A new NLO Material: L-Asparagine thiocyanate (LATC) for opto-electronic applications

L-asparagine monohydrade thiocyanate (LATC), which is potentially a non-linear optical crystal, was grown by the conventional slow evaporation solution technique (SEST) using doubly de-ionized water at room temperature. The lattice parameters were found by using single crystal X-ray diffraction analysis. Perfection of the grown crystal was confirmed by powder X-ray diffraction. The various functional groups were identified from FT-IR analysis. The optical parameters, such as the optical absorption, the band gap, photoluminescence and second harmonic generation (SHG), were analyzed on the grown crystal. The induced surface laser damage threshold was measured using a Q-switched Nd:YAG laser. The thermal behavior and stability of the grown crystal was analyzed by TG/DTA analysis. The dielectric constant (ε_r) and dielectric loss (tanδ) as a function of frequency has been investigated at different temperatures. The mechanical property of the grown crystal was studied using the Vickers micro hardness method.     

X-ray topography, photopyroelectric and two-photon absorption studies on solution grown benzimidazole single crystal

Benzimidazole (BMZ) is an organic nonlinear optical material, and it is possible to grow it in the laboratory by a slow evaporation solution growth technique using methanol as the solvent. Its nonlinear optical harmonic generation efficiency is 4.5 times higher than that of standard potassium dihydrogen phosphate (KDP) single crystal. It crystallizes with orthorhombic structure, which is noncentrosymmetric in nature, with lattice parameters a=13.58 Å, b=6.85 Å, c=6.97 Å. The functional groups of the grown specimen are confirmed by heteronuclear chemical shift correlation (HETCOR) analysis and it is found that other elements are not incorporated in the compound. The crystalline perfection is examined by high resolution X-ray diffraction (HRXRD), and its topographic image was recorded for the as-grown single crystal indicates the presence of some grain boundaries in the grown specimen. Thermal parameters such as thermal diffusivity (α), thermal conductivity (k), thermal effusivity (e), and heat capacity (c _p ) have been determined by a photopyroelectric thermal wave method. In addition, piezoelectricity, birefringence, and third-order nonlinear optical properties have been examined. The two-photon absorption coefficient of the title compound is determined by the open-aperture Z-scan technique.     

Investigation on the optical and electrical properties of MMTG crystal: A Lewis base adduct

The growth of nonlinear optical single crystal of manganese mercury thiocyanate glycol monomethyl ether (MMTG), a Lewis base adduct of manganese mercury thiocyanate (MMTC), is reported. MMTG crystallizes in orthorhombic structure with Pca2₁ space group. The optical band gap energy of the sample is found to be 3.5 eV. The sample is thermally stable up to 145 °C. The grown crystal is characterized by photoluminescence, dielectric, dc conductivity, photoconductivity and SEM studies. From the photoluminescence study, the suitability of the material for blue and green light generation is confirmed. The electric and dielectric response of the grown crystal is studied as a function of temperature and the results are discussed. The dc activation energy of the sample is found to be 0.048 eV.     

Growth and characterization of organic nonlinear optical material: 5-Nitroindole (5NI) for optical applications

Single crystals of organic nonlinear optical material 5-Nitroindole (5NI) has been grown by slow cooling solution growth technique using methanol as a solvent. The grown crystal was subjected to single crystal X-ray diffraction technique to determine the lattice parameters. Fourier transform infrared spectrum (FTIR) was recorded to identify the presence of functional groups. The optical properties such as the optical band gap, extinction coefficient (k), refractive index (n) and optical conductivity (σ) were calculated. The optical band gap of 5NI is 2.33 eV. The melting point and thermal stability of the crystal was analyzed from TG/DTA studies. Dielectric studies were carried out at different temperatures and frequencies.     

Growth,linear and nonlinear optical studies on guanidinium 4-nitrobenzoate (GuNB): An organic NLO material

Single crystals of guanidinium 4-nitrobenzoate (GuNB) were grown using solvent evaporation technique by mixing aqueous solutions of guanidine carbonate and 4-nitrobenzoic acid at ambient temperature. X-ray diffraction analysis characterized the unit cell parameters of the grown crystal and the crystal belongs to monoclinic system. The optical properties of the grown crystal have been studied by means of transmission measurements in the wavelength region between 200 and 1200 nm. The optical constants such as refractive index (n) and extinction coefficient (k) have been determined from the transmittance data. The optical band gap (E_g), the real and imaginary parts of the dielectric constant of the grown crystal was determined. Second harmonic generation (SHG) efficiency of the grown crystal has been studied using Nd:YAG laser and was measured as 3.2 times that of KDP. The low dielectric constant suggests the suitability of this compound material for NLO applications.     

Studies on the structural,optical, dielectric and mechanical properties of non-linear optical manganese mercury Tetrathiocyanate glycol mono methyl ether (MMTG) single crystal

Non-linear optical manganese mercury teterathiocyanate glycol monomethyl ether [MnHg(SCN)₄(C₃H₈O₂)] compound was synthesized and single crystals were grown from water-glycol monomethyl ether (1:1) mixed solvent by slow cooling method. Structure and crystallinity of the grown crystal were confirmed by both single crystal and powder X-ray diffraction analysis. Presence of functional groups and coordination of glycol monomethyl ether and thiocyanate in MMTG were confirmed by FT-IR analysis. Optical transmittance and second harmonic generation of the grown crystal were studied by UV–Vis spectrum and Kurtz powder technique. A dielectric study was performed on the MMTG single crystal to study the power dissipation of the material in the presence of alternating electric field. Mechanical behaviour was analysed using Vicker’s microhardness test. Optical surface damage measurement was carried out to confirm the suitability of MMTG crystal for NLO applications.     

Growth,structure and optical properties of an efficient NLO crystal-aqua maleatocopper(II)

A promising non-linear optical (NLO) crystal, aqua maleatocopper(II) (CuC₄H₂O₄·H₂O), was grown at room temperature by the controlled ionic diffusion technique. Fourier transform infrared spectrum could identify the various functional groups in the crystal. Structural analysis using single crystal XRD revealed that the compound crystallizes in the monoclinic system with space group P2₁ and unit cell parameters a = 7.7277(5) Å, b = 5.2967(3) Å, c = 7.7179(4) Å, α = γ = 109.170(5)°, β = 111.995(2)°. The thermal stability and decomposition pattern of the material were explored using thermogravimetry (TG) and differential thermal analysis (DTA). The optical band gap energy of the material was estimated as 2.2 eV from the diffuse reflectance spectroscopy. The Kurtz and Perry powder technique established the crystal to be an efficient non-linear optical (NLO) material.     

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.     

Synthesis,growth and physicochemical properties of an organometallic nonlinear optical crystal: Mercury cadmium chloride thiocyanate

SCN⁻ ligand based organometallic non-linear optical mercury cadmium chloride thiocyanate (MCCTC) crystals are grown from water plus methanol mixed solvent by slow evaporation technique. The grown crystals are confirmed by single crystal X-ray diffraction analysis. MCCTC exhibits a SHG efficiency which is nearly 17 times more than that of KDP. The dielectric constant, dielectric loss and ac conductivity measurements of the sample have been carried out for different frequencies (100 Hz to 5 MHz) and, temperatures (308–388 K) and the results are discussed. Photoconductivity study confirms that the title compound possesses negative photoconducting nature. The surface morphology of MCCTC was also investigated.     

Third order nonlinear optical properties of potassium dichromate single crystals by Z-scan technique

Single crystal of potassium dichromate (KDC) has been grown from aqueous solution by slow evaporation technique. The lattice parameters of the grown crystal were determined by X-ray diffraction analysis. The optical absorption studies reveal that the crystal has UV cut-off wavelength around 240 nm. Thermo gravimetric and differential thermal (TGA/DTA) studies revealed that the crystal thermally stable up to 397.1 °C. The mechanical strength of the grown crystal was carried out by Vickers micro hardness test. The crystal perfection was confirmed by etching studies. Third order nonlinear optical studies was performed using by single beam Z-scan technique using continuous Nd:YAG laser. Closed aperture Z-scan studies reveal the negative nonlinearity in the crystals and open aperture Z-scan reveals the saturation absorption. Also various parameters such as nonlinear refractive index n₂, absorption co-efficient β and nonlinear optical susceptibility χ⁽³⁾ were calculated for the grown crystal.     

Growth and characterization of L-histidinium fumarate fumaric acid monohydrate single crystal: A promising second and third order nonlinear optical material

L-histidinium Fumarate Fumaric acid Monohydrate (LHFFAM), an organic nonlinear optical single crystal[C₁₄H₁₉N₃O₁₁], has been synthesized and grown using aqueous solution by slow evaporation technique at room temperature. Crystal structure details were obtained from single crystal XRD. The coordination of functional groups was identified in the grown crystal by FTIR analysis. The UV-absorption studies evince the transparent nature of the crystal is in the visible region and the optical band gap energy E_g was evaluated. The TG/DSC analyses confirm the thermal stability for the as-grown crystal. The Vickers microhardness test was carried out on the grown crystals and there by Vickers hardness number (H_v), work hardening coefficient (n), yield strength (σ_y), stiffness constant C₁₁ were evaluated. The dielectric behaviour of LHFFAM has been determined in the frequency range 50 Hz to 5 MHz at various temperatures. Kurtz-Perry and Z-scan techniques were performed for the acentric crystal LHFFAM which highlighted good nonlinear response and hence proves it appropriate for frequency conversion process and photonic device fabrications.     

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.     

Orientational disorder and geometrical isomeric effect on nonlinear optical properties of poly bis(glycine)cadmium chloride

Poly bis(glycine)cadmium chloride (BGCC) crystals of both undoped and doped with thiourea (Tu) were grown from saturated solutions by a slow evaporation technique. The geometrical isomerism of the octahedral BGCC molecule is investigated using single crystal XRD, powder XRD and FT-IR. The significant difference between the two isomers namely facial (fac) and meridional (mer), is explained in terms of the different point group symmetries of C₃ and C₁, respectively. The loss of point group symmetry from C₃ to C₁ is attributed for the observed powder second-harmonic generation (SHG). Semi-empirical calculations from the optimized geometrical parameters also supported non-linear optical properties of the material.     

Refractive index, birefringence, third-order non-linearity and piezoelectric resonance studies of L-lysine monohydrochloride dihydrate single crystals

The principal refractive indices of L-lysine monohydrochloride dihydrate (L-LMHCl) single crystal for different wavelengths were measured by minimum deviation method at room temperature. The experimental values of refractive indices fit well with the theoretical Cauchy's equations. The birefringence and the crossing angle between the optical axes were calculated. The parameters of Sellmeier's single term dispersion equation were determined by least square method. A simple interferometric technique was used to observe the interference patterns along the optic plane and to qualitatively analyze the optical homogeneity of the grown crystal. The nonlinear refractive index (n₂) and nonlinear absorption coefficient (β) were also determined using Z-scan technique. The piezoelectric resonance in dielectric dispersions was observed at room temperature.     

Growth, Characterization and Theoretical Study of a Novel Organometallic Nonlinear Optical Crystal: CdHg(SCN)4(C2H5NO)2

A novel potentially useful second harmonic generation (SHG) organometallic nonlinear optical (NLO) crystal: cadmium mercury thiocyanate bis(N-methylformamide), CdHg(SCN)₄(C₂H₅NO)₂ (CMTN), has been prepared, and large high-optical-quality single crystals with dimensions up to 30 ×27×9 mm³ have been grown by the temperature-lowering method. Its structural, physicochemical and optical properties are characterized by elemental analyses, X-ray powder diffraction, Fourier transform infrared and Raman spectroscopy, thermal analysis, powder SHG measurements and UV/Vis/NIR transmission. The specific heat has been determined to be 515.5 J?mol^?1?K^?1 at 300 K. CMTN possesses good physicochemical stability up to 128.5^°C, exhibits powder SHG efficiencies 0.8 times that of urea and its UV transparency cutoff is 358 nm. By the use of the DFT/B3LYP/6-31G(d) method, the microscopic second order NLO behavior of CMTN has been investigated by computing the first-order hyperpolarizability together with that of CdHg(SCN)₄ (CMTC) and CdHg(SCN)₄(C₃H₈O₂) (CMTG) crystals. The results have been explained based on their crystal structures.     

A new metal-organic nonlinear optical material: L-Asparagine Indium chloride (LAIn) for photonics application

Single crystal of l-Asparagine Indium chloride (LAIn), a new semi-organic crystal was grown by slow evaporation method with deionized water as solvent at ambient condition. The crystal structure of LAIn has been determined by single crystal X-ray diffraction and the result shows that the crystal belongs to the orthorhombic system with P2₁2₁2₁ space group. The crystalline nature of grown crystal was analyzed by powder X-ray diffraction analysis. Optical parameters, such as absorbance, transmittance and optical band gap energy were analyzed using UV–Vis NIR transmittance data at the range of 190–800?nm. The ultraviolet (UV) emission nature of the sample was established from the sharp emission peaks in photoluminescence (PL) spectrum. The photo conductivity test exhibits that the grown crystal has positive photo conductive nature. The induced surface laser damage threshold (LDT) for the grown crystal was measured using Nd:YAG laser. The nonlinear optical efficiency of the LAIn crystal was studied using modified Kurtz-Perry powder technique. The hardness, Meyer index, yield strength and elastic stiffness constant were calculated for the grown crystal using Vickers microhardness tester. The variation of dielectric constant and dielectric loss of the grown crystals as a function of frequency has been investigated at different temperatures. The melting point and thermal stability of the LAIn single crystal have been studied by thermo gravimetric analysis and differential thermal analysis (TG/DTA).     

Enhanced properties of cadmium mercury thiocyanate bis(N-methyl formamide): A promising non-linear optical crystal

The present study deals with the synthesis and characterization of cadmium mercury thiocyanate bis(N-methyl formamide) or CMTN crystals where they were grown in two critical steps. In the first step, cadmium mercury thiocyanate (CMTC) single crystals were grown by intriguing cadmium chloride, mercuric chloride, and ammonium thiocyanate in 1:1:4 ratio and mixed with solvent by a slow solvent evaporation technique. The second step involves the reaction between CMTC and N-methyl formamide (NMF) in a 1:2 ratio leading to the formation of CMTN crystals. The growth parameters of CMTN grown crystals were optimized at different pHs (1- 5) and the solubility curve has also been reported. On characterization, the orthorhombic crystallinity having Pna2₁ space group of as-grown CMTN crystals has been revealed by single X-ray diffraction analysis (XRD) and the lattice cell parameters are found to be a = 15.195 Å, b =  7.722Å, c = 16.162 Å, and α = β = γ = 90°. Single the phase crystallinity of CMTN is observed by powder XRD pattern and the increase in the intensity of index peaks shows that there exists good coordination between the CMTC and NMF compounds. The FTIR analysis supported the presence of surface ligands groups of thiocyanate, while the Raman spectroscopy confirmed for the coordination of thiocyanate ions in the CMTN compound and thus both established for the metal-ligand bonding. The UV-vis spectroscopy showed the optical transparency of CMTN to have the cutoff wavelength at 335 nm and the Kurtz powder method for studying the second harmonic generation (SHG) output power is 5 times higher than the reference. Further increase of dielectric constant and dielectric loss with respect to the changes in frequency makes it a suitable material for the construction of photonic and non-linear optical (NLO) devices.     

The growth,thermal and nonlinear optical properties of single-crystal GdAl3(BO3)4

The nonlinear optical single-crystals GdAl₃(BO₃)₄ (GAB), space group R32, were grown by the top-seed solution growth (TSSG) method. The thermal properties and the nonlinear optical characteristics have been investigated. The two principal coefficients of thermal expansion along (100) and (001) were measured to be 5.30 × 10⁻⁶, 1.88 × 10⁻⁵ K⁻¹. The transmission spectrum was measured and the second-harmonic generation (SHG) was presented. By way of our designed cross superimposed laser crystal multiplier, the frequency doubling laser at wavelength 457.5 nm was measured to be 18.2 mW and the facular properties indicated the multiplier contributed to the improvement of the frequency doubling conversion efficiency.     

Surface studies on bimetallic thiocyanate ligand based single crystals of MnHg(SCN)4, CdHg(SCN)4 and ZnCd(SCN)4

Bimetallic SCN ligand based single crystals of manganese mercury thiocyanate (MMTC), cadmium mercury thiocyanate (CMTC) and zinc cadmium thiocyanate (ZCTC) are grown by slow solvent evaporation technique. The growth mechanism and surface features are investigated by optical microscopic techniques such as scanning electron microscopy (SEM) and atomic force microscopy (AFM). The laser induced surface damage measurements were carried out using a Q-switched Nd:YAG laser at 1064 nm with laser beam of 1.0 Hz and pulse duration 25 ps. The laser damage threshold values of MMTC, CMTC and ZCTC are found to be 15.9, 22.9 and 19.7 GW/cm², respectively. The SEM analysis of MMTC reveals the formation of elongated dendrite growth pattern caused by the fluctuations of Mn and Hg metal ligands when thiocyanate (SCN) bridges them. The etching study indicates the occurrence of different types of etch pit patterns like terraced triangles, pillars, pyramids and rods. The AFM images confirm the formation of three major hillocks with cavities in MMTC. The measured roughness values for CMTC crystal are very much lower than that of MMTC.     

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.