The influence of hydrogen annealing on magnetism of Co-doped TiO2 films prepared by sol–gel method

Co-doped TiO₂ (Co_xTi_1−xO₂, 0.05?x?0.2) films have been prepared on Si (0 0 1) substrates by sol–gel method. When heat treated in air, Co_xTi_1−xO₂ films are non-ferromagnetic at room temperature. However, after further annealed in a flowing hydrogen atmosphere, Co_xTi_1−xO₂ films show room-temperature ferromagnetism (RTFM). Measurements of magnetization (M) vs. temperature (T), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) fail to detect Co clusters in the hydrogenated Co_0.1Ti_0.9O₂ films, suggesting that RTFM in the hydrogenated Co_0.1Ti_0.9O₂ films may be intrinsic. But, metal Co appears in the hydrogenated Co_0.2Ti_0.8O₂ films, showing that RTFM in the hydrogenated Co_0.2Ti_0.8O₂ films is as least partly due to metal Co. These results indicate that hydrogen annealing can produce room-temperature ferromagnetism in Co_xTi_1−xO₂ films, but it should be carefully designed to avoid the formation of metal Co in the hydrogenated Co_xTi_1−xO₂ films.     

Combinatorial discovery of anomalous substrate effect on the photochemical properties of transition metal-doped epitaxial SrTiO3 heterostructures

Epitaxial Sr(V_xCr_yTi_1−x−y)O₃ (0≤x+y≤0.05) ternary composition spreads were grown on two different single crystal substrates, LaAlO₃ and Nb-doped SrTiO₃, by use of combinatorial laser molecular beam epitaxy with a specially patterned slide masking plate. The photocatalytic activity on the composition spreads was evaluated by the photo-reduction of Ag⁺ in an AgNO₃ aqueous solution to deposit Ag metal on the spreads. The V-doping effect was found to depend greatly on the substrate: the photodeposition of Ag was much enhanced in the composition region of SrV_0.05Ti_0.95O₃ only on the Nb-doped SrTiO₃, but not on the LaAlO₃ and non-doped SrTiO₃.     

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.     

(Mo + N) codoped TiO2 for enhanced visible-light photoactivity

A series of Ti_1−xMo_xO_2−yN_y samples were prepared by using sol-gel method and characterized by X-ray diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. All Ti_1−xMo_xO_2−yN_y samples are anatase phase. It is found that Mo, N mono-doping can increase visible light absorption, while (Mo + N) co-doping can greatly enhance absorption in whole visible region. Results of our first-principles band structure calculations reveal that (Mo + N)-doping, especially passivated co-doping can increase the up-limit of dopant concentration and create more impurity bands in the band gap of TiO₂, which leads to a greatly increase of its visible-light absorption without a decrease of its redox potential. It reveals that (Mo + N) co-doped TiO₂ is promising for a photocatalyst with high photocalystic activity under visible light.     

A combinatorial approach to the discovery and optimization of YCa4O(BO3)3-based luminescent materials

Thin films of YCa₄O(BO₃)₃ (YCOB)-based new luminescent materials were explored by the combinatorial pulsed laser deposition (PLD) method which enabled us to fabricate continuous composition spread film libraries. Strong red and green luminescence were found in the Y_1−xEu_xCOB (0 ≤ x ≤ 1), (YEuCOB) and Y_1−yTb_yCOB (0 ≤ y ≤ 1) (YTbCOB) films, respectively. The film libraries were characterized by photoluminescence (PL), PL decay, an electron-probe microanalyzer and an electron diffraction analysis. The luminescent intensities in the amorphous film libraries strongly depended on the chemical composition of each rare-earth (RE) ion. The optimum concentration of rare-earth ions in YEuCOB and YTbCOB were experimentally determined to be Eu = 7.5% and Tb = 20-30%, respectively.     

γ irradiation effect on the polarization and resistance of Li-Co-Yb-ferrite

The effect of γ irradiation on some physical properties of rare earth ferrite of the general formula Li_0.5+zCo_z Yb_xFe_2.5−2z−xO₄, (z=0.1, x=0.00, 0.025, 0.050, … , 0.200) is discussed. The temperature dependence of the polarization and resistance is studied in the range (300 K≤T≤700 K) at different frequencies (10 kHz≤f≤1 MHz). The relaxation time and the activation energy have been calculated before and after irradiation with γ rays doses of 1 and 3 Mrad. A comparison was made between the ac resistance before and after irradiation for the samples with (0.0≤x≤0.2). The results after irradiation with 1 Mrad γ rays showed that the resistance at the critical concentration decreases from 800 to 25 kΩ at room temperature. Furthermore, with increasing temperature the resistance ranged from R≈130 kΩ at T≈310 K to R≈0.13 kΩ at T≈640 K. Thus, it is possible to improve the conductivity of this type of rare earth ferrite materials to be used in technological applications at room as well as at high temperature.     

Epitaxial growth of titanium oxycarbide on MgO (0 0 1) substrates by pulsed laser deposition

Epitaxial TiC_xO_y thin films were grown on MgO (0 0 1) substrates by using pulsed laser deposition method. High-resolution X-ray diffraction and transmission electron microscopy were used to examine crystallinity and microstructure of epitaxial TiC_xO_y film on MgO. The chemical composition of the film is determined to be x ∼ 0.47 and y ∼ 0.69 by X-ray photoelectron spectroscopy. Atomic force microscopy revealed that the surface of TiC_xO_y film is very smooth with roughness of 0.18 nm. The resistivity of the TiC_xO_y film measured by four-point-probe method was about 137 μ Ω cm.     

The role of iron in the formation of the magnetic structure and related properties of La0.8Sr0.2Co1−xFexO3 (x=0.15, 0.2, 0.3)

La_0.8Sr_0.2Co_1−xFe_xO₃ (x=0.15, 0.2, 0.3) samples were studied by means of AC magnetic susceptibility, magnetization, magnetoresistance and ⁵⁷Fe Mössbauer spectrometry. Iron was found to take on a high spin 3d^5−α electronic state in each of the samples, where α refers to a partly delocalized 3d electron. The compounds were found to exhibit a spin-cluster glass transition with a common transition temperature of ∼53 K. The spin-cluster glass transition is visualized in the ⁵⁷Fe Mössbauer spectra as the slowing down of magnetic relaxation below ∼70 K, thereby showing that iron takes part in the formation of the glassy magnetic phase. The paramagnetic-like phase found at higher temperatures is identified below T_c≈195 K as being composed of weakly interacting, magnetically ordered nanosized clusters of magnetic ions in part with a magnetic moment oriented opposite to the net magnetic moment of the cluster. For each of the samples a considerable low-temperature negative magnetoresistance was found, whose magnitude in the studied range decreases with increasing iron concentration. The observed results obtained on the present compounds are qualitatively explained assuming that the absolute strengths of magnetic exchange interactions are subject to the relation ∣J_Co–Co∣<∣J_Fe–Co∣<∣J_Fe–Fe∣.     

The transport and magnetic properties of La–Pb–Mg–Mn–O manganites at low temperatures

The structure, transport properties and the magnetoresistance behavior in the temperature interval 77–400 K of the perovskite-like lanthanum manganites La_0.6Pb_0.4−xMg_x+yMnO₃ (x=0, 0.1, 0.2 and y=0, 0.2) were investigated. Polycrystalline bulk samples were prepared by sol–gel self-combustion and subsequent heat treatment at 1000 °C for different times, 40, 80, 160 and 320 min. All manganites exhibit a peak in the resistivity around 200–250 K, below the ferromagnetic ordering temperature (320–330 K). An isotropic and negative magnetoresistance has been observed in all compounds. Magnetoresistance MR exhibits a peak in the temperature range 130–150 K, below SC–metal transition temperature. Magnitude of MR at the peaks was nearly 27% in the magnetic field of 2 T. At room temperature, a magnetoresistance of 9.5% for La_0.6Pb_0.2Mg_0.2MnO₃ composition was obtained. Longer heat treatment time enhanced the magnetorezistive properties.     

Structural and optical properties of Ga2(1−x)In2xO3 films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Ga_2(1−x)In_2xO₃ thin films with different indium content x [In/(Ga + In) atomic ratio] were prepared on α-Al₂O₃ (0 0 0 1) substrates by the metal organic chemical vapor deposition (MOCVD). The structural and optical properties of the Ga_2(1−x)In_2xO₃ films were investigated in detail. Microstructure analysis revealed that the film deposited with composition x = 0.2 was polycrystalline structure and the sample prepared with x up to 0.8 exhibited single crystalline structure of In₂O₃. The optical band gap of the films varied with increasing Ga content from 3.72 to 4.58 eV. The average transmittance for the films in the visible range was over 90%.     

Positive secondary Ion emission from Si1−xGex bombarded by O2

The positive secondary ion yields of B⁺ (dopant), Si⁺ and Ge⁺ were measured for Si_1−xGe_x (0 ≤ x ≤ 1) sputtered by 5.5 keV ¹⁶O₂⁺ and ¹⁸O₂⁺. It is found that the useful yields of Ge⁺ and B⁺ suddenly drop by one order of magnitude by varying the elemental composition x from 0.9 to 1 (pure Ge). In order to clarify the role of oxygen located near surface regions, we determined the depth profiles of ¹⁸O by nuclear resonant reaction analysis (NRA: ¹⁸O(p,α)¹⁵N) and medium energy ion scattering (MEIS) spectrometry. Based on the useful yields of B⁺, Si⁺ and Ge⁺ dependent on x together with the elemental depth profiles determined by NRA and MEIS, we propose a probable surface structure formed by 5.5 keV O₂⁺ irradiation.     

Mg substitutions in ZnO-Al2O3 thin films and its effect on the optical absorption spectra of the nanocomposite

ZnO-Al₂O₃ nanocomposite thin films were prepared by sol-gel technique. The room temperature synthesis was mainly based on the successful peptization of boehmite (AlO(OH)) and Al(OH)₃ compounds, so as to use it as matrix to confine ZnO nanoparticles. The relative molar concentrations of xZnO to (1 − x) Al₂O₃ were varied as x = 0.1, 0.2 and 0.5. The optical absorption spectra of the thin films showed intense UV absorption peaks with long tails of variable absorption in the visible region of the spectra. The ZnO-Al₂O₃ nanocomposites thin films were doped with MgO by varying its molar concentrations as y = 0.05, 0.75, 0.1, 0.125, 0.15 and 0.2 with respect to the ZnO present in the composite. The MgO doped thin films showed suppression of the intense absorption peaks that was previously attained for undoped samples. The disappearance of the absorption peaks was analyzed in terms of the crystalline features and lattice defects in the nanocomposite system. The bulk absorption edge, which is reportedly found at 3.37 eV, was shifted to 5.44 eV (for y = 0.05), 5.63 eV (for y = 0.075) and maximum to 5.77 eV (for y = 0.1). In contrast, beyond the concentration, y = 0.1 the absorption edges were moved to 5.67 eV (for y = 0.125), 5.61 eV (for y = 0.15) and to 5.49 eV (for y = 0.2). This trend was explained in terms of the Burstein-Moss shift of the absorption edges.     

Development of a high-throughput thermoelectric screening tool for combinatorial thin film libraries

We have developed a high-throughput thermoelectric screening tool for the study of combinatorial thin films. This tool consists of a probe to measure resistance and Seebeck coefficient on an automated translation stage. A thin film library of the (Ca_1−x−ySr_xLa_y)₃Co₄O₉ ternary system has been fabricated on a Si (1 0 0) substrate, using combinatorial pulsed laser deposition by the natural-composition-spread method. We have demonstrated successful mapping of the resistance and Seebeck coefficient of this film library. The mapping indicates that the substitution of La for Ca results in an increase of both resistance and Seebeck coefficient, and that of Sr results in a decrease of resistance. The screening tool allows us to measure 1080 data points in 6 h.     

The effect of Mn substitution on thermoelectric properties of Ca3MnxCo4−xO9 at low temperatures

The effects of partial substitution of Mn for Co on the thermoelectric properties of Ca₃Mn_xCo_4−xO₉ (x=0, 0.03, 0.9), prepared by sol-gel process, were investigated at the temperatures from 380 K down to 5 K. The results indicate that the substitution of Mn for Co results in increase in thermopower at temperatures >∼80 K, and substantial (23-31% at 300 K) decrease in lattice thermal conductivity in the whole temperature range investigated. The temperature behavior of ZT suggests that Ca₃Mn_xCo_4−xO₉ with light Mn substitution would be a promising candidate for high-temperature thermoelectric applications.     

Thermodynamic and kinetic properties of Ho1−xTixCo2-hydrogen system

The hydrogen absorption behavior of Laves phase Ho_1−xTi_xCo₂ (x=0.1-0.6) alloys has been investigated by pressure-concentration (PC) isotherms and cyclic-, temperature- and pressure-dependent absorption kinetics. The PC isotherms and kinetics of hydrogen absorption have been studied in the pressure range 0.01-1 bar and temperature range 50-200 °C using Sievert's-type apparatus. The drastic changes in the induction period and particle size during the activation process have been discussed based on the kinetics of repeated hydrogenation cycles and scanning electron microscopy (SEM) images of the hydrides at different hydriding cycles, respectively. The experimental results of kinetic curves are interpreted using the Johnson-Mehl-Avrami (JMA) model, and the reaction order and reaction rate have been determined. The α-, (α+β)- and β-phase regions in Ho_1−xTi_xCo₂-H have been identified from the different slope regions of the first-order-type kinetic plots. The dependence of the reaction rate parameter on hydriding pressure and temperature in the (α+β)-phase region has been discussed.     

Effect of interface states associated with transitional nanophase precipitates in the enhancement of red emission from SrAl12O19:Pr by Ti incorporation

SrAl₁₂O₁₉:Pr³⁺, Ti⁴⁺ phosphor suitable for field emission displays is prepared by the wet chemical gel-carbonate method and the mechanism of enhancement in red photoluminescence (PL) intensity with Ti⁴⁺ therein has been investigated. The PL spectra of Pr³⁺ show both ¹D₂-³H₄ and ³P₀-³H₆ emission in the red region with very weak intensity when excited at 355 nm. The emission intensity has increased by about 100 times at room temperature in the compositional range SrAl_12−xTi_xO_19+x/2:Pr³⁺, with 0.1≤x≤0.3 in comparison to Ti-free SrAl₁₂O₁₉:Pr³⁺. TEM investigations show the presence of exsolved nanophase of SrAl₈Ti₃O₁₉, the precipitation of which is preceded by the presence of defect centers at the interfacial regions between the semicoherent transient phase and the parent SrAl₁₂O₁₉ matrix. The presence of transitional nanophase and the associated defects modify the excitation-emission process by way of formation of electronic sub-levels at lower energy (3.5 eV) than the band gap of SrAl₁₂O₁₉ (∼7 eV) followed by non-resonance energy transfer to Pr³⁺ level, leading to magnetic-dipole related red emission with enhanced intensity. The PL intensity of Pr³⁺ decreases at high Ti⁴⁺ concentrations (x>0.3) due to higher extent of segregation of non-emissive SrAl₈Ti₃O₁₉:Pr³⁺ phase.     

Dielectric, ferroelectric and pyroelectric properties of Pb[(Ni1/3Sb2/3)xTiyZrz]O3 ceramics

In the present study, various Pb[(Ni_1/3Sb_2/3)_xTi_yZr_z]O₃ where x+y+z=1, x=0.08 and y=0.44-0.49, ceramics in the morphotropic phase boundary (MPB) range were studied by dielectric and pyroelectric methods. The results of the investigations revealed an MPB composition range of y≅0.46. The study of the dielectric properties of these compounds as a function of temperature suggests that with increase in y the permittivity maximum increases and transition temperature shifts towards higher temperature. Well-saturated polarization versus electric field (P-E) hysteresis loops were obtained and values of P_r were calculated. The samples revealed good pyroelectric properties for y=0.44 and y=0.45 at room temperature with large figures of merit F_v=0.019 m²/C and F_D=1.34×10^-5Pa^1/2.     

Zn- and Cu-substituted Co2Y hexagonal ferrites: Sintering behavior and permeability

Y-type polycrystalline hexagonal ferrites Ba₂Co_2−x−yZn_xCu_yFe₁₂O₂₂ with 0≤x≤2 and 0≤y≤0.8 were prepared by the mixed-oxide route. Single phase Y-type ferrite powders were obtained after calcinations at 1000 °C. Samples sintered at 1200 °C show a permeability that increases with the substitution of Zn for Co and display maximum permeability of μ′=35 at 1 MHz for x=1.6 and y=0.4. A resonance frequency f_r=500 MHz is observed for Zn-rich ferrites with y=0 and 0.4. The saturation magnetization increases with substitution of Zn for Co. Addition of Bi₂O₃ shifts the temperature of maximum shrinkage down to T≤950 °C. Moreover, an increase of the Cu-concentration further lowers the sintering temperature to T≤900 °C, enabling co-firing of the ferrites with Ag metallization for multilayer technologies. However, low-temperature firing reduces the permeability to μ′=10 and the resonance frequency is shifted to 1 GHz. Thus substituted hexagonal Y-type ferrites can be used as soft magnetic materials for multilayer inductors for high frequency applications.     

Effect of microstructure on the conductivity of a NASICON-type lithium ion conductor

Sintering temperature is used to control the microstructure of Li_{1 + x + y}Al_xTi_2 − xSi_yP_3 − yO₁₂ (x = 0.3, y = 0.2), a NASICON-type glass-ceramic. Scanning Electron Microscope imaging, X-Ray Diffraction, and Electrochemical Impedance Spectroscopy are employed to show that increase in sintering temperature increases conductivity while generating secondary crystalline phases. Total conductivity is as high as 3.81 × 10⁻⁴ S cm⁻¹ for sintering temperatures above 1000 °C. Crystallization of dielectric phases places the optimal sintering temperature in the 900 °C to 1000 °C range. Thermal analysis of the glass precursor reveals the glass transition, and crystallization temperatures.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).