Anisotropy of the optical absorption in layered single crystals of MoRe0.001Se1.999

Energy gap of MoRe_0.001Se_1.999 single crystal has been determined by fundamental absorption methods. The incident light was polarized along c‐axis of the crystals. The interpretion of the data is given within frameworks of two and three dimensional models. Both direct and indirect transitions are involved in the absorption process. The indirect transition was found to be allowed with two phonons participating in the process. The three dimensional model could be used to describe the optical properties of the single crystal. The energy gaps depend upon the amount of the intercalating Re material, which show the anisotropy of the chemical bonds. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Anisotropy of optical absorption in layered single crystals

The optical energy gap of Re doped MoSe₂ single crystal Mo_0.995Re_0.005Se₂ has been measured at room temperature near the fundamental absorption edge. The incident light was kept normal to the basal plane i.e. along the c‐axis of the grown crystals. Results have been given on the basis of two and three dimensional models. Both direct and indirect transitions are involved in the absorption process. The indirect transition was found to be allowed with two phonons involved in the process. The three dimensional model and not the two dimensional could be used to describe the optical properties of Re doped MoSe₂ single crystal. Also, the optical energy gaps depend upon the amount of the intercalating Re material. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of temperature and isomorphic atom substitution on optical absorption edge of TlInS2xSe2(1‐x) mixed crystals (0.25 ≤ x ≤ 1)

The optical properties of the TlInS_2xSe_2(1‐x)mixed crystals (0.25 ≤ x ≤ 1) have been investigated through the transmission and reflection measurements in the wavelength range of 400–1100 nm. The optical indirect band gap energies were determined by means of the analysis of the absorption data. It was found that the energy band gaps decrease with the increase of selenium atoms content in the TlInS_2xSe_2(1‐x)mixed crystals. The transmission measurements carried out in the temperature range of 10–300 K revealed that the rates of change of the indirect band gaps with temperature are γ = –9.2×10^–4 eV/K, –6.1×10^–4 eV/K, –4.7×10^–4 eV/K and –5.6×10^–4 eV/K for TlInS₂, TlInS_1.5Se_0.5, TlInSSe and TlInS_0.5Se_1.5 crystals, respectively. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Specific features of the optical spectra in Tl2In2S3Se layered single crystals

The optical properties of Tl₂In₂S₃Se layered single crystals have been studied by means of transmission and reflection measurements in the wavelength range of 450‐1100 nm. The analysis of the absorption data revealed the presence of both optical indirect and direct transitions with energy band gaps of 2.16 and 2.42 eV, respectively. The observed coexistence of indirect and direct energy band gaps is related to the anisotropy of the Tl‐containing layered crystals. The dispersion of the refractive index is discussed in terms of the Wemple‐DiDomenico single‐effective‐oscillator model. The refractive index dispersion parameters: oscillator energy, dispersion energy, oscillator strength and zero‐frequency refractive index were found to be 4.78 eV, 43.58 eV, 13.18 × 10¹³ m^–2 and 3.18, respectively. From X‐ray powder diffraction study, the parameters of monoclinic unit cell were determined. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical Properties of Bi2Se3‐xAsx Single Crystals

Bi₂Se_3‐xAs_x single crystals with the As content of c_As = 0 to 2.0x10¹⁹ atoms/cm³ prepared from the elements of 5N purity by means of a modified Bridgman method were characterized by measurements of infrared reflectance and transmittance. Values of the plasma resonance frequency omega_p, optical relaxation time tau, and high‐frequency permittivity were determined by fitting the Drude‐Zener formulas to the reflectance spectra. It was found that the substitution of As atoms for Se atoms in the Bi₂Se₃ crystal lattice leads to a decrease in the omega_p values. This effect is accounted for by a model of point defects in the crystal lattice of Bi₂Se_3‐xAs_x. The dependences of the absorption coefficient K on the energy of incident photons were determined from the transmittance spectra. The optical width of the energy gap is found to decrease with increasing As content. The values of the exponent b from the relation of K ∼ lamda^b for the long‐wavelength absorption edge range within the interval 2.0 to 2.3, i.e. the dominant scattering mechanism of free current carriers in Bi₂Se_3‐xAs_x crystals is the scattering by acoustic phonons.     

Optical absorption spectra and related parameters of ammonium zinc chloride crystal in the antiferroelectric and commensurate phases

Optical absorption along the three crystallographic axes of (NH₄)₂ZnCl₄ single crystals is reported over a temperature range from 276 K to 350 K. Our results clearly confirm the antiferroelectric to commensurate phase transition at 319 K. Analysis reveals that at the absorption edge the type of transition is the indirect allowed one. The indirect band gaps at various temperatures are determined and their temperature dependence is estimated in the antiferroelectric and commensurate phases. Optical parameters related to the temperature dependence of the energy gap are evaluated. The single‐effective oscillator model was used to describe the imaginary part of the dielectric constant, which facilitate calculation of the dipole moment parameters. The steepness parameter is given, its value is used to estimate the temperature dependence of the indirect energy gap and the result is compared with that calculated graphically. In the region of the absorption edge, the absorption coefficient obeys Urbach's rule. Urbach characteristic parameters are determined and their temperature dependence is investigated. Correlation between different parameters is considered. Most of the results confirm the optical isotropic nature of AZC crystals. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temperature‐tuned band gap energy and oscillator parameters of Tl2InGaSe4 semiconducting layered single crystals

The optical properties of Tl₂InGaSe₄ layered single crystals have been studied through the transmission and reflection measurements in the wavelength range of 500‐1100 nm. The analysis of room temperature absorption data revealed the presence of both optical indirect and direct transitions with band gap energies of 1.86 and 2.05 eV, respectively. Transmission measurements carried out in the temperature range of 10‐300 K revealed that the rate of change of the indirect band gap with temperature is γ = – 4.4 × 10^‐4 eV/K. The absolute zero value of the band gap energy was obtained as E_gi(0) = 1.95 eV. The dispersion of the refractive index is discussed in terms of the single oscillator model. The refractive index dispersion parameters: oscillator wavelength and strength were found to be 2.53 × 10^–7 m and 9.64 × 10¹³ m^–2, respectively. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and third order nonlinear optical properties of bis(tetra‐n‐propylammonium) bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)cuprate(II)

A novel bis (dmit) complex of copper (II), [(C₃H₇)₄N]₂[Cu(dmit)₂] ( 1 ), where dmit is 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate, was prepared and structurally characterized by X‐ray single crystal diffraction. The copper (II) atom is tetracoordinated by four dmit S atoms, forming a nearly square planar arrangement. The [Cu(dmit)₂]^2‐ anions and the [(C₃H₇)₄N]⁺ counter‐cations form a three‐dimensional solid‐state structure by C–H…S hydrogen bonds. The third‐order nonlinear optical properties of the complex were determined by picosecond Z‐scan technique at a wavelength of 1064 nm. The results indicate the compound exhibits reverse saturation absorption and self‐defocusing performance. The molecular second‐order hyperpolarizability γ is calculated to be as high as (1.8±0.2)×10^‐30 esu. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of isomorphic atom substitution on the refractive index and oscillator parameters of TlInS2xSe2(1‐x) (0.25 ≤ x ≤ 1) layered mixed crystals

The optical properties of TlInS_2xSe_2(1‐x)mixed crystals (0.25 ≤ x ≤ 1) have been studied at room temperature through the transmittance and reflectivity measurements in the wavelength range of 400–1100 nm. The spectral dependence of the refractive index for all compositions of studied crystals were obtained. The dispersion of the refractive index is discussed in terms of the Wemple–DiDomenico single‐effective‐oscillator model. The compositional dependencies of refractive index dispersion parameters: oscillator energy, dispersion energy and zero‐frequency refractive index were revealed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of AgGa1‐xInxSe2 single crystals grown by Bridgman method

High‐pure and single‐phase AgGa_1‐xIn_xSe₂ (x=0.2) polycrystalline was synthesized by the mechanical and temperature oscillation method. Adopting the modified Bridgman method an integral AgGa_1‐xIn_xSe₂ single crystal with diameter of 14 mm and length of 35 mm has been obtained at the rate of 6 mm/day. It was found that there is a new cleavage face which was (101), and observed the four order X‐ray spectrum of the {101} faces. By the method of DSC analysis the melting and freezing points of the AgGa_1‐xIn_xSe₂ (x=0.2) single crystal were about 828°C and 790°C. The transmission spectra of the AgGa_1‐xIn_xSe₂ (x=0.2) sample of 5×6×2 mm³ were obtained by means of UV and IR spectrophotometer. The limiting frequency was 774.316nm and the band gap was 1.6eV. It can be found in the infrared spectrum that the infrared transmission was above 60% from 4000cm^‐1 to 600cm^‐1. The value of α in 5.3µm and 10.6µm were 0.022cm^‐1 and 0.1cm^‐1 respectively. All results showed that the crystal was of good quality. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical Absorption Edge of Mg + Zn: LiNbO3

The optical transmittance of LiNbO₃ single crystal double doped with MgO and ZnO was measured from the ultraviolet to the visible range. The wavelength dependence of the absorption coefficient α and its root α^1/2 (α versus hv and α^1/2 versus hv, respectively) were calculated and the characteristics of the absorption edge were discussed. The energy gaps E_g and E_g of the crystals which correspond to the direct transition and the indirect transition, respectively, and the energy of phonons taking part in the indirect transition were calculated. The effects of dopants Mg and Zn on the optical absorption properties are discussed. It was found that the energy E_g of our sample which was double doped with MgO and ZnO was smaller than that of congruent LN, causing the indirect transition absorption edge to move towards the infrared.     

Electron irradiation‐induced effects on optical spectra of (NH4)2ZnCl4: x Sr2+ single crystals

The effect of electron‐beam irradiation with different doses on optical constants of (NH₄)₂ZnCl₄: x Sr²⁺ crystals with x=0.000, 0.020, 0.039, 0.087 or 0.144 wt% has been studied. The optical transmission in the energy range 3.4‐6.4 eV was measured hence the absorption coefficient was computed as a frequency function. The absorption coefficient was also calculated as a function of electron‐beam dose. Irradiation with e‐beam did not affect the allowed indirect type of transition responsible for interband transitions of (NH₄)₂ZnCl₄: x Sr²⁺ crystals. Values of the optical energy gap E_g and optical moment E_p for electronic interband transition of unexposed and (NH₄)₂ZnCl₄: x Sr²⁺ crystals after e‐beam exposure were deduced. The area under the absorption band at 5.30 eV was used to evaluate the effect of e‐irradiation on optical parameters of samples with x=0.00, 0.020 or 0.039. A shift in the position and a nonmonotonic change in the intensity of this band with increasing e‐beam dose was observed. Changes in the E_g value were used to evaluate the effect of e‐beam exposure dose on (NH₄)₂ZnCl₄: x Sr²⁺ samples with x=0.087 or 0.144. The obtained results were compared with those obtained for the same crystals after irradiation with different γ‐doses.     

Growth and characterization of nonlinear optical zinc hydrogen phosphate single crystal grown in silica gel

Good optical quality single crystals of zinc hydrogen phosphate (ZnHPO₄) having dimensions up to 8×2×2 mm³ have been grown with the aid of sodium meta silicate gel. Single crystal XRD studies confirm that the crystal belongs to the orthorhombic system with space group P2₁2₁2₁. The functional groups present in the crystals were confirmed using FTIR technique. Optical absorbance shows very low absorption in the entire visible region. Differential thermal and thermo gravimetric analysis confirmed that the crystal is stable up to 193°C. Photoconductivity study reveals positive photoconductivity in the presence of photo active centers formed by trap energy levels. The NLO activity of the crystal was confirmed by Kurtz powder technique. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical band gap of zinc nitride films prepared by reactive rf magnetron sputtering

Polycrystalline Zn₃N₂ films are prepared on Si and quartz glass substrates by RF magnetron sputtering at room temperature. The structural and optical properties are studied by X‐ray diffraction and double beam spectrophotometer, respectively. X‐ray diffraction indicates that the Zn₃N₂ films deposited on Si and quartz glass substrates both have a preferred orientation in (321) and (442), also are cubic in structure with the lattice constant a=0.9847 and 0.9783 nm, respectively. The absorption coefficients as well as the film thickness are calculated from the transmission spectra, and their dependence on photon energy is examined to determine the optical band gap. Zn₃N₂ is determined to be an indirect‐gap semiconductor with the band gap of 2.11(2) eV. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical absorption spectra of LiNbO3, Fe:LiNbO3, and Zn:Fe:LiNbO3 single crystals grown by Bridgman method

The optical absorption spectra of LiNbO₃ (LN), Fe:LiNbO₃ (Fe:LN), and Zn:Fe:LiNbO₃ (Zn:Fe:LN) single crystals grown by Bridgman method were measured and compared. The absorption characteristics of the samples and the effects of growth process conditions on the absorption spectra were investigated. The Fe, Zn and Li concentrations in the crystals were analyzed by inductively coupled plasma (ICP) spectrometry. The results indicated that the overall Fe ion and Fe²⁺ concentration in Fe:LN and Zn:Fe:LN crystals increased along the growing direction. The incorporation of ZnO in Fe:LN crystal induced increase of Fe²⁺ in the crystal. Among Fe‐doped and Zn:Fe‐codoped LN single crystals, 3 mol% ZnO doped Fe:LN had a biggest change of Fe²⁺ ion concentration from bottom to top part of crystal. The effects of technical conditions (atmosphere and thermal history) on Fe²⁺ ion concentration were discussed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Substrate temperature effect on the optical properties of amorphous Sb2S3 thin films

Sb₂S₃ amorphous thin films were prepared by thermal evaporation of corresponding powder on thoroughly cleaned glass substrates held at temperature in the range 300‐473 K. X‐ray diffraction and atomic force microscopy have been used to order to identify the structure and morphology of surface thin films. The optical constants of the deposition films were obtained from the analysis of the experimental recorded transmission data over the wavelength range 400‐1400 nm. An analysis of the absorption coefficient values revealed an optical indirect transition with the estimation of the corresponding band gap values. It was found that the optical band gap energy decrease with substrate temperature from 1.67 eV at 300 K to 1.48 eV at 473K. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of temperature on the microcrystalline structure of thermally evaporated Sb2S3 thin films

Thin films of antimony trisulfide (Sb₂S₃) were prepared by thermal evaporation under vacuum (p=5×10^–5 torr) on glass substrates maintained at various temperatures between 293 K and 523 K. Their microstructural properties have obtained by transmission electron microscopy (TEM). The electron diffraction analysis showed the occurrence of amorphous to polycrystalline transition in the films deposited at higher temperature of substrates (523 K). The polycrystalline thin films were found to have an orthorhombic structure. The interplanar distances and unit‐cell parameters were determined by high‐resolution transmission electron microscopy (HRTEM) and compared with the standard values for Sb₂S₃. The surface morphology of Sb₂S₃ thin films was investigated by scanning electron microscopy (SEM). The optical transmission spectra at normal incidence of Sb₂S₃ thin films have been measured in the spectral range of 400–1400 nm. The analysis of the absorption spectra revealed indirect energy gaps, characterizing of amorphous films, while the polycrystalline films exhibited direct energy gap. From the photon energy dependence of absorption coefficient, the optical band gap energy, E_g, were calculated for each thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diamagnetic and photoabsorption characterisation of gel‐grown cadmium oxalate single crystals

Perfect single crystals of cadmium oxalate trihydrate have been grown using the slow and controlled reaction between Cd⁺² and (C₂O₄)^‐2 ions in agar‐agar gel, resulting in the formation of insoluble product Cd(COO)₂.3H₂O. The optimum growth parameters have been determined. The variation of magnetic moment of the grown crystals under an applied static magnetic field is studied and the material is found to be diamagnetic. The polarizability is found sensitive to optical band gap. An empirical relation between magnetic susceptibility and electronic polarizability has been established. Optical absorption spectra of the sample recorded in the range 200‐2500 nm reveal transitions involving absorption and emission of phonons. The detailed study supports the existence of allowed direct and indirect allowed gaps in the material. The direct allowed transition prevails in the region of relatively higher photon energy. Some feeble disorder in the crystal is conceived to be present. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of different solvents on the habit of meta‐nitroaniline single crystals

The habit of the organic non‐linear optical material meta‐nitroaniline (mNA) crystallized from different organic solvents such as acetone, benzene, ethyl acetate, n‐hexane, methanol and toluene were studied. Solubility of mNA in these solvents at various temperatures in the range between 288 and 323 K was determined by gravimetric method. Crystals were grown by restricted evaporation of solvents method. Solutions with different solvents having different chemical nature and polarity yielded crystals with different habits: one‐dimensional needles, two‐dimensional rhombic platelets and three‐dimensional octahedral. In addition, the mNA crystals show unidirectional growth behaviour along its polar [001] direction irrespective of the solvents used. All the grown crystals were found to be orthorhombic system with point group mm2 and space group Pbc2₁ which was confirmed by powder X‐ray diffraction study. Optical transmittance study showed that the grown mNA single crystals have optical transparency in the wavelength range between 430 and 1550 nm. SHG efficiency of the grown mNA crystal was 3 times grater than KDP. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation,physicochemical and third order nonlinear optical properties of bis(tetrabutylammonium)bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)mercurate(II)

Bis(tetrabutylammonium)bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)mercurate(II) was prepared and characterized by elemental analyses, electronic absorption, infrared and X‐ray powder diffraction spectroscopy. The specific heat of the crystal was measured to be 1878.2 J.mol^–1K^–1 at 300 K. The thermal decomposition process was investigated by means of thermogravimetric analysis and differential thermal analysis measurements in air together with infrared and X‐ray powder diffraction spectra. The third‐order nonlinear optical properties at 800 nm were measured by femtosecond optical Kerr gate technique by using CS₂ as reference. The third‐order optical susceptibility of its acetone solution at the concentration of 9.27 × 10^–4 M was obtained to be 2.53 × 10^–14 esu. The second‐order hyperpolarizability was estimated to be 1.7 × 10^–32 esu and the response time was about 226 fs. The third order nonlinear optical properties at 532 nm were investigated by using the Z‐scan technique with 20 ps. It exhibited self‐focusing effect and saturable absorption. The second molecular hyperpolarizability was estimated to be 8.4 × 10^–32 esu. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)