Semiorganic Nonlinear Optical Material Research Articles

Investigating the structural and mechanical behavioral properties of semi-organic nonlinear optical single crystal: L-arginine tetrafluoroborate

A semi-organic nonlinear optical material L-Arginine tetrafluoroborate (LAFB) was synthesized as single crystal using Slow Evaporation Technique. Various properties of this material were analyzed to make it suitable for NLO applications. The structural behavior of the material was determined by single crystal XRD and found that the crystal has orthorhombic structure and was synthesized with P212121 space group. The High-Resolution X-Ray Diffraction (HRXRD) study was conducted to determine the change in the lattice parameters resulting from strain, defects or by other means in LAFB material. The diffraction curve analysis show that the grown crystal consisted of interstitial type point defect. The Shock Damage Threshold (SDT) measures the stability of the compound against shock, the analysis exhibits that under Mach number 2.2 up to 10th shock no significant cracks were observed in the crystal but damage area of the crystal was increased. The mechanical behavior of the sample against highly intense laser was analyzed through Laser Damage Threshold (LDT). The calculated value of LDT was to be 0.75[Formula: see text]GW/cm2 for 1 pulse per second whereas it decreased to 0.57[Formula: see text]GW/cm2 for 10 pulse per second. To explore the mechanical properties of the material, Nano indentation was carried out, by which the values of H[Formula: see text][Formula: see text]MPa and E[Formula: see text][Formula: see text]GPa were obtained.

A self-defocusing third-order nonlinear optical material l-Alanine Barium Chloride single crystal used in optoelectronic device applications

Slow evaporation method was used to produce a single crystal of l-Alanine Barium Chloride (LABC), a semi-organic nonlinear optical material. The grown crystal non-centrosymmetric nature can be seen in the results of a single-crystal XRD analysis. Using Fourier transform infrared spectral analysis, the unique functional groups and chemical makeup of LABC compounds were found. The lower cut-off wavelength is observed down to 253 nm and direct optical band gap was calculated as 4.54 eV. A photoluminescence experiment found the LABC crystal emission spectrum. EDAX spectrum analysis revealed the crystal metal ion (Ba) existence. The Z-scan method with an Nd: YAG laser at 532 nm was used to analyse the third-order optical nonlinearity characteristics of LABC in detail. A Vicker's microhardness tester was used to measure the microhardness of the LABC crystal under the same load.

Dielectric properties and second harmonic generation of glycine doped bisthiourea cobalt and nickel malonates as new semiorganic non-linear optical materials

A new class of materials viz. glycine doped bisthiourea cobalt malonate (BTCoM-Gly) and glycine doped bisthiourea nickel malonate (BTNi-Gly) have been synthesized by simple solvent free mechanochemical method. The chemical composition was evaluated by chemical and elemental analysis. Incorporation of glycine in compound was confirmed by EDAX and FTIR techniques. FTIR studies also ascertained the coordination of metal ion to thiourea through sulphur atom. SEM images showed that both the compounds have linear array type morphology. Thermal stability of material has been investigated by TG and DTA showing BTNiM-Gly is more stable (74.85 °C). Transmittance spectra reveals that lower cut-off wavelength of BTCoM-Gly is 296 nm and that of BTNiM-Gly, 298 nm, indicating to have a good optical transmission in entire visible region, which is desired characteristic for non-linear optical (NLO) materials. The dielectric measurements of the compounds were accomplished with varying frequencies at ambient temperature. Dielectric constant and dielectric loss values of both compounds were decreased with the increase in frequency which ultimately enhanced the second harmonic generation (SHG) efficiency. The SHG conversion efficiency was measured by modified Kurtz-Perry powder technique and found to be 0.751 nm and 0.610 nm times higher than standard KDP for BTCoM-Gly and BTNiM-Gly respectively. The higher SHG conversion efficiency of the compounds illustrates non-linear optical nature of materials and their suitability for NLO applications.

The impact of lithium heavy ions induced amorphization on the structural and NLO properties of multiwalled carbon nanotubes (MWCNTs) doped tetrafluoro phthalate (TFP) crystal

The MWCNTs doped Tetrafluoro Phthalate crystal (TFP), a semi-organic nonlinear optical material was amalgamated, and single crystals were filled out from the water solution. The grown compound formed into a monoclinic crystal structure with the space group of P21. The unit cell parameters were identified and verified with single-crystal XRD studies. The grown crystal was irradiated by the Li3+ heavy ion beam. The Li3+ irradiation on the crystal starts the evolution of healthy surface H peaks in MWCNTs injected TFP crystal. As a result of beam interaction, the morphology of the crystal was modified. Hence after irradiation, the change in structural, functional, optical, and NLO properties of the doped crystal was analyzed with the characterization studies such as powder XRD, FT-IR, UV–Visible, and SHG analysis respectively. The results after irradiation were compared with the results before irradiation.

Growth and characterization of semi-organic non-linear optical L-threonine doped ZTS crystal

Single crystals of L-threonine doped zinc tris thiourea sulphate, a semi-organic nonlinear optical material was successfully grown by the slow evaporation technique. The crystalline nature and structural parameters of L-threonine doped ZTS crystal have been confirmed by single-crystal XRD analysis. The substantial enhancement in mechanical strength of ZTS crystal due to the incorporation of L-threonine has been carried out with Vicker’s microhardness analysis. The second harmonic generation (SHG) efficiency of the crystal has been confirmed by standard Kurtz-Perry powder analysis. Further, the electrical properties, such as plasma energy, Penn energy, Fermi energy, and electronic polarizability of the grown crystals have been theoretically calculated and compared with the classical Clausius–Mosotti equation.

Spectroscopic evaluation of Alanine Adipate nonlinear optical materials growth dynamics: Mechanical and thermal optimization

Semi organic nonlinear optical material of alanine adipate (AA) was grown by slow evaporation solution method using ethanol as a solvent. The synthesized material was subjected to various characterization techniques. The single crystal X-ray diffraction analysis was carried out and their lattice parameters were determined. The presence of various functional groups of AA and their vibrational modes were identified from Fourier transform infrared (FTIR). FT-Raman spectral study has been performed to confirm the functional groups. The optical transmittance of the material was identified from UV–VIS-NIR studies. and the optical energy gap of AA is determined as 4. 851 eV. Fluorescence spectrum was also carried out using spectrofluorometer and the emission peak was observed at 454. 48 nm confirming the blue emission of the prepared crystals. The mechanical property of the grown crystal was studied using Vicker's micro hardness tester and the mechanical parameter values are calculated. Mechanical measurement indicates that the grown crystal belongs to softer category. Thermal properties of AA were evaluated with thermogravimetric analysis, differential thermal analysis and differential scanning calorimetry. The second harmonic generation efficiency was found to be 1.06 higher than that of standard potassium dihydrogen orthophosphate (KDP).

Structural, conductivity and DFT studies of L-Histidinium phosphite – Ferroelectric phosphite single crystal

L-Histidinium phosphite [C6N3O2H10]+. [HPO3H]- abbreviated as HPI, is a semi-organic nonlinear optical material. In the present work HPI crystals were grown from the aqueous solution of HPI by slow evaporation technique. Single crystal XRD (SXRD) reveals that the resulting crystals predominantly exhibit monoclinic structure with space group P21. Sharp and well-defined peaks of the powder XRD pattern attested the good crystallinity of HPI and the pattern is in agreement with SXRD results. The different modes of vibrations of molecular groups and functional groups present in the HPI crystal was investigated using IR spectra. It is evident from the UV–Vis spectrum that HPI is transparent in the examined frequency regime. The TG-DTA studies ascertain that the crystal is thermal stable till 230 ​°C. A.C. and D.C. conduction mechanism in the grown crystals were studied from 119 ​K to 380 ​K for 1 ​kHz to 1 ​MHz frequency range. The pattern suggests that there is ferroelectric to paraelectric transition at 270 ​K. This transition temperature is higher than the glycine phosphite crystals. Detailed insight about the conduction mechanism in HPI crystals was analyzed by complex impedance and modulus studies. Density functional theory was applied to know in detail about the structure and non-linear optical characteristics of the grown crystal and it attested that HPI is NLO active at room temperature.

Te(CS(NH2)2)4SO4·2H2O: A Three-in-One Semiorganic Nonlinear Optical Crystal with an Unusual Quadrilateral (TeS4)6– Chromophore

The first tellurium(II) thiourea sulfate semiorganic nonlinear optical (NLO) material, Te(CS(NH2)2)4SO4·2H2O, was successfully obtained using the slow evaporation technique. The structure of this metal-free crystal featured three types of NLO-active units, namely CS(NH2)2, (SO4)2–, and (TeS4)6–, which synergistically contributed to its moderate second harmonic generation response (2.4 × KDP@1064 nm) and large birefringence (0.210@546.1 nm). Remarkably, this is the first example in which the quadrangular (TeS4)6– groups significantly contributed to the SHG effect and birefringence, and the first principles calculations revealed its special mechanism of NLO activity. These findings highlighted the exploration of semiorganic NLO materials and provide new opportunities for the discovery of new NLO crystals.

Synthesis, crystal growth and characterization of semi-organic NLO materials: L-valine copper chloride as optoelectronic sensor

Good quality single crystals of L-valine copper chloride were grown by slow evaporation solution growth technique with different concentrations (0.25, 0.50, 0.75 and 1.0 mol). Single-crystal X-ray diffraction technique reveals that the grown single crystals were crystallized in the monoclinic structure. Kurtz powder technique was used to test the nonlinear optical (NLO) activity of the samples which are semi-organic in nature. The optical properties of the crystals were investigated by UV–Vis absorption spectroscopy. The results revealed that the wider bandgap and large transparency in the visible region along with higher polarizability of the grown crystals are highly useful in optoelectronic sensors. The high transmittance and the low absorbance and reflectance of the material over a wide range of wavelength suggest that the material can be used as anti-reflection coating in solar thermal devices and nonlinear applications.

Crystal growth, structural, nonlinear, optical and theoretical investigations of L-histidinium trichloroacetate single crystals

The semi-organic nonlinear optical materials, L-histidinium trichloroacetate (LHTCA) single crystals are prepared by using solvent evaporation method. The prepared LHTCA crystal structures were analysed by X-ray examination. The UV–visible optical transparency of the grown crystal was accessed in the range of 200–1200 nm and it shows the LHTCA has high optical transparency in the UV region. From the Kurtz and Perry powder SHG method shows the NLO assets of the crystal, also laser damage threshold studies are analysed, and the grown crystals show the suitability for NLO applications. The quantum chemical computations have been carried out through DFT. It recognizes the geometrical and electronic structural properties, such as FMO, MEP and hyperpolarizability of the crystal and it suggests various intermolecular interactions especially hydrogen bonding. The various functional groups were analysed using FTIR and Raman spectra and the vibrational frequencies from experimental and theoretical values were evaluated. From the above analyses, the solution grown LHTCA crystal is suitable for NLO applications.

Linear and nonlinear optical properties of l-proline potassium bromide

L- Proline potassium bromide (LPPB), a semi organic nonlinear optical material was grown by slow evaporation method. The optical nature of the grown single crystal was investigated through UV–Vis-NIR analysis and shows that the LPPB crystal has very low absorption in entire characterized wavelength range 200–800 nm. The optical band gap was calculated and found to be ∼5.1 eV. The optical band gap (Eg), the real and imaginary parts of the dielectric constant of the grown crystal was determined. Furthermore, linear optical parameters such as Extinction coefficient (K), Reflectance (R), Refractive index (n), Electrical susceptibility (χc), Complex dielectric constant and Optical conductivity are calculated and its variation with incident photon energy is analysed. Second harmonic generation (SHG) efficiency of the grown crystal has been studied using Nd:YAG laser.

Structural, optical, spectroscopic and thermal investigations on novel semi-organic nonlinear optical material - Potassium boro-oxalate single crystal

In this work, a new semi-organic nonlinear optical material of Potassium boro-oxalate (KBO) is synthesized and subsequently a single crystal of size 7 × 5 × 3 mm3 is grown from the aqueous solution by slow evaporation technique at ambient temperature. Characterizations are performed on the single crystals to study the structural, thermal, linear and nonlinear optical (NLO) properties of the as-grown single crystals. Crystal and molecular structure of KBO are solved by direct method and further refinement is performed by full-matrix least-square method employing SHELXL-2014 software. Single crystal X-ray diffraction (SXRD) studies revealed that the grown crystal associates to triclinic crystal family with non-centrosymmetric space group P1. The Fourier transform infrared (FTIR) spectrum reflected the presence of various functional groups in the title compound. The Ultraviolet-visible-near infrared (UV-VIS-NIR) absorption and transmission spectrum are recorded to capture the suitability of the grown single crystals for various optical and NLO applications. The thermal decomposition and thermal stability of the KBO single crystals up to 187°C are investigated by TGA-DTG (Thermo Gravimetric - Differential Thermo Gravimetric), TGA-DTA (Thermo Gravimetric-Differential Thermal analysis) and DSC (Differential Scanning Calorimetry) curves. Kurtz-Perry powder technique is employed to explore the SHG (Second Harmonic Generation) efficiency of the KBO single crystals. SHG efficiency of KBO is found to be comparable to KDP.

Growth, structural, optical and thermal studies of semi-organic nonlinear optical potassium hydrogen oxalate single crystal

Single crystals of semi-organic nonlinear optical material potassium hydrogen oxalate are grown from the aqueous solutions of potassium hydroxide and oxalic acid in 1:1 stoichiometric ratio by slow evaporation solution growth method at room temperature. The grown crystals are subjected to various characterization techniques to explore their structural explication, thermal, linear and nonlinear optical perspectives for optoelectronic device applications. The monoclinic structure with non-centrosymmetric space group P21/c of the titular compound has been confirmed by single-crystal X-ray diffraction. The crystal packing is ruled by extensive networks of hydrogen bonds revealed by the detailed study of the refinement of the crystal structure. Optical transparency of the crystal in the entire visible region has been confirmed by ultraviolet–visible-near infrared (UV–Vis-NIR) analysis. The robust thermal stability of the grown crystal is ensured by thermogravimetric–differential thermal analysis. The presence of expected functional groups in the grown crystal has been confirmed by Fourier transform infrared spectroscopic studies. Second-harmonic generation efficiency has been calculated by Kurtz powder method.

Studies on Optical Constants and Solid State Parameters of a Semi-organic Nonlinear Optical Material L-Methioninium Nitrate for Optoelectronic Device Fabrication

Semi-organic nonlinear optical material L-methioninium nitrate have been synthesized by the slow evaporation technique at room temperature. The synthesized crystal structure lattice parameters are found to be a = 10.68 (2) Ǻ, b = 5.47 (2) Ǻ, c = 16.725.47 (2) Ǻ; α = γ = 90º, β = 100.7º by single crystal X-ray diffractometer. The grown crystal belongs to a monoclinic structure and non-centrosymmetric space group P21. Optical properties were determined from optical absorption studies to compute the absorption range, band gap, refractive index and electrical susceptibility of L-methioninium nitrate. Dielectric parameters of the sample carried out at different temperature in the frequency range from 100 Hz to 5 MHz. The solid parameters such as plasma energy, Penn gap, Fermi energy and polarizability of L-methioninium nitrate have been determined using dielectric studies. The second harmonic generation efficiency of the grown crystal has been confirmed by Kurtz and Perry technique. These preliminary investigations suggest that the present compound L-methioninium nitrate can serve as a potential material for optoelectronic device fabrication.

A methodical approach to physico-chemical analysis of bis (potassium hydrogen l-malate).malic acid – A semi-organic single crystal for nonlinear optical applications

Bis (potassium hydrogen l-malate).malic acid (PMM), a semi-organic nonlinear optical material was synthesized and crystals were grown from aqueous solution by slow evaporation solution growth technique (SEST). The lattice parameters and space group were confirmed by single crystal X-ray diffraction study. Powder X-ray diffraction study reveals the crystalline nature of the title material. Crystalline perfection of grown crystal was analyzed using high resolution X-ray diffraction rocking curve technique. Fourier transform infrared spectral analysis revealed the vibrational behaviour of chemical bonds of various functional groups. Surface feature of the grown crystal was analyzed through atomic force microscopy. Optical transmittance study shows that the grown crystal has good transparency in the entire visible region. The luminescent property of the title crystal was investigated through photoluminescence spectroscopy. Second harmonic generation efficiency was found using Kurtz-Perry powder technique. The laser-induced surface damage threshold value for the grown crystal as measured using a Nd:YAG laser. Thermal analyses reveal that the crystal is stable up to 230 °C. The mechanical strength of the crystal was assessed by Vickers microhardness tester. The dielectric behaviour and its parameters were established through dielectric study. Piezoelectric charge coefficient (d33) of the grown crystal was determined using piezoelectric analysis.

Crystal growth and impact a Bisthiourea on structural, optical, thermal and mechanical behavior of Potassium sulphato oxalate a novel semi organic nonlinear optical material

Crystal growth and impact a Bisthiourea on structural, optical, thermal and mechanical behavior of Potassium sulphato oxalate a novel semi organic nonlinear optical material

Growth, effect of protonation and hydrogen bonding interactions of L-Histidine nitrate monohydrate, a potential semi organic third order nonlinear optical material

Single crystal of l-Histidine Nitrate monohydrate (LHNM) has been grown from aqueous solution by evaporation technique. A comprehensive investigation of the NIR FT-Raman and FT-IR spectra was carried out with the aid of normal coordinate analysis following the scaled quantum mechanical force field methodology supported by the density functional theory (DFT) computations to analyze the effects of intramolecular charge transfer on the geometries and the vibrational modes contributing to the linear electro-optic effect of the organic NLO material. Effect of protonation and hydrogen bonding interactions has been analyzed using structural analysis, natural bond orbital analysis, and spectral analysis. The HOMO-LUMO energy gap value suggests the possibility of charge transfer within the molecule. Hyperconjugative interactions responsible for second hyperpolarizabilities have been described by NBO and AIM analyses. Hirshfeld surface analysis reveals that the van der Waals H⋯H (32.3%) contact plays a significant role in crystal packing and that a variety of NH⋯O intermolecular contacts and hydrogen bonds leads to the formation of intermolecular charge transfer occurring in LHNM. The nonlinear refractive index (n2), nonlinear absorption coefficient (β) and third-order nonlinear susceptibility (χ3) of LHNM have been determined by Z-scan technique, which points to its potential application in the field of optical limiting. The calculated value of laser damage threshold was 2.04 GW/cm2.

Synthesis, crystal structure, optical and third order nonlinear optical properties of phosphoric acid pyridine-1-ium-2-carboxylate

A semi-organic nonlinear optical material phosphoric acid pyridine-1-ium-2-carboxylate (PAPC) crystal has been synthesized and grown. Vibrational spectral analysis and NMR spectral analysis has been carried out. Mechanical studies on the grown crystal has been performed which disclose the material belongs to soft materials category. The thermal behaviour of the grown crystal has been investigated by thermogravimetric and differential thermal analysis. UV–Visible spectral analysis has been carried out which reveals that the grown crystal is transparent in the entire visible region with the lower cut-off wavelength of 298 nm and the derived optical constant attests the suitability of this material for non-linear optical applications. The third order nonlinearity has been studied by z-scan method and the enhanced third-order nonlinearity shows PAPC is a potential material for device applications. Second harmonic generation efficiency has been studied by Kurtz and Perry powder test and is found as 0.14 times greater than the KDP.

Vibrational and Homo-Lumo Analysis of L - Aspararginium Tartrate by Density Functional Theory

L - Aspararginium Tartrate (LAsT), a semi organic nonlinear optical material was synthesized by slow solvent evaporation technique. Fourier transform infrared (FT-IR) spectroscopic studies were performed for identifying different functional groups present in the compound and was compared with the theoretical data obtained from DFT studies. Non-linear optical (NLO) behavior of the LAsT was investigated by the determination of the dipole moment μ and the hyper polarizability β obtained by B3LYP/6-31G (d, p) method. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) with frontier orbital gap were presented.

Structural, Vibrational and Thermal Properties of Semi Organic Nonlinear Optical Glutamic Added Lithium Sulphate Monohydrate Crystal

Glutamic acid lithium sulphate monohydrate crystal is a new semiorganic nonlinear optical material. It was grown from a mixture of aqueous solution of glutamic acid and lithium sulphate monohydrate by slow evaporation technique at room temperature. The powder XRD analysis was carried out to identify the structural parameters of the grown crystals. The presence of functional groups of both reactants was qualitatively analyzed by means of Fourier transform infrared (FT-IR) spectrometer study. In UV-vis study, the existence of wide transparency window and band gap was investigated for optoelectronic device applications. In Kurtz-Perry powder technique, the second harmonic generation (SHG) efficiency of GLSMH crystal is found to be 1.933 times greater than that of KDP crystal.