Growth,structural, optical,DFT, thermal and dielectric studies of N-Benzyl-3-nitroaniline (B3NA): a promising nonlinear optical crystal

The non-linear optical material N-Benzyl-3-nitroaniline was synthesized and grown through an aqueous solution using a low temperature solution growth technique. This conforming monoclinic crystal structure with the P2₁ space group was established by the characterization study of single crystal X-ray diffraction. A powder X-ray diffraction analysis was performed to confirm crystalline nature. As one of the functioning groups of nitro-aniline revealed using the Fourier transform infrared spectrum and the prominent spectral band seen at 3404 cm^?1 is caused by stretching vibrations of the N–H group. The lower cut-off wavelength of the ultra violet-visible absorption and emission spectrum was found to be about 320 nm as the excitation of fluorescence and the emission of blue and red colors are expected at 459 nm and 688 nm. To determine the difference in energy between HOMO and LUMO by 9.6258, using the B3LYP/6-311G++ (d,p) method. The time-based DFT technique was used to calculate the first-order hyperpolarization (β)?=?1.214?×?10^–30 esu. Thermo gravimetric and differential thermal analysis measurements were used to determine the crystal’s moisturing toughness up to 282.87 °C. The relative dielectric constant changes with frequency. Kurtz Perry’s method confirmed 1.66 times the efficiency of second harmonic generation to this present crystal comparing KDP crystal. This data shows that there is a significant amount of promise that is used in optoelectronic materials.

     

Unidirectional growth,structural, optical and mechanical properties of LTA crystal

Nonlinear optical amino acid single crystal of l-tartaric acid was successfully grown by unidirectional Sankaranarayanan–Ramasamy method under ambient conditions for the first time. The grown single crystal was subjected to different characterization analyses in order to find out its suitability for device fabrication. The crystal system and lattice parameters were determined from the powder X-ray diffraction analysis. The crystalline perfection was evaluated using high-resolution X-ray diffractometry. It is evident from the optical absorption study that crystal has excellent transmission in the entire visible region with its lower cut off wavelength around 220 nm. The mechanical properties of the grown crystals were studied using Vickers microhardness tester.     

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 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.     

Growth and characterization of new semiorganic nonlinear optical single crystal L-Phenylalanine L-Phenylalaninium perchlorate (LPPAPC)

The new semi-organic nonlinear optical crystal, L-Phenylalanine L-Phenylalaninium perchlorate (LPPAPC) has been grown through synthesis between L-Phenylalanine and perchloric acid. The bulk crystals of dimension 5.5 × 0.4 × 0.3 cm³ were obtained by submerged seed solution method. The new compound was characterized by UV–Vis-NIR spectroscopic technique. In addition to that the solid-state structure of the crystal has been determined by single crystal X-ray diffraction technique. LPPAPC was thermally stable up to 272 °C as determined by TG/DTA studies. Also, the second harmonic generation (SHG) of the LPPAPC crystal was observed using Nd: YAG laser with a fundamental wavelength of 1064 nm.     

Structure–property relation and third order nonlinear optical absorption study of a new organic crystal: 1-(3,4-Dimethoxyphenyl)-3-(2-fluorophenyl) prop-2-en-1-one

A new third order centrosymmetric organic crystal: 1-(3,4-dimethoxyphenyl)-3-(2-fluorophenyl) prop-2-en-1-one (2FRDP) belonging to chalcone family has been synthesized and characterized by FTIR, CHNS and UV–Visible spectroscopy. Single crystal X-ray diffraction reveals that compound crystallizes in C2/c monoclinic space group. The X-ray powder diffraction of the crystal was carried out and hkl values are indexed for the diffraction pattern using mercury software. UV–Visible spectrum showed that 2FRDP is transparent in the entire visible region. The thermal stability of the grown 2FRDP crystal was analyzed by thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dielectric study revealed that, 2FRDP possesses low dielectric constant and dielectric loss at high frequency. The third order nonlinear optical absorption and the optical limiting experiment were carried out using open aperture Z-scan data using an Nd:YAG laser operating at the wavelength 532 nm.     

Crystal growth, thermal and optical studies of semiorganic nonlinear optical material: l-lysine hydrochloride dihydrate

Single crystals of l-lysine hydrochloride dihydrate (LLHCD), a nonlinear optical material, have been grown by slow cooling technique from its aqueous solution. LLHCD was found to be highly soluble in water. The grown crystals have been subjected to single crystal X-ray diffraction to confirm the structure and to estimate the lattice parameters. The vibrational structure of the molecule is elucidated from FTIR spectra. Thermal analysis revealed the thermal stability of the grown crystals. The optical transmittance spectrum shows that the material possesses good optical transparency in the entire visible region with a UV cut-off wavelength at 228 nm. The mechanical properties of the grown crystal have been studied using Vicker's microhardness test. The laser damage threshold of 52.25 MW/cm² has been measured by irradiating Q-switched Nd:YAG laser (1064 nm).     

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.

     

Investigating optical,electrical, and mechanical traits of thiourea admixtured KDP single crystals to explore NLO device applications

The 0.5 and 1 mol% thiourea “mixed” potassium dihydrogen phosphate (KDP) crystals have been developed by conventional slow solution evaporation method. The crystallographic parameters of grown crystals have been determined by employing single crystal X-ray diffraction technique. The functional groups of grown crystals were successfully identified by means of FTIR spectral analysis. The optical transmittance is 79%, 84%, and 89% for KDP, 0.5 mol thiourea mixed KDP, and 1 mol thiourea mixed KDP crystal. The energy band gap (E_g) of KDP, 0.5 mol thiourea mixed KDP, and 1 mol thiourea mixed KDP crystal is 3.71 eV, 3.61 eV, and 3.75 eV, respectively. The Kurtz–Perry test has been employed to determine the SHG efficiency and SHG efficiency of 0.5 and 1 mol thiourea mixed KDP crystal is 2.09 and 2.22 times superior to KDP crystal. Effect of thiourea mixing on hardness properties of KDP crystal have been scrutinized using the Vickers microhardness studies. The frequency dependent dielectric behavior of grown crystals has been analyzed at room temperature.

     

Growth and characterization of l-phenylalanine nitric acid, a new organic nonlinear optical material

A new organic nonlinear optical material L-phenylalanine nitric acid [2C₉H₁₁NO₂.H⁺. NO₃⁻] (LPN), was synthesized in mixed solvent of deionised water and methanol and single crystals of LPN was grown by slow evaporation method. Transparent crystals upto 2.9 × 0.3 × 0.05 cm³ were obtained. The grown crystals have been subjected to powder X-ray diffraction studies to identify the crystalline nature. Single crystal X-ray diffractometer was utilized to measure unit cell parameters and to confirm the crystal structure. The modes of vibration of different molecular groups present in LPN were identified by FTIR spectral analysis. Transmission spectra reveals that the crystal has low UV cutoff of 295 nm and has a good transmittance in the entire visible region enabling its use in optical applications. Thermal properties of the crystals have been investigated using thermogravimetric (TG) and differential thermal analyses (DTA), which indicate that the material does not decompose before melting. The existence of second harmonic generation signals was observed using Nd:YAG laser with fundamental wavelength of 1064 nm.     

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).     

Third order optical non-linear (Z-scan), birefringence,photoluminescence, mechanical and etching studies on melaminium levulinate monohydrate (MLM) single crystal for optical device applications

Z-scan studies on the grown crystal was investigated by diode-pumped Nd; YAG laser. Nonlinear refractive index (n₂) and third-order nonlinear optical susceptibility (χ³) values of MLM were found to be −1.0 × 10⁻⁸ cm²/W and 1.36 × 10⁻⁶ esu respectively. Powder X-ray diffraction analysis depicted that the crystal belongs to monoclinic system with space group P2₁/c. Birefringence study revealed the optical dispersion behavior of MLM crystal. Linear refractive index on (10-1) plane was measured by prism coupling technique and was estimated to be 1.4705. Hardness study was carried out along three different planes which exhibit hardness anisotropy of 41.11%. Meyer's index values of the grown crystal for the (10-1), (010) and (111) planes were found to be 2.39, 2.61 and 2.04 respectively. Etching studies on the prominent (10-1) growth plane was explained by two dimensional layer growth mechanisms. Photoluminescence study was performed on MLM crystal to explore its efficacy towards optical device fabrications.     

Synthesis,growth, and characterization of new stilbazolium derivative single crystal: 2-[2-(2,4-dimethoxy-phenyl)-vinyl]-1-ethyl-pyridinium iodide for third-order NLO applications

2-[2-(2,4-Dimethoxy-phenyl)-vinyl]-1-ethyl-pyridinium iodide (DMPI), a new organic stilbazolium derivative was synthesized and grown by slow evaporation technique. The crystal structure of the grown crystal was solved by single crystal X-ray diffraction analysis and it was found that DMPI crystallizes in triclinic structure with the centrosymmetric space group Pī. Various functional groups of the grown crystal were identified using FT-IR spectral analysis. The molecular structure of DMPI was further confirmed by ¹H NMR and ¹³C NMR spectral studies. The linear optical studies revealed that the grown crystal has a wide transparency range from 481 to 800 nm, which is suitable for opto-electronic and nonlinear optical applications. The luminescence spectrum of DMPI showed yellow emission radiation at 571 nm. TG/DTA analysis revealed that the grown crystal was thermally stable up to 232?°C. Microhardness studies confirmed the reverse indentation size effect of DMPI. The dielectric behaviour of DMPI was analyzed by dielectric studies with various frequencies at different temperatures. The surface damage threshold study showed that the grown crystal has higher optical radiation stability against 1064 nm Nd: YAG laser. Studies of its nonlinear optical properties using a Z-scan technique indicated that DMPI crystal possesses a saturable absorption and the self-focusing effect. Negative photo conducting nature of the grown crystal was obtained by photoconductivity measurements.     

Studies on the synthesis, structure, growth and physical properties of an organic NLO crystal: 2-Amino-5-nitropyridinium Phenolsulfonate

A noncentrosymmetric crystal was prepared from 2-amino-5-nitropyridine (2A5NP) and p-Phenolsulfonic acid, which was designed for second harmonic generation. Good quality single crystals of 2-amino-5-nitropyridinium Phenolsulfonate (2A5NPP) were successfully grown by the slow evaporation method with dimensions 10 × 4 × 3 mm³. The unit cell dimensions were determined from single crystal X-ray diffraction studies. The structural perfection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. Fourier transform infrared (FTIR) spectral studies have been performed to identify the functional groups. The optical transmittance window and the lower cutoff wavelength of the 2A5NPP have been identified by UV-vis-NIR studies. Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study its thermal properties. Powder test with Nd:YAG laser radiation shows a high second harmonic generation. The laser induced surface damage threshold for the grown crystal was measured using Nd:YAG laser.     

Elucidation of structural,optical, mechanical,dielectric, DFT and nonlinear optical response of 2-amino-1-methyl-5H-imidazol-4-one single crystal

A single crystal of 2-Amino-1-methyl-5H-imidazol-4-one (AMH) with chemical formula C₄H₇N₃O were synthesized using slow evaporation solution growth approach and analyzed its structural and optical features. Single crystal X-ray diffraction (SXRD) examination is used for measuring crystallinity as well as lattice characteristics of generated single crystals. AMH crystal has monoclinic structure and shows the space group P2₁/n, according to the result. The computed structural parameters were compared with the experimental observations and the presence of intramolecular charge transfer interactions were analyzed by Natural Bond Orbital analysis. Hirshfeld surface analysis has been used for visualizing various intermolecular interactions that exist within the synthesized material. The functional group in association with formed compound as well as absorption peaks and bands have been investigated and designated using FTIR spectroscopy. Using Vicker’s microhardness, we can assessed the mechanical strength and determined the work hardening coefficient as 3.1, which confirming the compound’s soft nature. UV–Visible absorbance spectral analysis have been utilized for examining the optical characteristics of the material, which shows the lower cut-off wavelength and optical bandgap as 300 nm and 3.9 eV, respectively. Frontier molecular orbital analysis is performed for explaining charge transfer exists within AMH and the material’s energy gap is estimated as 4.1 eV. The effective charge transfer interactions (ICT) are visualized by MEP plots. By the use of Gaussian ‘09 software package and Kurtz Perry powder technique, the compound’s nonlinear optical behaviour is verified in both theoretical and experimental modes. The dielectric behaviour of the synthesized material was interpreted and analyzed.

     

Synthesis,crystal growth and characterization of nonlinear optical organic crystal: p-Toluidinium p-toluenesulphonate

p-Toluidinium p-toluenesulphonate (p-TTS) an organic nonlinear optical crystal has been grown from the aqueous solution by slow evaporation solution growth technique. Single crystal X-ray diffraction analysis reveals that p-TTS crystallizes in monoclinic crystal system. The structural perfection of the grown p-TTS single crystal has been analyzed by high-resolution X-ray diffraction rocking curve measurements. Fourier transform infrared spectral studies have been performed to identify the functional groups. The optical transmittance window and the lower cutoff wavelength of the grown crystals have been identified by UV–vis–IR studies. Birefringence of p-TTS crystal has been studied using channel spectrum measurement. The laser damage threshold value was measured using Nd:YAG laser. The second harmonic conversion efficiency of p-TTS has been determined using Kurtz powder technique. Thermo gravimetric and differential thermal analyses were used to study its thermal properties. Dielectric constant, dielectric loss and AC conductivity of the grown p-TTS single crystal has been studied.     

Synthesis,growth, and two-photon absorption induced optical limiting action of cytosinium benzoate single crystal

Two-photon absorption induced optical limiting action was demonstrated in cytosinium benzoate (CB) under nanosecond laser (532 nm, 9 ns, and 10 Hz) excitation. Intensity dependent open aperture Z-scan experiment exposed the presence of reverse saturable absorption ascribed due to sequential two-photon absorption. Initially CB single crystals were grown at room temperature by slow evaporation solution technique. Single crystal XRD shows that CB belongs to monoclinic crystal system with P2₁/c space group. Fourier Transform Infrared spectrum was recorded to identify the presence of functional groups. Thermal studies shows that the crystal is stable upto 168 °C. Vickers microhardness studies confirm that the grown crystal was belongs to soft material category. Etching study shows linear rectangular etch patterns (5 s) and well defined stacking planes (10 s) for water etchant. Optical studies demonstrate that CB crystal possess lower cut-off (287 nm) and moderate linear transmittance in visible region. The optical energy band gap of CB crystal was estimated from photoluminescence studies as 3.1 eV. CB with higher two-photon absorption coefficient (1.26?×?10^–10 m/W) and lower onset limiting threshold (1.92?×?10¹² W/m²) can be a potential candidate for developing laser safety devices under nanosecond green laser excitation regime.

     

Laser damage threshold,antimicrobial efficacy and physicochemical properties of an organometallic L-proline lithium chloride monohydrate single crystal for NLO application and optoelectronic device fabrication

The potential metalorganic L-proline lithium chloride monohydrate single crystal was grown by slow evaporation method for evaluating optoelectronic device fabrication. From the single crystal XRD studies, the grown crystal was confirmed the molecular packing in monoclinic crystal lattice. The powder XRD data confirm the phase purity of the grown crystal. Vibrational absorption band assignments were recognized by FTIR and FT-Raman spectrum and they confirmed the presence of multiple functional groups in the grown crystal structure. Optical properties of the grown crystal were studied by using transmittance and absorption spectrum of UV–Vis–NIR analysis. The dielectric response of the grown crystal was studied in the frequency range between 50 Hz and 2 MHz for four temperature gradients. From the microhardness study, some mechanical parameters such as fracture toughness, brittleness index and yield strength were calculated. The photoluminescence activity of the grown crystal was deliberate in terms of optical peaks. The amino group participation over the optical scattering nodal regions for generating radiation absorption process to fascinate optical endurance was studied. TG/DTA curve shows that the LPLCM crystal was thermally stable up to 132 °C. The laser damage threshold value of the grown crystal was measured using multishot mode and it was found to be 7.78 GW/cm². The fractionation of the etching time prevents lattice from over etching and degradation of the mechanical properties of the grown crystal. LPLCM crystal showed higher antibacterial activity against one gram positive and one gram negative bacterial species. Second order nonlinear optical efficiency of the LPLCM crystal was studied at 1064 nm generated by a nanosecond pulsed Nd:YAG laser source.

     

Growth and spectral properties of Er:NaGd(WO4)2 crystal

A high optical quality Er³⁺-doped NaGd(WO₄)₂ single crystal with dimensions of ∅18 × 50 mm³ has been grown using the Czochralski method. The structure of the grown crystal was proved by X-ray powder diffraction. The accurate concentration of Er³⁺ ion in the crystal was measured. The absorption spectra, fluorescence spectra and fluorescence lifetime of the crystal were measured at room temperature. Green up-conversion luminescence has been observed when the crystal is excited at 965 nm.     

Crystal growth, thermal and optical studies on a metalorganic nonlinear optical material dipotassium boro maleate (DKBM)

A single crystal of dipotassium boro maleate (DKBM) was grown using slow evaporation method. The solubility of DKBM was determined for various temperatures. The structure of the grown crystal was confirmed by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) techniques. The Fourier transform infrared (FT-IR) study reveals the various functional groups present in the grown crystal. The UV-Vis-NIR spectra revealed the transmission properties of the grown crystal. Thermal stability of the crystal was investigated using thermo gravimetric analysis (TGA) and differential thermal analysis (DTA). The nonlinear optical (NLO) property of the crystal was confirmed by powder second harmonic generation (SHG) test.