Redshift Trend Research Articles

Structural and optical proprieties of doped cobalt oxide: CuxCo3−xO4 (x = 0.0; 0.1; 0.2; 0.4; and 0.6)

Copper cobaltite oxides of formula CuxCo3−xO4 (x=0.0; 0.1; 0.2; 0.4 and 0.6) were synthesized by hydrothermal conditions using polyethylene-glycol-400 (PEG-400) as surfactant. The as-prepared samples are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Rietveld fitted patterns confirm the formation of cubic spinel structure with Fd-3m space group. Particle size was determined from the XRD peak broadening analysis. The Cu-doping effect on the structural and optical properties of the copper cobaltite oxides was investigated. Phase purity of CuxCo3−xO4 was confirmed by X-ray diffraction studies. XRD results reveal that the lattice parameters and the theoretical density (dth) were found to increase with Cu-substitution. The direct and indirect band gap energies were found to decrease with increasing Cu-content from 1.72eV (x=0) to 1.39eV (x=0.6) and from 1.75eV for x=0 (Co3O4) to 1.40eV for x=0.6 (Cu0.6Co2.4O4) respectively, indicating a red shift trend when the Cu-content increases.

The study of structure and optical properties of Nanoparticles(NPs)-Cu/SiO2 multilayer films deposited alternately by magnetron sputtering technique

NPs-Cu/SiO2 multilayer films were deposited alternately by magnetron sputtering on single silicon and Corning glass substrate with different Cu target power at room temperature (RT) and 400°C. The structure of the NPs-Cu/SiO2 films was analyzed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical absorption property was investigated by Ultraviolet–visible spectroscopy (UV–Vis). The results of XRD and TEM indicate that Cu nanoparticles are basically spherical and disperse in the SiO2 matrix. The optical absorption peaks due to the surface plasmon resonance (SPR) of Cu nanoparticles are observed in the wavelength range of 590–650nm. The SPR peak for NPs-Cu/SiO2 multilayer films shows the red-shift trend with increasing Cu target power, however, the SPR peak shows the blue-shift trend with increasing the substrate temperature and the number of Cu layers.

Diversity of electronic transitions and photoluminescence properties of p-type cuprous oxide films: A temperature-dependent spectral transmittance study

Cuprous oxide films have been deposited on quartz substrates by a sol-gel method under various annealing temperatures. The X-ray diffraction analysis and Raman scattering show that all the films are of pure Cu2O phase. From comparison of photoluminescence with 488 and 325 nm laser excitations, the electronic transition energies and intensities present the annealing-temperature dependent behavior. The electronic band structures of the Cu2O film annealed at 800 °C, especially for the contribution of exciton series and high energy transitions, have been investigated by temperature dependent transmittance. The extracted refraction index and the high frequency dielectric constant both abruptly decrease until the temperature rises up to 100 K. Six transitions can be clearly identified and the red shift trend of Eo3-Eo5 transition energies with increasing the temperature can be found. Moreover, the anomalous behavior takes place at about 200 K from the Eo6 transition. The singularities indicate that the change in the crystalline and electronic band structure occurs as the temperature near 100 K and 200 K for the film.

A study of optical absorption of cysteine-capped CdSe nanoclusters using first-principles calculations.

Understanding the size-dependent structures and properties of ligand-capped nanoclusters in solvent is of particular interest for the design, synthesis and application of II-VI colloidal QDs. Using DFT and TDDFT calculations, we studied the structure and optical property evolution of the cysteine-capped (CdSe)N clusters of N = 1-10, 13, 16 and 19 in gas, toluene, water and alkaline aqueous solution, and made a comparison with their corresponding bare clusters. The cysteine binds with (CdSe)Nvia several patterns depending on the medium they exist in, affecting the cluster structures and in consequence their optical absorption. In general, the absorption bands of (CdSe)N blueshift when cysteine is added, and the shift varies with the interaction strength between the cluster and the ligand, and the dielectric constant of the solvent. However, bare clusters retain their size sensitivity, in particular the redshift trend with increasing cluster size, and some similarity was noted for the optical absorption of the bare and ligated clusters regardless of the gas or solvent media. Population analysis reveals that the excitations are mainly from orbitals distributing on the (CdSe)N part, while the ligand is negligibly involved in the excitations. This is an important feature for the II-VI QDs as biosensors with which the information of biomolecules is detected from the size dependent optical absorption or emission of the QDs other than the biomolecules.

Temperature-dependent band gap, interband transitions, and exciton formation in transparentp-type delafossiteCuCr1−xMgxO2films

Temperature-dependent interband transitions and exciton excitations of sol-gel derived ${\mathrm{CuCr}}_{1\ensuremath{-}x}$${\mathrm{Mg}}_{x}$${\mathrm{O}}_{2}$ $(2%\ensuremath{\le}x\ensuremath{\le}8%)$ films have been investigated by transmittance spectra (8--300 K) and photoluminescence (PL) spectra (77--300 K). An abnormal dependence of the optical band gap with the temperature has been found for the films with $x=0.02$ and 0.04. At the low-temperature region, the gap energy shows a redshift trend with decreasing temperature. It is due to the strong Cr $3d\text{\ensuremath{-}}\text{O}$ $2p\text{-Cu}$ $3d$ interaction in the upper part of the valence band, which can be weaken by heavily Mg doping. The spin-orbit interactions of ${\mathrm{Cr}}^{3+}$ ions in an octahedral environment make the $3d$ states more disperse, which can contribute to the relatively high conductivity. A well-defined low-energy absorption has been assigned to the spin-allowed $3d$ $\ensuremath{\rightarrow}$ $3d$ transition. Moreover, a strong exciton excitation around 1.8 eV has been observed due to the naturally low-dimensional structure of the delafossite, which can be modulated by temperature and hole concentration.

Alkali Metals-Substituted Adamantanes Lead to Visible Light Absorption: Large First Hyperpolarizability

Adamantane (Ad) is the parent molecule of diamondoids, which has been the subject of much chemical interest because of its highly symmetric cage structure. Many valuable papers demonstrated that the H atom of the methine position in Ad is highly reactive. Compared with highly symmetric carbon structures such as graphene and single-walled carbon nanotubes (SWCNTs), Ad only possesses σ bonds. In this work, we report a quantum chemical calculation on three complexes (Ad-Li, Ad-Na, and Ad-K), which were obtained by substituting the H atom of methine position in Ad with alkali metal (Li, Na, and K). Interestingly, the substitution by alkali metals leads to absorption within the visible region. The maximum absorption wavelengths of the complexes show a red shift trend from the Li to the K complex. This trend indicates that the crucial transition energy becomes smaller, which might lead to a larger nonlinear optical response. Among the three structures, the largest first static hyperpolarizability (βtot) of the ...

Temperature dependence of terahertz optical characteristics and carrier transport dynamics in p-type transparent conductive CuCr1−xMgxO2 semiconductor films

Terahertz reflectance spectra and electrical transport of CuCr1−xMgxO2 films have been studied in temperature range of 150–300 K. With increasing temperature, the phonon mode near 15 THz shows a redshift trend, and free carrier absorption below 6 THz becomes more prominent. Moreover, hole effective mass increases linearly from 0.028 to 0.48 m0 with the temperature and composition. Hall coefficient shows a turning-point at about 220, 206, and 194 K for the composition of x = 0.02, 0.06, and 0.10, respectively. The phenomena can be attributed to the transition of carrier transport mechanism from a thermal activation behavior to a variable range-hopping one.

Interband electronic transitions and phase transformation of multiferroic Bi1−xLaxFe1−yTiyO3 ceramics revealed by temperature-dependent spectroscopic ellipsometry

Optical properties and phase transition of Bi1−xLaxFe1−yTiyO3 (BLFTO) ceramics with different composition (0.02 ≤ x ≤ 0.10, 0.01 ≤ y ≤ 0.06) have been investigated by spectroscopic ellipsometry (SE) in the temperature range of −70–450 °C. The real part of the complex dielectric function ε1 increases with the temperature. Meanwhile, the imaginary part ε2 in the low-energy region decreases with the temperature and has an opposite trend in the high-energy side. Four typical interband transitions (Ea ∼ 2.50 eV, Eb ∼ 2.70 eV, Ec ∼ 3.60 eV, and Ed ∼ 4.25 eV) can be observed from the second derivative of the complex dielectric functions with aid of the standard critical point model. The critical point (CP) transition becomes broadening and shifts to a lower energy side as La and Ti compositions increase. Moreover, the CP transition energies show a red-shift trend with increasing the temperature until 320 °C, due to the lattice thermal expansion and electron-phonon interaction. The typical interband transitions and partial spectral weight present anomalies in the proximity of antiferromagnetic transition owing to the coupling between magnetic and ferroelectric order parameters and spin-lattice coupling for BLFTO multiferroic materials. It was found that the Néel temperature of BLFTO ceramics decreases from 364 to 349 °C with increasing doping composition of La and Ti elements. These phenomena can be attributed to the modification of electronic structure and magnetic order because the differences of electronegativity and ionic radii between Bi and La, Fe and Ti induce the variations on the bond angle and bond length between cations and anions. Moreover, the substitution for magnetic Fe3+ ions with nonmagnetic Ti4+ ions can reduce the exchange interaction between adjacent magnetic moments. Therefore, SE technique can be sensitive for detecting the phase/structural transitions of multiferroic oxides.

Structural, linear and third-order nonlinear optical properties of Cu nanocrystal in sodium borosilicate glass

Abstract Cu nanocrystals embedded in sodium borosilicate glass of varied Cu contents from 0.5 to 1.5 wt% have been successfully prepared through a sol–gel process. According to the results of X-ray diffraction (XRD) and the energy dispersive X-ray spectrometry (EDS), the metal Cu nanocrystals in cubic crystal system were well distributed inside glass matrix. Fourier Transform Infrared (FTIR) indicated the sodium borosilicate matrix had no major structural change for gels with different Cu contents. The optical absorption peaks due to the surface plasmon resonance of Cu particles were observed in the wavelength range of 550–600 nm. The absorption peak showed a red-shift trend with increasing Cu contents from 0.5 to 1.5 wt%. Transmission electron microscopy (TEM) revealed the existence of spherical Cu nanocrystals in the matrix. The diameter of Cu nanocrystals varied from 1 to 3.5 nm. Furthermore, the third-order nonlinear optical properties were investigated by Z-scan technique at 800 nm. Experimental results indicated the Cu nanocrystals have obvious positive refractive nonlinearities and reverse saturated absorption performance.

Temperature-dependent dielectric functions and interband critical points of relaxor lead hafnate-modified PbSc1/2Ta1/2O3 ferroelectric ceramics by spectroscopic ellipsometry

The electronic band structures and dielectric functions of (1−x)PbSc1/2 Ta 1/2O3−xPbHfO3 ceramics with different composition have been investigated by variable-temperature spectroscopic ellipsometry. Using the standard critical-point (SCP) model, three typical interband transitions can be observed from the second derivative of dielectric functions. The CP transitions, which are sensitive to B-site order degree, show a redshift trend with the temperature due to the electron-phonon interactions and lattice thermal expansion. The linear temperature coefficients are varied with oxygen vacancy, B-atom (Sc, Ta, Hf) arrangement, and Pb-O bonds owing to addition of PbHfO3.

Hydrothermal Preparation of Copper Doped NaTaO<SUB>3</SUB> Nanoparticles and Study on the Photocatalytic Mechanism

Effects of copper cations doping into wide band gap semiconductor photocatalysts of tantalate on morphology, visible light response, and photocatalytic performance were studied. A series of Cu-doped NaTaO3 catalysts were prepared by hydrothermal method. XRD and XPS results suggested that copper were successfully doped into the NaTaO3 nanocrystal in the Cu2+ state. TEM studies showed the formation of the cube shape nanoparticles of NaTaO3 as well as Cu-doped NaTaO3. UV-Vis diffuse reflectance spectra clearly indicated the red-shift in the series of copper doped NaTaO3 catalysts, resulting in a decrease in the band gap of NaTaO3. The trend of red shift was increased with an increase of copper doping concentration, whereas the photo-degradation methylene blue (MB) is not improved by the doping of copper ions. The simulation of energy band structure by density functional theory unfolded that the substitution of Ta5+ ions by Cu2+ ions results in forming an intermediate band (IB) upper the top of the valence band (VB), which is mainly attributed to the state of Cu 3d. The intermediate band is responsible for the red-shift caused by the doping of Cu ions. Meanwhile Cu species can become the recombination centers of photoinduced electrons and holes. Thus, the quickly recombination of e(-)h(+) pairs is one of the most significant factors which deteriorate the photoactivity of Cu-doped NaTaO3.

Size effect of silk fibroin peptide chains in the growth process

A theoretical study on 13 oligopeptides of glycine and alanine by density function theory (DFT) is given in this paper. Geometric structures, vibration frequency, average binding energies, dipole moment are studied, and IR spectra of the oligopeptides are examined. Results show that with increasing number of residues the average binding energies tend to a regular pattern, IR frequencies of typical functional groups start to shift, but stretching and bending vibrations of the groups show the opposite trend of red shift and blue shift. It is revealed that the physical and chemical properties of the silk fibroin peptide chain show size effect and anisotropic in the growth process. This phenomenon may come from the coupling effect of the similar groups, and the different effects of intramolecular hydrogen bond on the stretching and bending vibration.

Fabrication of porous ZnO via electrochemical etching using 10 wt% potassium hydroxide solution

We described the fabrication of porous ZnO using the electrochemical etching method. ZnO thin films deposited by radiofrequency sputtering were etched electrochemically using 10wt% KOH solution as an etching medium to obtain porous ZnO surface structure. A constant voltage of 15V was applied to enhance the etching process. The etched samples were then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy to examine their structural and optical properties. XRD spectra showed that by performing the electrochemical etching process, porous ZnO could be obtained without severely deteriorating the crystallinity of the samples. Moreover, SEM characterization revealed that hillock-type porous ZnO was fabricated successfully. In addition, the cross-sectional SEM images revealed that there were only minimal changes in the layer thickness after the ZnO had been etched for various lengths of time. This finding shows the dominance of the vertical etching process. Notably, the intensity of PL spectra increased and the PL excitation peak exhibited a red shift trend as the etching time increased. These observations are due to the increase of the surface to volume ratio of the ZnO surface and the strain relaxation along the dislocation and grain boundary.

Nonstandard cages in the formation process of methane clathrate: Stability, structure, and spectroscopic implications from first-principles

Endohedral CH(4)@(H(2)O)(n) (n = 16, 18, 20, 22, 24) clusters with standard and nonstandard cage configurations containing four-, five-, six-, seven-membered rings were generated by spiral algorithm and were systematically explored using DFT-D methods. The geometries of all isomers were optimized in vacuum and aqueous solution. In vacuum, encapsulation of methane molecules can stabilize the hollow (H(2)O)(n) cage by 2.31~5.44 kcal/mol; but the endohedral CH(4)@(H(2)O)(n) cages are still less stable than the pure (H(2)O)(n) clusters. Aqueous environment could promote the stabilities of the hollow (H(2)O)(n) cages as well as the CH(4)@(H(2)O)(n) clusters, and the CH(4)@(H(2)O)(n) clusters possess larger stabilization energies with regard to the pure (H(2)O)(n) clusters except for n = 24. The lowest energy structures of the CH(4)@(H(2)O)(20) and CH(4)@(H(2)O)(24) cages are identical to the building units in the crystalline sI clathrate hydrate. All of the low-energy cages (including both regular and irregular ones) have large structural similarity and can be connected by "dimer-insertion" operation and Stone-Wales transformation. Our calculation also showed that in the range of cluster size n = 16-24, the relative energies of cage isomers tend to decrease with increasing number of the adjacent pentagons in the oxygen skeleton structures. In addition to the regular endohedral CH(4)@(H(2)O)(20) and CH(4)@(H(2)O)(24) cage structures, some nonstandard CH(4)@(H(2)O)(n) (n = 18, 20, 22, 24) cages have lower energies and might appear during nucleation process of methane hydrate. For the methane molecules in these low-energy cage isomers, we found that the C-H symmetric stretching frequencies show a red-shift trend and the (13)C NMR chemical shifts generally move toward negative values as the cavity size increases. These theoretical results are comparable to the available experimental data and might help experimental identification of the endohedral water cages during nucleation.

Luminescence properties of Mn2+ ions doped Lu2CaMg2Si3O12 garnet phosphors

Yttrium aluminum garnet structure phosphors Lu2CaMg2Si3O12:Mn2+ were synthesized by conventional high temperature solid-state reaction in reductive atmosphere. The structure and optical properties of samples were characterized by application of powder X-ray diffraction (XRD) and photoluminescence spectroscopy. Results of X-ray diffraction (XRD) analysis showed that the phosphors mainly presented garnet structure with a few weak peaks of impurity phases. Lu2–xCaMg2Si3O12:xMn2+ (x=0.01–0.8) phosphors showed a broad emission band peaking at around 590 nm under ultraviolet (UV) light of 408 nm when Mn2+ concentration was less than 0.08 mol. With an increase in the Mn2+ concentration (above 0.08), another broad emission band peaking at 720 nm besides 590 nm was observed, which may be due to manganese ion having different valence and occupying different host lattice. The critical quenching concentrations of manganese ion in the wavelength of 590 and 720 nm were about 0.06 and 0.2 mol, respectively. With 408 nm excitation wavelength, emission color of the samples had a red shift trend as the Mn2+ concentration increased. All the results indicated that the Lu2CaMg2Si3O12:Mn2+ phosphors could be applicable to n-UV based white LEDs.

Temperature dependence of phonon modes, dielectric functions, and interband electronic transitions in Cu2ZnSnS4 semiconductor films

The quaternary semiconductor Cu(2)ZnSnS(4) (CZTS) has attracted a lot of attention as a possible absorber material for solar cells due to its direct bandgap and high absorption coefficient. In this study, photovoltaic CZTS nanocrystalline film with a grain size of about 10 nm has been grown on a c-plane sapphire substrate by radio-frequency magnetron sputtering. With increasing the temperature from 86 to 323 K, the A(1) phonon mode shows a red shift of about 9 cm(-1) due to the combined effects of thermal expansion and the anharmonic coupling to the other phonons. Optical and electronic properties of the CZTS film have been investigated by transmittance spectra in the temperature range of 8-300 K. Near-infrared-ultraviolet dielectric functions have been extracted with the Tauc-Lorentz dispersion model. The fundamental band gap E(0), and higher-energy critical points E(1) and E(2) are located at 1.5, 3.6, and 4.2 eV, respectively. Owing to the influences of electron-phonon interaction and the lattice expansion, the three interband transitions present a red shift trend with increasing temperature. It was found that the absorption coefficient in the visible region increases due to the modifications of electronic band structures. The detailed study of the optical properties of CZTS film can provide an experimental basis for CZTS-based solar cell applications.

Influences of Oxygen Pressure on Optical Properties and Interband Electronic Transitions in Multiferroic Bismuth Ferrite Nanocrystalline Films Grown by Pulsed Laser Deposition

Bismuth ferrite (BiFeO(3)) nanocrystalline films with the crystalline size of 27-40 nm have been grown on c-sapphire substrates under various oxygen pressures of 1 × 10(-4) to 1 Pa by pulsed laser deposition. The X-ray diffraction spectra show that the films are polycrystalline and present the pure rhombohedral phase. It was found that the Raman-active phonon mode E(TO1) shifts towards a higher energy side from 74 to 76 cm(-1) with increasing oxygen pressure, indicating a larger tensile stress in the films deposited at higher oxygen pressure. The X-ray photoelectron spectroscopy analysis suggests that the concentrations of both Fe(2+) ions and oxygen vacancies in the BiFeO(3) films increase with decreasing oxygen pressure. Moreover, the dielectric functions in the photon energy range of 0.47-6.5 eV have been extracted by fitting the transmittance spectra with the Tauc-Lorentz dispersion model. From the transmittance spectra, the fundamental absorption edge is observed to present a redshift trend with increasing the temperature from 8 to 300 K. Note that the optical band gap (E(g)) decreases with increasing the temperature due to the electron-phonon interactions associated with the interatomic distance in the BiFeO(3) films. However, the E(g) decreases from 2.88 to 2.78 eV with decreasing oxygen pressure at 8 K, which can be attributed to the increment of oxygen vacancies leading to the formation of some impurity states between the valence and conduction band. It can be concluded that the oxygen pressure during the film fabrication has the significant effects on microstructure, optical properties, and electronic band structure modification of the BiFeO(3) films.

CONSTRAINING HALO OCCUPATION PROPERTIES OF X-RAY ACTIVE GALACTIC NUCLEI USING CLUSTERING OFCHANDRASOURCES IN THE BOÖTES SURVEY REGION

We present one of the most precise measurement to date of the spatial clustering of X-ray selected AGNs using a sample derived from the Chandra X-ray Observatory survey in the Bootes field. The real-space two-point correlation function over a redshift interval from z=0.17 to z~3 is well described by the power law, xi(r)=(r/r0)^-gamma, for comoving separations r<~20h^-1 Mpc. We find gamma=1.84+-0.12 and r0 consistent with no redshift trend within the sample (varying between r0=5.5+-0.6 h^-1 Mpc for <z>=0.37 and r0=6.9+-1.0 h^-1 Mpc for <z>=1.28). Further, we are able to measure the projections of the two-point correlation function both on the sky plane and in the line of sight. We use these measurements to show that the Chandra/Bootes AGNs are predominantly located at the centers of dark matter halos with the circular velocity Vmax>320 km/s or M_200 > 4.1e12 h^-1 Msun, and tend to avoid satellite galaxies in halos of this or higher mass. The halo occupation properties inferred from the clustering properties of Chandra/Bootes AGNs --- the mass scale of the parent dark matter halos, the lack of significant redshift evolution of the clustering length, and the low satellite fraction --- are broadly consistent with the Hopkins et al. scenario of quasar activity triggered by mergers of similarly-sized galaxies.

Temperature dependent photoluminescence properties of needle-like ZnO nanostructures deposited on carbon nanotubes

The structural and optical properties of the needle-like ZnO nanostructure grown on the carbon nanotubes (ZnO/CNTs) have been studied by scanning electron microscope (SEM), X-ray diffraction (XRD), and photoluminescence (PL) spectra. It can be seen that there is about tens of nanometers in diameter of the single ZnO nanorod from the SEM picture. The XRD analysis shows that the prepared film is of typical wurtzite hexagonal phase without impurity. Temperature dependence of electronic transitions in the ZnO/CNTs has been investigated by PL in detail. The emission features in near band gap at 10 K reveal a redshift trend compared to ZnO single crystal, which is associated with the strong interfacial connection between ZnO and CNTs. Moreover, the intensities of all transitions in near band gap and visible regions decrease with increasing the temperature but increase with the excitation power. It can be concluded that the combined effect from ZnO and CNTs plays an important role in the PL response. The emission variations with the temperature for the ZnO/CNTs are the result of the electron–phonon interaction and the lattice thermal expansion.

Temperature dependence of electronic band transition in Mn-doped SnO 2 nanocrystalline films determined by ultraviolet-near-infrared transmittance spectra

Mn-doped SnO 2 (SMO) nanocrystalline films with the composition from 2.5 to 12.5% have been prepared on quartz substrates by pulsed laser deposition. The temperature dependence of electronic structures and optical constants in the SMO films have been investigated by transmittance spectra from 5.3 to 300 K. Optical response functions have been extracted by fitting the transmittance spectra in the photon energy range of 0.5–6.5 eV with the Adachi's model. It was found that the absorption edge presents a red-shift trend with increasing Mn composition, and the optical band gap (OBG) is varied between 4.22 and 3.44 eV. Moreover, as the Mn composition increases, the temperature dependence of OBG becomes weaker. The band gap narrowing value [(5.3 K)–(300 K)] has been reduced from 98 to 3 meV and linearly decreases with the Mn composition. The phenomena could be attributed to the transition from low doping level SnO 2 band-like states to Mn-related localized states. Moreover, the Urbach energy shows the degree of the structural disorder, which could be explained by an empirical formulas in different temperature regimes.