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.     

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.     

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.     

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.     

Crystal growth and characterization of a new co-ordination complex—barium tetrakis(maleate) dihydrate

Crystals of barium tetrakis(maleate) dihydrate [Ba₄(C₄H₂O₄)₄]^?2H₂O are grown in gelated hydrosilica matrix. Single crystal X-ray diffraction studies show that the crystal system is monoclinic with space group P2₁/c. The unit cell dimensions are a=9.3721(2)  Å, b=20.5880(7)  Å, c=14.0744(4) Å, α=γ=90°, β=90.289(2)°. Powder XRD studies confirmed the single phase nature of the grown crystals. The FTIR data is in conformity with the XRD results. The TG–DTA curves of the material indicate a three-step thermal decomposition. The response of the dielectric properties in the temperature range 30 °C to 500 °C is correlated with the TG–DTA results.     

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.     

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, thermal and mechanical characterization of an organic nonlinear optical material: 4-methyl-3-nitrobenzoic acid single crystal

Organic single crystals of 4-methyl-3-nitrobenzoic acid (4M3N) have been grown by slow evaporation solution growth technique at room temperature. The single crystal X-ray diffraction study reveals that 4M3N crystallizes in monoclinic system with space group P21/n. The crystalline perfection of the crystal was analyzed by high resolution X-ray diffraction (HRXRD) measurements. The functional groups present in 4M3N have been identified from FT-IR and FT-Raman spectra. The lower cut-off wavelength of 4M3N is found to be 404 nm and the optical band gap is calculated as 2.91 eV. The refractive index shows normal behavior with wavelength. The physio chemical changes, decomposition and stability of the 4M3N compound were established by TG-DTA studies. Vickers microhardness measurement concludes that 4M3N belongs to soft material (n=2.5) category. The LDT value is found to be higher than that of KDP and some of the important organic NLO materials. The third order nonlinear refractive index and nonlinear absorption coefficient of the 4M3N have been measured by Z-scan studies. The imaginary and real parts of the third-order susceptibility values were determined as Im χ³=9.129×10⁻¹¹ esu and Re χ³=1.4034×10⁻⁹ esu respectively. The dislocation density was calculated to be 3.0448×10⁶ cm⁻² which indicates the quality of the crystal.     

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.     

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.     

Optical energy gaps of undoped and Co-doped ZnIn2Se4 single crystals

Single crystals of undoped and Co-doped ZnIn₂Se₄ were grown by the vertical Bridgman technique. The optical energy gaps of the single crystals were investigated in the temperature range of 10–300 K from the optical absorption measurements. The indirect optical energy gaps of the single crystals were found to be 1.624 eV for undoped ZnIn₂Se₄ and 1.277 eV for Co-doped one at 300 K. Also, the direct optical energy gaps were given by 1.774 and 1.413 eV for undoped ZnIn₂Se₄ and co-doped one, respectively. The temperature dependence of the optical energy gaps was well fitted by the Varshni equation.     

YAG laser-induced β-BaB2O4 crystalline dot formation in Sm2O3–BaO–B2O3 glasses

A continuous-wave (CW) YAG laser (power: 0.75–0.9 J/s, irradiation time: 15 s–15 min) with a wavelength of 1064 nm is irradiated to 11.1Sm₂O₃·44.4BaO·44.4B₂O₃ glass, and the formation of β-BaB₂O₄ (β-BBO) crystalline dots with a diameter of 30–150 μm is confirmed from micro-Raman spectra. β-BBO crystals with around 200 μm length grow towards the interior of the glass. The incorporation of Sm³⁺ into β-BBO crystalline dots is suggested from micro-Raman and fluorescence spectra. The second harmonic generation is detected from the array (10×10=100 dots) of β-BBO crystalline dots, indicating that each crystalline dot formed by YAG laser irradiation is a nonlinear optical crystal. CW YAG laser irradiation to glass with Sm³⁺ ions is a nice technique for a spatially controlled crystal growth.     

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.     

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.     

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.     

Proton conduction in LaSrScO3 single crystals

Transparent single crystals of La_1−xSr_xScO₃ (x = 0.01, 0.03) were grown by the floating zone method. The optical and the electrical properties were studied by infrared absorption spectra and AC-impedance measurements, respectively. Our results showed that proton conduction becomes dominant in La_0.97Sr_0.03ScO₃ single crystals below 700 °C. The electrical conductivity increases as the amount of Sr increases. At 600 °C, La_0.97Sr_0.03ScO₃ had a proton conductivity of 4.89 × 10^− 3 S/cm. This value is almost the same as that in the literature for La_0.9Sr_0.1ScO₃ ceramic samples. It was revealed from infrared absorption spectra that several different sites are occupied by protons in this material. Furthermore, it was found that the intensity of high-frequency O–H bands can be related to the dopant-concentration dependence of the electrical conductivity.     

TL and OSL studies on lithium borate single crystals doped with Cu and Ag

Lithium borate (LBO) single crystals doped with Cu and Ag (0.25 mol% each) (Li₂B₄O₇:Cu,Ag) are grown by the Czochralski method. The thermoluminescence readout on Li₂B₄O₇:Cu,Ag crystals showed three glow peaks at～375, 441 and 516 K for the heating rate of 1  K/s. The thermoluminescence sensitivity of the grown Li₂B₄O₇:Cu,Ag single crystals is found to be 5 times TLD-100 and a linear dose response in the range 1 mGy to 1 kGy. The glow curve deconvolution reveals nearly first order kinetics for all the three peaks with trap depths 0.77, 1.25 and 1.34 eV respectively and corresponding frequency factors 1.6×10⁹, 1.3×10¹³ and 6.8×10¹¹ s^?1. The continuous wave optically stimulated luminescence (CW-OSL) measurements were performed on the LBO:Cu,Ag single crystals using blue light stimulation. The traps responsible for the three thermoluminescence peaks in Li₂B₄O₇:Cu,Ag are found to be OSL sensitive. The qualitative correlation between TL peaks and CW-OSL response is established. The photoluminescence studies show that in case of co-doping of Ag in LBO:Cu the emission at 370 nm in Cu states dominates over the transitions in Ag states implying doping of Ag plays a role as sensitizer when co-doped with Cu and increases overall emission.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Two photon absorption characteristics of bulk GaTe crystal

We have investigated the structural and optical properties of bulk GaTe crystal grown by vertical Bridgman method. Two photon absorption (TPA) properties of GaTe crystal have been investigated by the open aperture Z-scan technique under 1064 nm wavelength with 4 ns or 65 ps pulse durations. The TPA coefficients are greater in ns regime than that of ps regime. Upon increasing intensity of incident light from 5.02×10⁷ W/cm² to 1.07×10⁸ W/cm², the TPA coefficients increased from 3.47×10^?6 cm/W to 8.53×10^?6 cm/W for nanosecond excitation. Similarly, when intensity of incident light was increased from 6.81×10⁸ W/cm² to 9.94×10⁸ W/cm² the TPA coefficients increased from 3.53×10^?7 cm/W to 6.83×10^?7 cm/W for picosecond excitation. Measured TPA coefficient of GaTe crystal is larger than that of GaSe and GaS layered crystals.     

Crystal growth,optical and thermal studies of nonlinear optical γ-glycine single crystal grown from lithium nitrate

Single crystals of the nonlinear material γ-glycine have been grown in the presence of lithium nitrate by slow-evaporation method. Structural characterization of the grown crystals was carried out by powder and single crystal X-ray diffraction (XRD) methods and it is observed that the samples crystallize in hexagonal system with non-centrosymmetric space groups. The modes of vibrations of different molecular groups present in glycine have been identified by spectral analyses. UV–visible transmittance study was performed to analyze optical transparency of γ-glycine crystals and found that the crystal was transparent in the entire visible-NIR region. Second harmonic generation (SHG) conversion efficiency has been estimated as 62 mV and the output power by the crystal was 1.72 times that of potassium dihydrogen phosphate (KDP) crystal. The thermal stability and decomposition of the sample have been studied by thermal analysis and it is observed that the γ-glycine crystal have good thermal stability.