The structural, electronic and optical properties of CdxZn1 − xSe ternary alloys

The structural, electronic, and optical properties of Cd_xZn_1 − xSe alloys are investigated using the first-principles plane-wave pseudopotential method within the LDA approximations. In particular, the lattice constant, bulk modulus, electronic band structures, density of state, and optical properties such as dielectric functions, refractive index, extinction coefficient and energy loss function are calculated and discussed. Our results agree well with the available data in the literature.     

Thermal annealing effect of on optical constants of vacuum evaporated Se75S25−xCdx chalcogenide thin films

Chalcogenide glasses are interesting materials due to their infrared transmitting properties and photo induced effects exhibited by them. Thin films with thickness of 3000 Å of the glasses Se₇₅S_25−xCd_x with x=6, 8 and 10 at% prepared by melt quench technique were evaporated by thermal evaporation onto glass substrates under a vacuum of 10⁻⁶ Torr. The optical constants (absorption coefficient, refractive index and extinction coefficient) of as-prepared and annealed films have been studied as a function of photon energy in the wave length region 400-1000 nm. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It has been found that the absorption coefficient and optical band gap increase with increasing annealing temperatures. The refractive index (n) and the extinction coefficient (k) were observed to decrease with increasing annealing temperature.     

Effects of UV photon irradiation on SiOx (0 < x < 2) structural properties

Thin films of a-SiO_x (0 < x < 2) were prepared by reactive r.f. magnetron sputtering from a polycrystalline-silicon target in an Ar/O₂ gas mixture. The oxygen partial pressure in the deposition chamber was varied so as to obtain films with different values of x. The plasma was monitored, during depositions, by optical emission spectroscopy (OES) system. Energy dispersive X-ray (EDX) measurements and infra-red (IR) spectroscopy were used to study the compositional and structural properties of the deposited layers.Structural modifications of SiO_x thin films have been induced by UV photons’ bombardment (wavelength of 248 nm) using a pulsed laser. IR spectroscopy and X-ray photoemission spectroscopy (XPS) were used to investigate the structural changes as a function of x value and incident energy. SiO_x phase separation by spinodal decomposition was revealed. The IR peak position shifted towards high wavenumber values when the laser energy is increased. Values corresponding to the SiO₂ material (only Si⁴⁺) have been found for laser irradiated samples, independently on the original x value. The phase separation process has a threshold energy that is in agreement with theoretical values calculated for the dissociation energy of the investigated material.For high values of the laser energy, crystalline silicon embedded in oxygen-rich silicon oxide was revealed by Raman spectroscopy.     

Effect of Bi2O3 content on physical and optical properties of 15Li2O-15K2O-xBi2O3-(65−x) B2O3: 5V2O5 glass system

Multi-component bismuth borate glasses doped with vanadium ions 15Li₂O-15K₂O-xBi₂O₃-(65−x) B₂O₃: 5V₂O_5, (x=3, 5, 7, 10, 12 and 15) have been prepared using conventional melt quench technique. Characterization of the prepared glasses has been done using X-ray diffraction, differential scanning calorimetry and density measurements. The effect of Bi₂O₃ content on the optical properties of the present glass system is studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The origin of the Urbach energy is associated with the phonon-assisted indirect transitions. The density and molar volume studies indicate that Bi₂O₃ in these glasses is acting partly as network modifier and partly as network former. The variations in the optical band gap energies, density and molar volume with Bi₂O₃ content have been discussed in terms of changes in the glass structure. Values of the theoretical optical basicity, average crosslink density and the average electronic polarizability are also reported.     

Linear and nonlinear optical response of MgxZn1−xO: A density functional study

Total and partial density of states, frequency dependent complex refractive index including extinction coefficient, optical conductivity and transmission of Mg_xZn_1−xO (0≤x≤1) in rocksalt and wurtzite phases are calculated using full potential linearized augmented plane wave (FP-LAPW) method. The real part of refractive index decreases while the extinction coefficient, optical conductivity and transmission for rocksalt phase increases with the increase in Mg concentration. In wurtzite phase, ordinary and extraordinary indices decrease while extinction coefficient, optical conductivity and transmission increase in parallel as well as perpendicular to c-axis with the increase in the Mg concentration.     

Second-harmonic generation in the thermal/electrical poling (100−x)GeS2·x(0.5Ga2S3·0.5CdS) chalcogenide glasses

Utilizing Maker fringe (MF) method, second-harmonic generation (SHG) has been observed within the GeS₂-Ga₂S₃-CdS pseudo-ternary glasses through thermal/electrical poling technique. The SHG phenomenon was considered to be the result of breakage of the glassy macroscopic isotropy originated from the reorientations of dipoles during the thermal/electrical poling process. Under the same poling condition conducted with 5 kV and 280 °C for 30 min, the maximum value of second-order nonlinear susceptibility χ⁽²⁾ of the poled (100−x)GeS₂·x(0.5Ga₂S₃·0.5CdS) glasses was obtained to be ≈4.36 pm/V when the value of x is equal to 30. Nonlinear dependence of χ⁽²⁾ on compositions of these glasses can be well explained according to the theory related to the reorientation of dipoles.     

Optical properties of methane to 288 GPa at 300 K

Optical properties of solid methane (CH₄) were studied at high pressure and room temperature using a diamond anvil cell. Reflectivity and transmission measurements were used to measure the refractive index to 288 GPa. Fabry-Perot interferometery was used to measure the sample thickness to 172 GPa. This data was fitted to the derived expression of thickness vs. pressure that was then used to calculate the thickness to 288 GPa. This in turn was combined with optical absorption experiments to obtain the absorption coefficient and hence the extinction coefficient k^*. From combined reflection and absorption experiments the refractive index n=n_s+ik^* was obtained. The index of refraction and the ratio of molar refraction to molar volume showed a large increase between 208 and 288 GPa. This behavior indicated that a phase transformation of insulator-semiconductor might have occurred in solid CH₄ by 288 GPa.     

Influence of composition on electrical and optical properties of new chalcogenide thin films from Ge-Se-Tl system

Bulk Ge₂₀Se_80−xTl_x (x ranging from 0 to 15 at%) chalcogenide glasses were prepared by conventional melt quenching technique. Thin films of these compositions were prepared by thermal evaporation, on glass and Si wafer substrates at a base pressure of 10⁻⁶ Torr. X-ray diffraction studies were performed to investigate the structure of the thin films. The absence of any sharp peaks in the X-ray diffractogram confirms that the films are amorphous in nature. The optical constants (absorption coefficient, optical band gap, extinction coefficient and refractive index) of Ge₂₀Se_80−xTl_x thin films are determined by absorption and reflectance measurements in a wavelength range of 400-900 nm. In order to determine the optical gap, the absorption spectra of films with different Tl contents were analyzed. The absorption data revealed the existence of allowed indirect transitions. The optical band gap showed a sharp decrease from 2.06 to 1.79 eV as the Tl content increased from 0% to 15%. It has been found that the values of absorption coefficient and refractive index increase while the extinction coefficient decreases with increase in Tl content in the Ge-Se system. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. DC electrical conductivity of Ge₂₀Se_80−xTl_x thin films was carried out in a temperature range 293-393 K. The electrical activation energy of these films was determined by investigating the temperature dependence of dc conductivity. A decrease in the electrical activation energy from 0.91 to 0.55 eV was observed as the Tl content was increased up to 15 at% in Ge₂₀Se_80−xTl_x system. On the basis of pre-exponential factor, it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges.     

Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi₁₄W_1 − xLa_xO_{24 − 3x/2} (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi₂O₃ related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi₂O₃ type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ₈₀₀ = 1.34 S cm^− 1), but also shows significant phase separation at lower temperatures.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

High-temperature electrical properties of magnesiowustite Mg1 − xFexO and spinel Fe3 − x − yMgxCryO4 ceramics

Phase relationships, thermal expansion and electrical properties of Mg_1 − xFe_xO (x = 0.1-0.45) cubic solid solutions and Fe_{3 − x − y}Mg_xCr_yO_4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O₂)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10^− 6 K^− 1 at 300-500 K and (13.2-16.1) × 10^− 6 K^− 1 at 1050-1370 K. Mg_1 − xFe_xO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.     

K-Dependence and temperature dependence of N2-, H2-, and He-broadening coefficients for the J = 12-11 transition of acetonitrile CH3CN located near 220.7 GHz

Extensive experiments on the K = 3 component of the J = 12-11 rotational transition of acetonitrile CH₃C¹⁴N, located near 220.7 GHz, were performed at different temperatures in the range 235-350 K. They allow determining the N₂-, H₂-, and He-broadening coefficients, as well as their temperature dependences. More specific measurements on all the K-components of the involved transition perturbed by N₂ at 303 K allow to point out a clear decreasing of the broadening coefficient with increasing K. Narrowing effects are clearly observed, and experimental lines were analysed both with Voigt and speed dependent Voigt profiles; but no exhaustive lineshape study was carried out. All the experimental parameters are compared with results derived from a semiclassical calculation of collisional interactions, including electrostatic, induction, and dispersion energy contributions.     

Optical gain spectra of unstrained graded GaAs/AlxGa1 − xAs quantum well laser

We have calculated the optical gain spectra in unstrained graded GaAs/Al_xGa_1 − xAs single quantum well lasers as a function of the energy of the radiation, the quantum well width and the interface thickness. The optical gain spectra were calculated using the density matrix approach (Luttinger–Kohn method), considering the parabolic band model (conduction band), all subband mixing between the heavy and light holes (valence band), and the transversal electrical light polarization. Our results show that the optical peak gain is sensitive to the width and the graded profile of the interfaces, and is blue-shifted as a function of the interface width.     

Luminescence spectra and optical properties of TeO2-WO3-Li2O glasses doped with Nd, Sm and Er rare earth ions

New tellurite glass series of the form (70-x)TeO₂-20WO₃-10Li₂O-xLn₂O₃, where x=0, 1, 3 and 5 mol% and Ln=Nd, Sm and Er, were prepared. Density of the prepared glasses was measured and molar volume was calculated. Luminescence spectra of the prepared glasses were measured at room temperature using a micro-Raman spectrometer. The obtained luminescence intensity ratio was correlated with the rare earth ion concentration, the short distance between the identical rare earth ions r(Ln-Ln) and the glass density. Optical properties like refractive index, molar refractivity and optical polarizability were theoretically calculated in order to interpret the dependence of these properties on the rare earth ion content.     

X-ray photoelectron spectroscopy characterization of the layered intercalated compound K2xMn1 − xPS3

Polycrystalline powders of the layered MnPS₃ compound have been intercalated with K⁺ ions by ion-exchange to yield the K_2xMn_1 − xPS₃ intercalate. X-ray photoelectron spectroscopy has been applied to learn about the electronic structure of this compound. In particular, we have studied the XPS spectra of the Mn 2p and 3p, P and S 2p, K 2p and 3p core levels and of the valence band region. The binding energies for various core levels of the elements present in this compound and their observed chemical shifts are analyzed. The data give evidence for the lack of non-equivalent atoms of K, Mn, P and S. Shake-up satellites are present at the Mn 2p and 3p core levels. The occurrence of such lines allows us to hypothesize that K_2xMn_1 − xPS₃ is a large-gap insulating Mn compound. Confirmation that only an ion transfer accompanies the intercalation process is given from both the strong observed similarity with the corresponding XPS spectra in MnPS₃ and the observed binding energy positions of the K 2p and 3p levels. As regards the valence band XPS spectrum, the observed analogies with the corresponding XPS spectra of the pure compound and of other K compounds have allowed us to single out two regions and their probable contributors.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.     

AlN, GaN, AlxGa1 − xN nanotubes and GaN/AlxGa1 − xN nanotube heterojunctions

Semiconductor optoelectronic devices based on GaN and on InGaN or AlGaN alloys and superlattices can operate in a wide range of wavelengths, from far infrared to near ultraviolet region. The efficiency of these devices could be enhanced by shrinking the size and increasing the density of the semiconductor components. Nanostructured materials are natural candidates to fulfill these requirements. Here we use the density functional theory to study the electronic and structural properties of (10,0) GaN, AlN, Al_xGa_1 − xN nanotubes and GaN/Al_xGa_1 − xN heterojunctions, 0<x<1. The Al_xGa_1 − xN nanotubes exhibit direct band gaps for the whole range of Al compositions, with band gaps varying from 3.45 to 4.85 eV, and a negative band gap bowing coefficient of −0.14 eV. The GaN/Al_xGa_1 − xN nanotube heterojunctions show a type-I band alignment, with the valence band offsets showing a non-linear dependence with the Al content in the nanotube alloy. The results show the possibility of engineering the band gaps and band offsets of these III-nitrides nanotubes by alloying on the cation sites.     

On the short-range order of the SiOx (0 ≤ x ≤ 2) surface

Fine (oscillating) structure (FS) in the elastically scattered electron spectra (ESES) [O. Bondarchuk, S. Goysa, I. Koval, P. Melnik, M. Nakhodkin, Surf. Sci. 258 (1991) 239; O. Bondarchuk, S. Goysa, I. Koval, P. Melnik, M. Nakhodkin, Surf. Rev. Lett. 4 (1997) 965] was used to investigate surface structure of the SiO_x (0 ≤ x ≤ 2). SiO_x surface with different stoichiometry was prepared by implantation of 500 eV oxygen ions into a silicon wafer. Fourier transformation of the FS ESES contains one peak at 2.32 Å for Si, two peaks at 1.62 Å and 2.65 Å for a-SiO₂ and three peaks centered at 1.6-1.7 Å, 2.1-2.2 Å and 2.65-3.04 Å for SiO_x. Peaks at 1.62 Å and 2.65 Å are assigned to Si-O and O-O nearest distances correspondently. Ratio of the area under the peak at 2.65 Å to the area under the peak at 1.62 Å turned out to be not constant but grows linearly with the composition parameter x. The latter is considered to prove validity of the Random Bond Model to describe short-range order on the surface of non-stoichiometric silicon oxide.     

Optical band gap and optical constants in a-Se80Te20−xPbx thin films

The optical constants (absorption coefficient, refractive index, extention coefficient, real and imaginary part of dielectric constant) have been studied for a-Se₈₀Te_20−xPb_x (where x = 0, 2, 6, 10) thin films as a function of photon energy in the wave length range (500–1000 nm). It has been found that the optical band gap increases while the refractive index and the extinction coefficient (k) decreases on incorporation of lead in Se–Te system. The value of absorption coefficient (α) and the extinction coefficient (k) increases, while the value of refractive index (n) decreases with incident photon energy. The results are interpreted in terms of the change in concentration of localized states due to the shift in fermi level.     

Ultra-thin Si overlayers on the TiO2 (1 1 0)-(1 × 2) surface: Growth mode and electronic properties

The growth of thin subnanometric silicon films on TiO₂ (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiO_x (1 < x ? 2) on top of a further reduced TiO₂ surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiO_x overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO₂ (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiO_x clusters.