Influence of transition metal doping on tris(thiourea)zinc(II) sulphate crystals

Optical, thermal and dielectric properties of Ni(II)-doped tris(thiourea)zinc(II) sulphate single crystals grown by slow evaporation solution growth technique has been investigated. The lattice parameters of the as-grown crystals were obtained by single crystal X-ray diffraction analysis. The modes of vibrations of different functional groups present were identified by FT-IR studies. The surface morphological changes are observed in the doped specimen. The structure and the crystallinity of the material were confirmed by powder X-ray diffraction analysis. The UV–vis optical absorption spectrum shows the lower optical cut-off at ∼284 nm and the crystals are transparent in the entire visible region. The relative second harmonic generation efficiency measurements reveal the enhancement of efficiency by doping with small quantities of Ni(II).     

Enhancement of second harmonic generation efficiency: Cs(I)-doped tris(thiourea)zinc(II) sulphate crystals

The effect of dopant cesium (Cs(I)) over a concentration range from 1 to 10 mol% on the growth process, morphology, thermal and optical properties of tri(thiourea)zinc(II) sulfate (ZTS) single crystals grown by slow evaporation solution growth technique has been investigated. Incorporation of Cs(I) into the crystal lattice was well confirmed by energy dispersive X-ray spectroscopy (EDS). The lattice parameters of the as-grown crystals were obtained by single crystal X-ray diffraction analysis. The reduction in the intensities observed in powder X-ray diffraction patterns of doped specimen and slight shifts in vibrational frequencies in fourier transform infrared spectra (FT-IR) indicate the lattice stress as a result of doping. Thermal studies reveal the purity of the material and no decomposition is observed up to the melting point. High transmittance is observed in the visible region and the cut-off λ is ～280 nm. The surface morphology of the as-grown specimens was studied by scanning electron microscopy (SEM). The second harmonic generation (SHG) efficiency of the host crystal is enhanced greatly in the presence of high concentrations of the dopant.     

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.     

Growth and characterization of pure and doped organic nonlinear optical single crystal: l-Alanine alaninium nitrate (LAAN)

The pure l-alanine alaninium nitrate (LAAN) single crystals and LAAN crystals doped with lanthanum oxide (La₂O₃), sodium chloride (NaCl), urea (CH₄N₂O), glycine (C₂H₅NO₂) and thiourea (CH₄N₂S) were grown by slow evaporation method. The X-ray diffraction analysis, scanning electron microscopy (SEM), energy dispersive X-ray (EDAX) analysis, UV–vis spectral analysis, dielectric studies and powder SHG measurement are studied systematically. The slight changes in the lattice parameters were observed for the doped crystals compared to pure LAAN crystal. The incorporation of doping into the crystal lattice was confirmed by energy dispersive X-ray analysis. There is no change in the transmission window due to doping and the percentage of transmission in doped samples was found to increase as compared to that of pure LAAN crystal. The dielectric constant of pure crystal was found to be less than that of doped crystals. The AC conductivity was found to increase after doping and with the increase in temperature. A green radiation of 532 nm was observed from the pure and doped LAAN crystals confirming the second harmonic generation (SHG) of the crystals.     

EPR and Optical Absorption Studies of VO2+-Doped Diammonium Hexaaqua Magnesium(II) Sulfate

Electron paramagnetic resonance (EPR) studies of VO²⁺ impurity ion in single crystals of diammonium hexaaqua magnesium(II) sulfate are carried out at 9.5 GHz (X-band) at room temperature. Different spin-Hamiltonian parameters are determined. VO²⁺ is expected to enter the lattice substitutionally. Superhyperfine splitting is also observed. An EPR study of a powder sample is done that supports the data obtained from single crystal studies. Optical absorption studies are also performed at room temperature. The crystal field parameter (D_q), tetragonal parameters (D_s and D_t), and various bonding parameters are evaluated to estimate the covalency and nature of bonding of VO²⁺ with its different ligands.     

Effect of Mn(II) doping on crystalline perfection, nonlinear, optical and mechanical properties of KDP single crystals

The effect on crystalline perfection, second harmonic generation (SHG) efficiency, optical transparency and mechanical properties due to Mn(II) doping in KDP single crystals grown by slow evaporation solution technique by adding different quantities of MnCl₂ in the solution has been investigated. The actual incorporated quantity of Mn(II) in the crystals was evaluated by atomic absorption spectroscopy. Powder XRD study confirms the crystal system of KDP and found no additional phases at all doping levels (1 to 5 mol%). The influence of Mn(II) doping on the crystalline perfection has been assessed by high-resolution XRD and these studies revealed that the grown crystals could accommodate Mn(II) in the interstitial positions of the crystalline matrix of KDP only up to some critical concentration, above which the crystal developed structural grain boundaries. The relative SHG efficiency of the crystals was found to be increased sharply at low concentrations (1 mol%), and above this value it was decreased as the concentration increases though it is still higher than that of pure KDP. UV-Vis studies also revealed the same behavior with a significant enhancement at 1 mol% concentration and later gradually decreased. Good increment in the hardness values has been observed by increasing the doping concentrations.     

Growth and characterization of bis(thiourea) zinc carbonate (BTZC) a new nonlinear optical material by solution growth slow evaporation technique

A new semi-organic nonlinear optical bis(thiourea) zinc carbonate (BTZC) material has been synthesized. BTZC single crystals were grown from aqueous solution by slow evaporation method. The grown crystals were characterized by single crystal X-ray diffraction (XRD), powder XRD, FTIR, UV–visible, thermal, and second harmonic generation (SHG) analysis. Single crystal XRD study has been carried out to identify the lattice parameters. FTIR studies confirm the functional groups present in the grown crystal. Optical transmission studies have confirmed that the grown crystal is highly transparent. Thermo gravimetric and differential thermal analyses reveal the good thermal stability of the material. The SHG conversion efficiency of BTZC was determined using Kurtz powder technique and found 1.3 times more than that of KDP.     

Synthesis,spectral, thermal and optical characterization of benzyltributylammonium trichlorobarium(II) monohydrate crystal

A new nonlinear optical semiorganic crystal, benzyltributylammonium trichlorobarium(II) monohydrate was grown by slow evaporation solution growth method at ambient temperature. The powder X-ray diffraction pattern of the crystal confirms its crystallinity. The absorption spectrum of the material shows a peak at 265 nm and no absorption observed in the entire visible region indicates that the compound can be used as a nonlinear optical material. The optical transmittance spectrum of the grown crystal shows a lower cut-off wavelength at 235 nm with transparency of 88%. Thermal stability of the crystal was studied by thermogravimetry-differential thermogravimetry and differential thermal analyses (TG-DTG and DTA). The differential scanning calorimetry (DSC) analysis shows thermal anomalies in the heating and cooling cycles that indicates the occurrence of a first order phase transition. The various characteristics absorption chemical bands and BaCl₃⁻ vibration were assigned through fourier transform infrared (FTIR) spectral analysis. The second harmonic generation efficiency (SHG) of the grown crystal was analyzed by Kurtz–Perry powder technique using Nd:YAG laser. The dielectric constant and dielectric loss of the compound decrease with increase in frequency.     

Optical,thermal and mechanical characterization of Al(III)/Sb(III)-doped tris(thiourea)zinc(II) sulphate crystals

The influence of Al(III)/Sb(III)-doping on the properties of tris(thiourea)zinc(II) sulphate (ZTS) crystals grown by slow evaporation solution growth technique is reported. The as-grown crystals belong to orthorhombic system and cell parameters are, a = 7.77 Å, b = 11.13 Å, c = 15.47 Å, V = 1338 Å³ (Al(III)-doped) and a = 11.1996 Å, b = 7.770 Å, c = 15.5598 Å, V = 1368.3 Å³ (Sb(III)-doped). The structure and the crystallinity of the materials are further confirmed by powder X-ray diffraction analysis. The modes of vibrations of different functional groups present are identified by Fourier transform infrared studies. Thermogravimetric/differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. Surface morphological changes due to doping are observed by scanning electron microscopy. Microhardness study was carried out to elucidate the mechanistic behavior microhardness studies were carried out to elucidate the mechanistic behavior. Second harmonic generation activity is much better in the case of Sb(III)-doping. The specimen is also characterized by dielectric studies.     

Review on Tin (II) Sulfide (SnS) Material: Synthesis,Properties, and Applications

Tin (II) sulphide (SnS), a direct band gap semiconductor compound, has recently received great attention due to its unique properties. Because of low cost, absence of toxicity, and good abundance in nature, it is becoming a candidate for future multifunctional devices particularly for light conversion applications. Although the current efficiencies are low, the cost-per-Watt is becoming competitive. At room temperature, SnS exhibits stable low-symmetric, double-layered orthorhombic crystal structure, having a = 0.4329, b = 1.1192, and c = 0.3984 nm as lattice parameters. These layer-structured materials are of interest in various device applications due to the arrangement of structural lattice with cations and anions. The layers of cations are separated only by van der Waals forces that provide intrinsically chemically inert surface without dangling bonds and surface density of states. As a result, there is no Fermi level pinning at the surface of the semiconductor. This fact leads to considerably high chemical and environmental stability. Further, the electrical and optical properties of SnS can be easily tailored by modifying the growth conditions or doping with suitable dopants without disturbing its crystal structure.

In the last few decades, SnS has been synthesized and studied in the form of single-crystals and thin-films. Most of the SnS single-crystals have been synthesized by Bridgeman technique, whereas thin films have been developed using different physical as well as chemical deposition techniques. The synthesis or development of SnS structures in different forms including single-crystals and thin films, and their unique properties are reviewed here. The observed physical and chemical properties of SnS emphasize that this material could has novel applications in optoelectronics including solar cell devices, sensors, batteries, and also in biomedical sciences. These aspects are also discussed.     

Effect of Mn substitution on superconductivity in iron selenide(Li,Fe)OHFeSe single crystals

We synthesize a series of Mn substituted(Li, Fe)OHFeSe superconductor single crystals via a modified ion-exchange method, with the Mn concentration z(the atomic ratio of Mn:Se) ranging from 0 to 0.07. The distribution homogeneity of the Mn element incorporated into the lattice of(Li, Fe)OHFeSe is checked by combined measurements of high-angleannular-dark-field(HAADF) imaging and electron energy-loss spectroscopy(EELS). Interestingly, we find that the superconducting transition temperature T_c and unit cell parameter c of the Mn-doped(Li, Fe)OHFeSe samples display similar V-shaped evolutions with the increasing dopant concentration z. We propose that, with increasing doping level, the Mn dopant first occupies the tetrahedral sites in the(Li, Fe)OH layers before starting to substitute the Fe element in the superconducting Fe Se layers, which accounts for the V-shaped change in cell parameter c. The observed positive correlation between the T_c and lattice parameter c, regardless of the Mn doping level z, indicates that a larger interlayer separation, or a weaker interlayer coupling, is essential for the high-T_c superconductivity in(Li, Fe)OHFeSe. This agrees with our previous observations on powder, single crystal, and film samples of(Li, Fe)OHFeSe superconductors.     

Synthesis,growth and studies of undoped and sodium chloride-doped Zinc Tris-thiourea Sulphate (ZTS) single crystals

Single crystals of undoped (pure) and sodium chloride (NaCl)-doped Zinc Tris-thiourea Sulphate (ZTS) were grown from aqueous solutions by slow evaporation technique. Morphological alterations have been observed when NaCl is doped into ZTS crystals. Density of the grown crystals was measured by floatation method. The values of unit cell parameters from single crystal X-ray diffraction (XRD) studies show that pure and sodium chloride-doped ZTS crystals are in orthorhombic structure. Impurity concentration in the doped crystals was estimated by using an atomic absorption spectrometer. Second Harmonic Generation (SHG) test for the undoped and NaCl-doped ZTS crystals was performed by the powder technique of Kurtz and Perry using a pulsed Nd:YAG laser. Microhardness studies show that hardness number (H_v) increases with load for all the grown crystals of this work. From the values of work hardening coefficients, it is concluded that pure and sodium chloride-doped ZTS crystals belong to the category of soft materials. UV–vis–NIR spectra show that the grown crystals have wide optical transparency in the entire visible region. Birefringence studies of the grown samples have been performed by channelled spectrum method. The thermal stability of the materials is found to be increasing with the doping concentration of sodium chloride (NaCl) in the lattice of ZTS crystals.     

Spectral,thermal, optical and dielectric characterization of tris(tetraethylammonium) pentabromozincate(II) monohydrate crystals

Tris(tetraethylammonium) pentabromozincate(II) monohydrate, is a new semiorganic compound synthesized and crystallized by slow evaporation solution growth method at room temperature. The formation of the compound in the stoichiometric ratio was confirmed by elemental analysis. The crystalline nature of the compound was confirmed by powder X-ray diffraction method and the crystal system was found to be triclinic. The absorption spectrum of the compound shows absorption at 247 nm and it has wide transparency in the visible region. The lower cut-off wavelength and the optical transmittance window of the compound were identified by optical transmittance study. The thermogravimetric and differential thermal (TG–DTA) analyses were studied to find out the thermal stability of the synthesized compound. The thermal anomalies observed in the differential scanning calorimetry (DSC) analysis indicate that the compound shows a first order phase transition. The FTIR spectrum was used to characterize the various chemical bonds and water molecule present in the compound. The nonlinear optical property (NLO) of the material was analyzed by modified Kurtz–Perry powder technique and found that it has SHG efficiency three times greater than that of KDP. The dielectric constant and dielectric loss of the compound decrease with increase in frequency.     

Influence of l-alanine doping on crystalline perfection, SHG efficiency, optical and mechanical properties of KDP single crystals

Pure and l-alanine (LA) doped single crystals of potassium dihydrogen orthophosphate (KDP) were grown by slow evaporation solution technique (SEST) in aqueous solution at ambient temperature. Powder X-ray diffraction study was done to confirm the crystal system and lattice parameters of KDP. No additional phases were observed at all doping concentrations (1-7.5 mol%), which was further confirmed by FT-Raman spectroscopy analysis. The influence of LA doping on the crystalline perfection was assessed by high-resolution X-ray diffractometry (HRXRD) analysis. HRXRD studies revealed that the grown crystals could accommodate LA at the interstitial positions in the crystalline matrix of KDP up to some critical concentration without any deterioration in the crystalline perfection. Above this concentration, very low angle structural grain boundaries were developed and it seems that the excess LA above the critical concentration was segregated along the grain boundaries. The SHG efficiency was measured using the Kurtz powder technique. The relative SHG efficiency of the crystals was found to be increased with doping concentration up to 5 mol% and above this it decreases. Optical transmission study also revealed the same behavior with enhancement up to 5 mol% concentration and later decreased. The hardness values were found to be increased by increasing the doping concentration.     

Structural elucidation of Cu(II) ion doped in hexaaquozincdiaquobis(malonato)zincate host by EPR spectroscopy

In order to understand the structural behaviour of Cu(II) in a variety of ligand environments, single crystal electron paramagnetic resonance studies of Cu(II) doped in hexaaquazincdiaquabis(malonato)zincate [Zn(H₂O)₆][Zn(mal)₂(H₂O)₂] are carried out at 300 K. Angular variation of copper hyperfine lines in three orthogonal planes shows the presence of single site, with spin Hamiltonian parameters as g_xx=2.034, g_yy=2.159, g_zz=2.388, A_xx=3.39 mT, A_yy=4.89 mT and A_zz=13.72 mT. The g/A tensor direction cosines are compared with various Zn-O directions in the host lattice, which confirm that Cu(II) enters substitutionally in the lattice. The low value of A_zz has been explained by considering admixture of d_²x−²y ground state with d_²z excited state. EPR powder spectra at 300 and 77 K give identical spin Hamiltonian parameters (g_∥=2.367, g_⊥=2.088, A_∥=11.47 mT, A_⊥=2.63 mT). IR, UV-vis and powder XRD data confirm the structure and symmetry of the Cu(II) ion in the host lattice.     

Synthesis,spectral and thermal characterization of Bis(diethylammonium) tetrachloromercurate(II)-An nonlinear optical material

A new semiorganic compound, bis(diethylammonium) tetrachloromercurate(II) was grown by slow evaporation solution growth technique at ambient temperature from its aqueous solution. The crystal system and the cell parameters have been identified from the powder X-ray diffraction pattern. The UV–visible absorption of the compound shows absorption at 246 nm and there is absorption observed in the entire visible region indicates that the compound can be used as a nonlinear optical material. The UV–visible transmittance spectrum of grown crystal shows a lower cut-off wavelength at 275 nm and it was found that the crystal is suitable for optoelectronic applications. Thermal studies were carried out to find out the thermal stability and confirm the stoichiometric ratio of the compound. The thermal anomalies in DSC study indicate the occurrence of first order transition in the compound at low temperatures. The FTIR spectrum of the compound characterizes various functional groups. The various kinds of protons and carbons were assigned through NMR (¹H and ¹³C) spectroscopic techniques. The SHG efficiency of the compound was studied by Kurtz-Perry power technique and observed that it has SHG efficiency 1.5 times greater than that of potassium dihydrogen phosphate (KDP). The dielectric constant and dielectric loss of the compound decreases with increase in frequency.     

Vibrational Spectroscopic Studies on the Dicyclopropylaminecadmium(II)Tetracyanometallate(II) Benzene Clathrates

ABSTRACT

New Hofmann–T_d-type clathrates of the forms Cd(CPA)₂M(CN)₄.C₆H₆ (CPA = cyclopropylamine; M?Cd or Hg) prepared in powder form and characterized by FT-IR, FT-Raman, far-IR spectra, X-ray diffraction, and elemental analyses are reported. Vibrational assignments are proposed for the bands of the host lattice and guest molecule. It is shown that the spectra are consistent with a proposed crystal structure for the compounds derived from X-ray diffraction measurements. The C, H, and N analyses were carried out for all the compounds. All the vibrational modes of coordinated CPA are characterized. The spectral features suggest that these compounds are similar in structure to the Hofmann–T_d-type clathrates.     

Doping effects of transition metals on the superconductivity of (Li,Fe)OHFeSe films

The doping effects of transition metals(TMs = Mn, Co, Ni, and Cu) on the superconducting critical parameters are investigated in the films of iron selenide(Li,Fe)OHFe Se. The samples are grown via a matrix-assisted hydrothermal epitaxy method. Among the TMs, the elements of Mn and Co adjacent to Fe are observed to be incorporated into the crystal lattice more easily. It is suggested that the doped TMs mainly occupy the iron sites of the intercalated(Li,Fe)OH layers rather than those of the superconducting Fe Se layers. We find that the critical current density J_c can be enhanced much more strongly by the Mn dopant than the other TMs, while the critical temperature T_c is weakly affected by the TM doping.     

CaCu_xMn_(3-x)Mn_4O_(12)(x=0.2,0.4,0.6,0.8,1.0,1.2,1.4)的结构及磁电阻效应的研究

利用湿化学反应法制备了CaCuxMn3-xMn4O12(x=0.2,0.4,0.6,0.8,1.0,1.2,1.4)系列材料的前驱体,然后加入10wt%的KCL后,在850℃的纯氧中烧结制成样品。X射线衍射表明,CaCuxMn3-xMn4O12样品呈单相立方结构,空间群Im 3-。研究表明:随掺杂浓度x的增加,晶格常数减小,晶体结构发生畸变,从而直接影响材料的电输运性质。实验表明,样品在5T的外磁场下,随x的增大,样品的磁电阻MR呈现先增大后减小的趋势,在x=1.0时磁电阻达到最大,这可能是晶粒边界处粒子的自旋极化散射和双交换作用共同作用的结果。     

Growth, structural, spectral, mechanical and dielectric characterization of RbCl-doped l-alanine hydrogen chloride monohydrate single crystals

Pure (undoped) and RbCl-doped LAHC single crystals were grown successfully by the solution method with the slow evaporation technique at room temperature. The grown crystals were colourless and transparent. The solubility of the grown samples were found out at various temperatures. The lattice parameters of the grown crystals were determined by the single crystal X-ray diffraction technique and the diffracting planes were indentified by recording the powder X-ray diffraction pattern. UV-visible transmittance studies were carried out for the grown samples. Chemical analysis and atomic absorption studies indicate the presence of rubidium in the doped LAHC crystals. Nonlinear optical studies reveal that the SHG efficiency increases when the LAHC crystal is doped with rubidium chloride (RbCl). From microhardness studies, it is observed that the RbCl-doped LAHC crystal is harder than the pure sample. It is observed that the dielectric properties of the LAHC crystal are altered when it is doped with rubidium chloride.