Preparation and Properties of Ag—TiO2 Thin Films on Glass SUbstrates

Ag-TiO2 thin films were prepared on glasses.The morphology and structure of Ag-TiO2 films were investigated by XRD.SEM and FT-IR.The photocatalytic and hydrophilic properties of Ag-TiO2 thin films were also evaluated by examining photocatalytic degradation dichlorophos under sunlight illumination and the change of contact angle respectively.The research results show that the Ag-TiO2 thin film is mainly composed of 20-100nm Ag and TiO2 particles,The Ag-TiO2 thin films possess a super-hydrophilic ability and higher photocatalytic activity than that of pure TiO2 thin film.     

Effects of Nitrogen Doping on Microstructure and Photocatalytic Activity of Nanocrystalline TiO2 Powders

Nitrogen-doped TiO2 nanocrystalline powders were prepared by hydrolysis of tetrachloride titanium （TiCl4） in a mixed solution of ethanol and ammonium nitrate （NH4NO3） at ambient temperature and atmosphere followed by calcination at 400 ℃ for 2 h in air. FTIR spectra demonstrate that amine group in original gel is eliminated by calcination, and the TiO2 powder is liable to absorb water onto its surface and into its capillary pore. XRD and SEM results show that the average size of nanocrystalline TiO2 particles is no more than 60 nm and with increasing the calcination temperature, the size of particles increases. XPS studies indicate the nitrogen atom enters into the TiO2 lattice and occupies the position of oxygen atom. The nitrogen doping not only depresses the grain growth of TiO2 particles, but also reduces the phase transformation temperature of anatase to futile. The photocatalytic activity of the nitrogen-doped TiO2 powders has been evaluated by experiments of photocatalytic degradation aqueous methylene blue.     

Preparation of nanocrystalline BaTiO<Subscript>3</Subscript> ceramics

The high-dense nanocrystalline BaTiO₃ (BT) ceramics with grain size smaller than 100 nm have been successfully prepared by the two step sintering and the spark plasma sintering (SPS) process. The successive transitions in nanograin BT ceramics from rhombohedral to orthorhombic, tetragonal and cubic transitions, similar to those in coarse BT ceramics, were revealed by in-situ temperature dependent Raman spectrum. The multiphase coexistence and the diffused phase transition character were demonstrated in the 8 nm nanocrystalline BT ceramics. Supported by the National Basic Research Program of China (“973” Project) (Grant No. 2002CB613301) and the National Natural Science Foundation of China (Grant No. 50872093)     

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)     

Research and application of CO<Subscript>2</Subscript> refrigeration and heat pump cycle

The environmental problem caused by refrigerant has become the focus all over the world. As the most typical natural refrigerant, CO₂, of course, becomes the research focus. This paper introduces the development and application status of CO₂ refrigeration and heat pump technology. The researches on CO₂ refrigeration and heat pump, carried out by Thermal Energy Research Institute, Tianjin University, also are presented in this paper. Supported by the National Natural Science Foundation of China (Grant Nos. 50676064, 50506019) and the National Hi-Tech Research and Development Program of China (“863” Project) (Grant No. 2007AA05Z262)     

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）.     

Pool boiling on the superhydrophilic surface with TiO<Subscript>2</Subscript> nanotube arrays

Surface with TiO₂ nanotube arrays (TNTAs) is superhydrophilic and of great specific area. This paper investigates the pool boiling characteristics at the thermal interface with TNTAs. The results show that the TNTAs interface can enhance the pool boiling heat transfer compared to the pure Ti metal plate. The bubbles formed at the initial nucleation state are very small and released in higher frequency. The pool boiling heat transfer enhancement at the TNTAs interface may be attributed to the high density of nucleate site, high intrinsic heating area of nanotubes layer, superhydrophilicity and the vertically oriented nanotube structure. Supported by the National Natural Science Foundation of China (Grant No. 50846069)     

Formation of bulk ferromagnetic nanostructured Fe<Subscript>40</Subscript>Ni<Subscript>40</Subscript>P<Subscript>14</Subscript>B<Subscript>6</Subscript> alloys by metastable liquid spinodal decomposition

Nanostructured Fe₄₀Ni₄₀P₁₄B₆ alloy ingots of 3–5 mm in diameter could be synthesized by a metastable liquid state spinodal decomposition method. For undercooling ΔT > 260 K, the microstructure of the undercooled specimen had exhibited liquid state spinodal decomposition in the undercooled liquid state. The microstructure could be described as two intertwining networks with small grains dispersed in them. For undercooling ΔT > 290 K, the overall microstructure of the specimen changed into a granular morphology. The average grain sizes of the small and large grains are ≅ 30 nm and ≅ 80 nm, respectively. These prepared samples are soft magnets with saturation magnetization B _s ≅ 0.744 T. Supported by the Hong Kong Research Grants Council the National Natural Science Foundation of China (Grant No. 50861007) and Xinjiang University Doctoral Research Start-up Grant (Grant No. BS050102)     

Preparation of TiO<Subscript>2</Subscript> thin film by the LPD method on functionalized organic self-assembled monolayers

In this paper, uniform titania (TiO₂) films have been formed at 50° on silanol SAMs by the liquid-phase deposition (LPD) method at a temperature below 100°C. OTS (Octadecyltrichloro-Silane) self-assembled monolayers (SAMs) on glass wafers were used as substrates for the deposition of titanium dioxide thin films. This functionalized organic surface has shown to be effective for promoting the growth of films from titanic aqueous solutions by the LPD method at a low temperature below 100°C. The crystal phase composition, microstructure and topography of the as-prepared films were characterized by various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results indicate that the as-prepared thin films are purely crystallized anatase TiO₂ constituted by nanorods after being annealed at 500°. The pH values, concentration of reactants, and deposition temperatures play important roles in the growth of TiO₂ thin films. Support by the National Natural Science Foundation of China (Grant No. 50672055) and National Key Technology R&D Program (Grant No. 2006BAF02A28)     

Dielectric tunable properties of BaTi<Subscript>4</Subscript>O<Subscript>9</Subscript>-doped Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> microwave composite ceramics

BaTi₄O₉-doped Ba_0.6Sr_0.4TiO₃ (BST) composite ceramics were prepared by the conventional solid-state reaction and their structure, dielectric nonlinear characteristics and microwave dielectric properties were investigated. The secondary phase of the orthorhombic structure Ba₄Ti₁₃O₃₀ is formed among BST composite ceramics with the increase of BaTi₄O₉. At the same time, a duplex or bimodal grains size distribution shows fine grains in a coarse grain matrix. The degree of frequency dispersion of dielectric permittivity below T _m is increased initially and then decreased with respect to BaTi₄O₉. As the BaTi₄O₉ content increases, the tunability of composite ceramics decreases, while the Q value increases. Interestingly, 70 wt% BaTi₄O₉-doped BST has a tunability ∼4.0% (under 30 kV/cm biasing) versus a permittivity ∼68 and quality factor ∼134.1 (at ∼3.2 GHz). Supported by the Ministry of Science and Technology of China through 973-project (Grant No. 2009CB623302), the Cultivation Fund of the Key Scientific and Technical Innovation Project, Ministry of Education of China (Grant No.707024), Shanghai Committee of Science and Technology (Grant No. 07DZ22302), and Shanghai Foundation Project under 06JC14070     

Fabrication and magnetic properties of Sm3(Fe,Ti)29Nx/α-Fe dual-phase nanocomposite permanent magnetic material

Sm3(Fe,Ti)29Nx/α-Fe dual-phase nanometer magnetic material was fabricated through rapid solidification, crystallization and nitridation of Sm-Fe (Ti) alloy. The effect of combination of rapid solidification and Ti alloy addition on the phase formation and microstructure of the Sm-Fe alloy is investigated in this paper. The microstructure of amorphous phase and dual-phase nano-grain crystals before and after crystallization annealing were observed using a high-resolution transmission electron microscope (HREM). The dual-phase nano-grains after annealing were compacted together with a clear interface with the direct exchange-coupling mechanism. Different annealing processes were used to examine the melt-spun alloy. Comparison of the images of SEM showed that annealing at 750℃ for 10 min was most suitable to get homogeneous and nano-grains. No obvious kink was detected in the second quadrant of the hysteresis loop like a single hard magnet, and strong exchange coupling was found between hard magnets and soft magnets.     

Photocatalytic activity of lanthanum and sulfur co-doped TiO<Subscript>2</Subscript> photocatalyst under visible light

A novel lanthanum and sulfur co-doped TiO2 photocatalyst was synthesized by precipitation- dipping method, and characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and UV-Vis diffuse reflectance spectroscopy. Compared with the S-doped TiO, La-doped TiO2 and the standard Degussa P25 photocatalysts, the lanthanum and sulfur co-doped TiO2 photocatalyst （the molar percentage of La is 3.0%） calcined at 450 ℃ for 2 h showed the strongest absorption for visible light and highest activities for degradation of reactive blue 19 dye in aqueous solution under visible light（λ〉400 nm） irradiation. It was also discovered that the co-doping of lanthanum and sulfur hindered the aggregation and growth of TiO2 particles, and the doping of lanthanum reduced slightly the phase transition temperature ofTiO2 from anatase to rutile.     

The Influence of Annealing Temperature on the Structure and Properties of TiO2 Films Prepared by Sputtering

The TiO₂ films were prepared on slides by dc reactive magnetron sputtering, then the samples were annealed at 300°C, 350°C, 400°C, 450°C, 500°C and 550°C, respectively. X-ray diffraction (XRD) was used to obtain the TiO₂ film crystalline structure; X-ray photoelectron spectroscopy (XPS) was used to study the film surface stoichiometries; surface morphologies were studied by scanning electron microscopy (SEM); the contact angle was tested to indicate the TiO₂ film wettability; and the photocatalytic activity testing was conducted to evaluate the photocatalysis properties. The photocatalytic activity and contact angle testing results were correlated with the crystallinity, surface morphologies and surface ·OH concentration of TiO₂ films. The samples with a higher polycrystalline anatase structure, rough surface and high ·OH concentration displayed a better photoinduced hydrophilicity and a stronger photocatalysis. Funded by the National “863” Project Foundation (No. 2003LG0034)     

Sensing characterization of Sn/In/Ti nanocomplex oxides for CO,CH<Subscript>4</Subscript> and NO<Subscript>2</Subscript>

The nanocomplex oxides of Sn-In and Sn-In-Ti were prepared by controlled co-precipitation method as sensing materials of semiconductor gas sensors for detection of CO, CH4 and NO2. Through manipulating the Sn/In cation ratio, metal salt total concentration, precipitation pH value and aging time, the nanocrystalline powders were successfully derived with chemical homogeneity and superior thermal stability, compared with the single component oxides. The particle size and morphology, surface area, and thermal and phase stabilities were characterized using TEM, TG-DTA, BET and XRD. The sensing tests showed that the Sn-In composites exhibit high sensitivity and selectivity for CO and NO2. The introduction of TiO2 enhanced CH4 sensitivity and selectivity, particularly, additives of Pd and Al2O3 as a dopant and surface modification greatly enhanced the sensing properties. The sensitivity depended on the composition of composites, calcination temperature and operating temperature. The optimal values were (25%In2O3- 75%SnO2)-20%TiO2 for ternary composite, 600 and 300℃, respectively. Temperature-programmed desorption (TPD) studies were employed to explain the gas adsorption behavior displayed by the surface of nanocomposites and X-ray photoelectron spectroscopic (XPS) analysis was used to confirm the electronic interactions existing between oxide components. The sensing mechanism of the nanocomposites was attributed to chemical and electronic synergistic effects.     

Thermal-dynamical properties and pressure dependence of phonon spectrum of ordered Si<Subscript>50</Subscript>Ge<Subscript>50</Subscript> alloy based on <Emphasis Type="Italic">ab initio</Emphasis> methods

The phonon spectrum of ordered zincblende Si₅₀Ge₅₀ alloy is calculated by ab initio method. The energy band structure at zero pressure and the pressure dependence of phonon dispersion curves are shown up to 20 GPa. The calculation finds a pressure-induced softening of the transverse acoustic phonon mode and the mode frequency reaching zero at about 14 GPa, which indicate breaking of the symmetry and formation of a new phase under high pressure. Supported by the National Natural Science Foundation of China (Grant No. 50771090), the State Key Program for Basic Research of China (Grant No. 2005CB724404) and the Program for Changjiang Scholars and Innovative Team (Grant No. IRT0650)     

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)     

Theoretical calculation and experimental study of influence of oxygen vacancy on the electronic structure and hemocompatibility of rutile TiO2

In this work, the relationship between electronic structure and hemocompatibility of oxygen deficient rutile TiO_2−x was studied by both theoretical calculation and experimental study. Based on the local density functional theory, first-principals method was performed to calculate the electronic structure of rutile TiO₂ with different oxygen vacancy concentration. In the range of less than 10% of (or equal) physically realistic O vacancy concentration, the band gap of rutile TiO₂ increases with increasing O vacancy concentration, leading the TiO₂ changes from a p-type to an n-type semiconductor. The valance band of TiO₂ is predominated by O 2p orbital, while the conduction band is occupied by Ti 3d orbital for different O vacancy concentration. The O vacancy results in the occupation of electrons at the bottom of conduction band of TiO₂, and the donor density increases with increasing O vacancy concentration. When materials come in contact with blood, the n-type semiconductor feature of oxygen deficient TiO_2−x with the bottom of conduction band occupied by electrons would prevent charge transfer from fibrinogen into the surface of materials, thus inhibiting the aggregation and activation of platelets, therefore improving the hemocompatibility of rutile TiO_2-x . Supported by the National Basic Research Program of China (Grant No. 2005CB623904), National High-Tech Research Program of China (Grant No. 2006AA02A139) and National Natural Science Foundation of China (Grant No. 20603027)     

Electronic band structures of TiO<Subscript>2</Subscript> with heavy nitrogen doping

The first-principles density-functional calculation was conducted to investigate the electronic band structures of titanium dioxide with heavy nitrogen doping （TiO2-xNx）.The calculation results indicate that when x≤0.25,isolated N 2p states appear above the valence-band maximum of TiO2 without a band-gap narrowing between O 2p and Ti 3d states.When x≥0.50,an obvious band gap narrowing between O 2p and Ti 3d states was observed along with the existence of isolated N 2p states above the valence-band of TiO2,indicating that the mechanism proposed by Asahi et al operates under heavy nitrogen doping condition.     

Mechanism and behaviors of Cr3+-doped TiO2

TiO₂ powder and TiO₂ thin film on the surface of glazed ceramic tile were prepared by sol-gel method. The influences of different doping Cr³⁺ concentration on the photocatalytic activity of TiO₂ were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO₂ powder and film. The results indicate that photocatalytic activity of doping Cr³⁺-TiO₂ thin film is higher than that of powder, and the interaction between Cr³⁺-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr³⁺-doped energy level in TiO₂ is 0.62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr³⁺ dopant energy level, the semiconductor energy level model of Cr³⁺ in TiO₂ powder and thin film were established, and the doping mechanisms of Cr³⁺-doped in TiO₂ powder and thin film were analyzed. Foundation item: Project (20466001) supported by the National Natural Science Foundation of China     

Synthesis and structure of NaNbO<Subscript>3</Subscript> ceramic powders in ultrahigh pressure field

The NaNbO3 powders were synthesized and their crystal structure changes were analyzed by ultrahigh pressure up to 6 GPa. The results indicate that the pure NaNbO3 powders can be synthesized at 300℃ under a pressure of 4 GPa, to significantly restrain the Na element volatilization compared with the traditional synthesis method. It is found that the crystal structure of synthesized NaNbO3 changes from low symmetry to high symmetry with the increase of the pressure.