Third order nonlinear optical properties of potassium dichromate single crystals by Z-scan technique

Single crystal of potassium dichromate (KDC) has been grown from aqueous solution by slow evaporation technique. The lattice parameters of the grown crystal were determined by X-ray diffraction analysis. The optical absorption studies reveal that the crystal has UV cut-off wavelength around 240 nm. Thermo gravimetric and differential thermal (TGA/DTA) studies revealed that the crystal thermally stable up to 397.1 °C. The mechanical strength of the grown crystal was carried out by Vickers micro hardness test. The crystal perfection was confirmed by etching studies. Third order nonlinear optical studies was performed using by single beam Z-scan technique using continuous Nd:YAG laser. Closed aperture Z-scan studies reveal the negative nonlinearity in the crystals and open aperture Z-scan reveals the saturation absorption. Also various parameters such as nonlinear refractive index n₂, absorption co-efficient β and nonlinear optical susceptibility χ⁽³⁾ were calculated for the grown crystal.     

Growth,structural, spectral,thermal, electrical and optical characterization of a novel optical material: Triethanolamine picrate single crystals for optical applications

The Triethanolamine picrate (TEAP) single crystal was grown by slow evaporation technique. The grown crystal crystallizes in monoclinic system and P2_1/C is the space group determined by Single crystal X-Ray diffraction method. The vibrational modes and functional groups were elucidated from Fourier Transform InfraRed (FTIR) spectra and Fourier Transform Raman (FT-Raman) spectra. The Ultraviolet - Visible (Uv-Vis) studies accomplished the excitation wavelength of the grown crystal is around 203 nm and 354 nm and it is suitable to exhibit second harmonic generation signal. From the absorption data, remarkable optical properties such as optical band gap energy, extinction coefficient were evaluated. The mechanical strength of the grown crystal was examined by Vickers micro hardness test. The temperature of decomposition was confirmed by Thermo Gravimetric / Differential Thermal Analysis (TG/DTA). Kurtz and Perry technique were confirmed the Non-Linear Optics (NLO) property of the crystal. The electrical properties were explained using Dielectric studies.     

Studies on a novel organic NLO single crystal: L-asparaginium oxalate

A new organic nonlinear optical (NLO) material, L-asparaginium Oxalate (ASOX) was synthesized and single crystals of ASOX with dimension (10*5*5) mm³ was grown from aqueous solution by slow evaporation solution growth technique. Single crystal XRD data reveals that ASOX belongs to triclinic crystallographic system with non-centrosymmetric space group P1. The grown organic NLO crystal was subjected to various characterizations like PXRD, FT-IR analysis, thermal studies, micro hardness test and optical studies for identifying the transparency range and the emission spectrum. The laser damage threshold value was found to be 2.04 GW/cm². The second harmonic efficiency of the grown crystal was examined using Kurtz Perry powder technique and it was found to be 68% that of KDP. Hence it can be effectively employed for various optoelectronic and photonic applications.     

Structural,optical and electrical characteristics of a new NLO crystal

A new nonlinear optical (NLO) organic crystal 1-[4-({(E)-[4-(methylsulfanyl)phenyl]methylidene}amino)phenyl]ethanone (MMP) has been grown by slow evaporation technique at ambient temperature. The crystal structure of MMP was determined by single crystal X-ray diffraction. MMP crystallizes in non-centrosymmetric monoclinic system with space group P2₁. The FT-IR spectrum recorded for new crystal confirmed the presence of various functional groups in the material. MMP was found to be thermally stable up to 300 °C. The grown crystal was optically transparent in the wavelength range of 400–1100 nm. The second harmonic generation (SHG) efficiency of the crystal was measured by the classical powder technique using Nd:YAG laser and was found to be 4.13 times more efficient than reference material, urea. Third order nonlinear parameters were measured by employing the Z-scan technique. The laser damage threshold for MMP crystal was determined to be 4.26 GW/cm². The Brewster angle technique was employed to measure the refractive index of the crystal and the values for green and red wavelengths were found to be 1.35 and 1.33, respectively. The dielectric and electrical measurements were carried out to study the different polarization mechanisms and conductivity of the crystal.     

Growth,fabrication, and testing of bismuth tri-iodide semiconductor radiation detectors

Bismuth tri-iodide (BiI₃) is an attractive material for high energy resolution radiation detectors. For the purpose of this research, detectors were fabricated using single crystals grown from ultra-pure BiI₃ powder; synthesized by the Physical Vapor Transport (PVT) technique. This technique yielded powder with total impurity level of 7.9 ppm. Efforts were also made to purify commercial BiI₃ powder using a custom-built Traveling Zone Refining (TZR) system. Initial trial runs were successful in reducing the total impurity level of the commercial powder from 200 ppm to less than 50 ppm. Using the modified vertical Bridgman technique and a customized sharp tip ampoule, a large BiI₃ single crystal was grown. The crystal had a surface area of 2.2 cm² and a thickness of 0.8 cm, which corresponds to a volume of 1.78 cm³. Radiation detectors were fabricated and then tested by measuring their electrical characteristics and radiation response. An alpha particle spectrum (using a ²⁴¹Am α-source) was recorded at room temperature with a BiI₃ detector 0.09 cm thick and with a surface area of 0.16 cm². The electron mobility was estimated to be 433 ± 79 cm²/V.     

Experimental and theoretical studies on bis(glycine) lithium nitrate (BGLiN): A physico-chemical approach

Good quality and bulk size single crystal (size: 20×13×8 mm³) of bis(glycine) lithium nitrate (BGLiN) was grown by a slow evaporation solution technique from the aqueous solutions at constant temperature i.e. 27 °C using synthesized materials. Crystal system and lattice parameters were determined by single crystals as well as powder X-ray diffraction analysis. The lattice parameters of the titled compound are a=10.0223 Å, b=5.0343 Å, c=17.0510 Å, and V=860.312 Å³ and it crystallized in an orthorhombic system with space group Pca2₁ obtained by single crystal XRD. Elemental composition was confirmed by energy dispersive X-ray spectroscopic analysis. Optical absorption spectrum was recorded and various optical parameters such as optical transmission (~60%), and optical band gap (4.998 eV) were calculated. Photoluminescence study shows that the grown crystal is free from major defects. Crystalline perfection of the grown crystal was assessed and found good. Ground state optimized geometry has been obtained by using DFT with 6-31G(d,p) basis set. HOMO and LUMO energy gap was found to be 6.01 eV and dipole moment was 1.65 D.     

Synthesis,optical, dielectric,thermal and mechanical properties of a nonlinear optical amino acid crystal: Bis-glycine hydrobromide

A semi organic material Bis-glycine hydrobromide (C₄H₁₁N₂O₄⁺Br⁻) has been synthesized by slow solvent evaporation technique. The grown crystal was subjected to single crystal X-ray diffraction studies and its crystal parameters were confirmed. The FTIR analysis confirms the presence of various functional groups present in the title compound. The Kurtz powder second harmonic generation test shows that the crystal is a potential candidate for optical second harmonic generation. The UV–vis spectrum reveals the transparency of the crystal and enumerates the direct band gap energy of the material. The dielectric constant and the dielectric loss were studied as a function of frequency. The thermal studies indicate that the material is thermally stable up to 290 °C. The hardness number was calculated to be 110 kg/mm² from the Vicker's microhardness test.     

Optical, thermal, dielectric and ferroelectric behaviour of sodium acid phthalate (SAP) single crystals

Sodium acid phthalate (SAP), an efficient semi-organic crystal having dimensions 17×8×2 mm³ has been grown from aqueous solution by slow evaporation technique at room temperature within the period of 2 weeks. The lattice parameters of the grown crystals were determined using single-crystal X-ray diffraction analysis. The presence of functional groups was estimated qualitatively by Fourier transform infrared (FTIR) analysis. The band gap energy was determined using optical absorption studies. The TG/DTA analysis reveals that the SAP crystal is thermally stable up to 141.6 °C. The dielectric constant and dielectric loss was studied as a function of frequency and the corresponding activation energy (E_a) has been calculated for the grown crystal. Scanning electron microscope studies enunciate the ferroelectric domain patterns of the SAP crystal. Ferroelectric property of the grown crystal was confirmed by hysteresis loop studies.     

Physicochemical and quantum chemical calculations on new bis (2-amino-6-methylpyridinium 3,4–dimethoxybenzoate) dihydrate organic single crystal for third order nonlinear optical applications

In this work, organic new bis (2-amino-6-methylpyridinium 3,4-dimethoxybenzoate) dihydrate (2A6MD) single crystal was grown by slow evaporation method with the dimensions 20 × 4 × 10 mm³. The structure of grown crystal was confirmed via the single crystal X-ray diffraction. It showed that 2A6MD compound crystallizes in a monoclinic crystal system with Centro symmetric space group P2₁/n. Powder X-ray diffraction analysis confirmed the crystalline nature 2A6MD crystal. FT-IR and ¹H NMR spectra were carried out to confirm the functional groups and various hydrogen exposures in the 2A6MD crystal. UV-Vis spectrometer studies showed that 2A6MD crystal has a lower cut-off wavelength in the UV region and good optical transmittance in the entire visible region. Photoluminescence spectrum reveals the high emission peak at 366 nm with an excitation wavelength of 334 nm. Thermal stability and melting point of the synthesized 2A6MD crystal were investigated using TG-DSC measurement. Vickers's micro hardness test declares that mechanical stability of the grown crystal and their yield strength, elastic stiffness values were evaluated. The chemical etching was analyzed on the 2A6MD surface and the results expressed the growth feature of the crystal. Nonlinear absorption co-efficient, nonlinear refraction and third order susceptibility of synthesized 2A6MD crystal was evaluated by the Z- scan method. The density functional theory (DFT) computations with B3LYP/6-311++G (d,P) basis set to theoretically optimize the molecular geometry, HOMO-LUMO energies, molecular electrostatic potential, NBO analysis and first order hyperpolarizability of 2A6MD confirmed the nonlinear property.     

Customizing optical and dielectric traits of ammonium dihydrogen phosphate (ADP) crystal exploiting Zn2+ ion for photonic device applications

Current investigation is aimed to explore the influence of Zn²⁺ ion on structural, optical and dielectric characteristics of ammonium dihydrogen phosphate (ADP) crystal to explore its widespread suitability for photonic device applications. The slow solvent evaporation technique has been adopted to grow the Zn²⁺ ion influenced ADP (Zn-ADP) crystal. The energy dispersive spectroscopic technique has been employed to determine the constituent elements of Zn-ADP crystal. The optical transmittance of pure and Zn-ADP crystal has been examined within 200–1100 nm by means of UV–visible spectral analysis. The Kurtz–Perry test has been employed to determine the enhancement in second harmonic generation (SHG) efficiency of ADP crystal due to presence of Zn²⁺ ion. The SHG efficiency of Zn-ADP crystal is found to be 3.15 times greater than potassium dihydrogen phosphate (KDP) and 1.79 times higher than ADP. The Z-scan analysis has been performed at 632.8 nm to study the third order nonlinear optical attributes (such as nonlinear refraction (n₂), absorption (β) and cubic susceptibility (χ³)) of Zn-ADP crystal. Dielectric analysis has been carried out within the temperature range of 30 to 90 °C to evaluate the effect of Zn²⁺ ion on dielectric constant and dielectric loss of ADP crystal. The thermal stability of the grown crystal has been investigated within the temperature range of 40–500 °C. The application of developed Zn-ADP crystal for photonic devices has been discussed in vision of obtained results.     

AgGaSe2 : A highly photoconductive material

High resistivity single crystals of AgGaSe₂ were grown by the horizontal Bridgman technique. The near band edge photoconductivity of the grown crystal at room temperature was found to be up to 2×10⁴ times higher than the dark conductivity, under the illumination of 10⁻³ W/cm². The photoconductivity spectrum consists primarily of three peaks, which are attributed to the transitions from Γ₇(A), Γ₆(B) and Γ₇(C) states of valence band to the conduction band Γ₆. The crystal field splitting and the spin-orbit splitting were determined from these peak energy positions of the photoconductivity spectrum.     

Synthesis,vibrational, thermal,mechanical and third-order nonlinear optical properties of sodium 4-methyl-3-nitrobenzoate monohydrate crystal for optical limiting applications✰

A nonlinear optical (NLO) sodium 4-methyl-3-nitrobenzoate monohydrate (Na4M3N) single crystal was synthesized and grown by the slow cooling solution growth method using an ethanol-water (1:1) mixed solvent. Powder X-ray diffraction (PXRD) reveals the crystallinity of Na4M3N compound. The Na4M3N crystal was estimated with a single crystal XRD instrument and it was identified to be in the centrosymmetric space group (P2₁/c) having a monoclinic system. The vibrational, proton (¹H) and carbon (¹³C) NMR spectral analysis substantiates the functional groups, hydrogen and carbons in the synthesized compound. The Hirshfeld surfaces analysis was executed to know the different type of interactions present in the crystal. From the UV–vis spectrum, the optical band gap and cut-off wavelength of the Na4M3N crystal are endowed to be 5.06 eV and 254 nm respectively. The Na4M3N crystal was subjected to a thermogravimetric as well as differential thermal analysis for discerning the thermal characteristics. The LDT value of crystal was endowed to be 5.8 GW/cm² using Nd: YAG laser and the value is superior to that of KDP and Urea. The emission region of the compound was identified by the photoluminescence emission spectrum. The crystalline quality was again confirmed by lifetime measurements. The thermo-optic coefficient (dn/dt) was determined to be –3.5 × 10⁻⁵ K⁻¹. The reverse saturable absorption observed by third-order NLO studies dictates the suitability for optical limiting applications. Vickers microhardness test showed that Na4M3N crystal was a soft material. The average etch pit density (3.2 × 10³ cm⁻²) was determined from chemical etching studies. The complex dielectric constant, electric modulus and electrical conductivity values were measured as a function of frequency to get information on the conduction mechanisms.     

Crystal growth,structural and optical properties of an organic ion-complex crystal: 4-N,N-dimethylamino-4′-N′-methylstilbazolium iodide

4-N,N-dimethylamino-4′-N′-methylstilbazolium iodide (DMSI) compound was synthesized by Knoevenagel reaction method and the crystals were grown by solution growth method. From the single crystal X-ray diffraction study, it is confirmed that DMSI crystal belongs to monoclinic system. The bond-length alternation (BLA) of the DMSI molecule was found to be 0.11 Å, which is responsible for quadratic NLO response. The electronic transition properties and optical constants such as energy gap (E_g), linear refractive index (n₁) were determined using UV–visible and photoluminescence spectral studies. The second order nonlinear optical property of the crystal was examined using Kurtz–Perry powder test. Laser induced damage threshold on (0 0 1) plane of the optically polished crystal was found to be 1.24 GW/cm².     

Growth and characterization of a new organic nonlinear optical crystal: Vanillylideneaniline

Vanillylideneaniline with chemical formula C₁₄H₁₃NO₂ (VAN), a second order nonlinear optical (SONLO) organic single crystal was synthesized and grown for the first time from dimethyl formamide (DMF) employing slow solvent evaporation technique. Single crystal X-ray diffraction data reveals that the crystal belongs to noncentrosymmetric orthorhombic space group C222₁. The high-resolution diffraction curve containing single peak with full width at half maximum (FWHM) of 62 arc s ascertains VAN was perfectly crystallized and free from structural grain boundaries. The formation of the material was confirmed quantitatively by FTIR, ₁H¹ and ¹³C NMR spectral analyses. The UV–vis–NIR spectrum reveals the percentage of the transmission of VAN crystal in the entire region. The variations of dielectric constant (?_r) and dielectric loss (D) with frequency at different temperatures were investigated. The SHG of VAN crystal is confirmed by Kurtz Powder technique. The mechanical strength of the crystal was estimated by Vickers hardness test. VAN has yield strength of 8.70 MPa. Thus the grown organic VAN single crystal can be recommended as a promising candidate for SONLO application and device fabrication technology.     

Growth,structural, mechanical,spectral and dielectric characterization of NaCl-added Triglycine sulfate single crystals

Pure and sodium chloride (NaCl)-added Triglycine sulfate (TGS) crystals were grown from aqueous solutions by slow evaporation technique. The values of concentration of dopants in the mother solution were 0.2, 0.6 and 1 mol%. The solubility of the grown samples have been found out at various temperatures. The determination of unit cell parameters was carried out by single crystal XRD method and found that the grown crystals crystallize in monoclinic structure. The dielectric characterization for the pure and NaCl-doped TGS crystals was performed by measuring the dielectric parameters like dielectric constant and dielectric loss with various frequencies in the range 10²–10⁶ Hz and with the temperatures ranging from 30 to 70 °C and this study reveals an increase of dielectric constant and loss with the increase of NaCl concentration. Studies on mechanical properties like microhardness and density of the grown pure and NaCl-doped TGS crystals were carried out. UV–Visible transmittance studies were carried out for the grown samples. A sharp fall in the transmittance is observed at 228 nm for pure and NaCl-doped TGS crystals. Atomic absorption spectroscopic (AAS) study was done on the NaCl-doped TGS crystals to ascertain the presence of Na⁺ ions in the lattice.     

Spectroscopic properties of Tm -doped Ba3Gd2(BO3)4 crystal

crystal with the size up to Φ 13 mm×44 mm was grown successfully by the Czochralski technique and its optical properties were presented. The absorption cross-section and emission cross-section were presented. Also, the potential laser gain near 1.9 μm was investigated. In the framework of the Judd-Ofelt (J-O) theory, the intensity parameters were calculated to be: Ω₂=11.375×10⁻²⁰ cm², Ω₄=5.077×10⁻²⁰ cm² and Ω₆=6.524×10⁻²⁰ cm². The spectroscopic parameters of this crystal such as the oscillator strengths, radiative transition probabilities, radiative lifetime as well as the branching ratios were calculated, too. This crystal is promising as a tunable infrared laser crystal.     

Effective growth and characterization of piperazinium orthophthalate single crystal yielding high second harmonic generation efficiency

Good quality organic non-linear optical single crystal of piperazinium orthophthalate (PPA) was grown successfully by solution growth at room temperature by achieving the supersaturation state in slow evaporation method. The powder XRD analysis confirms the crystalline nature and structural parameters of the grown PPA crystal. The FTIR and Raman spectra confirm the existence of acid-base functional groups along with their vibrational mode exhibited, present in the grown PPA crystal. UV–Vis spectrum exhibits better transparency in the visible region with cut-off wavelength of 330 nm and the energy band gap (E_g) is analyzed to be 3.8 eV. Photoluminescence spectra shows good optical property with the excitation of 342 nm and two emission peaks in near edge UV band with blue emission at 364 and the energy transition in deep level defect states in crystals by exhibiting the green emission at 533 nm respectively. The thermal stability and the thermal absorption of the PPA crystal were identified by the TG - DTA analysis and obtained thermal stability was up to 88 °C. Vickers micro hardness test illustrates the mechanical stability of the grown PPA crystal and it belong to soft category (n = 4.6). Etching studies illustrates the growth pattern of the grown crystal using water as etchant. FE-SEM analysis shows the perfect smooth morphology of the grown PPA crystal. Second harmonic generation study illustrates the grown PPA crystal (λ = 532 nm) exhibit good nonlinear optical response.     

Growth and characterization of Catena-((μ4-dihydrogen oxalate)-bis(μ3-hydrogen oxalato)-(μ2-dihydrogen oxalate)-tetra-aqua-di-rubidium) {Rb(HC2O4)(H2C2O4)(H2O)2}1∞ single crystal for nonlinear optical applications

A versatile, optically active, metal organic frame work, Catena-((μ₄-dihydrogen oxalate)-bis(μ₃-hydrogen oxalato)-(μ₂-dihydrogen oxalate)-tetra-aqua-di-rubidium) {Rb(HC₂O₄)(H₂C₂O₄)(H₂O)₂}¹∞ (CDBDTR), was grown by the process of slow evaporation using water as the solvent. Single XRD showed that the crystal belongs to the triclinic crystal system with the space group P1. The assigned vibrational frequencies of the compound were identified by the FTIR and FT-Raman techniques. The UV–Vis spectrum revealed the cut off wavelength of the crystal to be 233 nm, and due to this low cut off, it occupies a place in optoelectronic devices. Using the UV-spectra, several optical constants were assessed. The surface morphology was studied using HR-SEM analysis. Energy dispersive X-ray analysis (EDXA) confirmed the presence of rubidium in the crystal. The thermal stability of the crystal was investigated using TG/DTA analysis. The dielectric response of the grown crystal has been thoroughly analysed. A photoluminescence study showed that the crystal has a high degree of luminescence, and its single peak emission affirms its highly ordered crystalline nature. The life time was also analysed. The crystal offers adequate resistance to laser radiation with a threshold value of 4.78 GW/cm². By the Kurtz–Perry technique, the second harmonic generation of the crystal was assessed. The third order nonlinearity was explored using the Z-Scan technique. The figures of merit W and T were calculated in order to find the aptness of the crystal as a promising candidate for optical switching and optical limiting applications.     

Growth and characterization of semi organic nonlinear optical l-Valine Ferric Chloride single crystal by solution growth technique

l-Valine Ferric Chloride single crystal is a new semi organic nonlinear optical material. It has been grown from a mixture of aqueous solutions of l-Valine and Ferric Chloride by slow evaporation solution growth technique at room temperature for the first time. Single crystal XRD analysis revealed that the crystal system belongs to Cubic P with cell parameters are a = 24.38 Å, b = 24.38 Å, c = 24.38 Å and volume is 14,485 Å³. The UV spectrum shows existence of wide transparency window suitable for optoelectronic applications. Thermal stability and melting temperature of the as grown crystal was identified from TG-DTA analysis. Spectroscopic studies have been carried out for analyzing the presence of functional groups, thermal stability and phase transition of the grown crystal. The dielectric loss and the dielectric constant of the crystals were measured as a function of frequency. Photoluminescence study was carried out for grown crystals and the maximum emission occurs has good optical transmission in the entire visible region. Second harmonic generation (SHG) conversion efficiency has been estimated.     

Studies on the optical and mechanical properties of non-linear optical 3-aminophenol orthophosphoric acid (3-amphph) single crystal

Single crystals of semiorganic material 3-aminophenol orthophosphoric acid (denoted as 3-amphph) of size 29 × 17 × 4 mm³ have been grown by the slow evaporation of an aqueous solution of deionized water at 50 °C. The crystal belongs to orthorhombic system with the non centrosymmetric space group P2₁2₁2₁. The lattice parameter values of 3-amphph crystal are a = 4.481(2) Å, b = 9.782(4) Å and c = 18.326(4) Å. The grown crystals are subjected to single crystal XRD studies to identify its morphology and structure. Optical transmittance and second harmonic generation of the grown crystals have been studied by UV–Vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of 3-amphph crystal has been used to calculate the refractive index n, the extinction coefficient k, reflectance R and both the real (?_r) and imaginary (?_i) components of the dielectric constant as a function of wavelength. The optical band gap of 3-amphph is 4.05 eV with direct transition. The anisotropic mechanical behavior of 3-amphph has been analyzed using Vickers microhardness test. The mechanism of growth is revealed by carrying out chemical etching using water as etchant.