In-situ analyses on the reactive sputtering process to deposit Al-doped ZnO films using an Al-Zn alloy target

The kinetic energies of generated ions were investigated during the reactive sputtering process to deposit Al-doped ZnO (AZO) films using an Al-Zn alloy target. The sputtering system was equipped with specially designed double feedback system to stabilise the reactive sputtering processes and analysis was performed with a quadrupole mass spectrometer combined with an energy analyser. Negative ions O⁻, O₂⁻, AlO⁻ and AlO₂⁻ with high kinetic energies corresponding to cathode voltage are generated at the partially oxidised target surface, after which some of the ions undergo subsequent charge exchange and/or dissociation. Positive ions O⁺, Ar⁺, Zn⁺ and Al⁺ with lower kinetic energies (around 10 eV) are generated by charge exchange of sputtered neutral O, Ar, Zn and Al atoms, respectively. As the target surface oxidises, cathode voltage decrease, the flux of high-energy negative ions increases and the electrical properties of the AZO degrade by ion bombardment as well as the AZO films that are deposited by conventional magnetron sputtering using an AZO target.     

Improved thermoelectric properties by adding Al for Zn in (ZnO)mIn2O3

The grain size and density of the sintered (Zn_1 − xAl_xO)_mIn₂O₃ bodies decreased with the small Al₂O₃ content (≤ 0.012), and then increased gradually by further increasing the Al₂O₃ content. The addition of Al for Zn in the (ZnO)_mIn₂O₃ led to an increase in both the electrical conductivity and the absolute value of the Seebeck coefficient. This indicates that the power factor was significantly enhanced by adding Al for Zn. The thermoelectric power factor was maximized to 1.67 × 10^− 3 W m^− 1 K^− 2 at 1073 K for the (Zn_0.992Al_0.008O)_mIn₂O₃ sample.     

Influence of Ga2O3 addition on transparent conductive oxide films of In2O3-ZnO

Influence of incorporation of Ga in amorphous In-Zn-O transparent conductive oxide films was investigated as a function of Zn/(Zn + In). For In-Zn-O films with no Ga₂O₃, the range of Zn/(Zn + In) ratio where the amorphous phase appears became narrow at a substrate temperature of 250 °C. With increasing Ga₂O₃ quantity, amorphous films were obtained even at a high substrate temperature of 250 °C in a wider range of Zn/(Zn + In) than that of In-Zn-O films with no Ga₂O₃. This means that the trend of crystallization at higher substrate temperature was disturbed with additional Ga incorporation. For the film deposited from ZnO:Ga (Ga₂O₃: 4.5-7.5 wt%) and In₂O₃ targets, we obtained a resistivity of 2.8 × 10⁻⁴ Ω cm, nearly the same value as that for an In-Zn-O film with no Ga₂O₃. The addition of more than 7.5 wt% Ga₂O₃ induced a widening of the optical band gap.     

Novel transparent conducting sol-gel oxide coatings

This work focuses on the preparation of novel ternary transparent conducting oxide coatings on glass by the sol-gel method. The coatings were deposited by spin-coating from solutions of appropriate metal precursors and heat-treated at different heat-treatment procedures. An increase in electrical conductivity was achieved by a final forming gas treatment. Best electrical and optical properties have been obtained for coatings of crystalline Zn₂SnO₄, Zn₃In₂O₆ and Zn₅In₂O₈ and X-ray amorphous ZnSnO₃ with resistivities in the order of 10^− 2-10^− 1 Ω cm, an average transmission in the visible of 85% and an average surface roughness of ∼ 1 nm. ZnGa₂O₄ and GaSbO₄ coatings showed no electrical conductivity. For Zn₂SnO₄ coatings, a restricted crystallite growth was observed probably due to phase segregation effects. Electrical properties of coatings in the system ZnO-In₂O₃ were interpreted on the basis of the percolation theory.     

High-rate deposition of high-quality Sn-doped In2O3 films by reactive magnetron sputtering using alloy targets

Sn-doped In₂O₃ (ITO) films were deposited on heated (200 °C) fused silica glass substrates by reactive DC sputtering with mid-frequency pulsing (50 kHz) and a plasma control unit combined with a feedback system of the optical emission intensity for the atomic O* line at 777 nm. A planar In-Sn alloy target was connected to the switching unit, which was operated in the unipolar pulse mode. The power density on the target was maintained at 4.4 W cm^− 2 during deposition. The feedback system precisely controlled the oxidation of the target surface in “the transition region.” The ITO film with lowest resistivity (3.1 × 10^− 4 Ω cm) was obtained with a deposition rate of 310 nm min^− 1 and transmittance in the visible region of approximately 80%. The deposition rate was about 6 times higher than that of ITO films deposited by conventional sputtering using an oxide target.     

Preparation and electrochemical properties of Cr doped LiV3O8 cathode for lithium ion batteries

Chromium was incorporated into lithium trivanadate by an aqueous reaction followed by heating at 100 °C. This Cr doped LiV₃O₈ as a cathode for lithium ion batteries exhibits 269.9 mAh g^− 1 at first discharge cycle and remains 254.8 mAh g^− 1 at cycle 100, with a charge-discharge current density of 150 mA g^− 1 in the voltage range of 1.8-4.0 V. The Cr-LiV₃O₈ cathode show excellent discharge capacity, with the retention of 94.4% after 100 cycles. These result values are higher than previous reports indicating that Cr-LiV₃O₈ prepared by our low temperature synthesis method is a promising cathode material for rechargeable lithium ion batteries. The enhanced discharge capacity and cycle stability of Cr-LiV₃O₈ cathode indicate that chromium atoms promote lithium transfer or intercalation/deintercalation during the electrochemical cycles and improve the electrochemical performances of LiV₃O₈ cathode.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

Insulator-conductor transition in 12CaO·7Al2O3 films: On the stability of the crystal lattice under Ar bombardment

Recent experimental studies suggest that thin films of a nano-porous complex oxide 12CaO·7Al₂O₃ (C12A7) are unusually stable under bombardment with energetic Ar⁺ ions [M. Miyakawa et al., J. Appl. Phys. 97 (2005) 023510.]. We employ classical Molecular Dynamics to study the processes induced by knock-on collisions of Ar⁺ with the C12A7 lattice. Our results suggest that such collisions predominantly affect the anion sublattice and form Frenkel defect pairs. We find that most of these Frenkel pairs are unstable and readily recombine with the extra-framework O²⁻ ions present in the lattice at stoichiometric concentrations of ∼ 1.2 × 10²¹ cm^− 3. This process is further facilitated by fast diffusion of the extra-framework O²⁻ ions. These results provide a useful insight in the design of new radiation-resistant materials.     

The influence of ambient conditions on properties of MgxZn1−xO films by sputtering

The Mg_xZn_1−xO films were prepared in different Ar-O₂ mixture ambience by magnetron sputtering. According to the X-ray diffraction (XRD) patterns and the energy dispersive X-ray spectroscopy (EDS) results, it was found that the Mg contents in the films varied with the different ratios of O₂/O₂+Ar, and the crystal quality of the films improved with the increasing of Mg contents. Meanwhile, the ultraviolet and visible (UV-vis) absorption spectroscopy indicated that the band gap of the films also increased. Moreover, it could be seen that the photoluminescence (PL) spectrum was different from that of undoped Zinc oxide (ZnO) films or the results in other reports on the Mg_xZn_1−xO films: there was no blueshift effect happening for the near-band-edge (NBE) emission in Mg_xZn_1−xO films with different Mg contents.     

Radiation damage study of MeV ions-implanted Nd:YVO4 crystal

Damage formation mechanism of Nd:YVO₄ implanted with MeV ions is investigated. MeV Si⁺ ions were implanted into Nd:YVO₄ crystal, and the lattice damage was measured using Rutherford backscattering spectroscopy/channeling (RBS/C) method. The damage creation kinetic indicates a significant contribution from electronic energy loss to the surface damage. A detailed analysis allows us to deduce the different contributions from electronic and nuclear stopping powers to the lattice damage production. An obvious difference in extent of damage from 1 MeV and 3 MeV Si⁺ implantations also implies that there exists a threshold value of the electronic energy deposition for damage formation. The exact value of threshold is obtained by comparison with the experimental data obtained from 3 MeV O⁺, F⁺ and Si⁺ implantation results, which turns out to be (1.7 ± 0.1) keV/nm.     

Varistor properties of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-In2O3 ceramics

The varistor properties of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-In₂O₃ ceramics were investigated for different concentrations of In₂O₃. The increase of In₂O₃ concentration slightly increased the sintered density (5.60-5.63 g/cm³) and slightly decreased the average grain size (3.4-2.9 μm). The breakdown field increased from 6023 to 14822 V/cm with increasing concentration of In₂O₃. The nonlinear coefficient increased from 17.6 to 44.6 for up to 0.005 mol%, whereas the further doping caused it to decrease to 36.8. In₂O₃ acted as an acceptor due to the donor concentration, which decreases in the range of 1.02 × 10¹⁷ to 0.24 × 10¹⁷/cm³ with increasing concentration of In₂O₃.     

Surface and electronic structure of Ga0.92In0.08N thin film investigated by photoelectron spectroscopy

The surface and electronic structure of Ga_0.92In_0.08N layers grown by metal organic chemical vapor deposition (MOCVD) have been investigated by means of photoemission. Stability of chemical composition of the surface subjected to Ar⁺ ion sputtering was proven by means of X-ray photoemission spectroscopy. The analysis of the relative intensities of In 3d, Ga 3p, and N 1s peaks showed that argon ion bombardment does not change significantly the relative contents of the layer constituents. Simultaneous efficient removal of the main contaminants (O and C) was observed during the sputtering procedure, proving that argon sputtering can be used as a method for preparation of clean Ga_1−xIn_xN surfaces.For a clean (0001)-(1×1) surface prepared by repeated cycles of Ar⁺ ion sputtering and annealing, electronic structure was investigated. The band structure was explored along the Γ-A direction of the Brillouin zone, measuring angle-resolved photoemission spectra along the surface normal. A similar set of data was also acquired for the same surface of GaN layer. Comparison of the collected data revealed an additional feature at the valence band edge, which can be ascribed to the presence of In in the layer.     

The effect of In ion on the optical characteristics of Er in Er/Yb:LiNbO3 crystal

The effect of In³⁺ ion on the optical characteristics of Er³⁺ ion in Er/Yb:LiNbO₃ crystal under 980 nm excitation has been investigated. The Er and Yb contents in the crystals were measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES). A significant enhancement of 1.54 μm emission was observed for Er/Yb:LiNbO₃ crystal doped with 1 mol% In₂O₃. The studies on the UV-vis absorption and the OH⁻ absorption spectra indicate that the threshold concentration of In³⁺ ion decreases with the Er/Yb doping in Er/Yb/In:LiNbO₃ crystal. The 1 mol% In₂O₃ doping results in the reduction of absorption cross section in the UV-vis region, meaning the formation of Er³⁺ cluster sites. The enhancement of 1.54 μm emission is attributed to the larger probabilities of the cross relaxation processes ⁴S_3/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2 (Er), ⁴S_3/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_9/2 (Er) and ⁴I_9/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_13/2 (Er) induced by Er³⁺ cluster sites.     

Electron energy loss spectroscopy study of the effect of low-energy Ar-ion bombardment on the surface structure and composition of Pt80Co20 (1 1 1) alloy

Electron energy loss spectroscopy has been employed for investigation of the effect of 600 eV Ar⁺-ion irradiation in the dose range 7×10¹⁶-4×10¹⁷ ions/cm² on the atomic structure and surface composition of alloy Pt₈₀Co₂₀(1 1 1). A method of the layer-by-layer reconstruction of the lattice interplanar distance changes based on the analysis of the plasmon spectra excitation was proposed. The ion bombardment was shown to result in a non-monotonic variation of the lattice interplanar distance due to formation of the stable defects, with the topmost layer being in the state of compression. Using the ionization energy loss spectra, a layer-by-layer concentration profile of the alloy components was reconstructed for different doses of ion irradiation of the surface. The Ar⁺-ion bombardment of the alloy was found to result in the preferential sputtering of Co and in the enrichment of the near-surface region by Pt atoms with formation of an altered layer, which is characterized by a non-monotonic concentration profile dependent on the irradiation dose. The results obtained are discussed in the framework of the models of preferential sputtering and radiation-induced segregation.     

Energetic negative ions in titanium oxide deposition by reactive sputtering in Ar/O2

The flux of energetic negative ions was measured during the preparation of TiO₂ in Ar/O₂ as a function of oxygen partial pressure. The Ti surface was so active that the small amount of O₂ contained in Ar was sufficient to oxidize the target surface. Ti target is also oxidized as similarly to the other metals such as Zr and Zn. Oxide islands form, which coalesce and cover the target surface with an oxide layer. The thickness of the Ti oxide layer on the target surface increased with increasing target current and Ar/O₂ gas pressure, which increased the oxygen flux incident on the target. This is due to the high reactivity of the Ti surface with oxygen. The data revealed that the flux of energetic negative ions in reactive sputtering of Ti in Ar/O₂ is fairly small compared with the sputtering of Zr and Zn. This indicates that the generation rate of negative ions on the Ti target during the reactive sputtering is very small.     

Structural,optical and electrical properties of In4Sn3O12 films prepared by pulsed laser deposition

Highly conducting (σ ∼ 2.6 × 10³ Ω⁻¹ cm⁻¹) In₄Sn₃O₁₂ films have been deposited using pulsed laser deposition (PLD) on glass and quartz substrates held at temperatures between 350 and 550 °C under chamber pressures of between 2.5 and 15 mTorr O₂. The crystallinity and the surface roughness of the films were found to increase with increasing substrate temperature. Electron concentrations of the order of 5 × 10²⁰ cm⁻³ and mobilities as high as 30 cm² V⁻¹ s⁻¹ were determined from Hall effect measurements performed on the films. Fitting of the transmission spectral profiles in the ultra-violet–visible spectrum has allowed the determination of the refractive index and extinction coefficient for the films. A red-shift in the frequency of plasmon resonance is observed with both increasing substrate temperature and oxygen pressure. Effective masses have been derived from the plasma frequencies and have been found to increase with carrier concentration indicating a non-parabolic conduction band in the material In₄Sn₃O₁₂. The optical band-gap has been determined as 3.8 eV from the analysis of the absorption edge in the UV. These results highlight the potential of these films as lower In-content functional transparent conducting materials.     

Synthesis of GaN nanorods by ammoniating Ga2O3 films on In2O3 layer deposited on Si (111) substrates

GaN nanorods were synthesized by ammoniating Ga₂O₃/In₂O₃ thin films deposited on Si (111) with magnetron sputtering. X-ray diffraction, Scanning electronic microscope and high-resolution TEM results show that they are GaN single crystals, the sizes of which vary from 2 to 7 μm in length and 200 to 300 nm in diameter. In₂O₃ middle layer plays an important role in the GaN nanorod growth.     

Chemical diffusion coefficient of lithium ion in Li3V2(PO4)3 cathode material

The kinetic properties of monoclinic lithium vanadium phosphate were investigated by potential step chronoamperometry (PSCA) and electrochemical impedance spectroscopy (EIS) method. The PSCA results show that there exists a linear relationship between the current and the square root of the time. The D?_Li values of lithium ion in Li_3-xV₂(PO₄)₃ under various initial potentials of 3.41, 3.67, 3.91 and 4.07 V (vs Li/Li⁺) obtained from PSCA are 1.26 × 10^− 9, 2.38 × 10^− 9, 2.27 × 10^− 9 and 2.22 × 10^− 9 cm²·s^− 1, respectively. Over the measuring temperature range 15-65 °C, the diffusion coefficient increased from 2.67 × 10^− 8 cm²·s^− 1 (at 15 °C) to 1.80 × 10^− 7 cm²·s^− 1 (at 65 °C) as the measuring temperature increased.     

Comparative analysis of crystal field effects and optical spectroscopy of six-coordinated Mn ion in the Y2Ti2O7 and Y2Sn2O7 pyrochlores

The electronic energy levels of the six-coordinated Mn⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B = Sn⁴⁺, Ti⁴⁺) have been computed using the exchange charge model of crystal field theory. The calculated Mn⁴⁺ energy levels and their trigonal splitting are in good agreement with the experimental spectra. The calculated crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ arises from an increased orbital overlap effect between the Mn⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. This increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Mn⁴⁺-O²⁻ bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇ and is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. The low temperature emission spectrum of Mn⁴⁺ activated Y₂Sn₂O₇ is analyzed in terms of a weak zero phonon line (R-line) with accompanying vibrational side bands.     

Enhanced thermoelectric properties of NaCo2O4 by adding ZnO

The primary phase present in the as-sintered Na(Co_1 − xZn_x)₂O₄ (0 ≤ x ≤ 0.1) bodies was the solid solution of the constituent oxides with a bronze-type layered structure. The electrical conductivity of the Na(Co_1 − xZn_x)₂O₄ samples significantly increased with an increase in ZnO content. The sign of the Seebeck coefficient for all samples was positive over the whole temperature range (723-1073 K), i.e., p-type conduction. The power factor of Na(Co_0.95Zn_0.05)₂O₄ showed an outstanding power factor (1.7 × 10^− 3Wm^− 1 K^− 2) at 1073 K. The power factor was above four times superior to that of ZnO-free NaCo₂O₄ (0.4 × 10^− 3Wm^− 1 K^− 2). This originates from an unusually large Seebeck coefficient (415 μVK^− 1) accompanied with high conductivity (127Ω^− 1 cm^− 1) at 1073 K.