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.     

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.     

Studies on vibrational, dielectric, mechanical and thermal properties of organic nonlinear optical co-crystal: 2,6-diaminopyridinium-4-nitrophenolate-4-nitrophenol

This article presents the vibrational, dielectric, mechanical and thermal properties of 2,6-diaminopyridine-4-nitrophenolate-4-nitrophenol co-crystals (DAP:NP) grown by slow evaporation solution growth technique. It crystallizes in orthorhombic noncentrosymmetric space group Pna2₁ with cell dimension a=10.86 Å, b=12.00 Å and c=13.53 Å; α=β=γ=90° with V=1764 Å³. Functional groups present in the molecule have been identified from FTIR study. Dielectric constant (ε_r), dielectric loss (tanδ) and ac conductivity (σ_ac) behaviors of the crystals have been studied at different temperatures. Presence of piezoelectric resonance peaks at lower frequency in dielectric measurements may increase the electro-optic coefficient of the crystals. Mechanical strength and its parameters of the grown crystals have been determined by Vickers microhardness test. TG/DTA analysis shows the melting point of the material is 150 °C and it undergoes two stages of decomposition.     

Growth and characterization of a new organic NLO material: Glycine nitrate

Single crystals of glycine nitrate [(C₂H₆NO₂)⁺ · (NO₃)⁻] were grown using submerged seed solution method. The crystals were characterized by using single crystal X-ray diffraction and density measurements. Spectroscopic, thermal and optical studies were carried out for analyzing the presence of the functional groups, thermal stability, decomposition and transparency of the sample. These studies showed that the crystals are thermally stable upto 145 °C and transparent for the fundamental and second harmonic generation of Nd:YAG (λ = 1064 nm) laser. Second harmonic generation (SHG) conversion efficiency was investigated to explore the NLO characteristics of this material. Microhardness and dielectric studies were also carried out.     

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.     

Optical, thermal, dielectric and ferroelectric behaviour of sodium acid phthalate (SAP) single crystals

Sodium acid phthalate (SAP), an efficient semi-organic crystal having dimensions 17×8×2 mm³ has been grown from aqueous solution by slow evaporation technique at room temperature within the period of 2 weeks. The lattice parameters of the grown crystals were determined using single-crystal X-ray diffraction analysis. The presence of functional groups was estimated qualitatively by Fourier transform infrared (FTIR) analysis. The band gap energy was determined using optical absorption studies. The TG/DTA analysis reveals that the SAP crystal is thermally stable up to 141.6 °C. The dielectric constant and dielectric loss was studied as a function of frequency and the corresponding activation energy (E_a) has been calculated for the grown crystal. Scanning electron microscope studies enunciate the ferroelectric domain patterns of the SAP crystal. Ferroelectric property of the grown crystal was confirmed by hysteresis loop studies.     

Optical,thermal and mechanical characterization of Al(III)/Sb(III)-doped tris(thiourea)zinc(II) sulphate crystals

The influence of Al(III)/Sb(III)-doping on the properties of tris(thiourea)zinc(II) sulphate (ZTS) crystals grown by slow evaporation solution growth technique is reported. The as-grown crystals belong to orthorhombic system and cell parameters are, a = 7.77 Å, b = 11.13 Å, c = 15.47 Å, V = 1338 Å³ (Al(III)-doped) and a = 11.1996 Å, b = 7.770 Å, c = 15.5598 Å, V = 1368.3 Å³ (Sb(III)-doped). The structure and the crystallinity of the materials are further confirmed by powder X-ray diffraction analysis. The modes of vibrations of different functional groups present are identified by Fourier transform infrared studies. Thermogravimetric/differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. Surface morphological changes due to doping are observed by scanning electron microscopy. Microhardness study was carried out to elucidate the mechanistic behavior microhardness studies were carried out to elucidate the mechanistic behavior. Second harmonic generation activity is much better in the case of Sb(III)-doping. The specimen is also characterized by dielectric studies.     

Growth and characterization of a novel organic nonlinear optical material: l-alanine 2-furoic acid

l-alanine 2-furoic acid (LA2FA), a novel organic third order nonlinear optical material was grown by slow solvent evaporation technique at room temperature. The grown single crystals were characterized by XRD, spectral, thermal, optical, dielectric and third order nonlinear properties. LA2FA crystallizes into triclinic system with the space group P1. The cell parameters are found to be a = 3.97 Å, b = 7.09 Å, c = 10.69 Å, α = 73.61°, β = 83.57°, γ = 84.21° and V = 286 Å3. The modes of vibrations of different molecular groups present in LA2FA were identified by FTIR studies. The optical transparency of the grown crystals was investigated by UV–visible spectrum. The absorption spectrum reveals that the crystal has a high UV cut off of 245 nm and photonic band gap of 2.5 eV. The scanning electron microscope (SEM) study has been carried out to determine the surface morphology of the grown crystal. The thermal behavior of the crystal investigated using thermo gravimetric (TG) and differential thermal analysis (DTA) indicates that the material does not decompose before melting. The third order NLO property was studied in detail by z-scan technique.     

Growth and physical properties of an organic crystal for NLO applications: Guanidinium phenyl arsonate (GPA)

Single crystals of organic material guanidinium phenyl arsonate (GPA) of size 28 × 14 × 10 mm³ were grown from propanol–water mixed solvent by slow solvent evaporation technique. The crystal belongs to monoclinic system with noncentrosymmetric space group Cc. The lattice parameter values of GPA crystals are a = 18.453 Å, b = 7.609 Å, c = 12.592 Å and β = 121.856°. The grown crystal was subjected to X-ray diffraction (XRD) study to identify its morphology and structure. Chemical etching study using propanol–water as etchant reveals the mechanism of growth. The formation of synthesized compound was confirmed by Fourier transform infrared (FT-IR) spectroscopy analysis. Optical transmittance and second harmonic generation (SHG) of the grown crystals were studied by UV–vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of GPA has been used to calculate the refractive index ‘n’ and the extinction coefficient ‘k’. The laser induced surface damage threshold for the grown crystal was determined using Nd:YAG laser. The mechanical behavior of GPA was analyzed using Vickers microhardness test.     

Growth, structural and optical studies on amino acid based new GSB crystals having non-linear optical characteristics

Transparent crystals of α-glycine with sodium nitrate and barium nitrate (GSB) have been grown from aqueous solution by slow evaporation technique at room temperature. Crystals of size 11 × 7 × 4 mm³ have been obtained in 3-4 weeks time. The solubility of GSB has been determined in water. The grown crystal belongs to orthorhombic system with cell parameters a = 4.684 a.u., b = 12.184 a.u. and c = 10.969 a.u. with unit cell volume of 625.99 (a.u.)³. 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 Nd-YAG laser (1064 nm), the optical second harmonic generation (SHG) conversion efficiency of GSB is found to be 0.648 times that of standard KDP. On exposure to light the GSB crystals exhibit positive photoconductivity. I-V characteristics, dielectrics studies and Vickers micro hardness measurement have been carried out. The GSB crystal exhibits more mechanical strength compared to the reported GSN crystals.     

Iminodiacetic acid doped ferroelectric triglycine sulphate crystal: Crystal growth and characterization

Single crystals of iminodiacetic acid (HN(CH₂COOH)₂) doped triglycine sulphate (IDATGS) crystals have been grown from aqueous solution containing 1-10 mol% of iminodiacetic acid at constant temperature by slow evaporation technique. The effects of different amounts of doping entities on the growth habit have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. The grown crystals were subjected to Fourier transform infrared (FTIR) spectroscopy studies to find the presence of various functional groups qualitatively. The dielectric permittivity has been studied as a function of temperature. An increase in the transition temperature (49.2-49.7 °C) of IDATGS crystals is observed. The dielectric constant (ε′_max) of IDATGS crystals vary in the range 922-2410 compared to pure TGS (T_c=49.12 °C and ε′_max=3050). Curie Weiss constants C_p and C_f in the paraelectric and ferroelectric phases were determined. The transition temperature (T_c) is found to decrease with increase in dopant concentration. P-E hysteresis studies show the presence of internal bias field in the crystal. Piezoelectric measurements were also carried out at room temperature. Domain patterns on b-cut plates were observed using scanning electron microscope. The micro hardness studies reveal that the doped crystals are harder than the pure TGS crystals. The low dielectric constant, higher transition temperature, internal bias field and hardness suggest that IDATGS crystals could be a potential material for IR detectors.     

Measurement of nonlinear refractive index of pure and doped KTP crystals by Z-scan technique using cw He–Ne Laser

Single crystals of pure, Mo and W doped KTP crystals were grown by flux technique. The grown crystals were subjected to various characterization studies such as EDX, powder XRD, FTIR and UV analysis. The SHG efficiencies of the pure and doped KTP crystals were measured by Kurtz–Perry technique and it was found that the doped KTP crystals exhibit higher values of SHG. Nonlinear refractive indexes were measured on different growth planes of pure and doped crystals by Z-scan method using a cw (continuous wave) He–Ne laser at 632.8 nm. The measured values of nonlinear refraction of different planes were in the order of 10⁻¹² cm²/W.     

Studies on the optical and mechanical properties of organic nonlinear optical 1-(4-fluorostyryl)-4-nitrostilbene (FNS) single crystal

A new organic nonlinear optical material 1-(4-fluorostyryl)-4-nitrostilbene (FNS) has been synthesized and single crystals of FNS were grown using solvent evaporation solution growth technique (SESGT) by 2-butanon solvent. Single crystal x-ray diffraction analysis reveals the unit cell parameters of the grown crystal are a = 9.494(4) Å, b = 9.864(2) Å, c = 19.501(7) Å and it belongs to monoclinic system with noncentrosymmetric space group. Optical transmittance of the grown crystal has been studied by UV-Vis-NIR spectrum. The optical properties of FNS have been studied by means of optical transmittance measurements in the wavelength range of 190–1100 nm The optical constants were calculated from the optical transmittance (T) data such as refractive index (n), extinction coefficient (k) and reflectance (R). The optical band gap (E_g) of FNS is 3.27 eV with direct transition. The complex dielectric (?) constant of the grown FNS crystal was determined. The second harmonic generation (SHG) efficiency of the grown FNS crystal has been studied by using Kurtz-Perry powder technique and it shows 12 times relatively greater than KDP.     

AgGaS2- and Al-doped GaSe Crystals for IR Applications

We report a systematic study of AgGaS₂- and Al-doped GaSe crystals in comparison with pure GaSe and S-doped GaSe crystals. AgGaS₂-doped GaSe (GaSe:AgGaS₂) crystal was grown by Bridgman technique from the melt of GaSe:AgGaS₂ (10.6 wt.%). Its real composition was identified as GaSe:S (2 wt.%). Al-doped GaSe (GaSe:Al) crystals were grown from the melt of GaSe and 0.01, 0.05, 0.1, 0.5, 1, 2 mass % of aluminium. Al content in the grown crystals is too small to be measured. The hardness of GaSe:S (2 wt.%) crystal grown from the melt of GaSe:AgGaS₂ is 25% higher than that of GaSe:S (2 wt.%) crystal grown by a conventional S-doping technique and 1.5- to 1.9-times higher than that of pure GaSe. GaSe:Al crystals are characterized by 2.5- to 3-times higher hardness than that of pure GaSe and by extremely low conductivity of ≤ 10^− 7 Om^− 1 cm^− 1. A comparative experiment on SHG in AgGaS₂-, Al-, S-doped GaSe and pure GaSe is carried out under the pumps of 2.12-2.9 μm fs OPA and 9.2−10.8 μm ns CO₂ laser. It was found that GaSe:S crystals possess the best physical properties for mid-IR applications among these doped GaSe crystals. GaSe:Al crystals have relatively low conductivity which have strong potential for THz application.     

Pyroelectric coefficient manipulation in doped TGS crystals

Pure and l-alanine doped Triglycine sulphate (TGS) crystals were grown in paraelectric phase (∼52 °C). Doped crystals show unequal growth rates along the ferroelectric axis. Pure TGS crystals show peculiar dielectric behavior in the ferroelectric phase, after crossing up and down the Curie point in two successive runs between room temperature and 80 °C. Much higher and unstable permittivity was found returning in the ferroelectric phase. At constant temperature (35 °C), permittivity follows a relaxation process, characterized by two relaxation times. l-Alanine doped TGS crystal shows more than one order of magnitude smaller permittivity and dielectric losses. Internal bias field of ∼1 kV/cm, induced by the dopant, made the crystal almost monodomain and pined polarization in one direction. Pyroelectric coefficient measurements were performed at constant heating rate of the samples, using a computer controlled He cryostat and Keithley 6517 electrometer. The temperature dependence of P⁺ polarization component, obtained by computer integration of the pyroelectric coefficient, was measured on a large temperature interval (−20/+80 °C). Pyroelectric coefficient of the doped samples was also measured by the same procedure, using a dc bias electric field, pointing in the opposite direction to the pined polarization. The polarization could be reversed, on the whole temperature range, by dc fields higher than bias or coercive field. Surprisingly, for the first time, the pyroelectric coefficient (p) was found constant on quite large temperature intervals. Doped TGS crystals show much smaller values of permittivity ?_r versus the pure one and consequently, get higher figure of merit M = p/?_r. The pyroelectric coefficient of this material can be tailored to become constant on a defined temperature range, under a dc field control. This characteristic makes this material valuable to be used as pyroelectric material for IR devices.     

Optical and dielectric studies of gel grown α-hopeite single crystal

Single crystals of α-hopeite exhibiting high transparency were grown by single diffusion gel growth technique. Single crystal X-ray diffraction analysis reveals that the crystal belongs to orthorhombic system. The values of several structural and physical parameters have been determined for the grown crystal. The optical absorption study reveals the transparency of the crystal and is noticed in the entire visible region and the cut-off wavelength was found to be 230 nm. The optical band gap found to be at 3.25 eV. The dependence of extinction co-efficient (k) and the refractive index (n) on the wavelength was also shown. The dielectric constant and dielectric loss of the crystal was studied as a function of frequency and temperature. Transport properties of the grown crystal have been studied from the Cole-Cole plot.     

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.     

Optical and electrical properties of SnS semiconductor crystals grown by physical vapor deposition technique

Tin sulfide (SnS) is a material of interest for use as an absorber in low cost solar cells. Single crystals of SnS were grown by the physical vapor deposition technique. The grown crystals were characterized to evaluate the composition, structure, morphology, electrical and optical properties using appropriate techniques. The composition analysis indicated that the crystals were nearly stoichiometric with Sn-to-S atomic percent ratio of 1.02. Study of their morphology revealed the layered type growth mechanism with low surface roughness. The grown crystals had orthorhombic structure with (0 4 0) orientation. They exhibited an indirect optical band gap of 1.06 eV and direct band gap of 1.21 eV with high absorption coefficient (up to 10³ cm⁻¹) above the fundamental absorption edge. The grown crystals were of p-type with an electrical resistivity of 120 Ω cm and carrier concentration 1.52×10¹⁵ cm⁻³. Analysis of optical absorption and diffuse reflectance spectra showed the presence of a wide absorption band in the wavelength range 300-1200 nm, which closely matches with a significant part of solar radiation spectrum. The obtained results were discussed to assess the suitability of the SnS crystal for the fabrication of optoelectronic devices.     

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.     

Comparative study on BIS thiourea cadmium acetate crystals using HRXRD, etching, microhardness, UV-visible and dielectric characterizations

〈1 1 1〉 oriented bis thiourea cadmium acetate (BTCA) crystal of diameter 15 mm and length 45 mm was grown for the first time by the unidirectional Sankaranarayanan-Ramasamy (SR) method. The conventional and SR method grown BTCA crystals were characterized by using high-resolution X-ray diffraction (HRXRD), chemical etching, Vickers microhardness, UV-vis, dielectric studies and differential scanning calorimetry. The HRXRD analysis indicates that the crystalline perfection of SR method grown crystal is good without having any low angle internal structural grain boundaries. The transmittance of SR method grown BTCA is 14% higher than that of conventional grown crystal. The dielectric constant was higher and the dielectric loss was less in SR method grown crystal. The crystals grown by SR method possess less dislocation density and higher microhardness.