Studies on the growth,structural, optical,thermal and electrical properties of nonlinear optical cadmium mercury thiocyanate glycol monomethyl ether single crystal

Single crystals of cadmium mercury thiocyanate glycol monomethyl ether (CMTG) were grown from a mixed solvent of glycol monomethyl ether (GME):water (1:1) by slow evaporation method. The crystal structure and morphology were confirmed by single crystal X-ray diffraction analysis. Presence of functional groups and the coordination of glycol monomethyl ether (GME) and thiocyanate (SCN⁻) in the CMTG compound were confirmed by FT-IR analysis. Optical transparency of the grown crystal was studied by UV–Vis spectroscopy. Thermal stability and decomposition process were studied by means of TGA and DTA analysis. Dielectric measurement on CMTG single crystal was carried out for various frequency and temperatures. The surface studies by scanning electron microscopy reveals the formation of layer growth pattern indicative of 2D nucleation mechanism. From the second harmonic output power measurement by Kurtz powder method, it is observed that CMTG is a potential material for nonlinear optical applications among the bimetallic thiocyanate adducts series.     

Synthesis,growth and physicochemical properties of an organometallic nonlinear optical crystal: Mercury cadmium chloride thiocyanate

SCN⁻ ligand based organometallic non-linear optical mercury cadmium chloride thiocyanate (MCCTC) crystals are grown from water plus methanol mixed solvent by slow evaporation technique. The grown crystals are confirmed by single crystal X-ray diffraction analysis. MCCTC exhibits a SHG efficiency which is nearly 17 times more than that of KDP. The dielectric constant, dielectric loss and ac conductivity measurements of the sample have been carried out for different frequencies (100 Hz to 5 MHz) and, temperatures (308–388 K) and the results are discussed. Photoconductivity study confirms that the title compound possesses negative photoconducting nature. The surface morphology of MCCTC was also investigated.     

Intracavity-frequency-doubling of a 946 nm Nd:YAG laser with cadmium mercury thiocyanate crystal

We report the intracavity-frequency-doubling of a 946 nm Nd:YAG laser with a CMTC crystal at room temperature. A cw output power of 1.64 mW of blue light at 473 nm is obtained. To our knowledge, this is the first time that CMTC crystal has been used to frequency double a 946 nm Nd:YAG laser.     

Studies on the structural,optical, dielectric and mechanical properties of non-linear optical manganese mercury Tetrathiocyanate glycol mono methyl ether (MMTG) single crystal

Non-linear optical manganese mercury teterathiocyanate glycol monomethyl ether [MnHg(SCN)₄(C₃H₈O₂)] compound was synthesized and single crystals were grown from water-glycol monomethyl ether (1:1) mixed solvent by slow cooling method. Structure and crystallinity of the grown crystal were confirmed by both single crystal and powder X-ray diffraction analysis. Presence of functional groups and coordination of glycol monomethyl ether and thiocyanate in MMTG were confirmed by FT-IR analysis. Optical transmittance and second harmonic generation of the grown crystal were studied by UV–Vis spectrum and Kurtz powder technique. A dielectric study was performed on the MMTG single crystal to study the power dissipation of the material in the presence of alternating electric field. Mechanical behaviour was analysed using Vicker’s microhardness test. Optical surface damage measurement was carried out to confirm the suitability of MMTG crystal for NLO applications.     

Effect of N ion implantation on the optical properties of an organometallic complex—Zinc cadmium thiocyanate single crystal

A highly efficient non-linear optical organometallic compound zinc cadmium thiocyanate (ZCTC) single crystal was grown by solvent evaporation method. The as grown single crystals were implanted with 45 keV N⁵⁺ ions having energy at various fluencies of 1 × 10¹⁵, 5 × 10¹⁵, 1 × 10¹⁶ and 5 × 10¹⁶ ions/cm². The surface modification induced by the ion implantation was studied using scanning electron microscopy. The UV spectrum shows an increase in absorbance with the increase in the dosage of the ions implanted. There is a red shift in the cut off wavelength due to implantation which may be attributed to the lattice damage produced during implantation. From the Raman spectra, it is observed that there is no shift in the peak positions or any extra peaks due to implantation confirming that the nitrogen ions are not substituted into the lattice. The FWHM, area and intensity of the Raman peak corresponding to CN stretching vibration were calculated and the influence of ion implantation on these parameters was discussed. The effect of implantation on the PL spectra was analysed and discussed in detail. The change in refractive index of the sample due to implantation was reported.     

一组新型络合物晶体结构与光学性能的研究

研究了二氯三烯丙基硫脲合镉(ATCC),二氯三烯丙基硫脲合汞(ATMC)和二溴三烯丙基硫脲合镉(ATCB)三种晶体的结构特点.首次报道了ATMC和ATCB晶体的非线性光学系数及倍频性能;文中分析比较了三种晶体的非线性光学性能;讨论了晶体结构与性能的关系,为探索高效非线性光学新材料提供依据.     

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.     

Studies on the electrical, linear and nonlinear optical properties of Manganese mercury thiocyanate bis-dimethyl sulfoxide, an efficient NLO crystal

Manganese mercury thiocyanate bis-dimethyl sulfoxide (MMTD), a novel organo-metallic nonlinear optical (NLO) crystal, was grown by a slow evaporation technique over a period of 30 days. The grown crystal was subjected to single crystal X-ray diffraction to determine the unit cell parameters. The optical properties of MMTD were investigated by UV-Vis-NIR, FTIR and FT-Raman spectroscopic techniques. The second harmonic generation (SHG) efficiency of the sample was measured using a Q-switched, mode-locked Nd:YAG laser and the results were compared with urea and manganese mercury thiocyanate (MMTC). The thermal parameters, such as the thermal diffusivity (α), thermal effusivity (e), thermal conductivity (k) and heat capacity (c_p) of MMTD were measured by the photopyroelectric (PPE) technique and the results are discussed. The dielectric response and mechanical properties of MMTD have also been investigated and reported.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Synthesis and crystal structure of bis(di-n-butyldithiocarbamato)(1,10-phenanthroline)cadmium(II)

A new mixed-ligand complex, Cd(S₂CN(C₄H₉)₂)₂Phen, is synthesized and investigated by thermal, element, and IR analyses and by diffractometry of polycrystals (DRON-3M, CuK_α radiation, Ni filter). The crystal structure was determined on a CAD-4 Enraf-Nonius automatic diffractometer (MoK_α radiation, θ from 1.5 to 25?, 2325 nonzero independent reflections, 190 refined parameters, R = 0.036 for I > 2Σ(I)). Crystal data for C₃₀H₄₄CdN₄S₄ : a = 15.592(3), b = 22.724(5), c = 9.922(2) å, space group Pbcn, V = 3515.5(12) å₃, Z = 4, M = 701.33, d_calc = 1.325 g/cm³. The structure involves monomeric molecules in which the cadmium atom has a distorted octahedral environment.     

Orientational disorder and geometrical isomeric effect on nonlinear optical properties of poly bis(glycine)cadmium chloride

Poly bis(glycine)cadmium chloride (BGCC) crystals of both undoped and doped with thiourea (Tu) were grown from saturated solutions by a slow evaporation technique. The geometrical isomerism of the octahedral BGCC molecule is investigated using single crystal XRD, powder XRD and FT-IR. The significant difference between the two isomers namely facial (fac) and meridional (mer), is explained in terms of the different point group symmetries of C₃ and C₁, respectively. The loss of point group symmetry from C₃ to C₁ is attributed for the observed powder second-harmonic generation (SHG). Semi-empirical calculations from the optimized geometrical parameters also supported non-linear optical properties of the material.     

Synthesis,crystal growth and characterization of novel semiorganic nonlinear optical crystal: Dichloro(beta-alanine)cadmium(II)

Semiorganic nonlinear optical material of dichloro(beta-alanine)cadmium(II) (DCBAC) have been synthesized and single crystals were grown by solvent evaporation method at room temperature. The lattice parameters of the grown crystals are determined by single crystal XRD. The modes of vibration of different molecular groups present in the sample were identified by the FTIR spectral analysis. Thermal stability of the crystal was investigated using thermo gravimetric analysis (TGA) and differential thermal analysis (DTA). The dielectric constants of the crystal were studied as a function of frequency and the results are discussed. The grown crystals are subjected to microhardness studies and the variation of the microhardness with the applied load is studied. The optical transmission spectra and second harmonic generation (SHG) were investigated to study its linear and nonlinear optical properties. The nonlinear optical (NLO) property of the crystal was confirmed by powder second harmonic generation (SHG) test. SHG efficiency is comparable to that of KDP.     

Theoretical study of diaquamalonatozinc(II) single crystal for applications in non-linear optical devices

The aim of the present paper is to employ theoretical methods to investigate the zero field splitting (ZFS) parameter and to investigate the position of the dopant in the host. These theoretical calculations have been compared with the empirical results. The superposition model (SPM) with the microscopic spin-Hamiltonian (MSH) theory and the coefficient of fractional parentage have been employed to investigate the dopant manganese(II) ion substitution in the diaquamalonatozinc(II) (DAMZ) single crystal. The magnetic parameters, viz. g-tensor and D-tensor, has been determined by using the ORCA program package developed by F Neese et al. The unrestricted Kohn–Sham orbitals-based Pederson–Khanna (PK) as the unperturbed wave function is observed to be the most suitable for the computational calculation of spin–orbit tensor (\(D^{\mathrm{SO}})\) of the axial ZFS parameter D. The effects of spin–spin dipolar couplings are taken into account. The unrestricted natural orbital (UNO) is used for the calculation of spin–spin dipolar contributions to the ZFS tensor. A comparative study of the quantum mechanical treatment of Pederson–Khanna (PK) with coupled perturbation (CP) is reported in the present study. The unrestricted Kohn–Sham-based natural orbital with Pederson–Khanna-type of perturbation approach validates the experimental results in the evaluation of ZFS parameters. The theoretical results are appropriate with the experimental ones and indicate the interstitial occupancy of \(\hbox {Mn}^{2+}\) ion in the host matrix.     

Structural, spectral and mechanical studies of bimetallic crystal: cadmium manganese thiocyanate single crystals

A nonlinear optical bimetallic thiocyanate complex crystal, cadmium manganese thiocyanate (CMTC) has been successfully synthesized. The growth of single crystals of cadmium manganese thiocyanate has been accomplished from aqueous solution using slow evaporation method. The presence of manganese and cadmium in the synthesized material was confirmed through energy dispersive spectrum (EDS) analysis. Structural analysis was carried out using powder X-ray diffractometer (PXRD) and crystalline perfection of the grown crystals was ascertained by high-resolution X-ray diffraction (HRXRD) analysis. Fourier transform infrared (FTIR) spectrum was taken to confirm the functional groups. The transmittance spectrum of the crystal in the UV–visible region has been recorded and the cutoff wavelength has been determined. The dielectric measurements for the crystals were performed for various frequencies and temperatures. The mechanical properties were evaluated by Vickers microhardness testing, which reveals hardness and stiffness constant of the crystals.     

Growth, structural, optical and electrical behavior of glycine potassium nitrate (GPN) crystal with non-linear optical response

New trapezoidal, non-linear optical crystals of glycine potassium nitrate (GPN) have been grown by slow cooling from solutions with an initial pH of 4.3. Chemical composition, phase formation and functional groups have been verified by CHN, EDAX, XRF, NMR, XRD, FTIR and Raman studies. UV studies show a much lower cut off wavelength (195 nm) compared to the much investigated glycine sodium nitrate (GSN). The powder SHG efficiency of GPN is found to be 0.6 times compared to that of potassium dihydrogen phosphate (KDP). Cut and polished crystals exposed to light indicate positive photoconductivity. Electrical conductivity studies show an activation energy of 0.16 eV and the dielectric loss is found to decay drastically at higher frequencies (1 MHz) which is desirable in electronic applications. Vickers microhardness studies indicate a Mayer's index value of 2.78. Well resolved, elongated and oriented etch pits have been observed on the side habit face (220) treated in glacial acetic acid for 5 s. Typical circular features resisting the formation of etch pits representing impurity elements have been observed on the cleavage faces. Moisture has been traced on the surface of the crystals subjected to heat treatment.     

A new molecular C60 complex with bis(methylenedithio)tetrathiafulvalene (BMDT-TTF): Synthesis, crystal structure, and properties

A new molecular C₆₀ complex of the composition (BMDT-TTF) · C₆₀ · 2CS₂ (I) with the bis(methylenedithio)tetrathiafulvalene (BMDT-TTF) organic donor is synthesized. The molecular and crystal structures of this complex are determined by x-ray diffraction. The (BMDT-TTF) · C₆₀ · 2CS₂ (I) compound crystallizes in a monoclinic crystal system. The main crystal data are as follows: a=13.550(5) Å, b=9.964(7) Å, c=17.125(8) Å, β=99.52(4)°, V=2280(2) ų, M=1229.45, and space group P2₁/m. Crystals of I have a layered structure: layers consisting of C₆₀ molecules alternate with layers composed of BMDT-TTF and CS₂ molecules. It is found that, in complex I, the donor and C₆₀ molecules are linked through the shortest contacts, which leads to a change in the molecular geometry of BMDT-TTF. The donor molecules in a crystal layer are characterized by the shortest S...S contacts. The IR data indicate the electroneutrality of the fullerene molecule. The electrical conductivity of (BMDT-TTF) · C₆₀ · 2CS₂ single crystals is measured using the four-point probe method at room temperature: σ_RT=2×10^?5 Ω^?1 cm^?1.     

氢键对2-(N-甲基)氨基-5-硝基吡啶分子非线性光学性质的影响

本文在杂化密度泛函理论水平上研究了溶剂对2-(N-甲基)氨基-5-硝基吡啶分子非线性光学性质的影响.在溶剂中,构造了包括氢键作用的超分子体系,在优化结构的基础上分别研究了由极化连续模型模拟的溶剂与该分子的长程相互作用、溶剂与该分子的氢键相互作用以及溶剂与包括氢键作用的超分子体系整体的相互作用对分子的几何结构、非线性光学性质、紫外吸收光谱和电荷分布等特性的影响.结果表明,溶剂中分子电偶极矩、线性极化率和第一超极化率都增大,而溶剂与溶质分子通过氢键形成的超分子结构与单体有着明显区别.因此,氢键对分子结构和性质的影响较大,从而将明显的影响该类分子的非线性光学性质.     

The effects of crystal structure on optical absorption/photoluminescence of bis(8-hydroxyquinoline)zinc

In this paper, the transformation processes of two types of bis(8-hydroxyquinoline)zinc: Znq₂ dihydrate and anhydrous (Znq₂)₄ were investigated by X-ray diffraction (XRD), infrared spectra (IR), scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG). The effects of crystal structure on optical properties of bis(8-hydroxyquinoiline)zinc were analyzed. Znq₂ dihydrate can be transformed into anhydrous (Znq₂)₄ during heating under vacuum. Reversal transformation occurs by the interaction between chloroform and (Znq₂)₄. But (Znq₂)₄ was partially transformed into Znq₂ dihydrate by the interaction between ethanol and (Znq₂)₄. The different molecular structure results in different crystal stacking and electronic structure, thereby affect its optical properties.     

Synthesis, crystal growth and characterization of a chiral compound (triphenylphosphine oxide cadmium iodide): A new semiorganic nonlinear optical material

Synthesis of semiorganic material, triphenylphosphine oxide cadmium iodide (TPPOCdI), is reported for the first time. Employing the temperature reduction method, a crystal of size 16×7×6 mm³ was grown from dimethyl sulfoxide (DMSO) solution. Three dimensional crystal structure of the grown crystal was determined by single crystal X-ray diffraction study. The complex crystallizes in the chiral orthorhombic space group P2₁2₁2₁. FTIR study was carried out in order to confirm the presence of the functional groups. UV-vis-NIR spectral studies show that the crystal is transparent in the wavelength range of 290-1100 nm. The microhardness test was carried out, and the load hardness was measured. Thermogravimetric and differential thermal analyses reveal the thermal stability of the crystal. Second harmonic generation efficiency of the powdered TPPOCdI, tested using Nd: YAG laser, is ∼0.65 times that of potassium dihydrogen orthophosphate.