Effects of C,N-Codoped on the Corrosion Resistance of TiO_2 Films Prepared by Plasma Surface Alloying and Thermal Oxidation Duplex Process

C,N-codoped TiO 2 films have been deposited onto stainless steel substrates using plasma surface alloying and thermal oxidation duplex process.Composition analysis shows that the films shield the substrates entirely.The TiO 2 films are anatase in structure as characterized by X-ray diffraction.The electrochemical measurements show that the equilibrium corrosion potential positively shifts from-0.275 eV for bare stainless steel to-0.267 eV for C,N-codoped TiO 2 coated stainless steel,and the corrosion curren...     

Effect of the sputtering parameters on the structure and properties of Cu<Subscript>3</Subscript>N thin film materials

Copper nitride (Cu₃N) thin films were successfully deposited on glass substrates by reactive radio frequency magnetron sputtering. The effects of sputtering parameters on the structure and properties of the films were studied. The experimental results show that with increasing of RF power and nitrogen partial pressure, the preferential crystalline orientation of Cu₃N film is changed from (111) to (100). With increasing of substrate temperature from 70 °C to 200 °C, the film phase is changed from Cu₃N phase to Cu. With increasing sputtering power from 80 W to 120 W, the optical energy decreases from 1.85 eV to 1.41 eV while the electrical resistivity increases from 1.45 ×10² Ω · cm to 2.99 × 10³ Ω · cm, respectively.     

Influence of thickness on the properties of solution-derived LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

LiMn₂O₄ thin films of different thickness were derived from solution deposition and heat treated by rapid thermal annealing. The phase identification and surface morphology were studied by X-ray diffraction and scanning electron microscopy. The electrochemical properties of the films were examined by galvanostatic charge-discharge experiments and electrochemical impedance spectroscopy. LiMn₂O₄ thin films of different thickness derived from solution deposition and rapid thermal annealing are homogeneous and crack free with the grain size between 20 nm and 50 nm. The specific capacity of these films is between 42 and 47 μAh·cm²·μm⁻¹. The capacity decreases with the increase of discharge current density. The capacity loss per cycle increases from 0.012% to 0.16% after being cycled 50 times as the film thickness increases from 0.18 μm to 1.04 μm. The lithium diffusion coefficients of these films are in the same order of 10⁻¹¹ cm²·s⁻¹.     

Effects of Substrate Temperatures on the Structure and UV-shielding Properties of TiO2-CeO2 Films Deposited on Glass by Radio-frequency Magnetron Sputtering

TiO2-CeO2 films were deposited on soda-lime glass substrates at varied substrate temperatures by rf magnetron sputtering using 40% molar TiO2-60% molar CeO2 ceramic target in Ar：O2=95：5 atmosphere.The structure,surface composition,UV-visible spectra of the films were measured by scanning electron microscopy and X-ray diffraction,and X-ray photoelectron spectroscopy,respectively.The experimental results show that the films are amorphous,there are only Ti^4＋ and Ce^4＋ on the surface of the films,the obtained TiO2-CeO2 films shou a good uniformity and high densification,and the films deposited on the glass can shield ultraviolet light without significant absorpition of visible light,the films deposited on substrates at room temperature and 220℃ absorb UV effectively.     

Microstructures and fatigue-free properties of the La<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by modified sol-gel technique

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) and Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were fabricated on Pt/TiO₂/SiO₂/Si (100) substrates by a modified sol-gel technique. X-ray diffraction indicated that these films were of single phase with random polycrystalline orientations. The surface morphologies of the films were observed by scanning electron microscope, showing uniform, dense films with grain size of 50–100 nm. Well-saturated hysteresis loops of the films were obtained in metal-ferroelectric-metal type capacitors with Cu top electrodes at an applied voltage of 400 kV/cm, giving the remanent polarization (2P _r) and coercive field (2E _c) values of the films of 25.1 μC/cm² and 203 kV/cm for BLT, and 44.2 μC/cm² and 296 kV/cm for BNT, respectively. Moreover, these capacitors did not show fatigue behaviors after up to 1.75×10¹⁰ switching cycles at the test frequency of 1 MHz, suggesting a fatigue-free character. The influences of the La³⁺ and Nd³⁺ doping on the properties of the films were comparatively discussed. Supported by the National Key Basic Research and Development Program of China (Grant No. 2006CB932305) and the Natural Science Foundation of Hubei Province, China (Grant No. 2004ABA082)     

Crystallization and Electrical Properties of （Ba0.4Pb0.3）Sr0.3TiO3 Thin Film by Pulsed Laser Deposition

（Ba0.4Pb0.3）Sr0.3TiO3 thin films were fabricated via pulsed laser deposition （PLD） technique on Pt/TiO2/SiO2/Si substrate. The crystallization of the films was characterized by XRD and FSEM, and the experimental results suggested deposition parameters, especially the deposition temperature was the key factor in forming the perovskite structure. The dielectric properties of the film deposited with optimized parameters were studied by an Agilent 4294A impedance analyzer at 1 MHz. The dielectric constant was 772, and the loss tangent was 0.006. In addition, the well-shaped hysteresis loop also showed that the film had a well performance in ferroelectric. The saturated polarization P, remnant polarization Pr and coercive field E were about 4.6 μC/cm2, 2.5 μC/cm2 and 23 kV/cm （the coercive voltage is 0.7 V）, respectively. It is suggested the film should be a promising candidate for microwave applications and nonvolatile ferroelectric random access memories （NvFeRAMs）.     

Optical waveguide and nonlinear properties of Bi<Subscript>3</Subscript>NdTi<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Neodymium-substituted bismuth titanate (Bi₃NdTi₃O₁₂, BNT) thin films were prepared on quartz substrates by a metal-organic solution deposition process. The crystalline structure was evaluated by X-ray diffraction. Waveguide property was investigated by using prism coupling technique and optical transmittance measurement. The optical nonlinearities of the film were measured by the top-hat Z-scan techniques and a large positive nonlinear refractive index, nonlinear refractive coefficient and two-photon absorption coefficient were determined to be 3.84 × 10⁻⁷ esu, 0.7523 cm²/GW and 4.81 × 10⁴ cm/GW, respectively. These results reveal that the BNT film may be a kind of new multifunctional materials.     

Correlations between the Optical Properties and the Microstructure of TiO2 Thin Films Prepared by Reactive Electron-beam Evaporation

High refractive index TiO₂ thin films were deposited on BK7 glass by reactive electron—beam (REB) evaporation at pressure of 2×10⁻² Pa, deposition rate of 0.2 nm/s and at various substrate temperatures from 120°C to 300°C. The refractive index and the thickness of the films were measured by visible spectroscopic ellipsometry (SE) and determined from transmission spectra. Optical properties and structure features were characterized by UV-VIS, SEM and XRD, respectively. The measurement and analysis on transmission spectra of all samples show that with the substrate temperature increasing from 120°C to 300°C, the refractive indices of thin films increase from 1.7 to 2.1 and the films after heat treatment have higher refractive indices due to its crystallizing. The XRD analysis results indicate that the structure of TiO₂ thin films deposited on BK7 glass at substrate temperatures of 120°C, 200°C and 300°C is amorphous, after post-annealing under air condition at 400°C for 1 hour, the amorphous structure is crystallized, the crystal phase is of 100% anatase with strong preferred orientation (004) and the grain size of crystalline is within 3.6–8.1 nm, which is consistent with results from SEM observation. WANG Xue-hua: Born in 1976. Funded by the Youth Project Foundation of Hubei Provincial Education Department (No. 2003B00)     

Preparation and characterization of CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>/SnO<Subscript>2</Subscript>:Sb films deposited on glass substrates by R.F. sputtering

CeO2-TiO2 films and CeO2-TiO/SnO2：Sb （6 mol%） double films were deposited on glass substrates by radio-frequency magnetron sputtering （R.F. Sputtering）, using SnO2：Sb（6 mol%） target, and CeO2- TiO2 targets with different molar ratio of CeO2 to TiO2 （CeO2：TiO2-0：1.0; 0.1：0.9; 0.2：0.8; 0.3：0.7; 0.4：0.6; 0.5：0.5; 0.6：0.4; 0.7：0.3; 0.8：0.2; 0.9：0.1; 1.0：0）. The films are characterized by UV-visible transmission and infrared reflection spectra, scanning electron microscopy （SEM）, Raman spectroscopy, X-ray photoelectron spectroscopy （XPS） and X-ray diffraction （XRD）, respectively. The obtained results show that the amorphous phases composed of CeO2-TiO2 play an important role in absorbing UV, there are Ce^3-, Ce^4- and Ti^4- on the surface of the films; the glass substrates coated with CeO2-TiO2 （Ce/Ti=0.5：0.5; 0.6：0.4）/SnO2：Sb（6 mol%） double films show high absorbing UV（〉99）, high visible light transmission （75%） and good infrared reflection （〉70%）. The sheet resistance of the films is 30-50 Ω/□. The glass substrates coated with the double functional films can be used as window glass of buildings, automobile and so on.     

UV-vis and photoluminescent spectra of TiO<Subscript>2</Subscript> films

TiO₂ fims have been deposited on glass substrates using DC reactive magnetron sputtering at different oxygen partial pressures from 0. 10 Pa.to 0.65 Pa. The transmittance (UV-vis) and photoluminescence (PL) spectra of the films were recorded. The results of the UV-vis spectra show that the deposition rate of the films decreased at oxygen partial pressure P(O₂)≥0.15 Pa, the band gap increased from 3.48 eV to 3.68eV for direct transition and from 3.27 eV to 3.34 eV for indirect transition with increasing the oxygen partial pressure. The PL spectra show convincingly that the transition for films was indirect, and there were some oxygen defect energy levels at the band gap of the films. With increasing the O₂ partial pressure, the defect energy levels decreased. For the films sputtered at 0.35 and 0.65 Pa there were two defect energy levels at 2.63 eV and 2.41 eV, corresponding to 0.72 eV and 0.94 eV below the conduction band for a band gap of 3.35 eV, respectively. For the films sputtered at 0.10 Pa and 0.15 Pa, there was an energy band formed between 3.12 eV and 2.06 eV, corresponding to 0.23 eV and 1.29 eV below the conduction band. ZHAO Qing-nan : Born in 1963 Funded by Natural Science Foundation of Hubei Province, China.     

Effect of Pb substitution on the microstructure and ferroelectric properties of Ba<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>TiO<Subscript>3</Subscript> ceramic

Ferroelectric Ba0.7Sr0.3TiO3（BST） and partially Pb^2＋ substituted for Ba^2＋ ceramics （Ba0.7-xPbx）Sr0.3TiO3 （x=0.1-0.4, BPST） were prepared by using conventional solid-reaction method. XRD analysis shows that the samples microstructure changes from cubic phase to tetragonal one with the Pb^2＋ content increasing. ESEM analysis shows that the Pb^2＋ substituted samples have a denser and more uniform surface morphology than that of pure BST. Measured electrical properties suggest that the Pb^2＋ substitution for Ba^2＋ in the BST system enhances the ferroelectric performance obviously when x=0.2. In addition, the substitution increases the samples Curie temperature （To） r （Ba0.5Pb0.2）Sr0.3TiO3 ceramic has good ferroelectric properties measured at a maximal electric field of 30 kV/cm under the condition of room temperature. The corresponding saturated polarization （Ps）, remnant polarization （Pr） and coercive field （Ec） is respectively 15.687 μC/cm^2, 8.100 μ C/cm^2 and 6.611 kV/cm. The measured Tc of （Ba0.5Pb0.2）Sr0.3TiO3 is 117 ℃.     

Effect of matrix composition on physical properties of Al<Subscript>3</Subscript>CON in-situ reaction reinforced corundum composite

60% white corundum used for aggregate, 5% aluminium powder for fixed additions and 35% various additives for matrix were prepared for specimens 1#,2#,3#. They were mixed uniformly with the suitable resin as a binder and pressed under pressure of 315 ton forging press, then dried at 200℃ for 24 h. Effects of various additives on 1500 ℃×2 h creep properties of Al3CON reinforced corundum composite were researched. The experimenal results show that creep coefficients of specimens 1#,2#,3# at 1500 ℃×2 h are 1.4×10^- 4, -9.4×10^-4, -22.6×10^-4, respectively. Crushing strength of the slide plate added with suitable additive A after fired at 1500 ℃ ×3 h reaches to 225 MPa, the creep rate is positive all the time from 0% to 0.014% at 1500 ℃ for 2 h. The microstructure result analysis shows that reinforced phases of Al3CON fiber composite have been formed after fired with Al powder in coke at high temperatures for specimen 1#, and the strength of the composite is increased. The hot modulus of rupture is up to 59 MPa at 1400 ℃ and the RUL is obviously higher than that at 1700 ℃. Its service life is two times as that of Al2O3-C slide plate when used in the process of pouring steel. The mechanism of creep rate resistance of the composites can be discovered by means of SEM and EDAX analysis. It is concluded that the active Al3CON and Al2O3 multiphases that were formed by N2 in gas, C, Al and Al2O3 inside the matrix of the composites during in-situ reaction,which gives the composites outstanding creep rate resistance for the dense zone resuiting from Al3CON oxidation that inhibits contraction at the high temperature. Besides, the matrix will turn into the multiphase with high refractoriness, N content and its Al3CON reinforced fiber will further increase accordingly. In addition, Al3CON formed by Al2O3 and C, Al in the matrix with N2 in gas will inhibit the creep rate and also greatly improve the creep rate resistance of the composites.     

Novel wide band gap alloyed semiconductors, <Emphasis Type="Italic">x</Emphasis>(LiGaO<Subscript>2</Subscript>)<Subscript>1/2</Subscript>-(1−<Emphasis Type="Italic">x</Emphasis>)ZnO,and fabrication of their thin films

Oxide semiconductor alloys of x(LiGaO₂)_1/2-(1−x)ZnO were fabricated by the solid state reaction between β-LiGaO₂ and ZnO and rf-magnetron sputtering. For the solid state reaction, the wurtzite-type single phases were obtained in the composition range of x⩽0.38. The formation range of the alloys was wider than that of the (Mg_1−x Zn _x )O system, because the β-LiGaO₂ possesses a wurtzite-derived structure and approximately the same lattice constants with ZnO. The electrical resistivity and energy band gap of the 0.38(LiGaO₂)_1/2-0.62ZnO alloyed ceramic were 0.45 Ωcm and 3.7 eV, respectively, at room temperature. For the alloying by sputtering, the films consisting of the wurtzite-type single phase were obtained over the entire composition range of x(LiGaO₂)_1/2-(1−x)ZnO. The energy band gap was controllable in the range from 3.3 to 5.6 eV. For the as-deposited film fabricated using the 0.4(LiGaO₂)_1/2-0.6ZnO alloyed ceramic target, the energy band gap was 3.74 eV, and the electrical resistivity, carrier density and the Hall mobility at room temperature were 3.6 Ωcm, 3.4×10¹⁷ cm⁻³ and 5.6 cm² V⁻¹ s⁻¹, respectively.     

Cyclic oxidation behaviors of MoSi<Subscript>2</Subscript> with different relative density

The influence of different relative density on the cyclic oxidation behaviors of MoSi2 at 1 273 K were studied. ＂Pesting＂ was not found in all MoSi2 materials after being oxidized for 480 h. All samples exhibited continuous mass gain during the oxidation process. The mass gains of MoSi2 with the lowest relative density （78.6%） and the highest relative density （94.8%） are increased by 8.15 mg·cm^-2 and 3.48 mg·cm^-2, respectively. The surface of the material with lower relative density formed a loose, porous and discontinuous oxidation scale, which accelerated oxygen diffusion and aggravated the oxidation process. However, a dense scale in the material with higher relative density is formed, which acts a diffusion barrier to the oxygen atoms penetrating into the matrix. The high temperature oxidation resistance of MoSi2 can be improved by increasing its relative density.     

Study on the isothermal oxidation behavior in air of Ti3AlC2 sintered by hot pressing

The isothermal oxidation behavior at 900–1300°C for 20 h in air of bulk Ti₃AlC₂ with 2.8 wt% TiC sintered by means of hot pressing was investigated in the work. The isothermal oxidation behavior generally followed a parabolic rate law. The parabolic rate constants increased from 1.39×10⁻¹⁰ kg²·m⁻⁴·s⁻¹ at 900°C to 5.56×10⁻⁹ kg²·m⁻⁴·s⁻¹ at 1300°C. The calculated activation energy was 136.45 kJ/mol. It was demonstrated that Ti₃AlC₂ had excellent oxidation resistance due to the continuous, dense and adhesive protect scales consisted of a mass of α-Al₂O₃ and a little of TiO₂ and/or Al₂TiO₅. In principle, the oxide scale was grown by the inward diffusion of O²⁻ and the outward diffusion of Ti⁴⁺ and Al³⁺. The rapid outward diffusion of cations usually resulted in the formation of cracks, gaps, and holes.     

Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> thin films prepared by sulfurizing different multilayer metal precursors

Cu₂ZnSnS₄ (CZTS) thin films were successfully fabricated on glass substrates by sulfurizing Cu-Sn-Zn multilayer precursors, which were deposited by ion beam sputtering and RF magnetron sputtering, respectively. The structural, electrical and optical properties of the prepared films under various processing conditions were investigated in detail. Results showed that the as-deposited CZTS thin films with the precursors by both ion beam sputtering and RF magnetron sputtering have a composition near stoichiometric. The crystallization of the samples, however, has a strong dependence on the atomic percent of constituents of the prepared CZTS films. A single phase stannite-type structure CZTS with a large absorption coefficient of 10₄/cm in the visible range could be obtained after sulfurization at 520°C for 2 h. The samples relative to the RF magnetron sputtering showed a low resistivity of 0.073 Ωcm and band gap energy of about 1.53 eV. The samples relative to the ion beam sputtering exhibited a resistivity of 0.36 Ωcm and the band gap energy is about 1.51 eV. Supported by the National Natural Science Foundation of China (Grant No. 10574106), the Planned Science and Technology Project of Guangdong Province (Grant No.2003C05005) and the Natural Science Fund of Zhanjiang Normal University (Grant No.200801)     

Ferroelectric properties of Bi<Subscript>4</Subscript>Zr<Subscript>0.5</Subscript>Ti<Subscript>2.5</Subscript>O<Subscript>12</Subscript> thin films prepared on LaNiO<Subscript>3</Subscript> bottom electrode by sol-gel method

The Bi4Zr0.5Ti2.5O12 (BZT) thin films were fabricated on the LaNiO3 bottom electrode using sol-gel method. The structure and morphology of the films were characterized using X-ray diffraction, AFM and SEM. The results show that the films have a perovskite phase and dense microstructure. The 2Pr and 2Vc of the Pt/BZT/LaNiO3 capacitor are 28.2 μC/cm2 and 14.7 V respectively at an applied voltage of 25 V. After the switching of 1×1010 cycles, the Pr value decreases to 87% of its pre-fatigue values. The dielectric constant (ε) and the dissipation factor (tanδ) of the BZT thin films are about 204 and 0.029 at 1 kHz, respectively. The films show good insulating behavior according to the test of leakage current. The clockwise C-V hysteresis curve observed shows that the Pt/BZT/LaNiO3 structure has a memory effect because of the BZT film's ferroelectric polarization.     

Structure and Electric Properties of （1-x）（Bi1/2Na1/2） TiO3-xBaTiO3 Systems

The structural, dielectric and piezoelectric properties of （1-x）（Bi1/2Na1/2） TiO3-xBaTiO3 ceramics were investigated for the compositional range, x=0.02, 0.04, 0.06, 0.08, 0.10. The samples were synthesized by a conventional solid-state reaction technique. All compositions show a single perovskite structure, and X-ray powder diffraction patterns can be indexed using a rhombohedral structure. Lattice constants and lattice distortion increase while the amount of BaTiO3 increases. The X-ray diffraction results show the morphotropic phase boundary （MPB） of （1-x）（Bi1/2Na12） TiO3-xBaTiO3 exists in near x=0.06-0.08. Temperature dependence of dielectric constant eT33/ε0 measurement reveals that all compositions experience one structural phase and two ferroelectric phases transition below 400℃： rhombohedral （or rhombohedral plus tetragonal） ferroelectric phase ←→ tetragonal antiferroelectric phase ←→ tetragonal paraelectric phase. Relaxor behaviors exist in the course of ferroelectric to antiferroelectric phase transition. Dielectric and piezoelectric properties are enhanced in the MPB range for （ 1-x）（Bi1/2Na1/2）TiO3-xBaTiO3.     

Preparation and ferroelectric properties of Bi<Subscript>3.4</Subscript>Ce<Subscript>0.6</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films grown by sol-gel method

We have investigated the preparation and properties of Bi_3.4Ce_0.6Ti₃O₁₂ thin films. The Bi_3.4Ce_0.6Ti₃O₁₂ thin films were fabricated on the Pt/Ti/SiO₂/Si substrates using sol-gel method. The structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The thin films showed a perovskite phase and dense microstructure. The dielectric constant and the dissipation factor of the Bi_3.4Ce_0.6Ti₃O₁₂ thin films were about 172 and 0.031 at 1 kHz, respectively. The 2P _r and 2E _c of the Bi_3.4Ce_0.6Ti₃O₁₂ thin films were 67.1 μC/cm² and 299.7 kV/cm, respectively, under an applied field of 600 kV/cm. The Bi_3.4Ce_0.6Ti₃O₁₂ film did not show fatigue up to 4.46×10⁹ switching cycles at a frequency of 1 MHz, and showed good insulating behavior according to the test of leakage current. Supported by the Natural Science Foundation of Hubei Province (Grants No. 2004ABA082)     

Nanocomposite films of V<Subscript>2</Subscript>O<Subscript>5</Subscript>−MoO<Subscript>3</Subscript> xerogel with poly ethylene oxide intercalation

Poly ethylene oxide (PEO)_x−V₂O₅−V₂O₅−MoO₃ (x=0, 0.5, 1) films were prepared by the sol-gel method. The synthesis and structure of the films were investigated by XRD, TG-DTA, FTIR, etc. The results show that V₂O₅−MoO₃ xerogel has a layered structure and its interlayer space increased from 1.3181 nm at x=0 to 1. 7898 nm at x=1 after the nanocomposite films were dried, and PEO in the interlayer changes the interface structure by forming hydrogen bonds with V=0 bands. CV measurement indicates that the intercalation of PEO improves insertion/extration properties of Li⁺ ions in the interlayer. ZHENG Jin-xia: Born in 1976 Funded by the National Natural Science Foundation of China (No. 50172036) and Natural Science Foundation of Hubei Province(No. 2001ABB083)