Nonlinear Optical Single Crystal Research Articles

Ultraviolet Nonlinear Optical Single Crystals of A Three-Dimensional Chiral Covalent Framework Containing Te-O-B-O Bonds.

Extending covalent organic frameworks (COFs) into crystalline carbon-free covalent backbones is an important strategy to endow these materials with more exotic functions. Integrating metal-free inorganic and organic components into one covalent framework is an effective way to address the issue of poor thermal/solvent stability in the field of nonlinear optics (NLO). However, constructing such structures is very challenging. Here, we linked 3-connected nods (BO3) and 2-connected organic building blocks (Te(Ph)2) together to produce colorless single crystals (size up to 400 µm) of a three-dimensional (3D) chiral covalent framework (CityU-22). The single-crystal X-ray diffraction (SCXRD) analysis reveals that CityU-22 has a non-carbon Te-O-B-O bond-based network with the srs topology. The chiral CityU-22 displays good stability under the treatment of different common solvents or heat (the decomposition temperature above 300 °C). Due to its non-π-conjugated backbone (-Te-O-B-O-), CityU-22 shows an ultraviolet NLO behavior with a second-harmonic generation (SHG) response similar to KH2PO4 (KDP).

Synthesis, crystal growth and characterization on a novel third-order nonlinear optical single crystal: 2-amino-3,5-dibromopyridinium-2-chloro-4-nitrobenzoate

Synthesis, crystal growth and characterization on a novel third-order nonlinear optical single crystal: 2-amino-3,5-dibromopyridinium-2-chloro-4-nitrobenzoate

Physicochemical properties of 2-amino-5-methylpyridinium 3-carboxy-4-hydroxybenzenesulfonate single crystal: An efficient material for optoelectronic applications

A novel third-order organic nonlinear optical (NLO) material with promising excellent properties in the crucial NLO application. For the first time high NLO active 2-amino-5-methylpyridinium 5-sulfosalicylic acid (2A5MP3C4H) has been rationally designed and single crystals have been grown by the slow evaporation solution growth technique (SEST). X-ray diffraction analysis revealed that 2A5MP3C4H belongs to the category of triclinic system and has a Centro symmetric space group of P1. Remarkably, the grown crystal exhibits competitive and even superior physical properties including high thermal stability and wider transparency than the standard NLO single crystal. The morphology of the as-grown 2A5MP3C4H crystal was equivalent to the theoretically produced morphology. Fourier transform infrared spectroscopy (FTIR) was used to investigate the molecular vibrations of 2A5MP3C4H. The optical characteristics of 2A5MP3C4H recorded optical transmittance spectrum reveals that the 2A5MP3C4H crystal possesses good optical transparency in the range between ultraviolet (UV) and near-infrared (NIR) regions. Intriguingly, the short cut-off edge of the grown crystal is found to be about 345 nm which is more favourable for developing modern photonic and optoelectronic devices application. The Laser Damage Threshold (LDT), were investigated to understand its effectiveness to be utilized in the area of optoelectronics and photonics. The thermal and mechanical stability of 2A5MP3C4H was tested using Thermo gravimetric Differential Thermal Analysis (TG-DTA) and Vickers hardness test. The third-order nonlinear optical properties of 2A5MP3C4H single crystals were analyzed, which involves studying the absorption coefficient and refractive index behaviour using a continuous wave laser. Additionally, the grown crystal exhibits outstanding third-order NLO response and wide LDT, which are crucial characteristics for developing practical NLO devices. There are various 2-amino-5-methylpyridine (2A5MP) derivative single crystals available in the literature. However 2A5MP3C4H crystal has not been reported earlier. So, we have carried out our researcher on this new novel crystal. Our findings consequently open a novel path for the logical design of enormous, thermally stable and NLO-active organic complexes for true NLO applications.

Investigation on growth, Hirshfeld surface, optical, thermal and topological properties of nonlinear optical p-nitrophenol single crystal

Investigation on growth, Hirshfeld surface, optical, thermal and topological properties of nonlinear optical p-nitrophenol single crystal

Synthesis, structure, growth, optical, and thermal studies of a third-order nonlinear optical single crystal: 4-dimethylaminobenzaldehyde 2,4-dinitrophenol (DMBDN)

Synthesis, structure, growth, optical, and thermal studies of a third-order nonlinear optical single crystal: 4-dimethylaminobenzaldehyde 2,4-dinitrophenol (DMBDN)

Studies on the synthesis, growth, and characterization of 2-cyanopyridinium salicylate single crystals for nonlinear optical applications

By employing methanol as the solvent in slow solvent evaporation method, a new nonlinear optical organic single crystal of 2-cyanopyridinium salicylate (2-CPSC) was grown. The lattice parameters of the 2-CPSC crystals were found out to be a = 7.7764(9) Å, b = 12.3938(17) Å, c = 12.3685(18) Å, and β = 94.44º using single crystal X-ray diffraction (SCXRD) analysis. The confirmation of crystalline nature was done by powder XRD analysis. The 2-CPSC crystal's chemical composition and functional groups were confirmed by Fourier transform infrared (FTIR) spectral analysis. The optical study was done by ultraviolet-visible-near infrared (UV–Vis-NIR) spectral analysis showing a cutoff wavelength of 338 nm. Studies on the grown 2-CPSC crystal's dielectric and Vicker's microhardness were also conducted. The linear dependence of photocurrent with the applied electric field was revealed for the grown crystals. The 2-CPSC crystal's third-order nonlinearity was investigated by the single-beam Z-scan technique using a continuous He-Ne laser. The open aperture Z-scan reveals the two-photo absorption mechanism and the closed aperture Z-scan study reveals the positive nonlinearity of the 2-CPSC crystals with third order susceptibility value of χ3=2.6763×10−6(esu). The density functional theory (DFT) method of B3LYP level with the 6–31++G(d,p) basis set was used for different quantum chemical calculations like geometry optimization, natural bond orbital (NBO) analysis, mulliken atomic charge, and molecular electrostatic potential (MEP). The higher nonlinearity of the 2-CPSC can be a potential alternative for commercially available potassium dihydrogen phosphate (KDP) and candidate for its application in nonlinear optical devices like optical limiting and optical switching.

Investigation on the growth, characterization, spectroscopic studies and computational analysis of nonlinear optical β-alanine tartrate single crystal

Investigation on the growth, characterization, spectroscopic studies and computational analysis of nonlinear optical β-alanine tartrate single crystal

Novel third order nonlinear optical stilbazolium crystal replaced with 3-methoxy benzaldehyde as donor for optical device applications

A novel organic nonlinear optical stilbazolium group single crystal of 1-methyl-2-[2-(3-methoxystyryl)]-pyridinium iodide (subsequently referred to as MSMI) was grown by the solution growth technique using the method of slow evaporation at ambient temperature. The Single-crystal XRD investigation indicates that the MSMI crystal belongs to a monoclinic crystal system with a centrosymmetric space group. CHN elemental analyser confirms the weight percentage of carbon (C = 51.00 %) hydrogen (H = 4.55 %) and nitrogen (N = 3.94 %) in the MSMI crystal structure. The presence of 16 hydrogen atoms and 15 carbon atoms in the MSMI was affirmed by the Nuclear Magnetic Resonance (NMR) spectroscopic analysis. Fourier Transform Infrared (FTIR) studies confirmed the fundamental vibrations for different functional groups found in the MSMI crystal. The Hirsfeld surface analysis figured out the hydrogen bond interaction and π…π interaction which supports the stability of the crystal structure. The crystal is found to exhibit transmittance of wavelength above 400 nm and has a band gap of 3.05 eV ascertained from UV–Vis-NIR spectroscopic analysis. Photoluminescence (PL) studies reveal that the title crystal has an emission wavelength of 572 nm. The surface characteristics of the title crystal were examined by Atomic Force Microscopy (AFM), and etching studies. The value of Meyer's number is n = 1.8 which is determined by the Vickers microhardness studies. The value of the third-order nonlinear refractive index (n2) is 4.662×10−8 cm2/W, the nonlinear absorption coefficient (β) is 1.305×10−3 cm/W, nonlinear susceptibility (χ(3)) is 9.297×10−5 esu and the optical limiting threshold is 11.43 J/cm2 was ascertained form the Z-scan technique. The results indicate that the MSMI crystal is a potential optical limiter and has promising applications in nonlinear optical devices.

The investigation of optical, thermal, mechanical and dielectric studies on non-linear optical single crystal: N-phthaloylphenylalanine (NPLP)

The investigation of optical, thermal, mechanical and dielectric studies on non-linear optical single crystal: N-phthaloylphenylalanine (NPLP)

Experimental and theoretical interpretations of structural, optical, mechanical and thermal properties of 2-aminopyridinium phthalate single crystals

Nonlinear optical good quality single crystals of 2-aminopyridinium phthalate single crystals are synthesized by solution growth technique. Structural parameters are elucidated by Single Crystal X-ray diffraction method which reveals that the material crystallizes in non-centrosymmetric crystalline framework. Vibrational assignments are interpreted by Fourier Transform Infrared spectral analysis. The thermal, mechanical and laser stability are explored by TG/DTA, microhardness and Laser Damage threshold analysis. The material has good emission nature in the violet emission region. The linear optical properties are elucidated with the help of UV–visible spectral analysis. The intermolecular charge transfer interactions are analyzed by HOMO-LUMO and MESP maps by using Gaussian ’09 software program. The second harmonic generation efficiency of the synthesized material are predicted by Kurtz Perry powder technique.

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.

Nucleation kinetics, chemical etching, hirshfeld surface, and photoluminescence of Rubidium hydrogen oxalate dihydrate NLO single crystal

The nucleation dynamics of a semi-organic Rubidium hydrogen oxalate dihydrate (RbHOH) crystal were assessed using double-distilled water as a solvent medium to obtain good quality crystal using the solution growth technique. Gravimetric analysis of solubility revealed that it has a positive temperature coefficient of solubility, which is appropriate for bulk growth. Other nucleation parameters such as metastable zonewidth, induction period, and interfacial energy were carried out using the classical theory of nucleation. The photoconductivity experiments reveal that the grown crystal exhibits a positive photoconductivity nature. Chemical etching and atomic force microscopy (AFM) experiments were performed on the produced crystal surface. From AFM experiments, effectively assessed amplitude parameters were calculated. Etching studies showed the presence of etch pit patterns such as tiny hillocks and rectangular shapes. Intermolecular interactions were analysed by using Hirshfeld surface analysis. In the photoluminescence (PL) studies, the grown crystal indicates green emission peaks at 519 nm, and the bandgap energy is found to be 4.8 eV. At room temperature, the refractive index of the RbHOH crystal was determined to be 1.669. The nonlinear optical (NLO) efficiency of the grown crystal was examined using a second harmonic generation efficiency test, and it was determined to be 0.58 times that of KDP.

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, growth, and optical applications of N, N′-bis (2-aminophenyl) ethane-1,2-diammonium picrate: An organic crystal

Futuristic organic nonlinear optical single AEDP crystal bearing the IUPAC nomenclature of N, N′-Bis(2-Aminoethyl) Ethane-1,2-Diammonium Picrate was grown via slow evaporation approach in aqueous solvent. The single crystal X-ray diffraction studies were employed for resolving lattice parameters of AEDP single crystal. The data regarding triclinic crystalline structure, bonds vibrations and symmetries of molecular vibrations of the prepared single crystal were realized adopting XRD, FT-IR and vibrational measurements techniques respectively. Evidences regarding excellent crystal optical transparency and maximum crystal non-linear optical properties for the prepared AEDP crystal in the range 200–2000 nm were revealed by Optical absorbance spectrum documented in the UV–vis–NIR wavelength range enhances the scope of unearthing and evolving potential nonlinear systems. Thermal stability and nonlinear optical (NLO) nature of AEDP crystal were inspected by applying differential thermal-thermo gravimetric analysis (DTA–TGA) and second harmonic generation test respectively. The promising features of the crystal leads towards application in the design of nonlinear optical devices and light-controlled electrical switches.

An Investigation on Optical, Mechanical and Thermophysical Properties of Sodium Sulfanilate Dihydrate Single Crystal for Optical Window And Microelectronics Applications

AbstractA nonlinear optical single crystal of sodium sulfanilate dihydrate (SSDH) is formed using the slow evaporation solution approach. Using X‐ray diffraction, the properties of the unit cell are extracted from a single crystal. Using UV‐Vis‐NIR spectroscopy, the optical transmittance of crystals is determined. Mechanical toughness is evaluated using a Vickers micro hardness test. Sodium sulfanilate dihydrate is synthesized as a single crystal and etched for analysis. Photoacoustic spectroscopy is used to examine the sample's thermal diffusivity. The crystal's thermophysical properties are vital for every element of heat transfer incidences, in addition to being employed in many other applications, including as Nd:YAG lasers, Nd:YLF lasers, acousto‐optics, and microelectronics industry applications.

Growth, structural, optical, thermal and terahertz time-domain spectroscopy of l-alanine single crystal: A potential amino acid based nonlinear optical material

In our present work, we focused on the terahertz (THz) based characterization of a very efficient organic nonlinear optical (NLO) single crystal of l-alanine (LA). Using the well-known slow evaporation solution growth method (SEST), an optically transparent amino acid-based LA crystal was effectively grown at room temperature. The structural information of the titled crystal was analyzed using powder X-ray diffraction (PXRD) which confirms the space group P212121 and orthorhombic structure of the crystal. Chemical etching of an as-grown single crystal was analyzed to identify the growth patterns. Fourier transform infrared (FTIR) and FT-Raman spectrometry were used to figure out the major functional groups that were present in the ingot crystal. The optical behaviour of LA crystal was observed through UV–Vis and Photoluminescence (PL) spectroscopies. The single crystal was found to have high transmission values over a wide range of wavelength. The PL results revealed that the main emission happens at 474 nm. Thermal stability of the titled compound was acquired by thermo-gravimetric and the differential thermo-gravimetric (TG-DTG) analysis. Open and closed aperture Z-scan measurements were used to analyze the third order nonlinear behavior of the as-grown sample using a femtosecond Ti-sapphire laser. To analyze the absorption peaks behavior Terahertz time-domain spectroscopy (THz-TDS) was also performed in the range 0.2–2.0 THz. The above study shows variation in absorption coefficient and refractive index at THz frequencies.

Synthesis, growth and investigation of an efficient nonlinear optical single crystal: glycine sodium fluoride

Synthesis, growth and investigation of an efficient nonlinear optical single crystal: glycine sodium fluoride

Growth, Structural, Spectroscopic and Thermal Analyses of Novel Organic Brucinum-3, 5 –Dihydroxybenzoate Dihydrate Single Crystals for NLO Applications

Along the line of available efficient nonlinear optical (NLO) organic single crystals in the literature, it is worthwhile to bring in a novel organic single crystal of Brucinium-3,5-dihydroxybenzoate dihydrate (B35D) which was successfully grown utilizing the technique of slow evaporation of solution at ambient conditions. As the solubility of B35D was found to be the highest in water-ethanol 1:1 mixed solvent among the conventional solvents, crystallization of B35D was accomplished by making use of the solvent. The required confirmation of the crystal structure of the crystal and its lattice parameter could be achieved by the single-crystal X-ray diffraction analysis such that B35D was found to be crystallized in the monoclinic system with the non-centrosymmetric space group C2. The recording of UV-Vis-NIR transmittance spectrum of the crystal was undertaken between the range of 300 and 900 nm whereby the lower optical cutoff wavelength was identified to be 321 nm. The spectral study of photoluminescence was carried out in the range of 300-600 nm by which the band gap energy was calculated to be about 3.8 eV (at 373 nm) indicating that B35D has a violet fluorescence spectrum. The thermal stability and melting point of the title crystal have been investigated through Thermo gravimetric and differential thermal analysis (TG-DTA) such that the thermal stability of the crystal was found to be 95.6 °C. The Nd: YAG Q-switched laser was employed so as to obtain the laser-induced surface damage threshold of the specimen which was estimated to be 3.1 GW/cm2. The Vickers microhardness test was implemented in order to arrive at the mechanical strength of the crystal. The performed non-linear optical study could reveal that the second-order harmonic generation (SHG) efficiency of B35D crystal is 2.16 times higher than KDP. So that B35D crystals are among the class of NLO materials.

A methodical investigation on the growth and characterization of a third-order nonlinear optical novel co-crystal of 8-hydroxyquinolinium phthalate: X-ray, Hirshfeld surface, optical, mechanical, thermal and DFT analysis

A novel non-linear optical single crystal of 8-hydroxyquinolinium phthalate has been as-synthesised by a slow evaporation solution growth technique. Single-crystal X-ray diffraction analysis affirms that it belongs to a monoclinic crystal system. While UV–visible spectroscopy shows its optical transparency with a direct band gap of 2.80 eV, a photoluminescence study confirms a principal yellow emission at 370 nm excitation. Furthermore, the mechanical and thermal properties along with the functional groups’ study have also been laid out in this paper. Intermolecular interactions present in the crystal are ascertained from Hirshfeld surface and fingerprint plot studies. The Z-scan technique has reportedly affirmed third harmonics generation in the same. Theoretical calculations using DFT modelling further testify to the experimental observations thereby laying out the framework of the mentioned crystal in terms of its optimized geometry, molecular electrostatic potential, frontier molecular orbital, natural bond orbital and natural population analysis along with vibrational assignments and UV absorption analysis.