, β = 109.115(2)° with space group P₂₁. Thermal behavior and stability of crystal were studied using thermogravimetric analyses (TGA) and differential thermal analysis (DTA) techniques. The suitability of this material for NLO application was studied by optical absorption studies and second harmonic generation (SHG) efficiency measurement by Kurtz–Perry powder method.     

A new method of synthesis on high-quality AgGaS2 polycrystalline

High-pure, single-phase, free of voids and high mass density AgGaS₂ polycrystalline was synthesized by a new method, i.e. two-temperature zone vapor-transporting together with the mechanical and melt temperature oscillation method (TVMMTOM), directly from high-purity (6 N) elements silver, gallium and sulfur with excess sulfur. The mechanism and advantages of the new method for synthesizing high-quality AgGaS₂ were discussed. It is found that the polycrystalline material synthesized by the new method is superior to that synthesized by the conventional method, what is more the new method can avoid the explosion of the synthetic quartz ampoule. Adopting the modified Bridgman method an integral and crack-free AgGaS₂ single crystal with diameter of 14 mm and length of 63 mm has been obtained. It was found that there was a (1 0 1) cleavage face and the four order X-ray spectrum of the {1 0 1} faces was observed. By the method of DSC analysis the melting and freezing points of the AgGaS₂ single crystal were about 995 and 955 °C. The transmission spectra of the AgGaS₂ sample of 10 × 8 × 2 mm³ were obtained by means of UV and IR spectrophotometer. The limiting wavelength was 470 nm and the band gap was 2.64 eV. It can be found in the infrared spectrum that the infrared transmission was above 55% from 4000 to 800 cm⁻¹, and the infrared transmittance of the crystal is up to 63% at 10.6 μm, which is higher than that of the crystal grown using polycrystalline materials synthesized by the conventional method. The value of α in 10.6 μm was 0.267 cm⁻¹. Above mentioned results showed that the crystal was of good quality and TVMMTOM is preferable for synthesizing high-quality AgGaS₂ polycrystalline materials.     

Color center of YAlO3 with cation vacancies

High quality pure YAlO₃ crystal with dimension of Φ 30 × 50 mm² was grown by Czochralski technique. UV irradiation and air annealing bring additional absorption in the region 200–800 nm. The absorption spectra of perfect YAlO₃ and YAlO₃ containing cation vacancy (aluminium vacancy and yttrium vacancy) were calculated using density functional theory code CASTEP. Comparison of the simulated absorption spectra with the experimental absorption spectra of YAlO₃ after UV irradiation and air annealing treatments shows that cation vacancies are responsible for part of the coloration on YAlO₃ crystal.     

InSb grown on Cd0.955Zn0.045Te by liquid phase epitaxy

InSb has been grown by liquid phase epitaxy using indium rich solutions with a supercooling of 2–5 °C onto (1 1 1) oriented Cd_0.955Zn_0.045Te substrates at 400–405 °C. The resulting epitaxial layers were extensively characterized using X-ray diffraction, optical microscopy, Raman spectroscopy and photoluminescence.     

Optical and dielectric studies of solution grown glycinium maleate single crystal

Bulk single crystals of glycinium maleate have been grown from aqueous solution by slow evaporation method by optimizing the growth parameters within a period of 15 days. From X-ray diffraction analysis, the crystal was found to crystallize in monoclinic structure (space group C_2/c) with a = 17.866 Å, b = 5.684 Å, c = 17.408 Å and β = 112.65°. Presence of characteristic functional groups was confirmed in FTIR analysis. UV–Vis spectral analysis has revealed the absence of any high absorbance region between the wavelengths ranging from 300 to 900 nm. The optical band gap was calculated and found to be 3.91 eV. The activation energy for conduction at different frequencies was calculated and found to decrease from 0.54 eV to 0.41 eV as frequency increased from 100 Hz to 2 MHz. The dielectric behavior, conduction mechanism and the optical characterization of the glycinium maleate single crystals are being reported for the first time.