Thermal, mechanical, electrical, linear and nonlinear optical properties of a nonlinear optical l-ornithine monohydrochloride single crystal

Optically transparent semiorganic nonlinear optical bulk single crystal of l-ornithine monohydrochloride (LOMHCL) of dimension 11×3×2 mm³ 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 technique. Thermal behavior of the grown crystals was studied by thermogravimetric analysis. The second harmonic generation (SHG) efficiency of LOMHCL 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 and photoconductivity studies are also carried out for the grown samples.     

Growth, EPR and optical absorption spectra of l-threonine single crystals doped with Cu ions

We investigated the crystal growth, electron paramagnetic resonance (EPR) and optical absorption spectra of l-threonine doped with Cu²⁺. The quality, size and habit of the single crystals grown from aqueous solution by the slow solvent evaporation and by the cooling methods vary when the impurities are introduced during the growth process. The variations with the magnetic field orientation of the EPR spectra of single-crystal samples at room temperature and 9.77 GHz in three crystal planes (ab, bc and ac) show the presence of copper impurities in four symmetry-related sites of the unit cell. These spectra display well resolved hyperfine couplings of the of Cu²⁺ with the I_Cu= of the copper nuclei. Additional hyperfine splittings, well-resolved only for specific orientations of the magnetic field, indicate that the copper impurity ions in the interstitial sites have two N ligands with similar hyperfine couplings. The principal values of the g and A_Cu tensors calculated from the EPR data are g₁=2.051(1), g₂=2.062(2), g₃=2.260(2), A_Cu,1=16.9(5)×10⁻⁴ cm⁻¹, A_Cu,2=21.8(6)×10⁻⁴ cm⁻¹, A_Cu,3=180.0(5)×10⁻⁴ cm⁻¹. The principal directions corresponding to g₃ and to A_Cu,3 are coincident within the experimental errors, reflecting the orientation of the bonding planes of the copper ions in the crystal. The values of the crystal field energies are evaluated from the optical absorption spectrum, and the crystal field and bonding parameters of the Cu impurities in the crystal are calculated and analyzed. The EPR and optical absorption results are discussed in terms of the crystal structure of l-threonine and the electronic structure of the Cu²⁺ ions, and compared with data reported for other systems. The effects of the impurities in the growth and habit of the crystals are also discussed.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.     

Growth and characterization of pure and doped organic nonlinear optical single crystal: l-Alanine alaninium nitrate (LAAN)

The pure l-alanine alaninium nitrate (LAAN) single crystals and LAAN crystals doped with lanthanum oxide (La₂O₃), sodium chloride (NaCl), urea (CH₄N₂O), glycine (C₂H₅NO₂) and thiourea (CH₄N₂S) were grown by slow evaporation method. The X-ray diffraction analysis, scanning electron microscopy (SEM), energy dispersive X-ray (EDAX) analysis, UV–vis spectral analysis, dielectric studies and powder SHG measurement are studied systematically. The slight changes in the lattice parameters were observed for the doped crystals compared to pure LAAN crystal. The incorporation of doping into the crystal lattice was confirmed by energy dispersive X-ray analysis. There is no change in the transmission window due to doping and the percentage of transmission in doped samples was found to increase as compared to that of pure LAAN crystal. The dielectric constant of pure crystal was found to be less than that of doped crystals. The AC conductivity was found to increase after doping and with the increase in temperature. A green radiation of 532 nm was observed from the pure and doped LAAN crystals confirming the second harmonic generation (SHG) of the crystals.     

Growth and characterization of potassium halides mixed l-arginine phosphate monohydrate semi organic nonlinear optical single crystals

Single crystals of pure and potassium halides additive mixed l-arginine phosphate monohydrate have been grown with good optical quality by slow temperature reduction method. Microbial growth aspects and coloration have been studied on the growth solutions. In addition to that the structural properties have been studied by powder X-ray diffraction method and Fourier transform infrared spectral analyses for the grown crystals. Thermal stability of the grown crystals were studied by thermo gravimetric (TG) and differential thermal analyses (DTA) and found that the grown crystals are suitable for device fabrication for frequency conversion applications.     

Growth and characterization of metal ions doped l-serine NLO single crystals for optoelectronic applications

Single crystals of pure and metal ions (K⁺, Na⁺ and Li⁺) doped l-serine have been grown by slow evaporation solution growth technique (SEST). Energy dispersive X-ray analysis (EDAX) and inductively coupled plasma optical emission spectroscopy (ICP-OES) prove the incorporation of metal ions into the doped crystals. The lattice parameters have been obtained from single crystal X-ray diffraction (XRD) studies. The presence of functional groups is identified by Fourier transform infrared (FTIR) and FT-RAMAN analyses. The thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) reveal that the thermal stability of lithium doped l-serine crystal is enhanced. The mechanical properties have been studied by vicker's microhardness test. UV–vis-NIR spectroscopy shows that the percentage of transmission is increased in lithium doped l-serine crystals. Potassium and lithium ions doped l-serine crystals have enhanced second harmonic generation (SHG) efficiency indicating that these crystals are potential candidates for non linear optical (NLO) applications.     

Crystalline perfection, optical and dielectric studies on l-histidine nitrate: A nonlinear optical material

Single crystals of l-histidine nitrate (LHN), a recently investigated nonlinear optical material, were grown by conventional solution technique. Crystal structure and vibrational modes of the grown crystals were confirmed by powder X-ray diffractometry and FT-Raman spectrometry, respectively. Crystalline perfection of the grown crystals was evaluated by employing an in-house developed high-resolution X-ray diffractometer (HRXRD) and it was found that the grown crystals were free from structural grain boundaries and the perfection was reasonably good. However, HRXRD could reveal the fact that the crystals contain predominantly the interstitial point defects. The birefringence was measured over a range of wavelength between 5480 and 5630 Å and it was found that its value is nearly constant and 10 times higher than that of KDP. The optical band gap was found to be ∼3.73 eV. The photoluminescence excitation and emission spectra for single crystals were recorded. The SHG efficiencies of LHN samples of different particle sizes were measured by the Kurtz and Perry technique and they removed the ambiguity in the values reported differently in the literature. Dielectric properties were studied as a function of temperature over a wide range of frequency. The optical and dielectric studies along with the crystalline perfection reveal that the LHN crystal could be a good candidate for nonlinear optical devices.     

Growth and characterization of new semi-organic l-proline strontium chloride monohydrate single crystals

The present communication deals with the synthesis, single crystal growth and characterization of a new nonlinear optical material l-proline strontium chloride monohydrate (l-PSCM). Single crystals have been grown using the slow solvent evaporation technique. Single crystal XRD analysis confirmed that the crystal belongs to the orthorhombic structure with lattice parameter a=6.6966(3) Å, b=12.4530(5) Å, c=15.2432(5) Å and space group P2₁2₁2₁. Presence of various functional groups in l-PSCM and protonation of the ions were confirmed by Fourier transform infrared spectroscopy (FT-IR) analysis. The melting point of the single crystal was found to be 126 °C using DSC. Ultraviolet-visible spectral analyses showed that the crystal has low UV cut-off at 226 nm combined with very good transparency of 90% in a wide range. The optical band gap was estimated to be 5.82 eV. Capacitance and dielectric-loss measurements were carried out at different temperatures in the frequency range 1 kHz-2 MHz. The dielectric constant and loss factor were found to be 21 and 0.03 at 1 kHz at room temperature, respectively. Microhardness mechanical studies show that hardness number (H_v) increases with load for l-PSCM single crystals the by Vickers microhardness method. Second harmonic generation (SHG) efficiency was found to be 0.078 times the value of KDP.     

Linear and nonlinear optical properties of a new organic NLO l-asparaginium l-tartarate (AST) single crystal

A new organic NLO material l-asparaginium l-tartarate (AST) was synthesized and good quality crystals were grown from aqueous solution. The solubility and metastable zone width for AST solution were determined. Single crystal X-ray diffraction and powder X-ray diffraction analyses were carried out to confirm structure and crystalline nature of AST crystal. Optical transmittance and second harmonic generation efficiency (SHG) of the grown crystal were studied by UV?vis?NIR spectrum and Kurtz powder technique respectively. The transmittance of AST crystal was used to calculate the refractive index (n), the extinction coefficient (k) and reflectance (R). The laser induced surface damage threshold for the grown crystal was measured using Nd:YAG laser.     

Unidirectional growth of l-lysine l-lysinium dichloride nitrate (l-LLDN) single crystals by the SR method

Bulk semi-organic single crystals of l-lysine l-lysinium dichloride nitrate (l-LLDN) were grown by Sankaranarayanan-Ramasamy (SR) method. The experimental parameters involved in the present work are discussed in detail. The cut-off wavelength and the transmittance of the crystal were determined by UV-vis-NIR spectral analysis. Mechanical stability of the crystal was determined by Vickers microhardness tester. Refractive index of the crystal was measured using Brewster’s angle method. A simple interferometric technique was used for measuring birefringence of the crystal. The frequency dependent dielectric constant (ε_r) and dielectric loss (tan δ) were also measured. The results were analyzed for the l-LLDN crystals grown by both conventional and unidirectional methods.     

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.     

Pressure-induced phase transformations in l-alanine crystals

Raman scattering and synchrotron X-ray diffraction have been used to investigate the high-pressure behavior of l-alanine. This study has confirmed a structural phase transition observed by Raman scattering at 2.3 GPa and identified it as a change from orthorhombic to tetragonal structure. Another phase transformation from tetragonal to monoclinic structure has been observed at about 9 GPa. From the equation of state, the zero-pressure bulk modulus and its pressure derivative have been determined as (31.5±1.4) GPa and 4.4±0.4, respectively.     

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 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 organic nonlinear optical crystal: l-Valinium salicylate (LVS)

The new organic NLO crystal l-valinium salicylate (LVS) was grown by slow evaporation method using the mixed solvent of methanol and water in equal ratio. The crystal structure parameters were observed by powder and single crystal X-ray diffraction (XRD). The various functional groups present in the grown crystal were confirmed by Fourier transform infrared spectroscopy (FTIR) technique. ¹H and ¹³C Fourier transform nuclear magnetic resonance (FT-NMR) spectra were recorded to elucidate the molecular structure. The optical absorption study confirmed the good transmission window of the title crystal suitable for optical applications. The second harmonic generation (SHG) efficiency of LVS was confirmed by Kurtz Perry technique.     

Studies on growth and characterization of l-alanine strontium chloride trihydrate single crystals for optical applications

The optically transparent nonlinear optical single crystals of l-alanine strontium chloride trihydrate (LASCT) were grown by slow evaporation solution growth method using water as solvent. The purity of the crystals was increased by the method of recrystallization. The grown crystals were analyzed by the single crystal X-ray diffraction pattern which proved that LASCT belongs to monoclinic crystal system. The presence of various functional groups and modes of vibrations were identified by FTIR spectroscopy. The optical absorption study confirms the suitability of the crystal for device applications. The thermal strength and the decomposition of the grown crystals were studied using TG/DTA analyses. The dielectric constant and dielectric loss measurements of the grown crystals at different frequencies of the applied field were measured and reported. The mechanical strength of the crystal is estimated by Vicker's hardness test. The nonlinear optical properties of the grown crystals were confirmed by second harmonic generation test which shows the suitability of NLO applications.     

Determination of second order nonlinear optical entities for l-alanine single crystals using semi-classical anharmonic oscillator model

The second order nonlinear optical properties associated with second harmonic generation and linear electro-optic effect have been computed for l-alanine amino acid single crystals using semi-classical anharmonic oscillator model. The data obtained for l-alanine were compared with the optical parameters of similar amino acid single crystal. The results have been discussed in detail.     

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.     

Growth,optical, mechanical and electrical studies of nonlinear optical crystal: l-Valinium oxalate

l-Valinium oxalate (LVO) 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. The microhardness studies reveal the mechanical strength of the grown crystal. The dielectric constant, dielectric loss and AC conductivity of the compound were calculated at different temperatures and frequencies to analyze the electrical properties. Nonlinear optical property was discussed to confirm the SHG efficiency of the grown crystal.