Semiorganic Crystal Research Articles

Spectroscopic, thermal, second order and third order NLO studies of N, N’ -dimethyl urea crystal

Nonlinear optical (NLO) crystals are classified into organic, inorganic and semi organic crystals and these crystals are used in the fields of optical communication, optical computing, frequency doubling, optical data processing and opto electronics. In this work an organic NLO crystal namely DMU crystal was prepared. Slow evaporation technique was adopted to grow the single crystals of DMU after the growth period of 35 days. The harvested crystals have been subjected to various characterization techniques like XRD, FTIR, FT-Raman, TG/DTA, SHG, EDAX, impedance, optical and Z-scan studies. From the studies, is observed that DMU crystal has orthorhombic structure and it has the melting point at 105 oC and has the decomposition point at 275 oC. The relative SHG efficiency of DMU crystal was found to be more than one and third order NLO parameters were evaluated. The optical band gap of DMU crystal was found to be 5.008 eV.The results from various studies were analyzed.

Spectroscopic, thermal, second order and third order NLO studies of N, N’ -dimethyl urea crystal

Nonlinear optical (NLO) crystals are classified into organic, inorganic and semi organic crystals and these crystals are used in the fields of optical communication, optical computing, frequency doubling, optical data processing and opto electronics. In this work an organic NLO crystal namely DMU crystal was prepared. Slow evaporation technique was adopted to grow the single crystals of DMU after the growth period of 35 days. The harvested crystals have been subjected to various characterization techniques like XRD, FTIR, FT-Raman, TG/DTA, SHG, EDAX, impedance, optical and Z-scan studies. From the studies, is observed that DMU crystal has orthorhombic structure and it has the melting point at 105 oC and has the decomposition point at 275 oC. The relative SHG efficiency of DMU crystal was found to be more than one and third order NLO parameters were evaluated. The optical band gap of DMU crystal was found to be 5.008 eV.The results from various studies were analyzed.

Growth, structural and optical properties of new semi-organic crystal of tris-thiourea zirconium chloride (TTZrC)

A novel semi-organic crystal of Tris Thiourea Zirconium Chloride (TTZrC) semi-organic material has been synthesized and reported for the first time. Grown crystal was characterized by XRD, FTIR, UV-Vis, PL and FE-SEM analyses. The grown semi-organic crystal could potentially be useful for various opto-electronic device applications.

Growth and characterization of semi-organic NLO single crystal

Growth and characterization of semi-organic NLO single crystal

Synthesis and physicochemical properties of bis(l-asparaginato) zinc(II): A promising new semiorganic crystal with high laser damage threshold for shorter wavelength generation

An exceedingly apparent nonlinear semiorganic optical crystals of bis(l-asparaginato)zinc(II) [BLAZ], was synthesized by a traditional slow evaporation solution growth technique. The cell parameters were estimated from single crystal X-ray diffraction analysis. Spectroscopic study substantiates the presence of functional groups. The UV spectrum shows the sustenance of wide transparency window and several optical constants, such as extinction coefficient (K), refractive index, optical conductivity and electric susceptibility with real and imaginary parts of dielectric constant were calculated using the transmittance data. The fluorescence emission spectrum of the crystal pronounces red emission. The laser induced surface damage threshold of the crystal was measured using Nd:YAG laser. The output intensity of second harmonic generation was estimated using the Kurtz and Perry powder method. The hardness stability was investigated by Vickers microhardness test. The decomposition and thermal stability of the compound were scrutinized by TGA-DSC studies. Dielectric studies were carried out to anatomize the electrical properties of the crystal. SEM analysis reveals the existence of minute crystallites on the growth surface.

Growth and Characterization of 4-carboxyanilinium Dihydrogen Phosphate Semi-organic Complex Crystal

Growth and Characterization of 4-carboxyanilinium Dihydrogen Phosphate Semi-organic Complex Crystal

Determination of Nucleation Kinetics and Crystal Perfection, Optical, Piezoelectric Properties of Semi-organic NLO Single Crystal-Sodium Acid Phthalate Hemihydrate

Semi-organic nonlinear optical single crystals of sodium acid phthalate hemihydrate were grown using slow evaporation technique. Single crystal X-ray diffraction study shows grown crystal belongs to the orthorhombic system with space group B2ab. Nucleation kinetics and nucleation parameters such as critical radius, interfacial tension, and critical free energy change are evaluated using the experimental data. The solubility and the nucleation of the crystal at different temperatures have been analysed. Sodium acid phthalate hemihydrate has a positive temperature coefficient of solubility. The metastable zone width and induction period have been experimentally determined for the optimized crystal growth conditions. UV–Vis–NIR study showed the title compound has high transparency in UV–Vis–NIR region. The nonlinear optical property was measured using Kurtz Perry powder technique and SHG efficiency was 1.1 times that of KDP. The photoconductivity analysis shows that sodium acid phthalate hemihydrate has positive photoconductivity nature. The chemical etching analysis was executed to assess the quality of the crystal. The piezoelectric coefficient d33 is higher than that of several other semi-organic single crystals. The SHG efficiency of the grown crystal is higher than that of several other semi-organic crystals.

Twisted intra-molecular charge transfer investigations of semiorganic triglycine phosphate single crystal for non linear optical applications

NLO materials are gaining importance in technologies such as optical communication, optical computing and dynamic image processing. Many NLO crystals grown by mixing amino acids with various organic and inorganic acids have been reported in the literature. Hence, glycine mixed semi-organic material will be of special interest as a fundamental building block to develop many complex crystals with improved NLO properties. A semi organic Single crystal of Triglycine Phosphate (TGP) which was grown and spectral analysis have been using FTIR and Raman spectral analysis. Natural Bond Orbital Analysis and the atomic natural charges are also predicted. HOMO LUMO energy gap value suggests the possibility of charge transfer within the molecule.

The effect of Ammonium Molybdate on mechanical property of Zinc (tris) Thiourea Sulfate (ZTS) crystal: A Novel NLO crystal

Zinc tris-Thiourea sulfate (ZTS) is one of the notable semi organic non linear optical crystals. In the present investigation 0.01N Ammonium Molybdate doped ZTS crystal was grownusing single diffusion gel growthtechnique which has an advantage over normally employed solution growth method, in terms of controlled nucleation and hence better perfection. A significant morphological alteration was observed due to doping. The functional groups of pure and doped ZTS crystals were recorded and identified using Fourier Transform Infrared Spectroscopic (FTIR) analysis. A study on hardness variation due to doping was conducted using Vickers' Hardness Tests. The increase in hardness observed can be assigned to the impurity hardening effect as found to increased due to effect of dopant. The results obtained are elaborated and discussed in the paper.

N[sbnd]H⋯O hydrogen bonded novel nonlinear optical semiorganic crystal (4-methoxyanilinium trifluoroacetate) studied through theoretical and experimental methods

The new semi-organic crystal of 4-methoxyanilinium trifluoroacetate (4MATFA) was designed through strong NH⋯O hydrogen bonds in the perspective of its nonlinear optical (NLO) properties. The crystalline state of 4MATFA was successfully attained by slow evaporation solution growth method at room temperature. The molecular structure of the grown crystal was determined by single crystal X-ray diffraction technique which confirms the importance of NH⋯O hydrogen bonds in the molecular assembly. The amino group of the cation and carboxylate group of the anion are hydrogen bonded through two primary chains C12(4) and C22(6) motifs and a secondary ring R44(12) motif leading to alternate hydrophobic and hydrophilic layers at z = 0 or 1 and at z = 1/2, respectively. The molecular geometry was optimized theoretically by Hartree-Fock (HF) and Density Functional Theory (DFT) methods with 6-311++G(d,p) basis set. The optimized molecular geometrical parameters and computed vibrational spectra demonstrated the presence of NH⋯O hydrogen bonds and the absence of expected NH⋯F hydrogen bonds. The strong NH⋯O tendency between the ions are observed as strong intensity isolated peak in computed IR spectra and strong intensity broad peak in experimental IR spectrum. Further, the calculated first (β) and second order hyperpolarizability (γ) values showed that the compound is good candidate for NLO applications. The chemical hardness, electro-negativity and chemical potential of the molecule were computed by HOMO – LUMO plot. The frontier orbital has lower band gap value, which indicate the possible optical activity of the molecule. The thermal stability of the grown crystals were confirmed by TG/DTA which showed the thermal stability of the compound upto 150 °C.

Time and temperature induced phase transformation in L‐isoleucine hydrochloride monohydrated crystal

Semi organic crystals have been intensively studied aiming applications in nonlinear optical (NLO). Such applicability requires crystals with both high quality and thermal stability, which make the full characterization of this material a topic issue. In this paper, single crystals of L‐isoleucine hydrochloride monohydrated (L‐Ile.H2O.HCl) was synthesized by slow evaporation technique and characterized by thermal analysis and X‐ray diffraction (XRD) measurements. XRD results at 298 K showed that the sample crystallize with the orthorhombic structure, and the lattice parameters obtained by Rietveld refinement were a = 5.873(3) Å, b = 24.814(4) Å, and c = 6.873(5) Å. Thermal analysis measurements shows four decomposition stages between 328 ‐480 K which were associated with loss of water by desolvation, loss crystallization water and decomposition of L‐Ile.HCl. XRD measurements as a function of temperature up to 428 K show an irreversible phase transformation. This transformation was obtained after 32 hours keeping the L‐Ile.HCl.H2O sample at 413 K. The analysis shows that phase transformation occurs due to water and chlorine losses without destroy the amino acid carbon chain and in the end of transformation only the precursor amino acid remains. L‐Ile.HCl.H2O present low thermal stability and the phase transformation is time and temperature dependent.

Nucleation kinetics, crystal growth and optical studies on lithium hydrogen oxalate monohydrate single crystal

Semi-organic lithium hydrogen oxalate monohydrate non-linear optical single crystals have been grown by slow evaporation solution technique at 40°C. The nucleation parameters such as critical radius, interfacial tension, and critical free energy change have been evaluated using the experimental data. The solubility and the nucleation curve of the crystal at different temperatures have been analyzed. The crystal has a positive temperature coefficient of solubility. The metastable zone width and induction period have been determined for the aqueous solution growth of lithium hydrogen oxalate monohydrate. The UV–vis–NIR spectrum showed this crystal has high transparency. The photoconductivity studies indicate lithium hydrogen oxalate monohydrate has positive photoconductivity behaviour. The low etch pit density observed on ( 0 0 1) crystal surface and the high resolution x-ray difraction analysis indicate the good quality of the grown crystals

Thermal and Optical Properties of Glycine Crystals with Additives of Nitrates

Semi-organic crystals of Glycine Sodium nitrate Calcium nitrate (GSC) with two different molar ratios were grown using slow evaporation technique. Crystals of size 22 × 16 mm were obtained within time period of 3-4 weeks at ambient temperature. The compositional study and purity of the crystals were determined using Energy Dispersive X-ray Analysis (EDAX) and CHN Analyzer. Surface of the crystals was studied at micrometer scale with optical microscopy. These crystals were characterized by powder X-ray diffraction and indexing of diffraction pattern was done based on monoclinic system. We also studied thermal properties of these crystals using TGA/DTA/DTG analysis. From UV-Vis spectra we could observe wide transparency window from these crystals in the visible region, which can be useful for opto-electronic applications.

Synthesis, growth and characterization of (tri) glycine barium chloride single crystal for applications in the domain of optoelectronics and photonics

The single crystal of (tri) glycine barium chloride, a semiorganic crystal has been grown from an aqueous solution by slow evaporation technique at room temperature. Glycine and barium chloride were used in molar ratio of 3:1 for synthesis. Good optical quality single crystal of size 18 × 10 × 5 mm3 was harvested in a period of 5 weeks (35 days) at pH value 5. The lattice parameters have been measured by single crystal XRD study. The crystalline nature has been confirmed by powder XRD study. Fourier transform infrared spectroscopy study confirmed the presence of functional groups in grown crystal. Transmission spectrum has been recorded and the cut-off wavelength has been determined as 234 nm. Also optical constants like band gap, refractive index, reflectance, extinction coefficient and electric susceptibility were determined from UV–Vis-NIR spectrum. The thermal behavior of the crystal was investigated by TG–DTA analysis, which reveals that crystal has thermally stable up to 169 °C. Non-linear optical property of the grown crystal has been confirmed using the Kurtz and Perry powder technique and result was compared with KDP. The dielectric behavior of the sample was analyzed with various frequencies at different temperatures. The photoconducting nature of the crystal was analyzed by photoconductivity study.

Synthesis, growth, structure, mechanical and optical properties of a new semi-organic 2-methyl imidazolium dihydrogen phosphate single crystal

A new semi-organic compound, 2-methyl imidazolium dihydrogen phosphate (2MIDP), was prepared and good quality single crystals of 2MIDP were grown by slow evaporation solution growth technique. Crystal structure elucidated using Single crystal XRD showed that 2MIDP crystallizes in monoclinic system with P21/c space group. FT-IR, UV-Vis-NIR, Fluorescence and FT-NMR spectra confirm the molecular structure of 2MIDP. The UV-Vis-NIR spectra established the suitability of the compound for NLO applications. TG-DSC showed that 2MIDP is thermally stable up to 200°C. Mechanical characteristics like hardness number (Hv), stiffness constant (C11), yield strength (σv), fracture toughness (Kc) and brittleness index (Bi) were assessed using Vicker’s microhardness tester. Third order nonlinear optical properties determined from Z-scan measurement using femto and picosecond lasers showed two photon reverse saturable absorption. The enhancement of nonlinear optical properties in femto second laser, revealed the suitability of 2MIDP for optical limiting applications.

Synthesis, structural and optical properties, ferromagnetic behaviour, cytotoxicity and NLO activity of lithium sulphate doped l-threonine

Lithium Sulphate doped l-threonine (Li2SO4-LT), a semi-organic crystal, has been synthesised and grown by slow evaporation technique at room temperature. The grown crystal was subjected to single crystal X-ray diffraction analysis in order to establish their crystalline nature. Li2SO4-LT crystal belongs to the orthorhombic crystal system (a=7.66Å, b=5.11Å, c=13.60Å) with space group P212121. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) study was carried out to quantify the concentration of lithium element in the grown crystal. The results show that 0.07mol of lithium sulphate has been incorporated into the parent system. The grown material has been found to possess wide transparency in the range 240–1100nm with lower cut-off wavelength at 240nm. The optical band gap was calculated as 4.92eV using optical absorption spectrum and Tauc's relation. Fourier transform infrared (FTIR) spectroscopic study was performed to identify the functional groups present in the grown crystal. The surface features of the grown crystal were analyzed using Scanning Electron Microscope (SEM) analysis. The magnetic property was studied with the help of Vibrating Sample Magnetometer (VSM). The coercivity and retentivity of the material were measured from the hysteresis curve as 550.06G and 79.50×10−6emu respectively. 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay method was performed to understand the cytotoxicity or anticancer activity of the sample. The cell viability and cytotoxicity of the sample against MCF-7 cells were estimated as 49.41% and 50.59% respectively at a concentration of 250μg. The second harmonic generation (SHG) efficiency was measured by the Kurtz powder technique using Nd:YAG laser and was found to be 1.46 times that of standard potassium dihydrogen phosphate (KDP).

Growth and characterization studies of an efficient semiorganic NLO single crystal: 2-Amino 5-nitropyridinium sulfamate (2A5NPS) by assembled temperature reduction (ATR) method

Semiorganic crystals of 2-amino 5-nitropyridinium sulfamate (2A5NPS) were grown by slow evaporation and slow cooling method. A asymmetric grown crystal was subjected to single crystal X-ray diffraction and X-ray powder diffraction by using Bruker Kappa APEX11 CCD diffractometer and Philips analytical powder X-ray diffractometer respectively. Vibrational frequency of 1:1 equimolar ratio single crystals of 2-amino 5-nitropyridinium sulfamate (2A5NPS) was measured using FTIR and thermal stability of the grown crystal of 2-amino 5-nitropyridinium sulfamate (2A5NPS) was also measured. Optical properties of the grown crystal and NLO test were also carried out.

Studies on an L-leucine hydriodide semiorganic crystal for frequency conversion applications

An L-leucine hydriodide semiorganic crystal has been synthesized and grown by a slow evaporation technique. The lattice parameters of the grown crystal have been confirmed using single-crystal x-ray diffractometry. Various functional groups present in the crystal were identified by Fourier transform infrared (FTIR spectral) assessment. The optical transmission percentage of the crystal was ascertained by UV–vis-near-infrared (NIR) studies. The thermal stability of the crystal was determined by thermogravimetric and differential thermal analysis curves. The mechanical behavior of the crystal was studied using the Vicker’s microhardness analysis. The dielectric properties of the crystal have been investigated for varying temperatures. The second-harmonic generation efficiency was measured by the Kurtz and Perry powder technique and the efficiency is comparable to that of potassium dihydrogen orthophosphate.

Structural, dielectric properties & Activation Energy on l-Histidine monohydrochloride phosphate – Nonlinear optical crystal

Single crystals of l-histidine monohydrochloride phosphate (LHP), semi organic crystal were grown by slow evaporation technique. The grown crystals were subjected to various studies such as single crystal X-ray diffraction (XRD), Dielectric properties such as frequency variation, temperature variation & activation energy of the grown crystal were found. Single crystal X-ray diffraction studies reveal the crystal belongto orthorhombic crystallographic system.

Studies on structural, optical, mechanical properties of undoped and doped l-histidine monohydrate monohydrochloride(LHMHCL)

Single crystals of l-histidine monohydrate monohydrochloride (LHMHCL), semi organic crystal were grown by slow evaporation technique. The grown crystals were subjected to various studies such as single crystal X-ray diffraction (XRD), Powder XRD, UV-vis studies, Fourier transform infrared (FTIR), Energy dispersive analysis by X-rays (EDAX). Single crystal X-ray diffraction studies reveals the crystal belong to orthorhombic crystallographic system.