Growth and characterization of two new NLO materials from the amino acid family: l-Histidine nitrate and l-Cysteine tartrate monohydrate

Single crystals of organic nonlinear optical (NLO) materials l-Histidine nitrate (C₆H₁₀N₃O₂)⁺ · (NO₃)⁻ and l-Cysteine tartrate monohydrate (C₃H₈NO₂S)⁺ · (C₄H₅O₆)⁻ · H₂O were grown by submerged seed solution method. Characterization of the crystals was made using single crystal X-ray diffraction. Fourier transform infrared (FTIR) spectroscopic studies, optical behaviour such as UV-visible-NIR absorption spectra and second harmonic generation (SHG) conversion efficiency were investigated to explore the NLO characteristics of the above materials. Microhardness measurements and dielectric studies of the compounds were also carried out.     

Growth and characterization of pure and potassium iodide-doped zinc tris-thiourea sulphate (ZTS) single crystals

Single crystals of pure and potassium iodide (KI)-doped zinc tris-thiourea sulphate (ZTS) were grown from aqueous solutions by the slow evaporation method. The grown crystals were transparent. The lattice parameters of the grown crystals were determined by the single-crystal X-ray diffraction technique. The grown crystals were also characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. The FT-IR spectrum was recorded in the range 400-4500 cm⁻¹. Second harmonic generation (SHG) was confirmed by the Kurtz powder method. The thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) studies reveal that the materials have good thermal stability. Atomic absorption studies confirm the presence of dopant in ZTS crystals. The electrical measurements were made in the frequency range 10²-10⁶ Hz and in the temperature range 40-130 °C along a-, b- and c-directions of the grown crystals. The present study shows that the electrical parameters viz. dc conductivity, dielectric constant, dielectric loss factor and ac conductivity increase with increase in temperature. Activation energy values were also determined for the ac conduction process in grown crystals. The dc conductivity, dielectric constant, dielectric loss factor and ac conductivity of KI-doped ZTS crystal were found to be more than those of pure ZTS crystals.     

l-Cystine hydrochloride: A novel semi-organic nonlinear optical material for optical devices

A new semi-organic nonlinear optical (NLO) material l-cystine hydrochloride (LCHCl) was grown in large size measuring 19 × 5 × 3 mm³ by slow solvent evaporation technique for the first time in literature. The cell parameter values were determined by single crystal X-ray diffraction studies. Fourier Transform Infrared spectroscopic analysis was carried out on the grown sample to ascertain the fundamental functional groups. Thermal behavior of the grown LCHCl sample was analyzed by TG & DTA analysis. The mechanical properties of the grown crystals have been studied using Vickers microhardness tester. The optical transmission studies and second harmonic generation (SHG) efficiency studies justified the device quality of the grown crystal and the SHG study reveals that the grown sample has nearly 1.2 times higher efficiency than that of potassium dihydrogen phosphate (KDP), a well known NLO material.     

Synthesis, growth, and characterization of a non-linear optical crystal-glycine lithium chloride

A new non-linear optical material, glycine lithium chloride, was synthesized and single crystals were grown by slow evaporation solution growth technique at constant temperature from its aqueous solution. Transparent and well-crystallized hexagonal prisms were obtained by controlled evaporation at a constant temperature of 45 °C. The grown crystals were characterized by X-ray diffraction methods, Fourier transforms infrared spectroscopy, and optical absorption spectrum. Single crystal X-ray diffraction analysis revealed that the crystal lattice of glycine lithium chloride is hexagonal with unit cell a = b = 7.023 Å, c = 5.478 Å, α = β = 90°, γ = 120°, V = 234 Å³. The dielectric response of the crystal with varying frequencies was studied. The second harmonic generation efficiency of the crystal was studied and is found to be larger than KDP.     

Growth and spectral characterization of β-Ga2O3 single crystals

Beta gallium oxide (β-Ga₂O₃) single crystals were grown by the floating zone technique. The absorption spectra and the luminescence of the crystals were measured. The absorption spectra showed an intrinsic short cutoff edge around 260 nm with two shoulders at 270 and 300 nm. Not only the characteristic UV (395 nm), blue (471 nm) and green (559 nm) lights, but also the red (692 nm) light can be seen in the emission spectra. The deep UV light was attributed to the existing of quantum wells above the valence band and the red light was owed to the electron-hole recombination via the vicinity donors and acceptors.     

The effect of MgO doping on optical properties of LiNbO3 single crystals

Undoped and MgO doped Lithium niobate single crystals were grown by the Czochralski technique. Comparative study of the optical properties of undoped and 7 mol% MgO doped LiNbO₃ crystal was undertaken. The effect of doping on refractive indices as well as second harmonic generation has been experimentally analyzed. The results of the polarization characteristics of second harmonic generation (SHG) support the major contribution of Li-O bonds to optical nonlinearity. MgO doping reduces the number of localized excitons and the grown LiNbO₃ crystal approaches the stoichiometric composition. This causes blue shift in the absorption edge of the crystals.     

Growth of high performance piezoelectric crystal Pb(Zn1/3Nb2/3)O3-PbTiO3 using PbO flux

Novel piezoelectric crystal (1 − x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃ (PZNT) has attracted much attention due to its high piezoelectric properties and potential applications in medical ultrasonic devices, sonar transducers, solid state actuators. However, the applications of PZNT crystals are limited by the lack of a simple and reproducible growth technique. In this work, large size PZNT crystals were grown by the vertical Bridgman method using 50 mol% PbO as a flux. The growth conditions were optimized as mole ratio of raw materials and flux = 1:1, soaking temperature 1150-1200 °C, soaking time 10 h, the lowering rate of the crucible 0.5 mm/h and the temperature gradient near solid-liquid interface about 50 °C/mm. The maximum size of as-grown PZNT crystal was about 60 mm in length. The crystal was oriented and its piezoelectric constant d₃₃ and coupling coefficient k₃₃ were measured over 2000 pC/N and 0.92, respectively.     

Crystal growth, thermal and optical studies of nonlinear optical material: Glycine potassium sulphate

A new nonlinear optical material glycine potassium sulphate (GPS) has been synthesized and optical quality crystals were grown from aqueous solution. This material has positive temperature coefficient revealed from the solubility studies. The grown crystals were characterized by employing several techniques such as single crystal and powder X-ray diffraction, thermo gravimetric analysis, FTIR and UV-vis-NIR spectra. The etching studies have been done on the (1 0 0) plane of the grown crystal. Preliminary measurements to find second harmonic generation efficiency of GPS has been carried out.     

Modeling and experimental investigation of short pulse Raman microchip laser

The results of experimental and theoretical investigations of passive Q-switch Raman microchip lasers based on Nd³⁺:LSB active medium and Ba(NO₃)₂ Raman crystal are presented. It has been demonstrated that intracavity Raman conversion in the microchip lasers is a simple and efficient method, capable of delivering high power pulses with sub-100 ps duration. Intracavity generation of the 1st Stokes pulses with duration from 180 down to 48 ps and a peak power of 48 kW has been performed and studied. High peak power and short duration of the 1st Stokes pulses in microchip laser with Ba(NO₃)₂ Raman crystal allows to easily perform extracavity harmonic generation and frequency sum mixing in LBO, BBO, and KTP crystals with discrete-tunable wavelength from ∼1200 down to ∼240 nm. We have developed a generalized model of Q-switched Raman microchip lasers, that takes into account spatial inhomogeneity of pump, laser, and Stokes beams, thermalization within the upper and lower multiplets of activator ions in laser medium, and saturable absorber bleaching and recovery. For the microchip lasers with different saturable absorbers, the model achieves very good agreement with the presented experimental results in a wide range of pump powers.     

Growth and characterization of a pure and doped nonlinear optical l-histidine acetate single crystals

Single crystals of pure, Cu²⁺and Mg²⁺ doped l-histidine acetate (LHA) were grown successfully by slow evaporation technique. The X-ray diffraction (XRD) studies were carried out for the pure and doped grown crystals. Absorption of these grown crystals was analyzed using UV-vis-NIR studies, and it was found that these crystals possess minimum absorption from 200 nm to 1500 nm. The pure and doped crystals are characterized by Fourier transform Raman (FT-Raman), thermal and photoconductivity studies. Vickers microhardness tests were carried out for the pure and doped crystals and the mechanical strengths were found. The dielectric constant and the dielectric loss with frequency were also studied.     

A new sodium samarium borate Na3Sm2(BO3)3

A new sodium samarium borate with composition Na₃Sm₂(BO₃)₃ (NSBO) has been synthesized by high temperature solid state reaction. The yellowish transparent single crystals of Na₃Sm₂(BO₃)₃ have been grown from the Na₂CO₃-H₃BO₃ flux system using the top-seeded solution growth (TSSG) method. X-ray diffraction analysis demonstrated that the NSBO crystals belong to orthorhombic systems and lattice parameters are a=5.0585 Å, b=11.0421 Å, c=7.0316 Å. The measurement of the infrared spectrum indicated that the basic anionic groups are the BO³⁻₃ groups. Furthermore, Na₃Sm₂(BO₃)₃ exhibits an optical second harmonic generation effect which is close to that of KDP (KH₂PO₄).     

Synthesis, growth and characterization of novel second harmonic nonlinear chalcone crystal

Nonlinear optical (NLO) materials are useful in many of the industrial applications. New NLO chalcone derivative (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (4N4MSP) crystals have been grown by slow evaporation technique at ambient temperature. The grown crystals were subjected to single crystal X-ray diffraction study. The crystal has noncentrosymmetric structure in the orthorhombic system with space group Aba2 and unit cell parameters a=14.0647(15) Å, b=33.738(4) Å and c=6.0039(6) Å. To confirm the presence of various functional groups in the compound, FT-IR spectrum was recorded. The crystal was subjected to TGA/DTA analysis to find its thermal stability. The grown crystals were characterized for their optical transmission and mechanical hardness. The second harmonic generation (SHG) efficiency of the crystal is obtained by classical powdered technique using Nd:YAG laser and its value is 28.57 times that of urea. The laser damage threshold for 4N4MSP crystal was determined using Q-switched Nd:YAG laser. The refractive index values for green and red wavelengths were measured by Brewster angle technique. The dielectric and electrical measurements were carried out to study the different polarization mechanism and conductivity of the crystal. Good thermal, mechanical, transmission and SHG response make it desirable for the NLO applications.     

Structural, dielectric, optical and ferroelectric property of urea succinic acid crystals grown in aqueous solution containing maleic acid

Urea-succinic acid crystals have been grown at room temperature from aqueous solution in the presence of maleic acid by a slow evaporation technique. The structural parameters were determined using powder X-ray diffraction (XRD) and found to have monoclinic symmetry (space group P2₁/m) with a=9.902, b=17.510, c=5.555 Å and α=γ=90°, β=96.46°. The transparency and optical analysis were carried out using UV-vis analysis. The optical band gap is found to be 4.71 eV. The presence of various functional groups was confirmed by FTIR analysis. The samples have shown piezoelectric behavior with a fairly good piezoelectric charge coefficient (d₃₃) of 5 pC/N, when it is poled at 7 kV/cm. The hysteresis loop was plotted and the remnant polarization and coercive field were found to be 2.8 μC/cm² and 4 kV/cm, respectively. The dielectric analysis was carried out as a function of temperature at various frequencies and the results were also discussed.     

Electrical properties of high Curie temperature (1−x)Pb(In1/2Nb1/2)O3-xPbTiO3 single crystals grown by the solution Bridgman technique

0.65Pb(In_1/2Nb_1/2)O₃-0.35PbTiO₃ (PINT65/35) (starting composition) single crystals were grown successfully through the solution Bridgman technique using PbO flux and PMNT67/33 seed crystals. Because of the composition variation, the final composition of achievable crystals is in a range of 0.32-0.34 with the corresponding T_c range of 265-269 °C. The (001) plates of as-grown PINT66/34 single crystals show high Curie temperature (T_c=269 °C) and rhombohedral-tetragonal phase transition temperature (T_rt=134 °C). Besides, good electrical properties with high dielectric constant (ε>3000), low dielectric loss (tan δ∼1.2%), high piezoelectric constant (d₃₃∼2000 pC/N) and large electromechanical coupling factor (k_t≈59%) at room temperature have been obtained on the (001) plates. The sound velocity, acoustic impedance and other piezoelectric parameters were also measured on the (001) plates in this study, which provide us more detailed information about PINT66/34 single crystals.     

Optical behaviour of VTE treated near stoichiometric LiNbO3 crystals

Near stoichiometric LiNbO₃ crystal wafers of thickness up to 2 mm were prepared by vapour transport equilibration technique (VTE) at various process temperatures. Crystals were characterised by measurement of the UV absorption edge, refractive index, second harmonic generation (SHG) efficiency, and conoscopy pattern analysis. The comparison of VTE treated crystals show that the blue shift in cut off wavelength occurred with the increasing process temperature (i.e. increasing Li/Nb ratio). The refractive indices were found decreasing with increasing process temperature of VTE samples. The SHG efficiency increases in the range of 1.98-2.3 times for the VTE processed samples with respected to congruent crystals. Conoscopy pattern reveals the optical homogeneity of the VTE treated crystal.     

Thermal, mechanical, and electronic properties of glycine-sodium nitrate crystal

Glycine-sodium nitrate, C₂H₅N₂NaO₅ (GSN), crystals were grown from aqueous solutions by slow cooling with a temperature lowering rate of 1 °C/day in the range of 40-22 °C. These crystals were analyzed by differential thermal and thermogravimetric analysis (DTA-TGA) and mechanical hardness tester in order to obtain their thermal and mechanical properties. Mechanical characterization was done by studying the variation of microhardness with applied load. The dielectric properties of GSN were calculated by using the CASTEP code within the framework of the generalized gradient approximation (GGA). For better understanding of the optical properties of GSN, the second derivative of ε₂(E) was evaluated. DTA-TGA analysis showed that the material has a thermal stability up to 198 °C. The microhardness test was carried out for several faces of GSN crystals, and the tests revealed a load dependence to hardness. Analysis of the second derivative of ε₂(E) allowed to obtain better resolution of the electronic transitions involving the energy bands. Besides, a theoretical representation of the orbitals’ energy diagram was obtained. A discussion about the relation of structure-properties and molecular character of GSN is presented here.     

Growth, thermal, optical and birefringence studies of semiorganic nonlinear optical thiosemicarbazide cadmium chloride monohydrate (TCCM) single crystals

A semiorganic nonlinear optical material (thiosemicarbazide cadmium chloride monohydrate) (TCCM) was synthesized and single crystals was grown from aqueous solution by slow evaporation method at ambient temperature. Crystal of average size up to 5×4×3 mm³ were harvested and characterized by powder X-ray diffractometry (XRD) and Fourier transfer infrared (FTIR) technique to confirm the identity of the compound formed. The thermal stability was analyzed by TG/DTA. The birefringence values (Δ_n) were determined in the wavelength region 540-6500 Å. The second harmonic generation (SHG) from the materials was confirmed using Nd:YAG laser.     

Growth and design of novel nonlinear optical material (NLO) ⿿ Glycine barium nitrate potassium nitrate (GBNPN) crystal

A potentially useful semi organic nonlinear optical (NLO) material ? glycine with barium nitrate and potassium nitrate (GBNPN) has been synthesized by slow evaporation technique. Good transparent GBNPN crystals were obtained in a time span of 3 weeks. The grown crystals were characterized by single crystal/powder XRD, UV?vis?IR absorption, FTIR, thermal analysis and powder SHG measurements have been studied. The grown crystals were thermally stable up to 137.53 °C. The GBNPN crystal exhibits second harmonic generation efficiency of about 1.35 times than that of potassium di hydrogen phosphate (KDP). Mechanical properties such as micro hardness (H_v) and Mayer's index, n, have been carried out by indentation method. The refractive index (μ) has been measured by the Brewster's angle method.     

Rational synthesis of α-MnO2 and γ-Mn2O3 nanowires with the electrochemical characterization of α-MnO2 nanowires for supercapacitor

An acidification-hydrothermal method was developed to synthesize α-MnO₂ nanowires, which was subsequently treated with ethanol, resulting in γ-Mn₂O₃ nanowire bundles on a large scale. The electrochemical characterization was carried out by cyclic voltammetry, which indicated that the α-MnO₂ nanowires in 0.5 mol L⁻¹ Na₂SO₄ aqueous electrolyte was of an excellent electrode material for supercapacitor at the scan rate of 10 mV S⁻¹ in the range of 0.0-0.85 V.     

Magnetic, electric, and optical functionalities of (PLZT)x(BiFeO3)1−x ferroelectric-ferromagnetic thin films

We have prepared a series of (PLZT)_x(BiFeO₃)_1−x transparent thin films with thickness of 300 nm by a thermal pyrolysis method. Only films with x≦0.10 formed a single phase of perovskite structure. The film where x=0.10 exhibited both ferromagnetic and ferroelectric properties at room temperature with spontaneous magnetization and coercive magnetic fields of 0.0027μ_B and 5500 G, respectively. The remanent electric polarization and coercive electric field for the film where x=0.10 were 3.0 μC/cm² and 24 kV/cm, respectively. Additionally, films with 0.02≦x≦0.10 showed both magneto-optical effects and the second harmonic generation of transmitted light.