Synthesis,crystal growth and characterization of novel semiorganic nonlinear optical crystal: Dichlorobis(l-proline)zinc(II)

Single crystals of the semiorganic material, dichlorobis(l-proline)zinc(II) (DCBPZ), were grown from aqueous solution. The grown crystals were tested by single crystal X-ray diffraction, energy-dispersive spectrometry, FT-IR, UV–vis and TG–DTA. The structural prefection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. The dielectric and mechanical behavior of the specimen was also studied. The SHG efficiency of DCBPZ is three times greater than that of KDP. Measuring transmittance of DCBPZ permitted the calculation of the refractive index n, the extinction coefficient K and both the real ?_r and imaginary ?_i components of the dielectric constant as functions of photon energy. The optical band gap of DCBPZ is 4.8 eV.     

KDP crystal doped with L-arginine amino acid: growth,structure perfection,optical and strength characteristics

Potassium Dihydrogen Phosphate (KDP) crystal doped with L-arginine (L-arg) amino acid with 1.4 wt% concentration in the solution was grown onto a point seed by the method of temperature reduction. For the first time an attempt was made to grow large-size (7 × 6 × 8 cm³) optically transparent crystals, which allowed to analyze the effect of L-arg additive on the physical properties of the different growth sectors ({100} and {101}) of KDP. The incorporation of L-arg into both growth sectors of the crystal was confirmed by the methods of optical and IR spectroscopy and found to be caused by the ability of the amino acid to form hydrogen bonds with the face {100} and electrostatically interact with the positively charged face {101} of KDP crystal. A slight variation in the unit cell parameters was reported, the elementary cell volume of KDP:L-arg crystal increased in comparison with the one of pure KDP by 2·10⁻² and 2.07·10⁻² Å³ in the sectors {100} and {101}, respectively. It was found that the doping of L-arg enhanced the SHG efficiency of KDP and depended on the crystal growth sectors. The SHG efficiency of KDP:L-arg was by a factor 2.53 and 3.95 higher in comparison with those of pure KDP for {101} and {100} growth sector, respectively. The doping was found to lead to softening of both faces by ∼3–10% and ∼14–17% in the sectors {101} and {100}, respectively. Investigation of the influence of L-arg molecules on the bulk laser damage threshold of the crystals showed that the bulk laser damage threshold of the samples of KDP:L-arg crystal was higher than the one of the pure crystal in the sector {101} and lower in the sector {100}. The correlation between microhardness and laser damage threshold were discussed. The study is helpful for further searching, designing and simulation of hybrid NLO materials.     

Studies on the nonlinear optical single crystal: Ammonium d,l-tartrate (C4H9NO6)

The organic nonlinear optical material ammonium d,l-tartrate single crystal has been successfully grown by slow evaporation solution technique (SEST). The grown crystals were characterized by single crystal XRD and the lattice parameters have been confirmed. The structural perfection of the grown crystal was analyzed by high-resolution X-ray diffraction measurement. The optical transmittance spectrum shows that the material has a good optical transparency in the entire visible region with the UV cut-off wavelength at 234 nm. Thermogravimetric and differential scanning calorimetric measurements were performed to study the thermal properties of the grown crystal. Chemical etching studies were attempted to determine the dislocation density of the grown crystal. Mechanical behavior was assessed using Vickers hardness testing carried out on (0 0 1) crystallographic plane. The Kurtz–Perry powder SHG technique confirms the NLO property of the grown crystal and the efficiency of AMT crystal was found to be 1.3 times that of standard KDP crystal.     

Comparative studies on formation and material characterization of L-histidine derivatives for nonlinear optical device applications

In this study, nonlinear optical crystalline materials L-histidinium hydrochloride monohydrate (LHHCL) and L-histidinium methyl ester dihydrochloride (LHMDHCL) were successfully grown by slow solvent evaporation technique. As-grown crystalline materials were subjected to X-ray structure analysis, FT-Raman spectroscopy, energy-dispersive X-ray spectroscopy, UV–Vis spectroscopy, frequency conversion analysis, dielectric and Vicker’s microhardness studies. According to XRD data, the grown crystal LHHCL was crystallized to an orthorhombic form having a space group P2₁2₁2₁, while LHMDHCL crystal belongs to a monoclinic form with a space group P2₁. The FT-Raman study confirms the existence of chemical groups and the formation of two different crystals. The chemical compositions of the as-grown crystalline materials were established by Energy-dispersive X-ray spectroscopy. The UV–Vis study substantiates the transparency of LHHCL and LHMDHCL in the wavelength regions of 232–1000 nm and 230–1000 nm, respectively. Using the Tauc equation, the bandgap energy was determined as 5.35 eV and 5.38 eV for LHHCL and LHMDHCL crystals, respectively. In addition, the grown crystals have shown a better frequency conversion efficiency in comparison to KDP samples. According to the dielectric study, dielectric characteristics such as dielectric constant and dielectric loss for the LHHCL and LHMDHCL crystals drop as frequency increases. The hardness of the LHHCL and LHMDHCL crystals was measured by Vickers microhardness test which reveals that the grown crystals follow the normal indentation size effect.

     

Growth and characterization of L-Glycine thiourea nonlinear optical single crystal for optoelectronic applications

l-Glycine thiourea single crystals have been grown by slow evaporation solution growth technique (SEST). The cell parameters were estimated from single crystal X-ray diffraction analysis and it was found that the material crystallized in the orthorhombic symmetry with space group P2₁2₁2₁ and the theoretical data were estimated. The powder X-ray analysis proved its crystalline nature without the formation of secondary phases. The presence of functional groups and the nature of bonds appearing in the material were identified by FTIR spectroscopy. Optical constants were estimated by UV–Visible spectrum and the lower cut off wavelength was observed at 200 nm. The scanning electron microscope analysis has been carried out to determine the surface morphology of the grown crystal. Energy dispersive spectrum was done to confirm the composition of elements present in the title material. The second harmonic generation (SHG) efficiency was done by Kurtz powder technique and the conversion efficiency was compared with KDP crystal of the title compound. Third order nonlinear optical susceptibility was measured using z-scan technique and it was found that the crystal has a positive refractive index which is self focusing in nature. The obtained results showed that l-glycine thiourea crystals are potential materials for NLO device fabrication.     

Impact of nickel doping on structural,optical, electrical,and third-order NLO behavior of piperazinium L-tartrate single crystals

Slow evaporation technique was used to grow single crystals of pure and nickel (Ni)-doped piperazinium L-tartrate (PPLT). Powder crystal X-ray diffraction was used to characterize the structural properties of the grown crystals. Fourier transform infrared spectroscopy was used to determine the functional groups. In the visible band, both pure and Ni-doped PPLT crystals have low absorbance, indicating their utility in nonlinear optical (NLO) applications. PPLT crystals, both pure and Ni doped, have bandgap energies that indicate their insulating nature, indicating their utility in electronic applications. The growth pattern and dislocation density of the crystal are revealed by etching analysis. The electric field response of generated single crystals was investigated in terms of dielectric constant and dielectric loss as a function of the frequency and temperature, with the findings described. The efficiency of nickel-doped PPLT crystal is 2.86 times larger than potassium dihydrogen phosphate (KDP), whereas the efficiency of pure PPLT is 1.38 times greater than KDP, according to NLO testing measured by Kurtz powder method. Because metal ions were incorporated into the crystal lattice, the SHG efficiency of nickel-doped PPLT was somewhat improved.

     

A study on the <Emphasis Type="SmallCaps">l</Emphasis>-lysine-iodic acid: semi organic non linear optical single crystals for electro-optic applications

Non linear optical single crystals of l-lysine-iodic acid (LLI) of dimensions upto 24?×?14?×?5 mm³ have been grown successfully by slow evaporation technique from aqueous solution. The crystal structure of the grown material was solved by single crystal X-ray diffraction analysis and it was found that the LLI crystal belongs to monocinic system with space group P2₁. Functional groups of the grown crystal were identified by Fourier Transform Infrared (FTIR) spectral analysis. The UV–Vis spectral analysis was carried out to measure the transparent range of the LLI crystal which is nearly 85% and the band gap energy is found to be 5.51 eV. Thermal stability and decomposition temperature of LLI crystal was found by means of TGA and DTA analyses. The mechanical behavior of the grown crystal has been employed using Vicker’s micro hardness technique. The Second Harmonic Generation (SHG) efficiency of the crystal was investigated and it was found to be 3.2 times of KDP. The particle size dependent SHG studies of LLI crystals were performed using Nd:YAG laser. The laser damage threshold value of LLI crystal is found to be 8.54 GW/cm². Dielectric study indicates the reasonable dielectric constant and low dielectric loss of LLI crystal which are essential properties to develop optoelectronic devices. The ac and dc electrical conductivity measurements were carried out at various temperatures. Photoconductivity study exhibits the negative photoconductivity nature of the LLI crystal and the results are discussed for the first time.     

Experimental and theoretical characterization of semiorganic nonlinear optical material l-leucine hydrobromide

Semiorganic nonlinear optical material l-leucine hydrobromide (LEHBr) has been synthesized and single crystals were grown by solvent evaporation method at a constant temperature of 35 °C. CHN test, FTIR and XRD analysis were performed for identification of the material. Thermal and mechanical stability of the grown crystal were investigated by DTA-TGA analysis and microhardness measurement respectively. Suitability of LEHBr for NLO application was studied by optical transmission study and second harmonic generation (SHG) efficiency measurement. SHG efficiency was found to be 4 times of KDP. First hyperpolarizability, dipole moment and polarizability of LEHBr were calculated at the framework of Hartree–Fock (HF) with 6-311G(d) basis set. First order hyperpolarizability was found to be 3.233 × 10⁻³³ esu which is 4.9 times of urea.     

Growth and characterization of a new non-linear optical l-histidinium dihydrogen phosphate single crystal

New non-linear optical single crystal of l-histidinium dihydrogen phosphate was grown by slow evaporation and temperature lowering technique from aqueous solution. Solubility studies have been carried out for three different solvents (water, acetone and ethanol). The grown crystals have been subjected to single crystal X-ray diffraction analysis to identify the cell parameters and morphology. Optical transmission spectra reveal the optical properties of the grown crystals. The NLO property of the crystal has been confirmed by Kurtz SHG test. Comparing the output power it has been confirmed that l-HDP crystals possess higher SHG efficiency than KDP. Thermal studies were carried out to check the thermal stability of the crystals.     

Synthesis and characterization of pure,urea and thiourea doped organic NLO l-arginine trifluoroacetate single crystals

Optically transparent l-arginine trifluoroacetate (LATF) single crystals by doping with organic materials urea and thiourea were grown by slow solvent evaporation technique. Powder X-ray diffraction confirms improvement in the crystalline quality for urea doped crystals. Urea doping in LATF also improves the percentage of transmittance. The vibrational frequencies of the grown crystals were assigned by Fourier Transform infrared spectroscopy. The thermal analysis (TG/DTA) indicated the better thermal stability for urea doped LATF crystals. EDAX analysis was carried out to calculate the percentage of elements present in doped and pure LATF. The hardness has been remarkably improved on urea and thiourea doped LATF crystals. The second harmonic generation (SHG) analysis showed 2.5 times than standard KDP for pure LATF and 2.2, 2.07 times than KDP for urea and thiourea doped LATF.     

Synthesis,crystal growth,structural, spectral,thermal, mechanical,linear and nonlinear optical studies of organic single crystal 4-Iodo 4-nitrostilbene (IONS): A potential NLO material

An organic nonlinear optical material 4-Iodo 4-nitrostilbene (IONS) has been synthesized and good optical quality single crystal was grown from ethyl methyl ketone solvent by the solution growth technique. Single and powder X-ray diffraction analyses reveals that the grown crystal belongs to monoclinic crystal system with noncentrosymmetric space group ‘P2₁’ and it has good crystalline nature. Functional groups and molecular structure of the title compound were confirmed by FTIR and ¹H NMR respectively. The UV–Vis–NIR absorption study reveals no absorption in the visible region and the cut-off wavelength was found to be at 412.84 nm, TG/DTA, mass spectral analysis, photoluminescence and microhardness studies have been carried out for the grown crystals and results are discussed in detail. The second harmonic efficiency of the IONS was determined by Kurtz–Perry powder technique which reveals that the IONS crystal (3.1 V) has greater efficiency i.e., 143 times to that of KDP (21.7 mV).     

Microhardness,chemical etching,SEM, AFM and SHG studies of novel nonlinear optical crystal – l-threonine formate

The crystal l-threonine formate, an organic NLO crystal was synthesized from aqueous solution by slow evaporation technique. The grown crystal surface has been analyzed by scanning electron microscopy (SEM), chemical etching and atomic force microscopy (AFM). SEM analysis reveals pyramidal shaped minute crystallites on the growth surface. The etching study indicates the occurrence of etch pit patterns like striations and step like pattern. The mechanical properties of LTF crystals were evaluated by mechanical testing which reveals certain mechanical characteristics like elastic stiffness constant (C₁₁) and young's modulus (E). The Vickers and Knoop microhardness studies have been carried out on LTF crystals over a range of 10–50 g. Hardness anisotropy has been observed in accordance with the orientation of the crystal. AFM image shows major hillock on growth surface. The second harmonic generation (SHG) efficiency has been tested by the Kurtz powder technique using Nd:YAG laser and found to be about 1.21 times in comparison with standard potassium dihydrogen phosphate (KDP) crystals.     

Growth and characterization of glycinium oxalate (GOX) single crystals

Glycinium oxalate (GOX) single crystals were grown by slow cooling solution growth method. The X-ray diffraction and Fourier transform infra red studies confirm the grown crystal. The hardness values of GOX are found to be higher than glycine. The increase in hardness may be due to the C-H---O bonding. The UV-Visible studies show that GOX crystals can be used for nonlinear applications. The dielectric measurement indicates that the GOX crystals have domains of varying sizes and varying relaxation time. The SHG output of GOX was 210 mV at given pulse energy of 5 mJ/s and KDP was 240 mV.     

Structural,thermal, dielectric,nonlinear optical properties and DFT investigations of a novel material 2-(6-chloropyridin-3-yl)-N'-(2,3-dihydro-1,4-benzodioxin-6-ylmethylidene)acetohydrazide for optoelectronic applications

A new organic nonlinear optical (NLO) material 2-(6-chloropyridin-3-yl)-N'-(2,3-dihydro-1,4-benzodioxin-6-ylmethylidene)acetohydrazide (CDA) has been synthesized by reflux method. Single crystals were grown by slow evaporation technique and the crystal structure was elucidated by single crystal X-ray diffraction method. Density functional theory (DFT) calculations at B3LYP/6–31+?+?G(d, p) basis set was used to predict the molecular geometry and were carried out further to comprehend the electronic structure, vibrational spectra, natural bonding orbitals (NBO), frontier molecular orbitals (FMO) and molecular electrostatic potential (MEP). An optical transparency at the cut-off wavelength of 355 nm was determined by UV–Vis–NIR spectroscopy. Thermal behavior of CDA was studied by TGA/DTA analysis. The dielectric constant (ε), dielectric loss (tan δ) and AC conductivity as a function of frequency and temperature was studied. Second Harmonic Generation (SHG) efficiency of the CDA was determined using Kurtz and Perry powder technique and was 0.5 times greater than that of the KDP crystal. The third-order nonlinear optical properties were investigated in solution by Z-scan technique using a continuous wave (CW) DPSS laser at the wavelength of 532 nm. The title compound exhibited significant two-photon absorption (β?=?2.228?×?10–4 cm W^?1), nonlinear refraction (n₂?=?1.095?×?10–8 cm² W^?1) and optical limiting (OL threshold?=?2.511?×?103 W cm^?2) under the CW regime. The nonlinear optical parameters were calculated using time-dependent Hartree–Fock (TDHF) method. The overall obtained results suggested that the studied CDA molecule could be a potential NLO material for frequency generator, optical limiters and optical switching applications.

     

Studies on lithium l-ascorbate dihydrate: An interesting chiral nonlinear optical crystal

Lithium l-Ascorbate dihydrate (LLA) is a new metal organic nonlinear optical crystal belonging to the saccharide family. Single crystals of LLA were grown from aqueous solution. Solubility of the crystal has a positive temperature coefficient facilitating growth by slow cooling. Rietveld refinement was used to confirm the phase formation. The crystal has prismatic habit with (010), (001) and (10−1) prominent faces. Thermal analysis shows that the crystal is stable up to 102 °C. Transmission spectrum of the crystal extends from 302 nm to 1600 nm. Dielectric spectroscopic analysis revealed Cole–Cole behaviour and prominent piezoelectric resonance peaks were observed in the range of 100–200 kHz. Second harmonic generation (SHG) conversion efficiency of up to 2.56 times that of a phase matched KDP crystal was achieved when the (010) plate of LLA single crystal was rotated about the +ve c axis, by 9.4° in the clockwise direction. We also observed SHG conical sections which were attributed to noncollinear phase matching. The observation of the third conical section suggests very high birefringence and large nonlinear coefficients. A detailed study of surface laser damage showed that the crystal has high multiple damage thresholds of 9.7 GW cm⁻² and 4.2 GW cm⁻² at 1064 nm and 532 nm radiation respectively.     

Growth and characterization of l-proline cadmium chloride monohydrate single crystals

A novel semi-organic material of l-proline cadmium chloride monohydrate (l-PCCM) has been successfully synthesized and single crystal was grown by slow evaporation solution growth technique at room temperature. The grown single crystals have been characterized by different instrumentation techniques like XRD, FTIR, UV-Vis-NIR and TG/DTA measurements. Its nonlinear optical property has been tested by Kurtz powder method. The mechanical properties of grown crystals have been studied using Vickers microhardness tester. Its relative SHG efficiency is two times higher than that of potassium dihydrogen phosphate (KDP) single crystal.     

Growth and characterization of hexamethylenetetramine crystals grown from solution

Organic nonlinear optical single crystals of hexamethylenetetramine (HMT; 10 × 10 × 5 mm³) were prepared by crystallization from methanol solution. The grown crystals were subjected to various characterization techniques such as single crystal XRD, powder XRD, UV-Vis and electrical studies. Single crystal XRD analysis confirmed the crystalline structure of the grown crystals. Their crystalline nature was also confirmed by powder XRD technique. The optical transmittance property was identified from UV-Vis spectrum. Dielectric measurements were performed as a function of frequency at different temperatures. DC conductivity and photoconductivity studies were also carried out for the crystal. The powder second harmonic generation efficiency (SHG) of the crystal was measured using Nd:YAG laser and the efficiency was found to be two times greater than that of potassium dihydrogen phosphate (KDP).     

Investigation of SR method grown 0 0 1 directed KDP single crystal and its characterization by high-resolution X-ray diffractometry (HRXRD), laser damage threshold, dielectric, thermal analysis, optical and hardness studies

0 0 1 directed potassium dihydrogen orthophosphate (KDP) single crystal was grown by Sankaranarayanan–Ramasamy (SR) method. The 0 0 1 oriented seed crystals were mounted at the bottom of the platform and the size of the crystals were 10 mm diameter, 110 mm height. Two different growths were tried, in one the crystal diameter was the ampoule's inner diameter and in the other the crystal thickness was less than the ampoule diameter. In the first case only the top four pyramidal faces were existing whereas in the second case the top four pyramidal faces and four prismatic faces were existing through out the growth. The crystals were grown using same stoichiometric solution. The results of the two growths are discussed in this paper. The grown crystals were characterized by high-resolution X-ray diffractometry (HRXRD), laser damage threshold, dielectric, thermal analysis, UV–vis spectroscopy and microhardness studies. The HRXRD analysis indicates that the crystalline perfection is excellent without having any very low angle internal structural grain boundaries. Laser damage threshold value has been determined using Nd:glass laser operating at 1054 nm. The damage threshold for the KDP crystal is greater than 4.55 GW cm⁻². The dielectric constant was higher and the dielectric loss was less in SR method grown crystal as against conventional method grown crystal. In thermal analysis, the starting of decomposition nature is similar in SR method grown KDP crystal and conventional method grown crystal. The SR method grown KDP has higher transmittance and higher hardness value compared to conventional method grown crystals.     

A Rare-Earth Selenite with Unexpectedly Well-Balanced Ultraviolet Nonlinear Optical Functionality,Sc(HSeO3)3

Establishing high performance ultraviolet (UV) nonlinear optical (NLO) selenite crystals with well-balanced properties is very challenging attributable to their strong absorption for UV light. Here a rare-earth selenite, Sc(HSeO₃)₃, with excellent UV NLO properties is introduced. Sc(HSeO₃)₃ crystallizing in the polar NCS space group, Cc, features a 3D archetiture built up by interconnected ScO₆ octahedra and HSeO₃ groups. The crystal exhibits remarkably well-balanced UV-NLO functionality, namely, the shortest absorption edge (214 nm) among NLO-active selenites, wide bandgap (5.28 eV), large phase-matchable SHG response (5 × KDP), and sufficiently large birefringence (cal. 0.105 @1064 nm). Detailed DFT calculations have been performed to elucidate the structure–property relationships. This work provides a new example of discovering novel UV NLO selenite materials.     

Materials synthesis,crystal growth and third nonlinear optical properties of semiorganic crystal: 4-dimethylaminopyridine lithium nitrate (DMAPLN) crystal

4-dimethylaminopyridine lithium nitrate crystal (4-DMAPLN) was synthesized by the slow evaporation solution growth technique. The titular crystal was subjected to various studies to recognize its physicochemical properties. The crystalline nature and orthorhombic crystal system were revealed by single crystal and powder XRD. FTIR spectroscopy study confirms the various modes of vibrations available in the titular crystal. Linear optical studies show the lower cut-off wavelength of 280 nm with an optical bandgap value (E_g) of 4.3 eV. The electrical behavior of the 4-DMAPLN crystal was studied using dielectric studies. The mechanical behavior of the grown crystal was analyzed using the Vicker’s microhardness study, revealing that the grown crystal belongs to the hard category. The second-order nonlinear optical (NLO) behavior of 4-DMAPLN crystal was measured using Kurtz–Perry powder techniques and it was found to be 1.17 times higher than reference KDP. Z-scan analysis reveals 4-DMAPLN is a suitable candidate for optical limiting applications.