Investigation on the bulk crystal growth,crystalline perfection,refractive index and piezoelectric properties of borate single crystals for piezoelectric and electro-optic applications

Low solubility potassium pentaborate tetrahydrate (KB5), ammonium pentaborate tetrahydrate (AB5) and mixed (KAB5) single crystals have been grown by the Sankaranarayanan-Ramasamy (SR) method. The crystal structures and space groups have been confirmed by powder XRD analysis. The direction of the grown crystal was confirmed by the back reflection X-ray Laue pattern. The crystalline perfection (CP) of the crystals have been evaluated using HRXRD studies. The transmittance spectra of the grown crystals were recorded by UV–Vis-NIR transmission studies showing that all the crystals have 90% transmittance in the entire visible region and found that the crystals' cut off wavelengths were below 200 nm. The optical studies such as refractive index (RI) and birefringence interferometry (BI) were reported. The RI for five different wavelengths of KB5, AB5 and KAB5 crystals were analyzed using the prism coupling method (PCM). Electromechanical behavior of the grown crystals was observed using piezoelectric coefficient (d₃₃) measurement. Vickers Microhardness (VMH) measurement carried out at 30 °C shows increased hardness as the load increases.     

Studies on growth,structural, optical and mechanical properties of xylenol orange dye admixtured l-arginine phosphate single crystal

Bulk single crystals of pure and xylenol orange (XO) admixtured l-arginine phosphate (LAP) were grown by slow cooling technique. The cell parameters and crystallinity of pure and dye admixtured LAP crystals were confirmed by single crystal and powder X-ray diffraction analyses. HRXRD analysis reveals the presence of xylenol orange dye in interstitial site of LAP crystal lattice and it confirms the crystalline perfection of grown crystals. The functional groups of grown crystals were confirmed by FTIR spectral analysis. UV–vis transmission studies show the characteristic absorption of xylenol orange admixtured LAP crystal. Vickers’ microhardness and laser damage threshold studies were carried out on these crystals. Kurtz and Perry powder test was conducted to measure the second harmonic generation efficiency of pure and dye admixtured LAP crystals.     

Studies on optical,mechanical, dielectric properties of bisthiourea nickel bromide NLO single crystal

Bisthiourea nickel bromide (BTNB) single crystal has been grown by solution growth technique at room temperature. The crystal structure and lattice parameters were determined for the grown crystal by single crystal X-ray diffraction studies. Optical constants like band gap, refractive index, reflectance, extinction coefficient and electric susceptibility were determined from UV–vis-NIR spectrum. Nonlinear optical property was discussed to confirm the SHG efficiency of the grown crystal. The mechanical strength of the grown crystal was analyzed using Vickers microhardness tester. The dielectric constant and dielectric loss of bisthiourea nickel bromide are measured in the frequency range of 50 Hz to 5 MHz at different temperatures. The ac conductivity studies were carried out on bisthiourea nickel bromide crystals. In order to investigate the growth mechanism and surface features, etching studies are carried out for the crystal. Photoconductivity studies were carried out on bisthiourea nickel bromide crystals.     

Effect of Mn(II) doping on crystalline perfection, nonlinear, optical and mechanical properties of KDP single crystals

The effect on crystalline perfection, second harmonic generation (SHG) efficiency, optical transparency and mechanical properties due to Mn(II) doping in KDP single crystals grown by slow evaporation solution technique by adding different quantities of MnCl₂ in the solution has been investigated. The actual incorporated quantity of Mn(II) in the crystals was evaluated by atomic absorption spectroscopy. Powder XRD study confirms the crystal system of KDP and found no additional phases at all doping levels (1 to 5 mol%). The influence of Mn(II) doping on the crystalline perfection has been assessed by high-resolution XRD and these studies revealed that the grown crystals could accommodate Mn(II) in the interstitial positions of the crystalline matrix of KDP only up to some critical concentration, above which the crystal developed structural grain boundaries. The relative SHG efficiency of the crystals was found to be increased sharply at low concentrations (1 mol%), and above this value it was decreased as the concentration increases though it is still higher than that of pure KDP. UV-Vis studies also revealed the same behavior with a significant enhancement at 1 mol% concentration and later gradually decreased. Good increment in the hardness values has been observed by increasing the doping concentrations.     

Effect of zinc chloride on structural, optical and dielectric behavior of solution grown anthracene crystal

Pure and ZnCl₂ doped anthracene (AN & ANZ) single crystals were grown by the slow evaporation method. In XRD studies a shift in peaks towards higher theta value and change in preferred orientation from (0 0 1) to (0 0 2) were observed as a result of doping. UV-vis spectra show a blueshift of various peaks in ANZ. Remarkable increases in dielectric constant and AC conductivity were observed along with a structure related phase transition at 40 °C in ANZ at atmospheric pressure itself. Good fluorescence properties with a strong green emission were observed in photoluminescence studies.     

Growth,optical, mechanical,dielectric and theoretical properties of picolinium maleate NLO single crystal

Nonlinear optical single crystals of picolinium maleate (PM) were grown by slow evaporation method. The grown crystal was subjected to single crystal X-ray diffraction analysis to confirm that the crystal belongs to the monoclinic crystal structure with space group P2₁/c. The optical transmission range of the grown crystal was measured by UV–Vis–NIR region with the lower cut-off wavelength as 330 nm. The optical bandgap is found to be 3.75 eV. Mechanical strength of the grown crystal was analyzed using Vickers microhardness tester. Dielectric constant and dielectric loss of picolinium maleate are measured in the frequency range from 50 Hz to 5 MHz at different temperatures. Further, electronic properties, such as valence electron plasma energy, Penn gap, Fermi energy and electronic polarizability of the grown crystal have been estimated.     

Studies on the optical and dielectric properties of a zinc thiourea chloride NLO single crystal

Single crystals of a nonlinear optical material, zinc thiourea chloride were grown by the slow evaporation technique. The crystal structure and lattice parameters of the grown crystal were determined by the single crystal X-ray diffraction studies. The single crystal XRD revealed that the material crystallized in a orthorhombic crystal system. Optical studies were carried out and it was found that the tendency of transmission observed from the specimen, with respect to the wavelength of light, is practically more suitable for opto-electronic applications. The optical band gap is found to be 4.30 eV. Optical constants such as the band gap, refractive index, reflectance, extinction coefficient and real (?_r) and imaginary (?_i) components of the dielectric constant and electric susceptibility were determined from the UV–vis–NIR spectrum. The dielectric constant and dielectric loss of zinc thiourea chloride were measured in the different frequency range from 50 Hz to 5 MHz at different temperatures. Further, electronic properties, such as valence electron plasma energy, Penn gap, Fermi energy and electronic polarizability of the grown crystal have been estimated.     

Growth,spectral, optical,and dielectric studies on novel semiorganic NLO single crystal: d-phenylglycine hydrochloride

Good quality novel semiorganic nonlinear optical single crystal of d-phenylglycine hydrochloride has been grown from the aqueous solution by low temperature solution growth method. X-ray diffraction reveals that the crystal crystallises into orthorhombic system with noncentrosymmetric space group P2₁2₁2₁. Experimental parameters are evaluated based on single-crystal XRD and the calculated values of the polarisability were compared with the values of polarisability using Clausius–Mossotti equation. The functional groups present in the grown crystal were confirmed by Fourier transform infrared spectral analysis. The ¹H and ¹³C FT–NMR has been recorded to elucidate the molecular structure. Ultraviolet–visible-near infra-red absorption studies on this crystal reveal that the minimum absorption region is around 228 nm. The optical band gap of the crystal was found to be 2.9 eV. The scanning electron microscope study has been carried out to determine the surface morphology of the grown crystal. Photoluminescence studies show that the material emits violet fluorescence. Thermal studies bring forth that the crystal is thermally stable up to 255 °C. Dielectric studies reveal that both the dielectric constant and dielectric loss decrease with the increase in frequency as like the typical semiorganic nonlinear optical crystals such as bisthiourea zinc chloride, bisthiourea cadmium chloride and l-arginine dihydrogen phosphate. Electrical conductivity measurements were carried out and the Arrhenius plot is used to determine the value of activation energy. The Kurtz powder analysis on the crystal confirms the existence of second harmonic generation properties. The SHG efficiency was found to be 1.15 times that of KDP 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.     

Investigation of dielectric, piezoelectric and ferroelectric properties of b-axis grown triglycine sulphate single crystal

Large single crystal of triglycine sulphate (dimension 100 mm along monoclinic b-axis and 15 mm in diameter) was grown using the unidirectional solution growth technique. The X-ray diffraction studies confirmed the growth/long axis to be b-axis (polar axis). The dielectric studies were carried out at various temperatures to establish the phase transition temperature. The frequency response of the dielectric constant, dielectric loss and impedance of the crystal along the growth axis, was monitored. These are typically characterized by strong resonance peaks in the kHz region. The piezoelectric coefficients like stiffness constant (C), elastic coefficient (S), electromechanical coupling coefficient (k) and d ₃₁ were calculated using the resonance-antiresonance method. Polarization (P)-Electric field (E) hysteresis loops were recorded at various temperatures to find the temperature-dependent spontaneous polarization of the grown crystal. The pyroelectric coefficients were determined from the pyroelectric current measurement by the Byer and Roundy method. The ferroelectric domain patterns were recorded on (010) plane using scanning electron microscopy and optical microscopy.     

Enhancement of the crystalline perfection of <0 0 1> directed KDP single crystal

<0 0 1> directed good quality potassium dihydrogen phosphate (KDP) single crystal has been grown by Sankaranarayanan–Ramasamy (SR) method with the vision to improve the crystalline perfection and efficiency. A seed crystal of diameter 25 × 15 × 3 mm³ was mounted in the ampoule, where the diameter of the ampoule was much bigger than the seed. The size of the crystal grown was 30 × 20 × 60 mm³. The obtained transparency for the crystal grown by SR method is 93% and by conventional method is 85% in the entire visible region. The HRXRD analysis indicates that the crystalline perfections of the crystals are excellent without having any very internal structural grain boundaries. The obtained FWHM for conventional method grown crystal is 12 arc s and for SR method is 6 arc s. Low dielectric loss indicates that the <0 0 1> directed crystal contains minimum defects. Higher mechanical stability was observed in SR method grown KDP compared to the other. Laser damage threshold value has been determined using Nd:YAG laser operating at 1064 nm. The optical transmission study and the powder SHG measurement show the suitability of the ingot for nonlinear optical applications.     

Studies on optical, mechanical and transport properties of NLO active l-alanine formate single crystal grown by modified Sankaranarayanan-Ramasamy (SR) method

Bulk single crystals of l-alanine formate of 10 mm diameter and 50 mm length have been grown with an aid of modified Sankaranarayanan-Ramasamy (SR) uniaxial crystal growth method within a period of ten days. The optical properties of the grown crystal were calculated from UV transmission spectral analysis. The second harmonic generation efficiency of the grown crystal was confirmed by Kurtz powder test. In order to determine the mechanical strength of the crystal, Vicker’s microhardness test was carried along the growth plane (0 0 1). Dielectric studies reveal that both dielectric constant and dielectric loss decreases with increase in frequency. Photoconductivity study confirms the negative photoconducting nature of the crystal.     

Determination of crystalline perfection,optical indicatrix,birefringence and refractive-index homogeneity of ZTS crystals

Single crystals of the semi-organic non-linear optical material zinc tris (thiourea) sulphate (ZTS) were grown by slow evaporation solution growth technique. The crystals were characterized for crystalline perfection and optical homogeneity using high-resolution X-ray diffraction (HRXRD) and optical interferometric techniques. The FWHM of 6 arc sec in HRXRD rocking curve shows the good crystalline quality. Transmittance of ∼75% shows that the crystal is free from volume defects. Conoscopy was used to assess the optical quality and investigate the optical indicatrix of the grown crystal. Birefringence values of the crystal along the three principal crystallographic axes were measured using birefringence interferometry. Mach–Zehnder interferograms exhibit good refractive-index homogeneity of the grown crystal.     

Growth,crystal perfection,optical and electrical properties of organic crystal: Brucinium 5-sulfosalicylate trihydrate

Single crystals of brucinium 5-sulfosalicylate trihydrate (B5ST) were grown from ethanol–water (1:1) mixed solvent by slow evaporation method. Structure and crystallinity of the grown crystal were confirmed by single-crystal X-ray diffraction analysis. Presence of functional groups and coordination of brucine and 5-sulfosalicylic acid (5SSA) were confirmed by FT-IR and FT-Raman analyses. Optical transmittance spectrum shows the crystal having 90% transmittance in the visible region. The laser-induced surface damage threshold for the grown crystal was measured as 13.64 GW cm⁻² with Nd:YAG laser assembly. Dielectric study was performed on the single crystal to study the power dissipation of the material in the presence of alternating electric field. Crystal defects and surface morphology are studied by dissolution solvent technique and it reveals the layer growth mechanism for B5ST compound.     

Liquid crystal deposition on poled, single crystalline lithium niobate

For the purpose of elucidating the mechanisms for molecular organization at poled ferroelectric surfaces, single crystalline lithium niobate (LN), ‘Z-cut’ along the (0 0 0 1) plane, has been prepared and characterized and subsequently exposed to liquid crystal molecules. As a model system we chose to study the anchoring of 4-n-octyl-4′-cyanobiphenyl (8CB) to LN. Liquid crystalline films are of interest because of their useful electronic and optical properties as well as chemical sensing attributes. Low-energy electron diffraction (LEED), atomic force microscopy (AFM), surface contact angle measurements (CA), and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface of lithium niobate as well as the nature of 8CB films grown on the surface. Atomically flat LN surfaces were prepared as a support for monolayer thick, 8CB molecular domains. 8CB liquid crystal molecules were deposited by an ambient vaporization technique and the films were analyzed using XPS and CA. Understanding electrostatic anchoring mechanisms and thin film organization for this molecule on uniformly poled surfaces allows for a fuller appreciation of how molecular deposition of other polarizable molecules on periodically poled and patterned poled lithium niobate surfaces would occur.     

Influence of l-alanine doping on crystalline perfection, SHG efficiency, optical and mechanical properties of KDP single crystals

Pure and l-alanine (LA) doped single crystals of potassium dihydrogen orthophosphate (KDP) were grown by slow evaporation solution technique (SEST) in aqueous solution at ambient temperature. Powder X-ray diffraction study was done to confirm the crystal system and lattice parameters of KDP. No additional phases were observed at all doping concentrations (1-7.5 mol%), which was further confirmed by FT-Raman spectroscopy analysis. The influence of LA doping on the crystalline perfection was assessed by high-resolution X-ray diffractometry (HRXRD) analysis. HRXRD studies revealed that the grown crystals could accommodate LA at the interstitial positions in the crystalline matrix of KDP up to some critical concentration without any deterioration in the crystalline perfection. Above this concentration, very low angle structural grain boundaries were developed and it seems that the excess LA above the critical concentration was segregated along the grain boundaries. The SHG efficiency was measured using the Kurtz powder technique. The relative SHG efficiency of the crystals was found to be increased with doping concentration up to 5 mol% and above this it decreases. Optical transmission study also revealed the same behavior with enhancement up to 5 mol% concentration and later decreased. The hardness values were found to be increased by increasing the doping concentration.     

Growth structural,spectral, optical and mechanical studies of gamma bis glycinium oxalate (GBGOx) new NLO single crystal by SEST method

Gamma bis glycinium oxalate (GBGOx) crystal was synthesized and grown by slow evaporation solution technique. The structure of pure GBGOx crystal has been examined by single crystal X-ray diffraction analysis. The confirmation with single crystal XRD reveals that the crystal belongs to monoclinic system with space group C₂. The FTIR spectrum was recorded to identify the expected functional groups. UV–vis-spectrum shows the lower cut off wavelength and 80% of transmittance in the UV–vis region. The photoluminescence measurement shows that the material is suitable for photonic devices. Preliminary measurement of green light emission using Kurtz powder technique indicates that their second harmonic generation (SHG) efficiency. The microhardness analysis revealed that the grown crystal belongs to soft material category. The encouraging results show that the GBGOx crystals have great potential applications in optical devices.     

Studies on the electrical, linear and nonlinear optical properties of Manganese mercury thiocyanate bis-dimethyl sulfoxide, an efficient NLO crystal

Manganese mercury thiocyanate bis-dimethyl sulfoxide (MMTD), a novel organo-metallic nonlinear optical (NLO) crystal, was grown by a slow evaporation technique over a period of 30 days. The grown crystal was subjected to single crystal X-ray diffraction to determine the unit cell parameters. The optical properties of MMTD were investigated by UV-Vis-NIR, FTIR and FT-Raman spectroscopic techniques. The second harmonic generation (SHG) efficiency of the sample was measured using a Q-switched, mode-locked Nd:YAG laser and the results were compared with urea and manganese mercury thiocyanate (MMTC). The thermal parameters, such as the thermal diffusivity (α), thermal effusivity (e), thermal conductivity (k) and heat capacity (c_p) of MMTD were measured by the photopyroelectric (PPE) technique and the results are discussed. The dielectric response and mechanical properties of MMTD have also been investigated and reported.