Semiorganic Nonlinear Optical Crystal 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.

Crystal growth and vibrational spectroscopic studies on the novel NLO active 2-amino-4-methylpyridinium fluoroborate single crystal by experimental and computational technique

A semi-organic non-linear optical (NLO) single crystal of 2-amino-4-methylpyridinum fluoroborate(2AFB) to be synthesized and characterized via single crystal X-ray diffraction technique (SXRD), UV–Vis, FTIR and FT-Raman spectra. The quantum chemical calculations were carried out using density functional method (DFT) with B3LYP/6–31+G(D) basis set. The intermolecular interaction and stability of the title molecule have been obtained by NBO analysis. The molecular electrostatic potential and frontier molecular orbital analysis give a visual representation of charge distribution of the title molecule. The N-H…F interaction within 2AFB molecule was investigated via AIM and RDG analysis. The optical quality and energy band gap of 2AFB single crystal were found out using UV–visible spectral analysis. The emission spectra of the grown 2AFB single crystal has been examined by fluorescence spectral analysis. 2D fingerprint plot confirms the H…F and H…H interactions that exhibit the most significant contribution in crystal packing. The outcome of SXRD, UV-visible, HOMO-LUMO, NLO and Z-scan values were compared with earlier reported compounds and amongst which the analysed compound 2AFB shows good NLO activity. The NLO activity of the title molecule was confirmed theoretically and experimentally by DFT method and Z-scan technique.

Investigation on the growth aspects and properties of rubidium hydrogen succinate hydrate single crystal for NLO applications.

A novel semiorganic nonlinear optical single crystal of rubidium hydrogen succinate hydrate (RbHSH) was grown at room temperature using the slow evaporation solution growth technique (SEST) with water as a solvent for nonlinear optical applications. The grown crystal is a triclinic system with a centrosymmetric space group of P1̄ and the compound is stabilized by intramolecular O-H-O and C-H-O bonding. FTIR spectral studies were used to determine the various functional groups present in the material. The optical transmission spectra of the grown crystal demonstrated that a transparency of 89%, with a low cut off wavelength of 240 nm and an energy band gap of 5.21 eV, which is beneficial to developing advanced photonic and optoelectronic devices in the solar blind UV area. The grown crystal is thermally stable upto 174 °C. The electrical properties of RbHSH crystal exhibit low dielectric loss and a low dielectric constant at high frequencies tends to have good optical characteristics. Mechanical analysis demonstrated that the grown crystal shows the normal indentation size effect (ISE) and falls into the hard material category with n = 1.4. Photoconductivity measurements revealed negative photoconductivity. Photoluminescence studies showed that RbHSH emits blue light with a wavelength of 484 nm. Hirshfeld surface analysis was used to analyze intermolecular interactions in the RbHSH crystal. The grown RbHSH crystal piezoelectric charge coefficient have been calculated (d33 = 13 pC N-1) and it is suitable for piezoelectric device applications. Under continuous-wave laser excitation, the third order nonlinear refractive index (n2), absorption coefficient (β), and susceptibility (χ(3)) of the RbHSH crystal were found to be 1.6639 × 10-12 (cm2 W-1), 1.1739 × 10-5 (cm W-1) and 4.86331 × 10-9 esu, respectively.

Synthesis, structural, spectral and optical analysis of a novel semi-organic nonlinear optical crystal: Bis (4-methylbenzylammonium) hydrogen phosphate monohydrate

Synthesis, structural, spectral and optical analysis of a novel semi-organic nonlinear optical crystal: Bis (4-methylbenzylammonium) hydrogen phosphate monohydrate

Growth and characterization of L - Methionine Barium Bromide (LMBB) semi-organic crystal for optical limiting applications

The semi-organic nonlinear optical single crystal was grown from an aqueous solution by a slow evaporation solution technique (SEST) at room temperature. The characterization of the crystal was made using single crystal x-ray diffraction analysis and it was found to be L-Methionine Barium Bromide (LMBB) crystallized in a monoclinic system with space group C2/c and the cell parameter values are a= 10.74Å, b= 7.39Å, c= 8.69Å, α = γ = 90°, β = 113.53°. The UV-Vis-NIR spectroscopic study revealed that the crystal has good optical transparency and a lower cut-off wavelength was found to be 246 nm and also evaluated linear optical properties such as extinction coefficient and reflectance. The luminescence behavior of LMBB has been analyzed by fluorescence (FL) spectral study. The presence of functional groups in the LMBB is confirmed by FT-IR and FT-Raman vibrational patterns. The hardness (Hv), Meyer’s index (n), elastic stiffness constant (C11), yield strength (σy), knoop hardness (Hk), fracture toughness (Kc), and brittleness index (Bi) were analyzed using Vickers microhardness tester. Dielectric behavior as a function of frequency was examined. The laser-induced damage threshold value was found to be higher than that of KDP. The surface morphology of the as-grown crystal was determined using the SEM technique. Energy dispersive X-ray analysis was used to determine the chemical composition of the LMBB crystal. The nonlinearity coefficient (β) is measured as 1.7 × 10−11 m/W using the open aperture Z-scan technique (Nd: YAG, 532 nm, 9 ns), which results from an effective two-photon absorption phenomenon. The resulting optical limiting behavior has a fluence threshold of 8.26 × 1012 W/m2 making the LMBB a potential candidate for optical limiting devices.

Structure, optical, thermal, SHG & photoluminescence studies of L-Serine cadmium chloride single crystals

Novel semi organic nonlinear optical single crystal of l-Serine Cadmium Chloride monohydrate has been synthesized by conventional slow evaporation method. The single crystal XRD have been employed to describe the crystal structure, space group, bond lengths, bond angles and co ordinates of hydrogen bond. The metal organic complexion between l-Serine and Cadmium chloride is taking place through oxygen atom of l-Serine. The lattice parameters obtained from PXRD technique have been found in good agreement with those obtained from SXRD. Williamson-Hall method has been used to determine the lattice strain of the grown crystal. The investigations of intermolecular interactions in LSCC crystal lattice are carried out by Hirshfeld surface analysis. The FTIR spectrum is utilized to determine the possible functional groups present in the crystal. The investigations on optical qualities of the crystal are carried out by incorporating UV–Visible and photoluminescence spectrum. The behaviour of refractive index below energy gap is carried out by Wemple – DiDomenico single oscillator model analysis. The thermal stability along with the decomposition temperature of the synthesized crystal is ascertained by thermogravimetric analysis. The kinetic and thermodynamic parameters of LSCC crystal have been calculated from C-R plot. Photoluminescence spectrum of the synthesized crystal was recorded by using an excitation wavelength of 320 nm. It suggested the suitability of the synthesized material as green laser diode. The SHG efficiency of LSCC crystal is clarified through the Kurtz-Perry technique.

Elucidation of optical, thermal, morphological and antimicrobial efficacy of L-tryptophan hydrochloride single crystals

An efficient semi-organic nonlinear optical single crystal of L-tryptophan hydrochloride (LTHC) of molecular formula C11H13N2O2Cl has been synthesized and its elemental composition was confirmed by EDS analysis. The crystallographic system and lattice parameters were found by single crystal XRD analysis which indicates the synthesized crystal corresponds to monoclinic system of space group P21 and its crystalline nature was identified by powder XRD analysis. The typical characteristic vibrational modes of the grown LTHC crystal were identified by FTIR spectral analysis. The grown crystal’s optical properties were analyzed by UV-Vis-NIR and Photoluminescence analyses. The wavelength dependent optical constants were also measured, and its refractive index at 532 nm was found to be 1.67. The grown crystal’s mechanical stability was determined with the help of Vicker’s hardness tester, which revealed that LTHC has soft material behaviour. TG-DTA-DSC tests were used to examine the thermal behaviour such as decomposition phenomena, phase transition, and melting point of the grown crystal, which revealed that it has high thermal stability up to 205 degrees. The dielectric behaviour, a.c. conductivity of LTHC crystal was studied by dielectric studies and its nonlinear efficiency was analyzed by Kurtz-Perry technique. The crystalline morphology of LTHC was examined by TEM and SEM analyses. Its optical damage property was analyzed by laser damage threshold analysis. The antimicrobial property of LTHC was also scrutinized against bacterial as well as fungal strains by Agar disk diffusion method. Finally, all these findings recommended that LTHC crystals could be useful in biomedical and nonlinear optics applications.

Growth and characterization of a semi-organic nonlinear optical single crystal: sarcosine barium chloride

Growth and characterization of a semi-organic nonlinear optical single crystal: sarcosine barium chloride

Crystal growth, structural, optical, thermal, dielectric, mechanical and NLO studies of L-tyrosine zinc carbonate single crystals

L-Tyrosine Zinc Carbonate (LTZC) a semi-organic nonlinear optical single crystal has been grown by slow evaporation solution technique. The lattice parameters of the grown crystals are found out by single crystals X- ray diffraction technique. The modes of vibrations of different functional groups present were identified by using Fourier Transform Infrared (FTIR) spectroscopic analysis. The UV–Visible optical absorption spectrum shows that the crystal has high transmission with lowest UV cutoff wavelength of 230 nm. The calculated band gap of LTZC crystal was found to be 5.13 eV. Dielectric constant and dielectric loss for various frequencies and temperatures were performed on LTZC crystal and the results were discussed in detail. The frequency dependence of ac conductivity for different temperatures was studied. The photoconductivity studies confirm that the crystal LTZC has negative photo conducting nature. The mechanical and thermal properties of the grown crystals have been studied. Surface morphological changes are observed in the grown LTZC crystal. The Non-linear optical second harmonic generation conversion efficiency of LTZC was determined using Q-switched Nd: YAG laser. The second harmonic generation conversion efficiency of LTZC is 2.12 times that of KDP.

Growth and characterization of thiosemicarbazide barium chloride [Ba(NH2NHCSNH2)Cl2]crystals: Novel potential NLO material

Semiorganic Nonlinear optical Crystals of Thiosemicarbazide Barium Chloride was grown by slow evaporation solution growth technique. The unit cell parameters were estimated by subjecting the crystal to single crystal X- ray diffraction. The Grown crystals were subjected to powder X- ray diffraction for analyzing the crystalline nature of the sample. The transmission spectrum of grown crystal was recorded by UV–Vis–NIR Spectrometer in the range between 200 nm and 800 nm which addressed the high percentage of transmission of the sample in the entire visible region. The presence of functional groups was studied by FT- IR analysis. Thermal Stability and melting temperature of the grown crystal was identified from TG –DTA analysis Dielectric behaviour of the grown crystal was studied and the results are discussed in detail. Second harmonic generation (SHG) conversion efficiency has been estimated as 1.21 times greater than potassium dihydrogen phosphate crystal.

Synthesis, growth, optical studies and antimicrobial activity of a new semiorganic nonlinear optical crystal L-valine bariumchloride

A semi organic nonlinear optical single crystal of L-valine barium chloride was grown from an aqueous solution by the method of slow evaporation technique at room temperature. The grown crystal was characterized by powder X- ray diffraction confirms the presence of chloride. Single crystal X-ray diffraction studies confirm that the grown crystal belongs to the monoclinic system. The functional groups presented in the crystal were confirmed by FT-IR technique. The UV–vis-NIR spectrum indicates that the crystal has very good absorption in the entire visible and NIR region spectrum indicating the stability of the materials for NLO applications. The grown crystal was subjected to EDX to confirm the presence of the elements. The crystal was stable up to 260⁰C and fully decomposed at 907⁰C. Hence the thermal behaviour and the stability of crystal were studied by TGA, DTA and DSC. The second harmonic generation SHG efficiency was studied by Kurtz-Perry powder technique. The minimum inhibitory concentration (MIC) of the crystal for antibacterial activity was studied using micro dilution bioassay as described by ELOFF.

Comments on the paper “Growth, structural, optical and thermal studies of semi-organic nonlinear optical potassium hydrogen oxalate single crystal”

The authors of the title paper (Appl Phys A 126:394, 2020) report to have grown a new nonlinear optical potassium hydrogen oxalate (KHO) single crystal, which exhibits second harmonic generation response. In this comment, it is shown that these claims are erroneous since KHO is a well-known solid which crystallizes in the centrosymmetric P21/c space group.

Structural, optical, mechanical, and electrical measurements on single crystals of L-Alanine sodium sulphate

Optically High quality transparent semi-organic nonlinear optical bulk single crystal of L-Alanine Sodium Sulphate (LASS) has been grown from the aqueous solution by slow solvent evaporation technique. The grown crystal structure and lattice parameters were determined by both Powder and Single-crystal X-ray diffraction techniques. The various functional groups present in the grown crystals were analysed by FTIR technique.UV–visible transmittance spectrum was recorded by the study the optical transparency of grown crystal. The grown crystals were subjected to thermogravimetric and differential thermal analysis (TG/DTA) used to find the thermal stability of the crystal. The second harmonic generation (SHG) efficiency of LASS crystal was determined by using Kurtz and Perry powder technique. The mechanical property of the grown crystals has been studied using Vicker’s microhardness tester. Dielectric studies are also carried out for the grown samples of different temperatures.

Synthesis and Characterization of NLO Material L-Valine L-Valinium Perchlorate Monohydrate for Photonics Applications

L-valine L-valinium perchlorate monohydrate single crystal has been synthesized by slow evaporation technique at room temperature. The crystal structure and space group of the crystal were confirmed by single crystal X-ray diffractometer. Optical behavior of the crystal was analyzed by using UV-visible spectrophotometer. Thermal stability was discussed by using thermo gravimetric analysis. Mechanical strength of the grown crystal was studied using Vickers microhardness tester. Nonlinear optical property was explored to confirm the second harmonic generation efficiency of the grown crystal. These preliminary investigations suggest that the title compound can serve as a potential material for photonics applications. Full Text: PDF ReferencesD. J. Williams, "Nonlinear Optical Properties of Organic and Polymer Materials" (ACS Symposium series 233, American Chemical Society, Washington, DC, 1983). CrossRef K. Bouchouit, Z. Sofiani, B. Derkowska, S. Abed, N. Benali-cherif, M. Bakasse and B. Sahraoui, "Investigation of crystal structure and nonlinear optical properties of 2-methoxyanilinium nitrate", Opt. Commun. 278, 180 (2007), CrossRef K. Bouchouit, H. Bougharraf, B. Derkowska-zielinska, N. Benali-cherif and B. Sahraoui, "Reversible phase transition in semi-organic compound p-Nitroanilinium sulfate detected using second harmonic generation as a tool", Opt.Mater. 48, 215 (2015), CrossRef J. H. Joshi, S. Kalainathan, M. J. Joshi and K. D. Parikh, "Crystal growth, spectroscopic, second and third order nonlinear optical spectroscopic studies of L-phenylalanine doped ammonium dihydrogen phosphate single crystals", Arab. J. Chem. 13, 5018 (2020), CrossRef A. Vijayakumar, A. Ponnuvel and A. Sasikala, "Growth and characterization of α and β form of L-histidine dihydrochloride single crystals", Mater. Today 14, 338 (2019), CrossRef C. Usha, R. Sathakuamri, Lynnette Joseph, D.Sajan, R.Meenakshi, and A.Sinthiya, "Growth and combined experimental and quantum chemical study of glycyl-L-Valine crystal", Heliyon 5, e01574 (2019), CrossRef P. Maadeshwaran and J. Chandrasekaran, "Synthesis, growth and characterization of l-valine cadmium chloride monohydrate—A novel semiorganic nonlinear optical crystal", Optik 122, 1128 (2011) CrossRef S. Pandiyaran, M. Umadevi, R. K. Rajaraman and V. K. Ramakrishnan, "Infrared and Raman spectroscopic studies of l-valine l-valinium perchlorate monohydrate", Spectrochim. Act A Mol. 62, 630 (2005) CrossRef S. Pandiarajan, B. Sridhar and R. K. Rajaram, "L-Valine L-valinium perchlorate monohydrate", Acta Crystallogr. E, 57, 0466 (2001) CrossRef M. Lydia Caroline and S. Vasudevan, "Growth and characterization of l-phenylalanine nitric acid, a new organic nonlinear optical material", Mater. Lett. 63, 41 (2009) CrossRef J. Tauc, R. Grigorovici and A. Vancu, "Optical Properties and Electronic Structure of Amorphous Germanium", Phy. Solid. Stat. 15, 627 (1966), CrossRef J. Tauc, A. Menth and D.L. Wood, "Optical and Magnetic Investigations of the Localized States in Semiconducting Glasses", Phys. Rev. Lett. 25, 749 (1970) CrossRef B. Thirumalaiselvam, R. Kanagadurai, D. Jayaraman and V. Natarajan, "Growth and characterization of 4-methyl benzene sulfonamide single crystals", Opt.Mater. 37, 74 (2014) CrossRef J. Bowman and M. Bevis, "The evaluation of the structure and hardness of processed plastics by the Vickers microhardness test", Colloid Polym. Sci. 255, 954 (1977) CrossRef S. K. Kurtz and T. T. Perry, "A Powder Technique for the Evaluation of Nonlinear Optical Materials", J. Appl. Phy. 39, 3798 (1968) CrossRef M. Prakash, D. Geetha and M. Lydia Caroline, "Crystal growth, structural, optical, spectral and thermal studies of tris(l-phenylalanine)l-phenylalaninium nitrate: A new organic nonlinear optical material", Spectrochim. Act A Mol. 81, 48 (2011) CrossRef

Comment on: “Experimental and Theoretical Investigations of Tetrakis (Thiourea) Palladium Chloride Semi-Organic Non-Linear Optical Crystal: An Approach to NLO Application” [(2018) Silicon 10 (3):841–850

In a recent paper [(2018) Silicon 10 (3):841–850] Rajagopalan et al. studied the physical properties of the Tetrakis (Thiourea) Palladium Chloride Semi-Organic Non-Linear Optical Crystals. The authors have used a wrong approach to calculate the reflectance spectra of the samples and obtained values of this parameter are incorrect. Consequently, other reported optical parameters in the commented paper that are calculated based on the reflectance such as refractive index and dispersion parameters evaluated from the Wemple-Didomenico single oscillator model are wrong.

Growth and investigations of 3rd order NLO properties of novel semi organic tartaric acid lithium sulfate single crystal for photonics application

Single crystals of tartaric acid lithium sulfate (TALS), a semi-organic nonlinear optical crystal has been successfully grown by slow evaporation solution growth technique. Single crystals were grown in a life span of 3 weeks. The grown crystals were characterized by single crystal X-ray diffraction to identify the lattice parameters. Fourier Transform Infra Red studies confirm the presence of various functional groups present in the crystal. Optical, mechanical, microscopic image and thermal stabilities of the title crystal was carried out to know the properties of the titled compound. Third order non-liner studies have also been studied by Z-scan techniques. Nonlinear absorption and nonlinear refractive index were found out and the third order bulk susceptibility of compound was also estimated. The negative sign in the refractive index indicates the self-defocusing nature of the crystal.

Investigations on surface and mechanical properties of bis-thiourea cadmium iodide – A non-linear optical crystal

The semi-organic non-linear optical crystals of bis-thiourea cadmium iodide (BTCI) were grown from slow evaporation of their aqueous solutions. The grown crystals were confirmed with XRD, FTIR, and DSC analysis. The as-grown (010) crystal faces reveal growth striations. The structural perfection was assessed by the wet chemical etching method; acetic acid and formic acid are the best etchants to reveal dislocations. The strength and deformation characteristics of the crystals were assessed through laser damage tolerance, Vickers, and Knoop hardness measurements. The change in hardness is approximately 26% for every 40–45° shift in the orientation of the crystal, indicating anisotropy in hardness. The work hardening index calculated from Meyer's plot helps in distinguishing the indentation size effect. The yield strength and Young's modulus calculated using the standard relations indicate that the crystal is suitable for desired applications.

Synthesis and characterization of L-threonine lithium chloride (LTLC): A new semiorganic nonlinear optical single crystal for laser applications

A novel new nonlinear optical material of semi organic L-Threonine Lithium chloride (LTLC) was synthesized and crystal-clear single crystal was grown by slow evaporation solution growth technique at the ambient temperature. The grown transparent single crystal was characterized by single crystal X-ray diffraction (SCXRD), optical absorption spectrum, Fourier transforms infrared spectroscopy and Fourier transforms Raman spectroscopy. Single crystal X-ray diffraction analysis reveals that LTLC is an orthorhombic crystal structure with the non-centrosymmetric of P212121 space group. The absorption range was evaluated from UV–vis-NIR and the optical band gap was calculated by Tauc’s plot and Photoluminescent spectra were obtained to investigate the optical properties. The dielectric response was studied under various temperatures. The second harmonic generation (SHG) efficiency was studied by Kurtz Perry method.

Second and third order nonlinear optical, mechanical, surface characteristics of bis(thiourea) manganese chloride (BTMC) grown by slow cooling technique used for frequency conversion applications

A semiorganic nonlinear optical (NLO) single crystal of bis(thiourea) manganese chloride (BTMC) is grown successfully by slow cooling technique using water as solvent at temperature 45 °C. The optically good quality crystal of BTMC was grown with dimension up to 8 × 8 × 2 mm3 in a period of 2–3 weeks. The grown crystal crystallizes in orthorhombic crystal system which was confirmed by single crystal X-ray diffraction analysis. The various functional groups of BTMC were identified through FT-IR spectroscopic analysis. The lower cut-off wavelength of 280 nm was revealed from optical transmittance spectrum of UV. The mechanical behavior of BTMC crystal was analyzed by Vicker’s microhardness study and also the various mechanical parameters were determined. Vickers micro hardness test revealed, the titular crystal belongs to harder material category. The SHG efficiency is estimated from Kurtz-Perry powder method and it found to be 0.33 times than the reference material. The dielectric behavior, photo conducting nature and surface properties have been analyzed for grown BTMC crystal. The presence of synthesized elements was confirmed by EDAX study. The third order nonlinear optical susceptibility chi^{left(3 right)} of the material is measured using Z-scan technique and it is found to be 5.1202 × 10−14 esu.

Synthesis, growth and characterization of semiorganic nonlinear optical single crystal bis(thiourea) barium nitrate (BTBN) for frequency conversion

Abstract A novel semiorganic nonlinear optical (NLO) crystal, bis(thiourea) barium nitrate (BTBN) was synthesized and grown by slow evaporation method. Structure of the new crystalline compound was confirmed by single crystal X-ray diffraction analysis and it showed that BTBN belongs to orthorhombic crystal system. The crystalline nature of the BTBN was confirmed by powder X-ray diffraction study. Important functional groups of BTBN were identified by FT-IR spectroscopic analysis. UV-Vis-NIR spectral study showed that the grown crystal is transparent in the entire visible region with low cut off wavelength of 304 nm. BTBN exhibits a SHG efficiency which is nearly 2.38 times higher than that of KDP. The BTBN crystal has high mechanical strength and belongs to soft category, which was confirmed by micorhardness study. The thermal stability of BTBN was determined from TGA and DTA thermal study which revealed that the BTBN crystal has thermal stability up to 243.1 °C. The surface properties and presence of elements was analyzed by SEM and EDAX study, respectively.