Photoluminescence of bis(8-hydroxyquinoline) zinc (Znq2) and magnesium (Mgq2)

Absorption and photoluminescence (PL) spectra, PL quantum efficiency, and PL lifetime have been investigated on bis(8-hydroxyquinoline) zinc (Znq₂) and magnesium (Mgq₂) in solutions and powder. Znq₂ and Mgq₂ have the lowest-energy absorption band at 376 and 396 nm in acetonitrile solution, respectively, and emission band with peak at 555 and 480 nm. The PL quantum efficiency is 0.03 and 0.45 for Znq₂ and Mgq₂ in the solution, respectively, while 0.45 and 0.36 in powder. Unlike the case of powders, two PL lifetimes are obtained in solutions. The longer lifetime is attributed to molecule having interaction with its neighboring molecule, while the shorter one to the isolated single molecule.     

Cation mobility and structural changes on the water removal in zeolite-like zinc hexacyanometallates (II)

The cation (A⁺) mobility and structural changes on the water molecules removal in zeolite-like zinc hexacyanometallates series, Zn₃A₂[Fe(CN)₆]₂·xH₂O with A=Na, K, Rb and Cs, were studied from X-ray diffraction data recorded for hydrated and anhydrous samples at room temperature and at 77 K. The crystal structure for the anhydrous phases were solved and refined and then compared with those corresponding to their hydrated form. On the water molecules removal the charge balancing cation (A⁺) migrates to favor a stronger interaction with the N ends of the CN bridges where the framework negative charge is located. This cation-framework interaction model is supported by the recorded IR spectra for both hydrated and anhydrous samples. The new cation position induces distortion for both the cavity shape and their windows and also leads to cavity volume reduction. This is relevant for the properties of this family of solids as porous materials and their behavior in adsorption and separation processes, among them for hydrogen storage.     

Zinc-8-hydroxyquinoline intercalated in calcium bentonite: A promising DO sensor

Zn(II) and 8-hydroxyquinoline were made to react in an in situ solid−solid reaction in the interlayer space of Ca-bentonite from Thailand, resulting in [Zn(8-hydroxyquinoline)₂]²⁺, the well known -Znq₂. X-ray diffraction patterns showed that the interlayer space of the bentonite increased from 1.56 to 1.67 nm on going from Zn(II)-bentonite to Znq₂-bentonite, which confirmed the intercalation of Znq₂ in bentonite. The intercalated Znq₂-bentonite compound was mixed with a solution of polystyrene in toluene and coated as a film on a polystyrene sheet. The fluorescence intensity of Znq₂-bentonite film was measured in the presence of dissolved oxygen (DO). It was found that the fluorescence intensity of the film decreased as dissolved oxygen increased, which is a promising result for developing an optical dissolved oxygen sensor (DO sensor). The fluorescence quenching by oxygen followed the Stern-Volmer plot.     

Synthesis,crystal growth,and characterization of piperazinediium bis (4-aminobenzoate) dihydrate - An efficient third-order nonlinear optical single crystal for opto-electronic applications

Organic compound of protonated Piperazinediium bis (4-aminobenzoate) dihydrate C₄H₁₂N₂²⁺2(C₇H₆NO₂⁻).2(H₂O) (PZ4AB) was synthesized and crystal was grown by slow evaporation solution growth technique. Powder X-ray diffraction and High resolution X-ray diffraction studies affirmed the crystalline perfection of the grown crystal. Fourier transform infrared spectral analysis ascertained the frequencies of various functional groups present in PZ4AB crystal. Optical transmittance and optical band gap estimation explored the optical phenomena of PZ4AB crystal. The laser-induced surface damage threshold value of PZ4AB crystal was measured to be 1.0615 GW/cm² for the 1064 nm Nd:YAG laser radiation. From Thermogravimetric and differential scanning calorimetric studies, the stability of PZ4AB crystal was ascertained. The dielectric manner was endowed as a function of frequency and temperature. The mechanically soft nature of the crystal was assessed by Vickers hardness measurement which exhibited the reverse indentation size effect. The nonlinear refractive index, absorption coefficient and the third-order nonlinear susceptibility of crystal were divulged by Z-scan technique.     

Optical absorption spectrum of diammonium nickel bis(tetrafluoroberyllate) hexahydrate

The optical absorption spectrum of diammonium nickel bis (tetrafluoroberyllate) hexahydrate (NH₄)₂Ni(BeF₄)₂.6H₂O has been investigated at the laboratory and liquid nitrogen temperatures. The spectrum is characteristic of the Ni²⁺ ion in an octahedral crystal field. Splitting of one of the bands at the liquid nitrogen temperature are attributed to the spin-orbit interaction.     

The use of hot‐stage microscopy and thermal micro‐Raman spectroscopy in the study of phase transformation of metoclopramide HCl monohydrate

The aim of this work was to investigate the transformation behavior of metoclopramide HCl with monohydrate (MCP HCl H₂O) using differential scanning calorimetry (DSC), thermogravimetric analysis, hot‐stage microscopy (HSM), and thermal micro‐Raman spectroscopy. The results of the present study indicate that the three‐step phase transformation of MCP HCl H₂O was clearly determined via the thermal‐dependant Raman spectral changes. These three steps of phase transformation were dehydration, recrystallization, and new crystal formation, which were markedly correlated with the endothermic and exothermic results of DSC study and the observations of HSM. The results generally evidence that MCP HCl H₂O crystals were first dehydrated to form an anhydrous sample, then recrystallized and transformed to a new crystal form of MCP HCl. Copyright © 2011 John Wiley & Sons, Ltd.     

Intercalation behavior of barium phenylphosphonate

The dependence of basal spacing and water content of BaC₆H₅PO₃·xH₂O on the relative humidity was studied. Intercalates of 1-alkylamines (C₂-C₁₀) and 1-alkanols (C₃-C₁₀) were prepared from barium phenylphosphonate dihydrate and also from anhydrous host and characterized by powder X-ray diffraction and thermogravimetric analysis. The intercalates of alkanols and alkylamines prepared from dihydrate are quite stable at ambient conditions and contain one guest molecule per formula unit. The guest molecules are probably arranged in monomolecular way and are perpendicular to the host layers in the case of amines or tilted to the host layers at an angle of about 80° in the case of alkanols. The intercalates prepared from anhydrous host are unstable and their basal spacings indicate parallel arrangement of the guests chains. Formation of mixed intercalates was not observed when barium phenylphosphonate dihydrate was contacted with a mixture of alkanols or amines.     

Electronic structure and optical properties of wurtzite-kesterite Cu2ZnSnS4

As promising light-absorber material for solar cells, Cu₂ZnSnS₄ was found to have another crystal structure (wurtzite-kesterite) in addition to the conventional zinc blende-kesterite structure. Structural flexibility of Cu₂ZnSnS₄ opens up an avenue to develop light-absorber material with novel exciting properties and applications. However, its electronic and optical properties have not been comprehensively studied yet. For this purpose, the method of density functional theory within hybrid functional of PBE0 was adopted to study the structural, electronic, and optical properties of wurtzite-kesterite Cu₂ZnSnS₄ in this Letter. The calculated results suggested that the energy of its band gap is about 1.372 eV and it has obvious optical anisotropy. Furthermore, its crystal structure leads local internal fields that are especially beneficial to suppress the recombination of photoexcited electron–hole pairs.     

Characterizations of octahedral zinc oxide synthesized by sonochemical method

The ultrasonic reaction of zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) was investigated by varying the concentration of the reactants, the irradiation time, and the type of sonicator. The morphology, composition, and phase structure of the products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopy. Octahedral zinc oxide (ZnO) micropowders were formed at low concentrations, 0.05 M, of Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ in both lab-made sonicator and commercial ultrasonic bath. However, at concentrations between 0.1 and 1.0 M Zn(NO₃)₂-C₆H₁₂N₄ mainly plate-like zinc hydroxide nitrate hydrate (Zn₅(OH)₈(NO₃)₂(H₂O)₂) resulted with only a small fraction of ZnO, irrespective of the irradiation time employed, highlighting the sensitivity of the system to the concentration of the starting materials. Heat treatment of Zn₅(OH)₈(NO₃)₂(H₂O)₂ at 350 °C in air affords a ZnO phase of irregular morphology. Octahedral ZnO is found to exhibit slightly lower IR absorption and similar UV absorption to that of commercial prismatic hexagonal ZnO, although an extra peak due to small quantities of Zn₅(OH)₈(NO₃)₂(H₂O)₂ is observed.     

Sonication-assisted synthesis of a new cationic zinc nitrate complex with a tetradentate Schiff base ligand: Crystal structure,Hirshfeld surface analysis and investigation of different parameters influence on morphological properties

A nanostructured cationic zinc nitrate complex with a formula of [ZnLNO₃]NO₃ (where L = (N²E,N^2′E)-N¹,N^1′-(ethane-1,2-diyl)bis(N²-((E)-3-phenylallylidene)ethane-1,2-diamine)) was prepared by sonochemical process and characterized by single crystal X-ray crystallography, scanning electron microscopy (SEM), FT-IR and NMR spectroscopy and X-ray powder diffraction (XRPD). The X-ray analysis demonstrates the formation of a cationic complex that metal center is five-coordinated by four nitrogen atom from Schiff base ligand and one oxygen atom from nitrate group. The crystal packing analysis demonstrates the essential role of the nitrate groups in the organization of supramolecular structure. The morphology and size of ultrasound-assisted synthesized zinc nitrate complex have been investigated using scanning electron microscopy (SEM) by changing parameters such as the concentration of initial reactants, the sonication power and reaction temperature. In addition the calcination of zinc nitrate complex in air atmosphere led to production of zinc oxide nanoparticles.     

Characterization of mechanochemically synthesized imidazolates of Ag, Zn, Cd, and Hg: Solid state reactivity of nd cations

Silver, zinc, cadmium, and mercury imidazolates have been synthesized mechanochemically by milling imidazole and the metal oxides in an agate mortar. The reaction products were characterized by FTIR and XRPD techniques. The results obtained for the mechanochemical imidazolates have been compared with those obtained by precipitation reported in the literature. The mechanochemical Ag imidazolate has the same orthorhombic crystal structure as the precipitated one. The mechanochemical Zn imidazolate has a tetragonal structure with similar crystal parameters to those of Zn(Imz)₂H₂O, but no water molecules are present in the structure. This new anhydrous form is a polymorph of the one obtained by precipitation. The mechanochemical Cd imidazolate has a monoclinic structure which is the polymorph of the precipited orthorombic form. The mechanochemical Hg imidazolate presents a hexagonal structure which is a polymorph of the orthorombic structure obtained by precipitation. The influence of the nd¹⁰ electronic configuration of the cations on the mechanochemical reaction is discussed.     

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.To explore the growth mechanism, the samples have been prepared in different irradiation time and also cetyltrimethylammonium bromide (CTAB) has been used as the capping reagent.     

An atypical coordination in hexacyanometallates: Structure and properties of hexagonal zinc phases

In hexacyanometallates, the involved transition metals are usually found with octahedral coordination. The exception corresponds to the hexagonal zinc phases where this metal appears tetrahedrally coordinated to N ends from the CN ligands. Those zinc hexacyanometallates where such atypical coordination appears were identified and for four of them the crystal structure was refined from X-ray diffraction powder patterns using the Rietveld method. Zinc hexacyanoferrates (III), hexacyanocobaltate (III), hexacyanoiridate (III) and the mixed zinc-cesium hexacyanoferrate (II) were found to be dimorphic, cubic (Fm-3m) and hexagonal (R-3c), related to the zinc atom in octahedral or tetrahedral coordination, respectively. In the absence of an exchangeable cation, the hexagonal phases result anhydrous. This last feature was attributed to a low polar character for the pores surface. The Mössbauer spectrum of hexagonal zinc hexacyanoferrate (III) is an unresolved quadrupole splitting doublet (Δ=0.18 mm/s). The iron nucleus is sensing a weak electric field gradient related to a relatively high symmetry for its ligands and charge environment. The IR spectrum appears to be an excellent sensor to identify the coordination for the zinc atom in a given sample. For the tetrahedral coordination, the CN stretching absorption was found at least 8 cm⁻¹ above the frequency observed for this vibration in the octahedral one. For hydrated phases, the crystal water evolves on heating preserving the material porous framework. The temperature at which the material becomes anhydrous parallels the polarizing power of the charge balancing cation sited within the channels. Hexagonal Zn-Cs ferrocyanide becomes anhydrous at 100 °C, while for the Zn-Na analogue a heating close to 200 °C is required. The stability temperature range for the anhydrous phases depends on the nature of the engaged hexacyanometallate anion; the higher stability was observed for hexacyanoferrates (II). Zinc ferricyanide shows the weaker magnetic interaction for the hexagonal modification due to an unfavourable geometry for the overlapping path between the unpaired electrons on the iron(III) atoms. The open 3D porous network is formed by relatively large ellipsoidal cavities, three per cell, communicated through elliptical openings (windows), six per cavity. For dimorphic zinc hexacyanometallates (III), the most compact structure (higher density) corresponds to the hexagonal modification, however, it has the largest cavity windows and cavity (pore) size, and also the higher thermal stability.     

Synthesis of nanocrystalline and mesoporous zinc sulphide from a single precursor Zn(SOCCH3)2Lut2 complex

We report the formation of mesoporous zinc sulphide, composed by the fine network of nanoparticles, which was formed via a single precursor Zn(SOCCH₃)₂Lut₂ complex. The complex was chemically synthesized using zinc carbonate basic, 3,5-lutidine and thioacetic acid, in air. The metal precursor complex was characterized using different conventional techniques. Thermogravimetric analysis (TGA) result indicates that the decomposition of the complex starts at 100 °C and continues up to 450 °C, finally yielding ZnS. ZnS nanocrystals were characterized by powder X-ray diffraction (XRD) technique, field emission scanning electron microscopy (FESEM), N₂-sorption isotherm, UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The grain diameter of nanocrystals was found to be 4-5 nm. The material followed Type-IV N₂-sorption isotherm, which is the characteristic of mesoporous materials. The band gap energy, as obtained from optical measurements was around 3.8 eV.     

Effect of sintering aid (CdCl2) on the optical and structural properties of CdZnS screen-printed film

Sulphides of zinc and cadmium have been utilized effectively in various opto-electronic devices. In the present work cadmium zinc sulphide (Cd_0.4Zn_0.6S) thin film has been deposited on ultra clean glass substrate by a simple inexpensive screen-printing method using cadmium sulphide, zinc sulphide, anhydrous cadmium chloride and ethylene glycol. Cadmium chloride has been used as sintering aid and ethylene glycol as a binder. Effect of sintering aid on the optical and structural properties of prepared cadmium zinc sulphide film has been investigated. The optical band gap (E_g) of the film has been studied by using reflection spectra in wavelength range 325–600 nm. It is found that reflection spectra suffer a drastic fall at two places, which is indicative of two band gaps of film viz. 2.38 eV and 2.9 eV corresponding to CdS and Cd_0.6Zn_0.4S, respectively. This is suggestive of the fact that cadmium zinc sulphide is a wide band gap semiconducting material. X-ray diffraction also confirms the formation of Cd_0.6Zn_0.4S composition.     

Third-order optical nonlinearity of (Ba0.7Sr0.3)TiO3 ferroelectric thin films fabricated by soft solution processing

(Ba_0.7Sr_0.3)TiO₃ (BST) ferroelectric thin films with perovskite crystal structure were fabricated by soft solution processing on a quartz substrate. The third-order nonlinear optical properties were investigated by using Z-scan technique. Positive nonlinear refractive index and nonlinear absorption coefficient were determined to be 4×10⁻⁷ esu and 1.2×10⁻⁶ m/w, respectively. The real part and imaginary part of third-order optical nonlinear susceptibility were calculated and the values were 6.43×10⁻⁸ and 5.14×10⁻⁸ esu, respectively. All of these results show ferroelectric BST thin film is promising for applications in nonlinear optical devices.     

Optical properties of anatase and rutile titanium dioxide: Ab initio calculations for pure and anion-doped material

The optical properties of rutile and anatase titanium dioxide (TiO₂) are calculated from the imaginary part of the dielectric function using pseudopotential density functional method within its generalized gradient approximation (GGA) and a scissors approximation. The fundamental absorption edges calculated for the unit cell of both rutile and anatase are consistent with experimentally reported results of single crystal rutile and anatase TiO₂ and with previous theoretical calculations. A significant optical anisotropy is observed in the anatase structure which holds promise for investigating the band gap modification with better visible-light response and provides a reliable foundation for addressing the effect of impurities on the fundamental absorption edge/band gap of anatase TiO₂. Further calculations on the electronic structure and the optical properties of C-, N-, and S-doped anatase TiO₂ are performed. The results are analyzed and discussed in terms of optical anisotropy and scissors approximations.     

Effect of sol–gel pH on XRD peak broadening,lattice strain,ferroelectric domain orientation,and optical bandgap of nanocrystalline Pb1.1(Zr0.52Ti0.48)O3

Nanocrystalline Pb_1.1(Zr_0.52Ti_0.48)O₃ (PZT) samples were prepared using a citrate–nitrate sol–gel process near the morphotropic phase boundary. The effect of pH on the lattice parameters (tetragonality and lattice constants), crystal structure [strain broadening, relative phase content, ferroelectric domain (FD) orientation and nanocrystallite size], microstructure (grain size and particle morphology) and optical bandgap was investigated. The samples were characterized using X-ray diffraction (XRD), the size strain plot (SSP) method, Fourier-transform infrared spectroscopy, and the classical Tauc relation. The particle morphology was investigated using field-emission scanning electron microscopy. The XRD results revealed a perovskite structure and coexisting tetragonal and rhombohedral phases for all PZT samples. Lattice strain and peak broadening were determined from SSP and XRD results. The behavior of these parameters was in agreement for all pH values. The optical bandgap for PZT was estimated from UV-vis absorption spectra. We found that for PZT the maximum relative tetragonal phase content, c/a ratio, and FD orientation along the a-axis occurred at pH 4.     

Raman study of phase transformation of TiO2 rutile single crystal irradiated by infrared femtosecond laser

Titanium dioxide (TiO₂) rutile single crystal was irradiated by infrared femtosecond (fs) laser pulses with repetition rate of 250 kHz and phase transformation of rutile TiO₂ was observed. Micro-Raman spectra show that the intensity of E_g Raman vibrating mode of rutile phase increases and that of A_1g Raman vibrating mode decreases apparently within the ablation crater after fs laser irradiation. With increasing of irradiation time, the Raman vibrating modes of anatase phase emerged. Rutile phase of TiO₂ single crystal is partly transformed into anatase phase. The anatase phase content transformed from rutile phase increased to a constant with increasing of fs pulse laser irradiation time. The study indicates the more stable rutile phase is transformed into anatase phase by the high pressure produced by fs pulse laser irradiation.     

Synthesis and investigation of nonlinear optical properties of semiconductor ZnS nanoparticles

ZnS nanoparticles were prepared by a simple chemical method and using PVP (poly vinylpyrrolidone) as capping agent. The sample was characterized by UV-vis spectrophotometer, X-ray diffraction (XRD) and Z-scan technique. XRD pattern showed that the ZnS nanoparticles had zinc blende structure with an average size of about 2.18 nm. The value of band gap of these nanoparticles was measured to be 4.20 eV. The nonlinear optical properties of ZnS nanoparticles in aqueous solution were studied by Z-scan technique using CW He-Ne laser at 632.8 nm. The nonlinear absorption coefficient (β) was estimated to be as high as 3.2×10⁻³ cm/W and the nonlinear refractive index (n₂) was in order of 10⁻⁸ cm²/W. The sign of the nonlinear refractive index obtained negative that indicated this material exhibits self-defocusing optical nonlinearity.